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Beryllium Edward S Grew Download

The document provides information about the book 'Beryllium: Mineralogy, Petrology, and Geochemistry' edited by Edward S. Grew, which includes various chapters on the mineralogy, petrology, and geochemistry of beryllium. It also contains links to related ebooks and resources for further exploration of beryllium's properties and applications. The book is part of a series published by the Mineralogical Society of America and includes a foreword and a detailed table of contents.

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0% found this document useful (0 votes)
10 views82 pages

Beryllium Edward S Grew Download

The document provides information about the book 'Beryllium: Mineralogy, Petrology, and Geochemistry' edited by Edward S. Grew, which includes various chapters on the mineralogy, petrology, and geochemistry of beryllium. It also contains links to related ebooks and resources for further exploration of beryllium's properties and applications. The book is part of a series published by the Mineralogical Society of America and includes a foreword and a detailed table of contents.

Uploaded by

klambisyila
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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•VII PITFTO 1 J L Û

ffiffilLu] O C M 1 M Ï Ï I S T T

.UOIIÏ1® IM

BERYLLIUM:
MINERALOGY, PETROLOGY,
AND GEOCHEMISTRY

EDITOR: E d w a r d s . G r e w

University of Maine, Orono, Maine

Series Editor: Paul H. Ribbe


Virginia Polytechnic Institute and State University
Blacksburg, Virginia

M M E I M L O O T C A L S O C I E T Y ©il  M Ï Ï E M C Â

Waisflnflnngii® nn9
COPYRIGHT 2 0 0 2

MINERALOGICAL SOCIETY OF A M E R I C A

The appearance of the code at the bottom of the first page of each chapter
in this volume indicates the copyright owner's consent that copies of the
article can be made for personal use or internal use or for the personal use
or internal use of specific clients, provided the original publication is
cited. The consent is given on the condition, however, that the copier pay
the stated per-copy fee through the Copyright Clearance Center, Inc. for
copying beyond that permitted by Sections 107 or 108 of the U.S.
Copyright Law. This consent does not extend to other types of copying
for general distribution, for advertising or promotional purposes, for
creating new collective works, or for resale. For permission to reprint
entire articles in these cases and the like, consult the Administrator of the
Mineralogical Society of America as to the royalty due to the Society.

REVIEWS IN MINERALOGY
AND GEOCHEMISTRY
(Formerly: REVIEWS IN MINERALOGY)

I S S N 1529-6466

Volume 50

Beryllium:
Mineralogy, Petrology, and Geochemistry

I S B N 0-93995062-6

Additional copies of this volume as well as others in


this series may be obtained at moderate cost from:

THE M I N E R A L O G I C A L S O C I E T Y OF A M E R I C A
1 0 1 5 EIGHTEENTH STREET, N W , SUITE 6 0 1
WASHINGTON, D C 2 0 0 3 6 U . S A .
BERYLLIUM: Mineralogy, Petrology, and Geochemistry
FOREWORD

The book has been several years in the making, under the experienced and careful
oversight of Ed Grew (University of Maine), who edited (with Larry Anovitz) a similar,
even larger volume in 1996: BORON: Mineralogy, Petrology, and Geochemistry (RiMG
Vol. 33, reprinted with updates and corrections, 2002). There are 14 chapters in
BERYLLIUM, and an overview of their contents may be found in the Introduction
(Chapter 1). Addenda and corrections to BERYLLIUM (and other volumes in this series)
are posted at http://www.minsocam.org .

Paul HRibbe, Series Editor


Blacksburg, Virginia
November 6, 2002

COVER

The cover illustrates the entry for beryllium in the Periodic Table. From upper left to
right, it gives the atomic number, valence state (the only one known in minerals),
chemical symbol, atomic weight and electronic configuration. Unlike boron, beryllium
has no diagnostic flame color, so I selected for the block a color of the Be mineral
euclase, BeAlSi04(0H). Beryllium minerals have found use as colorful gemstones, the
best known which are aquamarine (blue to green from Fe), emerald (green from Cr3+),
and alexandrite (red and green from Cr3+), others are chrysoberyl (green-yellow from
Fe3+), morganite (pink from Mn) and Euclase. See George Rossman's site:
http://minerals.gps.caltech.edu/FILES/Visible/index.html
The blue color in the cover is from a zoned euclase from Zimbabwe, which corresponds
to the absorption spectra below kindly provided by Rossman. This mineral is blue
because the Fe i+ /Fe 3+ intervalance band centered near 670 nm absorbs the red end of the
visible spectrum but allows the blue end to pass. Fe i + bands are seen near 850 and 1250
nm and a weak Fe3+ feature is near 440 nm. Sharp OH overtones appear near 1430 nm.
The three spectral curves in the figure are for linearly polarized light vibrating in the
directions in which the alpha, beta and gamma indices of refraction would be measured.

2.0
ß Hue last;
Zimbabwe

0.0
500 1000 1500 2000
Wavelength (nm)

1529-6466/02/0050-000035.00 DOI: 10.2138/rmg.2002.50.0


Reviews in Mineralogy and Geochemistry Volume 50

Table of Contents
1 Mineralogy, Petrology and Geochemistry of Beryllium:
An Introduction and List of Beryllium Minerals
Edward S. Grew

RATIONALE FOR VOLUME 1


B R I E F HISTORY OF B E R Y L L I U M 1
ECONOMICS OF B E R Y L L I U M 2
BOILING POINT 2
VALENCE 2
TOXICITY OF B E R Y L L I U M 4
B E R Y L L I U M ABUNDANCE 4
ANALYZING B E R Y L L I U M 4
Microbeam methods 5
MINERALOGY OF B E R Y L L I U M 5
Minerals containing essential beryllium 5
Minerals containing non-essential beryllium 17
B E R Y L L I U M STUDIES 23
Beryllium in terrestrial systems 24
Cosmogenic isotopes 24
Spectroscopy o f beryllium in minerals 25
CONCLUSION 25
ACKNOWLEDGMENTS 27
REFERENCES 28
APPENDIX 1. List of valid and potentially valid mineral species
containing essential beryllium 51
APPENDIX 2. List of problematic species 74
APPENDIX 3. Mineral synonyms o f recent origin 76

2 Behavior of Beryllium During Solar System and


Planetary Evolution: Evidence from Planetary Materials
Charles K. Shearer
INTRODUCTION 77
BEHAVIOR OF BE DURING EVOLUTION OF THE EARLY SOLAR SYSTEM:
EVIDENCE FROM METEORITES 81
Introduction 81
Classification of meteorites 81
Be abundance in meteorites 82
Behavior of Be during solar system condensation 84
Behavior of Be in chondrites and chondrules 91
BULK BE OF PLANETS AND BEHAVIOR OF BE DURING PLANETARY ACCREATION...97
BEHAVIOR OF BE DURING PLANETARY MAGMATISM. EXAMPLE: MOON 101
Introduction 101
Be in lunar basalts 103
Comparison between lunar and terrestrial basalts 104
Differences between crystalline mare basalts and volcanic pyroclastic glasses 106
Models for lunar basaltic magmatism as implied from the behavior of Be 108
BE IN MARTIAN METEORITES: 111
Table of Contents

EVIDENCE FOR MARTIAN WATER AND SOIL 111


Introduction 111
Water on Mars Ill
Martian soil? 112
USEFULNESS OF BE IN FUTURE PLANETARY STUDIES 113
ACKNOWLEDGMENTS 114
REFERENCES 114

3 Trace-Element Systematics of Beryllium in Terrestrial Materials


Jeffrey G. Ryan
INTRODUCTION 121
HISTORY OF BERYLLIUM ANALYSIS AND PAST STUDIES 121
BERYLLIUM IN MAJOR GEOLOGICAL RESERVOIRS 123
Beryllium in volcanic rocks—analytical studies 123
Experimental studies 127
Implications of beryllium partitioning for Be-systematics in volcanic rocks 129
Sediments and sedimentary rocks 130
Metamorphic rocks and minerals, and mineral/fluid partitioning 130
Oceans and the hydrosphere 134
DISCUSSION 136
Beryllium abundances in the mantle 136
Insights from beryllium behavior into subduction zone chemical fluxes 137
The global beryllium inventory 140
CONCLUSIONS 140
ACKNOWLEDGMENTS 140
REFERENCES 141

4 Rates and Timing of Earth Surface Processes


From In Sftw-Produced Cosmogenic Be-10
Paul R. Bierman, Marc W. Caffee, P. Thompson Davis, Kim Marsella,
Milan Pavich, Patrick Colgan, David Mickelson

INTRODUCTION 147
METHODS 149
Sample preparation 149
Isotopic analysis of l0 Be 156
INTERPRETING NUCLIDE DATA 159
Depth - production relationship 160
Model exposure ages 160
Model erosion rates 160
Erosion after exposure 161
Muons 161
Utilizing the 26AI/'°Be ratio 161
Nuclide production rates 162
ILLUSTRATIVE CASE STUDIES 165
Dating landforms 165
Constraining the magnitude of bedrock erosion by glaciers,
including the Laurentide Ice Sheet, North America 172
Understanding the history of clasts exposed at and near Earth's surface 176

vi
Table of Contents
Estimating bedrock erosion rates 181
River incision into rock 189
LOOKING B A C K W A R D A N D FORWARD 195
ACKNOWLEDGMENTS 196
REFERENCES 196

5 Cosmogenic Be-10 and the Solid Earth: Studies in Geomagnetism,


Subduction Zone Processes, and Active Tectonics
Julie D. Morris, John Gosse, Stefanie Brachfeld, Fouad Tera

INTRODUCTION 207
BACKGROUND 208
l0
Be measurements 208
Atmospheric l 0 Be in marine sediments and glacial ice 209
In situ cosmogenic 10 Be 211
,0
BE A N D GEOMAGNETISM 215
Introduction 215
Magnetic modulation of the primary galactic cosmic ray flux 217
Relative Paleointensity Recording in Sediment 220
Paleointensity as a correlation tool 221
The asymmetric sawtooth 225
Milankovitch periodicities in geomagnetic paleointensity records 227
Summary 230
SUBDUCTION A N D MAGMATISM AT CONVERGENT MARGINS 230
Introduction 230
l0
Be on the subducting plate 230
l0
Be in volcanic arcs: A global summary 235
l0
Be and magmatic processes 239
Future directions 243
TECTONIC APPLICATIONS OF IN SITU , 0 BE 243
Introduction 243
Exposure chronology of tectonic events 245
Bedrock erosion, stream incision, terrace deformation, and orogen-scale denudation 250
Paleoaltimetry 254
Summary 256
CONCLUSIONS 256
ACKNOWLEDGMENTS 257
REFERENCES 258

6 Environmental Chemistry of Beryllium-7


James M. Kaste, Stephen A. Norton, Charles T. Hess

INTRODUCTION 271
ANALYSIS F O R ' B E 271
P R O D U C T I O N A N D DELIVERY OF 7 BE T O THE E A R T H ' S S U R F A C E 272
7
BE DISTRIBUTION IN V E G E T A T I O N A N D SOILS 276
7
BE IN F R E S H W A T E R S 277
' B E IN T H E M A R I N E E N V I R O N M E N T 279
APPLICATIONS OF 7BE 281
SUMMARY AND CONCLUDING REMARKS 284
ACKNOWLEDGMENTS 285
REFERENCES 285

vii
Table of Contents

7 Environmental Chemistry of Beryllium


J. Vesely, S.A. Norton, P. Skrivan, V. Majer, P. Krâm, T. Navrâtil, J.M. Kaste

INTRODUCTION 291
BERYLLIUM IN THE ATMOSPHERE 291
BERYLLIUM IN PRECIPITATION 292
BERYLLIUM IN THROUGHFALL 294
BERYLLIUM IN FLORA AND FAUNA 294
BERYLLIUM IN SOIL 296
CHEMICAL WEATHERING 297
BERYLLIUM IN SOIL WATER AND GROUNDWATER 299
BERYLLIUM IN LAKES AND STREAMS 300
South America 301
Pearl River, China 301
SPECIATION OF BERYLLIUM IN WATER 305
PARTITION (DISTRIBUTION) COEFFICIENTS OF BERYLLIUM 306
BETWEEN WATER AND PARTICULATE MATTER 306
BERYLLIUM IN SEDIMENT 308
MASS BALANCE OF BERYLLIUM IN WATERSHEDS 310
ACKNOWLEDGMENTS 312
REFERENCES 312

8 Beryllium Analyses by Secondary Ion Mass Spectrometry


Richard L. Hervig

INTRODUCTION 319
INSTRUMENTATION 319
Primary ion beams 319
Secondary ions 320
ANALYSES FOR BERYLLIUM 321
The aluminum problem 321
Energy distribution of beryllium ions 322
Quantification of the beryllium signal 323
Negative secondary ions 327
LIMITS OF DETECTION 327
APPLICATIONS 329
Beryllium concentrations 329
Analyses of beryllium isotope ratios 329
Ion imaging of beryllium 330
CONCLUSIONS 330
ACKNOWLEDGMENTS 331
REFERENCES 331

9 The Crystal Chemistry of Beryllium


Frank C. Hawthorne, Danielle M.C. Huminicki

INTRODUCTION 333
CHEMICAL BONDING 333
STEREOCHEMISTRY OF Be(p4 POLYHEDRA IN MINERALS 333
Variation in <Be-(p> distances 334
Variation in Be-cp distances 334
General polyhedral distortion in Be-bearing minerals 334
viii
Table of Contents

MOLECULAR-ORBITAL STUDIES OF Be(p4 POLYHEDRA 336


Prediction o f equilibrium geometries 336
Deformation electron-density maps 339
Interpretation o f spectroscopic data 339
B E R Y L L I U M MINERALS AND THE IONIC MODEL 340
HIERARCHICAL ORGANIZATION OF C R Y S T A L STRUCTURES 342
POLYMERIZATION OF Be(p4 AND OTHER Tip4 TETRAHEDRA 342
A STRUCTURAL HIERARCHY FOR BERYLLIUM MINERALS 343
Isolated 7<p4 groups 344
Finite clusters o f 7tp4 groups 345
Infinite chains o f 7<p4 tetrahedra 345
Infinite sheets o f 7*(p4 tetrahedra 353
Infinite frameworks of T<p4 tetrahedra 362
THE [Be 2 0 6 ] GROUP 381
SOLID SOLUTION OF BERYLLIUM WITH OTHER CATIONS IN MINERALS:
CRYSTAL CHEMISTRY 382
Beryl 382
Milarite 383
Beryllium-bearing cordierite 384
Beryllium-bearing hellandite 385
Rhodizite 386
Hyalotekite 387
"Makarochkinite" 389
Sapphirine-related structures 391
Be-bearing micas 391
General observations on solid-solution relations involving beryllium 392
ACKNOWLEDGMENTS 393
REFERENCES 398

10 Mineralogy of Beryllium in Granitic Pegmatites


Petr Cerny

INTRODUCTION 405
CLASSIFICATION OF GRANITIC PEGMATITES 406
SYSTEMATICS OF THE B E R Y L L I U M MINERALS 408
FROM GRANITIC PEGMATITES 408
Oxides 408
Hydroxides 409
Borates 409
Phosphates 410
Arsenates 414
Beryllium-bearing silicates 414
Silicates of beryllium 415
Beryllosilicates and berylloaluminosilicates 415
BERYLLIUM AS A SUBSTITUENT IN SILICATES 426
PARAGENETIC, PETROLOGIC AND GEOCHEMICAL RELATIONS 427
LTC versus NYF assemblages 427
Primary versus late minerals 428
Controls on mineral assemblages 428
CONCLUDING REMARKS 433
ACKNOWLEDGMENTS 434
REFERENCES 434

ix
Table of Contents

11 Beryllium in Silicic Magmas and


the Origin of Beryl-Bearing Pegmatites
David London, Joseph M. Evensen

INTRODUCTION 445
BERYLLIUM CONTENTS OF PEGMATITIC MELTS AT BERYL SATURATION 445
Experimental evidence 445
Comparison to bulk compositions of pegmatites 448
BERYLLIUM BUDGETS FOR MAGMAS AT THEIR ANATECTIC SOURCES 452
Beryllium contents of protoliths 452
Mineral/melt partition coefficients 452
THE BERYLLIUM CONTENT OF SILICIC IGNEOUS ROCKS 456
Obsidians and rhyolites 456
Granites 466
THE BERYLLIUM BUDGET FROM MIGMATITE TO PEGMATITE 476
Beryl saturation in pegmatites 480
ACKNOWLEDGMENTS 481
REFERENCES 482

12 Beryllium in Metamorphic Environments


(emphasis on aluminous compositions)
Edward S. Grew

INTRODUCTION 487
BERYLLIUM CONTENTS OF NON-PELITIC METAMORPHIC ROCKS 488
BERYLLIUM CONTENTS OF SEMI-PELITIC, PELITIC
AND OTHER ALUMINOUS ROCKS 490
Unmetamorphosed rocks 490
Metamorphosed rocks 490
Relationship between whole-rock Be content and mineral assemblage 496
DESCRIPTION OF SELECTED MINERALS WITH MAJOR BERYLLIUM 497
Aenigmatite group and related minerals 497
Be-bearing cordierite (Mg > Fe)-sekaninaite (Fe > Mg) 511
Euclase '. 514
Taaffeite group 515
BERYLLIUM CONTENTS OF SELECTED ROCK-FORMING MINERALS 519
General statement 519
Mica group 520
Feldspar group 528
Staurolite 528
Almandine 529
Orthopyroxene 529
Miscellaneous calcium silicates 529
Kyanite 530
Distribution of beryllium among common rock-forming minerals 530
The special case of boron 532
Crystallographic features favoring incorporation of Be in minerals 534
CONCLUSION 536
ACKNOWLEDGMENTS 537
REFERENCES 537

x
Table of Contents

13 Be-Minerals: Synthesis, Stability, and Occurrence


in Metamorphic Rocks
Gerhard Franz, Giulio Morteani

INTRODUCTION 551
SYNTHESIS AND STABILITY EXPERIMENTS 552
Experimental techniques 552
System B e 0 - H 2 0 555
System B e 0 - A l 2 0 3 (and related R 3 + 2 0 3 ) 555
System B e 0 - M g 0 - A l 2 0 3 556
System Be0-Si0 2 -H 2 0-(F) 557
System Be0-Al 2 0 3 -Si0 2 -H 2 0-(F) 558
System B e 0 - M g 0 - A l 2 0 3 - S i 0 2 - H 2 0 564
System N a 2 0 - B e 0 - M g 0 - A l 2 0 3 - S i 0 2 - H 2 0 564
System N a 2 0 - K 2 0 - B e 0 - A l 2 0 3 - S i 0 2 - H 2 0 - ( F ) 568
System L i 2 0 - K 2 0 - B e 0 - M g 0 - A l 2 0 3 - S i 0 2 - H 2 0 - F 569
System B e 0 - Z n 0 - S i 0 2 569
System B e 0 - M n 0 - F e 0 - Z n 0 - S i 0 2 - S 2 570
Systems BeF 2 —fluorides of alkalis and alkaline earths 570
OCCURRENCE IN METAMORPHIC ROCKS 570
Metamorphosed pegmatites, granites and silicic volcanoclastic rocks 570
Metamorphic emerald-chrysoberyl-phenakite deposits .573
Metamorphic-hydrothermal Be-mineralization 577
Summary and open questions 579
ACKNOWLEDGMENTS 581
REFERENCES 581

14 Non-pegmatitic Deposits of Beryllium:


Mineralogy, Geology, Phase Equilibria and Origin
Mark D. Barton, Steven Young

INTRODUCTION 591
Economic sources of beryllium and beryllium minerals 594
TYPES OF DEPOSITS 595
BERYLLIUM MINERAL COMPOSTIONS 604
Beryl group—(•,Na,Cs,H 2 0)(Be,Li) 3 (Al,Sc,Fe + 3 ,Cr,Fe + 2 ,Mg) 2 [Si 6 0i8] 604
Helvite group—(Mn,Fe,Zn) 4 [BeSiO„] 3 S 609
Other minerals 611
BERYLLIUM MINERAL STABILITIES 611
Pressure-temperature-activity relationships 612
Solubility relationships 618
MAGMATIC BERYLLIUM ENRICHMENTS 619
Strongly peraluminous to metaluminous systems 620
Peralkaline-metalummous systems 621
HYDROTHERMAL OCCURRENCES ASSOCIATED WITH FELSIC MAGMATISM 623
Peraluminous magma-related systems 624
Metaluminous magma-related systems 631
Peralkaline magma-related systems 639
Igneous-related emerald deposits 643
NON-MAGMATIC OCCURRENCES 649
Fe-Mn(-Zn) oxide-rich occurrences 649
Basinal (and metamorphic?) brine-related emerald deposits 649

xi
Table of Contents

Metamorphic occurrences 650


Weathering and placers 652
S Y N O P S I S O F D E P O S I T C H A R A C T E R I S T I C S AND ORIGINS 653
Global-scale patterns 653
System-scale patterns 654
Origins 658
ACKNOWLEDGMENTS 658
A P P E N D I X A: Summary o f Beryllium Deposits by Region 659
A P P E N D I X B: Selected Studies Relevant to Beryllium Mineral Stabilities 671
REFERENCES 672

xii
1 Mineralogy, Petrology and Geochemistry of Beryllium:
An Introduction and List of Beryllium Minerals
Edward S. Grew
Department of Geological Sciences
5790 Bryand Center, University of Maine
Orono, Maine 04469
[email protected]

RATIONALE FOR VOLUME


In 1996, in collaboration with Lawrence Anovitz, I edited Boron Mineralogy,
Petrology and Geochemistry, volume 33 in the Reviews in Mineralogy series, a book that
has been reprinted with addenda in 2002 (further addenda and corrections are posted at
http://www.minsocam.org, where you may also find corrections to this volume). Many of
the same reasons for inviting investigators to contribute to a volume on boron apply
equally to a volume on beryllium. Like B, Be poses analytical difficulties, and it has been
neglected in many geochemical, mineralogical and petrological studies. However, with
the development of instruments to measure cosmogenic isotopes, greater availability and
refinement of the ion microprobe, and with overall improvement in analytical technology,
interest in Be and its cosmogenic isotopes has increased, and more studies are being
published. Thus, I decided that it was an appropriate time to invite those actively
involved in research on Be to contribute to this volume, which is intended to be a
companion to Boron Mineralogy, Petrology and Geochemistry. NOTE: In this chapter,
individual review papers are referred to by author name(s) and chapter number.

