Contrib Mineral Petrol

DOI 10.1007/s00410-009-0465-7

ORIGINAL PAPER

Stability and chemical equilibrium of amphibole in calc-alkaline

magmas: an overview, new thermobarometric formulations
and application to subduction-related volcanoes
Filippo Ridol Alberto Renzulli Matteo Puerini

Received: 15 October 2008 / Accepted: 13 November 2009

Springer-Verlag 2009

Abstract This work focuses on a rigorous g analysis

y of the widespread p occurrence of amphiboles p with dehydration
positional and textural relation-
physicalchemical, compositional (breakdown) rims made of anhydrous anhydydro
yd rro
ous
us phases
p and/or glass,
lity and the development of new
ships of amphibole stability related to sub-volcanic processes proce
ro
o esssses
es such
suuch as magma mixing
ations for amphibole-bearing calc-
thermobarometric formulations and/or slow ascent ntt during
n duriring
ri
inngg extrusion,
exxtr
trus
u iioon, conrms
c that crystal
uction-related systems. Literature
alkaline products of subduction-related destabilizat
destabilization aattioon occurs
atio occccurs with
wiitth relatively
rel
rel
e ativvely lowlo TP shifts. At the
01,120C, \1,200 MPa, -1 B
experimental results (5501,120C, stab
abbil
i it
stabilityity ccurves,
urv
ur vees,
s, the
thee variance
th varariaanc
n e of
of the
the system
syste decreases so that
DNNO B ?5), H2OCO2 solubility models, a multitude off ammp phhibol
amphiboleibbol
olele ccomposition
om
o mpopositi
siition
tiio
on
n and physicalchemical
physicalc conditions
lkaline products (whole-rocks
amphibole-bearing calc-alkaline kss and
annd aare
arre sstrictly
ttrric
icttlly llinked
innke
k d ttoo each other. This allowed al us to retrieve
glasses, representing 38 volcanoes worldwide
worldwide), dee), crustal
crusta
cr usst l and
and
nd soommee eempirical
some mpirical thermobarometric formulations formu which work
high-P (13 GPa) mantlee amphibole
amphibolle compositions
coommpos
poosi
sitition
o s have
haavve iindependently
innde
d pendently with different compos compositional components
iboless of
been used. Calcic amphiboles of basalt-rhyolite
bas
asal
asal
alt-
t-rrh
hyyo
olite
liite
te volcanic
volcannic
vo (i.e. Si*, AlT, Mg*, [6]Al*) of a single phase (amphibole),
mak
akit
products display tschermakiticiticc pargasite
paarrg
gasit
gas
assit
ite (37%),
(377%%)), magne- and are therefore easily applicable to all types of calc-
siohastingsite (32%) and mma agn
gnes
gne essio
i ho
io horn
orn
magnesiohornblendernbl
nbbllende (31%) com- alkaline volcanic products (including hybrid hy andesites). The
positions with aluminium um n nuum
umb
mb
number ber (i.e. Al# = [6]Al/ Si*-sensitive thermometer and the fO2Mg* equation
AlT) B 0.21. A few volcanic
nic amphiboles
nic
ni amphiboles (*1%) show high account for accuracies of 22C (rest) and 0.4 log units
Al# ([0.21) and are inferred to represent xenocrysts of (maximum error), respectively. The uncertainties of the
crustal or mantle materials. Most experimental results on AlT-sensitive barometer increase with pressure and
calc-alkaline suites have been found to be unsuitable for decrease with temperature. Near the PT stability curve, the
using in thermobarometric calibrations due to the high Al# error is \11% whereas for crystal-rich (porphyritic index
([0.21) of amphiboles and high Al2O3/SiO2 ratios of the i.e. PI [ 35%) and lower-T magmas, the uncertainty
coexisting melts. The pre-eruptive crystallization of con- increases up to 24%, consistent with depth uncertainties of
sistent amphiboles is conned to relatively narrow physi- 0.4 km, at 90 MPa (*3.4 km), and 7.9 km, at 800 MPa
calchemical ranges, next to their dehydration curves. The (*30 km), respectively. For magnesiohornblendes, the
[6]
Al*-sensitive hygrometer has an accuracy of 0.4 wt%
(rest) whereas for magnesiohastingsite and tschermakitic
pargasite species, H2Omelt uncertainties can be as high as
Communicated by J. Blundy. 15% relative. The thermobarometric results obtained with
the application of these equations to calc-alkaline amphi-
Electronic supplementary material The online version of this bole-bearing products were nally, and successfully,
article (doi:10.1007/s00410-009-0465-7) contains supplementary
material, which is available to authorized users. crosschecked on several subduction-related volcanoes,
through complementary methodologies such as pre-eruptive
F. Ridol (&)  A. Renzulli  M. Puerini seismicity (volcano-tectonic earthquake locations and fre-
Dipartimento di Scienze Geologiche,
quency), seismic tomography, FeTi oxides, amphibole
Tecnologie Chimiche e Ambientali,
University of Urbino Carlo Bo, 61029 Urbino, Italy plagioclase, plagioclaseliquid equilibria thermobarometry
e-mail: lippo.ridol@uniurb.it and melt inclusion studies. A user-friendly spreadsheet

123
 Contrib Mineral Petrol

(i.e. AMP-TB.xls) to calculate the physicalchemical con- equilibrium between anhydrous minerals and the liquid
ditions of amphibole crystallization is also provided. phase (i.e. glass), such as those of Putirka et al. (2003) and
Putirka (2005), give reliable temperatures when applied to
Keywords Calcic amphibole  Phase equilibria  phases synthesized from calc-alkaline magmas (e.g. Ridol
Amphibole breakdown  Thermobarometry  et al. 2008) but are highly inaccurate in estimating
Magma plumbing systems the depth (i.e. pressure) of shallow feeding systems
(rest, standard error of estimate = 160170 MPa, i.e. *6 km;
see also Putirka 2008). In addition, all of these geother-
Introduction mobarometers, calibrated on the equilibrium of two or
more phases, can be hardly applicable to hybrid and vari-
Subduction-related volcanoes are characterized by calc- ously re-homogenized magmas such as andesites (e.g.
alkaline magmas stored, before eruption, within relatively Devine et al. 1998, 2003; Ridol et al. 2008). Single-phase
shallow chambers in the upper crust (*315 km). Unex- empirical barometers working with the total aluminium
pected and violent eruptions of such volcanoes are often content of amphibole have been calibrated from the
triggered by the intrusion, into the shallow reservoirs, experimental results on calc-alkaline granitoid or rhyolitic
of higher-temperature magmas from the lower crust rocks (Johnson and Rutherford 1989; Thomas and Ernst
(2540 km) or the mantle ntle wedge (e.g. Nye and Turner 1990; Schmidt 1992; Anderson n aand
n Smith 1995), and
1990; Swanson et al. 1994; Benz et al. 1996; Hall et al. are commonly used to est ssttim
mate
estimate atte tthe
he pre-eruptive pressure
he
kett et al. 2007; Ridol et al. 2008;
2004; Lees 2007; Luckett (and depth) of silicicc ((e.g. e.g
e.g.
e. g.. Ru
R uth
therrfo
fo and Devine 1996;
Rutherford
Rutherford and Devine 2008). These magma intrusions and Bachmann and annd Dunga
D
Dungangan 20
ga 002
2002; 02 ; T hoorn
rn
Thornber et al. 2008) and
ede eruptions in the order of a few
mixing processes precede interm rm
rmed
meddiaate
intermediate te ((e
e.gg. Sam
(e.g. manie
anie
an
Samaniego iego
iego
go eett al. 22008) magmas. How-
weeks to months and control the physicalchemical and eev ver
er, R
ever, idol
id
Ridololl etet aal.
l. ((2008)
l. 2 08
2008) demonstra
demonstrated that most of the
compositional evolutionn of magma in the shallow cham- cha
ham-m- aabbovve bbarometers
above a om
ar omet eterrs calculate pressure
et pressures that are extremely
nd Devine 2003; Martel et
bers (e.g. Rutherford and et al.
al. 1999;
19999
99; innaccu
aacccu
cura
rate
inaccurateattee when compared to experim experimental results (average
Pichavant et al. 2002; Ridol et al. 2008). 2008
20 08).
)).. Pre-eruptive
Prre-
Pre-
e- up
e-erup
upttiiv
vee eerror
err
errror 280 MPa).
seismicity is one of thehe mostt reliable
reeli
liab
iable
able
ab le tools
tool
to ols of
ol of eruption
eruupt
pt n
ption It will be demonstrated that not all the experimental data
hee capacity
forecasting, as it has the ccaap
capa
paacciity
t to t rapidly
rap
rapi
ra piidl
dly
ly indicate
ind
ndic
icate the are suitable to retrieve thermodyna thermodynamic parameters and
depth and strength off magmarock
magm
ma gma
maarrockk or or magmamagma
magmamagma extrapolate thermobarometric formu formulations for volcanic
bvo
volccan
interactions in the subvolcanic anicc systems
syssttems (Aspinal et al.
sy rocks due to the high bulk water con content used in the H2O
1998; Moran et al. 2008;8;; Ridol
Riddol
Rid ol et et al. 2008). Nevertheless, impermeable capsules.
the interpretation of the earthquakes preceding eruptions More recently, the scientic community started to
(e.g. hypocenter, wave velocity, frequency) tends to be embrace the need of ltering the experimental data to
tricky and, sometimes, erroneous if the depth and the size limit the propagation of bias errors and to increase the
of the magma reservoirs are miscalculated or completely accuracy of thermobarometric formulations (e.g. crystal-
unknown. It is, therefore, crucial to have the ability to linity \30%; Lange et al. 2009). In this work, a rigorous
easily and accurately estimate the conditions (P = pres- literature selection and comparison of natural and syn-
sure, T = temperature, volatile content) and depth at/from thetic amphiboles of calc-alkaline magmas mainly based
which calc-alkaline magmas interact and rise to the sur- on texture and mineral chemistry is proposed. It will be
face, as such information is essential in forecasting erup- demonstrated that amphibole in equilibrium with calc-
tions and minimizing their socio-economic impact. alkaline melts crystallizes at physicalchemical conditions
Thermobarometric applications such as QUILF program not far from its instability boundary, and is prone to
(Andersen et al. 1993), two-phase thermometers such as the destabilization with relatively small TP changes. Near
titanomagnetiteilmenite (Andersen and Lindsley 1988) the stability curve of amphibole the variance of the sys-
and amphiboleplagioclase (Holland and Blundy 1994), tem (in terms of composition and physicalchemical
are among the most used, and currently, the most reliable conditions) is low, allowing us to formulate several
formulations to constrain the crystallization temperature of empirical thermobarometric equations easily applicable to
volcanic rocks (e.g. Swanson et al. 1994; Heliker 1995; all types of amphibole-bearing calc-alkaline rocks
Devine et al. 1998; Murphy et al. 1998; Bachmann and (including intermediate hybrid products). Finally, the
Dungan 2002; Ridol et al. 2008; Pallister et al. 2008). capability of these equations to recover the conditions of
However, Blundy and Cashman (2008) showed that these magma crystallization is crosschecked with other ther-
thermometers, when applied to experimental phases, gene- mometric and seismic results constraining the uppermost
rally tend to under or overestimate temperature with errors plumbing systems of several active subduction-related
up to *300C. Thermobarometric models, based on the volcanoes throughout the world.

