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
Koktokay pegmatite,Xinjiang, China,and #33 is an
emeraldfrom Djebel Zabarah,Egypt (Grubessiet al.
1990).Anal''tical dataaregivenin Table 1. Table2 is
a list of all the samples,with details of color and
provenance.For the chemical composition,structural
parametersand mineral associationsof the samples
other than the three new ones, the reader is referred
to Tables3 and4 in Aurisicchio et al. (1988).
Infrared-absorptionspectrawere recordedin the
4000 to 300 cm-l region using the Perkin Elmer
models5808 and983 spectrometers. Both instruments
gavea resolutionbetterthan 3 cm-l acrossthe range
examined.Sampleswere preparedas compressed
disks of powderedberyl and KBr (2 to 5 weight 7o)
to minimize polarizationeffects.To avoid the effect of
absorbedwater,the KBr was dehydratedat 150oCfor
24 hoursprior to analysis.TransparentKBr disks were
preparedalwaysusing the sameamount(200 mg)
of a mechanicallyground powder compactedunder
1010Pa pressure.Experimentswere performed
at room temperature andat -l80oC on the samedisks,
using a liquid-nitrogen-cooled cell. The temperature
was monitoredvia a thermocoupleplacedcloseto the
disk. Control measurementswere performed on a
sampleof powderedberyl, before and after heatingat
1000'C.As to thepotentialfreezingof HrO in beryl or
in KBr (moistrue),its absorptionband shouldbe in the
rangefrom 3350 to 3150 cm-r (Farmer 1974);none
wasobserved.
fHrol
\-/
tr
/H2o\
\;l
\_,/
tr
(Hzo)
v-/
ALKALI
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).
57
The spectracollected at the temperatureof liquid
nitrogenshowedthe bestresolutionof specificabsorp-
tion bands,permittingbetterinsight into the spectra.
The actual IR spectracan be obtained from the
authors.Correlationswith structuralparametersare
basedon a smaller number of points becauseonly
15 samplesof beryl were analyzedby single-crystal
X-ray diffraction.
DrscussloN
OH-stretchingregion,3800- 3400cm-t
In the 380G-3400cm-r frequencyrange,absorption
bandswere assignedby Wood & Nassau(1968)
to two types of HrO molecules,defined as 6pe I (the
2-fold axis of symmetryof the HrO moleculenonnal
to the crystal's6-fold axis)andtype II (the2-fold axis
of symmetryof the HrO moleculeis parallel to the
crystal's 6-fold axis). Our observationsconfirm
the existenceof thesetwo types of H2O,and they also
suggestthe presence ofOH groupsassociated with the
alkalisin the channelsGigs. lA, B, C), as explained
below. At room temperature,absorbancesdue to
molecularH2O are easily distinguished:3698_cm-l
generatedby HrO of type I, and 3663 cm-' plus
3600 cm-r indicativeof H2O of type II (Fig. 2).
Samplesof 'onormal"beryl (e.9.,sample11) showthe
almost exclusivepresenceof type-I H2O. However,
i--\
I Hzol
\ [,i
tNal
/HoO\
.\-1
ALKALI
NaRICH RICH
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
structureof cordierite;Wallace& Wenk (1980) and
Armbruster (1986) obtainedsimilar HrO spectra
for this mineral, and correlatedtype-tr HrO with the
presenceof alkali ions in the channels.
