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55

The CanadinnMineralo gist


Vol.32,pp.55-68(1994)

INFRARED AND CRYSTALCHEMISTRY


SPECTROSCOPV
OFTHEBERYLGROUP

CARLO AITSICCHIO
Centrodi Stadioper gli Equilibrt Sperimentaliin Minerali e Rocce,ConsiglioNaziotmledelle Ricerche,
P.leA. Moro 5, 00185Roma,Italy

ODINO GRTIBESSI
Dipartimentodi Scienzed.ellaTena. Universitddegli Srudidi Roma "ln Sapienza",P.le A. Moro 5, 00185Romn,Italy

PIERREZECCHINI
Iaboratoire de Cristallographieet ChimieMinlrale, Universitt de FrancheComtd,25030BesangonCedex,France

ABSTRACT

The infrared spectraof 27 natural and two syntheticsamplesof powderedberyl were measuredat room (25oC)and liquid
nitrogen(-180"C) temper,rtures. Water moleculesoccur in two different orientations(type I and type il), for which absorption
bandsare clearly visible a[ low temperatures.The ratio ofthe absorbances due to type-Il and type-I O-H stretchingmodesat
36A0n698 and 366013698cm-l show a positive correlation with Na content, and show that high concentradonof alkalis
is responsiblefor the type-tr configuration.The presenceof hydroxyl gtoups,in a H2O (type II) - Na - (OH) configuration,is
proposedfor alkalirich beryl on the basis of the 3658 cm-l absorbance.The absorptionfrequenciesfor different samples
of beryl are correlatedwith structuraland compositionalparameters.Unsubstitutedberyl, beryl with substitutionsin the
octahedralsite,andberyl with substifutionsin the tetrahedralsite,areclearly discriminatedusing absorptionbandsin the range
106G-1020cm-I. The relationshipshelp to reconcilecontroversiesconcemingthe properassignmentof absorptionfrequencies
to structuraldetails.

Keywords:beryl, crystalchemistry,infrared spectrum,HrO orientation.

SotvruIarng

Le spectreinfrarouge de vingt-sept 6chantillonsnatuels et de deux 6chantillonssynth6tiquesde b6ry1ont 6td mesur6s


i temt'rature ambiatrte(25'C) ainsi qu'i la temp€raturede l'azote liquide (-180"C). Les moldculesd'eau setrouventdansune
de deux orientationsdiff6rentes(dites de type I et de type tr); leurs bandesd'absorptionsont renduestrds 6videntesdansles
spectresobtenush bassetemp6rature.Le rapport des absorptionsduesau mode d'6tirement de la liaison O-H de type I et
de type II, 3600/3698et 366013698 cm-I, montrentune corr6lationpositive avec la teneuren Na, et ddmontrentque la
teneur6lev6een alcalins est responsablede la prdsencede mol6culesd'eau de fype II. Des groupesd'hydroxyle dans une
configurationH2O (type II) - Na - (OH) seraientresponsablesde l'absorption i 3658 cm-r dansle b6ryl enrichi en alcalins.
Les frdquencesd'absorptiondansles diff6rents6chantillonsde b6ry1sont analys6esen fonction desparamdtresstructurauxet
compositionnels.Nous pouvonsdistinguer facilement le b6ryl sanssubstitution,le b6ryl ayant une substitutionimpliquant
le site l coordinenceocta6drique,et le b6ry1ayantune substitutionimpliquantle site b coordinencet6tra6drique,en utilisant les
bandesd'absorptiondansI'intervalle 1060-1020cm-l. lrs relationsque nous d6crivonscontribuenti 6claicir les aspects
controvers6sde I'attribution desfr6quencesd'absorptionaux caractaresstructuraux.
(Traduitpar la R6daction)

Mots-clls: b6ry1,chimie crislalline, spectreinfrarouge,orientationdesmol6culesd'eau.