BRIEF HISTORY OF BERYLLIUM


The Be mineral beryl and its colored variants emerald, aquamarine, and
"chrysoberyl" (= golden beryl, not the present chrysoberyl) were known to the ancients,
and Pliny the Elder had noted that many persons considered emerald and beryl "to be of
the same nature" (Sinkankas 1981, p. 20; also Dana 1892; Weeks and Leicester 1968).
However, not until 1798 was it realized that beryl contained a previously unknown
constituent; analyses before then yielded only silica, alumina, lime and minor iron oxide
(Vauquelin 1798; Anonymous 1930; Weeks and Leicester 1968; Greenwood and
Earnshaw 1997). The mineralogist René Just Haiiy asked Nicolas Louis Vauquelin (Fig.
1) to analyze beryl and emerald in order to test his supposition that these two minerals
were identical as his measurements of crystals, hardness and density implied. In the
process, Vauquelin (1798) not only demonstrated the near chemical identity of beryl and
emerald, the latter differing in its tenor of chrome, but also isolated a new earth from
both, his terre du béril, similar yet distinct from alumina. The editors of the Annates de
Chimie et de Physique proposed to name it glucine (Greek, sweet) because its water-
soluble salts had a sweet taste, and because this name would be easy to remember.
However, Klaproth (1802, p. 79) thought it would be more sensible to call the new earth
"Beryllerde (Beryllina)" because yttrium salts are also sweet-tasting, and the name
beryllium is now generally accepted for the element.

Because Be is so similar to Al, chemists were confused about the valency and atomic
weight of Be. Avdeyev, Brauner and Mendeleyev argued that the periodic law required
Be to be divalent (Mendeleyev 1897). Divalency was confirmed in 1884 when the vapor
density of beryllium chloride was found to correspond to the formula BeC^, a confir-
mation that Mendeleyev considered "as important in the history of the periodic law as the
discovery of scandium" (Mendeleyev 1897, v. 2, p. 485; Stock 1932; Everest 1973).
1529-6466/00/0048-0001 $05.00 D01:10.2138/rmg. 2202.50.01
2 Chapter 1: Grew

Figure 1. Postage stamp honoring N.-L. Vauquelin issued by the


French government in 1963. For more information on the stamp see
"Phil - Ouest: Timbres de l'Ouest de la France"
<http://www.le-larm.com/PhilOuest/DO/index.htm?FenD=
http://www.le-lann.com/Phil-Ouest/DO/Album.html>.
Reproduction courtesy of Roy Kristiansen.

ECONOMICS OF BERYLLIUM
Beryllium is a strategic material because of its very low absorption cross-section
with respect to thermal neutrons, which, together with other special properties, makes Be
a good neutron moderator material (Everest 1973; Greenwood and Eamshaw 1997;
Emsley 2001). It is also the best reflector of neutrons, so that overall, it finds wide
application in nuclear reactors. Indeed, the neutron was discovered in 1932 when Be was
bombarded by alpha-particles. Beryllium is transparent to X-rays. For such a light metal,
Be is strong and refractory (Table 1), and resistant to corrosion because of an oxide film.
Beryllium metal finds extensive applications in alloys with copper, aluminum and other
metals, and BeO is an excellent refractory finding some use in ceramics.

Table 1. Selected information on elemental beryllium


PHYSICAL PROPERTIES ISOTOPES
Property Value Isotope Half-life
Atomic No. 4 6
Be 5.0 x 10"21 sec
7
Atomic Wt. 9.012182(3) Be 53.28 days
Configuration [He]2s2 s
Be ~7x 10"17 sec
Density, 20 °C 1.848 g/cm3 "Be stable
10
Melting point 1287°C Be 1.52 x 106 years
Boiling point 2471°C "Be 13.8 sec
12
Valence 2 Be 24. ms
14
Be 4.3 ms
Source of information: CRC Handbook of Chemistry and Physics. 79th Edition ( 1998-1999);
ms = millisecond

Although the metal was first isolated in 1828, independently by Wohler (1828) and
Bussy (1828), commercially feasible processes took over 100 years to develop as demand
for beryllium, its alloys and its compounds increased. Isolating high-purity beryllium
metal and working it have both proved to be technologically difficult. Beginning in 1898
chemists have attempted to apply electrolysis of Be fluorides for commercial production
(e.g., Stock, 1932), but current production of Be metal depends largely on reduction of
Introduction and List of Beryllium Minerals 3

BeF2 with Mg or electrolysis of Be chloride-alkali chloride electrolytes (Schwenzfeier,


1955; Windecker, 1955; Everest, 1973; Greenwood and Earnshaw 1997).
Until about 1960, pegmatitic beryl was the primary source of beryllium and the U.S.
was forced to import over 90% of the beryl that its beryllium industry needed during the
period 1936-1952 (Griffith 1955). However, in the 1960s, the situation changed radically
with the exploitation of epithermal deposits such as Spor Mountain, Utah (Staatz and
Griffits 1961; Staatz 1963; Barton and Young, Chapter 14), which, together with
hydrothermal deposits, became the primary source of economic beryllium (Everest 1973;
Wood 1992). A similar shift to the plutonic equivalents of Spor Mountain, i.e.,
hydrothermal bertrandite-phenakite-fluorite deposits such as Yermakovskoye, Buratiya in
Transbaikalia, took place in the former Soviet Union (Ginzburg 1975; Novikova et al.
1994; Kupriyanova et al. 1996). The beryllium ore in the epithermal deposits, commonly
bertrandite, is less refractory than beryl, and the larger size of the deposits result in their
being more economic to process. Table 2 summarizes some present-day production and
consumption statistics on beryllium. Kupriyanova et al. (1996) recommended increased
exploration for and exploitation of Be deposits in Russia in order to meet the increased
demand for Be as Russia's economy stabilizes, implying that the demand for beryllium is
an indicator of a country's technological and industrial development.

Table 2. A few economic facts on beryllium.


Year(s) 1997-2000* 2001*
PRODUCTION IN METRIC TONS

Worldwide 280-344 280


U.S. 180-243 180
China 55 55
Russia 40 40
Kazakhstan 4 4
Other countries 1-2 2
1998 APPARENT CONSUMPTION IN METRIC TONS

U.S. 300-385 295f


PRICE (U.S. DOLLARS) PER POUND OF METAL

Domestic, vacuum-cast ingot 327-421 338f


USE

Electronic components plus estimated 80% of total consumption


aerospace & defense applications
Source: U.S. Geol. Survey Minerals Information, Mineral Commodity Summary for
Beryllium , January, 2002, at
http://minerals.usgs.gov/minerals/pubs/commodity/beryllium/100302.
* Production amounts for 2000 and 2001 are estimated
' Estimated

This brief overview of Be economics would not be complete without mention of the
wide use of Be minerals as gemstones, notably emerald and aquamarine (varieties of
beryl) and alexandrite (chrysoberyl); taaffeite-group minerals, euclase, phenakite and
tugtupite are also fashioned into gemstones.
4 Chapter 1: Grew
TOXICITY OF BERYLLIUM
Beryllium is highly toxic, and the hazard to humans is greatest in industrial settings;
toxicity of Be compounds has also discouraged experimental investigations. However,
officials were slow to realize this toxicity until it was shown in the late 1940s that lung
beryllium disease ("berylliosis") was caused by Zn-Be silicate (synthetic beryllian
willemite) used as an ingredient in phosphors (Skilleter 1990). A resurgence of beryllium
disease in the 1990s led to regulations arbitrarily cutting the occupational exposure limit
value from 2^g/m 3 set in the 1940s to 0.2^g/m 3 pending research to identify the real
threshold limit below which disease will not occur (Ratney 2001). Vesely et al. (Chapter
7) review the literature on the environmental chemistry of Be and the spread of this
anthropogenic contaminant, which can be toxic to aquatic plants and animals.

BERYLLIUM ABUNDANCE
Despite its low atomic number, Be is a rare element in meteorites and the stellar
atmospheres, although less so in interstellar space, a paradox realized as early as 1926,
and attributed to destruction of Be at high stellar temperatures (Goldschmidt 1954;
Shearer, Chapter 2; see below). Beryllium is also a rare element on earth, but just how
rare, required more effort. Goldschmidt and Peters (1932) reckoned that Be would be
enriched in the Earth's crust because they expected Be to be lithophile like Li, and that
given the similarity of Be to Al in chemical behavior, Be could have been readily
overlooked as Washington (1931) conjectured was the case in igneous rocks. This
situation stimulated Goldschmidt and Peters (1932) to conduct the first geochemical
survey of Be contents in terrestrial rocks and minerals, as well as in meteorites and
confirmed thereby the rarity of Be in meteorites and in all but a few rocks.
Current estimates are that the Earth's upper crust averages 3 ppm Be, which
represents a 50-fold enrichment over the inferred content in primitive mantle, 60 ppb Be
(Taylor and McLennan 1985, 1995; Wedepohl 1995); for the crust as a whole, Be is the
47th most abundant element (Emsley 2001). Like boron, Be is a quintessential crustal
element.
ANALYZING BERYLLIUM
The analysis of the stable isotope 9 Be as a trace element in bulk samples has come a
long ways since Goldschmidt and Peters (1932) carried out their survey using a flame-
emission technique (Ryan, Chapter 3). The advent of plasma emission spectrometry
(either inductively coupled or direct current-generated) around 1980 pushed detection
limits down to the 0.1 ppm range. As a result, mantle and basaltic rocks could be
analyzed with precision and accuracy, which was not possible with flame photometry,
atomic absorption and fluorimetry, the methods available at that time. Major advances in
the analysis of the cosmogenic isotopes 10Be and 7 Be has opened up many new
opportunities for geochemical studies of Be (reviewed in this volume by Bierman et al.,
Chapter 4; Morris et al., Chapter 5; and Kaste et al., Chapter 6).
Beryllium as a major constituent in minerals presents an even greater challenge to
the analyst than boron (Anovitz and Grew 1996). Its chemical behavior is similar to Al,
so separation of Be from Al "demands a somewhat complicated procedure" (Washington
1931). As a result, it has been overlooked in minerals, and not only early in the history of
mineralogy, e.g., chrysoberyl (Seybert 1824). In the late 19th and early 20th centuries
many Be minerals were introduced as new without evidence that Be was an essential
component, e.g., bavenite, milarite (Palache 1931) and barylite (Aminoff 1923). Even in
more recent characterizations Be was not often sought, e.g., roggianite; compare
Passaglia (1969a,b) and Galli (1980) with Passaglia and Vezzalini (1988). In contrast,
Introduction and List of Beryllium Minerals 5

kolbeckite was originally reported to contain Be (Palache et al. 1944) and subsequently
was found not to have it (Hey et al. 1982).
Single-crystal structure refinement (SREF) is a powerful tool for measuring Be
independently of classical wet chemistry and microbeam technology (Hawthorne and
Grice 1990; Ottolini andOberti 2000).
Microbeam methods
Electron microprobe. Over the last ten years, several microbeam technologies have
been developed for in situ analysis of Be. The great advantage of in situ analysis is that
much less sample is needed and spatial variation in Be content can be assessed; petrology
was revolutionized in the 1960s when compositional zoning of elements with Z > 11 (Na)
in individual minerals could be mapped and quantified with the electron microprobe. For
lighter elements, particularly Be, such capability seemed out-of-reach, and relatively
recently Raudsepp (1995, p. 215) characterized the prospect of quantitative electron
microprobe analysis as "presently dim." Nonetheless, the outlook has been improving.
Meeker and Evensen (1999; also Evensen and Meeker 1997) assess the difficulties of Be
analysis with the electron microprobe. One is crystallographic orientation, which is not
normally a problem for heavier elements (Z > 10). Dyar et al. (2001) analyzed Be in
phenakite and hambergite and reported BeO contents within ±1-2 wt % of the ideal BeO
contents of 45.4-53.3 %, whereas Kleykamp (1999) reported successful analysis of Be in
the synthetic compound Li 2 Be 2 03. Current top-of-the-line microprobes (e.g., JEOL 8200,
Cameca SX 100) feature Be-analytical capability.

Ion microprobe. A widely used microbeam method for Be analysis is secondary ion-
mass spectroscopy (SIMS) with the ion microprobe (Ottolini and Oberti 2000; Hervig,
Chapter 8).
Inductively coupled plasma mass spectrometry. Another promising technology is
laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), which is
finding increasing application in the earth sciences (e.g., Durrant 1999; Sylvester 2001).
However, relatively few investigators have applied it specifically to Be analyses, whether
in earth sciences (Bea et al. 1994; Zack 2000; Flem et al. 2002), or in other sciences
(Crain and Gallimore 1992). Beryllium can be measured as one of many elements in a
trace-element package using Ar as a carrier gas (e.g., Bea et al. 1994; see Grew, Chapter
12). However, by restricting menus to 6-12 elements, conditions can be optimized, i.e.,
the ICP-MS is tuned for maximum sensitivity for a certain mass range and, in the case of
Li, Be and B, sensitivity is markedly increased using He as carrier gas (Zack 2000).
Nuclear microprobe. Beryllium can also be analyzed with a nuclear microprobe
using particle-induced gamma-ray emission (PIGE) spectrometry (Volfinger and Robert
1994; Rio et al. 1995; Lahlafi 1997; Calligaro et al. 2000; Kim et al. 2000). Detection
limits depend on the nuclear reaction used and appear to be very sensitive to experimental
conditions. This limit is reported to be 700-1800 ppm Be in some studies and thus only
minerals containing substantial Be can be analyzed, e.g., emerald (Calligaro et al. 2000).
In others, the reported limit was only 20 ppm, so that Be at trace levels in Li mica could
be monitored (Volfinger and Robert 1994); Lahlafi (1997) obtained comparable (but not
specified) detection limits in a study of trace Be in synthetic micas.

MINERALOGY OF BERYLLIUM
Minerals containing essential beryllium
About 110 mineral species, i.e., naturally occurring, inorganic solid compounds,
have been reported to contain essential Be as of 2002. By essential, I mean that the
6 Chapter 1: Grew

mineral cannot form in the absence of Be. These minerals have been tabulated in
Appendices 1 and 2; names not yet approved by the International Mineralogical
Association (IMA) Commission on New Minerals and Mineral Names (CNMMN) are
given in quotation marks in both appendices: The 98 valid and potentially valid species
include 8 oxides and hydroxides, 4 borates, 25 phosphates and arsenates lacking silicate,
and 61 silicates.
Valid species. A total of 89 minerals are considered valid species (Appendix 1),
which includes species approved by the IMA CNMMN, beginning in 1959. Although
absent from some lists of Be minerals (e.g., Ross 1964; Beus 1966), hyalotekite is
included in my list because Be is reported in all analysis in which it was sought (cf. the
Y-dominant, Be-free analogue kapitsaite, Pautov et al. 2000; Sokolova et al. 2000).
Hawthorne and Huminicki (Chapter 9) review hyalotekite compositions and conclude
that two end-member compositions are needed to describe reported compositions even if
substitutions involving Y, Pb and K are ignored, and that one of these two end members
contains essential Be (also Hawthorne 2002).
Potentially valid species. Nine minerals are considered potentially valid species
(Appendix 1). Although not confirmed by IMA CNMMN, available data suggest that
they meet the criteria for being distinct species (Nickel and Grice 1998), i.e., in terms of
composition (e.g., several minerals in the gadolinite group, Y- and Sc-dominant milarite)
or crystal structure (triclinic Fe- and Mn-dominant analogues of roscherite).
Problematic species. The validity of 12 minerals is considered unproven (Appendix
2). These are incompletely studied minerals (e.g., "glucine"), minerals whose status as
distinct species requires confirmation (triclinic modification of leucophanite, Li-dominant
analogue of odintsovite), or minerals that are likely a variety of another species
("gelbertrandite"), as well as minerals of purely historical interest (e.g., "muromontite"). I
include these minerals in order to draw attention to the need for fiirther mineralogical
research, particularly in the gadolinite group, to which six of the problematic species
belong.
How the appendices were compiled:
Column 1 in Appendices 1 and 2 gives the name and relationships, e.g., the group to
which the mineral belongs (as defined in Fleischer's Glossary of Mineral Species,
Mandarino 1999) and any analogues, e.g. bazzite (Sc-dominant analogue of beryl and
stoppaniite), the crystal system and a generalized formula in which major substitutions
are indicated. In a few cases, a formula with specific coefficients is given instead; this
seems appropriate when only one complete analysis has been reported, e.g.,
minasgeraisite. Hawthorne and Huminicki (Chapter 9) give idealized end-member
formulae based on crystal structure refinements in their Appendix A.
Column 2 gives in broad terms the environments where the mineral occurs.
Column 3 gives the type locality in italics (if known) together with other localities. I
have added "and others" to indicate that the list is not complete. Locality information for
minerals found in the former Soviet Union is largely taken from Pekov (1994, 1998); the
original authors generally provided few specifics on localities. Areas unusually prolific in
numbers of Be mineral species are listed in Table 3.
Column 4 gives sources for the information provided in Appendix 1, including any
reviews of the mineral. The original description is listed first, whether consulted or not;
references not consulted are so indicated in the bibliography. In some cases, partial
descriptions of a given mineral were published before the mineral was introduced as a
distinct species. If a cited paper has been abstracted in American Mineralogist, e.g., in
Introduction and List of Beryllium Minerals 7

Table 3. Areas unusually prolific in number of beryllium mineral species

SPECIES LOCALITY R E F E R E N C E ( S ) IN ADDITION


Type 1 Total 2 TO A P P E N D I X 1

10 12 Langban and Harstigen Fe-Mn deposits, Holtstam & Langhof (1999)