The low-temperatureinfrared-absorptionspectra
show a markedincreasein absorbances due to both
fype-I andtype-Il HrO (Ftg.3).Moreover,a changein
the ratio of intensitiesof the bandsattributedto type-tr
H2O bands was observed.The absorbanceat
3663 cm-l increases,whereasthat at 3600 cm-l
decreases. This observationmay be explainedby
assumingthat at room temperature,the 3663 cm-1
band is not a single absorption,but in fact a com-
bination of at least two absolptionbands,one due to
type-tr H2O at 3663 cm-l (a very weak shouldermay
be seenon somespectra),and one at 3658 cm-l due to
the OH-Na association.Na-poor samplesgenerate
only a minor effectat 3658cm-l (samples10, 12,26,
28), but the absorbanceincreasesfor Na-rich beryl
(samplesl, 4,23). This correlation,coupledwith the
increasein absorbanceat a low temperature(Katz
1962),explainstlre increasedabsorbanceandbroaden-
ing ofthe 3663cm-1band.FigurelC showsapossible
configurationfor an OH and an alkali cation. Several
authors(Wickersheim& Buchanan1959, 1967,
Manier-Glavinazet al. 1989.Schmetzerand Kiefert
1990)suggested the presenceof (OH)- groupsin the
beryl structure, either in the oxygen sites or in
the channels;Sherriff et al. (L991) found the presence
of OH compatiblewith the availableevidenceand dis-
cussedits potential site-allocation.However,a definite
structuralassignmentis not feasibleat present.We
favor the channelhypothesis,becausethe measured
frequencyof absorptionfits that of hydroxyl linked to
an alkali cation (Ross L972).Charyebalancingof
underbondedoxygen seemsto rule out such a link;
however, the (OH)- group may be attractedto a
channelcation in a similar fashion as the H2O dipole.
Taking into accountthe absorbances,I36q6,I366s
(= overlapof 3663 and 3658 cm I; and Irux of the
threebands,correlatedto type-Il, type-(tr+OH),and
type-I HrO, respectively,the ratios Rl = I36s6/I36e6
and R2 = lzre/Itasshave beencalculated.The sodium
contentGigs. 44, B) showsa good positivecorrela-
tion with both ratios, indicating a preferenceof the
type-II and type-(II+OH) configurations in
the presenceof channelalkalis.This canbe considered
a reasonableconfigurationalong the channel,and it
shouldgeneratetwo O-H stretchingfrequencies.
The sodium content (y) can be expressedby a
functionsuchasy =
Y*, (1 - e-eRt)
shownon Figures4.{ and 48, whereysarrepresents
the maximum sodium content in beryl (close to
0.5 atomsper formula unit, pfu), & is a constant(close
to 0.5 for Rl and 0.4 for R2). The samecorrelation
appliedto measurements made at room temperature
is rather poor, with considerablescatterin the experi-
mental data. The frequencvof the broad band at
3600 cm-l appearsto be affectedby sodiumcontent.
Sampleswith no sodiumhavea maximum absorbance
at 3600cm-r (samplel1). In sampleswith mediumto
high sodium content, the frequency is displaced
to 3588cm-1.ff both cesiumand sodiumarepresenr,
the absorptionband is closeto 3595-3597cm-I. This
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,
as doesthe band position as a function of Si-O bond
lenglh @g. 5B). In contrast,a plot of the Be-O bond
lenglh versusthe band frequency does not show any
meaningful trend. These observationsconfirm that
(i) the 1200cm-r band(1203-1150cm-r; is generated
by vibration in the (SiuOrr)ring (Hofmeister et al.
1987); (ii) the shifts in the frequencyresult indirectly
from substitutionsin the tetrahedrally(?') and octa-
hedrally coordinatedsites, which modiff slightly the
geometryof the ring tetrahedra;and (iii) the corre-
lationsin Figure5 (A, B, C, and D) providea semi-
quantitativeestimateof alkali contentin the beryl.
"Normal" beryl showsa narow, low-absorbance
band at 1020cm-r, which increasesin intensity and
broadenswith extent of substitutionin the octa-
 CRYSTAI CIIEMISTRY OF THE BERYL GROUP
hedrallycoordinated site (Fig. 6, samples3L,1,4,5,
23,24). In contrast,this absorbance shrinksand ulti-
mately vanisheswith increasingextent of substitution
in the tetrahedrallycoordinated(7') site. Instead,an
absorptionbandat 1060cm-1appbarsif the extentof
substitutionsin the ?o site attains0.19 atomsper
formula unit, and its intensity increaseswith further
substitution (Fig.6, samples8, l?,26, 17,28,32,27,
20). Thesetwo bandsmay be relatedto variationin
the lengthsof the "external bonds" Si-O-Be and
Si-O-Al, respectively@lyusnina1964).
An absorptionband at 950 cm-1 showsthe same
correlationsas the 1200 cm-l vibration. Thus the
950 cm-l frequencyis very likely due to anothertype
of Si-O-Si ring vibration (Plyusnina1964,Hofmeister
et al.1987\.
