2021
45
Mónica Blasco Cas ellón
Geochemical cha ac e isa ion o
low empe a u e ca bona e
geo he mal sys ems. P oblema ic
and applica ions
Depa amen o
Di ec o /es
Ciencias de la Tie a
Gimeno Se ano, Ma ía José
© Uni e sidad de Za agoza
Se icio de Publicaciones
ISSN 2254-7606
Mónica Blasco Cas ellón
GEOCHEMICAL CHARACTERISATION OF LOW
TEMPERATURE CARBONATE GEOTHERMAL
SYSTEMS. PROBLEMATIC AND APPLICATIONS
Di ec o /es
Ciencias de la Tie a
Gimeno Se ano, Ma ía José
Tesis Doc o al
Au o
2019
Reposi o io de la Uni e sidad de Za agoza – Zaguan h p://zaguan.uniza .es
UNIVERSIDAD DE ZARAGOZA
Geochemical cha ac e isa ion
o low empe a u e ca bona e
geo he mal sys ems.
P oblema ic and applica ions
Mónica Blasco
PhD Thesis
2019
Ea h Sciences Depa men
2019
Geochemical cha ac e isa ion o low
empe a u e ca bona e geo he mal sys ems.
P oblema ic and applica ions.
Tesis doc o al p esen ada po
MÓNICA BLASCO CASTELLÓN
cumpliendo odos los equisi os pa a ob ene el í ulo
de Doc o po la Uni e sidad de Za agoza
Di ec o a de esis:
D a. Ma ía José Gimeno Se ano
P o eso Ti ula de la Uni e sidad de Za agoza
Za agoza, 2019
Ag adecimien os
La ayuda, dedicación y apoyo de un g an núme o de pe sonas ha conseguido que es a esis
doc o al llegue a buen in y es oy sumamen e ag adecida a odas ellas.
A mi di ec o a, Ma ía José Gimeno Se ano, po u apoyo cons an e, ayuda desin e esada an o
en emas académicos como pe sonales a lo la go de muchos años y no solo du an e es os
úl imos cua o y la in inidad de ho as dedicadas a es e es udio. A Luis Auqué, po que has
guiado odo es e abajo y no cabe ninguna duda de que sin i no hubiese sido posible, po que
me has hecho ap ende odo lo que sé, po u me iculosidad e implicación y po las ho as de
con e saciones sob e cualquie ema.
A Quique Oli e , po u ayuda en los análisis y p epa ación de las mues as. A Juan Mandado,
po u paciencia en el mic oscopio y la ayuda con odas las o os. A Ma ía Pila As a y Pa icia
Ace o po ues as opiniones y consejos. A Ja ie Gómez, po es a ahí y echa una mano
siemp e que podías.
A los abajado es de los Balnea ios en que se oma on las mues as, po su disposición y ayuda.
Igualmen e, a las pe sonas anónimas que nos o ecían su ayuda.
A Niklaus Wabe y Ch is oph Wanne , po ecibi me en la Uni e sidad de Be na du an e mi
es ancia en Suiza.
G acias ambién a Ch is oph Wanne , de la Uni e sidad de Be na, y a Ca mine Apolla o, de la
Uni e sidad de Calab ia, que han ac uado como e iso es ex e nos de es a esis.
Quie o ambién ex ende mi ag adecimien o ue a del ámbi o académico ya que el apoyo y
comp ensión de mi amilia, pa eja y amigos ha sido decisi o pa a que es a esis salie a adelan e.
G acias po es a ahí, apoya me, aconseja me y anima me en los malos a os. G acias
especialmen e a mis pad es que siemp e han con iado en mí, me han apoyado, espaldado y han
hecho odo lo posible pa a que yo llegue donde me p oponga. También a Manuel Ma ínez, que
es quien ha es ado más ce ca de mí en odo momen o y ha sido mi apoyo incondicional y me
daba un poqui o más de ue zas cada día. G acias ambién po u ayuda con las igu as de odos
los abajos y con el diseño y maque ación de es a esis.
Finalmen e, ag adezco ambién a odas las pe sonas que de una o ma u o a han in e enido en
el desa ollo de es a esis y han hecho es e camino un poqui o más ácil.
Gene alo e iewo he hesisdisse a ion
This hesis disse a ion is s uc u ed in he ollowing six chap e s.
Chap e 1 consis s o a gene al in oduc ion o he s udied opic, he cha ac e isa ion o low
empe a u e geo he mal sys ems hos ed in ca bona e ocks, explaining he p oblems and
di icul ies in his ype o s udies and hei impo ance. I also includes a s a emen o he main
objec i es o he esea ch and he explana ion o he main con ibu ions o he PhD candida e in
he di e en s ages o he in es iga ion. In Chap e 2 he loca ion and he main geological and
hyd ogeological ea u es o he s udied a eas a e p esen ed. Chap e 3 con ains a de ailed
explana ion o he me hodology ollowed o de elop his hesis ( his chap e is comple ed wi h a
con e ence pape p esen ed as supplemen a y ma e ial, S.1, whe e he possible unce ain ies
when wo king wi h geochemical codes and di e en da abases a e e alua ed).
Chap e 4 p esen s he Resul s o he s udy and i is he main body o his hesis since i p esen s
he i e pape s ha o m his disse a ion. Al hough hese pape s a e independen and each one
p esen s a di e en s udy, all o hem deal wi h di e en low empe a u e and ca bona e
geo he mal sys ems wi h he objec i e o 1) e alua ing he bes me hodologies o hei
cha ac e isa ion, 2) iden i ying he main seconda y p ocesses and he e olu ion o he wa e s
and 3) discussing he in e es o his ype o sys ems. The las pape , unde e iew a he
momen , shows a mo e speci ic s udy on he a agoni e p ecipi a es associa ed o one o he
he mal sys ems. B oadly, hese pape s p esen he ollowing s udies:
Pape 1:
This pape p esen s he cha ac e isa ion o he low empe a u e geo he mal sys em o
Tie mas, hos ed in ca bona es om he Paleocene-Eocene. The ese oi empe a u e has
been s ablished by he combina ion o classical chemical geo he mome e s (SiO2-qua z, Na-
K, K-Mg and Na-K-Ca), speci ic geo he mome e s o ca bona e sys ems (Ca-Mg), iso opic
geo he mome e s and geo he mome ical modelling. Addi ionally, he in luence ha mobile
elemen s (i.e. no con olled by mine al equilib ium) ha e in he chemical cha ac e is ics and
mine al equilib ia in he ese oi has also been e alua ed. Since a a ou able ec onic
s uc u e o CO2 s o age has been ecognised in he Paleocene-Eocene ca bona es o his
a ea, he chemical cha ac e isa ion o hese wa e s is going o be use ul o be e unde s and
he po en ial geochemical p ocesses in a CO2 deep geological s o age.
Pape 2:
The geochemical and geo he mome ical cha ac e isa ion o he low empe a u e geo he mal
sys em o A nedillo, hos ed in Ju assic ca bona e ocks, is p esen ed in his. The ese oi
empe a u e has been es ima ed, as in pape 1, by he combina ion o chemical
geo he mome e s (classical and speci ic), iso opic geo he mome e s and geo he mome ical
modelling. One o he mos ele an esul s om his wo k was he calcula ion o he o de
deg ee o he dolomi e p esen in his aqui e . Since dolomi e is a mine al phase wi h
impo an he modynamic unce ain ies associa ed wi h i s o de deg ee, his calcula ion has
been e y use ul in his and in u he s udies (see below).