Bergslagen ore region, Varmland Co.,
Sweden
6.53 22 Nepheline-syenite pegmatites, Oslo Raade et al. (1980); Engvoldsen et al. (1991);
Region, Norway Andersen et al. (1996)
6 17 Granite pegmatites, Minas Gerais state, Bhaskara Rao & Silva (1968);
Brazil (18 species in Brazil overall) Atencio (2000a,b)
5.54 19 Ilimaussaq and Igaliko peralkaline Semenov (1969); Engell et al. (1971);
complexes, southwest Greenland Petersen & Secher (1993); Markl (2001b)
5 9 Granite pegmatite, Tip Top Mine, Custer Campbell & Roberts (1986)
Co., South Dakota, USA
4.54 15 Lovozero and Khibiny peralkaline Vlasov et al. (1966); Semenov (1972);
complexes, Kola Peninsula, Russia Khomyakov (1995), Men'shikov et al.
(1999); Yakovenchuk et al. (1999);
Pekov (2000)
4 14 Granite pegmatites, Oxford County, King & Foord (1994, 2000)
Maine, U.S.A. (15 for state as a whole)
4 15 Granite pegmatites and greisens, Middle Yarosh (1980);
Urals (Yekaterinburg area), Russia Pekov (1994, 1998)
2 12 Hsianghualing tin deposit, Hunan, China Huang etal. (1988)
2 8/10 Granite pegmatites, Baveno, Novara, Albertini (1983); Nova (1987);
Italy Pezzotta et al. (1999)
2 8 Granite pegmatites of central Lacroix (1922); Behier (1960);
Madagascar, e.g., Sahatany River area, Wilson (1989); Lefevre & Thomas (1998);
Anjanabonoina pegmatite Pezzotta (1999)
2 4 Metamorphosed Fe-Mn-Zn deposit, Palache (1935); Frondel & Baum (1974);
Franklin, New Jersey, USA Dunn (1995)
1 14/16 Skarn, Lupikko, Pitkaranta, Karelia, Eskola (1951); Nefedov (1967); Nikol'skaya
Russia (including beryl in pegmatite) & Larin (1972); Nefedov et al. (1977);
Schmetzer (1983); Pekov (1994, 1998)
1 11/12 Heftetjern granite pegmatite, Tordal, Juve & Bergstol (1990); Raade & Kristiansen
Telemark, Norway (2000), R. Kristiansen (pers. comm.)
1 9/10 Granite pegmatites, Pike's Peak Raines (2001)
batholith, Colorado, USA
1 8 Granite pegmatite, Foote Mine, Kings Marble & Hanahan (1978)
Mountain, Cleveland Co., North
Carolina, USA
1 8 Li pegmatites, Erajarvi area, Finland (7 Volborth (1954b); Mrose & von Knorring
in the Viitaniemi pegmatite) (1959); Lahti (1981)
1 5 Pegmatites, Khmara Bay, Enderby Land, Grew (1981, 1998);
Antarctica Grew et al. (2000)
1 5 Be-enriched gneiss, Hogtuva near Mo i Lindahl & Grauch (1988);
Rana, Nordland County, Norway Grauch et al. (1994)
0 15/17 Peralkaline pegmatites, Mont Saint- Mandarino & Anderson (1989); Horvath &
Hilaire, Quebec, Canada Gault (1990); Chao et al. (1990);
Horvath & Pfenninger-Horvath (2000a,b)

Note: 'Number of species for which area is the type locality. 2Number of species from Appendix 1 confirmed
in the given area/possible species, including unconfirmed identifications. 3Chiavennite was discovered
simultaneously at Chiavenna and Tvedalen; the former is considered the type locality. 4Tugtupite was
discovered almost simultaneously at Ilimaussaq and Lovozero; the former is considered the type locality.
8 Chapter 1: Grew

that journal's section "New Mineral Names", then the volume number and page of the
abstract is given in square brackets following the citation. Chemical Abstracts is cited if
no abstract were published in American Mineralogist. If the original description were
incomplete or erroneous, papers reporting the correction are also cited. A common error
in original descriptions is overlooking the presence of Be in the mineral. Information has
also been obtained from the review papers listed in Table 3. Crystal structure refinements
are cited if the cited formula is based on them. Hawthorne and Huminicki (Chapter 9)
discuss all minerals for which the crystal structure has been refined and cite the papers
reporting the latest refinements. Cerny (Chapter 10) considers every mineral found (or
reported) in granitic pegmatites. Other chapters are cited if the mineral is considered in
detail.
Information on the Be minerals listed in Appendix 1 also can be found in recently
published compendia such as Dana's New Mineralogy (Gaines et al. 1997), Handbook of
Mineralogy (Anthony et al. 1995, 1997, 2000), Encyclopedia of Mineral Names
(Blackburn and Dennen 1997), Strunz Mineralogical Tables (Strunz and Nickel 2001),
and the International Encyclopedia of Minerals (Mandarino, Editor-in-Chief, in
preparation). Chemical analyses of each mineral are given in the Handbook of
Mineralogy. Detailed descriptions, with hard-to-obtain information on minerals found in
the former Soviet Union, are given in the Russian-language Mineraly handbooks
(volumes 3 and 4, three issues each, 1972-1996, Chukhrov et al., 1972, 1981a,b; 1992a,b;
Bokiy et al., 1996). These compendia (except the International Encyclopedia of
Minerals, which was not available at the time) have been invaluable in assembling the
information in Appendix 1. Older compendia providing useful information on Be
minerals are Dana's System of Mineralogy, 6th (Dana 1892) and 7th editions (Palache et
al. 1944, 1951); Beus (1966), Vlasov (1966), Ginzburg (1976), Burt (1982) and Clark
(1993); Beus and Vlasov provide coverage in English of papers published in Russian and
Chinese. Zeolite minerals, including tvedalite, a possible zeolite, are briefly described in
the report of the subcommittee on zeolites (e.g., Coombs et al. 1997). Country-wide
overviews of Be mineral occurrences (see also Appendices 1 and 2) include Pekov (1994,
1998) for the former USSR (14 new species, 46 overall), Kristiansen (1999a,b) and
Nijland et al. (1998) for Norway (9 new species, 31 overall), Atencio (2000a,b) for Brazil
(6 new species; 18 overall, all but one in Minas Gerais), and Hiigi et al. (1968) and Hiigi
and Rowe (1970) for Switzerland (2 new species, 11 overall). Information on type
minerals is also provided for Norway (Raade 1996) and Australia (Sutherland et al.
2000).

I have tried to be consistent in my two chapters in the transcription of geographic


names from other writing systems; most importantly, Russian and Chinese. However, I
have not insisted other contributors adhere to the same transliterations because there are
often two or more variants in the literature itself. Examples include Yermakovskoye/
Ermakovskoe (Be deposit in Buryatiya, Russia), Hsianghualing/Xianghualing (Be deposit
in Hunan, China).
Information that is too involved, incomplete or contradictory and consequently in
need of further comments that could not be accommodated in Appendices 1 and 2 is
given below under the name of the mineral in question.
Appendix 3 lists mineral synonyms of recent origin, the accepted equivalents, the
original description, and the source of the renaming. A complete listing of mineral
synonyms may be found in Clark (1993), de Fourestier (1999) and Bayliss (2000).
Dubious reports. In compiling Appendix 1,1 have accepted published information as
Introduction and List of Beryllium Minerals 9

reported in good faith. However, there are a few cases where the reported information
could be fraudulent or misleading, and these are not included in the list, but are
mentioned here instead. Behoite has also been reported from Clear Creek, Burnet Co.,
Texas (Crook 1977), but given Crook's record of falsification with regard to other
minerals (Peacor et al. 1982), this report of behoite should be viewed with caution.
Kingsbury (1961, 1964) reported a detailed study of danalite and helvite and an
occurrence of rhodizite from Meldon dyke, Okehampton, Devon, UK, respectively. By
rights, both papers should be cited in Appendix 1. However, the findings by Ryback et al.
(1998, 2001) that Kingsbury falsified localities of other minerals he reported casts serious
doubts on the value of Kingsbury's (1961, 1964) studies of Be minerals.
Aminoffite. The original analysis (Hurlbut 1937) and crystal structure refinement
(Coda et al. 1967; Hawthorne and Huminicki, Chapter 9) disagree on the Be/Si ratio and
presence of Al. The mineral reported from Tuva, Russia by Kapustin (1973a,b) does not
appear to be aminoffite: (1) the chemical analyses do not agree with those reported by
Hurlbut (1937) or by Coda et al. (1967); (2) powder X-ray data differ from those on the
type material (Mandarino 1964).
Bavenite. This mineral varies considerably in composition and most available
analyses show excess Be relative to the idealized formula given in most references,
Ca4Be2Al2Si9026(OH)2. Beryllium varies inversely with Al according to the formula
Ca4(Be0H)2+xAl2-xSi9026-x, where 0 < x < 1,
or Ca 4 Be 2 Al2Si9026(0H)2 - Ca 4 Be 3 AlSi9026(0H)3
(Switzer and Reichen 1960; Berry 1963; Beus 1966; Cannillo et al. 1966; Petersen et al.
1995). The status of H is less clear; available chemical data show little evidence for an
increase of H with Be. Petersen et al. (1995) reported a broad absorption band in their
infrared spectrum that they attribute to molecular H2O, whereas Komarova et al. (1967)
found no such absorption features. Mark Cooper and Frank Hawthorne are currently
carrying out a systematic study of bavenite crystal chemistry.
Bertrandite and "gelbertrandite" (cf. sphaerobertrandite). "Gelbertrandite" appears
to be a colloidal or cryptocrystalline bertrandite containing variable amounts of molecular
water that is lost easily on heating, and is thus not a valid species (Semenov, 1957; Pekov
1994, 2000). The variety of bertrandite in the Be-bearing tuff at Spor Mountain, Utah has
chemical and physical properties intermediate between Lovozero "gelbertrandite"
(Semenov 1957) and bertrandite proper (Montoya et al. 1962).
Beryllite. Beryllite is recognized as a distinct species yet shows certain similarities to
sphaerobertrandite and bertrandite. For example, beryllite Be/Si ratio of 2.8 to 3.1 is
variable from specimen to specimen and is close to sphaerobertrandite Be/Si, now shown
to be 3.0. A bigger compositional difference is the presence of substantial H2CT in
beryllite analyses. Although most low angle reflections in the powder X-ray diffraction
patterns for beryllite and bertrandite are different, higher angle reflections (d < 2.2 A) are
remarkably similar.
Bevyllonite. Nysten and Gustafsson (1993) and Charoy (1999) reported small Na
deficits in electron microprobe analyses of beryllonite; Charoy (1999) also reported
substantial F (0.64-1.19 wt %). Formulae calculated from Charoy's (1999, Table 2)
analyses are Na0.93Be0.99P1.00O3.92F0.08 and Na0.92BeP1.01O3.96F0.04 (assuming ideal Be
content in second formula); these suggest that F (+ OH?) incorporation and Na deficit
could be related through (F,OH)DO.iNa_i.
Bityite. The Mica Subcommittee of the IMA CNMMN (e.g., Rieder et al. 1999)
defined bityite, end-member composition CaLiAl2(AlBeSi2)Oio(OH)2, as a trioctahedral
10 C h a p t e r 1: G r e w
[61
brittle mica with Li > • . However, this definition overlooks both the variable Be
content of bityite and solid solution between margarite and ephesite, ideally
NaLiAl2(Al 2 Si2)Oio(OH)2. A definition citing Be as well as Li contents might have been
preferable, e.g., that a Ca-rich mica with Be > 0.5 apfu as well as [61Li > • would
qualify as bityite (Lahti and Saikkonen 1985). Grew (Chapter 12) considers bityite-
margarite solid solution in more detail.
Faheyite. This phosphate is one of the few Be minerals for which a crystal structure
has not been reported (Hawthorne and Huminicki, Chapter 9). The idealized formula
originally given for the mineral, (Mn 2+ ,Mg,Na)Fe 3+ 2Be2(PC>4)4 - 6H20, is not balanced, so
most compendia simplify it to (Mn 2+ ,Mg)Fe 3+ 2Be2(P0 4 ) 4 -6H20 (e.g., Mandarino 1999).
However, this simplification ignores the substantial Na reported in the original analysis,
0.93 wt % N a 2 0 , corresponding to 0.20 Na per formula unit in a formula (Appendix 1)
calculated from the original analysis corrected for insoluble quartz and muscovite
(Lindberg and Murata 1953). Several tenths wt % Ca are also reported in a semi-
quantitative spectrogram. These findings suggest the possibility of a partially occupied
(Na,Ca) site distinct from an M site occupied by divalent cations, but impurities could
also be contributing to the difficulty of deducing a proper formula.

Gadolinite group. The mineral gadolinite-(Y) was first described by Geyer (Geijer)
inl788 as "schwarzer Zeolith" (black zeolite) in material collected by C.A. Arrhenius and
analyzed by Johan Gadolin in 1794 as "ytterbite", but Klaproth (1802) was the first to
apply the name "gadolinite" (Dana 1892). Klaproth (1802) named the mineral in honor of
Gadolin for his discovery of "yttria" (Y oxide mixed with Er, Tb and other REE oxides)
in it (Weeks and Leicester 1968). Because gadolinite was the original source of the Y and
related rare earths, Flink (1917c) opined that maybe it played a larger role in the history
of inorganic chemistry than any other mineral.
The gadolinite group (Table 4) includes the valid Be silicates gadolinite-(Y),
gadolinite-(Ce), hingganite-(Y), hingganite-(Yb) and minasgeraisite-(Y), as well as the
borosilicates calcybeborosilite-(Y), datolite, and homilite (Mandarino 1999; DeMartin et
al. 2001; Hawthorne and Huminicki, Chapter 9); the status of bakerite is under study. In
addition, there are several minerals that have not been approved by the IMA C N M M N as
valid species (Appendices 1, 2), namely, "calcio-gadolinite", calcium-rich gadolinite
(Oftedahl 1972 reported Ca replaces Fe and not rare earths and Y as in calcio-gadolinite),
Engstrom's "erdmannite" (Dana 1892; Ito and Hafner 1974; Raade 1996), "gadolinite-
(Nd)" (Kartashov and Lapina 1994); "hingganite-(Ce)", "hingganite-(Nd)" (Kartashov
and Lapina 1994), and the unnamed minerals reported by Miyawaki et al. (1987), Chao et
al. (1990); Delia Ventura et al. (1990), Wight and Chao (1995), and Jambor et al. (1998).
Several of these minerals are potentially valid species. R. Miyawaki (pers. comm.) is
preparing proposals to IMA C N M M N for Ce- and Nd-dominant analogues of hingganite-
(Y) and hingganite-(Yb), which may be "hingganite-(Ce)" and "hingganite-(Nd)"
according to the Levinson modifier, and the Ca-rich hingganite-like mineral with solid
solution towards YCaFe3+o.33Be2Si2C>8(OH)2 that was described by Miyawaki et al.
(1987). The Ca-rich hingganite-like mineral is compositionally calcian, ferroan
hingganite-(Y) because (Y, REE) > Ca and • > Fe, but has lower symmetry than
hingganite-(Y), i.e., P2\ vs. P2i/a, and thus could be a distinct species. Several of the
other unnamed minerals are similarly intermediate in composition between valid or
potentially valid species for which a distinct end-member formula can be written (bold
font in Table 4); space groups of these other intermediate phases have not been reported.

The end member compositions are related by both homovalent substitutions on one
site, most importantly, CeY.i (and other rare earths) and CaFe.i, and coupled heterovalent
substitutions involving different sites, most importantly, CaB(YBe).i, CaFe 3+ (YFe 2+ ).i,
Introduction and List of Beryllium Minerals 11

and • ( 0 H ) 2 F e . i 0 . 2 (Burt 1989; Miyawaki and Nakai 1996; Pezzotta et al. 1999).
DeMartin et al. (2001) noted that no convincing evidence has been reported for the

Table 4. Idealized formulae for minerals of the gadolinite group.


1
Bakerite Ca4B4(B04)(Si0 4 )3(0H)3 • H 2 0 ( ? )

Calcybeborosilite-(Y) Y2DB2(Si20g)02

"Calciogadolinite-(Ce)" (see Appendix 2) CaCeFe2+Be2(Si20g)0(0H)

"Calciogadolinite-(Y)" CaYFe3+Be2(Si20g)02
(Ito 1967; Povarennykh 1972)

Datolite Ca 2 DB 2 (Si 2 O g )(OH) 2

Gadolinite-(Ce) Ce 2 Fe 2 + Be 2 (Si 2 0 g )0 2

"Gadolinite-(Nd)" Nd 2 Fe 2 + Be 2 (Si 2 0g)0 2

Gadolinite-(Y) Y 2 Fe 2 + Be 2 (Si 2 0g)0 2

"Hingganite-(Ce)" Ce 2 DBe 2 (Si 2 Og)(OH) 2

"Hingganite-(Nd)" Nd 2 DBe 2 (Si 2 Og)(OH) 2

Hingganite-(Y) Y 2 DBe 2 (Si 2 Og)(OH) 2

Hingganite-(Yb) Yb 2 DBe 2 (Si 2 Og)(OH) 2

Homilite Ca 2 Fe 2 + B 2 (Si 2 0g)0 2

Minasgeraisite-(Y) Y 2 CaBe 2 (Si 2 0g)0 2

Unnamed YCaFe 3+ o.3 3 üo.67Be 2 Si 2 Og(OH) 2


Note: Bold indicates mineral (valid species or not) for which an end-member composition is given. The
status of bakerite as a distinct species is currently under study. It probably corresponds to a B-rich datolite.
(N. Perchiazzi & A. Kampf, pers. comm.). The vacancies indicated by • mark the absence of Fe 2+ or Ca
(as in minasgeraisite), but are not true voids due to the presence of two protons (Demartin et al. 2001).

presence of substantial Fe 3+ in fresh, unoxidized samples or for Ca substitution of Fe 2+ .


Thus, only the substitutions CaB(YBe)_i and •(OH)2Fe_iO-2 are important in describing
compositional variations among Y-dominant gadolinite-group minerals. In addition,
DeMartin et al. (2001) noted that the latter substitution should be written (OH)2Fe_iO-2
because there are no vacancies on the site occupied by Fe; when Fe is absent, two protons
take its place. Demartin et al. (2001) called into question the existence of minasgeraisite-
(Y) in which Fe 2+ is largely replaced by Ca.
Study of this mineral group is complicated by difficulties in analyzing individual
rare earth elements, distinguishing Fe 3+ and Fe 2+ , complications due to the presence of
other constituents (e.g., Bi, Th, U), and in detecting the presence of small amounts of
hydroxyl, as well as by the common metamictization and alteration.
Gainesite group (gainesite, mccrillisite, selwynite). The analyses yield formulae
deficient in Be relative to the ideal formulation Na(Na, K, Cs)BeZr2(P04)4-l-2H 2 0. In
gainesite and mccrillisite, this deficiency is largely made up by Li, whereas in selwynite,
Al + Be = 0.54 and Li was not detected. Neither the question of charge balance and
stoichiometry nor the location of the water molecules has been addressed in a systematic
crystallographic study of these minerals.
Herderite. Haidinger (1828a,b) did not analyze the type herderite, and subsequently,
12 Chapter 1: Grew

no one has conclusively demonstrated that the type material is F dominant. There were
several attempts to determine F and OH in herderite from Ehrenfriedersdorf in the late
19th century, but the results were contradictory and resulted in considerable controversy,
no doubt due to the difficulty of analyzing for F by the methods then in use (Weisbach
1884; Genth 1884; Winkler 1885; Leavens et al. 1978; Dunn et al. 1979; King and Foord
1994; Jahn 1998). Leavens et al. (1978) analyzed 41 samples by electron microprobe and
found all to be OH dominant, assuming ideal F+OH content, but material from the type
locality, Ehrenfriedersdorf, was not available for this survey. No chemical data are
available for the herderite reported from Italy and Pitkaranta (see below), and Dunn and
Wight (1976) analyzed the Brazilian gem only for F. In summary, a complete chemical
analysis of herderite has not yet been published.
Haidinger (1828a,b) also provided no information on the paragenesis for the type
herderite, which was part of A.G. Werner's collection, now housed in the museum of the
Bergakademie Freiberg (Massanek et al. 1999). The holotype specimen was recently
found anew after having been lost. This and other specimens from the Sauberg district
near Ehrenfriedersdorf show herderite with apatite, "gilbertite" (mixture of muscovite
with kaolinite), quartz, cassiterite, wolframite and fluorite in vugs (Jahn 1998; Massanek
et al. 1999; Massanek, pers. comm.), purportedly from veins cutting mica schist (Franke
1934; Schneiderhohn 1941, p. 131). The provenance of the herderite gemstone studied by
Dunn and Wight (1976) is unknown except that it is from Brazil. There are also reports of
herderite from Baveno and Cuasso al Monte, Italy (respectively, Guelfi and Orlandi
1987; Gramaccioli and Gentile 1991), but these reports need confirmation (F. Pezzotta,
pers. comm.). Herderite is on the list of Be minerals for Mokrusha, Murzinka Region,
Ural Mountains and for Pitkaranta, Karelia, Russia (Fersman 1940; Nefedov 1967;
NikoTskaya and Larin 1972; Pekov 1994), but in neither case is the identification as
herderite backed by F analysis. Compared to hydroxylherderite, herderite remains a
poorly characterized mineral, particularly in regard to the physico-chemical conditions
that are conducive to incorporation of F in excess of OH.

