Geological Socie y o Ame ica
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GEOLOGY
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Volume 47
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Numbe 12
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www.gsapubs.o g 1161
Manusc ip ecei ed 9 July 2019
Manusc ip accep ed 26 Augus 2019
h ps://doi.o g/10.1130/G46734.1
© 2019 The Au ho s. Gold Open Access: This pape is published unde he e ms o he CC-BY license.
CITATION: Canals, A., Van D iessche, A.E.S., Pale o, F., and Ga cía-Ruiz, J.M., 2019, The o igin o la ge gypsum c ys als in he Geode o Pulpí (Alme ía, Spain):
Geology, . 47, p. 1161–1165, h ps://doi.o g/10.1130/G46734.1
The o igin o la ge gypsum c ys als in he Geode o Pulpí
(Alme ía, Spain)
A. Canals1, A.E.S. Van D iessche2, F. Pale o3 and J.M. Ga cía-Ruiz3*
1 Depa men de Mine alogia, Pe ologia i Geologia Aplicada, Facul a de Ciències de la Te a, Uni e si a de Ba celona,
08028Ba celona, Spain
2 Uni e si é G enoble Alpes, Uni e si é Sa oie Mon Blanc, CNRS, IRD, IFSTTAR, ISTe e, 38000 G enoble, F ance
3 Labo a o io de Es udios C is alog á icos, Ins i u o Andaluz de Ciencias de la Tie a, Consejo Supe io de In es igaciones
Cien í icas–Uni e sidad de G anada, E-18100 A milla, G anada, Spain
ABSTRACT
The Geode o Pulpí (Alme ía, Spain) is an ∼11 m3 o oid ca i y, he walls o which a e co -
e ed wi h me e -sized idiomo phic and highly anspa en gypsum (CaSO4•2H2O) c ys als.
We pe o med a ho ough s udy based on ield wo k, and pe og aphic and geochemical
da a collec ion, which aimed o econs uc he geological his o y leading o he o ma ion o
his geode. The geode is hos ed in mine alized T iassic ca bona e ocks wi h a discon inuous
mine al sequence om i on-ca bona es and ba i e o celes ine and inally gypsum (mic oc ys-
alline and seleni e). Da a om luid inclusions show ha ba i e p ecipi a ed abo e 100 °C,
celes ine a ∼70 °C, and gypsum below 25 °C. All δ34S sul a e phases all be ween T iassic
and Te ia y e apo i e alues. Ba i e and gypsum, ei he mic oc ys alline o la ge seleni e
c ys als, show a iable δ
34
S and δ
18
O composi ions, whe eas celes ine and cen ime ic seleni e
gypsum ha e homogeneous alues. We p opose ha he g ow h o he la ge seleni e c ys als
in he Geode o Pulpí was he esul o a sel - eeding mechanism consis ing o iso olume ic
anhyd i e eplacemen by gypsum a a empe a u e o 20 ± 5 °C, episodically con ibu ed
by a ipening p ocess enhanced by empe a u e oscilla ions due o clima ic change.
INTRODUCTION
One o he miles ones o ecen mine alogy
has been he disco e y o la ge gypsum c ys als
in di e en loca ions a ound he plane (Ga cía-
Ruiz e al., 2008). Among hem, he mos spec-
acula is he Ca e o C ys als in Naica (Mexi-
co). Howe e , he e a e o he places wi h la ge
seleni e c ys als ha a e in e es ing because o
hei beau y, such as he ca e o c ys als in he
El Tenien e mine (Chile) and he Geode o Pulpí
(Spain), o due o hei his o ical and a chaeolog-
ical in e es , such as he mines o Lapis Specu-
la is in Segób iga (Spain; Be ná dez-Gómez and
Guisado di Mon i, 2007). Explaining he o ma-
ion o hese c ys als is a challenge because hey
a e he esul o a p ocess o c ys al g ow h unde
condi ions ex emely close o equilib ium, i.e., in
which ime plays a key ole, and he e o e labo a-
o y analogues a e ine icien . Fu he mo e, wi h
he excep ion o he na u al labo a o y o Naica,
whe e he hyd o he mal sys em is s ill ac i e and
some o he c ys al g ow h condi ions a e s ill
measu able (e.g., Ga cía-Ruiz e al., 2008; Van
D iessche e al., 2019), mos o he known lo-
ca ions whe e gian c ys als o gypsum can be
ound a e oday hyd ologically inac i e.