Pape 3:
In his pape he s udy ini ia ed in pape 2 wi h he A nedillo he mal sys em is comple ed
wi h he s udy o he Fi e o geo he mal wa e s since bo h sys ems belong o he same aqui e
a deph. Howe e , al hough he wa e s eme ging in bo h si es a e o m he same ese oi
some di e ences ega ding he composi ion, mine al equilib ia and empe a u es a deph a e
e iden . The e o e, a e he geo he mome ical cha ac e isa ion o he Fi e o wa e s
(chemical and iso opic geo he mome e s and geo he mome ical modelling) he s udy has
ocused on he iden i ica ion and e alua ion o he main p ocesses esponsible o hese
di e ences and o he geochemical e olu ion o he wa e s in he aqui e . The main
p ocesses iden i ied a e he albi isa ion and dedolomi isa ion p ocesses igge ed by hali e
dissolu ion. This s udy was pe o med by using di ec and in e se modelling me hodologies
and he esul s ha e been gene alised o be applicable o o he ypes o en i onmen s.
Pape 4:
The Alhama – Ja aba geo he mal sys em hos ed in ca bona es om Ju assic and Uppe
C e aceous is cha ac e ised in his pape . This is also a low empe a u e sys em, bu he
ese oi empe a u e is e en lowe han in he p e ious he mal sys ems, which inc eases
he complica ions in he empe a u e es ima ion due o he lack o some mine al equilib ia
(p esen in he p e ious cases), and/o o he he modynamic unce ain ies a ec ing some o
he mos p obable mine al equilib ia in low empe a u e condi ions (ca bona es and clays).
The ese oi cha ac e isa ion o hese wa e s is addi ionally complica ed because hey a e
a ec ed by seconda y p ocesses such CO2 loss and mixing (in he case o Ja aba).
Ne e heless, chemical geo he mome e s and geo he mome ical modelling ha e been used
ying o deal wi h he abo e men ioned p oblems and we inally s a e a p oposal o a
sui able p ocedu e o be used in hese cases.
Pape 5:
The s udy o he Fi e o a e ines is ini ia ed in his pape . These p ecipi a es a e cons i u ed
mainly by a agoni e and, he e o e, p o ide an excellen oppo uni y o s udy his calcium
ca bona e mine alogical phase, conside ably less s udied han calci e. Mo eo e , o he
a e ines wi h high calci e p opo ions a e also p ecipi a ed om he same wa e and can be
used o compa ison and esul discussion. In his pape wo common conce ns in he s udy
o calcium ca bona e deposi s a e add essed. Fi s , he possible ac o s con olling he
p ecipi a ion o calci e and/o a agoni e a e discussed and e alua ed in his sys em. Then, he
s able iso ope signa u e is e alua ed since s able iso ope signa u es in a e ines and u as
a e used in paleoclima ic and paleoen i onmen al econs uc ions and he s udy o an ac i e
p ecipi a ing sys em a p esen can help o shed ligh on he in e p e a ion and unde s anding
o pas deposi s. Se e al δ18O ac iona ion equa ions a e applied and he esul s sugges an
appa en equilib ium si ua ion. Howe e , his si ua ion does no seem cohe en wi h he high
CO2 loss deduced om he geochemis y o wa e s and he δ13C alues measu ed in he
a e ines and he wa e s. This in e es ing esul has also been in es iga ed and discussed.
In Chap e 5 a join discussion is p esen ed in eg a ing he esul s o he a ious pape s and
highligh ing he mos impo an indings. Mo eo e in his chap e some u u e esea ch lines o
comple e his s udy a e p oposed and, inally he main conclusions a e shown. Finally, he
bibliog aphic e e ences o he disse a ion a e lis ed.
Abs ac
The s udy and cha ac e isa ion o high empe a u e geo he mal sys ems has ocused he in e es
o esea che s since long ago gi en hei high possibili ies o exploi a ion (ene gy p oduc ion).
Howe e , he in e es on low empe a u e sys ems has become ele an only ecen ly. One o he
easons is ha he echnological ad ances allow nowadays using he hea o hese sys ems o
di e en uses. The o he is ha hey p esen simila cha ac e is ics o he ones expec ed in CO2
geological s o ages. The e o e, he me hodology used o hei cha ac e isa ion is di ec ly
applicable in he s udies o cha ac e isa ion o u u e s o age si es and hey can be used as
analogues o he deduc ion and e alua ion o possible p ocesses aking place in hese s o ages.
The e a e se e al issues wi h he low empe a u e geo he mal sys ems ha make hei s udy
mo e complica ed han hose wi h high empe a u e. The i s p oblem is ha wa e s a dep h do
no always a ain he mine al equilib ia on which he geo he mome ical echniques a e based,
because a low empe a u e he eac ions a e slowe . The di icul ies inc ease in he case o
ca bona e aqui e s wi h a mo e es ic ed numbe o mine al phases ha make unsui able he use
o he adi ional geo he mome ical echniques (ca ion geo he mome e s o albi e-K- eldspa
equilib ium).
In his hesis a ious low empe a u e geo he mal sys ems hos ed in ca bona e ocks ha e been
cha ac e ised. In some o hese sys ems he p esence o de i al ma e ial in he aqui e has
allowed he success ul applica ion o he adi ional echniques. Howe e , in o he cases, he
geo he mome ical cha ac e isa ion had o ely mainly on ca bona es (calci e and dolomi e) and
aluminosilica e phases, which in some cases p esen impo an he modynamic unce ain ies
(o de deg ee in dolomi e, and c ys allini y and composi ion in he case o he aluminosilica es).
Conside ing all hese di icul ies, one o he main esul s o he hesis is he p oposal o a
me hodology o deal wi h hem by e alua ing he o de deg ee o he dolomi e p esen in he
aqui e and pe o ming sensi i i y analyses o he he modynamic da a o aluminosilica es.
Ano he impo an issue ea ed in his hesis is he e alua ion o he in luence o hali e
dissolu ion in he aqui e . The s udy pe o med in pape 3 has demons a ed ha his p ocess is a
decisi e ac o in he con ol o he chemical e olu ion o he wa e s igge ing he anhyd i e
dissolu ion and he dedolomi isa ion and albi isa ion p ocesses. Due o his in e es ing inding,
an impo an pa o he s udy ocused on he analyses o hese p ocesses unde di e en
condi ions by means o geochemical simula ions.
The in e es o he s udy o hese special geo he mal sys ems is no limi ed o he wa e
cha ac e isa ion. Ano he e y in e es ing subjec is he s udy and cha ac e isa ion o he
ca bona e p ecipi a es, a e ines, which gene a e om he wa e s. The iso opic in o ma ion o
hese deposi s is used in paleoclima ic and paleon i onmen al econs uc ions and, he e o e, he
s udy o ecen a e ines can p o ide e y aluable in o ma ion. Two samples o a e ines
p ecipi a ed in wo pipes in he Fi e o spa ha e been s udied in his hesis. They p ecipi a ed
om e y simila wa e s bu one is almos pu e a agoni e and he o he has highe calci e
p opo ions. This ac has p o ided an excellen oppo uni y o s udy and compa e bo h mine al
phases wi h espec o hei p ecipi a ion and o he iso opic ac iona ion. The use o se e al
a agoni e s able iso ope ac iona ion equa ions sugges ha he p ecipi a ion o he Fi e o
a e ines ook place close o an appa en equilib ium si ua ion despi e he high CO2 ou gassing
iden i ied, which has also been discussed in de ail. Finally, using se e al na u al a agoni es, a
δ18O ac iona ion equa ion has been p oposed which is e y close o one o he mos used
expe imen al equa ions o a agoni es.
Resumen
El es udio y ca ac e ización de sis emas geo e males de al a empe a u a ha a aído siemp e el
in e és de los in es igado es debido a sus g andes posibilidades de ap o echamien o
(p oducción de ene gía). Sin emba go, el in e és en sis emas de baja empe a u a ha sido meno
y sólo ecien emen e ha comenzado a c ece . La azón de es e c ecien e in e és es que los
a ances ecnológicos pe mi en ac ualmen e el uso del calo con enido en es os sis emas pa a
di e en es usos, algo que en el pasado e a in iable. O o mo i o de in e és es que es os sis emas
p esen an ca ac e ís icas simila es a las espe ables en los almacenamien os geológicos de CO2.