123
Contrib Mineral Petrol

Literature data selection and ltering purpose of comparison with volcanic amphiboles. These
are represented by crustal (from eclogite-facies assem-
A total of *580 calc-alkaline products (among whole- blages and gneisses) amphiboles (Kullerud 1996; Leger
rocks/starting materials and glasses), *550 amphibole et al. 1996; Kullerud and Erambert 1999; Coogan et al.
compositions (among natural and experimental analyses) 2001; Engvik et al. 2001) and experimental amphibole
and an innumerable amount of phase proportions (vol% crystals in equilibrium with garnet, olivine, pyroxene,
and/or wt%) of a multitude of basalt-rhyolite extrusives spinel, chlorite and, locally, plagioclase, obtained at
(from 38 worldwide volcanoes) and of experimental prod- 6801,075C and high-P conditions (*13 GPa; hereafter
ucts have been selected from literature (for references see high-P data) from starting material of mantle compositions
Table 1; Fig. 1; see Supplementary material 1). Both vol- (Niida and Green 1999; Molina and Poli 2000; Fumagalli
canic and experimental data have been selected to assure, as and Poli 2005; Adam et al. 2007). Amphiboles from mantle
much as possible, the chemical equilibrium among the xenoliths were not selected because they may have formed
phases. Although in magmatic system the equilibrium is or re-equilibrated during the slow magma ascent to the
generally not the rule, subsystem scales of local equilibrium surface (e.g. Moine et al. 2001; Artemieva 2009).
conceivably range from 10-4 (interface between phases) to The Table of Supplementary material 1 reports the
105 cm (magma body) (Pichavant et al. 2007). ) p
dataset of experimental results considered in this study and
In this work, we referr to volcanic amphiboles as all the physic
used to constrain the physicalchemical iiccal
alc
lcch
heem conditions of
posits (basic/intermediate enclaves
crystals of volcanic deposits crystallizatiio
amphibole crystallization on
n at
at relatively
rela
reelaatiively low pressure (here-
ones of which show homogenous
included), the inner zones after low-P data). dataa).
). This
Thhis
is nal
nal
n a dataset
data
data
da t seet was chosen from an
composition (i.e. chemicalal equilibrium) on the scale of a few initial, muchmuch
mu ch larger
ch laarg
ger group
grrou
oup of
oup of experiments
experim
ex and published
rysts (both pristine and with break-
microns such as phenocrysts pap
pa peerrss,
papers, s, which
whi
whi
hicch h were
weere
w re ltered
teere
l red with
red with the following
fo criteria. We
down or resorption rims),ms), poikilitic (i.e. large crystals crystaals
ls on
o nly
nl
onlyly selected
sele
se lecctteed
d experiments
expe
ex peri
r ments obtained throughth crystallization
ases) and euhedral (cognate) ggabbro
enclosing anhydrous phases) abbbr
bro
bro methhods
me
methods odds on on starting
sta
tarting materials with calc-alkaline
ca composi-
mogeneous amphibo
crystals. Pristine and homogeneous amphiboles bolees of
bo of ccognate
og
ogna
nate tion
tion
ti ons (from
tions (fr
f om basalt to dacite; Fig. 1). C Crystallization exper-
cause they ar
gabbros were selected because aree inferred
in
nffere re
red
ed ttoo crystallize
ccry
ry
rystal
y aalllizee iiments
ments assure the chemical equilibrium equilibriu among the phases
in equilibrium with the magmamagm gmma at at the
the
h thermal
tth
herrma
m l boundary
bou
ou dary
ound at the constrained intrinsic parameters parameter (i.e. P, T, volatile
layers (i.e. chamber oor, w alllss an
walls aand/or
d/or
d/or roof)
ro
roof
ooff) ttoo fform
orm cumulates
or cumulates fugacity) (e.g. Pichavant et al. 2007). Given G that amphibole
9aa; S
(e.g. Fichaut et al. 1989a; tewa
te
Stewartwart
rt ett al
aal.
l. 1996; Rutherford in intermediate and silicic deposits is always associated
and Devine 2003; Mortazavirttazaav vii and
and Sparks
Sparks 2004; Ridol with plagioclase (Table 1), at P B 500 50 MPa, we avoided
et al. 2006, 2008). It is wow
worthrth noting that all the selected plagioclase-free experimental results results.
studies of calc-alkaline volcanoes report amphiboles with We ltered out all the experimental results, the mass
breakdown or resorption rims in at least one deposit of each balance calculation of which showed a residual sum [ 2
P
volcano (ref. Table 1; Fig. 1). The breakdown reaction is due (i.e. r2). Any experimental amphibole the composition
to amphibole rim dehydration and has been explained by pre- (variable Al2O3 content), mineral chemistry (non-balanced
eruptive magma mixing (isobaric heating) and/or slow formula), and texture (skeletal, swallow-tailed or needle-
magma ascent (isothermal decompression) (Garcia and shaped microstructures) of which suggested chemical dis-
Jacobson 1979; Conte 1993; Rutherford and Hill 1993; equilibrium at the xed physicalchemical conditions was
Schmidt and Sigmarsson 1998; Browne and Gardner 2006; not considered.
Buckley et al. 2006; Ridol et al. 2008). However, amphi- A set of amphibole-free experimental results showing per-
boles with breakdown rims retain the pre-breakdown centage of crystallization between 5 and 30 was selected to
chemical equilibrium as they show inner zones with homo- countercheck the physicalchemical and compositional pattern
geneous composition (e.g. Ridol et al. 2008). Quenched of the amphibole stability curve. See Supplementary material 1
crystals and microlites usually constituting micro-vesicu- for further comments on the selected low-P database.
lated basic/intermediate inclusions (mac enclaves; e.g.
Chen et al. 2009) and vein-type amphiboles of gabbros
(indicating uid-rock interaction at the cumulate zone; e.g. Compositional relationship between amphiboles
Ridol et al. 2008) have both been discarded because they and calc-alkaline melts
show textural and compositional disequilibria inferred to
derive from fast growth and/or high water activity. The liquid line of descent of amphibole-bearing
As the magma, during ascent, can carry up to the surface calc-alkaline magmas
a number of amphibole xenocrysts formed at non-volca-
nic conditions, representative amphiboles from crustal The liquid line of descent from basic (basalt) to silicic
and mantle environments have been chosen solely for the (rhyolite) calc-alkaline magmas is of paramount importance

123
 Contrib Mineral Petrol

Table 1 Compositional and modal variations of amphibole-bearing deposits from worldwide calc-alkaline volcanoes
Ref. Volcano Location Rock compositiona Pl Amp Olv Cpx Opx Oxides Bi K-feld Qtz

1 Aoso Japan Basalt-dacite 733 B5 B1 B10 B4 tr-2 B7

2 Batur Indonesia Basalt-rhyolite 732 B2 B8 B5 B7 tr-1
3 Cayambe Ecuador Andesite-rhyolite 1025 B1 B2 B2 510 23 B5
4 Cerro Negro Ecuador Basalt-dacite 828 B7 B7 B12 B4 tr-3 B5
5 Colima Mexico Andesite 2028 tr-1 12 27 37 tr
6 El Chichon Mexico Basaltic andesite-andesite 530 38 16 tr-2 B2
7 El Reventador Ecuador Basalt-dacite 520 tr-4 B1 5 24 12
8 Iliniza Ecuador Basaltic andesite-rhyolite 540 B20 B5 B25 tr
9 Iriga Philippines Basalt-andesite 723 B5 B10 19 Btr B2
10 Lascar Chile Basaltic andesite-dacite 1022 B8 B4 B15 tr-7 15 B1 Btr
11 Lassen California Andesite-dacite 20 tr-1 12 tr tr tr 1 tr-1
12 Mt. Bulusan Philippines Basaltic andesite-rhyolite 20 15 tr 78 34 37 B5 tr tr
13 Mt. Drum Alaska Basaltic andesite-rhyolite 1157 B10 B3 B3 B9 B2 B4 B2
14 Mt. Dutton Alaska basaltic andesite-dacite 2335 B2 tr tr tr-5.0 tr B2
15 Mt. Pelee Lesser Antilles Basalt-dacite 1835 B2 B1 B7 38 B3
16 Mt. Shasta rnia
California Basaltic andesite-dacite tr-25 B8 B5 B8 B7 tr
tr tr
17 Mt. St. Helens Washington
ngton Andesite-dacite 2252 28 38
38
8 tr-2
ttrr-2
2
18 Okataina New Zealand Rhyolite 1020 tr-4 Btr
Btr tr-1
tr-1
tr 1 tr-3 510
19 On-take Japan Basalt tr-24 B44 B12
B12 B8
B8 B3
B3 B1
B1
20 Pinatubo Philippines
pines Basalt-dacite 1329
132
29 935
993
35
35
3 B6
B6 B19
B19
19 tr-2 Btr B2
21 Redoubt Alaskaa Andesite-dacite 1845
184
18
184
45 tr-7
tr--7 14
1 4 13 13
22 Rindjani Indonesia
esia Basalt-dacite 1035
103
1035
5 B2
B2 B8 B4 14
23 San Juan Colorado
ado Andesite-dacite
Andesit
itee--daaci
it cite
te 2428
242
2428 27
27 B1 35 410 14
24 San Pedro Chile Basaltic
alttiic andesite-dacite
Basal an
nd
des
esitte-
e da
dac
aci
cite
i 521
521 tr-4 Btr tr-1 tr-1 B1 B1
25 Santorini Greecee Basalt-rhyolite
Basalt-
tt--rh
rhyo
yoli
oli
littee 1524 26 tr tr tr-2 14
26 Shiveluch Kamchatka
haattka
tka Andesite
Ande
Andesi
de site
te 1636 832 tr tr tr-3 15
27 Soufrie`re Hills West Indies
Ind
n iiees
nd Andesite
Andesite
And 3035 610 Btr 25 36 Btr
28 Spurr Alaskaa Basaltic andesite-dacite 938 B2 B6 tr-8 B9 B2
29 Taupo New Zealand Andesite-dacite B24 B3 B3 B6 B11 Btr
30 Towada Japan Basalt-dacite tr-30 B1 115 115 B1
31 Zitacuaro Mexico Basaltic andesite-andesite 1931 13 B9 712 7 35 tr-4
Pl plagioclase, Amp amphibole, Olv olivine, Cpx clinopyroxene, Opx orthopyroxene, Oxides magnetite and ilmenite, Bi biotite, K-feld K-
feldspar, Qtz quartz tr trace amounts (i.e. 0 \ DRE \ 0.5); blank not present
a
Compositional ranges of all the erupted products. Phenocryst proportions expressed as dense-rock-equivalent (DRE, i.e. modal composition);
mac inclusions are not taken into account
1 Toya et al. (2005); 2 Reubi and Nicholls (2004); 3 Samaniego et al. (2005); 4 Gorini (2008); 5 Luhr (2002); 6 Andrews et al. (2008); 7 Aguilera
et al. (1988), Ridol et al. (2008), Samaniego et al. (2008); 8 Hidalgo et al. (2007); 9 Viozzi (2008); 10 Matthews et al. (1999); 11 Clynne (1999);
12 McDermott et al. (2005); 13 Richter et al. (1994); 14 Miller et al. (1999); 15 Fichaut et al. (1989a, b), Gourgaud et al. (1989), Pichavant et al.
(2002); 16 Grove et al. (2003, 2005); 17 Rutherford and Devine (1988), Rutherford and Hill (1993), Gardner et al. (1995a), Heliker (1995),
Pallister et al. (2008), Rutherford and Devine (2008), Thornber et al. (2008); 18 Shane et al. (2005); 19 Ujike and Stix (2000); 20 Bernard et al.
(1996), Pallister et al. (1996), Rutherford and Devine (1996); 21 Browne and Gardner (2006), Swanson et al. (1994), Wolf and Eichelberger
(1997); 22 Foden (1983); 23 Bachmann et al. (2002), Bachmann and Dungan (2002); 24 Costa and Chakraborty (2004), Costa and Singer (2002),
Costa et al. (2004); 25 Mortazavi and Sparks (2004); 26 Dirksen et al. (2006), Humphreys et al. (2006); 27 Buckley et al. (2006), Couch et al.
(2001), Murphy et al. (2000), Rutherford and Devine (2003); 28 Nye and Turner (1990); 29 Nakagawa et al. (1998), Smith et al. (2005); 30
Hunter and Blake (1995); 31 Blatter and Carmichael (1998)

to understand the chemical relationships between amphi-
boles and melts. Generally, the differentiation trend of
calc-alkaline liquids is characterized by the increase of
alkali (*29 wt%) followed by the lowering of Al2O3
(2014 wt%), CaO (131 wt%), MgO (\14 wt%) FeO
(\12 wt%) and TiO2 (\2 wt%). Representative trends of
calc-alkaline liquids are reported in the diagrams of Fig. 1.
Figure 1ac show total alkali (Na2O ? K2O) and FeO ver-
sus SiO2 variations of volcanic products (whole-rocks), low-
P melts (starting materials and glasses of the experiments on

123
Contrib Mineral Petrol

Fig. 1 a Total alkali (Na2O ? K2O), b Al2O3 and c FeO versus SiO2 c (a) 14 Volcanic whole-rocks and glasses Volcanic amphiboles
diagrams for experimental and natural amphiboles, and calc-alkaline
products (whole-rocks and glasses). Blue arrows in b show peculiar 12 low-P exp. glasses low-P exp. amphiboles
whole-rock trends inferred to derive from contamination and/or high-P exp. glasses high-P exp. amphiboles

Na2O + K2O wt%

fractional crystallization (see text) whereas the green arrow follows 10
the general liquid line of descent of volcanic extrusives; representa-
tive plagioclase compositions (Pl) are also shown. References for 8
whole-rock compositions of 31 volcanoes can be found in Table 1.
Additional amphibole-bearing whole-rock compositions include 6
Ceboruco (Mexico; Chertkoff and Gardner 2004), Egmont (New
Zealand; Stewart et al. 1996), Mt. Butay (Philippines; Castillo et al. 4
1999), Narcondam (India; Pal et al. 2007), Unzen (Japan; Nakada and
Motomura 1999, Sato et al. 1999, Holtz et al. 2005), Nevado 2
Sabancaya (Peru; Gerbe and Thouret 2004) and Medicine Lake B BA-A D R
(California; Grove et al. 1997) volcanoes. Experimental data refer- 0
ences are reported in Supplementary material 1 and in the text. 40 44 48 52 56 60 64 68 72 76 80
Abbreviations: B basalt, BA basaltic andesite, A andesite, D dacite, SiO2 wt%
R rhyolite
(b) 28 up to 45-36
(An89) Pl
24 An30
calc-alkaline rocks), high-P mantle melts (starting materials
and glasses of the experiments at relativelyy high-P g condi- 20
mphiboles. Figure 1b also illustrates
tions) and associated amphiboles. All2O3 wt%
16
ation of representative plagioclases.
the compositional variation
sion, crustal amphiboles will be dealt
In order to avoid confusion, 12
ection.
with in the following section.
Plagioclase is the most abundant mineral in calc-alka- 8
line volcanic extrusivesves (modal contents of amphibole amphibbo olle 4
higher than or equal too plagioclase are rare, Tablee 1) 1) and
andd B BA A D-R
gabbro cumulates (e.g. Fichaut et al. 1989a; 19899a; Swanson
Swa
Swa
wanso
wan on
n et
et al.
all. 0
40 44 48 52 56 60 6
64 68 72 76 80
1994; Heliker 1995; Costa 2000; 2000 0; Ridol
Riddooll etet al.
al 2008).
20
2 0088))..
SiO2 wt%
ion off si
During the differentiation ssilicate
ili
lica
cate
ca te liquids
te liiquid
quids
qu ids from
id fro
rom basalt
bbassal
a t to
rhyolite in the crust, pplagioclase
lagiio
la occla lase
see evolves
evvolve
ollve
v s from
fro
r m anorthite-
anorthite- (c) 25
ess in
rich to albite-rich species iincreasing
ncr
ccrreeaaasiing
ng inn S iO2 (*4562 wt%)
SiO
and decreasing in C CaOaOO (An ( n 8930 wt%). This is
(A 20
followed by the reductioncti
tion
tiio of plagioclase Al2O3 content
FeO wt%