INTR0DUc"iloN of the cla ratio, bond distances,and site occu-


pancieson the position of vibration bands.This
Substitutionsinvolving tetrahedrallyand octa- type of analysis can help to characterizemate'
hedrally coordinatedcations and the presenceof rials commonly found in very small amounts.
channelconstituents(e.g., H2O, Na, OH) influ- We also proposea solution to discrepancies in
ence the infrared (IR) absorptionspectrumof the assignmentof the IR bandsto Be-O and ring
beryl, In this paper, we explore the influence Si-O-Si bonds.
56 THE CANADIAN MINERALOGIST

The availabilityof a largenumberof beryl samples TAALE .I. CHEMICALCOMPOSMONOF BERYLSAMPLES


that coverthe fulI rangeof chemicalvariationrecog-
nized to dateinvited a systematicstudy by infrared-
sio2 64.36 63.65 @.7E
absorptionspectroscopyin order to characterizefully Al:o: t3.99 17.54 14.u
t}te broadly variablecrystal chemistryof beryl. In a Cr2Oj 0.32 0 . 1I
previous paper (Aurisicchio er al. 1988), we re- FeO f.il 0.07 a.72
MgO 2.68
evaluatedthe complexcrystal-chemistryof beryl on MnO *t
the basisof new chemicaldataand X-ray refinements Tio2 0.22
of the structureof beryl samplesof diffLrentcompo- BeO 13.03 11.37 13.11
Li2o 0.05 o.97 0.04
sitions and from different sources.Our evaluation CaO 0.23
showedthat the main substitutionsinvolve divalenr Na2O 2.03 1.60 1.64
Kro o.z2
and trivalent ions (Fe2+,Mn2+nMg2+,Fe3+,Cr3+), CVO 0.33 2.57
as well as Vs+ and Ti4+for Al in the octahedrally Rbzo 0.06
coordinatedsite and Li for Be in the tetrahedrally L.O.r 2.00 1.97 2.01
Total l@.12 t00.26 99.61
coordinated(7') site. Substitutionsgiving rise to
chargeimbalancerequirethe incorporationof alkali Nmben oliom on the basisof 18 atoms of orygen
ions (Na) into the channelinthe2a position,between
si 6.016 6.025 6.033
the stackedsix-memberedSi rings, whereasCs, Rb, Al 1.541 1.957 t.628
andK enterthe 2Dposition,at the centerofeach ring. Cr A.O24 0.008
The HrO moleculesfit in the 2a sitesonly. The effects re3+ o.oo9 0.006 0.008
Fd+ o.o7i 0.048
of thesesubstitutionson the cell pafirmetersled to the Mg 0.373 : o:r
definition of two solid-solutionsserieson the basis Mn 0.006
of the cla ratio: i) octahedrallysubstitutedberyl, with Ti 0.015
Be 2.Y25 2.585 ^:^
cla valuesfrom 0.991to 0.996,with substitutionsin Li 0.019 0.369 0.015
the O site: Me3+Al_tor Rr*rnuoorMe2*I_rAl*,, and Ca 0.o23
(ii) tetrahedrallysubstitutedberyl, with c/a valuesin Na 0.368 0.294 0.296.
K_ 0.027 o:*
therangefrom 0.999to 1.003,with substitutions in the Cs 0.013 0.103
?' site:Ry+"r.*",Li+fl-rBe-,. Rb 0.002
ctq 0.9927 0.9986 0.9938
The two seriesdepart,with oppositeslope,from
oonormal" (1.e.,unsubstituted)beryl (c/a in the range
Sampl€831 snd gt havebeenanalyzedby lhe authorclollofllng tho
0.9974.998),which showsa composirioncloseto the same lechniqu€8as d6orlb€d ln Aurlslcchloel al. (1988). Sando
ideal stoichiometry,with a very low degreeof substi- @ wa8 analyzedby lhe wst-{hemloal methodIn $o Geoohemhlry
tution in both sites(cl Figs.5 and 6 in Aurisicchioer Infit|J|€ ol the Alademla Slnie, Gulymg, Chlna. Deh: bdw llmll
ot dstsc{on; # by ohtrge balm@; L.O.l.:16 on lgntdon.
al. 1988).tn the frst series,a increasesfrom 9.22 ro
9.27 A, and the c parameterremainsapproximately
constant.In contrast,in the secondseries,the para-
m e t e r a r e m a i n sa p p r o x i m a t e l yc o n s t a n t b
, ut c
increases from 9.20to 9,24A. Two endmemberscan TABLEA DESCHPnONANOL@AUTIES OF BEFYLSPECIIdENS
be derived from the above variations awav from
unsubstituted "normal"berylAlrBerSiuO,r. - zHrO: N'SAMPLE LOCALITY N'SAMPLE LOCALITV
Ill RlAlMe2+Be1Si6O1s.zH2O,oCtahedrally I Dukblue CslsfemMioe 1? V$ypde S.Pi@ircanpo,
substitutedberyl, and PigtIMq bl@ Tusny,Italy
Tusny, Italy 18 Psle pift Mr. Bity regio4
[2] Rf Al2BerLiSi6O,r.zHrO, rerrahedrally subsrituted 2 Liglnbl@ Calefemmine, MadagM
beryl, Pi(rMt4
T|r@y, Iraly
19 Ligbtblue
@ of 20
M@c@tu,
Sdiru Mne,
whereRt+= Na, Cs,Rb, K, in the sequence of decreas- 3 DIL blue South Mom Cmdonq B@il
aned Pi€dnort, ltaly 20 Pale pilk ltrsw G@iC
ing averageabundances, asproposedby Bakakjnet al. 4 Dsrkg@ Mingon" SMValey, rinof t9 SalinoMne,
(1970). aed Pakise B@il
5 Ligh g@ Val Vig@, Pi€dfron! 22 Hr*, Nuitu r€gio4
Italy lvlni lvtle, A&t!i
6 BIue Mohaveco.,Arizo!4 23 G|@ Habaclml
E>csRn/GNTAL lon7rs Smithenid ,511ib69; Aeiis
Indimio! 24 Ct@ l[onu4 Aebdia
7 Pink-rcd aned Wai W8h Momie 26 Lieln gr@ Urslr Mou.daiB
IR spectraof two syntheticand 2l natural samples @rc B@vd Co. U&l Rlsia
8 Piok-red aned W8h Wah Mouuainc 27 Piok Mujee lfee
of beryl from differentsources,chemicallycharacter- rin Bavq Co., Ub[ Z€nb€is
izedby Aurisicchio et at. (1988), are the subjectof 10 Ddkgr@
ll Palegr@
Muo,Colombia
Jos,Nigqis
28 P8lepink PalaNdng
Califomir
this investigation.Beryl samples#31, #32 and #33 12 Blue K6oi, Zinbabw 3l Dak g|a . . Sada T@ifir,
13 Ligh blue MNink4 Bnzil
arenerr acquisitionssincethe 1988paperappeared. Urals Mmils, R!$ia 32 Whib ltukotohai
The first (#31) is an emeraldfrom the St. Teresifla 15 Verypde
bl@
Cecrig@hi,
Vsldosla,
piikilh
33 Dukg@
,(egia! c1li!8
q€belzabatb,.
mine, Brazil; #32 is a beryl transitionalfrom oonormal', Piednplt,ttaly EgDl
16 Ye[@ Fonvictorianel4 St Colorls S]dhaic
to the tetrahedrally substitutedvariety from the ?lnbabve 52 Darkgrd Synhdio
CRYSTAL CHEIVtrSTRYOF THE BERYL GROTJP 57