Changesin the frequencyof an absorptionband
at 805 cm-r can be correlatedwith cla ratio" bond
length Be-O(2), and extent of substitutionin the
octahedrallyand tetrahedrallycoordinated, (?') sites
(Figs. 7A, B, C, D). The correlationis particularly
good in, the secondand fourth case.In contrast,
a lot of,this frequencyversusthe Si-O bond length
doesnot shqw any meaningfultrend. Consequently,
we assigntt$s absorptionband to the Be-O vibration,
in agreementwith Plyusnina(1964) and Hofmeister
et al. (1987). Gervais& Piriou (1972) assignedthis
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.
67
bandto Si-O-Si vibrations;Adams& Gardner(1974)
also suggestedthis as a tentative interpretation.
However,our observationsdo not supportsuch a
conclusion.
Two absorptionbandsat 700 and 560 cm-l are
evidentin the spectraof tetrahedrallysubstituted
beryl, recordedat the temperatureof liquid nitrogen
(Figs.8A, B). They appearinitially as a pair of small
shoulders,but both absorbances increasewith progres-
sive entry of Li into the / site. However,they are not
presentin the octahedrallysubstitutedseries.The two
bands,assignedin previousinvestigationsto tlie vibra-
tions of the BeO, tetrahedrain general (Plyusnina
1964,Hofmeisteret a\.1987), seemdiagnosticof
tetrahedrallycoordinatedLi in beryl Qarte 1964).
The absorptionbandsat 525 and500 cm-r can be
correlatedwith the Al-O(2) bond length (Fig. 9 for the
525 cm-t plot). The band shift increaseswith degree
of distortion of the octahedron,particularly where
larger divalent cations substitutefor Al: sample3,
with 0.619 O4g,Fe2*)atomsper formulaunit, lies at
the extremity of the trend. Thus the pair of 525 and
500 cm-1 absorptionbandsis assignedto vIAl-O
vibrations,in accordance with Plyusnina(1964);our
data do not supportthe interpretationof Gervais
& Piriou (1974),who assignedthesebandsto vibra-
tions of the SiOotetrahedra.
68 TIIE CANADIAN MINERALOGIST
CoNcr-usroNs
Low-temperaturestudiesprovide improved resolu-
tion of the infrared spectra,which provesto be parti
cularly advantageous in the H-O region. The two
types of HrO recognizedpreviously, and hydroxyl
groupsassociatedwith alkalis, can be characterized.
The type-Il H2O-Na-(OH) associationproposedfor
alkali-rich beryl correlateswith its reducedcontent
of tWe-I H2O.
The principal vibrations in the 1200-400cm-1
range are diagnosticof the three groups of beryl
compositions:octahedrallysubstituted,tetrahedrally
substitutedand unsubstitutedor "normal" (Aurisicchio
et al.1988\.
A correlation with structural data permits the
assignmentof the 1200 cm*l absorptionband to
Si-O-Si ring vibrations,and the 810 cm-r absorption
to vibrationofthe Be-O bond.The two bandsat 1060
and 1020 cm-l are generatedby vibrationsof the
"externalbonds" Si-O-Be and Si-O-A1, respectively;
they also provide a meansof identifying of the three
compositional typesof beryl.
The absorptionbandsat 700 and 560 cm-l may be
relatedto the replacementof Be by Li in the linking ?"
tetrahedra.In contrast"the absorbancesat 525 and
500 cm-1 are generatedby A1-O vibrations, and the
patternsof the bandspermit estimatesof degreeof
substitutionin the octahedrallycoordinatedsite.
The abovecorrelationscan be usedfor an approxi-
mate determination of the cla ratio, bond lengths at
different sites,degreeof substitutionfor A1 and Be,
and total alkali content. Such an indirect approach
may be particularly valuable for the study of very
small samples.
ACKNOWLEDCEMENTS
This work was financially supportedby the Italiaa
National Council of Research(C.N.R.,Rome,Italy)
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.
Foord, R.F. Martin, and two anonymousreferees.The
authorsare also indebtedto Dr. P. Cern! for a critical
WALLAcE, J.H. & WsNr, H.-R. (1980):Structurevariationin
review,usefulsuggestions andextensiveimprovement
of the Englishtext.
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