(*3622 wt%), which always remains higher than that of 15

calc-alkaline liquids (Fig. 1b). In contrast, volcanic
amphiboles (Al2O3 *17 to *7 wt%) do not play any role 10
in the aluminium fractionation and show a decreasing
aluminasilica pattern (Fig. 1b). D-R
5
Some subduction-related calc-alkaline volcanoes (El
Reventador, Ecuador; Shiveluch, Kamchatka; Pinatubo, B BA A
Philippines; Rindjani, Indonesia; Egmont, New Zealand) 0
40 44 48 52 56 60 64 68 72 76 80
show a convex alumina versus silica pattern with some
SiO2 wt%
basic products having lower or similar FeO and Al2O3
contents to the adjacent andesites or basaltic andesites
(Foden 1983; Bernard et al. 1996; Stewart et al. 1996; from basaltic magmas (e.g. Foden and Green 1992;
Dirksen et al. 2006; Ridol et al. 2008) (Fig. 1b, c). This is McCarthy and Patino Douce 1997; Patino Douce 1999;
shown by blue arrows in Fig. 1b which simulate the con- Muntener et al. 2001; Green 2006; Chadwick et al. 2007;
nection between the heterogeneous mantle materials (i.e. Montanini et al. 2008; Ridol et al. 2008).
high-P melts and amphiboles) and the main Al2O3SiO2 The crucial point is that, although these processes
pattern of the calc-alkaline products (green arrow). These somehow change the bulk iron/silica and alumina/silica
Al-poor patterns are inferred to derive from mantle/crust ratios of basic to intermediate (hybrid) products, they do
assimilation or signicant fractionation of garnet (to form not signicantly affect the liquid lines of descent which
ultramac cumulates at relatively high water contents) and/ gradually decrease towards rhyolite compositions. The
or plagioclase (at H2O \ 2.5% and high PT conditions) Al2O3 content of volcanic amphiboles gradually decreases

123
 Contrib Mineral Petrol

(a) 3.6 (b) 3.0 Magnesiohornblendes

Tschermakitic pargasites
3.2 Magnesiohastingsites
2.8 2.6 Consistentamphiboles
Consistent amphiboles
AlT (apfu) 2.4 Inconsistentamphiboles
Inconsistent amphiboles

AlT (apfu)
2.2
2.0
1.6 1.8
Al# = 0.21
1.2 1.4
0.8 Cmm Volcanic amphiboles
Crustal amphiboles 1.0
0.4
Al# = 0 High-P (mantle) amphiboles
0.0 0.6
0.0 0.4 0.8 1.2 1.6 2.0 2.4 2.8 0.5 0.9 1.3 1.7 2.1 2.5
[4] [4]
Al (apfu) Al (apfu)

Fig. 2 AlT versus [4]Al diagrams for natural and experimental
amphiboles. a reports the composition of natural amphiboles (i.e.
volcanic amphiboles, crustal amphiboles) and high-P (mantle)
experimental amphiboles. The compositional eld of volcanic
amphiboles is bounded by the Al# = 0.21 (eq. AlT = 1.266[4]Al)
and Al# = 0 (i.e. AlT = [4]Al) lines which join at the compositions of
ideal cummingtonite (Cmm). b Shows the relationship between low-P
experimental (consistent and inconsistent) and volcanic (i.e. tscher-
makitic pargasite, magnesiohastingsite, and magnesiohornblende)
amphiboles. Errors B to symbol size. See text for further
explanations

with increasing SiO2 following the pattern of calc-alkaline 2006). This formula calculation led to the identication of
magmas (Fig. 1b). This suggests that the alumina/silica only calcic-amphiboles, mainly belonging to the magne-
ratios of amphiboles and melts are strictly linked to each siohornblende, magnesiohastingsite and tschermakite sub-
other and evolve, roughly but consistently, in the same groups. However, the 13 cation calculation determines the
direction. The variation of iron in amphiboles does not minimum alkali content in A-site [i.e. A(Na ? K)] and
ifferentiation path, whereas alkali,
follow any signicant differentiation octahedral aluminium ([6]Al), andd the th
hee maximum
m ferric iron
show an opposite trend with respect to the liquid line of (Fe3?). For this reason, wee counterchecked
cou
co unnte
tercche the nomencla-
descent (Fig. 1a, c). ture of amphiboles calculating
calccul
ulat ing their
atin heir formula
the
the
hei f r
fo on the basis of
at the general Al2O3 versus SiO2
It is worth noting that 15 cations, whichwhhic i h leads
leads
ds too the
ds the maximum
maxim iim
m A
(Na ? K) and
[6] ?
patterns shown by the low-P experimental melts and Al, and
and
nd minimum
min
mi niimu
mum Fe
mum Fe33? eestimations
es timations (Leake et al. 1997).
ti
amphiboles, are roughly shifted to higher aluminium con- Th
T
Thes
hese
Theseese ccalculations
es alcu
al
lcuula
lattiionss iindicate
nddicate that all of the t previously named
tents compared to the average trend of whole-rocks whole-rockks and andnd tssch
c errma
makite
kitees hhave
ki
tschermakites ave A(Na ? K) slightly sli higher than
volcanic amphiboles, suggesting that some of of these
thheese 0.5 aapfu,
0.5
0. pfu, and are, therefore, in th
pf this work re-named
coon
experiments may not be suitable for constrainingnssttrrai
raiiniing
ng the tth
he nat-
he nat
at- tts
scchhermakitic pargasites. It is worth noting
tschermakitic n that the cation
c-alkalin
ural conditions of calc-alkaline inne magma
maga ma
ma crystallization
cry
cr
crys
yssttaallllizaatti
tion differences between the two formula methods m are generally
le)
(Fig. 1b). High-P (mantle)e am aamphiboles
mphib
phib
ph ibol
ibo
oless sh
show
show w even
evven
en higher low (\0.3 apfu on the total cations) cations and both indicate
alumina/silica ratios andd arearee generally
geneeraally characterized
chaharacterized by Mg-rich species [i.e. Mg/(Mg ? Fe2?) [ 0.5].
onntteent
ent
higher alkali and iron contentsnts
ts than
tha
haan
n volcanic
volcanic amphiboles. Volcanic calc-alkaline amphiboles ((number of analyses:
444) show tschermakitic pargasite (37%) magnesioha-
Mineral chemistry and the AlT[4]Al eld stingsite (32%) and magnesiohornblende (31%) composi-
of volcanic amphiboles tions while the 93 selected low-P amphiboles (57
magnesiohornblendes and 36 tschermakitic pargasites)
Mineral formulae for volcanic and low-P experimental show no magnesiohastingsite. Crustal amphiboles show a
amphiboles were calculated following the International wide compositional range, from calcic species (i.e. sada-
Mineralogical Association (IMA) recommendation for nagaite, ferropargasite, pargasite, magnesiohastingsite,
calcic-amphiboles, where Fe3?/Fe2? ratio is determined by hastingsite, tschermakite, magnesiohornblende, edenite,
charge balance after adjusting the tetrahedral (Si, Al, Ti) tremolite) to sodio-calcic amphiboles (magnesiotaramite
plus octahedral (Al, Ti, Cr, Fe, Mn, Mg) cations to 13 and magnesiokatophorite) whereas high-P experimental
(Leake et al. 1997). The adoption of this method is sup- (mantle) amphiboles have pargasite and, in few cases (i.e.
ported by the fact that most of the structural renements of Molina and Poli 2000), barroisite compositions.
natural, volcanic amphiboles, such as magnesiohastingsite, Figure 2 shows that these compositional differences are
magnesiohornblende and tschermakitic hornblende, indi- roughly predictable in terms of AlT and [4]Al contents, and
cate the presence of small (\0.05 apfu) or no R2? cations Al# (hereafter aluminium number, i.e. [6]Al/AlT, calculated
(Fe, Mn, Mg) in the B (i.e. M4)-site (e.g. Clowe et al. 1988; on the basis of 13 cations). As the calculated [4]Al is
Pechar et al. 1989; Phillips et al. 1989; Bojar and Walter inversely correlated to Si, it can be used as a differentiation

123
Contrib Mineral Petrol

index which decreases from basic (low-Si) to silicic (high-Si) Al2O3 versus SiO2 pattern of extrusive rocks and glasses
amphiboles (Figs. 1b, 2a, b). Figure 2a shows the AlT (Fig. 1b). By contrast, inconsistent experimental amphi-
versus [4]Al diagram for the selected natural (volcanic and boles show Al# similar to crustal amphiboles and/or
crustal) amphiboles and high-P experimental (mantle) experimental pargasites (i.e. [0.21) and are often in equi-
crystals which have been used to constrain the main eld of librium with melts characterized by high Al2O3/SiO2 ratios.
volcanic amphiboles in which Al# is B0.21. It is worth The reasons of these anomalous amphibole/melt composi-
noting that most of the volcanic amphiboles fall in this eld tions seem to be mainly due to the excess of water. Glasses
and that the Al# = 0.21 and Al# = 0 lines converge at the associated with inconsistent amphiboles are generally
composition of an ideal Al-free amphibole [e.g. cum- characterized by high water contents (4.513.0 wt%,
mingtonite, [ ]Mg7Si8O22(OH)2]. A few volcanic amphi- average 8.3 wt%) and were synthesized in a wide range of
boles (*1%) show high Al# ([0.21) and are inferred to oxygen fugacity (-3 \ DNNO \ ?4.8). By contrast, low-
represent xenocrysts of crustal or mantle materials. Indeed, Al# amphiboles are found in equilibrium with H2Omelt of
all of the high-P (mantle-derived) experimental crystals 3.78.2 wt% (average 5.9 wt%) and were synthesized at
and most of the crustal amphiboles are well above the 0.21 fO2 between NNO - 1 and NNO ? 2.7, consistent with
Al# line. Although some crustal amphiboles fall in the the normal values of calc-alkaline magma crystallization
volcanic eld, they show different compositions [e.g. (Gill 1981; Carmichael 1991; Martel et al. 1999; Behrens
hastingsite; Mg/(Mg ? Fe2?) \ 0.5] and are notably enri- and Gaillard 2006). In addition, the amount of glass
ched in Cl (0.55.0 wt%, Leger et al. 1996; Coogan et al. produced by the inconsistent amphibole experiments
2001). Possible amphibole ole xenocryst compositions have (3187 wt%, average 61 wt%; average avveerraag Pl/Amp = 1.4) is
been identied among the he Unzen (Nakada and Motomura generally lower than that of of the
thhe consistent
co
onnsis amphibole data
phreys et al. 2006) and Soufriere
1999), Shiveluch (Humphreys (4688 wt%, average 773 3w tt%
%) which,
wt%) wh
whichh, similarly to volcanic
Hills (Rutherford and Devine 2003) volcanic products. products (T Tabblee 11),
(Table ) sh
), hows hhig
shows iggher pplagioclase/amphibole
higher l
However, these crustal and high-P mantle amphiboles will ratioss (a ave
vera
rage
(average gee P
g Pl /Ampp = 2.0)
l/A
Pl/Amp 2.
2 .0
0)). The
2.0). The di discussion of the main
not be discussed further.. ccation
caati
tion
tion
on vavvariations
ari
riat
iat
a ioons in
in vo olcanic and experimental
volcanic expe amphiboles
ompositional scheme for volcanic
Figure 2b denes a compositional volc
lcanic
lc anic
an ic (bbot
o h con
(both cconsistent
onsiist
on stennt aand
ndd inconsistent), and th the estimated errors of
amphibole classicationn and shows the composition compo posi
po s tion
on of
on of the
thhe ccalculated
alcu
al culated atoms per formula units (apfu), is reported in
cul
phiboles. It illustrates
low-P experimental amphiboles. illussttrrat
a es
es that
that
at the
t e dif-
th ddif
iff- Su
S upplementary material 1.
Supplementary
ferent amphibole speciess can bee roughly
rouughly
ghly distinguished
gh d st
di stin
ingu
guis
ished by by
their different Al# and [4]
4]
All cco
compositions.
omp
mpososit
os it ons
itio ns. Above
Abobove
ve 1.5
ve 1.5 apfu The amphibole-melt chemical equilibr
equilibrium
of [4]Al, volcanic amphiboles
bole
bo les
le
es can
can
an be
be roughly
roug
ro ughlhly divided into
oww-A
magnesiohastingsites (low-Al#) Al##) and
anndd tschermakitic
tschermakitic parga- The chemical equilibrium of experime
experimental amphibole-melt
err [4
sites (high-Al#). At lower [[4]
4]
Al content (i.e. 0.91.5 apfu),
Al pairs is assured by the crystallizatio
crystallization of homogeneous
P
amphiboles evolve to magnesiohornblende compositions phases and low errors (i.e. r2) in the mass balance cal-
suggesting complete solid solution among high-Si and culation of the phase proportions.
low-Si amphiboles. Low-Al amphiboles should show solid Element partition coefcients (Di = CAmp i /Cliquid
i ) of
solution with cummingtonite which sometimes occurs in low-P experimental amphibole-melt (both consistent and
pumiceous high-silica volcanics (such as dacite-rhyolite inconsistent) pairs are correlated with [4]Al (i.e. the amphi-
tephra, pumice-lapilli bed and pyroclastic-ow deposits). bole differentiation index) in the diagrams of Fig. 3. The
Cummingtonite is the last phase to crystallize in equilib- maximum volatile content in amphibole has been roughly
rium with high-SiO2 (78 wt%) melts (e.g. Bernard et al. estimated assuming the total occupation of the OH-site by
1996; Pallister et al. 1996; Rutherford and Devine 1996; OH- and shows quite constant values (1.831.99 wt%).
Shane et al. 2005, 2008; Tappen et al. 2009). The alu- According to the cation variation analyses (see Sup-
minium miscibility gap between cummingtonite (Al2O3 plementary material 1), the partition coefcients of
1.23.1 wt%) and magnesiohornblende (Al2O3 down to 5.5 inconsistent pairs show higher DAl and lower DH2 O than
wt%) seems to be related to the lack of representative those of consistent amphibole data (Fig. 3b, h). Low-Al#
database compositions, as magnesiohornblende crystal (consistent) pairs generally show narrower and more steady
zoning to cummingtonite have already been documented variations with DSi, DAl, DFe, DMg and D(Na?K) which are
(Clynne et al. 2008). roughly correlated with [4]Al in the amphiboles (Fig. 3a, b,
The low-P amphibole-bearing experimental data (see d, e, g). Although TiO2, FeO, MgO and CaO decrease
Supplementary material 1) has been divided into consistent during magma differentiation processes (see previous sec-
(45) and inconsistent (44) amphiboles (Fig. 2b). Consistent tion), the partition coefcients (of consistent data) roughly
amphiboles are crystals with Al# B 0.21 and were syn- increase exponentially from basic to differentiated amphi-
thesized in equilibrium with melts overlapping the main boles (i.e. from high to low [4]Al content species; Fig. 3cf)