Koktokay pegmatite,Xinjiang, China,and #33 is an The spectracollected at the temperatureof liquid


emeraldfrom Djebel Zabarah,Egypt (Grubessiet al. nitrogenshowedthe bestresolutionof specificabsorp-
1990).Anal''tical dataaregivenin Table 1. Table2 is tion bands,permittingbetterinsight into the spectra.
a list of all the samples,with details of color and The actual IR spectracan be obtained from the
provenance.For the chemical composition,structural authors.Correlationswith structuralparametersare
parametersand mineral associationsof the samples basedon a smaller number of points becauseonly
other than the three new ones, the reader is referred 15 samplesof beryl were analyzedby single-crystal
to Tables3 and4 in Aurisicchio et al. (1988). X-ray diffraction.
Infrared-absorptionspectrawere recordedin the
4000 to 300 cm-l region using the Perkin Elmer DrscussloN
models5808 and983 spectrometers. Both instruments
gavea resolutionbetterthan 3 cm-l acrossthe range OH-stretchingregion,3800- 3400cm-t
examined.Sampleswere preparedas compressed
disks of powderedberyl and KBr (2 to 5 weight 7o) In the 380G-3400cm-r frequencyrange,absorption
to minimize polarizationeffects.To avoid the effect of bandswere assignedby Wood & Nassau(1968)
absorbedwater,the KBr was dehydratedat 150oCfor to two types of HrO molecules,defined as 6pe I (the
24 hoursprior to analysis.TransparentKBr disks were 2-fold axis of symmetryof the HrO moleculenonnal
preparedalwaysusing the sameamount(200 mg) to the crystal's6-fold axis)andtype II (the2-fold axis
of a mechanicallyground powder compactedunder of symmetryof the HrO moleculeis parallel to the
1010Pa pressure.Experimentswere performed crystal's 6-fold axis). Our observationsconfirm
at room temperature andat -l80oC on the samedisks, the existenceof thesetwo types of H2O,and they also
using a liquid-nitrogen-cooled cell. The temperature suggestthe presence ofOH groupsassociated with the
was monitoredvia a thermocoupleplacedcloseto the alkalisin the channelsGigs. lA, B, C), as explained
disk. Control measurementswere performed on a below. At room temperature,absorbancesdue to
sampleof powderedberyl, before and after heatingat molecularH2O are easily distinguished:3698_cm-l
1000'C.As to thepotentialfreezingof HrO in beryl or generatedby HrO of type I, and 3663 cm-' plus
in KBr (moistrue),its absorptionband shouldbe in the 3600 cm-r indicativeof H2O of type II (Fig. 2).
rangefrom 3350 to 3150 cm-r (Farmer 1974);none Samplesof 'onormal"beryl (e.9.,sample11) showthe
wasobserved. almost exclusivepresenceof type-I H2O. However,