Hingganite subgroup. Minerals of this subdivision of the gadolinite group (see


above) have been introduced under a variety of names and compositions depending on
whether Y or one of the rare earth elements were dominant (Table 4, Appendix 3). It
should be noted that the crystal structure reported by Yakubovich et al. (1983) is for
hingganite-(Y), not hingganite-(Yb), the title of this paper notwithstanding. The analysis
given for hingganite-(Y) in Table 1 of Voloshin et al. (1983) corresponds to a formula
very close to the "chemical formula" cited by Yakubovich et al. (1983).
Hsianghualite. The mineral was originally described in an abstract (Huang et al.
1958), which resulted in some confusion, e.g., in the Si02 content and in the origin of the
name. Beus (1966, under the name "syanchualite", which is the transliteration of the
Russian rendition of the original Chinese name) and Vlasov (1966) give the most
complete descriptions in English. The name is from the locality, which means "fragrant
flower." Three early analyses reported Li < 2 per formula unit, 0.03-0.60 wt % Na 2 0, 0-
0.54 wt % AI2O3 and 0.41 wt % H 2 0 + (Vlasov 1966; Chukhrov et al. 1972), which
suggested the possibility of limited solid solution with analcime, which has been reported
to contain 0.33 wt % BeO (Semenov 1972). However, two new analyses reported by
Huang et al. (1988) gave Li > 2 per formula unit, 0.09 wt % A1 2 0 3 , 0.22 wt % N a 2 0 and
no H 2 0 + . The structure was refined independently by Academy (1973) and by
Rastsvetaeva et al. (1991), who reported somewhat different coordinates for the atoms,
but agree that hsianghualite has symmetry 12{i and is closely related to analcime.
F and Ca occupy positions very close to those occupied in analcime by H 2 0
and Na, respectively, whereas the Li position has no equivalent in analcime, i.e.,
Introduction and List of Beryllium Minerals 13

Li2Ca3[Be3Si30i2]F2 and •2(Na2D)[Al2Si40i2]'2H20. Hsianghualite has remarkably high


density (Z)meas = 2.97-3.00, Z)caic = 2.95-2.98 g/cm 3 ) and refractive index (n = 1.613) for a
zeolite, especially one containing over 20% (Li 2 0 + BeO). Calculation of the Gladstone-
Dale relationship (Mandarino 1979, 1981) using £>cak yields -0.002 to +0.009, values well
within the "superior" category (±0 to ±0.019), i.e., the density and refractive index are
consistent with the chemical composition despite the abundance of light elements.
Compared to cubic analcime (a = 13.725 A), hsianghualite packs 108% more molecular
weight into 82% the volume, so no wonder it is significantly denser and has a higher
refractive index.
Hurlbutite. Charoy (1999) reported 0.53-0.79 wt % F, 0.52-0.80 SrO and 0.09-0.25
wt % N a 2 0 using an electron microprobe, suggesting possible solid solution in a mineral
generally found to be free of impurities above the trace level (Mrose 1952; Stanek 1966;
Nysten and Gustafsson 1993). Volborth (1954b) reported 1.51 wt % N a 2 0 , 0.95 wt %
K2O and 1.31 wt % SiC>2 in a wet-chemical analysis, but these constituents could be due
to impurities.
Leijite group. This group includes leifite, its Cs-dominant analogue telyushenkoite,
and, potentially, a K-dominant analogue (Sokolova et al. 2002). New refinements of the
crystal structures of leifite and telyushenkoite by Sokolova et al. (2002) are the latest
attempts to derive a viable formula for leifite, which is often given as
Na 2 (Si,Al,Be) 7 (0,0H,F)i4 (e.g., Mandarino 1999; Blackburn and Dennen 1997),
evidently derived from (Na,H 3 0)2(Si,Al,Be) 7 (0,0H,F)i4 (Micheelsen and Petersen 1970),
although Coda et al. (1974) deduced Na 6 [Sii6Al2(Be0H)2039]-1.5H 2 0 from their
refinement of the crystal structure. Most compositional data do not fit either formula.
The formula given by Hochleitner et al. (2000), Na6.7K<i[(F,OH)2|Be2Al2-3Sii6-i5039],
and a formula consistent with the structure refined by Sokolova et al. (2002),
" 4 (Na,D) s (H20,D)Na6Be2(Al,Si,Zn)3Sii5039F2, are in better accord with more recent
analyses, most of which gave total alkalis 3 7, total F < 2, Al ranging from 2 to 3 per 41
(0,0H,F), and Be 3 2 per formula unit (Khomyakov et al., 1979; Petersen et al., 1994b;
Larsen and Asheim, 1995; Men'shikov et al. 1999). However, Khomyakov et al. (1979)
and Men'shikov et al. (1999) reported F approaching 3 per formula unit and ambiguity
remains concerning the presence of molecular water or hydroxyl. In their structural
refinement of leifite, Sokolova et al. (2002) reported electron density at the B site, which
they concluded must be due to molecular H2O, but could not find a position for OH. In
contrast, Larsen and Asheim (1995) found evidence for hydroxyl but not for molecular
H2O in the infrared spectrum of leifite from Norway. However, the leifite from Norway is
K-dominant, and by analogy with telyushenkoite, it could lack H2O at the B site
(Sokolova et al. 2002).

Although Miller (1996) indicated that leifite is a potential ore of Be in the Strange
Lake granitic pegmatite (Quebec-Labrador, Canada), he did not describe any unaltered
leifite, but only pseudomorphs containing a Ca-Y silicate (gerenite, Jambor et al. 1998)
replacing leifite. However, John Jambor (pers. comm.) has confirmed the presence of
unaltered leifite in the Strange Lake intrusive.
Leucophanite and meliphanite. These minerals are compositionally distinct and Al
is an essential constituent of meliphanite: the ideal formulae are Ca4Na4Be4Si8024F4 and
Ca 4 (Na,Ca) 4 Be 4 AlSi7024(F,0)4, respectively (Grice and Hawthorne 2002). Analytical
data available in the literature (Appendix 1; also Dana 1892; Portnov 1964; Chao 1967;
Shatskaya and Zhdanov 1969; Khomyakov 1972; Ganzeyeva et al. 1973; Zubkov and
Galadzheva 1974; Novikova 1976e) show that substitution of Na by Ca is overall more
extensive in meliphanite than in leucophanite and there is little overlap between the two
minerals in terms of Na, Ca, Al and Si; a few leucophanite samples have compositions
14 Chapter 1: Grew

approaching the ideal end-member composition CaNaBeSi2C>6F. Most wet chemical


analyses of leucophanite and meliphanite gave H 2 0 + , often 0.5-2 wt%, but infrared
spectra do not support the presence of a hydrous component. Grice and Hawthorne
(2002) found no evidence for OH in a sample each of meliphanite and a leucophanite
studied by infrared spectroscopy, confirming the results of most previous infrared studies
of these minerals (Novikova et al. 1975; Novikova 1976e; Povaremiykli and Nefedov
1971), whereas Shatskaya and Zhdanov (1969) reported absorption features for both OH
and H2O in an infrared spectrum of leucophanite. Of 30 leucophanite samples analyzed
for rare earth elements (REE) and Y, total REE and Y ranged from 0.1 to 8 wt% (as
oxide) in about 25 of them, i.e., several samples contained more than the total REE
reported in a possible triclinic polymorph, 3 wt% (Cannillo et al. 1992; Appendix 2).
Grice and Hawthorne (2002) were not able to detect triclinic symmetry in one of these
REE-rich samples. Rare earths and Y were sought in 12 meliphanite samples, yielding up
to 0.55 wt% REE + Y oxide. Strontium can replace Ca, e.g., 1.1 wt% SrO in leucophanite
from Tajikistan (Grew et al. 1993).

Lovdarite. Petersen et al. (2002a) reported that the formula for lovdarite from
Ilimaussaq, Greenland deviated in stoichiometry from that deduced by Merlino (1990)
material from Lovozero and given in Appendix 1; i.e., Ilimaussaq lovdarite is variably
deficient in K and Na, somewhat deficient in Be, but has a small excess of Si.
Magnesiotaaffeite-2N'2S. Kozhevnikov et al. (1975) gave their locality only as
"eastern Siberia", and Pekov (1994) gave no information on this occurrence. N.N. Pertsev
(pers. comm.) informed me that the locality is Sakliir-Shulutynskiy pluton, eastern Sayan,
Russia.
"Makarochkinite". Although Grauch et al. (1994) suggested that "makarochkinite"
was the same as hogtuvaite, Hawthorne and Huminicki (Chapter 9) note that dominance
of Ti at one site in "makarochkinite" would make it a distinct species because Ti is not
dominant at any site in hogtuvaite (see also Hawthorne 2002), i.e., an end member for
"makarochkinite" could be Ca2(Fe2+5Ti)02[Si5Be0i8] and that for hogtuvaite could be
Ca2(Fe2+4Fe3+2)02[Si5Be0i8]. However, presently available samples of "makarochkinite"
do not contain sufficient Ti to justify recognizing "makarochkinite" as a distinct species
on this basis.
Meliphanite. This mineral was originally described under the name "melinophane"
(Scheerer 1852), a spelling that was often used in the Russian-language literature until
recently and occasionally used elsewhere. Scheerer (1852) named this mineral for both its
yellow color and similarity to leucophane, but he did not specify whether he based his
name on the Greek root i^sXi (meli - honey) or ixqXivoi; (melinos - quince yellow) for
the yellow color. Dana (1867, p. 405) criticized the name "melinophane" as "wrong and
bad" presuming Scheerer confused "meli" with roots based on i^s/Uv- (melin-), and thus
proposed revising Scheerer's name to meliphane, the presently accepted form (with the
suffix "ite" added). However, could Dana (1867) have neglected the possibility that
Scheerer meant quince-yellow instead, as Raade (1996) presumed? Scheerer studied
material from near Stavern, which is east of Langesundstjord, but did not further specify
the type locality. One possibility is Batbukta on the island Stokkoya between Langesund
and Helgeroa, where Brogger and Reusch collected meliphanite in 1873 (Larsen 2000;
see also Andersen et al. 1996). Presently meliphanite is regarded as the most abundant Be
mineral in the alkaline pegmatites of the Langesundstjord-Tvedalen area (Andersen
et al. 1996).

"Muromontite" and "berylliumorthite". The minerals analyzed in the cited papers are
metamict and often partially decomposed, so interpretation of the analytical
data is difficult. Dana (1892, p. 526) wrote that "muromontite" is "apparently related to
Introduction and List of Beryllium Minerals 15

allanite", but Kerndt (1848), who originally described "muromontite", did not suggest this.
He compared "muromontite" with allanite and gadolinite; "muromontite" has a
morphology like that of allanite, but it was also found in grains lacking crystal faces.
Kerndt noted that these three minerals did differ mainly in composition, and that they also
differ in physical properties, but he realized that better euhedral crystals and more reliable
chemical data would be needed to confirm whether the three were distinct species. The
composition of "muromontite" has some features of allanite, most notably SiC>2 content,
but the dominance of Y over Ce, presence of Be and low Ca is suggestive of gadolinite-
(Y), i.e., Kerndt's (1848) analysis gave Si0 2 31.09, A1 2 0 3 2.23, Y 2 0 3 37.14 (includes all Y
earths), Ce 2 0 3 5.54, La 2 0 3 3.54, FeO 11.23, MnO 0.91, MgO 0.42, BeO 5.52, CaO 0.71
N a 2 0 0.65, K 2 0 0.17, H 2 0 and loss on ignition 0.85, Sum 100 wt %, although the BeO
content is little more than half that expected in gadolinite. Beryllium was subsequently
reported in allanite from other localities, e.g., Forbes and Dahll (1855) reported 3.71 wt %
BeO in an allanite from southern Norway. However, the composition of this mineral
deviates from that expected in allanite by its high H 2 0 and total Fe (as FeO) contents,
respectively 12.24 and 22.98 wt %. Quensel and Alvfeldt (1945) described their
"berylliumorthite", i.e., beryllium allanite, with 3.83 wt % BeO from Skuleboda, Sweden
as "decomposed muromontite". Although crystallographic measurements gave angles
consistent with those for allanite, its composition deviates markedly from that of allanite
(Hasegawa 1960), most notably the deficiency in Si0 2 (23.96 wt %), excessive H 2 0 + (7.98
wt %) and presence of substantial C 0 2 (8.84 wt %). Iimori's (1939) analysis of allanite
lacking crystal faces and containing 2.49 wt % BeO from Iisaka, Japan gives

(REEo.76Cao.86Mno.l7Tho.oi)s-1.8o(Fe 2+ 0.88Zro.o 3 )s-0.9l(All.46Fe 3+ o.4 2 )5;-1.88Beo.58Si 2 .990l 2 (OH),


a formula calculated assuming ideal OH content (Iimori's 3.33 wt % H 2 0 corresponds to
2.17 H per formula unit). The formula has an excess of tetrahedral cations (Be + Si =
3.57 vs. Si = 3 in allanite) and a deficit of ions in octahedral and higher coordination
(4.59 vs. 5 in allanite). Iimori (1939) also reported an increase in Be content in weathered
material and concluded that this was further evidence that Be was present in the unaltered
allanite, which became enriched in Be during weathering. In summary, the existence of a
Be-rich mineral related to allanite remains unproven, and it is doubtful whether the many
reports of minor Be in allanite are really due to incorporation of Be in the allanite
structure rather than to impurities and alteration, especially alteration associated with
metamictization (see below).

Odintsovite. Petersen et al. (2001) cited low analytical totals and low Na contents
as suggestive that the mineral from Ilimaussaq is the Li-dominant analogue (Appendix 2),
K 2 (Na,Ca) 4 (Li,Na)Ca 2 (Ti,Fe 3+ ,Nb) 2 0 2 [Be 4 Sii 2 0 36 ], of the type odintsovite, but Li was
not analyzed in the Ilimaussaq mineral.
Phenakite. The lion's share of phenakite localities are in granite pegmatites, and the
reader is referred to Cerny (Chapter 10) for a general discussion of these and to Gaines et
al. (1997) and Anthony et al. (1995) for listings of the best known localities, though
neither compendium gives the background literature on the localities. The localities and
references given in Appendix 1 emphasize occurrences other than granitic pegmatites.
Roscherite, greifensteinite and zanazziite. "What exactly is roscherite?" (J. Jambor,
1991, Am Mineral 76, p. 1732). The question has yet to be answered (Hawthorne and
Huminicki, Chapter 9). The confusion began early: Be was overlooked in the type
roscherite (Lindberg 1958), which was reported to contain only Al (Slavik 1914), and the
"roscherite" studied crystallographically by Fanfani et al. (1975) was later shown to be
zanazziite (Leavens et al. 1990). On the basis of the dominant cation in the M l site as
defined by Leavens et al. (1990; Mg,Fe 2+ site of Fanfani et al. 1975), monoclinic
16 C h a p t e r 1: G r e w

members of the roscherite group include an Mn-dominant species ("roscherite-lAf' of


Strunz and Nickel 2001), an Fe-dominant species (greifensteinite) and an Mg-dominant
species (zanazziite)(Appendix 1). Triclinic modifications of Mn-dominant roscherite, i.e.,
"roscherite- 1A" of Strunz and Nickel (2001), and of Fe-dominant roscherite were
reported by Fanfani et al. (1977) and Leavens et al. (1990), respectively, thereby
implying the existence of a triclinic modification of zanazziite as well. Nonetheless, this
by no means exhausts all the possibilities. The M2 site as defined by Leavens et al.
(1990; Al site of Fanfani et al. 1975) is occupied by variable amounts of Al, Fe 3+ , Mn 3+ ,
Fe 2+ , Mn 2+ , Mg and/or is partially vacant ( • ) , and charge is balanced by variations in the
OH/H2O ratio (Hawthorne and Huminicki, Chapter 9). Consequently the number of
possible species in a roscherite group is large. In addition to the localities listed in
Appendix 1, unanalyzed minerals identified simply as roscherite have been described in
granitic pegmatites from the Charles Davis mine, North Groton, New Hampshire and
three other pegmatite mines in New Hampshire (Henderson et al. 1967); the Tip Top
mine, Custer Co., South Dakota (Peacor et al. 1983; Kampf et al. 1992; cf. analyzed Mn-
dominant material reported by Campbell and Roberts 1986); Weinebene, Carinthia,
Austria (Walter et al. 1990; Sabor 1990); and Bendada, Beira Alta, Portugal (Schnorrer-
Köhler and Rewitzer 1991).

Sphaerobertrandite. Until recently, sphaerobertrandite had been considered a Be-


and H 2 0-rich variety of bertrandite (Pekov 1994, 2000). However, a new study of
material from Lovozero, Kola Peninsula and from Tvedalen, Norway (UK-10 of
Andersen et al. 1996) shows that sphaerobertrandite is a distinct species; its validity was
approved by a special decision of the CNMMN IMA in 2001 (A.O. Larsen and I. V.
Pekov, pers. comm.; Pekov et al. in press). It turns out that sphaerobertrandite is
markedly distinct from bertrandite in composition, symmetry and cell size (Table 5).
Bukin (1967, 1969) reported synthesis of sphaerobertrandite that he distinguished from
his synthetic bertrandite.

Table 5. Comparison of bertrandite and sphaerobertrandite.

Bertrandite * Sphaerobertrandite * *
Ideal formula Be4Si207(0H)2 Be3Si04(0H)2
Symmetry - space group Orthorhombic - Cmc2i Monoclinic -P2\!c
a (A) 8.716(3) 5.081(3)
6(A) 15.255(3) 4.639(1)

C (A) 4.565(1) 17.664(9)

ß(°) 90 106.09(5)
F(Ä3) 607.0 t 400.0
Source of data: *Giuseppetti et al. (1992). **A.O. Larsen & I.V. Pekov (pers. comm.); Pekov et al. (in
press). '( el volume calculated from the individual dimensions; Giuseppetti et al. (1992) gave 592.22 A3

Tvedalite. The crystal structure has not been solved (Hawthorne and Huminicki,
Chapter 9). S. Merlino (pers. comm., 1992, to Strunz and Nickel 2001, and 2002 to me)
developed a possible model for the structure based on the structural features of
chiavennite whereby tvedalite had monoclinic symmetry (space group C2im) and a
formula Ca2Mn2Be 3 Si60i6(0H)6 - 2H20. However, Merlino was not able to confirm this
model with diffraction data: single crystal diffraction data are unavailable and powder
diffraction data did not sufficiently support the model.
Introduction and List of Beryllium Minerals 17

Uralolite. Reports of this phosphate from Taquaral and Galileia, Minas Gerais,
Brazil were mentioned by Gaines et al. (1997), King and Foord (1994) and Anthony et al.
(2000), but no details or citations were given. Specimens of uralolite on beryllonite from
Linopolis (~30 km north of Galileia) have been available commercially.
Vayrynenite. Electron microprobe analyses of vayrynenite (Ni and Yang 1992; Nysten
and Gustafsson 1993; Roda et al. 1996; Huminicki and Hawthorne 2000), plus wet-
chemical analysis of gem-quality material (Meixner and Paar 1976), gave much lower Ca,
Na, K, and Al contents (except Al in one case) than the relatively high CaO (0.53-1.82 wt
%), N a 2 0 (0.20-1.42 wt %), K 2 0 (0.03-1.18 wt %) and AI2O3 (0.40-2.78
wt %) contents reported in other wet chemical analyses (Volborth 1954b,c; Volborth and
Stadner 1954; Mrose and von Rnorring 1959; Gordiyenko et al. 1973). Impurities such as
beryllonite, herderite, hurlbutite, apatite or muscovite, which are associated with
vayrynenite, could be responsible for these high values. Constituents reported in significant
amounts in electron microprobe analyses include F, i.e., 0.86 wt % F, equivalent to 0.08 F
per formula unit, in gem-quality material from Pakistan (Huminicki and Hawthorne 2000),
and Al, i.e., 0.90 wt % AI2O3, equivalent to 0.03 Al per formula unit, in a sample from
Spain (Roda et al. 1996). The latter could be substituting for Be (Gordiyenko et al. 1973).