Es o hace que la me odología u ilizada pa a su ca ac e ización pueda se di ec amen e aplicable
en los es udios p e ios de los u u os almacenamien os y, además, hace que los p opios sis emas
geo e males puedan se u ilizados como análogos pa a la deducción y e aluación de los
p ocesos que pod ían ene luga en dichos almacenes.
El p incipal p oblema en el es udio de los sis emas de baja empe a u a es que las aguas en
p o undidad no siemp e alcanzan el equilib io mine al en el que se basan las di e en es écnicas
geo e momé icas, ya que a bajas empe a u as las eacciones son más len as. En el caso de
a a se de acuí e os ca bona os las di icul ades son incluso mayo es, ya que las ases
mine alógicas p esen es en el ese o io son más es ingidas que en o o ipo de acuí e os y las
écnicas geo e momé icas adicionales (geo e móme os ca iónicos o el equilib io albi a-
eldespa o po ásico) no siemp e son aplicables. En algunos de los sis emas ca bona ados
es udiados hay ambién algo de ma e ial de í ico en el acuí e o y se han podido usa las écnicas
adicionales con buenos esul ados. Sin emba go, en o os casos, la ca ac e ización
geo e momé ica ha enido que basa se en los ca bon os (calci a y dolomi a) y en algunas ases
aluminosilica adas con los consiguien es p oblemas de ince idumb es e modinámicas (el g ado
de o den en la dolomi a, o la c is alinidad y composición pa a los aluminosilica os).
En es a esis, a a és del es udio de a ios sis emas geo e males de baja empe a u a alojados en
ocas ca bona adas, se p opone una me odología pa a hace en e a es os p oblemas y
limi aciones. Es a consis e en ealiza una e aluación del g ado de o den de la dolomi a p esen e
en el acuí e o y un análisis de sensibilidad de los da os e modinámicos de aluminosilica os.
O o ema de g an in e és es udiado en la esis es la e aluación de la impo ancia de la
disolución de hali a en el acuí e o. Es e es udio ha demos ado que es un ac o muy impo an e
en el con ol de la e olución química de las aguas pues o que desencadena la disolución de
elec ici y p oduc ion while in low- and e y-low empe a u e sys ems he hea is di ec ly
used, o example, in hea ing and e ige a ion sys ems, ag icul u e applica ions (e.g.
g eenhouses, aquacul u e (e.g. ish a ms), indus ial p ocesses o balneo he apy (Sánchez
e al., 2011).
Hos ock. B oadly, geo he mal sys ems can be di ided in o olcanic (including olcanic
and plu onic ocks), clas ic-sedimen a y and ca bona e-sedimen a y (and hei
me amo phosed ocks). The impo ance o aking in o accoun his classi ica ion is ha he
ocks in e ac ing wi h he luid will de e mine i s geochemis y.
Hea sou ce. Unde his ca ego y geo he mal sys ems a e di ided in olcanogenic and non-
olcanogenic. Volcanogenic sys ems a e hose whe e he hea sou ce is magma and hey
a e always high- empe a u e sys ems. In non- olcanogenic sys ems he luid is hea ed by
deep ci cula ion as a esul o he egional geo he mal g adien o due o ec onic ac i i y
and hey can esul in bo h, high and low empe a u e sys ems.
The sys ems s udied in his hesis can be classi ied as non- olcanogenic, liquid-domina ed, low-
empe a u e sys ems in dynamic equilib ium and hos ed in ca bona e sedimen a y ocks.
The e a e many s udies ocused on sys ems o high- o medium- empe a u e because hey can
be easily used o ene gy p oduc ion. The numbe o s udies abou low- empe a u e sys ems is
much less, al hough hey a e inc easing because he echnological ad ances p o ide new
echniques which allow using hese low empe a u e esou ces on a la ge scale (Sánchez e al.,
2011). Chemical cha ac e isa ion o he mal wa e s along wi h he iden i ica ion o he main
wa e - ock in e ac ion p ocess esponsible o ha and he ese oi empe a u e es ima ion,
should be he i s s eps when e alua ing he geo he mal po en ial o a geo he mal a ea
(D’Amo e and A nó sson, 2000) and his ype o cha ac e isa ion is he one pu sued in his
esea ch.
The e is a second eason why he in e es on his ype o sys ems is inc easing and i is ela ed o
he social conce n abou he global wa ming and he need o educing he a mosphe ic ca bon
dioxide emissions (e.g. Eche a ia and Xiu, 2014; Me z e al., 2005). One o he ways o
educing he ca bon dioxide emi ed o he a mosphe e is i s cap u e in he emission’s plan s and
i s s o age in oceans, in geological o ma ions, in ino ganic ca bona es o h ough indus ial
ixa ion (e.g. Me z e al., 2005). F om all hese s o age op ions, p obably he mos iable is he
geological s o age in deep o ma ions, speci ically in he deep saline aqui e s (e.g. Bachu, 2000;
Choi e al., 2014; Elío e al., 2015; He zog e al., 1997). In his con ex , low- empe a u e
geo he mal sys ems p o ide an excellen analogy o he s o age si es since hey ha e many
simila i ies in e ms o empe a u e, salini y, dep h and geological con ex . The cha ac e isa ion
2
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
o hese geo he mal sys ems can be used o ob ain a be e unde s anding o he possible
p ocesses expec ed in his ype o s o ages as i has been done by di e en au ho s such as
Auqué e al. (2009), Choi e al. (2012), Flaa hen e al. (2009) Gal e al. (2012), Güleç and Hil on
(2016) o Lu e al. (2011).
The s udied sys ems a e hos ed in ca bona e o ma ions in con ac wi h e apo i es and in some
cases wi h some dispe se de i al ma e ial. These hos ing ocks, in con as wi h he olcanic o
clas ic cases, ha e some pa icula i ies ha make hei s udy e y in e es ing and necessa y. The
in e ac ion o he wa e s wi h hose ocks will de e mine he geochemis y o he wa e s and he
mine al equilib ia in he deep ese oi which, in u n, will condi ion he applicabili y o he
geo he mome ical echniques, one o he mos ele an aspec s in he cha ac e isa ion o a
he mal a ea.
When he hos ing ocks a e olcanic o clas ic he mine al assemblage a dep h is qui e la ge and
hei he modynamic da a a e well known (e.g. albi e o K- eldspa ). Howe e , in ca bona e
sys ems he mine al se is limi ed o ca bona es and some aluminosilica es, some o which a e
a ec ed by he modynamic unce ain ies ha make he geo he mome ical cha ac e isa ion o
he sys em mo e di icul . Tha is why i becomes necessa y o add ess his issue and o iden i y
he bes app oach o he p oblem.
Finally, he g owing in e es on hese he mal sys ems has no only o do wi h he wa e s bu
also wi h he ca bona e solids ( a e ines) ha can p ecipi a e in he sp ings. Apa om
helping o ully cha ac e ise he geo he mal sys em, he s udy o hese solids and hei s able
iso ope signa u es, can be e y use ul o be e unde s and he iso opic ac iona ion in ancien
a e ines imp o ing hei use o paleoclima ic and paleoen i onmen al econs uc ions (e.g.
And ews, 2006; Capezzuoli e al., 2014; Fo d and Pedley, 1996; Fouke e al., 2000; Ga ne e
al., 2004; Jones and Renau , 2010; Kele e al., 2011, 2008; Lachnie , 2015; Liu e al., 2006,
2010; Osáca e al., 2016, 2013; Pedley, 2009; Pen ecos , 2005).
1.1 Objec i eso he esea ch
The gene al objec i e o his esea ch is o inc ease he knowledge on low empe a u e
geo he mal sys ems associa ed o ca bona e ocks. In his gene al con ex he ollowing speci ic
objec i es a e add essed:
To ob ain a comple e geochemical and geo he mome ical cha ac e isa ion o he low
empe a u e and ca bona e geo he mal sys ems o Tie mas, A nedillo-Fi e o and
Alhama-Ja aba.