i--\
fHrol I Hzol
\ [,i
\-/
tr tNal

/H2o\ /HoO\
\;l
\_,/ .\-1
tr
(Hzo)
v-/

ALKALI
ALKALI NaRICH RICH
FREE

Frc. 1. A. Cha::nelconfigurationof alkali-free beryl, with HrO of qpe I, I: vacancies.B. Channelconfigurationof sodium-
rich beryl, with type-Il HrO. C. Channelconfigurationof alkali-rich beryl promotinga OH- group.Modified after Aines &
Rossman (1984).
58 TI{E CANADIAN MINERALOGIST

n
tl
I rl
tl

tl
ii rl
l1
ll rl
ll
t: ri
lr

ll
\l
\i - 25"C
- 180C
-*i + type-Iwater
+ fSpe- II water
!I t rt lt l
;lI
tl
1l

T 1l
tl
l1
I

20 ll
il
It
I
I
I
'cni'l
o00 SToo' 3400
FIG.2. IR spectrashowingevidenceoftype-I and type-tr H2O in beryl: O: octahedrally
substitutedberyl, T: tetrahedrallysubstitutedberyl, N: normal or unsubstitutedberyl;
samples 1, 12,and,20 (seeTable2).

with increasedsubstitutionsfor Al (octahedrally H2O becomesdominant; the dipole effect of H2O


substitutedberyl:.e.g., sample 1) and for Be (tetra- moleculeattractsits oxygento the alkali cation in the
hedrally substitutedberyl: e.g., sample 20), coupled 2a site,andturnsits 2-fold axis parallel to the channel,
with incorporationof alkalis into channels,type-Il Le.,parallel to the 6-fold axis of beryl.
CRYSTAL CHEMISTRY OF T}IE BERYL GROUP 59

water
tYpe
-rf
rl
r t-l
ttl
.l.r.l

t
3800

Frc. 3. Transmissioninfraredspectraof beryl in the range3800- 3500cm-r at the temperatureof liquid nitrogen(-180'C).
60 TTIE CANADIAN MINERALOGIST

A B
0,40 0.40

-i^.^ i o.so
;
"=
; +
o
so,20 v0.20

o
z z.
0.10

0.00 +-* 0.00.H


0.00 1.00 2.00 5.00 4 00 5.00 0.00 r.do z.do r.do r.do s.oo
- ^ ^ ^
KOIIO JOUU / JOYd
f a ^ ^ ^
Rotio 3660/3698
Ftc. 4. Ratiosof the intensitiesof the absorptionbands3600/3698(A) and3660/3698@) (typeIVtypeI) at -180'C versasthe
sodiumcontent,in atomsper formula unit. A logarithmicfunction fits the experimentaldatavery well.