Welshite. Grew et al. (2001) published two empirical formulae based on new data,
one of which is given in Appendix 1, the other is Ca 2 Mg3. 8 Mn o..iFe 2+ o.iFe 3+ o. 8 Sb 5+ i. 2 02-
[Si2.8Bei.8Fe3+o.65Alo.5Aso.250i8]. Hawthorne and Huminicki (Chapter 9) discuss possible
welshite end members and concludes that a mixture of Ca 2 Mg 4 Sb202[Si3Be30i8] and
Ca 2 Mg 5 Sb02[Si3Al30i8] best describes the empirical formula in Appendix 1 if certain
simplifications are assumed.
Minerals containing non-essential beryllium
Beryllium contents in the great majority of minerals, including important rock-
forming minerals, are mostly 10 ppm or less and rarely exceed 100 ppm Be (e.g., London
and Evensen, Chapter 11; Grew, Chapter 12), even in Be-rich environments. Beryllium is
thus an incompatible element in most geologic systems (Ryan, Chapter 3). However,
several minerals have been reported to incorporate Be in substantial amounts (i.e.,
>0.1 wt % BeO or 350 ppm Be) or form series with isostructural Be minerals, although
Be is not essential for their formation (e.g., Beus, 1956, 1966; this paper, Table 6).
Wet chemical analyses. Assessing the validity of the Be determinations is not easy.
Older studies reporting significant Be by wet chemical analysis of bulk samples are
suspect given the overall difficulty of Be analyses and its confusion with Al, and given
the probability of impurities, particularly in secondary or metamict minerals. An example
where impurities have contaminated analyzed material is the supposedly beryllian
secondary mineral tengerite, Y2(C03)3-2-3H 2 0. Beryllium reported by Hidden (1905) and
Iimori (1938) was attributed to admixed Be minerals by Miyawaki et al. (1993). The
situation with "foresite" is not clear: 0.71 wt % BeO was reported in two of the four
analyses cited by Dana (1892, p. 585). "Foresite" was later shown to be a mixture of
stilbite and cookeite (Cocco and Garavelli 1958), but this finding leaves the source of Be
unexplained; it could be either contamination or confusion with Al.
One example of possible confusion with Al (or another constituent) is the humite-
group in which substantial BeO was reported in two studies (Jannasch and Locke 1894;
Zambonini 1919). Neither of the analyzed Be-bearing humite-group mineral is from a
Be-enriched environment. Although both Jannasch and Locke (1894) and Zambonini
(1919) checked specifically that Be was present and Al absent or nearly so, these reports
need confirmation. It should be noted that Ross (1964) suggested the possibility of Be
incorporation in olivine- and humite-group minerals. Given that the presence of
significant B in olivine and several humite-group minerals has been well documented
H
•S«
o
m
m

13
o,
p.
18
Mineral Formula Substitution Maximum Be References
(AND RELATED (including Be BY WHICH Be is FOR SUBSTITUTIONS
BERYLLIUM WHERE KNOWN) INCORPORATED Formula Wt% AND MAXIMUM
MINERAL) units oxide CONTENTS

Ö-
î-1
Allanite-(Ce), Not known 5.52 Cf. "Muromontite"

I I

o
o

U O
I F EC
allanite-(Y)

O ÙQ
'L

m
U T: O
O

Zi
Analcime Not known 0.33 Semenov (1972)

<
m
m
O
Boralsilite Not known 0.126* 0.27* Grew et al. (1998a);
Grew (Ch 12)*

9
y,

pq
pq

'OF
Calcybeborosilite- 0.62- 3.72- Semenov et al. (1963);

fe
U hH
(Y) 0.87 5.09 Pekov et al. (2000)

>H —
(D
Chevkinite-(Ce) Not known 2.15 Price (1888)

'öS
s íj

U
• a is-íT W
Ciprianiite Similar to substitution for 0.82 1.95 Oberti et al. (2002); Della

k,

Si
(isostructural with hellandite? Ventura et al. (2002)

u.xo
^ • X
hellandite)
C h a p t e r 1: G r e w

o ^
M fe- W H ^ O

S
>3 ¿i X

- S m
o o O
Clinohumite Not known 1.30 Zambonini (1919)

<-> £ W H Í Í S A oo
w . H fe^ fe
m fe fe
Î
z

Z
"

•-
•<
pq

¡4
i?
ci
Cordi erite (sodian 0.437 1.77 Cerny & Povondra

1
o

^
Ö
orthorhombic) (1966), Povondra &

<D
0.65

fer O

^S - 4
5 VI

Z
cq i
Langer (1971);

? ¡r
-Ç X
Grew (Ch 12)"

O
«J
m
eq
Cordi erite/indialite- 4.40" Hölscher & Schreyer

<D

ffi 1
O
X

S ¿
-3 <
JS m
«

O ^
.^ m


BeMg-cordierite (theoreti (1989)

s OJr

^oo ffl
(synth. hexagonal) cally)


A
S?
5-

CI
Cordi erite/indialite- 3.00 Evensen & London

I S

JTP
9,

•J- ~
m

¿ K O
^

beryl (synth. (in press), London &


[JH
< GO
O ^SN

o
o "s
orthorhombic and Evensen (Ch 11)

11

z ™ m« a
Z
hexagonal)

Î C j V I^

s. * -S1+rt
Introduction and List of Beryllium Minerals 19

CN
O
o
CN 3 c ^
2
<D o
oC
LT ^ s sr ff u
(o D« O _
oo ^ ^
I % H- =¡3 5
ä
§ " « 1 3 oo <-3 -Q
y
> ^ « « « u s B •o • «
ja So
s* «S >
ä3 8ö^ C
13
's- is is
(D (D S ^r <D
-- os o
OQEÌK O O Pi C- ÖÖ
Q O

m
y
eq

A r-i
EC j O H J o EC
eq C
w eq
o w & ^ S- o
EC
«•
w ec w
tó • ec < o < o Si
oo
o v Xo 00
Ph EG • «
b H ii ii -a
+ •oS i j ; a
w c> c> s <
EC «
w m swt P«h m u ra z; ^ EC O
O ci < m tó —
ci" <C m Ph
in • O
• S2. Urt '—
u
U y '

J
c
>1

e l-S
o c c
0
o
20 Chapter 1: Grew

^ oo
n oo<N
oN
OO s m fl
iS h [i
&
c P u ON - -

2 c 5o K
<3 % k
6 S B 2 s
2 <3u 3 O
£ £ •2o
cS ^o ON
^ to-H > <D
to o° U
^ r^ ^SObP o¡-h ¡-i
ifi S o
o a x> S 11 a £ O i to
J2 >W
>O a D
03 o > ffi O o
Pi Ui c-
o o O fe

°T) £O
<

<D
-Q ¡£L
&
« t
O to
-Q
& 03
<D
m
•<o
D JS"
C/5
a a a §
•o m,
< 1

Zi
o AO
OK
m o-Q.
, m ph Ch
^ nB ga
n
Wo
Ph M ^n
^ m
u o (3 < m Z j B
60
m
ci < O
z; u u

I
O —
u s
00
^ 5 a a
NO^ 43
3 .2
•3 « i)
H
Introduction and List of Beryllium Minerals 21
Notes for Table 6: Italics indicate values obtained on synthetic materials. M a x i m u m Be contents
are revised from original reports. ''In addition to the references cited in Chapter 12, Visser et al.
(1994) reported Be data on cordierite. Maxima are for the corresponding beryllium mineral.
'Schiller (1895) reported the humite to be monoclinic, and thus the analyzed mineral is either
clinohumite or chondrodite although the stoichiometry corresponds to humite. Formulae from
Mandarino (1999). i Based on crystal structure refinement and does not correspond exactly to the
laser probe analysis. § Based on semiquantitative laser probe analysis. Calculated from the formula.

Clay minerals. A virtually unexplored, but potentially major, carrier of Be is the


smectite group in which up to 2.8 wt % BeO (0.5 Be per 10 O, 2 0 H , 2H 2 0, Montoya et
al. 1962, cf. Table 6). The crystallographic position of Be in these minerals is not known.
Metamict minerals. Allanite is most widespread of the metamict minerals reported
to incorporate Be; and a distinct species "muromontite" (up to 5.52 wt % BeO, Appendix
2) was thought to be related to allanite (see above). In a compilation of 126 wet-chemical
analyses of allanite, Hasegawa (1960) cited 15 (plus two Be-rich varieties discussed
under "muromontite" above) with a BeO determination (trace to 1.35 wt %), including
the analyses reported by Dana (1892), Nagashima (1951) and Hasegawa (1957, 1958).
Significant amounts of BeO (0.28-0.47 wt %) were reported by Labuntsov (1939),
Kimura (1960), and Khvostova (1962) in four samples, whereas Khvostova (1962) found
only 3.2-252 ppm Be (<0.07 wt % BeO) in six others. Machatschki (1948) suggested that
Be replaces Si and [41A1 and Beus (1956, 1966) specified two substitutions for achieving
charge balance:
2Ca 2+ + [Si0 4 ] 4 " = 2REE 3+ + [Be0 4 ] 6 "
[Si0 4 ] 4 " = [Be0 2 (F,0H) 2 ] 4 ".
Machatschki (1948) concluded that incorporation of Be in allanite implied that the
epidote-group as a whole had [(Si,Be,Al)(0,0H)3] chains. However, epidote-group
minerals are not chain silicates, and there is little tetrahedral Al in allanite (Deer et al.
1986). In general, Be substitution for Si is difficult (Hawthorne and Huminicki, Chapter
9), and substantial Be substitution of Si in allanite does not appear likely.
Another rare-earth mineral reported to contain substantial beryllium is steenstrupine
from Ilimaussaq, South Greenland (Moberg 1898, 1899). Three full analyses by Blom-
strand were given; one of crystal fragments and two of more altered, massive and less
dense material containing more H 2 0 , but only in the latter two analyses were BeO and
Al 2 03 determined separately, giving 1.22-1.93 wt % BeO (Table 6). Semenov (1969) was
unable to confirm the presence of Be in his samples of steenstrupine from Ilimaussaq, but
he found 2.65 wt % BeO in a "brown Ce-silicate" differing from steenstrupine in
containing no P.
Analyses of the zircon-like mineral "alvite" included (BeO + Al 2 03) contents of
4.40-14.11 wt %, but the presence of significant BeO was not demonstrated because it
was not specifically separated from Al 2 03 (Forbes and Dahll 1855; Bedr-Chan 1925).
The relatively high Be contents in these metamict minerals, as well as in chevkinite,
fergusonite, homilite, microlite, samarskite, and yttrotantalite cited by Warner et al.
(1959), as well as "hydro-thorite" (Semenov 1972), are most likely to have resulted from
impurities or analytical difficulties or both, with the possible exception of homilite, a
gadolinite-group mineral (Table 4). Beus (1966) suggested admixed gadolinite and
adsorption of Be in a colloidal system.
Vesuvianite—a case study. This mineral is an example in which authoritative
mineralogists reported a significant Be content and subsequent investigators have
searched especially for it, particularly as vesuvianite appeared to be a possible
22 Chapter 1: Grew

commercial source of Be. Palache and Bauer (1930) reported 9.20 wt % BeO in
vesuvianite from Franklin, New Jersey and speculated that Be could be generally present
in vesuvianite but overlooked because of its being determined as Al. Washington (1931)
went further in suggesting that Be-bearing vesuvianite (or another mineral) could explain
the high Al contents of some igneous rocks because Be was analyzed as Al. Re-analysis
(spectrographic) of the Palache and Bauer (1930) material gave only 0.17 wt % BeO,
leading Hurlbut (1955) to conclude that the original analysis was in error. Hurlbut (1955)
also reported wet-chemical and spectrographic analyses of 1.56-3.95 and 1.1 wt %,
respectively, on another portion of the Palache and Bauer (1930) Franklin sample and
cited several hundred unpublished analyses using a portable laboratory of vesuvianite
from the western U.S. yielding BeO contents up to 1.5 wt %. Other investigators (Meen
1939; Glass et al. 1944; Eskola 1951; Kuchukova 1955; Beus 1957; Kapustin 1973b;
Shpanov et al. 1976) have reported relatively high Be contents ranging from 0.5 to 1.5 wt
% BeO. Beus (1957) noted the close association of Be with OH and F in Hurlbut's (1955)
analyses of Franklin vesuvianite and in an analysis of a sample from Kazakhstan and
suggested that Be substitutes for Si with charge balanced by (F,OH) substitution for O,
i.e., Si + 2 0 = Be + 2(F,OH).

However, other studies have failed to confirm significant Be in vesuvianite. In their


crystallographic study of the vesuvianite that Meen (1939) reported to contain 1.07 wt %
BeO (equivalent to 1.27 Be per 18 Si), Rucklidge et al. (1975) failed to find Be at a
possible tetrahedral site. Allen (1985) refined the occupancy of a T site of vesuvianite
from Luning, Nevada assuming the presence of Be and obtained about 2 Be per formula
unit, but no Be was found by ion microprobe. Groat et al. (1994) found B, Al and Fe at
this site (their T l ) in vesuvianite from other localities, a result that implies B, Al and/or
Fe could be occupying Allen's (1985) T site in the Luning sample. Other studies have
turned up no more than 0.3 wt % BeO (e.g., Goldschmidt and Peters 1932; Silbermintz
and Roschkowa 1933; Neumann and Svinndal 1955; Henriques 1964; Eskola 1951;
Warner et al. 1959; Serdyuchenko and Ganzeyeva 1976), even in vesuvianites from Be
deposits (0.00064-0.034 wt % BeO, Shpanov et al. 1976; Novikova et al. 1994; 0.2 wt %
BeO, Holser 1953). BeO contents ranging from 0.002 to 0.15 wt % that Groat (1988) and
Groat et al. (1992) obtained by atomic absorption on 16 vesuvianite samples are probably
the most reliable values reported for this mineral to date. These results suggest that
significant Be in vesuvianite is a will-o'-the-wisp. Nonetheless, it remains entirely
possible that under certain conditions Be could be a major constituent in vesuvianite; this
has been demonstrated for B, which can be present in amounts sufficient to form the B
analogue, wiluite (Groat et al. 1994, 1998).

Modem technology. More recent studies based on microbeam techniques such as


secondary ion mass spectroscopy (ion microprobe, see Hervig, Chapter 8) or laser-
ablation inductively-coupled plasma emission mass spectroscopy appear to be more
reliable because the problem of impurities in bulk samples is avoided. These methods
allow the analyses of very small samples where impurities pose the greatest problem or
preclude wet chemical analysis altogether. Examples include boralsilite, werdingite and
sillimanite (Table 6; Grew, Chapter 12). Analysis of these relatively fine-grained
minerals, which are often intergrown with other phases, was greatly facilitated by use of
the ion microprobe.
Best of all is supplementing chemical data with crystallographic or experimental
studies that both confirm chemical analysis and elucidate the mechanism by which Be is
incorporated. For example, the substitution by which Be is incorporated in cordierite,
hellandite-group minerals, indialite and sapphirine-khmaralite has been reasonably well
established by crystallographic or experimental studies (Table 6; Hawthorne and
Introduction and List of Beryllium Minerals 23

Huminicki, Chapter 9; London and Evensen, Chapter 11; Grew, Chapter 12). On the
basis of a semiqualitative "laser probe" analysis and deficiency in Si + A1 in the formula,
Ronsbo et al. (1990) calculated that significant Be was present in the Na titanosilicate
vinogradovite from the Ilimaussaq complex, and this calculation was confirmed in a
single crystal refinement (Kalsbeek and Ronsbo 1992). Vlasov et al. (1966) reported 0.08
wt % Be in vinogradovite from Lovozero. Beryllium is inferred to substitute for Si and A1
occupying the Si(2) site in vinogradovite with charge balance achieved by the
substitution NbBe(TiAl).i (Table 6).
Hellandite group. The hellandite group differs from cordierite, sapphirine and other
Be-bearing minerals in that Be does not substitute for B or Si, the only tetrahedral cations
in this structure. Instead Be occupies a largely vacant site displacing H, its only occupant
in Be- and Li-free hellandite (Oberti et al. 1999, 2002; Ottolini and Oberti 2000; Delia
Ventura et al. 2002; Hawthorne and Huminicki, Chapter 9).
Calcybeborosilite-(Y). This gadolinite-group mineral from a peralkaline pegmatite at
Dara-i-Pioz, Tajikistan (Semenov et al. 1963; Poavarennykh 1972; Rastsvetaeva et al.
1996; Pekov et al. 2000) is a valid species through "grandfathering" (Am. Mineral.
86:1537; J. Jambor, pers. comm.). However, Be is not an essential constituent, and
thus it is not included in Appendix 1, but in Table 6. Its composition, e.g.,
Cao.96(Yo.74Ceo.ioREEo.i8)s-i.o2Uo.o4Tho.oiFe o.28Mno.o5Beo.62Bi.i8[Si208](OHi.350o.52Fo.i3),
ideally (Y,Ca)2(D,Fe)(B,Be) 2 (Si208)(0H,0)2, meets the criteria for a valid species, i.e.,
(Y,REE) > Ca distinguishes it from datolite and B > Be distinguishes it from gadolinite-
(Y) and hingganite-(Y). The theoretical end-member is Y 2 DB2(Si208)02.
Datolite (?). The composition of unnamed mineral B, e.g.,
Cai.07(Yo.34Ceo.24Ndo.22REEo.l5)s-0.95Tho.llFe2+o.48Beo.54Bl.24Si2.2208(OH)2,
from a sanidinitic ejectum in pyroclastic rocks at Lake Vico, Latium, Italy (Delia Ventura
et al. 1990; Delia Ventura, pers. comm., 1999) has Ca > (Y,REE), and thus appears to be
beryllian, REE-rich datolite (Table 6), i.e., Be is not an essential constituent.

BERYLLIUM STUDIES
Beryllium in extraterrestrial systems. Why is beryllium so rare?
Beryllium has been a rare element since the very beginning of time: the calculated
primordial Be abundance is negligibly small and the standard model of Big-Bang
nucleosynthesis is "hopelessly ineffective in generating 6 Li, 9 Be, 10B and U B " (Vangioni-
Flam et al. 2000). These three light elements are "fragile" as a result of "selection
principle at the nuclear level" (Vangioni-Flam et al. 2000), and are destroyed in stellar
interiors. Beryllium and boron "are thought to be secondary elements formed from
supernovae by spallation reactions between cosmic rays, alpha particles, and protons and
heavier nuclei such as carbon, oxygen, and nitrogen in the interstellar medium" ("Editors'
Choice", Science, v. 290, p. 1263, 2000, in reference to Primas et al. 2000a; also
Cameron 1995). However, data on Be abundances obtained with the Hubble Space
Telescope (Pagel 1991), Very Large Telescope in Chile ("Editor's Choice", op. cit.) and
other new instrumentation show that Be is present in unexpected amounts in primitive
metal-poor stars in the halo of our Galaxy; suggesting primary Be nucleosynthesis in the
early galaxy, the so-called halo phase (e.g., Fields et al. 2000; Vangioni-Flam and Cassé
2001). "Editors' Choice" (op. cit.) even suggested the possibility of "primordial
beryllium," i.e., revision of the standard model of Big Bang nucleosynthesis allowing for
some synthesis of Be within a few minutes after the Big Bang (also Greenwood and
Earnshaw 1997). Despite attempts to reconcile data obtained from increasingly
sophisticated and sensitive instrumentation with theory on light element (LiBeB)
24 Chapter 1: Grew

abundances in the cosmos, investigators disagree, questions remain unresolved, and more
data are called for (e.g., Thorburn and Hobbs 1996; Ramaty et al. 1998; Vangioni-Flam et
al. 1999, 2000; Parizot and Drury 1999; Fields et al. 2000; Primas et al. 2000a,b; King
2002).
Shearer (Chapter 2) reviews the behavior of Be in our corner of the cosmos, the
Solar System, with an emphasis on meteorites, the Moon and Mars, and the implications
of this behavior for the evolution of the solar system.
Beryllium in terrestrial systems
Beryllium is a lithophile element concentrated in the residual phases of magmatic
systems (e.g., Goldschmidt and Peters 1932; Goldschmidt 1958). Be contents of MORBs,
arc basalts and ultramafic rocks are mostly <1 ppm (e.g., most recently, Santos et al.
2002; see Ryan, Chapter 3). Residual phases include acidic plutonic and volcanic rocks,
whose geochemistry and evolution are covered, respectively, by London and Evensen
(Chapter 11) and by Barton and Young (Chapter 14), while granitic pegmatites, which
are well-known for their remarkable, if localized, Be enrichments and a wide variety of
Be mineral assemblages, are reviewed by C e r n y (Chapter 10).
Alkaline rocks tend to be more enriched in Be than acid rocks (e.g., some evolved
alkaline volcanic systems, Ryan, Chapter 3), and some Be deposits are associated with
alkaline rocks (Barton and Young, Chapter 14). As regards alkaline plutonic systems,
Goldschmidt (1958) noted that nepheline syenites contain more Be than other igneous
rocks. Nonetheless, average Be contents of a given complex can vary considerably, e.g.,
in Russia, from 2 ppm in the BotogoF massif, eastern Sayan region to 12 ppm in the
Lovozero complex, Kola Peninsula (Beus 1966, Table 118), and from one rock type to
another in a given complex, e.g., from 4 to 24 ppm Be in the Lovozero complex (Beus
1966, Table 117; Vlasov et al. 1966; Hormann 1978). Extreme enrichments are
encountered locally, most notably in the Ilimaussaq complex, South Greenland, where
peralkaline nepheline syenites (naujaite and lujavrite) range 7-44 ppm Be (Engell et al.
1971); Markl (2001a) reported 330-1970 ppm Be on 4 lujavrite samples. Regrettably
alkaline plutonic rocks are not reviewed in this volume as acid rocks are, an unfortunate
omission.