3
1. In oduc ion
To es and e alua e he applicabili y, in low empe a u e sys ems hos ed in ca bona e
ocks, o di e en geo he mome ical echniques p o en o be e y use ul in o he
sys ems (i.e. high empe a u e wi h g ani ic o basal ic ocks).
To es ablish he mos sui able app oaches o he a ious p oblems and limi a ions ound
and p opose an adequa e me hodology o hese sys ems.
To e alua e he possible applica ions o he ob ained esul s o he s udy and
unde s anding o CO2 s o age si es.
A inal objec i e is he cha ac e isa ion o he a e ines deposi ed om he Fi e o he mal
wa e s. The wo main issues a e: 1) o iden i y he main mine al phases p esen s in he
a e ines (calci e and/o a agoni e) and discuss he main ac o s esponsible o i ; and 2) o
e alua e he s able iso ope signa u e o he a e ines and i s ac iona ion o help wi h he
in e p e a ion o ancien a e ines when hey a e used in paleoclima ic and paleoen i onmen al
econs uc ions.
1.2 PhDcandida econ ibu ions
Al hough he publica ion o he di e en pape s ha con o m his hesis disse a ion would no
ha e been possible wi hou he collabo a ion o he co-au ho s, my con ibu ion o hem is
p esen in e e y single s ep gi en.
The main asks du ing he de elopmen o his doc o al hesis can be summa ised as ollows:
Bibliog aphic e ision o he li e a u e ela ed o ca bona e sys ems o low empe a u e
and ca bona e p ecipi a es, among o he issues o in e es s.
Planning and pe o mance o he wa e sampling campaigns ca ied ou and he
p epa a ion o he samples o analyses.
S udy o he solid samples wi h ield emission scanning elec on mic oscope (FESEM)
and he pe og aphic mic oscope wi h he help and guidance o he co-au ho s.
P epa a ion o he solid samples o he X-Ray Di ac ion analyses.
T ea men o he analy ical da a and, along wi h he co-au ho s, in e p e a ion o he
esul s.
W i ing o he manusc ip s wi h he guidance and assis ance o he co-au ho s.
Syn hesis o he esul s and conclusions o p epa ing his hesis disse a ion wi h he
guidance and assis ance o my hesis supe iso .
Apa om his, I ha e p epa ed and p esen ed many o he ob ained esul s in di e en
In e na ional and Na ional Cong esses.
4
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
2. STUDY AREAS
Al hough he pape s p esen ed in he Resul s sec ion con ain a comple e desc ip ion o he
geology o he a eas a ound he selec ed geo he mal sys ems, a summa y o he geological and
hyd ogeological in o ma ion is included in his sec ion.
The h ee s udied sys ems ha e some impo an cha ac e is ics in common ha ha e been he
eason o selec hem o his s udy: hey ha e low empe a u e wa e s and hei aqui e s a e,
mainly, in ca bona e ocks. All o hem a e loca ed in Spain, he Tie mas and he Alhama-Ja aba
sys ems in he A agon egion, and he A nedillo-Fi e o sys em be ween Na a a and La Rioja
egions, as shown in Figu e 1.
Figu e 1. Spain map showing he gene al loca ion o he h ee s udied geo he mal sys ems: Tie mas and
Alhama-Ja aba sys ems in A agon Region, and he Fi e o-A nedillo sys em in Na a a and La Rioja
Regions.
2.1 Tie masgeo he malsys em
The Tie mas sp ings a e in he no hwes o he Za agoza p o ince close o he bo de wi h
Na a a a an al i ude o abou 580 m a.s.l..The wa e s eme ge in he no h sho e o he Yesa
ese oi , which co e s he sp ings du ing mos o he yea . Only du ing a ew mon hs a e
summe , when he i iga ion campaign emp ies he ese oi , he le el o he ese oi descends
enough o lea e he sp ings unde exposu e (Figu e 2).
The medicinal and he apeu ic p ope ies o hese wa e s a e known since long ago, a leas
since Roman imes, who ga e i he name o “Tie mas” due o he exis ence o he mal wa e s
(González, 1867). The e was a illage associa ed o he sp ings and wi h he same name bu i
was looded in 1959 o ill in he ese oi (A mijo, 2006). Nowadays he closes illage is
Sigües, abou 10 Km o he eas .
Figu e 2. Tie mas pho og aphs. Panel a: Yesa Dam when he le el goes down and he Tie mas sp ings
a e exposed. The mal wa e s can be seen in he sho e nex o he uins o he old illage. Panel b: One o
he poin s whe e he mal wa e s eme ge.
a
b
6
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
2.1.1 Geology
The sys em is loca ed in he he A agonian p e-Py enees, in he Jaca-Pamplona Basin, bounded
by he Bol aña an icline and he Pamplona aul , on he eas and wes , espec i ely, by he Axial
Zone and he Inne Ranges on he no h and by he Ou e Ranges on he sou h.
The Jaca-Pamplona Basin comp ises ma e ials om T iassic o Miocene wi h a Paleozoic
basemen o sedimen a y and me asedimen a y ocks (Sau a and Teixell, 2006; Figu e 3) bu
only he ocks om he C e aceous and mo e mode n, ou c op (IGME, 1973; La asoaña e al.,
1996). This basin is o g ea s uc u al complexi y wi h wo s uc u al ends gi ing place o wo
aul sys ems o NNE-SSW and E-W di ec ion (IGME, 1973; Figu e 3).
The T iassic ocks a e ep esen ed by he Bun sands ein (conglome a es, sands ones, lu i es) and
Keupe (e apo i es, lu i es, limes ones) acies (Pueyo e al., 2012). O e hem, (as he e a e no
Ju assic ocks in he a ea) he ma ine deposi s om he Uppe C e aceous appea , cons i u ed by
limes ones, dolos ones, ma ls and, on he op, he sands ones and conglome a es o he Ma bo e
Sands ones (Faci, 1997; IGME, 1973).
The Uppe C e aceous is o e laid by he Paleogene ma e ials: Paleocene Al eoline Limes ones,
Lowe -Middle Eocene Gua a Limes ones and Tu bidi es o he Hecho G oup (Faci, 1997;
IGME, 1973). The Al eoline Limes ones a e mainly ca bona es and calca eni es wi h abundan
bioclas s (Faci, 1997; IGME, 1973). The Gua a Limes ones consis o bioclas ic limes ones wi h
bioclas s in he bo om and ma ls in he op (Faci, 1997; IGME, 1973; Puigde àb egas, 1975).
The Hecho G oup is cons i u ed by siliciclas ic u bidi es and ma ls wi h impo an ca bona e
mega-laye s (up o 200 m hickness) in e cala ions (Bauluz e al., 2008; Faci, 1997; IGME,
1973).
Then, a eg essi e se ies was deposi ed in he Middle o Uppe Eocene cons i u ed by he
Sabiñánigo Sands ones, he A guís-Pamplona Ma ls and he Belsué-A a és Ma ls and
Sands ones, o e laid by e apo i ic ma e ials (anhyd i e, hali e and po assium sal s) indica i e o
he ansi ion o a pa alic en i onmen (Ayo a e al., 1995; Faci, 1997; IGME, 1973). Finally,
he basin was illed by he allu ial con inen al sedimen s du ing he Oligocene and Miocene
(Faci, 1997; IGME, 1973).
7
2. S udy a eas
Figu e 3. C oss sec ion showing he gene al s uc u e and geology o he Tie mas geo he mal sys em (modi ied om ALGECO2 po jec ; IGME, 2010). The s uc u al
complexi y o he a ea can be app ecia ed. The aqui e is hos ed in he Uppe C e aceous-Paleocene limes ones (da k g een). The app oxima e loca ion o Tie mas
sp ings and he possible echa ge is shown. Blue a ows ep esen he low di ec ion. A geological map can be ound in he esul s sec ion, pape 1.
