Beryllium: Mineralogy, Petrology, and Geochemistry 9781501508844, 9780939950621

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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

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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

1529-6466/02/0050-000035.00

1000 1500 Wavelength (nm)

2000

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

2

1 1 2 2 2 4 4 4 5 5 5 17 23 24 24 25 25 27 28 51 74 76

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 Introduction Water on Mars Martian soil? USEFULNESS OF BE IN FUTURE PLANETARY STUDIES ACKNOWLEDGMENTS REFERENCES

3

111 111 Ill 112 113 114 114

Trace-Element Systematics of Beryllium in Terrestrial Materials Jeffrey G. Ryan

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

4

121 121 123 123 127 129 130 130 134 136 136 137 140 140 140 141

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

vi

147 149 149 156 159 160 160 160 161 161 161 162 165 165 172 176

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

5

181 189 195 196 196

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

6

207 208 208 209 211 215 215 217 220 221 225 227 230 230 230 230 235 239 243 243 243 245 250 254 256 256 257 258

Environmental Chemistry of Beryllium-7 James M. Kaste, Stephen A. Norton, Charles T. Hess

INTRODUCTION ANALYSIS F O R ' B E 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 7 BE DISTRIBUTION IN V E G E T A T I O N A N D SOILS 7 BE IN F R E S H W A T E R S ' B E IN T H E M A R I N E E N V I R O N M E N T APPLICATIONS OF 7BE SUMMARY AND CONCLUDING REMARKS ACKNOWLEDGMENTS REFERENCES

vii

271 271 272 276 277 279 281 284 285 285

Table of

7

Contents

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

INTRODUCTION BERYLLIUM IN THE ATMOSPHERE BERYLLIUM IN PRECIPITATION BERYLLIUM IN THROUGHFALL BERYLLIUM IN FLORA AND FAUNA BERYLLIUM IN SOIL CHEMICAL WEATHERING BERYLLIUM IN SOIL WATER AND GROUNDWATER BERYLLIUM IN LAKES AND STREAMS South America Pearl River, China SPECIATION OF BERYLLIUM IN WATER PARTITION (DISTRIBUTION) COEFFICIENTS OF BERYLLIUM BETWEEN WATER AND PARTICULATE MATTER BERYLLIUM IN SEDIMENT MASS BALANCE OF BERYLLIUM IN WATERSHEDS ACKNOWLEDGMENTS REFERENCES

8

291 291 292 294 294 296 297 299 300 301 301 305 306 306 308 310 312 312

Beryllium Analyses by Secondary Ion Mass Spectrometry Richard L. Hervig

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

9

319 319 319 320 321 321 322 323 327 327 329 329 329 330 330 331 331

The Crystal Chemistry of Beryllium Frank C. Hawthorne, Danielle M.C. Huminicki

INTRODUCTION CHEMICAL BONDING STEREOCHEMISTRY OF Be(p4 POLYHEDRA IN MINERALS Variation in distances Variation in Be-cp distances General polyhedral distortion in Be-bearing minerals

viii

333 333 333 334 334 334

Table of Contents MOLECULAR-ORBITAL STUDIES OF Be(p4 POLYHEDRA Prediction o f equilibrium geometries Deformation electron-density maps Interpretation o f spectroscopic data B E R Y L L I U M MINERALS AND THE IONIC MODEL HIERARCHICAL ORGANIZATION OF C R Y S T A L STRUCTURES POLYMERIZATION OF Be(p4 AND OTHER Tip4 TETRAHEDRA A STRUCTURAL HIERARCHY FOR BERYLLIUM MINERALS Isolated 76F. 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 Mndominant material reported by Campbell and Roberts 1986); Weinebene, Carinthia, Austria (Walter et al. 1990; Sabor 1990); and Bendada, Beira Alta, Portugal (SchnorrerKöhler and Rewitzer 1991). Sphaerobertrandite. Until recently, sphaerobertrandite had been considered a Beand 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 * Ideal formula Symmetry - space group

Be4Si207(0H)2 Orthorhombic -

Cmc2i

Sphaerobertrandite * * Be3Si04(0H)2 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)

607.0 t

400.0

F(Ä3)

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 wetchemical 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 rockforming 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 humitegroup 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

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Introduction and List of Beryllium Minerals

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