Not all Be concentrations have obvious magmatic affinities, either granitic or


alkaline, e.g., one class of emerald deposits results from Be being introduced by heated
brines (Franz and Morteani, Chapter 13; Barton and Young, Chapter 14). Pelitic rocks are
an important reservoir of Be in the Earth's crust and their metamorphism plays an critical
role in recycling of Be in subduction zones (Ryan, Chapter 3); eventually, anatectic
processes complete the cycle, providing a source of Be for granitic rocks (London and
Evensen, Chapter 11; Grew, Chapter 12).
In summary, I should emphasize that despite presentation in different chapters the
systems and processes ranging from sedimentary through metamorphic and hydrothermal
to magmatic (including pegmatitic) really constitute a continuum (and not a linear one)
and should be considered holistically. That is, there are transitions from one system to
another, and the boundaries staked out by authors for the material covered in individual
chapters are to some degree rather arbitrary.
Cosmogenic isotopes
The cosmogenic isotopes 7 Be and 10Be (Table 1) have found increasing applications
in the geological sciences. The shorter-lived isotope 7Be has wide applications in
environmental studies (Kaste et al. Chapter 6). The use of the longer lived 1 Be to assess
erosion rates was first proposed in 1985 and has rapidly expanded because of advances in
Introduction and List of Beryllium Minerals 25

analytical technology, leading to studies as diverse as soil production and erosion


accelerated by agriculture (Greensfelder 2002; Bierman et al., Chapter 4). Beryllium-10
can yield independent temporal records of geomagnetic field variations for comparison
with records obtained by measuring natural remnant magnetization, be a chemical tracer
for processes in convergent margins, and can date events in Cenozoic tectonics (Morris et
al., Chapter 5).
Spectroscopy of beryllium in minerals
Infrared and Raman. Powder infrared spectra of more than 35 Be minerals have
been illustrated or discussed by Plyusnina (1963), Povarennykh and Nefedov (1971),
Ross (1974a,b), Strens (1974), Moenke (1974), and Povarennykh et al. (1982) or by
investigators cited in these papers; additional spectra are included in the descriptions of
new minerals or in reports of new finds. A comprehensive investigation of infra-red
(including single crystal spectra of beryl) and Raman spectroscopic properties of Be in
bromellite, chrysoberyl, phenakite, bertrandite, beryl and euclase, was carried out by
Hofmeister et al. (1987), who used the results to calculate heat capacities for comparison
with experimental heat capacities of these phases. Pilati et al. (1998) obtained single-
crystal Raman and infrared spectra on phenakite in order to make lattice-dynamical
calculations.

Nuclear magnetic resonance. Beryllium-9 (I = 3/2) has favorable nuclear magnetic


resonance (NMR) properties such as a small quadrupole moment (Q = 5.288 x lO^rn 2 )
and good receptivity (78.7 relative to 13C), but Be toxicity has discouraged research
(Bryce and Wasylishen 1999). Another unfavorable factor cited by Bryce and Wasylishen
(1999) is the narrow chemical shift range (<50 ppm) for 9 Be, where ppm refers to parts
per million of the energy of the applied magnetic field (typically given in hertz). Minerals
studied by NMR of 9 Be include beryl (Sherriff et al. 1991) and tugtupite (Xu and Sherriff
1994) as well as synthetic chrysoberyl (Yeom et al. 1995), synthetic bearsite (Harrison et
al. 1993), synthetic zeolites (e.g., Han et al. 1993), and synthetic materials unrelated to
minerals (papers on "minerals" cited by Bryce and Wasylishen 1999).

Electron energy-loss spectroscopy. Parallel electron energy-loss spectroscopy


(parallel EELS) in conjunction with transmission electron microscopy provides
information on elemental composition, coordination, site symmetry, and bonding of
atoms at very high spatial resolution (Garvie and Buseck 1996). Beryllium features have
been studied in rhodizite, chrysoberyl, phenakite, bromellite, beryl, weinebeinite, Be-Te
alloys and in synthetic Be-B-bearing materials (Brydson et al. 1988a,b 1989; Engel et al.
1988; Liu and Williams 1989; Hofer and Kothleitner 1993; Garvie et al. 1997; Garvie
and Rez in prep.). EELS is also a valuable microanalytical tool for light elements. For
example, Engel et al. (1988) quantified the cell contents of rhodizite and obtained 4.9 ±
0.5 Be per 28 oxygen, in good agreement with the 4.55 Be obtained by crystal structure
refinement of a sample from the same locality (Pring et al. 1986), and Hofer and
Kothleitner (1993) reported Be/Si = 0.49 ± 0.05 in beryl (vs. 0.5 nominal). While the K-
edges of Be and B are well resolved in EELS spectra, interferences between the Be K
edge and the L2,3 edges of Mg, Al, Si and P introduces complexities for interpreting and
quantifying spectra of silicate and phosphate minerals (Hofer and Kothleitner 1993;
Garvie and Buseck 1999). For example, the addition of Mg made it impossible to
quantify spectra of Mg-bearing beryl although Mg-poor beryl was amenable to
quantification (Hofer and Kothleitner 1993).

CONCLUSION
As was the case with the boron volume, the present volume can be considered a
progress report on the current state of research on Be and on applications of Be in the
26 Chapter 1: Grew

earth, planetary and cosmic sciences. It is intended also to be a guide and stimulus to
further research on Be in these sciences. With this objective in mind I summarize
directions for future research noted by contributors to the volume:
Planetary science. Shearer (Chapter 2) notes that early solar system processes,
volatile elements in the lunar and martian mantles and surficial geochemical processes on
Mars are three of many areas where more Be data could be beneficial.
Geochemistry. Ryan (Chapter 3) notes the absence of reliable data on the Be content
of the mantle-derived rocks, so mantle Be content must estimated indirectly. This is not
merely a question of sample availability; the main difficulty is analytical: mantle Be
contents are too low to analyze by currently available technology. Surprisingly, the
published data available for sedimentary rocks is relatively limited and old compared to
data available on their metamorphic equivalents. This complicates assessing variations in
Be content with metamorphic grade.
Cosmoeenic isotopes. Bierman et al. (Chapter 4) notes that the accuracy of
measuring °Be far outstrips the accuracy of interpreting the measurements, i.e., the
science has not kept up with technology. Moreover, measurements using 10Be and 26Al, a
complementary cosmogenic nuclide, provide evidence for erosion rates faster than those
suggested by stratigraphic and geomorphic observations, a discrepancy than needs
resolution if evolution of the Earth's surface is to be properly understood. Pairing of
dating using 10Be and the currently developing (U-Th)/He method has potential for
proving insight into late Cenozoic tectonic evolution (Morris et al., Chapter 5).
Application of the shorter-lived isotope 7 Be to various environmental studies is also
relatively new, and understanding its distribution and residence times in various
terrestrial ecosystems is far from complete (Kaste et al., Chapter 6).
Beryllium on Earth's surface. Vesely et al. (Chapter 7) note the limited information
on Be distribution and mobility in soils and on diagenetic processes affecting Be in
sediments, two critical links in the Be cycle on the Earth's surface. There is little data on
Be concentrations in lake water.
Mineralogy. Although beryl is the most abundant Be mineral and by far the most
studied (see Cerny, Chapter 10, London and Evensen, Chapter 11, Franz and Morteani,
Chapter 13), it is also the most complex chemically, a situation belied by the
conventional rendering of its formula as BesA^SieOis. Beryl incorporates significant
variable amounts of Na, Cs, and H2O in large channels (e.g., most recently, Pankrath and
Langer 2002), as well as Li for Be and Mg, Fe and Sc for Al, so modeling its stability
relations is a daunting task. Thus, many questions concerning beryl stability remain
unanswered. This stability has practical as well as academic implications, most
importantly in understanding the origin of emerald (Franz and Morteani, Chapter 13;
Barton and Young, Chapter 14).
While compiling the list of Be minerals, I encountered problem areas in the
characterization of less common Be minerals. Several of these are currently being
addressed, e.g., bavenite and aminoffite, but others, e.g., beryllite and "glucine," are also
in need of more thorough characterization. A framework for defining new species in the
gadolinite group is much to be desired before more individual species are proposed to the
IMA CNMMN. The vector representation constructed by Burt (1989) could provide such
a framework; Miyawaki and Nakai (1996) used a somewhat different representation.
DeMartin et al. (2001) urged crystallographic study of minasgeraisite-(Y) because the
presence of significant Ca on the site normally occupied by Fe2+ "would require a
considerable structural re-arrangement" in their opinion.
The incorporation of variable amounts of Be in minerals in which Be is either
Introduction and List of Beryllium Minerals 27

essential or non-essential is another problem area needing detailed and systematic


crystallographic study. The conditions favoring substitution of Be for Al, Si and other
constituents are not fully understood, for example, why do sapphirine, hogtuvaite and
welshite incorporate significant amounts of Be, whereas the closely related mineral
aenigmatite apparently does not? The incorporation of Be in otherwise vacant sites could
be important in more cases than is generally recognized. This mechanism clearly applies
to the hellandite group (Oberti et al. 1999, 2002) and could apply to other minerals such
as vesuvianite, in which B is incorporated on a normally vacant site (e.g., Groat et al.
1994). Incorporation of Be even at trace levels raises questions in the case of olivine and
clinopyroxene, in which a suitable site is not obvious (Ryan, Chapter 3).
Petrology. An area needing much work is the distribution of Be among rock-forming
minerals and between these minerals and melt. London and Evensen (Chapter 11) and
Grew (Chapter 12) have noted the gross inadequacy of available data, a significant
portion of which are contradictory; Evensen and London (2002) have made a major
contribution to rectifying the situation on Be partitioning in experimental granitic
systems. Understanding the Be budget in crustal and mantle rocks depends on knowing
which minerals are primary hosts of Be, particularly when obvious sinks such as
cordierite and sapphirine are absent. Is Be lost from rocks as they are buried, heated and
melted? Determining he extent to which Be is incorporated in melts (or lost to vapor)
depends on knowing the fractionation between solid phases, melt and fluid. Overall,
systems including Be and Be minerals are less well studied experimentally than
corresponding systems without Be and common rock-forming minerals (Franz and
Morteani, Chapter 13). In addition, the role of halogens has received relatively little
attention from experimentalists although these elements, particularly F, play a major role
in natural systems where Be is abundant. Experimental studies of Be in various fluid
systems are needed to gain a better understanding of transport mechanisms for Be in
hydrothermal environments, where many economic deposits of Be metal and minerals are
formed (Barton and Young, Chapter 14), and deep in the Earth's crust, the source of most
granites and associated Be-enriched pegmatites.

ACKNOWLEDGMENTS
I thank the following individuals who provided references that were not available
from Interlibrary Loan or valuable information: Daniel Antencio, Peter Buseck, Herman
Cho, Giancarlo Delia Ventura, Pete Dunn, Gerhard Franz, Laurence Garvie, Joel Grice,
Detlef Günther, Ulf Hälenius, George Harlow, Elsa Horväth, Läszlö Horväth, John
Jambor, Vandall King, Roy Kristiansen, Alf Olav Larsen, Henry Longerich, Andreas
Massanek, Olaf Medenbach, Stefano Merlino, Ritsuro Miyawaki, Per Nysten, Nikolay
Pertsev, Federico Pezzotta, and Stanislav Vräna. George Rossman kindly provided the
optical absorption spectrum for euclase and background information on it, and helped to
determine the corresponding color for use on the cover of the volume. Roy Kristiansen
very generously loaned me several critical publications from his personal library and
made every effort to keep me abreast of the vast literature on Be minerals; he also
supplied the image reproduced in Figure 1. Irina I. Kupryanova provided information on
the names of specific localities for Be minerals in Russia. Nikita Chukanov and Igor
Pekov kindly provided information on greifensteinite and sphaerobertrandite,
respectively, in advance of publication. Staff of the Interlibrary Loan Department of
Fogler Library, University of Maine, is thanked for their willingness to search for both
obscure and old articles in a variety of languages and scripts, and their patience with my
continual requests. Richard Bideaux, Carl Francis, Roy Kristiansen, Joseph Mandarino
and Igor Pekov are thanked for their thoughtful and thorough comments on this
introductory chapter. Financial support was provided by the U.S. National Science
28 Chapter 1: Grew

Foundation, grants OPP-9813569 and OPP0087235, to the University of Maine.


The following are thanked for reviewing other chapters of this volume: Mark Barton,
Edward Brook, Donald M. Burt, Petr Cerny, Jim Channell, Bernard Charoy, Andrew
Christy, Jack Dibb, Don Dingwell, Carl Francis, Gerhard Franz, Vanessa Gale, Sergey
Krivovichev, Jana Kubiznäkovä, Devendra Lai, William P. Leeman, David Lindsey,
David London, Steve Ludington, Roger Mitchell, Peter Nabelek, Colin Neal, Curtis
Olsen, Luisa Ottolini, Lee Riciputi, Kevin Righter, Jeff Ryan, Denis M. Shaw, Steve
Simon, Peter Wallbrink, Steve Young, and one reviewer who wished to remain
anonymous.

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Some interesting notices of Scottish querns have been given by Sir Arthur
Mitchell. [1061]
The upper stone, ornamented with raised lines, shown in Fig. 180, from a cut
kindly lent me by the Society of Antiquaries of Scotland, was found in trenching a
moss in the parish of Balmaclellan, New Galloway, with some curious bronze
objects of “late-Celtic” workmanship. [1062]
An upper stone (18 inches), ornamented in a nearly similar way, was found near
Stranraer, [1063] Wigtownshire, and another, with a tribrach instead of a cross, at
Roy Bridge, [1064] Inverness-shire. {260}
Some ornamentally carved upper stones of querns, one of them with spiral and
leaf-shaped patterns upon it, much like those on the bronze ornaments of the
“late-Celtic” Period, have been discovered in Anglesea. [1065]

Fig. 180.—Balmaclellan.

Querns of green sandstone are stated, by Sir R. Colt Hoare, [1066] to be


numerous in British villages and pit-dwellings in Wiltshire, as indeed they are in
other counties, [1067] though formed of various kinds of grit. They rarely occur in
barrows, though burnt granite querns have been found with burnt bones in
cromlechs in Jersey. [1068]
Some observations on querns by the Rev. Dr. A. Hume, are published in the
Archæologia Cambrensis . [1069] As these utensils belong, for the most part, to
Roman and post-Roman times, I have thought it needless to enter into any more
minute description of their forms, or of the circumstances under which they have
been found.
CHAPTER XI.
GRINDING-STONES AND WHETSTONES.

Before proceeding to the consideration of other forms of


implements, it will be well to say a few words with regard to those
which have served for grinding, polishing, or sharpening tools and
weapons, and more especially such as there is every reason to
suppose, were employed to give an edge or finish to other materials
than metal, though the whetstones of the Bronze Period must not be
passed by unnoticed.
I have already mentioned the fact that the grindstones on which
stone celts and axes were polished and sharpened, were not like
those of the present day, revolving discs against the periphery of
which the object to be ground was held; but stationary slabs on
which the implements to be polished or sharpened were rubbed.
Considering the numbers of polished implements that have been
discovered in this country, it appears not a little remarkable that
such slabs have not been more frequently noticed, though not
improbably they have, from their simple character, for the most part
escaped observation; and even if found, there is usually little, unless
the circumstances of the discovery are peculiar, to connect them
with any particular stage of civilization or period of antiquity. In
Denmark and Sweden, however, these grinding-stones, both of the
flat and polygonal forms already described, are of comparatively
frequent occurrence. Specimens are figured by Worsaae, [1070]
Sophus Müller, and others, and were also given by Thomsen, [1071]
so long ago as 1832. He states that they have been found in
Scandinavia, in barrows and elsewhere in the ground, with half-
finished stone celts lying with them, so that there can be no doubt
as to the purpose for which they were intended. They are also
described by Nilsson [1072] and Montelius. [1073] {262} Both slabs and
prismatic pieces of sandstone have been found in the Swiss Lake-
dwellings, [1074] several of the former with concavities on one or
both faces, resulting from stone hatchets having been ground upon
them. [1075]
In France the discovery of numerous ‘polissoirs ’ has been noticed, some of them
of very large dimensions. They are abundant in the Departments of la
Charente [1076] and la Dordogne, [1077] and some fine examples are in the
Museum of Troyes (Aube). One, nearly 3 feet long, with hollows of different
characters, apparently for grinding different parts of tools and weapons, is figured
by M. Peigné Delacourt; [1078] an oval concavity upon it is 2 feet 3 inches long by
1 foot wide, and seems well adapted for grinding the faces of large celts. Another
fine example was in the possession of Dr. Léveillé, [1079] at Grand Pressigny, and
a large specimen, also from Poitou, is in the Musée de St. Germain. Several have
been found in Luxembourg [1080] and Belgium.
Flat grinding-stones of smaller dimensions have been found in the turbaries of
the Somme and in the Camp de Catenoy. [1081] A narrow sharpening stone 5
inches long is recorded to have been found with stone hatchets and other
implements in the Cueva de los Murciélagos, in Spain. [1082] Polissoirs have also
been observed in India. [1083]
The Carreg y Saelhau, [1084] or Stone of the Arrows, near Aber, Carnarvonshire,
has numerous scorings upon it, a quarter or half an inch in depth; and, though
doubtless used for sharpening tools and weapons of some kind, it seems to belong
to the metallic age. Canon Greenwell informs me that he observed a rock close to
a camp on Lazenby Fell, Cumberland, with about seventy grooves upon it from 4
to 7 inches long and about 1 inch wide and deep, pointed at either end, as if from
sharp-ended tools or weapons having been ground in them. The grooves are in
various directions, though sometimes in groups of four or five together, which are
parallel with each other. In the course of his investigations in the barrows on the
Yorkshire Wolds [1085] he has found a few of the flat slabs for grinding or
polishing, though of small size. One of them, formed of a flat piece of red
sandstone about 4 1 ⁄ 2 inches by 3 1 ⁄ 2 inches, with both faces bearing marks of
having been in use for grinding, lay close to a deposit of burnt bones. Another
somewhat similar fragment of sandstone (2 3 ⁄ 4 inches by 2 1 ⁄ 2 inches), which also
bore traces of attrition, was found in a barrow at Helperthorpe.
In another barrow at Cowlam, [1086] Yorkshire, E. R., was a rough piece {263}
of grit, 2 1 ⁄ 4 inches long, with one end slightly hollowed, apparently by grinding
celts, and a large flat compact laminated red sandstone pebble about 8 3 ⁄ 4 inches
by 3 inches, with both faces ground away, the one being evenly flat and the other
uneven. In the same barrow occurred one of the flint rubbers to be subsequently
described, and also a quartzite pebble (2 1 ⁄ 2 inches long) that had been used as a
hammer-stone. A portion of a whetstone of Pennant or Coal-measure sandstone
was found in the long barrow at West Kennet, Wiltshire, [1087] in which also
occurred a thin ovoidal knife of flint, ground at the edges.
I have in my own collection a very interesting specimen of this kind from
Burwell Fen, near Cambridge. It is a thin slab of close-grained micaceous
sandstone, about 5 1 ⁄ 2 by 4 inches, slightly hollowed and polished on both faces
by grinding. With it were found two celts of flint, 4 1 ⁄ 2 and 5 inches long, of
pointed oval section, one of them polished all over, and the other at the edge only,
which in all probability had been sharpened on this very stone. In the same place
were two long subangular fragments of greenstone of the right form, size, and
character to be manufactured into celts, and which had no doubt been selected for
that purpose.
A grinding-stone with a celt lying in it, found at Glenluce, [1088] Wigtownshire,
has been figured.
On the Sussex Downs I have found flat pebbles 3 or 4 inches long, which have
evidently been used as hones, but whether for stone or metallic tools it is
impossible to say. Fragments of polished celts and numerous flakes and “scrapers”
of flint were, however, in their immediate neighbourhood. Among the modern
savages of Tahiti [1089] who used hatchets of basalt, a whetstone and water
appear to have been always at hand, as constant sharpening was necessary. It
seems probable therefore that there must have been a constant demand for such
sharpening-stones in this country, and that many of them ought still to exist. With
flint hatchets, the constant whetting was, however, no doubt less necessary than
with those of the different kinds of basalt. Their edges, if carefully chipped, will
indeed cut wood without being ground at all.
Mr. Bateman mentions “a flat piece of sandstone rubbed hollow at
one side” as having been found in a barrow at Castern,
Staffordshire, [1090] but it is uncertain whether this was a grindstone.
It may have been used only as a mortar, for with it was a round
piece of ruddle or red ochre, “which from its abraded appearance
must have been in much request for colouring the skin of its
owner.” [1091] In a barrow on the West Coast of Kintyre, there also
occurred a piece of red Lancashire or Westmoreland iron-ore or
hæmatite worn flat on the side, apparently by having been rubbed
upon some other substance. Nodules of ruddle are also said to {264}
have occurred, interspersed with the charcoal in a barrow at Broad
Down, near Honiton. [1092]
In one of the ancient habitations in Holyhead, [1093] was a large
stone 11 inches long, probably used for grinding hæmatite, with
which it was deeply tinged; and a small stone box found with celts
and other relics at Skara, Skaill, Orkney, [1094] contained a red
pigment.