8
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
2.1.2 Hyd ogeology
The po en ial aqui e o he Tie mas he mal wa e s is conside ed o be hos ed in he Paleocene
– Eocene ma ine ocks: he Al eoline Limes ones, Gua a Limes ones and he u bidi es om he
Hecho G oup (Faci, 1997; ITGE-DGA, 1994; Sánchez, 2000; Sánchez e al., 2004, 2000).
The echa ge a eas a e no p ecisely de ined by hey a e hough o be in he Paleocene and
Eocene ou c ops loca ed o he no h o he sp ings in he Ley e, Illón and O ba Sie as o in he
Inne Ranges (ITGE-DGA, 1994; Figu e 3).
The low o he wa e s om he echa ge a eas o he sp ings in he N-S di ec ion is in e up ed
by he NNE-SSW ac u es which make he low e ical and p oduce he ascen o he wa e s o
su ace and hei eme gence wi h low a es o abou 200 L/s and empe a u es close o 40 ºC
(ITGE-DGA, 1994).
2.2 Alhama‐Ja abageo he malsys em
Con inuing in he A agón egion, his sys em is one o he main he mal sys ems in Spain wi h
se e al sp ings in he su oundings o he Alhama de A agón and Ja aba illages, sepa a ed
abou 12 km om each o he .
In Ja aba, he wa e s sp ing close o he Mesa i e a an ele a ion o 737 m a.s.l.. The e a e 14
ca alogued sp ings bu he e a e many o he s wi hou an o icial classi ica ion, some o hem
isible and o he s benea h he wa e s o he i e (Figu e 4; Auqué e al., 2009; ITGE-DGA,
1994). These wa e s we e also known since oman imes when hey we e named “aguas de las
nin as” bu i was in 1120 when he i s pool was buil in he loca ion whe e La Vi gen spa is
placed nowadays (ITGE-DGA, 1994; Ma ín, 2016). Since hen he use o he he mal wa e s
has inc eased and he acili ies ela ed o hem also. The e a e 5 exploi a ions in Ja aba a
p esen : h ee spas (La Vi gen, Se ón and Sicilia) and wo bo ling plan s (Fon ecab as and
Luna es).
The e a e wel e ca alogued sp ings in Alhama eme ging a an ele a ion o 660 m a.s.l..
Al hough he oman emains a e sca ce in his place, hese wa e s we e men ioned by la in
his o ians such as P olomeo o Plinio. The i s acili y da es om 1122 and i was named “La
Casi a” o “Baños Viejos de San Roque” (ITGE-DGA, 1994; Ma ín, 2016). The e a e se e al
sp ings exploi ed a p esen in he wo spas o he illage (Te mas Palla es and Alhama de
A agón) and also addi ional oun ains in he municipali y (Figu e 5).
9
2. S udy a eas
Figu e 4. Ja aba pho og aphs. Panel a: Mesa Ri e , in which nume ous eme gences o wa e s appea .
Panel b: oun ain o he mal wa e in he Se ón Spa. Panel c: Small pond nex o he Mesa Ri e whe e
he mal wa e s eme ge.
2.2.1 Geology
The sys em is loca ed in he Ibe ian Chain, be ween i s wes limi and he e ia y Almazán
Basin. The ma e ials in his a ea ange om Paleozoic o Qua e na y (IGME, 1991; Figu e 6).
The basemen o he a ea consis s o Paleozoic ocks cons i u ed, mainly, by qua zi es, schis s
and phylli es. These a e ollowed by he common T iassic acies: Bundsands ein
(conglome a es, sands ones and clays), Muschelkalk (limes ones, dolos ones and ma ls) and
Keupe (ma ls, clays and e apo i es). The Ju assic in he a ea is sca ce and i is only ep esen ed
by a ma ine ca bona e o ma ion om he ansi T iassic-Ju assic, simila o he Co es de
Tajuña Fo ma ion, and cons i u ed by dolomi ic b eccias and massi e dolos ones.
a
bc
10
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
Figu e 5. Alhama de A agón pho og aphs. Panels a and b: wo oun ains o he mal wa e s in he illage.
Panel c: he mal lake inside he Te mas Palla és Spa, whe e he e a e se e al he mal wa e s sp ings.
The Lowe C e aceous o e lies he Ju assic and i consis s o he U illas Sands ones (Albian)
and he ma ine ca bona e o ma ions om he Uppe C e aceous: San a Ma ía de las Hoyas
(limes ones, ma ls, sands ones and clays), Nue alos (limes ones, dolomi ic limes ones and
dolos ones wi h ossils), Mon e de (noduli ic limes ones), Ja aba (massi e dolos ones and
limes ones wi h bioclas s), Pan ano de la T anque a (dolomi ic b eccias and dolos ones wi h
ma ls in e cala ions a bo om), Hon o ia del Pina (bioclas ic limes ones) and Bu go de Osma
(limes ones).
ab
c
11
2. S udy a eas
3. METHODOLOGY
A desc ip ion o he me hodologies used in his PhD hesis is p esen ed in his sec ion. Each
pape con ains i s speci ic Me hodology sec ion and he e o e, only a gene al o e iew o he
main echniques o analysis and da a ea men is desc ibed he e.
3.1 Bibliog aphic e iew
The i s necessa y s ep was o pe o m an in-dep h bibliog aphical compila ion:
To unde s and he s a e o he a in he knowledge o low- empe a u e geo he mal
sys ems hos ed in ca bona e ocks, and o he a agoni e a e ines, and he main
p oblems associa ed o hei s udy.
To lea n abou he a ious me hodologies and echniques o, inally, be able o selec he
mos adequa e ones o each speci ic case.
To ob ain he necessa y in o ma ion abou he h ee s udied geo he mal sys ems
ega ding he geological con ex and he p e ious geochemical and/o hyd ological
s udies.
3.2 Sampling
A sampling campaign was ca ied ou in Oc obe 2015 when se e al wa e samples we e aken
in A nedillo and Fi e o sp ings (Figu e 9) ollowing he p ocedu e desc ibed below. In he case
o Tie mas and Alhama-Ja aba sys ems he s udy was pe o med using he analy ical da a
ob ained in p e ious sampling campaigns pe o med by he Geochemical Modelling G oup o
he Uni e si y o Za agoza ollowing he same me hodology. The Fi e o a e ines samples
we e also aken p e iously by he membe s o he Geochemical Modelling G oup in wo
di e en poin s: in an old pipe ha no longe exis s and which discha ged wa e om he
cooling pool in he Becque spa, and he o he in a cu en ly ac i e pipe ha discha ges he
wa e om he same spa o he i e .
Figu e 9. Pho og aphs aken du ing he sampling campaign. In panel a some o he ma e ial used in he
sampling is shown. In panel b he he mal wa e is being il e ed in he ield by using a ki asa o. In panel c
he pH is measu ed in si u. Finally, in panel d he bo les in which wa e samples ha e been aken a e
labelled.
3.2.1 Wa e sampling
As i is known, a wa e sample is a sys em in cons an e olu ion since aken un il i is analysed.
E en being isola ed om he en i onmen , i will e ol e depending on he ini ial condi ions in
he sys em and he en i onmen al condi ions. This will lead o a change in he physico-chemical
cha ac e is ics o he wa e , which, in u n, will make he ob ained analy ical da a no
ep esen a i e o he eal condi ions in he sp ings. The pa ame e s which su e he as es
a ia ion a e pH and empe a u e and he e o e, hey mus be de e mined in si u. I is also
impo an o de e mine he alkalini y and he anion as soon as possible. Finally, he ca ions and
iso opes can be analysed la e on as long as he wa e sample has been ea ed and s abilised
co ec ly ( il e ed and acidi ied). Taking hese p ecau ions in o conside a ion a speci ic p o ocol
was ollowed o he wa e sampling and i is desc ibed nex .
cd
ab
20
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
pH and empe a u e we e de e mined in each sampling poin by a The mo O ion 250A pH-
me e wi h combined pH elec ode ORION 815600 Ross wi h empe a u e compensa ion. The
pH-me e was calib a ed wi h he s anda d bu e solu ions o pH 7.0 and 10.00. The elec ical
conduc i i y was measu ed wi h a conduc i ime e Jenway 4200 wi h a K=1 p obe and
au oma ic co ec ion o empe a u e.