The sameeffect was observedin the closely related frequencyof absorptionfits that of hydroxyl linked to
structureof cordierite;Wallace& Wenk (1980) and an alkali cation (Ross L972).Charyebalancingof
Armbruster (1986) obtainedsimilar HrO spectra underbondedoxygen seemsto rule out such a link;
for this mineral, and correlatedtype-tr HrO with the however, the (OH)- group may be attractedto a
presenceof alkali ions in the channels. channelcation in a similar fashion as the H2O dipole.
The low-temperatureinfrared-absorptionspectra Taking into accountthe absorbances,I36q6,I366s
show a markedincreasein absorbances due to both (= overlapof 3663 and 3658 cm I; and Irux of the
fype-I andtype-Il HrO (Ftg.3).Moreover,a changein threebands,correlatedto type-Il, type-(tr+OH),and
the ratio of intensitiesof the bandsattributedto type-tr type-I HrO, respectively,the ratios Rl = I36s6/I36e6
H2O bands was observed.The absorbanceat and R2 = lzre/Itasshave beencalculated.The sodium
3663 cm-l increases,whereasthat at 3600 cm-l contentGigs. 44, B) showsa good positivecorrela-
decreases. This observationmay be explainedby tion with both ratios, indicating a preferenceof the
assumingthat at room temperature,the 3663 cm-1 type-II and type-(II+OH) configurations in
band is not a single absorption,but in fact a com- the presenceof channelalkalis.This canbe considered
bination of at least two absolptionbands,one due to a reasonableconfigurationalong the channel,and it
type-tr H2O at 3663 cm-l (a very weak shouldermay shouldgeneratetwo O-H stretchingfrequencies.
be seenon somespectra),and one at 3658 cm-l due to The sodium content (y) can be expressedby a
the OH-Na association.Na-poor samplesgenerate functionsuchasy =
only a minor effectat 3658cm-l (samples10, 12,26,
28), but the absorbanceincreasesfor Na-rich beryl Y*, (1 - e-eRt)
(samplesl, 4,23). This correlation,coupledwith the shownon Figures4.{ and 48, whereysarrepresents
increasein absorbanceat a low temperature(Katz the maximum sodium content in beryl (close to
1962),explainstlre increasedabsorbanceandbroaden- 0.5 atomsper formula unit, pfu), & is a constant(close
ing ofthe 3663cm-1band.FigurelC showsapossible to 0.5 for Rl and 0.4 for R2). The samecorrelation
configurationfor an OH and an alkali cation. Several appliedto measurements made at room temperature
authors(Wickersheim& Buchanan1959, 1967, is rather poor, with considerablescatterin the experi-
Manier-Glavinazet al. 1989.Schmetzerand Kiefert mental data. The frequencvof the broad band at
1990)suggested the presenceof (OH)- groupsin the 3600 cm-l appearsto be affectedby sodiumcontent.
beryl structure, either in the oxygen sites or in Sampleswith no sodiumhavea maximum absorbance
the channels;Sherriff et al. (L991) found the presence at 3600cm-r (samplel1). In sampleswith mediumto
of OH compatiblewith the availableevidenceand dis- high sodium content, the frequency is displaced
cussedits potential site-allocation.However,a definite to 3588cm-1.ff both cesiumand sodiumarepresenr,
structuralassignmentis not feasibleat present.We the absorptionband is closeto 3595-3597cm-I. This
favor the channelhypothesis,becausethe measured suggests that the "3600 cm-I" absolptionfrequencyis
CRYSTAL CHEMISTRY OF TIIE BERYL GROI,'P

c/a ratio

^{X e
xR
a--.i
I

E
o
c
.9
at
o
CL
ttg
(E
dl

BonddistanceSi-O(1)(A)
a
E
o
c
.9 a.3il
o E4
o
CL ^6a5.4
Eg L/3
(E 'lj1
o al a3

Substitution in octahedral site (7d

E
o
.9
o L24
o !
l, 419
CL
E
tr
(u 431
to a' a3

14
Substitutionin tetrahedalsite (%)

Fro. 5. Frequenciesof the band at 1200 crr-t versus the cla raao (A), bond distanceSi-O(l) @), substitutionin the octa-
hedrally coordinatedsite (C), and substitutionin the tetrahedrallycoordinatedZ'site @).
CRYSTAL CHEIVtrSTRYOF T1IE BERYL GROTJP 63

Ftc. 6. Transmissioninfrared spectraof beryl in the range 1100-850cm-I at a T of


-180oC, showingthe trend ofthe bandsat 1020and 1060cm-r. Transitionfrom octa-
hedrallysubstituted beryl (samples31, l,23,24, 15, 10, 13), through"normal"
(unsubstituted)beryl (samples8, 1,2,26, l7), to tetrahedrallysubstitutedberyl
(samples 28,32,n,20),