123
 Contrib Mineral Petrol

(a) 0.9 (b) 1.0

0.9
0.8

DSi 0.8

DAl
0.7
0.7

0.6
0.6

0.5 0.5
0.8 1.2 1.6 2.0 2.4 0.8 1.2 1.6 2.0 2.4
[4] [4]
Al (apfu) Al (apfu)

(c) 13 (d) 18
11 15

13
9
10

DFe
DTi

7
8
5
5
3 3

1 0
0.8 1.2 1.6 2.0 2.4 0.8 1.2 1.6 2.0 2.4
[4] [4]
Al (apfu) Al (apfu)

(e) 100 (f) 10

80 8

60 6
DMg

DCa

40 4

20 2

0 0
0.8 1.2 1.6 2.0
.00 2.44 0.8
08 1.2 1.6 2.0 2.4
[4] [4]
Al (ap
Al (apfu)
apfu
apfu
ap fu)
u)
u) Al (apfu)

(g) 1.0 (h) 0.5

0.8 0.4
D(Na+K)

DH2O
O

0.6 0.3

0.4 0.2

0.2 0.1
0.8 1.2 1.6 2.0 2.4 0.8 1.2 1.6 2.0 2.4
[4] [4]
Al (apfu) Al (apfu)

Fig. 3 Amphibole-melt partition coefcients (D) of Si (a), Al (b), Ti amphiboles. Errors estimated by adding the relative uncertainties of
(c), Fe (d), Mg (e), Ca (f), alkali (g) and H2O (h) versus [4]Al amphibole and melt element oxides. When not reported error bars are
diagrams for the experimental (consistent and inconsistent) amphi- Bto the symbol size. Symbols as in Fig. 2
boles. Solid lines show the compositional variations of consistent

and are always [1. By contrast, silica, alumina, alkali, and
water are incompatible and their D (i.e. 0.60.8, 0.50.9,
0.20.7, 0.20.4, respectively) indicate that amphiboles do
not play any important role in the fractionation of these
elements. The decreasing pattern of D(Na?K) from basic to
silicic amphiboles (Fig. 3g), is negatively correlated with
the increase of alkali content during differentiation
(Fig. 1a). By contrast, alumina of consistent pairs (Fig. 3a,
b) follows the decreasing Al2O3 trend of calc-alkaline
magmas (Fig. 1c). This demonstrates that the content of Al
in (consistent) amphiboles is strongly driven by the com-
position of the calc-alkaline liquids whereas Si, Ti, Fe, Mg,

123
Contrib Mineral Petrol

Fig. 4 a T-Si*, b DNNO-Mg*, (a) 1,050 (b) 3.0

c H2Omelt-[6]Al* and d P-AlT
correlations for the consistent 1,000 2.5
amphiboles. Gray circles [1]
2.0
indicate amphiboles with the 950

T (C)
[2]

NNO
higher thermal stability. In b 1.5
and c, error bars represent the 900
expected analytical and 1.0
methodological uncertainties, 850
0.5
respectively. T and P errors are
smaller than the symbol size 800 0.0
(a, d). See text for indices and 6.5 7.0 7.5 8.0 8.5 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Si* Mg*
equations
(c) 7.5
(d)
7.0 1,000
H 2 O melt (wt.%)

6.5 800

P (MPa)
6.0 [4]
600
5.5 [3]
400
5.0
4.5 200

4.0 0
-1.6 -1.4 -1.2 -1.0 0.0 0.5 1.0
1.0
0 1.5 2.0 2.5 3.0
[6]
Al* AlT (apfu)
Al (

Ca, and alkalis are mainly

nly required to satisfy the charge amphib
amphibole ib o
ib olle major
major
ajjor
or cations
ccaation
ns to
to Si,
Si,
i, we empirically
em calculated
ucture. See Supplementary mate-
balance in the crystal structure. siillicon
sil
a silicon icco
onn index
inndeex (SiSi*) w
(Si which
hich correlat
correlated to temperature,
ments on cation variations.
rial 1 for additional comments iin
nddiicaate
indicate te a higher
hig her R2 (i.e. 0.84) (Fig. 44a):
igher
he
T 151:487Si 2; 041
151:487Si
15 1
4 6 6
where Si Si 4 3 2
15  2 Ti   Fe9 Fe3:3
Al Al Ti
ygen fugacity
Thermobarometric, oxygen fug
ugac
ug
gaccit
ityy and
and
nd hygrometric
hygrom
hy grrome
om
metri
ric
ic 2 1:8
B B A A

formulations
Mg
26 Ca5 1:3 
Na
15 2:3 :
Na

Given that, inconsistent amphiboles
aam
mphhib es show
iboles how different com-
sh
positions with respect too volcanic
volc
vo l anic crystals (Fig. 2; see
Supplementary material 1) and anomalously high DAl and
low DH2 O (Fig. 3), only consistent experimental data are
used to retrieve thermobarometric formulations. Recently,
Lee et al. (2009) retrieved two empirical formulations
which link, independently, pressure and temperature to
the composition of experimental mac melts. As the
composition of amphibole follows the liquid line of des-
cent of calc-alkaline magmas and that the sum of different
cations yields to the improvement of the compositional
correlations (see Supplementary material 1), an entirely
empirical approach has been used to obtain thermobaro-
metric equations exclusively dependent on the amphibole
composition. Compositional indices, obtained by sum-
ming fractions of the amphibole major cations, are used
as input variables in order to improve the performances of
the T, fO2 and H2Omelt equations (Fig. 4). For example,
our linear regression analysis on the variation of tem-
perature with composition of consistent amphiboles indi-
cates that the best coefcient of determination is found
for Si or [4]Al (i.e. R2 0.64). By adding fractions of the
This T-Si
T *
formulation indicates a rest and a maximum
error of 22 and 57C, respectively.
respectively When applied to
high-Al# amphiboles synthesized at mantle conditions
(13.0 GPa, i.e. Niida and Green 1999; Adam et al. 2007),
Eq. 1 shows a rest of 56C. This suggests that temperature is
little affected by P and Al2O3 variation, and that the calcu-
lation of Si* is the only requirement to minimize uncertain-
ties of formula calculation (see Supplementary material 1),
and the use of compositions obtained with slightly different
analytical (e.g. different standards and conditions of electron
microprobe analyses) and experimental approaches.
Consistent experimental results used for the oxygen
fugacityamphibole composition regression analyses were
those, the DNNO of which were accurately determined,
controlling the fH2 of the uid pressure medium and/or
calculated by the magnetiteilmenite compositions in the
experimental products (18 in total; see Supplementary
material 1). According to the results of Scaillet and Evans
(1999) and Ridol et al. (2008), among major amphibole
cations the relative oxygen fugacity (DNNO) is best cor-
related to Mg (R2 = 0.84). The calculation of a magnesium
index (i.e. Mg*) allowed us to obtain a slightly improved
R2 (0.89) of the DNNO-equation (Fig. 4b):

123
 Contrib Mineral Petrol

DNNO = 1:644Mg  4:01 2 *2,100 ppm, respectively (Wallace 2005; Blundy et al.
6 2006). At temperatures of 800 and 1,050C, these CO2
where Mg Mg Si
47  Al
9  1:36 Ti Fe3
3:7 Fe2
5:2  values account for additional pressures (PCO2 * P - PH2O,
B A A

Ca
20  2:8Na
9:5 : i.e. partial pressure of CO2) of about 50 and 390 MPa,
This formulation accounts for a maximum error respectively (as calculated by the solubility model of
(0.41 log unit) and rest (0.22 log unit) in agreement with Newman and Lowenstern 2002). Disregarding these
the uncertainty expected by experimental petrologists pressures would produce crustal depth underestimations
(logfO2 0.20.3; e.g. Scaillet and Evans 1999; Pichavant (calculated assuming a crust specic weight of 2.89 g/cm3;
et al. 2002). Carlson and Raskin 1984) of 1.8 and 13.8 km, respectively.
The water content in the melt (H2Omelt), calculated with The minimum value estimated for primary CO2 in arc
the solubility models of Moore et al. (1998) and Newman basaltic magmas is *3,000 ppm (Wallace 2005), account-
and Lowenstern (2002), did not show any good correlation ing, by itself, for a depth underestimation of about 18 km
with amphibole composition. By contrast, the composition (PCO2 [ 500 MPa).
of consistent amphiboles has been found to be related to Test of Eq. 4 with all the consistent amphiboles indi-
H2Omelt measured in references listed in the Table of cates an R2 of 0.87. Calculated rest is 54 MPa but it
Supplementary material 1 indicating that the mineral strongly decreases at P \ 450 MPa (i.e. 39 MPa), where
chemistry of amphibole is affected by the fH2O. the average relative error is 14%. At 1 GPa, the relative
A hygrometric formulation was retrieved using only the error can be as high as 33% but it decreases to 8% for the
endes because they are the most
consistent magnesiohornblendes amphiboles at the physicalchemical a stability
sa
st boundaries
heir composition continuously
abundant (i.e. 19) and their (Fig. 4d). It is worth notingg that thhat the
the high-P
th h consistent
varies from Al# 0.0 to 0.2121 (Fig. 2). In addition, uncer- amphiboles synthesized at XH2O = 1 (i.e. Foden and
at XH
tainties of the hygrometric equation at high pressures, due Green 1992; Tab ble
Tablel 1)1) arere characterized
re chhar
arac
acteri
teer zeed by a rather high
astingsites in our experimental
to the lack of magnesiohastingsites Al# (*0.21)
(*0. 0..2
0 211) and
anndd often
ofte
of teen show
sho
ho
h ow moderately
modeoderatel different cation
od
dataset, have been found to be minimized by discarding the pro
pr oppo
orrttiion
proportions ons
ns with
wiitth respect
resspect too natural volcanic
res vol amphiboles
asite pairs. [6]Al in amphibole is
H2Omelttschermakitic pargasite is ((ee.gg. Fig.
(e.g. F
Fig
igg. 2;
2; see
see
ee Supplementary
Supplementary material
Su materia 1). In addition,
ontent in the melt which,
mainly sensitive to water content whicch,
h, how-
hoow-
w- tth
hes
e e amphiboles
these ampmphi
phi
hibo
ib
booles were synthesized using
ol usin the piston cyl-
ever, is best correlated (R2 = 0.83) to an octahedral
oct
ctah
aheddra
ral alu-
alu
lu- innder
deer apparatus,
inder apparatus, the uncertainty of which whic (up to 20% i.e.
minium index ([6]Al*; Fig. 4c) by: 200 MPa; Boyd and England 1960) is much
200 m higher than
H2 Omelt 5:2156 Al 12:28
2:2
288 3 gas and hydrothermal autoclaves (i.e. 4 MPa). Experi-
4 6
6 Ca  B A mental results showing moderately low crystallinity
where 6 Al 6 Al 13:9 i T C 22
Al
 Si
Si
S
5
Tii
 Fe3e  Mg
1:7 1:2 (1235%) are plotted near the PT stability curve
A
2:7
Na
 1:56K  Fe#
1:6 : (Fig. 5b) and indicate P errors below 11% (average
The standard error of estimate (0.41 wt%) calculated for 6.5%). For lower-T consistent amphiboles of crystal-rich
25 consistent amphiboles, including tschermakitic parga- products (3550%; Fig. 5b) the maximum uncertainty is
sites, is similar to the accuracy of the by difference inferred to be up to 25%. However, the mineral chemistry
analytical method (i.e. 0.5 wt%) employed by most of the of amphibole is much closer related to the physical
experimental petrologists to measure H2O content (see chemical conditions and melt composition than the per-
Supplementary material 1). However, we suggest taking centage of crystallinity of the rock. Rocks with different
into account the maximum relative error (15%) rather than bulk composition brought to the same physicalchemical
rest, in particular for magnesiohastingsite species. conditions, in general, produce similar amphibole and
Although this formulation could be used to roughly melt composition and different crystal percentages. In
retrieve PH2O, and hence crustal depth, we strongly sug- addition, the less evolved the composition of the starting
gest calculating the conning pressure (P) with the fol- material in the experimental charge, the lower the per-
lowing barometric equation (Fig. 4d): centage of synthesized glass, rendering its analyses and
the related mass balance calculation much more difcult.
P 19:209e1:438AlT ; R2 0:99 4
This suggests that the consideration of rock crystallinity
This was retrieved from nine consistent amphiboles may generate misleading results, in particular for mixed
synthesized at the higher temperature (in the range of intermediate volcanic products. However, the dashed red
1301,000 MPa) with XH2O (i.e. H2O/(H2O ? CO2) in the curve, dividing crystal rich and poor zones in Fig. 5a, has
experimental charges) of 0.81.0 (see Supplementary been maintained because it has been shown to be useful
material 1). in evaluating the maximum P uncertainties of amphiboles
It is worth noting that melt inclusions in dacite-rhyolite plotted far and near the stability curve (i.e. 25 and 11%,
and basalt arc magmas have CO2 contents up to *450 and respectively).