Samples o ca ion, anion and iso ope analyses we e aken sepa a ely in polye hylene bo les
p e iously washed wi h ul apu e HNO3, insed wi h dis illed wa e and ai -d ied. Samples o
anions and 34S we e aken in 500 ml bo les and samples o ca ions and oxygen and deu e ium
iso opes in 100 ml bo les. Samples o ca ion and oxygen and deu e ium iso ope analyses we e
il e ed h ough 0.1 μm, by using a Ki asa o and, in he case o ca ions, he samples we e also
acidi ied o pH less han 1 wi h ul apu e HNO3. Samples o 13C de e mina ion we e aken in
small c ys al ials con aining me cu y chlo ide o a oid he mic obial ac i i y.
3.3 Analy ical echniques
3.3.1 Wa e samples
The de ailed desc ip ion below co esponds o he analy ical p ocedu e ollowed o he Fi e o
and A nedillo wa e samples aken du ing he de elopmen o his doc o al hesis. Fo he o he
sys ems he analy ical echniques we e simila and he de ails a e included in he co esponding
pape s in he esul s sec ion.
3.3.1.1 Alkalini yde e mina ion
As explained abo e, alkalini y should be de e mined wi hou delay, so i was measu ed in he
Geochemis y Labo a o y o he Ea h Science Depa men a he Uni e si y o Za agoza, only a
ew hou s a e he sampling (Figu e 10). I was measu ed wi h a Me le i a o using H2SO4
0.02N and de e mina ion o he inal poin a pH = 4.5 wi h a pH-me e The mo O ion 250A.
3.3.1.2 Anionanalyses
Chlo ide, sulpha e and luo ide we e also analysed in he Geochemis y Labo a o y o he Ea h
Science Depa men a he Uni e si y o Za agoza wi h he assis ance o En ique Oli e ,
labo a o y echnician, in 24 hou s a e collec ion.
Chlo ide and luo ide we e de e mined by a selec i e ion analyse equipmen , wi h he speci ic
chlo ide elec ode ORION 94-17B and luo ide elec ode ORION 94-09. The de e mina ion was
done by di ec measu emen using CISA and Tisab II as in e e ence supp esso o chlo ide and
21
3. Me hodology
luo ide, espec i ely. Sulpha es we e de e mined by colo ime y using a modi ica ion o he
Neme h me hod (Neme h, 1963).
3.3.1.3 Ca ionanalyses
Ca ions we e analysed in he Scien i ic and Technological Cen e a he Uni e si y o
Ba celona. Ca, Na, K, Mg, S and Si we e de e mined by Induc i ely Coupled Plasma Emission
Spec ome y (ICP-OES) wi h a Pe kin Elme Op ima 3200 l equipmen in s anda d condi ions.
The es o he mino ca ions we e analysed by Induc i ely Coupled Plasma Mass Spec ome y
(ICP-MS) wi h an Agilen 7500ce equipmen in s anda d condi ions.
3.3.1.4 S ableiso opeanalyses
S able iso opes we e also analysed in he Scien i ic and Technological Cen e a he Uni e si y
o Ba celona. δ18O and δ2H in wa e , δ13C in he dissol ed ino ganic ca bon, and δ34S and δ 18O
in dissol ed sulpha es, we e analysed by Con inuous Flow Iso ope-Ra io Mass Spec ome y
(CF-IRMS) wi h a Del a plus xp The mo ishe equipmen . δ18O, δ2H and δ13C we e di ec ly
analysed using he seconda y s anda ds aceable o ce i ied s anda ds: NBS18, NBS19,
SMOW and SLAP. δ34S and δ 18O in dissol ed sulpha e we e measu ed a e p ecipi a ing i as
BaSO4 (0.2 mg in sil e capsule o oxygen and 0.3 mg in in capsule o sulphu ) and using he
NBS-127, SO-5 and SO-6 seconda y s anda ds.
Figu e 10. Alkalini y measu emen in he Geochemis y Labo a o y o he Ea h Sciences Depa amen o
he Uni e si y o Za agoza.
22
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
3.3.2 Solidsamples
3.3.2.1 Pe og aphicaland ex u als udy
The samples we e i s desc ibed a e obse a ion a hand-size scale. A mo e de ailed s udy o
hei cha ac e is ics and ex u es was done h ough hei s udy by con en ional op ical
pe og aphical mic oscope on polished hin sec ions and ield emission scanning elec on
mic oscope (FESEM).
Thin sec ions we e done by he Se ice o p epa a ion o ocks and ha d ma e ials a he
Uni e si y o Za agoza And hey we e s udied by pe og aphic mic oscope in he Ea h Science
Depa men o he Uni e si y o Za agoza. The FESEM obse a ion was ca ied ou in he
Se ice o op ical mic oscopy a he Uni e si y o Za agoza and i was pe o med on ca bon-
coa ed samples using a ield emission scanning elec on mic oscope Ca l Zeiss MERLINTM
(Ca l Zeiss G oup, Jena, Ge many).
3.3.2.2 Mine alogicalanalyses
The samples we e sepa a ed in se e al subsamples, co esponding o di e en bands, using a
mic o-d ill and hen hey we e c ushed wi h a s eel jaw c ushe and g ound o a size ac ion
below 60 μm. The bulk mine alogical composi ion was de e mined by X- ay di ac ome y
(XRD) using a PANaly ical X’Pe PRO MPD powde di ac ome e in B agg-B en ano θ/2θ
geome y o 240 millime es o adius wi h a ocalizing Ge (111) p ima y monoch oma o , a
X’Cele a o de ec o and using CuKα1 adia ion: λ = 1.5406 Å a he X-Ray Di ac ion Uni in
he Scien i ic and Technical Cen e s o he Uni e si y o Ba celona (Spain). Semi-quan i a i e
phase analysis o he iden i ied c ys alline phases was done by means o he Rie eld me hod
(Rie eld, 1969).
3.3.2.3 Ca bonandoxygeniso opeanalyses
δ13C and δ18O analyses we e pe o med a he S able Iso ope Analysis Se ice o he Uni e si y
o Salamanca. The CO2 ex ac ion o he analyses was done ollowing s anda d echniques
(McC ea, 1950) wi h an ISOCARB de ice connec ed o a SIRA se ies 10 mass spec ome e
om VG Iso ech.
23
3. Me hodology
3.4 Da aanalysisandcalcula ions
3.4.1 Wa e da a ea men
The i s ea men o he da a was h ough hei ep esen a ion in ion-ion plo s, and o he mo e
speci ic diag ams like he Pipe diag am o bina y plo s showing he iso opic signa u es, he
sa u a ion indexes and o he e olu iona y ends.
Apa om hese basic explo a i e e alua ions he p incipal me hodologies used o de e mining
he ese oi empe a u e o he s udied geo he mal sys ems ha e been he chemical and iso opic
geo he mome e s and he geo he mome ical modelling. O he use ul geochemical modelling
app oaches ha e been used o e alua e he eliabili y o he analyses o o in e he main
p ocesses con olling he chemical e olu ion o he wa e s. A sho summa y is p esen ed nex .
3.4.1.1 Chemicalgeo he mome e s
The use o chemical geo he mome e s is he me hodology adi ionally used o he empe a u e
es ima ion in a deep ese oi . A chemical geo he mome e is an empi ic o expe imen al
calib a ion based on he chemical eac ions ha con ol he elemen al con en s o he wa e s and
a e dependen on empe a u e (e.g. Ma ini, 2004; T uesdell, 1976). In ha way, he empe a u e
a dep h can be calcula ed knowing he elemen al con en s o he wa e s. Al hough his
echnique is widely used i has some impo an limi a ions ha should be aken in o accoun .