meters(c/a ratio, bonds lengths, site occupancies)as


due to a combinationof at leastthree different absorp-
tion bands: type-Il H2O, OH-Na, and OH-Cs grvenby Aurisicchio et al. (1988),and comparedwith
vibrations(Figs. 1B, C). The width of this absorption,
interpretationspublishedin the literature.
which increaseswith amount of cesium, is in agree- The absorptionband at 1200cm-1is assignedby
ment with the hypothesisof multiple absorptionsin many authors to Si-O-Si ring vibrations (Gervais
this range of wavenumbers.This peculiar strusture & Piriou 1972,Adams & Gardner1974,Hofrneister
could supportthe presenceof (OH)- ions in the 2a et al. L987),or to the vibration in BeOatetrahedra
site. (Plyusnina1964).An analysisofthis absorptioncorre-
lated to the clatato Gtg. 54) showsthat in "normal"
The analytical results show that the lowest content
of type-I H2O correspondsto the highest amountsof beryl, the frequencyis closeto 1200cm-I, whereasthe
sodium and tlat, at low temperature,tle increasing sampleswith substitutionsin the octahedrallyand
absorptionat 3658 cm-l may be correlatedwith tetrahedrallycoordinated(7') sitesshow a similar shift
sodiumwithin the channels.This is in good agteement of the bandto lower frequencies.
with the assumedpresenceof (OH)- groups in the Plots of the position of the 1200cm-l band against
vicinity of sodium. cla ratto (Frg.5A,)showa goodpositive correlationfor
o'normal"
the trend from octahedrallysubstitutedto
Strur:turalvibrartonsin theinterval1200400 cm-l beryl, and a negative one for the trend from
'onormal"to tetrahedrallysubstitutedberyl.
In order to relate eachabsorptionband in the range The extent of substitutionsfor Al and Be in beryl
1200-400 cm-l to the structure,the wavenumbers @gs. 5C, D) leadsto an incorporationof alkali ions
were systematically correlated with structural para- (nfl. The two effects causea shift and broadeningof
TIIE CANADIAN MINERALOGIST

E
o
c
.9 ^r,
o
o
CL
'it
c
o
o a ?^^^G a
'^' 3n .a
'
t aa a?t? #t
^.oo^^'
a, 31^a, 2324

t24

c/a ratio

I 818
E
o
g
.9 814
o
oo-
t,
c(6
lo

Bond distanceBe.O(2)(A)
CRYSTAL CIIEMISTRY OF THE BERYL GROUP

E
o
c
.9
o
o
o-
Eg
(!
6

Substitutionin octahedralsite (o/d

E
o
.9
q,
o
CL
t,g
tu
co

Substitutionin tetrahedralsite (o/d

Frc. 7. Frequenciesofthe band810 crrt.tversuslhe claratto (A), bonddistanceBe-O(2) (B), substitutionin the octahedrally
coordinatedsite (C), and substitutionin the tetrahedrallycoordinatedZ' site (D).
66 TIIE CANADIAN MINERALOGIST

cm'1

max= 86.47T 19

t,
f
l-
It .
llYllh = 1741r
1000 800 600 cm
ftc. 8. Infrared absorptionspectraof beryl in the range 1200-300cm-l at the temperature
of liquid nitrogen, showing fwo weak shouldersat 200 and 560 cm-1, increasingin
intensity with extent of Li-for-Ba substitution.Sample8: "normal" beryl, sample19:
alkali-rich bervl.

the band and define a good negativecorrelation, from substitutionsin the tetrahedrally(?') and octa-
as doesthe band position as a function of Si-O bond hedrally coordinatedsites, which modiff slightly the
lenglh @g. 5B). In contrast,a plot of the Be-O bond geometryof the ring tetrahedra;and (iii) the corre-
lenglh versusthe band frequency does not show any lationsin Figure5 (A, B, C, and D) providea semi-
meaningful trend. These observationsconfirm that quantitativeestimateof alkali contentin the beryl.
(i) the 1200cm-r band(1203-1150cm-r; is generated "Normal" beryl showsa narow, low-absorbance
by vibration in the (SiuOrr)ring (Hofmeister et al. band at 1020cm-r, which increasesin intensity and
1987); (ii) the shifts in the frequencyresult indirectly broadenswith extent of substitutionin the octa-
CRYSTAI CIIEMISTRY OF THE BERYL GROUP 67

hedrallycoordinated site (Fig. 6, samples3L,1,4,5, bandto Si-O-Si vibrations;Adams& Gardner(1974)