Fig. 180A .—Lamberton Moor.

There can be little doubt of this red pigment having been in use
for what was considered a personal decoration by the early
occupants of Britain. But this use of red paint dates back to a far
earlier period, for pieces of hæmatite with the surface scraped,
apparently by means of flint-flakes, have been found in the French
and Belgian caves of the Reindeer Period, so that this red pigment
appears to have been in all ages a favourite with savage man. The
practice of interring war-paint with the dead is still observed among
the North American Indians. [1095]
“The paints that warriors love to use
Place here within his hand,
That he may shine with ruddy hues
Amidst the spirit land.”
Some few of the grinding-stones found in this country resemble those of
polygonal form found in Denmark, [1096] in so far as they are symmetrically
shaped and have been used on all their faces. One 13 1 ⁄ 2 inches long, found on
Lamberton Moor, [1097] Berwickshire, is shown in Fig. 180A ., kindly lent by the
Society of Antiquaries of Scotland.
In the Christy Collection is such a sharpening-stone, nearly square in section,
about 9 1 ⁄ 4 inches long, and of the form shown in Fig. 181. Both the faces and
sides are worn slightly concave, as if from grinding convex surfaces such as the
edges of celts, though it is impossible to say with any degree of certainty that this
was really the purpose to which it was applied. It is said to have been found near
Barcoot, in the parish of Dorchester, Oxon, in 1835, not far from a spot where a
{265} stone celt had been found a few years previously. In the same collection is
a Danish whetstone of precisely the same character, but rather broader at one end
than at the other.

Fig. 181.—Dorchester. 1⁄2

A grinding-stone, 26 inches long, was found at Ehenside Tarn, [1098]


Cumberland.
Fig. 182.—Rudstone.
1⁄1

In Fig. 182 is shown, full size, a very curious object formed of compact mica-
schist, which has the appearance of having served as a whetstone or hone. It has
been ground over its whole surface. The flatter face is towards the middle
somewhat hollowed—rather more so than is shown in the section—and shows
some oblique scratches upon it as if from rubbing a rather rough object upon it. It
was found in 1870 by Canon Greenwell, with other relics accompanying an
unburnt body in a barrow at Rudstone, near Bridlington. [1099] About midway
between the head and the knees was a series of articles in this descending order.
On the top was this whetstone—if such it be—resting on a carved jet ring, like Fig.
372, which lay on the boss of a large jet button. Below this was another jet
button, like Fig. 371, face downwards. Close by lay a half-nodule of pyrites and a
round-ended flint flake, which will be subsequently noticed. Nearer the face was a
dagger-knife of bronze, with three rivets through it, and two more for fastening
together the two plates of ox-horn of which the hilt had been composed. The
whetstone may have been that used for sharpening this instrument.
An instrument of slate of nearly the same {266} form was found in a cairn at
Penbeacon, [1100] Dartmoor, and was regarded by Mr. Spence Bate as a tool used
in fashioning clay vessels. Dr. Thurnam [1101] has suggested that if covered with
leather these stones may have served as bracers or arm-guards for archers.
Two pieces of a dark-coloured slaty kind of stone, of nearly the same form and
size as the Yorkshire specimen, and lying parallel with each other, were found by
Sir R. Colt Hoare [1102] at the feet of a skeleton, together with a little rude
drinking-cup, in a barrow near Winterbourn Stoke. A stud and ring of jet, probably
of the same character as those from Rudstone, and a piece of flint rudely chipped,
as if intended for a dagger or spear, were also found. No bronze objects were
discovered, but the cist appears to have been imperfectly examined.
I have already mentioned [1103] that in grinding and
polishing the concave faces of different forms of
perforated stone axes, it is probable that stone rubbers
were used in conjunction with sand. Even the smaller
Fig. 183.— flat and rounded faces may have been wrought by
Fimber. similar means. That rubbers of some kind must have
1
⁄2 been used, is, I think, evident from the character of the
surfaces, especially of those which are hollowed; and
the most readily available material for the formation of
such rubbers, was doubtless stone. There is therefore an à priori
probability of such stone grinding-tools having been in use; and if
we find specimens which present the conditions which such tools
would exhibit, we are almost justified in assuming them to have
served such purposes. Now in the collection of Messrs. Mortimer, of
Driffield, Yorkshire, are several pieces of flint and portions of pebbles
of schist, flint, and quartz found in that neighbourhood, which are
ground at one end into a more or less rounded form, and exhibit
striæ running along, and not across, the rounded surface. They
have, in fact, all the appearance of having been used with coarse
sand for grinding a concavity in another stone, such, for instance, as
the concave face of the stone axe shown in Fig. 125. I am indebted
to their kindness for the specimen shown in Fig. 183, which consists
of a short piece of a conical nodule of flint, the large end of which
has been used for grinding in ancient times, the striated face being
now considerably weathered. In the Greenwell Collection is a rubber
of the same kind from Weaverthorpe on the Yorkshire Wolds. Mr. H.
S. Harland [1104] has found other specimens in Yorkshire, of which he
has kindly given me several. Polishers [1105] are also found in
Scotland. A polisher of somewhat similar character, but made of
serpentine, was found in the {267} Lago di Varese, near Como,
where a number of stone implements were also discovered.
At a later period larger rubbers of the same kind were used to
smooth the flutings of Doric columns. I have seen some among the
ruins of the temples at Selinunto, in Sicily.
Some long narrow rubbers, apparently intended for grinding out
the shaft-holes of perforated axes, have been found in the Swiss
Lake-dwellings; and I have a slightly conical stone, about an inch in
diameter, from Mainz, which may have been used for the same
purpose.
In the barrow at Cowlam, already mentioned, besides the grinding-stones of
grit, there was a piece of flint roughly chipped into a cubical form, and having one
face partly ground smooth. It may have been used for polishing the surfaces of
other stone implements, or possibly merely as a muller. It is shown in Fig. 184.
The striæ run diagonally of the square face.
In the collection formed by Canon Greenwell, is also a sandstone pebble, 2 1 ⁄ 2
inches in diameter, which has been “picked” into shape, and has one face smooth
as if used for grinding. It was found in a barrow on Ganton Wold, East Riding. A
roughly conical piece of oolitic sandstone, 2 1 ⁄ 2 inches high, in places “picked” on
the surface, and with the base apparently used for grinding, was found with a
contracted body and some flint flakes, in another barrow on Ganton Wold. [1106]
Fig. 184.—Cowlam. 1⁄2 Fig. 185.—Amesbury. 1⁄2

In the Wiltshire barrows several rubbing-stones (or what appear to be such) of a


peculiar form have been found, of which one is shown in Fig. 185. It is of close-
grained grit, possibly from the Lower Greensand, and was discovered with two
others in a harrow on Normanton Down, near Amesbury. Two more were in the
collection of the late Rev. Edward Duke, of Lake, near Salisbury, to whose kindness
I am indebted for the loan of the specimen. Both are now in the British Museum.
These instruments vary but little in shape, size, or character, being usually of a
truncated half-ovoid form, with a rounded groove along the flat surface, and are
formed of sandstone.
One was found in a barrow at Upton Lovel, [1107] with flint celts, a perforated
stone axe-head, various implements of bone, a bronze pin or {268} awl, and other
objects. Another occurred in a barrow at Everley, [1108] with a bronze chisel, an
unused whetstone of freestone, and a hone of bluish colour; and another with a
skeleton, a stone hammer, a bronze celt, a bone tube, and various other articles in
a barrow at Wilsford. [1109] Two or three of these sharpening stones, found in a
barrow at Roundway, near Devizes, are in the Museum of the Wilts Archæological
Society. One of these has been figured. [1110] A pebble with shallow grooves on
each face found at Mount Caburn, Lewes, [1111] may possibly belong to this class
of implements, though it may have been a hammer. A rubbing-stone of this kind
was found at Topcliffe, [1112] Yorkshire, but not in a barrow.
Sir R. C. Hoare considered whetstones of this kind to have been used for
sharpening and bringing to a point, pins and other implements of bone, and they
seem well adapted for such a purpose, and are still so used by the Eskimos. They
may also have served for smoothing the shafts of arrows. Serpentine pebbles with
a groove in them are used for straightening arrow-shafts by the Indians of
California, [1113] and shaft rubbers of sandstone have been found in
Pennsylvania. [1114]
The Rev. W. C. Lukis found a similar stone (4 1 ⁄ 4 inches) in a barrow in Brittany.
It is now in the British Museum. Another from a dolmen in Lozère [1115] has been
thought to be for sharpening the points of bone instruments. Stones of the same
form have been found in Germany; two from the cemetery near Monsheim [1116]
are preserved in the Museum at Mainz. They are rather more elongated than the
English examples. A specimen very like Fig. 185 has been found in
Denmark. [1117] They seem also to occur in Hungary. [1118] I have a grooved
stone of this kind from the Lago di Varese, Como, where the manufacture of flint
arrow-heads was carried on extensively. An object found with polished stone
instruments in the cave Casa da Moura, Portugal, [1119] not improbably belongs to
this class of grooved sharpening stones.
From their association with bronze objects,
they appear to belong to the Bronze rather than
to the Stone Period; and the same holds good
with the more ordinary form of whetstone, of
which an example is given in Fig. 186. The
Fig. 186.—Hove. 1⁄2 original was found in the tumulus at
Hove, [1120] near Brighton, which contained
the stone axe-head already mentioned, a
beautiful amber cup, and a bronze dagger. Another, of compact red sandstone,
3 3 ⁄ 8 inches long, with the perforated end rounded, was found in a barrow on Bow
Hill, [1121] Sussex, and is now in the British Museum. Another, 3 inches long,
bluish grey in {269} colour, was found with a bronze dagger and a stone axe-
hammer in an urn at Broughton [1122] in Craven, in 1675.
Two perforated whetstones were found with a bronze dagger and pin in the Silk
Hill Barrow, [1123] Wilts. Another, with the perforation in a sort of loop at the end,
was found with two daggers and a crutched pin of bronze, associated with burnt
bones in a barrow at Normanton. [1124] Whetstones, in some cases not
perforated, have occurred in other Wiltshire barrows, associated with bronze
daggers at Wilsford [1125] and Lake, [1126] and with flint daggers or spear-heads
at Durrington. [1127] The smooth stone found with a flint dagger in a barrow near
Stonehenge, [1128] may also possibly have been a whetstone. Two from barrows
at Knowle, [1129] Dorset, and Camerton, Somerset, have been figured by Dr.
Thurnam. Another of the same kind was found in a barrow at Tregaseal, [1130] St.
Just, Cornwall, and two others with urns at Brane Common, [1131] in the same
neighbourhood. Others not perforated are recorded from Cottenham, [1132]
Cambs. One from Anglesea [1133] has been figured.
Two of greenish stone (chlorite?) one 2 5 ⁄ 8 inches long, perforated at the end,
were found at Drewton, [1134] near North Cave, Yorkshire; and another of similar
material, 2 inches long, was found near some “Picts’ houses,” [1135] Shapinsay,
Orkney. Half of a whetstone was found with a bronze dagger and numerous flint
flakes by Mr. Morgan in a barrow at Penhow, [1136] Monmouthshire; and a much-
used whetstone was found in a barrow near Scarborough, [1137] but the form of
neither is specified. Several, both pierced and otherwise, have been recorded from
Scotland. [1138] One with the boring incomplete was found with a flint knife in a
cist at Stenton, [1139] East Lothian, and another, perforated, with a thin bronze
blade and an urn at Glenluce, [1140] Wigtownshire. It appears possible that some
of the stones found in Scotland and perforated at one end, described by
Wilson [1141] as flail-stones, may after all be merely whetstones. The perforated
form is common in Ireland, and is usually found in connection with metal
objects. [1142] I have a narrow hone of rag-stone, perforated at one end, which
was found with a remarkable hoard of bronze objects, including moulds for
socketed celts and for a gouge, in the Isle of Harty, Sheppey. An almost identical
whetstone is in the Zurich Museum.
Whetstones, perforated at one end, have occurred in the Swiss Lake-
dwellings. [1143] Most of those found in the ancient cemetery of Hallstatt, [1144]
in the Salzkammergut, were perforated in the same manner, and in {270} some
cases provided with an iron loop for suspension. They are usually of sandstone,
and not formed from slaty rocks.
A whetstone, 5 1 ⁄ 4 inches long, the two flat faces of which had evidently been
used for sharpening flat blades, while in the centre of each is a deep groove,
probably caused by sharpening pointed tools, such as awls or needles of bronze,
was found at Ty Mawr, Anglesea, near a spot where a number of bronze celts,
spear-heads, &c., had previously been dug up. It has been figured by the late
Hon. W. O. Stanley, [1145] whose cut is here reproduced as Fig. 187. The ends of
the stone are somewhat battered from its having been also used as a hammer.

Fig. 187.—Ty Mawr.

The same explorer discovered in hut-circles in Holyhead Island [1146] other


whetstones of the same character, in one instance with two principal grooves and
minor scorings crossing each other at an acute angle, and in another with three
parallel grooves in the face of the stone. There can be little doubt that these
sharpening stones belong to a period when the use of metal for cutting and
piercing instruments was fully established.
There are frequently found in Ireland and Scotland flat pebbles of
quartz and quartzite, sometimes ground on the edges or faces, or on
both, and having on each face an indentation running in a somewhat
oblique direction to the longer axis of the pebble. Specimens [1147]
have been figured by Sir William Wilde, who describes them as sling-
stones. The flat faces of some have all the appearance of having
been abraded by a pointed instrument. I have never met with this
form in England, but in the National Museum at Edinburgh is a
grooved pebble exactly like those found in Ireland, from the broch,
at Kintradwell, [1148] Sutherlandshire, and another from that at
Lingrow, Orkney. One from Borness, [1149] {271} Kirkcudbrightshire,
has been figured. Others have been found at Dunino, [1150] Fife, and
Dunnichen, [1151] Forfarshire. This latter has an oval hollow on one
face and a groove on the other.
This pebble variety is rarely found in Scandinavia, but another and
probably rather later form, in which the pebbles have been wrought
into a long shuttle-like shape, is abundant. Some of these are
provided with a groove along the sides, which would admit of a cord
being fastened round them, by which to suspend them from the
girdle. On one or both faces there is often a similar indentation to
those on the Irish specimens, on which, however, it is, as a rule,
deeper than on the Scandinavian. On the latter, the grooves have
sometimes more the appearance of having been produced by
repeated slight blows than by friction. Specimens are engraved by
Worsaae [1152] and Nilsson. [1153] The latter regards them as
belonging to the Stone Age. They occurred, however, with numerous
objects of the early Iron Age at Thorsbjerg, [1154] and have even
been found with remains of both bronze and iron bands around
them, instead of any more perishable cord.
These grooved stones are not to be confounded with the ordinary
form of hammer-stone, [1155] but belong to a distinct category. They
were, in all probability, used as a means for obtaining fire, by
striking them with a pointed piece of iron. They constitute, in fact,
the “flint” part of a modification of the ordinary “flint and steel.”
Whetstones are, of course, commonly found with Roman domestic
antiquities; with Saxon, which are usually of a more purely
sepulchral character, they are rarely discovered. Canon Greenwell
found, however, two whetstones, one as much as 24 inches long, in
graves of this period, at Uncleby, Yorkshire.
In one of the German cemeteries on the Rhine, corresponding to
ours of Anglo-Saxon date, a small rubbing or sharpening stone,
almost celt-like in form, was found. [1156]
In Dutch Guiana [1157] a small form of grinding-stone of quartz,
apparently of the same age as the stone hatchets of that country, is
known as a thunderstone, and great medicinal powers are ascribed
to it by the natives. I must, however, return to the sharper forms of
stone implements.
CHAPTER XII.
FLINT FLAKES, CORES, ETC.