The applica ion o his p inciple assumes ha he elemen al con en s o he wa e s ha e no
changed du ing hei ascen om he deep ese oi o he su ace and, he e o e, he
cha ac e is ics o he wa e s in he sp ing a e conside ed o be ep esen a i e o he condi ions a
dep h. This assump ion is no always ue due o he possible modi ica ions caused by seconda y
p ocesses ac ing du ing he ascen o su ace such as dissolu ion/p ecipi a ion o mine al phases,
CO2 ou gassing o mixing wi h o he wa e s. Ano he assump ion ha has o be accep ed is ha
he wa e s ha e a ained he equilib ium in he ese oi wi h he mine al phases conside ed o
he calib a ion o he geo he mome e s.
Se e al chemical geo he mome e s and calib a ions a e a ailable in he scien i ic li e a u e bu
no all o hem can be used in all sys ems. The classical ca ionic geo he mome e s p o ide e y
good esul s in high empe a u e sys ems hos ed in g ani ic o basal ic ocks, since he
equilib ium wi h he app op ia e mine al phases a e easily a ained in hose sys em ( o example
wi h albi e and K- eldspa in he case o he Na-K geo he mome e ; A nò sson e al., 1983; As a
e al., 2010; Auqué e al., 1997; Buil e al., 2006; Choi e al., 2005; D´Amo e e al., 1987;
Fouillac and Micha d, 1981; Fou nie , 1981, 1977; Giggenbach e al., 1983; Giggenbach, 1988;
24
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
Kha aka and Ma ine , 1989; Ma ine e al., 2006; Mu lu and Güleç, 1998; Pingi o e e al., 2002;
Sonney and Vua az, 2010; S e ánsson and A nó sson, 2000). The applica ion o hese ca ionic
geo he mome e s is much mo e complica ed (and i is usually conside ed inadequa e) in low
empe a u e ca bona e sys ems since hose mine al phases a e no always p esen and i hey a e,
he low empe a u e o he wa e s makes di icul o a ain he equilib ium (Chiodini e al., 1995;
D’Amo e and A nó sson, 2000; Ka imi and Moo e, 2008; Le e e al., 2002; López-Chicano e
al., 2001; Sonney and Vua az, 2010). In e es ingly, howe e , hey ha e been success ully used
in some sys ems in which hey we e conside ed inadequa e (e.g. Apolla o e al., 2012;
Fe nández e al., 1988; Gökgöz and Ta kan, 2006; Micha d and Bas ide, 1988; Mohammadi e
al., 2010; Pas o elli e al., 1999; Wang e al., 2015).
Th ough he di e en pape s p esen ed in he Resul s sec ion a as a ie y o chemical
geo he mome e s a e e alua ed and hei applica ion in ca bona e sys ems o low empe a u e is
discussed, including he classical ca ionic geo he mome e s, he silica geo he mome e s and,
mo eo e o he geo he mome e s speci ically calib a ed o be applied in sys ems wi h hese
cha ac e is ics. All hese geo he mome e s and calib a ions a e summa ised in Table 1 and a
b ie desc ip ion o hem is p esen ed below.
Silicageo he mome e s
The wo main silica geo he mome e s a e he SiO2-qua z and SiO2-chalcedony
geo he mome e s which ely on he qua z o chalcedony equilib ium in he deep ese oi .
Va ious calib a ions a e a ailable and some o he mos common ha e been used he e (Table 1).
All he qua z-silica geo he mome e s we e de eloped om expe imen al da a on silica
solubili y. Rega ding chalcedony, he calib a ion by Fou nie (1977) and Fou nie and Po e
(1982) we e de i ed om solubili y expe imen s abo e 125 ºC ex apola ed o low
empe a u es. The calib a ion om A nò sson e al. (1983) is based on da a om na u al
samples om Icelandic d ill-holes.
Gene ally speaking, qua z is he silica phase con olling he dissol ed silica concen a ions a
high empe a u es while chalcedony con ols hem a low empe a u es. The e o e, i is expec ed
ha he SiO2-qua z geo he mome e would be adequa e a empe a u es o 150-225ºC while he
SiO2-chalcedony geo he mome e would be be e a lowe empe a u es (D’Amo e and
A nó sson, 2000; Fou nie , 1977; Ma ini, 2004). Howe e , in some cases i is jus he opposi e
and he e o e, he bes op ion is o ollow he ecommenda ion by Fou nie (1991) and check
always bo h geo he mome e s o iden i y he go e ning silica phase.
25
3. Me hodology
Table 1. Chemical geo he mome e s and calib a ions conside ed in he s udy. Concen a ion uni s o he
elemen s in ol ed a e all in mg/L excep o he SiO2-qua z calib a ion p oposed by Micha d (1979) and
he Na-Li and Li geo he mome e s in which he concen a ions a e exp essed in mol/L.
1β=4/3 should be used i he empe a u e ob ained is lowe han 100 ºC; i wi h ha alue o β he
empe a u e i highe han 100 ºC, he empe a u e should be ecalcula ed conside ing β = 1/3.
2Σeq is he summa ion (in eq/L) o he majo dissol ed species. Chiodini e al. (1995) pe o med hei
calib a ion o he Ca-Mg geo he mome e by using a diso de ed dolomi e.
Geo he mome e Calib a ion Au ho
SiO2-qua z
1315
5.205273.15 T uesdell (1976)
1309
5.19273.15 Fou nie , (1977) and
Fou nie and Po e (1982)
1322
0.435273.15 Micha d (1979)
SiO2-chalcedony 1032
4.69273.15 Fou nie , (1977) and
Fou nie and Po e (1982)
1112
4.91273.15 A nò sson e al. (1983)
Na-K 1390
1.75log
273.15 Giggenbach (1988)
1217
1.483log
273.15 Fou nie (1979)
K-Mg 4410
13.95log
273.15 Giggenbach e al. (1983)
Na-K-Ca 1647
log
log
√
2.062.47
273.15
Fou nie and T uesdell
(1973)1
Na-Li 1000
0.33log
273.15 Fouillac and Micha d (1981)
Li 2258
1.44log273.15 Fouillac and Micha d (1981)
Mg-Li 2200
5.47log
√
273.15
Kha aka and Ma ine (1989)
Ca-Mg 979.8
3.1170log
0.07003∑
273.15
Chiodini e al. (1995)2
SO4-F 1797.7
0.7782log
0.08653∑
273.15
Chiodini e al. (1995)2
26
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
Na‐Kgeo he mome e
This geo he mome e is based on he equilib ium be ween Na+ and K+ in he solu ion and albi e
and K- eldspa (e.g. D’Amo e and A nó sson, 2000). Se e al calib a ions ha e been de eloped
and he ones used he e a e he Fou nie , 1979 and he Giggenbach, 1988 calib a ions, bo h o
hem de i ed empi ically om deep geo he mal wells. In some cases he equa ion p oposed by
Ve ma and San oyo, (1997), which was p oposed a e imp o ing he Fou nie (1979) equa ion,
has also been used.
The applicabili y o his geo he mome e will be condi ioned o he exis ence o he albi e – K-
eldspa equilib ium a dep h, which is no always a ainable in low empe a u e ca bona e
sys ems p oducing incohe en ly high empe a u es (D´Amo e e al., 1987).
K‐Mggeo he mome e
This geo he mome e is con olled by he equilib ium o K- eldspa and a Mg-bea ing phase a
dep h, such as chlo i e, saponi e o mon mo illoni e (e.g. Ma ini, 2004). Giggenbach e al.
(1983) de eloped he calib a ion empi ically om deep geo he mal wells.
This equilib ium is a ained mo e quickly han he albi e – K- eldspa and i can be app oached
a empe a u es as low as 25 ºC (Ma ini, 2004). This ac makes his geo he mome e mo e
adequa e in sys ems o lowe empe a u e bu , on he con a y, i also implies an s ong esponse
du ing he ascen o he wa e s and cooling due o he as up aking o Mg (D’Amo e and
A nó sson, 2000; Ma ini, 2004).