In his pape , we ocus on he Geode o Pulpí
(Alme ía, Spain), an ∼11 m3 o oidal geode dis-
co e ed in 1999 C.E. wi hin he abandoned
Mina Rica (“ he Rich Mine”), in sou heas Spain
(Fig.1; Pale o e al., 2001). The walls a e co -
e ed wi h la ge (∼0.5 m), blocky seleni e c ys-
als o g ea anspa ency (Fig.2). Ga cía-Guinea
e al. (2002, p. 349) p oposed ha he c ys als
o med by he in il a ion o an aqueous solu ion
ha “ a ied wi h ime om eshwa e in he ea -
lie s ages o seawa e -like in la e s ages, mos
likely as a esul o dissolu ion- ec ys alliza ion
o ea lie ma ine e apo i es.” He e, we p es-
en he esul s o de ailed geological mapping
o unde g ound mining wo ks oge he wi h a
mine alogical and geochemical s udy o Mina
Rica, wi h he aim o deciphe he geological his-
o y leading o he o ma ion o he la ge c ys als
in he geode.
GEOLOGICAL SETTING
The Mina Rica is loca ed in he eas e n pa
o he Be ic Co dille a, he wes e nmos seg-
men o he Eu opean Alpine bel , esul ing om
he ea ly Cenozoic collision be ween he A i-
can and Eu asian pla es. The mining complex
is loca ed in he eas bounda y o he Eas e n
Be ic shea zone, which is s ill ac i e and con-
ibu es o he de o ma ion o his pa o he
Ibe ian Peninsula (O uño e al., 2012, and e -
e ences he ein). Speci ically, he mine a ea is
enclosed in a no heas -sou hwes dex al shea
band o e p in ed by sinis al NNE-SSW aul s,
which a e ela ed o he Cocón-Te e os aul
zone. This shea co ido ex ends beyond he
domain o he mine owa d he no h and sou h,
and i is pa ially co e ed by slope deposi s (col-
lu ial) om he Sie a del Aguilón (Fig.1).
The complex s uc u e o he Mina Rica
can be desc ibed as a kilome e -scale len icula
bedding–ca bona e compe en body, bounded
by wo main sub e ical no heas -sou hwes
dex al aul s and su ounded by less compe-
en ba en phylli es. Bo h li hologies a e cu by
dex al eas -wes and sinis al NNE-SSW and
no hwes -sou heas aul s (Fig.1). The ca bon-
a e beds wi hin he lens a e a anged as s eeply
wes -dipping NNE-SSW and no heas -sou h-
wes isoclinal olded sequences, o ming wide
bands bounded by NNE-SSW aul s (Fig. DR1
in he GSA Da a Reposi o y1). These ac u es
*E-mail: [email p o ec ed]
1GSA Da a Reposi o y i em 2019396, supplemen a y in o ma ion, including a geological ske ch o he i s le el o he Mina Rica mine; iso ope da a; supplemen-
a y igu es; luid inclusions including me hodological de ails and da a; a able o iso opic composi ion; and U-Th age o ca bona e speleo hem, including expe imen al
de ails, is a ailable online a h p://www.geosocie y.o g/da a eposi o y/2019/, o on eques om edi ing@geosocie y.o g.
Published online 15 Oc obe 2019
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show e iden signs o agile eac i a ion, o m-
ing b eccias. Cu ing all hese s uc u es, he e
a e wo se s o open ension ac u es, o ien ed
no heas -sou hwes and NNW-SSE, which dip
60° eas and 40° wes , espec i ely.
Based upon hei mac oscopic appea ance,
we di e en ia ed he ollowing ma e ials: ba -
en phylli es, i e ca bona e uni s (mainly do-
los one), mic oc ys alline gypsum, wo b eccia
uni s, and Fe-ca bona e o e bodies (Fig. DR1).
Ba en phylli es and ca bona e ocks belong
o he T iassic o he Alpuja ide Complex de-
sc ibed by Ma in-Rojas e al. (2014), al hough
hei s a ig aphic posi ion and eal hickness
we e no possible o es ablish because band dis-
ibu ion is bounded by aul s. The mic oc ys al-
line gypsum packages, up o 5 m in hickness,
a e conco dan wi h he bedded dolos ones and
belong o he s a ig aphic pile; o he mic oc ys-
alline, less con inuous gypsums a e younge
in age, as hey eplace he o e ca bona e (Fig.
DR2A). One b eccia uni co esponds o a main-
ly dedomi iza ed homoli hic ca bona e b eccia
wi h he e ome ic clas s up o me e size. An-
o he g a i a ional collapse b eccia illing a dis-
solu ion ca i y is hos ed in one o he mic o-
gypsum packages. The li hology o he b eccia
clas s co esponds o he su ounding ocks, bo h
mine alized and nonmine alized (Fig. DR2C).