123
Contrib Mineral Petrol

Fig. 5 PT (a), logfO2-T (b) and T-H2Omelt (c) diagrams for the c Tsc-Prg Pl Ol Cpx
selected volcanic amphiboles as determined by amphibole thermoba- (a) Opx Mgn Ilm
rometry. Error bars represent the expected rest (22C) and maximum 1,000
Tsc-Prg + Pl 3.3 km
logfO2 errors (0.4 log unit). a and c display representative error bars Cpx Opx
7.3
indicating the variation in accuracy with P and H2Omelt. In a the Mgn Ilm km
800
maximum relative P errors range from 11% (at the maximum thermal
stability curve; black dotted line) to 25% (at the upper limit of

P (MPa)
600 Cpx Mgn
consistent amphiboles; black dashed line). The maximum depth Ol Pl
uncertainties, calculated using a crust specic weight of 2.7 g/cm3, Mg-Hbl + Pl 3.6
Opx Mgn km
are also reported. The isopleths, showing the anhydrous SiO2 content 400 Ilm Bt SiO2 52%
(wt%) of the melt (e.g. SiO2 63%), and the PT stability limits 1.5 km
constrain the equilibrium of phases such as biotite (Bt), plagioclase SiO2 76%
200
(Pl), orthopyroxene (Opx), clinopyroxene (Cpx), magnetite (Mgn), SiO2 63%
ilmenite (Ilm) and olivine (Ol) with consistent amphiboles 0.4 km SiO 2 70%
(Mg-Hbl magnesiohornblende, Tsc-Prg tschermakitic pargasite). The 0
550 650 750 850 950 1,050 1,150
red dashed curve roughly divides consistent experimental products
T (C)
with different crystallinity (i.e. 3550 wt% at lower T and 1235 wt%
at higher T). b shows the NNO and NNO ? 2 curves (from ONeill H
St and Pownceby (1993). The maximum thermal stability (black (b) -8
dotted line) and the (lower) limit (black dashed line) of consistent +2
O
amphiboles are also reported in c where the black and blue error bars -9 NN
indicate the maximum relative error (15%) and rest (0.4 wt%),
respectively. See Fig. 2 for symbols and text for employed formu- -10
lations and further explanationss logfO 2
-11

Application and analysis of the thermobarometric -12

formulations
-13
3
O
The following sections concern
ncern the testing of the thermo- -14
14
4 NN
barometric equations and their use to constrain the physi- phhyyssi-
i- 700
700 800 900 1,000 1,100
crysttal
calchemical conditions of amphibole crystallization alli
liza
zatiioonn inin T (C)
related) volcanoes
calc-alkaline (subduction-related) volca
caan
nooes
es in in both
bothh conti-
bo con
co ntti-
Figs. 5,
nental and oceanic crusts (Figs. 5, 6).
6).
). Fo
For
or aall
llll o
off th
tthe
he volcanic
vvol
ollcaniic
(c) 1,150
amphiboles, T, DNNO, H2Ome e t and
melt
mel and P we
an w
were
erree cacalculated
alccu ullaatted with 1,050
Eqs. 14, respectively. The he aabsolute
abs
bso
bsol
bs ollutte logfO
log
ogfOfO2 were deter-
mined with the equation of of ONeill
ONe
O Neill
e l H St and Pownceby 950
T (C)

(1993) (see also Hirschmann nn et

et alal. 2008)
2008). The paragenetic
relationships (only in Fig. 5a) and the stability limits of 850

consistent amphiboles in basalt-rhyolite calc-alkaline

750
magmas are also reported (Fig. 5a, c). This can be used to
conduct a rough evaluation of the equilibrium of amphibole 650
with the other phases. Among anhydrous phases, plagio-
clase is mainly found in equilibrium with amphibole in 550
intermediate-silicic liquids. At high-PT conditions, in 2 3 4 5 6 7 8 9 10 11
H2Omelt (wt.%)
basaltic andesite-basalt melts, plagioclase seems to disap-
pear as olivine starts to crystallize. Consistent amphiboles
are never in equilibrium with quartz. Quartz and other
anhydrous phases (e.g. garnet) are generally found in conditions of instability. In addition, as shown by the red
equilibrium with inconsistent amphiboles at higher pres- dashed curve which divides consistent experimental pro-
sures (see ref. in the Table of see Supplementary material 1). ducts with different crystallinity (i.e. 3550% and 1235%;
The maximum thermal stability curve and the upper Fig. 5a), the PT shifts needed to bring amphibole beneath
limit of consistent amphiboles constrain the crystallization the stability curve decrease with the increase of melt
of amphibole in a relatively narrow PT eld (Fig. 5a). content in the magma, i.e. for crystal-poor and less viscous
Amphibole is prone to destabilization with relatively small magmas.
physicalchemical changes. For example, temperature As the equations of the curves in Fig. 5 were roughly
increases of 100C at 1,000 MPa and decompressions of estimated by the analyses of the selected experimental
100 MPa at 750C are enough to bring amphibole to PT data, they are not published in this work. However, the

123
 Contrib Mineral Petrol

Fig. 6 P (and depth)T MOUNT ST. HELENS SOUFRIRE HILLS

diagram for the amphiboles of 0 0
frequent earthquake zone shallow reservoir
Mount St. Helens (Washington), 3.9 km 3.4 km
Soufrie`re Hills (West Indies),
Redoubt (Alaska) and El 200 10.3 km 200 6.0 km
Reventador (Ecuador) 12.7 km
volcanoes as calculated by intermittent

P (MPa)

P (MPa)
400 400
amphibole thermobarometry of seismic zone
the present work. Dashed aseismic basic source
zone 600
horizontal lines mark depths 600 23.5 km
2004-2006 phenocrysts
derived from seismology. In the 1980-1986 phenocrysts
diagram of El Reventador May 18, 1980 phenocrysts 800 MOHO 30 km
volcano the seismogram symbol 800 gabbros
gabbro inclusions 30.8 km
Hornblendes Pargasites
at 10.8 km represents 1,000
hypocenter of 6th October 750 850 950 1,050 750 850 950 1,050
volcano-tectonic earthquake. T (C) T (C)
MOHO depth beneath Soufriere
Hills volcano is from
Christensen et al. (2008). 0 REDOUBT EL REVENTADOR
0
Arrows indicate in-curve 4.8 km shallow reservoir
stability path as inferred by 6.6 km magma 100
zoned amphiboles. Stability 200
9.5 km plexus 6.6 km
curves as in Fig. 5a. See text for 200
(MPa)

depth versus P calculation and 10.8 km 11.2 km

(MPa)
low-Al pphenocrysts
y 300

P (MPa
P (MP

further explanations 400 high-Al phenocrysts 13.0 km

poikilitic crystals 400 intermediate
interm
med
edi
diiate
d t zone
zzo
onnee

ba
gabbro crystals

sic
Pumice
Pumi
Pum
u ce pphenocryst
um
umi heno
eeno
noocrys
crryst
cry
0
500

s
600 23.5 km Lava-1
Lava
av
ava
ava-1
va-1
va 1 zoned
zoned
ned
n edd phenocryst
phe
ph
heenoc
h occ yst
ocr
o

ou
r
Lava-1
Lav
Lava
L av -1 phenocryst
ph
hen
he
heno
eeno
nnocry
ccrys
rys
yst

ce
deep source 600
00
0 Lava-1
Lava
L
Lav
aav
v -1
va 1 poi
ppoikilitic
oiki
oi
iikiliticc crystal
crrys
ysta
y s l
23
2 km
29.3 km Lava-2
Lav
av
va-2 phenocryst
phenocryst
800 700
000
0
750 850 9500 1,0
1,050
0550
0 750
775
5 850 950 1,050
T (
((C)
C)
C) T (C
(C)

constraints of these curves are

re reported
reporteed in in the
the
he diagrams
diiaag
diag gra
ramss of
of a the Al*-sensitive equation. For these reasons,
th
the re this baro-
whiich
user-friendly spreadsheet, which ch also
alsoo includes
al inccllu
in uddess the
thhe calcu-
callcu-
cal metric formulation is not published in this work. We
miccal
lation of the physicalchemical al conditions
conddiittioon
cond
co nss (Eqs.
((E
Eqsqs. 14) of strongly suggest using Eq. 4 with amphibole
amphib compositions
i.e
amphibole crystallization (i.e..ee. AMPTB.xls).
AM MP PT
TB.B xls).
xll It is worth having Al# B 0.21 and Mg/(Mg ? Fe F 2?) [ 0.5. The
diitio
noting that at low PT conditions ions
onnss th
tthee pattern of the maxi- maximum absolute uncertainties of Eq Eq. 4 from 90 to
mum stability curve (Fig. 55a)) iis consistent i t t with ith th th
the ther- 800 MP
MPa ((*3.430.2
3 4 30 2 kkm off crustal
t l ddepth),
th at the stability
modynamic constraint for Mg-rich cummingtonite (Evans curve (crystal-poor zone) and the upper limit of consistent
and Ghiorso 1995), which is the lowest-T and last amphi- amphiboles (crystal-rich zone), are shown in the PT dia-
bole species to crystallize in equilibrium with highly dif- gram of Fig. 5a. Equation 4 should only be applied to
ferentiated calc-alkaline melts (see Compositional calcic-amphiboles of calc-alkaline products. If applied to
relationship between amphiboles and calc-alkaline melts). amphiboles synthesized at mantle conditions (Niida and
Similar to T, DNNO and H2Omelt, we also tried to cali- Green 1999; Adam et al. 2007), Eq. 4 highly underesti-
brate a barometric formulation by correlating pressure to mates pressure (up to 2 GPa). In addition, amphibole veins
an aluminium index (Al*) on the whole set of consistent in gabbro cumulates inferred to be formed by mac mine-
experimental amphiboles. Although this formulation rals-uid interactions at a precise crustal depth (Ridol
showed slightly better R2 (0.91 vs. 0.87) and rest (42 vs. et al. 2008), account for estimated pressures (as calculated
54 MPa) than the P-AlT Eq. 4, the maximum relative error by Eq. 4) with differences of up to 73 MPa (i.e. *2.8 km
calculated at the stability curve was up to 16% (instead of of crustal depth). The application of any thermobarometric
11% of Eq. 4). The PAl* formulation, applied to equations to suspected xenocrysts (which often show pat-
magnesiohornblende and tschermakitic pargasites, pro- chy compositions, e.g. Humphreys et al. 2006), microlites
duces similar results to Eq. 4 (average differ- and any late-stage amphiboles crystallized in a uid enri-
ence 24 MPa) but tends to highly underestimate ched environment or by disequilibrium processes (e.g.
pressure (down to -280 MPa) for magnesiohastingsite quenched crystals of mac microvesiculated inclusions,
species. It is inferred that the lack of magnesiohastingsite vein-type amphiboles of gabbros), is not recommended
in our dataset of experimental amphiboles would unbalance even if they show Al# \ 0.21.

123
Contrib Mineral Petrol

Themobarometric results versus amphibole species nonbridging oxygens linked to the tetrahedra in the melt,
react with carbon dioxide and water to produce bridging
Figure 5 shows the physicalchemical conditions calcu- oxygens, CO32- and OH-. This, presumably, is also the
lated for the entire dataset of volcanic amphiboles. In the reason for the fact that magnesiohastingsite amphiboles
PT diagram (Fig. 5a), magnesiohastingsites, which pos- have not yet been synthesized as they should crystallize at
sibly crystallize from andesite-basalt liquids, are the high temperatures and CO2 concentrations.
amphiboles showing the greatest thermal stability (up to The lowest-H2Omelt (3.43.8 wt%) magnesiohastingsites
1,064 22C) consistent with the pattern of the maximum can be found in the products of different volcanoes
stability curve. Most of the amphiboles plot within the (Rindjani in Indonesia, Foden 1983; Cayambe in Ecuador,
crystal-poor zone (i.e. between the maximum stability, Samaniego et al. 2005; El Chicon in Mexico, Andrews
black dotted, and 35% crystallinity, red dashed, curves) and et al. 2008; Egmont in New Zealand; Stewart et al. 1996,)
account for pressure uncertainties of \11%, whereas some and indicate relatively low fO2 (DNNO \ ?1) and con-
tschermakitic pargasites are in the crystal-rich zone where ning P (245346 MPa). They plot in the basaltic andes-
P errors can be as high as 25%. The boundary curve iteandesite zone at the boundary between dacite and
between rhyolite and dacite melts (i.e. at SiO2 70 wt%) andesite melts (i.e. SiO2 63 wt%), next to the maximum
roughly divides the crystallization elds of magnesio- thermal stability of amphibole (T 932965C; Fig. 5).
akitic pargasite, none of which fall
hornblende and tschermakitic Using these physicalchemical conditions con nd and the melt
in the eld of basalticc melts (i.e. at SiO2 \ 52 wt%). composition (SiO2 62 wt%)) off a rrepresentative eprre
ep experiment
osition of melt inclusions found in
According to the composition of Pichavant et al. (2002),
(2002
0 )),, we
02 we ccaallcccul
ullat
calculated ate with the solubility
the magnesiohornblendee crystals of Pinatubo volcano model of Moore Moo
oooree et al.
o all (1998),
(1
19998
9 ),), PH H2O between 96 and
(anhydrous SiO2 77 wt%; %; Rutherford and Devine 1996), 122 M MPaPaa and
P annd P C 2 (i
CO
PCO (i.e.
i.ee. P fr
from
rom m Eq Eq. 4 minus PH2O) of
many magnesiohornblendes ndes plot beyond the SiO2 76% 144222
222
2
142224 224 MPaM Pa. In
Pa
Pa.
MPa. In aaddition,
dd
d dittio
ion, with the solubility model of
curve. N
Ne ewm
wman
Newman an aan nd Lowenstern
and Low
oweennstern (2002), we roughly constrained
nerally increases from hi
Oxygen fugacity generally hhigh
ighh PT
P T th
he CO
the CO2 co ccontent
ontent to be between 660 an and 1,450 ppm (results
magnesiohastingsite (down own to NNO - 0.3) 0..3)
3) to to shallow
shal
allo
allloow ob
o bbta
taiinned with both rhyolite and basal
ta
obtained basalt melts). It is worth
magnesiohornblende (up to NNO ? 2.5) 2.5
2. 5)) sppec
eciees (Fig.
species (Fi
Fig.
g 5b),
5b),, noting that these intermediate values for f andesite melts are
consistent with the values es and
anndd va
vvariation
rriiat
atiioon inferred
inf
nfererreed for
for
or calc- between the minimum CO2 contents for primary basalts
alkaline magmas (DNNO om -
O ffrom
rom
ro -1 1 ttoo? ?3, 3,, ee.g.
3 .g.
g Gill 1981; (3,000 ppm) and those measured in melt me inclusion of rhyo-
Carmichael 1991; Martell eett al.
al.
l. 19999
9 ;M
1999; Mu ntener et al. 2001;
untener lite-dacite magmas (\450 ppm) (W (Wallace 2005). This
006
Behrens and Gaillard 2006).06).
06 ). strongly suggests that the real values of H2Omelt are con-
Figure 5c shows H2OmeltT T pairsi off the th different
diff t vol-l i t t with
sistent ith Eq.
E 3 and d associated
i t d iinferred uncertainties
canic amphiboles (Eqs. 1, 3) and the stability eld of (Fig. 5c).
consistent amphiboles which is roughly constrained by the
maximum stability curve and the (lower) limit of consistent
amphibole crystallization. Magnesiohornblendes are all Test of the thermobarometric results and subvolcanic
located within the eld of consistent amphiboles. Some processes
tschermakitic pargasites fall beneath the limit of consistent
amphiboles although the estimated water contents account In order to test the amphibole thermobarometric equations,
for uncertainties of 15%. In contrast, the maximum thermal we used amphibole compositions from the products of
stability limit (dotted curve) is inconsistent with the low some calc-alkaline subduction-related volcanoes (Mt. St.
H2Omelt calculated for magnesiohastingsite and the Helens, Washington; Soufriere Hills, West Indies;
expected uncertainty for this species (i.e. 15%) (Fig. 5c). It Redoubt, Alaska; El Reventador, Ecuador), the plumbing
is inferred that large amounts of CO2 in the system, at systems of which have already been constrained by several
relatively high temperature and low H2Omelt, are able to authors through seismicity (tomography and pre-/sin-
stabilize the crystallization of OH-bearing phases, such as eruptive hypocentric depths) and other thermobarometric
amphibole because of the production of molecular OH. studies. The characteristics of the sub-volcanic systems
Indeed, at high-T conditions, the solubility of molecular (e.g. depths, reservoir/s size, and processes) were mainly
OH in the melts increases with the dissolved CO2, which is inferred by the correlation of the amphibole textures and
mainly present in the form of carbonate (e.g. Blank and thermobarometric results with the eruptive sequences.
Broker 1994). For example, King and Holloway (2002) Amphibole crystallization depths are calculated accounting
found that the contents of CO2 and H2O species in andesite for average specic weights of 2.70 and 2.89 g/cm3 for
melts (at 1,300C and 1 GPa) are strongly linked to each continental (Lucassen et al. 2001) and oceanic (Carlson and
other. These authors proposed a reaction where the Raskin 1984) crusts, with the exception of Mount St.