The different forms of implements and weapons which have been


treated of in the preceding pages have, for the most part, been
fashioned from larger or smaller blocks of stone, reduced into shape
by chipping; the chips having apparently been mere waste products,
while the block from which they were struck was eventually converted
into the tool or weapon required. With the majority, though by no
means all, of the Neolithic forms which we still have to pass in review,
the reverse holds good; for the raw materials, if I may so term them,
from which the bulk of them were made, were flakes or splinters of
flint struck off from larger blocks, in such a manner that it was the
splinters that were utilized. The block from which they were struck,
instead of being the object of the manufacture, became, when all the
available flakes had been removed from it, mere refuse, to be thrown
away as useless.
Before considering any of the various tools and weapons into which
these flakes or splinters were converted by subsequent or secondary
working, it will be well to say a few words about the simpler forms of
flakes, and the cores or nuclei from which they were struck.
I have already, in speaking of the manufacture of stone
implements, described the manner in which flakes or spalls are, at the
present day, struck off by successive blows from the parent block or
core, and have suggested the probable methods employed in ancient
times for producing similar results. Remarks on the method of
production of flint flakes have also been made by Sir W. Wilde, [1158]
Sir John Lubbock, [1159] Mr. S. J. Mackie, [1160] Prof. T. McK.
Hughes, [1161] and others. I need not, therefore, re-open the subject,
{273} though it will be well again to call attention to some of the
distinctive marks by which artificially formed flakes may be
distinguished from mere splinters of natural origin. The formation of
these latter is usually due either to the flint, while still embedded in
the chalk, having received some violent shock from disturbance of the
stratum; or to unequal expansion, which sometimes causes flints to
split up into rudely prismatic forms, much like those assumed by
starch in drying, and sometimes causes cracks on the surface, which
enable water and frost to complete the work of splitting them.
Occasionally, nearly flat planes of fissure are caused by the expansion
of some small included particle of a different mineralogical character
from the surrounding flint. In such cases a series of concentric and
more or less circular rings may usually be traced on the surface
surrounding the central particle, which apparently mark the intervals
of repose, when its expansion had ceased for a time to exert sufficient
force to continue the fissure. This kind of fracture is most prevalent in
flints upon or near the surface of the ground, such as those in drift-
deposits.
In hardly any instances of natural fracture does the surface of the
splinter show any trace of its having been produced by a blow, though
the violent impact of one stone upon another, by means of a fall from
a cliff, or of other natural causes, might produce a splinter of the
same form as if it had been struck off by a hammer. There would,
however, be the mark of the blow on one face only of such a splinter,
whereas in a perfectly artificial flake the traces of the blow by which
each facet was produced would be discernible. On the sea-shore,
natural splinters of flint, resulting from the blow of one wave-borne
pebble on another, may occasionally be found, some of them having a
kind of secondary working at the edges, the result of attrition among
the pebbles on the shore.
If a blow from a spherical-ended hammer be delivered at right
angles on a large flat surface of flint, the part struck is only a minute
portion of the surface, which may be represented by a circle of very
small diameter. If flint were malleable, instead of being slightly elastic,
a dent would be produced at the spot; but, being elastic, this small
circle is driven slightly inwards into the body of the flint, and the
result is that a circular fissure is produced between that part of the
flint which is condensed for the moment by the blow, and that part
which is left untouched. As each particle in the small circle on which
the hammer impinges may be considered to rest on more than one
other particle, it is {274} evident that the circular fissure, as it
descends into the body of the flint, will have a tendency to enlarge in
diameter, so that the piece of flint it includes will be of conical form,
the small circle struck by the hammer forming the slightly truncated
apex. That this is not mere theory will be seen from the annexed
woodcut, Fig. 188, showing a cone of flint produced by a single blow
of a hammer. [1162]
Sometimes, as has been shown by Prof. T. McK.
Hughes, F.R.S., the sides of the cone are in steps, the
inclination varying from 30° to 110°. This is probably
to some extent due to the character of the blow, and
Fig. 188.—Artificial the form of the hammer.
Cone of Flint. If the blow be administered near the edge, instead
of in the middle of the surface of the block, a
somewhat similar effect will be produced, but the cone in that case
will be imperfect, as a splinter of flint will be struck off, the fissure
probably running along the line of least resistance; though, owing to
the suddenness of the blow, the conical character of fracture is at first
produced at the point of impact. This fracture will vary to some extent
in accordance with the angle at which the blow is given, and the
character of the hammer; but in all cases where a splinter of flint is
struck off by a blow, there will be a bulb or projection, of a more or
less conical form, at the end where the blow was administered, and a
corresponding hollow in the block from which it was dislodged. This
projection is usually known as the “bulb of percussion,” a term, I
believe, first applied to it by the late Dr. Hugh Falconer, F.R.S.; and on
every flake, all the facets of which are purely artificial, this bulb will be
found at the butt-end of the larger flat face, and the hollow
depressions, or portions of depressions, on all the other facets. If on a
splinter of flint such a bulb occurs, it proves that it must have resulted
from a blow, in all probability, but not of necessity, given by human
agency; but where the bulb is on the principal face, and analogous
depressions, or portions of them, are visible on the several other
faces, and at the same end of a flake, all of them presenting the same
character, {275} and in a definite arrangement, it is in the highest
degree probable that such a combination of blows must be the result
of design, and the features presented are almost as good a warrant
for the human origin of the flake as would be the maker’s name upon
it. When, however, several of such flakes are found together, each
bearing these marks of being the result of several successive blows,
all conducing to form a symmetrical knife-like flake, [1163] it becomes
a certainty that they have been the work of intelligent beings.
In size and proportions flakes vary considerably, the longest English
specimens that I have seen being as much as 8 or 9 inches long,
while some, which still appear to have been made use of as tools, are
not more than an inch in length. Their proportional breadth is almost
as variable.
With regard to the classification and nomenclature of these objects,
I would suggest that the name of flake should be limited to such
artificial splinters of flint as, either in their section or outline, or in
both, present a certain amount of symmetry, and appearance of
design; and that the ruder forms, such as would result from chipping
some large object into shape, without any regard to the form of the
parts removed, should be called chips or spalls. [1164] Such as show
no bulb of percussion may be termed splinters. The Scottish name for
flakes is “skelbs.”
The inner, or flat face of a flake, is that produced by the blow which
dislodged it from the parent block, core, or nucleus. The outer, ridged
or convex face comprises the other facets, or, in some instances, the
natural surface of the flint. The base, or butt-end of a flake, is that at
which the blows to form it were administered; the other end is the
point.
Flakes may be subdivided into—
1. External, or those which have been struck off by a single blow
from the outer surface of a nodule of flint. Many of these are as
symmetrical as those resulting from a more complicated process of
manufacture, and they have frequently been utilized, especially for
scrapers.
2. Ridged flakes, or those presenting a triangular section. One face
of these sometimes presents the external crust of the flint, as in Fig.
190. In others, the ridge has been formed by transverse {276}
chipping, as is the case with the long flakes from Pressigny (Fig. 6),
but this method appears to have been almost unknown in Britain.
3. Flat, where the external face is nearly parallel to the internal, and
the two edges are formed by narrow facets, as in Fig. 200.
4. Polygonal, where the external face consists of many facets, as in
Fig. 192.
These several varieties may be long or short, broad or narrow,
straight or curved, thick or thin, pointed or obtuse. The character of
the base may also vary, being rounded or flat, thick or thin, broad or
narrow.
The cores from which flakes have been struck are, of course, of
various forms, some having had only one or two flakes removed from
them, and others several. In the latter case they are often more or
less regularly polygonal, though only few of the facets will be of the
full breadth of the flakes, as the external face of every successive
flake carries off some part of the traces of those previously struck off.
Not unfrequently some of the facets are arrested at a little distance
from the end where the blows were struck, in consequence of the
flake having broken short off, instead of the fissure continuing to the
end of the block. Occasionally, and more especially on the Yorkshire
Wolds, the nuclei are very small, and much resemble in character
those found, with numerous flakes, in India, in the neighbourhood of
Jubbulpore. [1165]
It has been suggested [1166] that cores were occasionally made on
purpose for use as tools; but this appears very doubtful. Of course, if
a core were at hand, and seemed capable of serving some special
purpose, it would be utilized.
The core here engraved of the full size in Fig. 189 was
found by myself at Weaverthorpe, Yorkshire. I have
already suggested that in striking off such small flakes as
those removed from this core, some sort of punch may
have been used, instead of the blows being administered
directly by a hammer. We have no conclusive evidence as
to the purpose to which such minute flakes were applied,
but they may have been fashioned into drills or scraping
or boring tools, of very diminutive size. Such small
Fig. 189.—Weaverthorpe. objects are so liable to escape observation, that though
1⁄1 they may exist in considerable numbers, they are but
rarely found on the {277} surface of the ground.
Numerous flakes, however, quite as minute, with their
edges showing evident signs of wear, are present among the refuse left by the cave-
dwellers of the Reindeer Period of the South of France. As will subsequently be
seen, these minute flakes have been also found in Egypt and in Asia, as well as in
Britain. See Fig. 232 A to 232 F . There is a class of ancient Scandinavian harpoon-
heads, the stems of which are formed of bone with small flint flakes cemented into
a groove on either side so as to form barbs. Knives of the same kind are
subsequently mentioned.
Among the Australians [1167] we find very minute splinters of flint and quartz
secured to wooden handles by “black-boy” gum, and forming the teeth of rude saws
and the barbs of javelins. Some remarkably small flakes have also been found in the
diamond-diggings of South Africa in company with fragments of ostrich-egg shell,
such as with the aid of the flakes might have been converted into the small
perforated discs still worn as ornaments by the Bushmen.
There are but few published notices of the discovery of English cores of flint,
though they are to be found in numbers over a considerable tract of country,
especially where flint abounds.
I have recorded their finding at Redhill, [1168] near Reigate, and at Little Solsbury
Hill, [1169] near Bath. I also possess numerous specimens from Herts,
Gloucestershire, Sussex, Bedfordshire, Suffolk, and Yorkshire. In several instances
two series of flakes have been struck off, the one set at right angles to the other.
More rarely the flakes have been obtained from both ends of the block.
A core from the Fens [1170] is in the Museum of the Cambridge Antiquarian
Society, and several were found, with other worked flints, in the chambered Long
Barrow at West Kennet, Wiltshire.
Numerous specimens from Peter’s Finger, near Salisbury, and elsewhere, are in
the Blackmore Museum; and a number were found by General Pitt Rivers in his
researches at Cissbury, Sussex, and by Canon Greenwell at Grime’s Graves. [1171]
Mr. Joseph Stevens has described specimens from St. Mary Bourne, [1172] Hants.
They are recorded also as found with flakes at Port St. Mary, [1173] Isle of Man.
A long bludgeon-shaped nodule of flint, from one end of which a succession of
flakes had been struck, was found in a grave, with a contracted skeleton, in a
barrow near Winterbourn Stoke, [1174] Wilts.
Illustrations of cores, and of the manner in which flakes have been struck from
them, have been given by various authors. [1175]
The existence of flakes involves the necessity of there having been cores from
which they were struck; and as silicious flakes occur in almost all known countries,
so also do cores. A series of French nuclei is {278} figured by Mortillet, [1176] and a
fine example from Olonetz, [1177] Russia, by Worsaae. They have also been found
in the Arabian desert. [1178] Those of large size and of regular polygonal form are
rare in Britain and Ireland, and, indeed, generally in Europe. Some of the largest
and most regular occur in Scandinavia. I have also some good examples from
Belgium. Many of the cores from Spiennes, near Mons, were subsequently utilized
as celts; and the same was the case to some extent at Pressigny, the large cores
from which have already been described. The Mexican [1179] and East Indian [1180]
forms, in obsidian and cherty flint, have also been mentioned. They are unsurpassed
for symmetry and for the skill exhibited in removing flakes from them.
Fig. 190.— Fig. 191.—Redhill. Fig. 192.— Fig. 193.—
Newhaven. 1 ⁄ 2 Reigate. 1 ⁄ 2 Icklingham. 1 ⁄ 2 Seaford. 1 ⁄ 2

It is worthy of remark that cores and flakes of obsidian, almost identical in


character with those from Mexico, but generally of small size, have been found in
Greece, principally in the island of Melos. [1181] Specimens are in the Christy
Collection, and I possess several. Obsidian nuclei are also found in Hungary.
Simple flakes and splinters of flint have been found in considerable numbers over
almost the whole of Britain. Of the four here shown, Fig. 190 was found near
Newhaven, Sussex; Fig. 191 near Reigate, Surrey; Fig. 192 near Icklingham,
Suffolk; and Fig. 193 at Seaford, Sussex. At each of these places they occur in great
numbers on the surface, and near Reigate some thousands were collected nearly
forty years ago by Mr. Shelley, [1182] of whose discoveries I have given an account
elsewhere. The counties in which they principally abound are perhaps {279}
Cornwall, [1183] Devonshire, [1184] Dorsetshire, Wilts, Hants, [1185] Surrey, [1186]
Oxfordshire, [1187] Sussex, Suffolk, Norfolk, Derbyshire, Lancashire, [1188] and
Yorkshire; but they may be said to be ubiquitous. In some parts of Devonshire, and
especially near Croyde, they occur in great numbers, so great, indeed, as to have
led Mr. Whitley [1189] to suppose them to have been formed by natural causes
rather than by human agency. Far more rational accounts of them have been given
by Mr. Townshend M. Hall, [1190] Mr. H. S. Ellis, [1191] and Mr. C. Spence
Bate. [1192]
Flakes and splinters of flint frequently occur in and around ancient encampments
and settlements, as well as in association with interments both by cremation and
inhumation. Many of the immense number of “spear-heads” collected by Mr.
Bateman in his investigations were of the simple flake form, and others were flakes
with but slight secondary working at the edges, such as will hereafter be noticed.
Many other instruments which he discovered were merely flakes, such as the thick-
backed cutting instrument of flint three inches long, with a bronze dagger and two
small balls of stone, in a barrow containing a skeleton near Pickering, [1193] which
would appear to have been of this character. They occurred with burnt bones in
cinerary urns at Broughton, [1194] Lincolnshire, in one case with a flat bronze
arrow-head; at Summer Hill, [1195] near Canterbury; with a flint arrow-head at
Sittingbourne; [1196] with burnt bones and bronze daggers in a barrow at
Teddington, [1197] Middlesex; at Penhow, [1198] Monmouth; and in the Gristhorpe
Barrow, [1199] near Scarborough; with burnt bones in a circle of stones near
Llanaber, [1200] Merionethshire, where no flint occurs naturally; with burnt bones in
an urn beneath a tumulus at Brynbugeilen, [1201] Llangollen; in a barrow near
Blackbury Castle, [1202] Devon; and in one on Dartmoor; [1203] and at
Hollingsclough and Upper Edge, [1204] Derbyshire. Flakes, not of flint, but of a hard
silicious grit, occurred in a cist with burnt bones near Harlech; [1205] and of some
other hard stone in a cist in Merionethshire. [1206] Other instances have been cited
by General Pitt Rivers, [1207] who found several rough flakes and splinters of grit
and felspathic ash in cairns near Bangor, North Wales. Some of these showed signs
of rubbing and use on their edges; in some cases they had the appearance of
having been scraped by metal. Whether they were the weapons and tools of the
people buried in the cairns, or {280} merely votive offerings, appeared to be
somewhat doubtful. The urns associated with them were such as might well belong
to the Bronze Period.
Flint flakes are described as found in graves with contracted interments at
Amble, [1208] Northumberland; Driffield, [1209] Yorkshire; Ballidon Moor, [1210]
Derbyshire; Littleton Drew, [1211] and Winterbourn Stoke, [1212] Wilts. Canon
Greenwell [1213] has also found them in great numbers with interments of different
characters. They occurred with extended burials at Oakley Park, [1214] near
Cirencester. In some of the long barrows they are especially numerous, upwards of
three hundred having been found by Dr. Thurnam at West Kennet, [1215] while
there were three only in that of Rodmarton, [1216] and two were found at the base
of the cairn in the chambered tumulus at Uley, [1217] Gloucestershire. Another
accompanied a skeleton in a long barrow near Littleton Drew. [1218] Sir Richard Colt
Hoare speaks of a great quantity of chipped flints, prepared for arrows or lances, as
having been found in barrows on Long Street Down, [1219] and at Brigmilston,
Wilts; [1220] but, as a rule, he seems not to have taken much notice of such simple
forms. Others have been discovered with ashes at Helmingham, [1221] Suffolk.
It is, however, needless, to cite more instances of their occurrence with
interments belonging to the Stone and Bronze Ages, as the presence of flakes and
chippings of flint is in such cases the rule rather than the exception.
In Scotland, where flint is a scarcer natural product, they are also found. As
instances, I may cite one found in an urn within a cist at Tillicoultry, [1222]
Clackmannanshire; and in a cist in Arran. [1223] In some parts of
Aberdeenshire [1224] and Banffshire they are numerous, and in the Buchan district
are associated with shell mounds, or kjökken-möddings. They occur also in
Lanarkshire and Elgin. [1225] In Orkney [1226] they abound: as also at the Bin of
Cullen, [1227] where a manufactory of arrow-heads seems to have existed. In cists
in Roxburghshire [1228] were sepulchral urns and numerous flint flakes; and in
Argyllshire [1229] there were in a cist with a skeleton flint flakes in such numbers as
to form a heap from eighteen inches to two feet in height. Some of white quartz
have been found associated with arrow-heads in Banffshire. [1230] Little
heaps [1231] of six or eight were found in each corner of a grave at Clashfarquhar,
Aberdeen. They abound on the sand-hills near Glenluce and on the Culbin Sands.
Of ancient encampments or settlements where flint flakes occur in {281}
numbers, I may mention Maiden Bower, near Dunstable; Pulpit Wood, near Prince’s
Risborough; Cissbury, [1232] Beltout Castle, and other encampments in Sussex;
Little Solsbury Hill, near Bath; Castle Ring, [1233] Cannock Chase; Avebury, [1234]
Wilts; and Callow Hill, [1235] Oxfordshire. They have been found in wonderful
abundance on the surface in the counties already mentioned, and their occurrence
has been noticed near Bradford Abbas; [1236] near Folkestone; [1237] at
Possingworth Manor, [1238] Uckfield; near Hastings; [1239] at Stonham [1240] and
Icklingham, Suffolk; near Grime’s Graves, Norfolk; [1241] at St. Mary Bourne, [1242]
Hants; and in a turbary at Heneglwys, [1243] Anglesea, an island in which no flint
occurs naturally. Two from Carno, Montgomeryshire, are engraved in the
Archæologia Cambrensis . [1244] They have also been found under a submerged
forest on the coast of West Somerset. [1245] I have seen a few flakes made from
Lower Tertiary conglomerate.
In districts where flint was an imported luxury, other stones, usually containing a
large proportion of silica, and when broken presenting a conchoidal fracture, served,
so far as the material allowed, the same purposes as flint. Of this a few instances
have already been given. In some cases even laminated sandstones, shales, and
slates seem to have been utilized. Numerous relics of this kind, some so rude that
their purposes may appear doubtful, were found by the late Mr. S. Laing, [1246] in
Caithness. Large oval flakes, made from sandstone pebbles, occurred in very great
numbers in and around the ancient dwelling at Skaill, Orkney. In form, however,
these approximate more nearly to the Pict’s knives, of which hereafter, than to
ordinary flakes. The method of their manufacture has been described by Mr.
Laing. [1247]
A curious stone knife or dagger, found beside a stone cist in Perthshire, [1248] is
described as a natural formation of mica-schist, the peculiar shape of which has
suggested its adaptation as a rude but efficient implement.
Some rude spear-heads of flint and greenstone are said to have been found near
Pytchley, [1249] Northamptonshire; and some of Kentish rag at Maidstone. [1250] I
have also seen them made of Oolitic flint.
Flakes of quartzite have been found, together with some of flint and quartz and
with polished celts, in some of the caverns inhabited during the Neolithic Period in
the Pyrenees of the Ariège, [1251] and also in the Lake Settlement of Greug. [1252]
When we consider how well adapted for cutting purposes were
{282} these simple flakes of flint, and how they constituted, as it
were, the raw material for so many of the more finished forms, such
as arrow-heads, of which the consumption in ancient times must have
been enormous; and when, moreover, we take into account that in
producing a well-formed flake many waste flakes and mere splinters
must probably have been struck off, and that in forming the large
implements of flint almost innumerable chips or spalls must have been
made, their abundance on the sites of ancient dwelling-places is by no
means surprising, especially as the material of which they are formed
is almost indestructible.
Such fragments of flint must have been among the daily necessities
of ancient savage life, and we can well understand the feeling which
led the survivors of the departed hunter to place in his grave not only
the finished weapons of the chase, but the material from which to
form them, as a provision for him in “the happy hunting grounds,” the
only entrance to which was through the gate of Death.
The occurrence of flint chips and potsherds in the soil of which
barrows are composed, may in some cases be merely the result of
their being made up of earth gathered from the surface of the
ground, which from previous occupation by man was bestrewn with
such remains. It is, however, often otherwise, especially when the
flakes are in immediate association with the interment. The practice of
throwing a stone on a cairn is no doubt a relic of an ancient
custom. [1253] The “shards, flint, and pebbles” which Ophelia should
have had thrown on her in her grave may, as has been suggested by
Canon Greenwell, [1254] point to a sacred Pagan custom remembered
in Christian times, but then deemed irreligious and unholy.
The presence of flint flakes in ancient graves is not, however,
limited to those of the so-called Stone and Bronze Periods, but they
occur with even more recent interments. For it seems probable that
the flint was in some cases buried as a fire-producing agent, and not
as the material for tools or weapons. In a cist at Lesmurdie, [1255]
Banffshire, apparently of early date, were some chips of flint which
appeared to the discoverer to have been originally accompanied by a
steel or piece of iron and tinder. The oxide of iron may, however, have
been merely the result of {283} the decomposition of a piece of iron
pyrites. At Worle Hill, [1256] Somersetshire, “flint flakes, prepared for
arrow-heads,” were found with iron spear-heads and other objects,
though it is very doubtful whether they were in true association. In
Saxon graves, [1257] however, small nests of chipped flints are not
unfrequent, and the same is the case with Merovingian and Frankish
interments, sometimes accompanied by the steels or briquets , [1258]
at other times without them. I have a wrought flint of this class,
curiously like a modern gun-flint, from an early German grave near
Wiesbaden. Occasionally flakes of other materials than flint occur.
Their presence in graves is regarded by M. Baudot as due to a
reminiscence of some ancient rite of sepulchre. In the Anglo-Saxon
burial-ground at Harnham Hill, [1259] near Salisbury, and at Ozengal,
steels were also found. Canon Greenwell found a steel, in form much
like those of modern date, in a Saxon grave at Uncleby in the East
Riding of Yorkshire. As has been pointed out by Mr. Akerman,
Scheffer [1260] informs us that so late as the seventeenth century, the
Lapps were buried with their axe, bow, and arrows, and a flint and
steel, to be used both in a life to come and in finding their way to the
scene of their future existence.
Flakes and rudely chipped pieces of flint are also of very common
occurrence on the sites of Roman occupation, as, for instance, at
Hardham, [1261] Sussex, where Prof. Boyd Dawkins found them
associated with Roman pottery. At Moel Fenlli, [1262] also, in the vale
of Clwyd, there occurred with Roman pottery some flint flakes which
have been figured as arrow-heads, and with them what is termed a
stone knife, but which is, however, more probably a whetstone used
to sharpen those of steel. I have myself noticed flint flakes at
Regulbium (Reculver), Verulamium (St. Alban’s), and on other Roman
sites. Many of them were no doubt used for producing fire, but the
more finished flakes may possibly have served as carpenters’ tools for
scraping, in the same way as fragments of glass are in use at the
present day.
There is, however, another cause why rude splinters of flint {284}
should accompany Roman remains, especially in the case of villas in
country districts, for the tribulum , or threshing implement employed
both by the Romans and other ancient civilized nations, was a “sharp
threshing instrument having teeth,” [1263] in most cases of flint.
Varro [1264] thus describes the tribulum :—“Id fit e tabulâ lapidibus aut
ferro exasperatâ, quæ imposito auriga aut pondere grandi trahitur
jumentis junctis ut discutiat e spicâ grana.” Another form of the
instrument was called traha or trahea . In the East, in Northern Africa,
Spain, Portugal, Madeira, Teneriffe, and probably other parts of the
world, threshing implements, which no doubt closely resemble the
original tribula , are still in use. The name is still preserved in the
Italian trebbiatrice , the Spanish trilla , and the Portuguese trilho , but
survives, metaphorically alone, in our English tribulation . In Egypt
their name is nureg , and in Greece ἁλωνίιστρα, from ἁλωνία, a
threshing-floor. Drawings of various tribula have been given by
various travellers, [1265] and the implements themselves from different
countries may be seen in the Christy Collection and in the Blackmore
Museum. They are flat sledges of wood, five to six feet in length, and
two or three in breadth, the under side pitted with a number of
square or lozenge-shaped holes, mortised a little distance into the
wood, and having in each hole a flake or splinter of stone. I have
seen them in Spain mounted with simple pebbles. In those from
Madeira the stone is a volcanic rock, but in that from Aleppo—
preserved in the Christy Collection, [1266] and shown in Fig. 194—each
flake is of cherty flint and has been artificially shaped. Occasionally
there are a few projecting ribs or runners of iron along part of the
machine, but in most instances the whole of the armature is of stone.
As each trilho is provided with some hundreds of chipped stones, we
can readily understand what a number of rough flakes might be left in
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