GEOLOGICAL HISTORY
The Mina Rica is a polyme allic (Pb-Zn-
Fe-Ag) ein and man o deposi hos ed in do-
lomi ized T iassic ocks. This is a widesp ead
base-me al– ype deposi in he sou heas o
he Ibe ian Peninsula ha is ela ed o olca-
nic ac i i y du ing he Miocene (A ibas and
Tosdal, 1994). In Mina Rica, he i s and main
mine aliza ion s age occu ed a e he Se a-
allian de o ma ion (Sanz de Galdeano, 1990)
and be o e 5.6 Ma. This uppe ime cons ain ,
co esponding o he sea-le el all o he Mes-
sinian c isis, is based on he limi ound by Dyja
e al. (2015) o simila Fe-Ba mine aliza ions a
Almag e a-He e ias (Fig.1). Side i e and an-
ke i e eplaced de o med ca bona e ock wi h
ba i e as a la e phase. The mul imodal dis i-
bu ion o homogeniza ion empe a u es (Th) in
ba i e luid inclusions does no allow us o de-
e mine i s g ow h empe a u e, al hough abo e
100 °C is plausible (see Fig. DR4). Ba i es ha e
δ34S (20.3‰ ± 0.6‰) and δ18O (15.5‰ ± 0.8‰)
composi ions alling inside, o close o, he Te -
ia y ma ine box (Fig.3A). In addi ion o he
T iassic pile, anhyd i e was p esen along wi h
o e mine als.
A second mine aliza ion s age is cha ac e -
ized by celes ine (S SO4) o ming ib ous ib-
bons a ound i on ca bona e o es, and cemen ing
b eccias occu ing in agile s uc u es p oduced
by he eac i a ion o ac u es ela ed o Messin-
ian comp ession desc ibed by Sanz de Galdeano
(1990). The Messinian comp ession induced
upli o he a ea, leading o oxida ion and dis-
solu ion o p e ious i on mine aliza ion. The
empe a u e dec eased, and he wa e looding
he sys em induced dedolomi iza ion and disso
-
lu ion o anhyd i e, bo h o which a e known o
elease s on ium (Al-Hashimi, 1976; Kau man
e al., 1990) and he e igge ed celes ine p e-
cipi a ion. The ew wo-phase luid inclusions
ound in celes ine p o ide T
h
da a ( om 63.0 °C
o 74.4 °C) consis en wi h a low- empe a u e
Figu e 1. (Uppe panel) Loca ion o Mina Rica on he s uc u al schema o he Be ic Co dille a
(Spain). (Lowe panel) Zoom iew showing main s uc u es o he mine a ea; b own bodies co -
espond o ca bona e lenses. Blue a ow s uc u es a e compa ible wi h he Se a allian shea
band, and ed a ows co espond o Messinian eac i a ion and he Cocón-Te e os aul zone.
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o ma ion en i onmen . Celes ine shows homo-
geneous δ34S alues (20.0‰ ± 0.2‰) close o
a Te ia y ma ine e apo i e iso opic signa u e
(Playà e al., 2000), and δ18O alues ha a y
om 15.0‰ o 17.6‰ (Fig.3A). The a ea was
loca ed a ha ime in a ma ginal Messinian ba-
sin (Sissingh, 2008).
Once he s on ium was exhaus ed, and he
empe a u e dec eased, mic oc ys alline gyp-
sum was o med. Relics o anhyd i e in he
mic oc ys alline gypsum T iassic packages
a e s ill p esen (Fig. DR2B). While he ma-
jo ou c ops o mic oc ys alline gypsum ha
we mapped ha e homogeneous δ
34
S alues
(+17.7‰ ± 0.2‰; gypsum A; Fig.3A) and
ma ch alues o T iassic e apo i es in he Alpu-
ja ide Complex (O íe al., 2014), mic oc ys-
alline gypsum om less con inuous ou c ops
shows highe and mo e sca e ed δ
34
S alues
(+19.2‰ ± 0.6‰, gypsum B; see Fig.3A). This
las gypsum could ha e p ecipi a ed om he
excess o calcium and sul a e, esul ing no only
om anhyd i e dissolu ion, bu iso olume ic
anhyd i e eplacemen by gypsum. Bo h se s o
mic oc ys alline gypsum ha e a wide ange o
δ
18
O alues (be ween +13.7‰ and +17.3‰, and
be ween +15.4‰ and 18.5‰; Fig.3A).