123
 Contrib Mineral Petrol

Helens (see following sections). In all the cases, these zone, next to the upper limit of consistent amphiboles
depths represent the distance calculated from the summit (Fig. 6). The minimum depth of 3.6 0.4 km indicated by
crater (Fig. 6). amphiboles is approximately at the base of the frequent
earthquake-zone. Euhedral amphiboles within gabbronorite
Mount St. Helens (Washington) laminated inclusions crystallized in the intermittent seismic
zone (*6.4 and 8.5 km) at temperatures of 822 and 879C,
Mount St. Helens (MSH) is one of the most studied vol- while a subeuhedral pokilitic amphibole in an olivine
canoes in the word which, after a dormancy of hornblende norite suggests an inherited crystal accumula-
*150 years, had two main eruptive cycles (i.e. 19801986 tion at conditions next to the thermal stability boundary of
and 20042006) characterized by the emission of dacite amphibole (1,010C, 419 MPa). A breakdown-free, zoned
products (e.g. Rutherford et al. 1985; Scandone and phenocryst from the 18 May 1980 dacite (Rutherford and
Malone 1985; Lees and Crosson 1989; Pallister et al. 1992, Hill 1993) indicates an in-curve PT path from the aseis-
2008; Rutherford and Hill 1993; Heliker 1995; Blundy mic zone to the intermittent-aseismic zone border
et al. 2006, 2008; Mastin et al. 2008; Moran et al. 2008; (16.2 ? 10.1 km), also suggesting that during the
Rutherford and Devine 2008; Scott et al. 2008; Thornber 150 year dormancy the intermittent zone was magma free
et al. 2008). or at near-solidus conditions. However, melt inclusions in
Moran et al. (2008) studied the shallow crustal seis- the 18 May 1980 dacite indicate pressure as low as
micity of MSH which occurred during 19802006. From 150 MPa (Blundy et al. 2006). Therefore, in order to fully
the summit crater, the MSH sub-volcanic system can be assess the applicability of our model a larger number of
arthquake-zone (*0.03.9 km,
divided into a (a) frequent earthquake-zone amphibole analyses for the 18 May 1980 800 erupted products
due to ascent of magma and nd the formation of the dacite are needed.
domes), (b) quiescent period riod (*19872000)seismic The values of oxygen ffugacity ugac
ug ween NNO - 0.4 and
gaacciitty bbetween
bet
eettwee
we
rmittent seismic zone; *3.9
active zone (hereafter intermittent NNO ? 2.0 indic cat
a edd by th
indicated he aamphiboles
the mpphiibolees are in the range
10.3 km) and (c) aseismic zone at depths C *10.3 km obtained byy Fe F eT
FeTiTi ooxide
xide
dee p paair
pairsi s (-0.7
( \ DNNO \ ?3;
(Fig. 6). Petrologic studies suggest that during eruptive Pallis
ste
ter eett al.
Pallister al. 2008).
2008
2008
20 0 ).
) ThThe highly
The hig
ighly variable P, T and fO2 are
quiescence, a shallow crustal al zone made of a well mixed cconsistent
cons
coons
nsis
iste
tent
tent
n with
withh th
wi he large
the laarrge H2Omelt range inferred to be in
lar
ected to repeated injections
dacite crystal-mush, is subjected injecttio
ions
n ofof eqqui
u li
libr
briu
equilibriumium with
ium
iu wiitth MSH amphiboles (i.e. (i.e 4.711.3 wt%).
higher-temperature magmass and assimilation
assimilattiioon of of dacitic
dacitic
ic
ic Th
Thehe aamphibole
mphibole indicating the highes highest H2Omelt (i.e.
roof material and surroundingng gabbroic
gabbro oic
ic rock.
rock
ro cckk. The
Th hee eruptions
erruppti
to on
ns 1 1.7 wt%) approaches the limi
11.3
11 limit of consistent
rigg
gggeerredd byy additional
are believed to have been triggered aad
ddiditi
tion
tion
onall repleni-
reeplleni- amphiboles (Al# 0.20, 964C, 830 MPa MPa) and shows the
shment of basic/intermediate te magma
maagm g a and/or
andd/o/or uid
/or uuiid exsolu-
exsolu- greatest depth (30.8 7.7 km). These pphysicalchemical
reki
re kind
kind
tion and expansion in this rekindling dling
ng (recharging)
(recharging) zone
(r conditions are not far from those of an ex experiment, which
nbe
beer et
b
(Pallister et al. 2008; Thornber et al.
a 2008). produced slightly inconsistent amphib amphiboles (Al# 0.25,
Figure 6 shows PT pairs forf selected
l d MSH amphiboles hib l 960 MPMPa, 841C841C, H2Omelt 10 10.3 3 wt%, % NNO NN ? 2.7; Prou-
(i.e. Rutherford and Hill 1993; Heliker 1995; Rutherford teau and Scaillet 2003). It is worth noting that Gardner
and Devine 2008; Thornber et al. 2008), calculated et al. (1995b) experimentally constrained the water content
according to Eqs. 4 and 1 of the present work, which are in the melt of historically erupted MSH dacite products to
grouped on the basis of their texture and eruption dates (i.e. be between 3.7 and 6.5 wt%.
phenocrysts in 20042006, 19801986 and 18 May 1980
deposits, and euhedral amphiboles of gabbros included in Soufriere Hills (West Indies)
the 19801986 deposits). The reported depths from the
volcano summit were estimated with the depth versus P During the 19951996 eruptive crisis, the upper-crust
formula (2b) of Blundy et al. (2008), determined for a beneath the Soufriere Hills volcano experienced two seis-
2.55 km high (from the sea level) truncate edice. mic breaks, at *3.4 and 6.0 km (Aspinal et al. 1998) that
Amphibole temperatures span an overall range of can be traced to the boundaries of an andesite reservoir, in
7921,010C, which is consistent with the FeTi oxide which the main magma mixing processes normally occur
thermometry (from 800 to [950C; Pallister et al. 2008; before the most explosive eruptions (e.g. Murphy et al.
Rutherford and Devine 2008). The occasional approach of 2000; Rutherford and Devine 2003; Buckley et al. 2006).
the magma to the solidus conditions, inferred to occur in This is consistent with the recent results of Luckett et al.
the subvolcanic system of MSH (e.g. Pallister et al. 2008; (2007) who related the hypocenters of hybrid earthquakes
Thornber et al. 2008), is conrmed by the presence in to the presence of a magma body at depth of 34 km and
19801986 products of several amphiboles with relatively the study of Christensen et al. (2008) which indicated
low crystallization temperatures that plot in the crystal-rich a seismic reector at 56 km. The onshoreoffshore

123
Contrib Mineral Petrol

SEA-CALIPSO seismic reection/refraction experiments Although only some amphibole compositions are available
of Christensen et al. (2008) also indicated that the MOHO from literature, the well-established geometry and location
beneath Soufriere Hills is at a depth of about 30 km of this upper-crust magmatic reservoir, together with
(Fig. 6). FeTi oxide pairs in both Soufriere Hills volcanic accurate compositional and textural studies of the Redoubt
and experimental products suggest that during mixing the volcano amphiboles (i.e. Swanson et al. 1994; Wolf and
temperature increases from *830 to 880C at about Eichelberger 1997), give a good opportunity to evaluate the
NNO ? 1 (Devine et al. 1998), while rare homogeneous precision of our thermobarometric equations.
orthopyroxene in the andesite and clinopyroxenes in old The low-Al phenocrysts, poikilitic amphiboles and
Soufriere Hills basalt, give QUILF temperatures in the euhedral crystals in a hornblende-pyroxene-plagioclase
range of 1,0201,080C (Murphy et al. 1998). gabbro (4.19.9 km; 807915C), correlate well with the
In short, the well mixed 19951996 products are made entire depth range of the magma plexus (Fig. 6). Low-Al
of two compositional amphibole types which have been elongate phenocrysts from the early dacite, suggest ux
roughly named as hornblende (high-Si crystals mainly regimes in the complex fracture-conduit zone between 4.1
found in the andesites) and pargasite (low-Si amphiboles in and 6.1 km. Although the early erupted andesite magma
the mac enclaves; Murphy et al. 2000; Rutherford and mostly contains pargasitic (high-Al) amphiboles, it also
Devine 2003; Buckley et al. 2006). Although these shows a group of less abundant magnesiohornblendes with
amphiboles show magnesiohornblende and tschermakitic Al2O3 in the range of 710 wt% (Wolf and Eichelberger
or simplicity, we prefer to main-
pargasite compositions, for main 1997). It is worth noting that amphiboles amphi hiib with alumina
he above authors. Figure 6 reports
tain the names given by the compositions approaching 10 wt%, wt%
%, are
aree consistent with the
erred from the amphibole ther-
the magmatic zones inferred lower part of the shallo shallowloow magma
maggm
maa chamber
ch
cha
ch (i.e. magma
mobarometry of the present esent work for these crystals. plexus). The hornblendepyroxeneplagioclase
ho
orrnbn lend nddeepy
p ro
oxe
xeneppp gabbro
Hornblende phenocrysts conrm the presence of a shallow should repr prresen
esen
es
representent ppart
aarrrt off tthe
he solidied
he soliidi
so died conduits (4.4 km),
chamber at 3.15.2 km (766847C) whereas pargasites wh her
ereeaas the
whereas th
hee twwo poikilitic
two po
poioiiki
kiliti
tiic amphiboles
amphiboles (texturally consis-
suggest a deeper basicc reservoir (i.e. 12.723.5 km, kmm, ttent
teent
ent
nt wi
with thh low
low ux
lo ux
ux regimes)
reeg
regigiiimes) possibly crystallized
cry at the base
946994C) conned to well above the depthh off the thhe of th he magma
the maggma
mag m plexus and in some magma ma pocket in the
ornblendes crystalli
MOHO. Consistently, hornblendes ize
z d at
crystallized at higher
higghe
her
her llo
owerm
werm
we rmost part or the complex fractures-conduits
lowermost fractu zone.
relative fO2 values (DNNO?1.3
NNO?1.3 to to ??2.0)
2..0)) and
2 and lower
an lowwer T
Thhe basic magma in equilibrium with high-Al
The hi phenocrysts,
H2Omelt (5.56.2 wt%) thanhan the
the deeper
th deeeep
peer pargasite
par
arga
arga
gasi
site
te crystals
te crrystals originated from depths of 23.529.3 km (1,0051,014C)
(DNNO ?0.4 to ?1.0, H2Omelt mell 8
8.410.7
.4
4 0.77 wt%).
410 wt%
wt %)). and, presumably, carried up ancient hornblendeplagio-
clase cumulates (13.0 km, 939C) to th the shallow chamber
Redoubt (Alaska) and then to the surface.
Fe
FeTi Ti oxide pairs indicating tempera temperatures of 840950C
During the 19891990 eruptive crisis, low PS wave at 12 log units above the NNO buffer (Swanson et al.
velocities and earthquake hypocenter locations in the upper 1994; Browne and Gardner 2006) are consistent with the
crust beneath Redoubt volcano showed a well-dened temperature and fO2 of the amphiboles in the magma
magmatic zone (magma plexus) at a depth between 9.5 and plexus (807914C, DNNO ?1.0 to ?1.7, H2Omelt 5.3
4.8 km from the summit crater, characterized by an 7.3 wt%). In contrast, high-Al amphiboles appeared to
uppermost section (base at *6.6 km) made of complex have crystallized at lower fO2 (DNNO ?0.2 to ?0.7) and
fractures and aborted conduits, along which, the magma higher water contents (9.410.4 wt%).
can migrate and/or stagnate (Benz et al. 1996; Fig. 6). In
this period, Redoubt volcano erupted andesitedacite El Reventador (Ecuador)
products inferred to derive from magma mixing (e.g. Nye
et al. 1994; Swanson et al. 1994). The early product is a After a dormancy of 26 years on 3 November 2002, El
dacite pumice, mainly containing low-Al2O3 (710 wt%) Reventador volcano started a new eruptive cycle (2002-
amphiboles with no or thin breakdown rims (Wolf and present) with a climatic eruption, which lasted *24 h and
Eichelberger 1997). By contrast, the subsequently erupted produced pyroclastic deposits with andesite compositions.
andesite magmas have both low-Al and high-Al (Al2O3 The emission of hybrid andesitebasaltic andesite lavas
1316 wt%) amphiboles. Swanson et al. (1994) divided the (containing abundant gabbro cumulates) from the summit
amphiboles into elongate phenocrysts (both high- and low- crater (Lava-1) and a parasitic vent (Lava-2) started on 6
Al), and poikilitic crystals. During extrusion, two types of and 21 November, respectively (Hall et al. 2004; Ridol
amphibole-bearing cognate gabbros where deposited, i.e. et al. 2008; Samaniego et al. 2008). The 2002-present
medium-grained hornblende-plagioclase and hornblende- eruptive phase was announced on 6 October by a 4.1
pyroxene-plagioclase cumulates (Swanson et al. 1994). magnitude volcano-tectonic earthquake with a hypocenter