23,24). In contrast,this absorbance shrinksand ulti- also suggestedthis as a tentative interpretation.
mately vanisheswith increasingextent of substitution However,our observationsdo not supportsuch a
in the tetrahedrallycoordinated(7') site. Instead,an conclusion.
absorptionbandat 1060cm-1appbarsif the extentof Two absorptionbandsat 700 and 560 cm-l are
substitutionsin the ?o site attains0.19 atomsper evidentin the spectraof tetrahedrallysubstituted
formula unit, and its intensity increaseswith further beryl, recordedat the temperatureof liquid nitrogen
substitution (Fig.6, samples8, l?,26, 17,28,32,27, (Figs.8A, B). They appearinitially as a pair of small
20). Thesetwo bandsmay be relatedto variationin shoulders,but both absorbances increasewith progres-
the lengthsof the "external bonds" Si-O-Be and sive entry of Li into the / site. However,they are not
Si-O-Al, respectively@lyusnina1964). presentin the octahedrallysubstitutedseries.The two
An absorptionband at 950 cm-1 showsthe same bands,assignedin previousinvestigationsto tlie vibra-
correlationsas the 1200 cm-l vibration. Thus the tions of the BeO, tetrahedrain general (Plyusnina
950 cm-l frequencyis very likely due to anothertype 1964,Hofmeisteret a\.1987), seemdiagnosticof
of Si-O-Si ring vibration (Plyusnina1964,Hofmeister tetrahedrallycoordinatedLi in beryl Qarte 1964).
et al.1987\. The absorptionbandsat 525 and500 cm-r can be
Changesin the frequencyof an absorptionband correlatedwith the Al-O(2) bond length (Fig. 9 for the
at 805 cm-r can be correlatedwith cla ratio" bond 525 cm-t plot). The band shift increaseswith degree
length Be-O(2), and extent of substitutionin the of distortion of the octahedron,particularly where
octahedrallyand tetrahedrallycoordinated, (?') sites larger divalent cations substitutefor Al: sample3,
(Figs. 7A, B, C, D). The correlationis particularly with 0.619 O4g,Fe2*)atomsper formulaunit, lies at
good in, the secondand fourth case.In contrast, the extremity of the trend. Thus the pair of 525 and
a lot of,this frequencyversusthe Si-O bond length 500 cm-1 absorptionbandsis assignedto vIAl-O
doesnot shqw any meaningfultrend. Consequently, vibrations,in accordance with Plyusnina(1964);our
we assigntt$s absorptionband to the Be-O vibration, data do not supportthe interpretationof Gervais
in agreementwith Plyusnina(1964) and Hofmeister & Piriou (1974),who assignedthesebandsto vibra-
et al. (1987). Gervais& Piriou (1972) assignedthis tions of the SiOotetrahedra.

E
C)
c
.9
aD
o
CL
!
g
TE
co

Al- O(2)
Bonddistance
Ftc. 9. Frequenciesof the bandat 525 cm-r ver.r,6the bond distanceA1-O(2) in A.
68 TIIE CANADIAN MINERALOGIST