As a esul o he wa e low along agile
s uc u es, ela ed ei he o ea ly Pliocene up-
li (Agui e, 1998) o o Pleis ocene e ical
mo emen s o he a ea (Boccale i e al., 1987),
gypsum was p ecipi a ed as cen ime e -sized
seleni e c ys als. All luid inclusions in hese
gypsums a e monophase, and, a e lase -in-
duced apo phase ea men (K üge e al.,
2013), he measu ed Th displayed a mean alue
o 17 ± 5.0 °C (Fig.3B). The analyzed iso o-
pic composi ions (δ
34
S = +18.8‰ ± 0.3‰ and
δ
18
O = +18.0‰ ± 0.4‰) a e compa ible wi h
a dissol ed sul a e sou ce om he T iassic
e apo i e pile.
Inside he mine, sca ce i egula decime e
pods o dissemina ed sul ides (Pb-Zn-Ag-Cu-
Sn-Sb) a e p esen . Some sul ides we e o med
a e celes ine and show a a iable iso ope com-
posi ion (δ34S om −6.6‰ o +9.9‰) compa
-
ible wi h local bac e iogenic sul a e educ ion
(Eh lich e al., 2015). Mo eo e , e idence o
oxida ion o sul ides (mainly ma casi e) was
also obse ed. This could ha e acidi ied he
wa e , leading o dissolu ion o he mo e pe -
meable and eac i e li hologies (dedolos one,
homoli hic b eccias, and ba en dolos one)
and o ming ca i ies ha we e la e illed
by he e oli hic b eccias. Ba en ca bona es,
i on ca bona es, celes ine, and mic oc ys al-
line gypsum-anhyd i e we e ound as clas s in
hese b eccias (Fig. DR2C). Finally, a ca. 60 ka
(U-Th age), he pe cola ion o me eo ic wa e s
led o he o ma ion o ca bona ed speleo hems
coa ing seleni e c ys als in he shallowe le els
o he mine. Thus, he seleni e gypsum wi hin
he big geode was o med a e he celes ine
s age and be o e he ca bona e speleo hems.
The nex sec ion is a desc ip ion o some sin-
gula i ies ha help o p opose a mechanism o
hei o ma ion.
FORMATION OF THE GEODE
The e a e se e al cha ac e is ics ha indi
-
ca e he Mina Rica seleni e c ys als o med
om a calcium sul a e– ich solu ion a low su-
pe sa u a ion alues. Fi s , he small numbe o
la ge c ys als wi hin he geode and hei homo-
geneous size indica e an ul aslow nuclea ion
low, de i ed om a low supe sa u a ion alue
main ained o a long ime wi hou la ge luc-
ua ions. The longe c ys al lying in he loo
o he geode g ew unde he same condi ions
as he blocky c ys als. The {100} con ac win
indica es enhanced g ow h kine ics in he een-
ance angle o he win, demons a ing as e
g ow h along he c-axis (O álo a and Ga cía-
Ruiz, 2014). Second, he seleni e c ys als a e
anspa en and pu e, con aining small amoun s
o impu i ies o ming g ow h bands o solid in-
clusions a mic ome e scales. Fu he mo e, we
ound con inui y in g ain size, coa sening om
po phy oblas ic o seleni ic (Fig. DR3), and we
ecognized ghos s o gypsum g ain bounda ies
in he seleni ic c ys als. Se e al mechanisms can
be en isaged o he o ma ion o supe sa u a ed
solu ions o calcium sul a e, namely, he mal
di e ence, salini y a ia ion, and solubili y di -
e ences among calcium sul a e phases.
14 16 18 20
22
14
16
18
20
22
δ18
O (‰)
δ34S (‰)
Ba i e
Celes ine
Gypsum mic o A
Gypsum mic o B
Gypsum seleni e cm
Gypsum seleni e
Te ia y ma ine
e apo i es
Be ic T iassic e apo i es
A
B
Figu e 3. (A) Sul u and
oxygen iso ope alues
ob ained om sul a e
mine als (ba i e, celes ine
and gypsum) e ie ed
om Mina Rica, sou h-
eas Spain (Table DR1
[see oo no e 1]). Values
o T iassic and Te ia y
e apo i es a e om O í
e  al. (2014) and Playà
e  al. (2000), espec-
i ely. Line co esponds
o iso opic ac iona ion
be ween dissol ed sul-
a e and gypsum a 20 °C
(Van D iessche e  al.,
2016). (B) Tempe a u e o
homogeniza ion (T
h
) o
luid inclusions in seleni e
gypsum c ys als; do s
co espond o cen ime e -
size c ys als.