123
 Contrib Mineral Petrol

at a depth of 10.8 2.3 km (epicenter 5 1.2 km SW compositions of the early erupted pyroclastic ow prod-
from the summit crater; Fig. 6) which was followed by ucts. The relatively thin (1.8 1.0 km) intermediate zone
nine seismic aftershocks (personal communication M. of solid rock (denoted by gabbro inclusions with diffuse
Segovia, Instituto Geosico, Escuela Politecnica Nacional, amphibole veins) between the shallow reservoir and the
Quito, Ecuador). After these seismic events, the distant basic source (Fig. 6), is consistent with the proposed model
seismic stations (1425 km) could only detect *10 h of of convective self-mixing in an homogenous (andesite)
supercial pre-eruptive activity on 3 November. Ridol shallow chamber, fuelled by a uid-driven heat transfer
et al. (2008) studied the petrology of the 2002 products from the deeper basaltic andesite chamber (Ridol et al.
and suggested that from 6 October a relatively low-T, 2008).
shallow, previously self-mixed andesite reservoir
(850952 65C; 8.210.3 km) was intruded by (and mixed Other thermobarometric comparisons among key
with) a higher temperature ([1,000C), deeper origin subduction-related volcanoes
([12.7 km) basic magma which triggered the 3 November
eruption. In this work, we integrated the amphibole com- In this section, some thermobarometric data obtained from
positions of Ridol et al. (2008) with new microprobe a representative number of calcic-amphibole compositions
analyses of the 2002 El Reventador products. Representa- ([7) for each of the volcanoes have been compared to the
tive amphibole thermobarometric results are reported in results of other geothermobarometers. The whole of the
Fig. 6. temperature ranges reported for the FeTi oxide pairs of
The roof of the shallow chamber inferred from the Mt. Pelee (840902C, DNNO ?0.4 to ?0.8; Martel et al.
breakdown-free phenocrysts of the pyroclastic deposits, is 1998), Pinatubo (808967C, DNNO ?1.7 to ?2.2; Pall-
constrained at 874C and 176 MPa (i.e. 6.6 km) whereas ister et al. 1996), San Pedro (840990C, (840
(8 40 *NNO ? 1;
osely matches the 6 October pre-
the reservoir oor, closely Costa and Chakraborty 2004) 20004
04)
4) and
and
nd Shiveluch
S (834978C,
ypocenter locations and is consistent
eruptive earthquake hypocenter DNNO ?1.5 to ?2.1; ?2.11;; Humphreys
1 Huump
mphr
phhrreys et
e al. 2006) volcanoes
ted from the large poikilitic amphi-
with the depth calculated roughly agree agr
g eeee with
with the
thhe results
res
esul
sul
ultss obtained
ob
btaa with amphibole
boles (11.2 0.3 km),, the textures of which suggest a thermomo
m obabaro
thermobarometryrome
ro m ttrry (8141,061C
(814
4
4 1,
1,061
06
0 61C and DNNO ?0.3 to ?1.9
C and
ddition, a zoned amphibole in Lava-
stationary regime. In addition, for Mt.
fo
for Mtt.. Pelele e,
Peele 1 0227C and DNNO
e, 7811,027C
781
781 1, DN ?0.8 to ?2.2 for
1 indicates an in-curveve cooling-decompression path pat
atth and
andd P naatuubo
Pi
Pinatubo, bo, 891970C
bo, 89 91 970C and DNNO ?0.9
19
19 ? to ?1.4 for San
suggests the intrusion into the shallow reservoi oir of
oi
reservoir of a batch
b tc
batch
ch Peedro,
drro,
d
Pedro, 8001936C and DNNO ?0.7
o, 801936C
8 ?0 to ?2.5 for Shiv-
of basic magma from m a depth of 1 133 0.
00.3
3 km,
km where
wheerre
wh eelluch). Temperatures and fO2 for th
eluch). the amphibole cores of
continued to grow at 9.410.4 4 kkm.
m The
m. Th
T he ba
bbasic
asic
ic phenocrysts
phhen
enoccrystts Unzen rhyodacite (781843C; DNN DNNO ?1.2 to ?1.7), the
in both Lava-1 and L ava-
av a-2,
a-
Lava-2, -2,
2, im
iimplyply tthat
pl hat the
ha
hat the
he high-T rim of which commonly show quenched qu textures, are
(9861,026C) intruding ng m aggm
magma maa ca ccame
am
mee from a deeper similar to the ranges of 790 20C and DNNO ?1.5 to
altt) rreservoir,
(basaltic andesitebasalt) eservo
es oir,
irr the depth of which ?2.0 estimated by the Venezky and an Rutherford (1999)
extends down to *23 km km.. IItt iiss worth noting that the depth from the FeTi mineral cores. Differences Differ of temperatures
uncertainty of the earthquake hypocenters which mark the and fO2 between FeTi oxides and amphibole thermometry
early intrusion of basic magma (i.e. 2.3 km), in this case, are probably due to the tendency of ilmenite and titano-
is higher than that given by the amphibole barometer magnetite to re-equilibrate during mixing (e.g. Devine
(1.0 km). et al. 1998, 2003), whereas amphibole is inclined to
The calculated temperature range covered by the 2002 breakdown or develop overgrowths, preserving the pre-
amphiboles (8741,026C) is perfectly consistent with the mixing composition. Depths of 3.75.1 km indicated by
temperatures constrained by Ridol et al. (2008) with amphibole phenocrysts for the 19901995 erupted products
several thermometric formulations (see above). DNNO of Unzen volcano, are consistent with the roof depth of the
calculated by Eq. 2 (between ?0.1 and ?1.5, 0.4 log shallow magma body (*3.9 km) suggested by pre-eruptive
unit) is slightly lower than that estimated with the seismicity (Umakoshi et al. 2001).
Mg#-formulation of Ridol et al. (2008) (i.e. between ?1.0 Amphiboleplagioclase equilibria (Holland and Blundy
and ?2.5). However, the Mg#-equation was calibrated 1994) in the extrusives of Batur, Santorini and Shiveluch
without ltering the experimental data and accounts for volcanoes yield temperatures of 9301,020 (Reubi and
uncertainties up to 1.5-log unit. Nicholls 2004), 8121,010 (Mortazavi and Sparks 2004)
H2Omelt is calculated to be between 5.5 and and 775906C (Dirksen et al. 2006), respectively. These
9.3 wt% (0.4 and 1.4 wt%, respectively). The lowest data are consistent with the thermometric results obtained
water contents are consistent with the range of with Eq. 1 (i.e. 967988C for Batur, 8581,017C for
5.15.5 1.0 wt% (Ridol et al. 2008) calculated by the Santorini, 801936C for Shiveluch). Putirka (2005) ther-
hygrometer of Putirka (2005) from the plagioclaseglass mometer, applied to the plagioclase-melt inclusion pairs in

123
Contrib Mineral Petrol

the products of Shiveluch volcano produced temperatures Suggestions and comments of the two reviewers (B. Scaillet and an
(819975C; Humphreys et al. 2006) slightly higher than anonymous referee) and of the executive editor J. Blundy were
appreciated and strongly contributed to the improvement of this
the amphibole thermometric results (see above). Finally, article.
the average H2Omelt measured in magnesiohornblende melt
inclusions of Pinatubo volcano (5.83 0.5 wt% on 15
analyses; Rutherford and Devine 1996) is practically the
same as that calculated with our hygrometric equation (i.e. References
5.49 0.4 wt%) on the reported mean composition of the
analyzed crystals (5 analyses). It is worth noting that the Adam J, Oberti R, Camara F, Green TH (2007) An electron
microprobe, LAM-ICP-MS and single-crystal X-ray structure
difference in H2Omelt estimated with the two methods is
renement study of the effect of pressure, melt-H2O concentra-
lower than the expected uncertainties. tion and fO2 on experimentally produced basaltic amphiboles.
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123
 APPENDIX 1
Additional material to the article Ridolfi F, Renzulli A, Puerini M. (2010) Stability and
chemical equilibrium of amphibole in calc-alkaline magmas: an overview, new
thermobarometric formulations and application to subduction-related volcanoes.
Contributions to Mineralogy and Petrology

Low-P experimental database

The Appendix Table reports the low-P experimental results selected from literature in this work.
Most of the selected experiments were fluid-saturated with initial XH2O (i.e. H2O/(H2O+CO2) in
the experimental charges of 0.81.0, and were conducted at controlled and/or buffered oxygen
fugacity (1<NNO<+4.8, i.e. logfO2 units from the NiNiO buffer) and fixed PT conditions
(7501075C, 100960 MPa), using different types of gas vessels (T 5C, P 4 MPa). Some
experiments (i.e. Foden and Green 1992; Alonso-Perez et al 2009; Mntener et al 2001) were
obtained using piston cylinders (T 8001120510C) at relatively high pressures (8001200 MPa)
on intermediate-basic calc-alkaline rocks.
Several authors accurately determined the composition of all the phases phasees (silicate
(
(s glasses
included) and their proportions (wt%) by mass balance calculations (i.e. Moore Moo oore
rree and
an Carmichael
1998; Martel et al 1999; Scaillet and Evans 1999; Mntener et al al 2001;
20001
01; Pichavant
Piich
P chav
h va et al 2002;
et 2003; Costa et al 2004; Holtz et al 22005;
Prouteau and Scaillet 0055;; A
00 lloonsso-
o-Pe
Alonso-PerezPerreez eett al 2009). Water
esized glasses (H2Omelt) was determined
content in the synthesized determ rm
minned
ed by
by the
thhe authors
auth
auut or
ors
rs with var various analytical
cal
aallcu
cuula
lati
la
ation
methods, solubility models and mass balance calculations tiion
ons (s
((see
see
ee rreference
effer
erennce in the AppenAppendix Table for
further details).

Appendix Table. Physical-chemical

al-chemiicaal co
cond
conditions
onnd
dit
itioons
itio n of
of the
the
th
he selected
seelectted
ed experiments on calc-alkaline starting m
materials.
Data source Starting
Sta
St
Star
ttaarting
g material
maattteri
mat eriiall Amp
A No-A P (MPa) T (C) Fluidin. XH2Oin. NNO H2Omelt H2Omelt
a
Alonso-Perez et al (2009)* aandesite
nd
nde
desit
desitsite
te 9 (9) 800 / 1,200 800 / 950 5/8 1.0 1.0 7.6 / 13.0
Costa et al (2004) da
ddacite
dac
a it
ac iite
t 14 (14) 1 195 / 211 800 / 900 10 / 12 0.8 / 1.0 1.1 / 3.0 4.5 / 6.1 -0.6 / 0.4
Foden and Green (1992)* basalt 9 (5) 5 500 / 1,000 950 / 1,120 2 / 5 1.0 ~5.0 / 10.3
b
Gardner et al (1995b) dacite 3 (3) 9 100 / 350 850 0.2 / 1.0 0.7 / 1.2 5.7 / 7.0 -0.6 / 0.2
c
Grove et al (1997) andes. - bas. andes. 2 100 / 200 880 / 1,000 1.0 0.0 3.9 / 5.1d
Grove et al (2003) basalt 1 (1) 800 1,045 1.0 0.0c 8.9*
c
Holtz et al (2005) dacite 5 (5) 100 / 300 800 / 855 10 0.8 / 1.0 0.0 3.7/ 7.6 -0.8 / 0.6
Martel et al (1999) andesite 2 (1) 1 213 / 227 876 / 1,041 10 0.8 / 1.0 0.9 / 2.6 4.0 / 6.9 -0.7 / 1.1
McCanta et al (2007) dacite 3 (3) 300 850 / 900 1.0 1.0c 7.1 / 7.3d
c
Moore and Carmichael (1998) andes. - bas. andes. 3 (3) 6 61 / 285 900 / 1,075 11 / 17 1.0 0.0 2.5 / 6.6
Mntener et al (2001)* andes. - bas. andes. 2 (2) 1,200 1,070 4/5 1.0 6.4 / 9.0
Pichavant et al (2002) basaltic andesite 5 (5) 2 395 / 427 945 / 1,016 15 0.6 / 1.0 0.4 / 1.3 4.3 / 8.2 -1.0 / 1.2
Rutherford and Devine (2003) andesite 4 (1) 1 130 / 200 825 / 880 1.0 1.0c 4.5 / 6.0d
Rutherford and Devine (2008) dacite 4 (0) 140 / 234 850 / 900 1.0 -1.0 / 1.0c 4.8 / 6.5d
Prouteau and Scaillet (2003) dacite 11 (11) 2 400 / 960 750 / 950 / 15 / 1.0 2.1 / 4.8 4.4 / 10.5
Sato et al (2005) dacite 12 (12) 185 / 300 800 / 850 4 / 10 1.0 0.0 / 4.0c 5.5 / 6.9d
Scaillet and Evans (1999) dacite 7(7) 2 209 / 389 780 / 899 10 / 15 0.6 / 1.0 0.8 / 2.6 3.1 / 8.5 -0.2 / 1.1

*obtained by piston cylinder, presumably at water-undersaturated conditions. Amp: number of selected amphibole compositions,
brackets show the number of reported glass compositions associated with amphibole. No-A: number of selected amphibole-free glass compositions.
Fluidin. : approximate wt.% of H2O-CO2 liquid or pure water loaded in the experimental charges. XH2Oin.: molar fraction of water
[H2O/(H2O+CO2)] in the charges. Oxygen fugacity expressed as log units above the Ni-NiO buffer (NNO) was controlled
by the fH2 of the fluid pressure medium (0.5 log units) with the exception of a (intrinsic approach of Kgi et al 2005), b
(ilmenite-magnetite
c
pairs in the experimental products) and (buffered with different solid sensors). H2Omelt: water content (wt.%) measured by the authors
through different analytical methods or by mass balance (~); d H2O in the melt calculated in this work by the solubility model of Moore et al (1998)
or Newman and Lownstern (2002). H2O: difference between measured and calculated water contents. See text and Appendix for further explanations.