CoNcr-usroNs AuRrsrccHro,C., Ftoneveur, G., Gnunrsst, O. & ZNtszr,


P.F.(1988):Reappraisal of the crystalchemistryof beryl.
Low-temperaturestudiesprovide improved resolu- Am.M ineral. 73, 826-837.
tion of the infrared spectra,which provesto be parti BAKAKTN, V.V., Ryt-ov,G.M. & Bpr-ov,N.V. (1970):X-ray
cularly advantageous in the H-O region. The two diffraction data for identification of beryl isomorphs.
types of HrO recognizedpreviously, and hydroxyl Geochem.Int. 7, 924-933,
groupsassociatedwith alkalis, can be characterized.
The type-Il H2O-Na-(OH) associationproposedfor V.C. (1974): The Infrared Spectra of Minerals.
FARMER,
alkali-rich beryl correlateswith its reducedcontent Monograph4, MineralogicalSociety,London,U.K.
of tWe-I H2O.
Gsnvers, F. & Pnrou, B. (1972): Etude des spectes de
The principal vibrations in the 1200-400cm-1 r6flexion infrarouge du b6ryl dans la 16gion
range are diagnosticof the three groups of beryl 280-1400cm-r. C.R.Acad. Sci.ParisB2il4.252-255.
compositions:octahedrallysubstituted,tetrahedrally
substitutedand unsubstitutedor "normal" (Aurisicchio GRUBEssr,O., AunrsrccHro,C. & CAsrIGLtoNl,A. (1990):
et al.1988\. The Pharaohs'forgotten emerald mines. "L Gemmol.
A correlation with structural data permits the 22(3),16+177.
assignmentof the 1200 cm*l absorptionband to
HoFMErsrER, A.M., HoERINc,T.C. & Vtnco, D. (1987):
Si-O-Si ring vibrations,and the 810 cm-r absorption Vibrational spectroscopy of beryllium aluminosilicates:
to vibrationofthe Be-O bond.The two bandsat 1060 heat capacity calculation from band assignments.P&ys.
and 1020 cm-l are generatedby vibrationsof the Chem. M iner. 14. 2O5-224.
"externalbonds" Si-O-Be and Si-O-A1, respectively;
they also provide a meansof identifying of the three Karz, A. (1962):Hydrogenin alpha qulartz.Philips Research
compositional typesof beryl. Reports l7 (3), 133-279.
The absorptionbandsat 700 and 560 cm-l may be
MaNreR-Gr-evn{Az, V., Coury, R. & Lecacss, M. (1989):
relatedto the replacementof Be by Li in the linking ?" The removalof alkalis from beryl: structuraladjusfinents.
tetrahedra.In contrast"the absorbancesat 525 and Can. M ineral. n. 663-671.
500 cm-1 are generatedby A1-O vibrations, and the
patternsof the bandspermit estimatesof degreeof Pr,wsrnte, I.I. (1964):Infraredabsorptionspectraof beryls.
substitutionin the octahedrallycoordinatedsite. Geochern. Int., 13-21.
The abovecorrelationscan be usedfor an approxi-
Ross,S.D. (1972);lnorganic Infrared and RamanSpectra.
mate determination of the cla ratio, bond lengths at
McGraw-Hill. New York.
different sites,degreeof substitutionfor A1 and Be,
and total alkali content. Such an indirect approach Scrunrzrn, K. & Ktrnnnr, L. (1990): Water in beryl - a
may be particularly valuable for the study of very contribution to the separability of natural and synthetic
small samples. emeraldsby infrared spectroscopy.J. Gemmol.22(4),
215-223.
ACKNOWLEDCEMENTS
SHrrnrrl,8.L., GRIrtlDy,H.D., Hannaat, J.S.,Hewruoruw,
F.C. & eeRNY,P. (1991):The incorporationof alkalisin
This work was financially supportedby the Italiaa beryl: multi-nuclear MAS NMR and crystal-structure
National Council of Research(C.N.R.,Rome,Italy) sttdy. Can.M ineral. 29,271,-285.
and by Ministero della Ricerca Scientifica e
dell'Universitd (Rome,Italy). The presentationwas Tenre,P. (1964):IdentificationofLi-O bandsin the infrared
considerablyimprovedby critical reviewsof Drs. E.E. spectraof simple lithium compoundscontainingLiOa
Foord, R.F. Martin, and two anonymousreferees.The tetrahedra.Spectrochim.Acta 20, 238-239.
authorsare also indebtedto Dr. P. Cern! for a critical
WALLAcE, J.H. & WsNr, H.-R. (1980):Structurevariationin
review,usefulsuggestions andextensiveimprovement Am. Mineral. 65,96-11I.
low cordierites.
of the Englishtext.
WrcKERsHErM, K.A & BucueNAN,R.A. (1967):Some
RmnnsNcFs remarksconcerningthe specfraof water and hydroxyl
ADAMS, I.R.(1974):Single-crystal
D.M.& GanoNnR, vibra- groupsin beryl. J. Chem.Phys.42, 1468-1469.
tional spectraof beryl and dioptase.J. Chem.Soc.,
Dalton Trans.,Part 2, Inorg. Chem.,1502-1505. - &- (1959): The nearinfrared spectrumof beryl.
Am Mineral.U.M0-445.
AINES,R.D. & RossueN,G.R. (1984):The higb temperature
behaviorof water and carbondioxide in cordieriteand Wooo, D.L. & NAssAU,K. (1968):The characterization of
beryl. Am. Mineral. 69,319-327. the bery1and emeraldby visible and infrared absorption
An. Mineral. 53,777-800.
spectroscopy.
ARMBRUSTtsR, T. (1986):Role of Na in the structureof low-
cordierite:a single-crystalX-ray study.Am. Mineral. Tl, ReceivedJanuary5, 1993,revisedmnnwcript acceptedApril
746-757. 28. 1993.