Gp
Figu e 2. Geode o Pulpí
(Alme ía, Spain). Lowe
inse is de ailed iew o
he wall; no ice how i is
possible o see he wall
h ough he c ys als.
G ay ma e ial is al e ed
sul ides, mainly py i e and
ma casi e. Gp—gypsum.
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The Th alues ob ained om he analysis o
seleni e luid inclusions showed ha he g ow h
empe a u e was much colde han he phase
ansi ion empe a u e o anhyd i e/gypsum
(∼58 °C) and e en colde han he empe a u e
o maximum solubili y o gypsum (∼45 °C).
This is also suppo ed by he ac ha , a oom
empe a u e, all he inclusions ound in seleni e
c ys als a e monophase. The e o e, he o ma-
ion o la ge c ys als based on a slow cooling
a e ac oss he anhyd i e/gypsum ansi ion em-
pe a u e, like he one accoun ing o he gian
c ys als o Naica, is e y unlikely (Fig.4).
Cooling om he empe a u e o maximum
solubili y o gypsum o he measu ed g ow h
empe a u e (∼20 °C) esul s in a di e ence o
concen a ion ha is oo small (0.7 mmol/kg)
o accoun o he massi e c ys alliza ion o
gypsum wi hou a con inuous ex e nal supply
o calcium sul a e. Conside ing he a ia ion in
he solubili y o calcium sul a e wi h NaCl, he
mixing o eshwa e and ma ine wa e , e en
i en iched in calcium and magnesium sul a e,
does no lead o he o ma ion o a supe sa u-
a ed solu ion wi h espec o gypsum. Also, he
signi ican a ia ions in he iso ope composi ion
o seleni e and mic oc ys alline gypsum sugges
a local sul a e sou ce a he han an ex e nal one
(Fig.3A). The e o e, i seems una oidable ha
he c ys als o he geode o med unde a a he
cons an empe a u e a ound 20°C. This could
occu by he mechanism known as Os wald
ipening (Kahlwei , 1975; Che no , 1984), a
solu ion-media ed ec ys alliza ion unde con-
s an empe a u e by which he smalle gypsum
c ys alli es in he mine will dissol e o eed
he la ge ones. Howe e , Os wald ipening o
sligh ly soluble mine als like gypsum will yield,
in he bes o he cases, jus a coa sening o he
mic oc ys alline acies (Voo hees, 1985).
The e iciency o Os wald ipening o ac-
coun o he o ma ion o la ge c ys als is much
enhanced when he smalle solid pa icles in he
sys em a e ei he amo phous o belong o an
uns able polymo phic o hyd a e phase (S ee el
and Van Cappellen, 1990). This is he case a
Mina Rica, because he p esence o anhyd i e
igge ed a sel - eeding p ocess, d i en by he
excess calcium and sul a e esul ing om he
iso olume ic anhyd i e eplacemen by gyp-
sum, and subsequen and concomi an gypsum
g ow h. This mechanism wo ks a a cons an
empe a u e wi hin he ange o empe a u e o
he gypsum s abili y ield and, along wi h ip-
ening, would accoun o he slow g ow h a e
leading o la ge c ys als o high op ical qual-
i y. In addi ion, he na u al g ow h condi ions
a Pulpí p o ided ano he well-known mecha-
nism ha enhances ipening, namely, he exis-
ence o empe a u e oscilla ions (Mills e al.,
2011), which, acco ding o ou measu emen s,
would be a ound 20 ± 5 °C. These oscilla ions
would be a e lec ion o he luc ua ions o a mo-
sphe ic empe a u e a a plane a y scale (Hansen
e al., 2013) and would occu p o ided ha he
g ow h en i onmen emained unde wa e and
was loca ed ela i ely close o he su ace. The
low- empe a u e alues o he luid inclusions
indica e ha , a he ime o he o ma ion o
he seleni e c ys als, he Mina Rica was loca ed
ela i ely close o he su ace, and he e o e i s
empe a u e was a ec ed by clima e changes.
ACKNOWLEDGMENTS
Financial suppo was p o ided by P ojec s CGL2010–
16882 and CGL2010–12099-E (Minis e io de
Educación y Ciencia [MEC]) and CGL2016–78971-P
(MEC). We acknowledge logis ic suppo om Magí
Baselga, he Town Council o Pulpi, and he Jun a de
Andalucia (P oyec o de Excelencia RNM 5384). We
a e g a e ul o Y es K üge o his assis ance du ing
monophase inclusion measu emen s. Van D iessche
acknowledges unding om he F ench na ional p o-
g am EC2CO–Biohe ec , SULFCYCLE.
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