-1-
Uncertainties in the calculated atoms per formula unit (apfu)
The accuracy of the estimated atoms per formula unit generally depends on the electron microprobe
uncertainty which increases with the absolute abundance of the element oxides (i.e. <1% at the >10
wt% level, 510% at the 1 wt% level, 1020% at the 0.21 wt% level, and 2040% at the <0.1
wt% level; e.g. Harlov et al 2006, Ridolfi et al 2006). For Fe3+-Fe2+, A(Na+K) and [4]Al cation
calculations relative errors are generally estimated to be up to 28%, 20% and 3%, respectively
(Jobstraibizer and De Pieri 1984; Blundy and Holland 1990).
To our knowledge, no formula calculation allows to quantitatively appreciate the content of Ti
in the T-site. Although it is generally considered to be irrelevant, our site allocation indicated the
presence of small amounts of [4]Ti (< 0.13 apfu) in a few volcanic magnesiohornblendes. For most
of the amphiboles, the calculated [4]Al (tetrahedral aluminium) represents virtually the whole of Al
and Ti in the tetrahedral site and is inversely correlated to Si. As a consequence, the octahedral Ti
for most of the amphiboles is equivalent to the total titanium content and, algebraically, the relative
uncertainty of [4]Al (+ [4]Ti) is expected to be similar to that of Si (<1%). For [6]Al we assumed an
average error of 10% because its content is usually 10 times lower than that of [4]Al (Appendix
Figure).

Cation variation in volcanic and experimental amphiboles

The comparison of natural and experimental amphibole m compositio
compositions ioonnss lled
eed
d sseveral
eve
evv authors (e.g.
87; Blundy and Holland 1990; Holland and Bl
Hollister et al 1987; B undy
Blundy dy 11994;
dy 99994;4 A nndd
Anderson and Smith
1995; Bachmann and Dugan 2002; Rutherford and Devine Deevivine
inee 2008)
2008)) to to identify
iden
id en
entify some Al-driven
ons (i.e. simultaneous introduction
coupled substitutions introductio ioon off ccations
aattio
ions
onnss iin
n two
two or
tw o more aamphibole sites in
equired to maintain char
the proportion required aarrggee bbalance)
charge alancce)
al e) w hhiich
which ch aarere believed to be sensitive to
temperature (i.e. edenite, Ti-tschermak,
Ti-tscherma maak,k, pplagioclase
llaagi
gioc
ocllaas
ase an
aand
nd ttiitanium substitutions), pressure (i.e. Al-
titanium
nge) and oxygen
tschermak exchange) oxyg
y en
yg en fugacity
fug
u acaciitty (f ((fO
fO2).
). TThehe edenite exchange was relate
he related to the Si + A[ ]
[4] A
 Al + (K + Na) ssubstitution
ubsttit
ub itut
utio
ioon vector
vector
ve ccttor
or inn th the solid solutions tremolite ([ ]Ca2R2+5Si8O22(OH)2) -
edenite (NaCa2R2++5Si7A AlO
Al lO222(O
((OH)
OH)H)2) and ornblende ([ ]Ca2R2+4(Al,Fe3+)Si7AlO22((OH)2) - pargasite
and hhornblende
an
2+
(NaCa2R 4AlSi6All2O2222(O (OH)
OH)
H 2)).. Using
Using this mechanism, the variation in temperatu temperature was correlated
to the phase reactions
ioonnss albite
albit
lbb te + tremolite  4quartz + edenite and hornblende + alb albite  pargasite +
4 quartz (Blundy andand
n Holland 1990). 1990) The plagioclase mechanism regards the substitution su of Si +
B
Na and [4]Al + BCa between edenite and richterite (i.e. Na(CaNa)R2+5Si8O22(OH)2), and involves
plagioclase by the variation of its albite and anorthite components (e.g. Blundy and Holland; 1990;
Holland and Blundy; 1994). Anderson and Smith (1995) proposed that variation in temperature also
causes the aluminium of granitoid-amphiboles to vary by two titanium substitutions (i.e. [6]Ti + R2+
 2[6]Al and [6]Ti + [4]Al  [6]Al + Si) whereas changes in oxygen fugacity would promote the
Fe3+  [6]Al exchange.
Bachmann and Dungan (2002) found that ~50% of the total Al variation in the amphiboles of
the Fish Canyon rocks, is due to the edenite exchange whereas another 2530% of the total
aluminium changes according to the Ti-tschermak substitution (2Si + Mn  2[4]Al + [6]Ti). These
authors inferred that the pressure-sensitive Al-tschermak substitution (Si + R2+  [4]Al + [6]Al), due
to the reaction 2quartz + 2anorthite + biotite  orthoclase + tschermakite
([ ]Ca2(R2+3AlFe3+)Si6Al2O22(OH)2), does not significantly change the aluminium content of
amphibole in the Fish Canyon extrusives. Nevertheless, all of the previous experimental studies on
granitoid-amphibole barometry suggested that, at nearly constant temperature, the AlT shows a
linear correlation with pressure (e.g. Johnson and Rutherford 1989; Thomas and Ernst 1990;
Schmidt 1992). In addition, Rutherford and Devine (2008) found that amphiboles synthesized at
200300 MPa (900C) are characterized by a higher tschermak component than those crystallized at
lower pressure (200 MPa, ~860850C).
The Appendix Figure shows the most significant variations of cations (and cation sums) in the
selected volcanic and low-P experimental amphiboles (both consistent and inconsistent).

-2-
Amphiboles show a continuous solid solution in which high-Al amphiboles gradually evolve to
magnesiohornblende compositions. In general, magnesiohastingsites display higher [4]Al and A[Na +
K] than tschermakitic pargasites (App. Fig. a, b) and are often characterized by breakdown rims
(e.g. Ridolfi et al 2008).
Appendix Figures ah show the linear regression patterns obtained from the whole dataset of
volcanic magnesiohornblendes, tschermakitic pargasites and magnesiohastingsites. According to
Bachmann and Dungan (2002), ~50% of the aluminium variation seems to be due to the edenite-
exchange because the A[Na + K] vs. [4]Al positive correlation account for a slope of 0.53 (App. Fig.
b) although the low square regression (i.e. R2 = 0.51) suggests that not all amphiboles follow this
linear relationship. The remaining Al variation appears to be due to a tschermak-type mechanism,
such as (Si + [4]Ti) + R2+  [4]Al + ([6]Al + [6]Ti). Indeed, the [6]Al + Ti vs. [4]Al correlation is
characterized by a slope of 0.49 (App. Fig. c) and the only crystals with [4]Ti (up to 0.13 apfu)
contents are the most evolved and low-[6]Al magnesiohornblendes.
On the basis of the simultaneous decrease of the PT conditions in a generic liquid line of
descent, the edenite and tschermak-type substitutions should proceed at the same time because the
([6]Al + Ti) + A(Na
Na + K) vs. [4]Al correlation shows a slope of 1.0 and a higherr R2 (i.e. 0.68; App.
Fig. d). However, r, R2+ cations are better correlated to Fe3+ (R2 = 0.64; Ap A
App.
pp. ig. f) rather than [4]Al
p. Fig.
Fig
ig.
2
(R = 0.23; App. p. Fig. e), suggesting that the P-sensitive tshermak-reaction tsherm maakk--rreeac
m action
act on isi affected by the
volatile content in n the melt. For instance, amphibole oxidation oxidati t oon
n is
is believed
beeli
liev
ved d ttoo increase
incr
cr
cr the Fe3+/Fe2+
2+ - 3+ 2-
ratio through the reaction Fe + OH  Fe + O + 0.5H 0.55H2 ((Clowe
Clow
Clow
Clowe et et aall 1988;
1988
19 88; Blundy
Bl and Holland
1990) and the protraction
otraction of this process woul would
ulld llead
uld eeaad too aamphibole
mphi
mp hiboole
le bbreakdown.
reakdown. H However, the ferric
iron correlation considerably improves upon pon the
upon
po thhe addition
aadddi
diti on of
tion of Ca
Ca in the B-site to the th bivalent cations
2+ 2
(R ) in the C-site ite (slope = 1.07 1.07,
07, R = 00.74)
07 .7
74)
4) ((App.
App. F
App
Ap ig. g). This would suggest
Fig. sugg an alternative
mechanism such as Fe3+ + BNa Na  c[Fe
[[FFe2+
2
+ Mg]
Mg] g] + B[Ca +Fe2+] which would not involve, oxidation
in the OH-site.
Appendix Figures
iggur ress a,
ures d,
a, ccd, fh show
d, fh show that most of the inconsistent amphiboles amphibole (associated with
high H2O in the m melt)
eelltt)) aare haracterized by high Al, and low R and Fe3+ contents.
re characterized
re cha
cha [6] 2+
conte This indicates
roomotes an anomalous R2+ + Fe3+  [6]Al exchange, overba
that, high H2Omeltltt ppromotes
rom overbalancing the cation
proportions in the B and C sites. This phenomenon does not appear to considerably affect the T-site
vs. A-site substitutions of the edenite-exchange because both consistent and inconsistent
amphiboles fall in the A[Na + K]-[4]Al zone of the volcanic amphiboles (App. Fig. b).
Several experimental amphiboles in Appendix Table show that, at constant PT conditions and
composition of the starting materials, an increase in XH2O and oxygen fugacity correlates to an
increase in [6]Al and Mg. Scaillet and Evans (1999) and Ridolfi et al (2008) noted that the relative
oxygen fugacity is exponentially correlated to the increase of Mg/(Mg + Fe) in the C-site. The Mg
vs. FeT (i.e. Fe3+ + Fe2+) diagram for volcanic amphiboles (such as magnesiohornblende,
magnesiohastingsite and tchermakitic pargasite) shows a well constrained negative correlation
(slope = 1.14, R2 = 0.64) (App. Fig. h). At constant PT conditions, oxygen fugacity is
proportional to water fugacity and H2Omelt (e.g. Scaillet and Evans 1999) whereas Si, [4]Al, A[Na +
K] and part of [6]Al in amphiboles are mainly fixed by the edenite and tschermak reactions. The
increase of water and relative oxygen fugacity in the melt control the composition of amphibole, the
Fe3+ and Fe2+contents of which are buffered by the fO2-sensitive substitution (Fe3+  [6]Al; e.g.
Anderson and Smith 1995) and oxidation exchange (Fe2+ + OH-  Fe3+ + O2- + 0.5H2; Clowe et al
1988; Blundy and Holland 1990). As a consequence, amphibole would be forced to acquire Mg and
OH- from the magma to maintain the charge balance and prevent oxidation and dehydration.

References
Literature material of this appendix is reported in Ridolfi et al (2010).

-3-
 1.0 1.0
(a) (b)
0.8 0.8
slope = 0.53

[Na + K] (apfu)
R2 = 0.51
Al (apfu)

0.6 0.6

0.4 0.4
[6]

1
= 0.2
Al#

A
0.2 0.2

0.0 0.0
0.5 0.9 1.3 1.7 2.1 2.5 0.5 0.9 1.3 1.7 2.1 2.5
[4]
[4]
Al (apfu) Al (apfu)
1.2 2.0
(c) (d)
1.0 1.6

Al + Ti + (Na+K)
slope = 0.49
slope = 1.0
Al + Ti (apfu)

0.8 R2 = 0.55
1.2 R2 = 0.68

A
0.6
0.8
0.4
[6]

[6]

0.4
0.2

0.0 0.0
0.5 0.9
9 1.3 1.7 2.1 2.5 0..5
0.55 0.9
0.9
9 1.3
1.3 1.7 2.1 2.5
[4] [4]
Al (apfu) Al
4.5 4.5
4..5
4 .5
(e) (f)
4.0 4.0
R (apfu)
R (apfu)

3.5 3.5
2+
2+

3.0 3.0
slope = -0.5 slope = -0.84
R2 = 0.23 R2 = 0.67
2.5 2.5
0.5 0.9 1.3 1.7 2.1 2.5 0.0 0.4 0.8 1.2 1.6 2.0
[4] 3+
Al (apfu) Fe (apfu)
6.5 4.5
(g) 4.0
(h)
6.0

3.5
5.5
R + Ca

Mg

3.0
2+

5.0
2.5

4.5 slope = -1.07

2.0 slope = -1.14
R2 = 0.74
R2 = 0.64
4.0 1.5
0.0 0.4 0.8 1.2 1.6 2.0 0.5 0.9 1.3 1.7 2.1 2.5 2.9
3+
Fe
FeT (apfu)

Appendix Figure. Cation variations in natural and experimental amphiboles. (a) reports the limit of Al# =
0.21 (broken line), whereas (b) through (h) show the slope and R2 of the correlation obtained with all
volcanic amphiboles (solid line). Uncertainty bars indicate the maximum possible error calculated at the
average value. Errors derived from sums were estimated by adding the absolute uncertainties. Average
errors of [4]Al, Mg, and FeT (i.e. Fe3+ + Fe2+) are  to the symbol sizes. Symbols as in Fig. 2 of the article.

-4-