Giggenbachdiag am
This is no s ic ly a geo he mome e bu a way o e alua e he wa e equilib ia and he
possibili ies o using he ca ion geo hemome e s. I is he combina ion o he Na-K and K-Mg
geo he mome e s in a e na y diag am p oposed by Giggenbach (1988). Iso he mal equilib ium
lines a e ep esen ed in he diag am o he Na/K and K/Mg a ios, and he in e sec ion o bo h
iso he ms a di e en empe a u es d awn he ull equilib ium line (Figu e 11), which indica es
ha wa e s ha e a ained he equilib ium wi h espec o he phases on which Na-K and K-Mg
geo he mome e s a e based on. Giggenbach (1988) delimi ed he ields o pa ially equilib a ed
wa e s (o ma u e wa e s) and imma u e wa e s (Figu e 11) in he diag am, meaning ha i a
wa e is in he second ield i is unsui able o he use o hese geo he mome e s (Giggenbach,
1988). I he wa e is in he pa ially equilib a ed wa e s ield bo h geo he mome e s can be
e alua ed.
27
3. Me hodology
wa e s a e expec ed o be in equilib ium wi h. The mine als ha ha e been conside ed in he
sys ems s udied in he hesis a e calci e, dolomi e and anhyd i e, since hey a e hos ed in
ca bona e ocks in con ac o e apo i ic acies, and some o he s such as qua z, albi e, K-
eldspa and o he aluminosilica es since he wa e s a e also in con ac o some de i al ma e ial
(see he pape s o mo e in o ma ion).
Al hough his echnique, like he chemical geo he mome e s, is also based on he assump ion o
he mine al equilib ia a dep h, i p esen s se e al ad an ages o e hem:
- I allows a be e iden i ica ion o he mine al equilib ia in he deep ese oi (Micha d
e al., 1986; Micha d and Fouillac, 1980; Micha d and Roekens, 1983).
- The modelling can be pe o med conside ing wo di e en app oaches: 1) in closed
sys em condi ions, assuming he only p ocess a ec ing wa e s is cooling du ing he
ascen ; o 2) in open sys em condi ions, assuming he wa e s unde go eequilib a ion
p ocesses du ing he ascen and allowing p ecipi a ion – dissolu ion o mine al phases.
- Finally, by using di e en app oaches, he ac ion and e ec s o seconda y p ocesses can
be iden i ied and co ec ed as o example CO2 ou gassing (Paland i and Reed, 2001;
Pang and Reed, 1998) o mixing wi h shallowe and coole wa e s (Pang and Reed,
1998).
Di ec andin e semodelling
The main aim o he geochemical modelling is o ind he model ha explains he cha ac e is ics
o he wa e s and is able o p edic how hey would e ol e unde ce ain condi ions. These
models can be ob ained in a di ec o in an in e se way (e.g. Plumme , 1992, 1984).
The in e se modelling is also known as mass balance calcula ion. I de ines he mass ans e s
aking place be ween wo, o mo e, connec ed poin s in a sys em om he known chemical
cha ac e is ics o he wa e s in hose poin s. The model p edic s he mine als ha p ecipi a e o
dissol e, he ion exchanges, he ingass o ou gass p ocess and he quan i ies o hese eac ions.
This ype o calcula ion p o ides all he ma hema ically possible combina ions o mass ans e
eac ions which would explain he obse ed concen a ion changes be ween he wo connec ed
poin s, in he o m o se e al possible models. The limi a ion is ha his calcula ion only
conside s he mass balance p inciple wi hou aking in o accoun he he modynamic easibili y
o he conside ed eac ions (e.g. Zhu and Ande son, 2002).
The di ec modelling, also known as eac ion pa h calcula ions, consis s o p edic ing he
e olu ion o a wa e unde ce ain es ablished condi ions om he known chemical composi ion
o ha wa e . The hypo he ic composi ion o he inal wa e is p edic ed along wi h he mine als
34
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
ha will p ecipi a e o dissol e when ce ain eac ions a e assumed o ake place in he sys em.
In his case he calcula ion conside s he he modynamic p inciples (Zhu and Ande son, 2002).
A good ag eemen be ween some o he mass balance models and he eac ion pa h calcula ions
would suppo he easibili y o hose eac ions in he sys em.
3.4.2 Solidda a ea men
As he s udy o he a e ine samples has been mainly ocused on he e alua ion o he s able
iso ope ac iona ion, only his ea men is summa ised nex .
3.4.2.1 S ableiso ope ac iona ion
The iso opic signa u e o ca bona e p ecipi a es ( a e ines o speleo hems) is widely used in
paleon i onmen al and paleoclima ic econs uc ions since he iso opic ac iona ion be ween
wa e and he p ecipi a ing ca bona e, calcula ed as p e iously exp essed in equa ion 1, is a
unc ion o empe a u e (e.g. And ews, 2006; Capezzuoli e al., 2014; Fo d and Pedley, 1996;
Fouke e al., 2000; Ga ne e al., 2004; Jones and Renau , 2010; Kele e al., 2011, 2008;
Lachnie , 2015; Liu e al., 2006, 2010; Osáca e al., 2016, 2013; Pedley, 2009; Pen ecos ,
2005). Howe e , he in e p e a ion o he iso opic con en s is no always easy since he
ac iona ion can be a ec ed by ac o s such as he CO2 ou gassing o he p ecipi a ion a es (e.
g. Fouke e al., 2000; Kele e al., 2008; 2011). Ano he di icul y is ha a ious ac iona ion
equa ions ha e been p oposed o calci e–wa e ac iona ion and a agoni e–wa e ac iona ion
bu he e is no an ag eemen abou i hey a e ac ually ep esen a i e o he eal equilib ium
(e.g. Kele e al., 2015; Lachnie , 2015). The e o e, he s udy o ecen p ecipi a es, whe e he
iso opic da a o wa e and solid ca bona e a e a ailable, p o ides use ul in o ma ion o ob ain a
be e in e p e a ion o ancien ca bona e p ecipi a es.
The δ13C da a in his s udy canno be used o his pu pose because hey we e measu ed in he
dissol ed ino ganic ca bon (DIC) which could be conside ed o be as HCO3- and he
ac iona ion be ween a agoni e (o calci e) and HCO3- has been epo ed o be independen o
empe a u e (Rubinson and Clay on, 1969; Tu ne , 1982; Romanek e al., 1992). Only he δ13C
ac iona ion be ween a agoni e (o calci e) and he dissol ed CO2 is empe a u e-dependan
(e.g. Chacko e al., 2001; Romanek e al., 1992; Scheele and Hoe s, 1992).
Rega ding he δ18O, se e al δ18O a agoni e – wa e equilib ium equa ions ha e been applied
(Table 3):
35
3. Me hodology
Table 3. Di e en δ18O equilib ium equa ions conside ed. Tempe a u e (T) is in Kel in and δ18O alues
a e s. V-SMOW.
Equilib ium equa ion Au ho
δ18Oa agoni e-wa e
100018.041000
31.12 G ossman and Ku
(1986)
100018.561000
33.49 Pa e son e al. (1993)
100018.561000
32.54 Tho old e al. (1997)
100016.741000
26.39 Whi e e al. (1999)
100018.451000
32.54 Böhm e al. (2000)
100020.441000
41.48 Zhou and Zheng (2003)
100017.881000
30.76 Kim e al. (2007)
100012.8155.7933.7554∗103.2966∗
102.2189∗108.9981∗101.636∗
10
Chacko and Deines
(2008)1
100022.51000
46.1 Wang e al. (2013)
δ18Oa agoni e/calci e-
wa e 1000201000
36 Kele e al. (2015)
δ18Ocalci e-wa e 100018.031000
32.17 Kim and O’Neil (1997)
100017.41000
28.6 Coplen (2007
1x = 106/T2, whe e T is Kel in
- G ossman and Ku (1986) de i ed hei equa ion om a agoni ic o amini e a,
gas opods and scaphods in he empe a u e ange o 2.5 o 26 ºC.
- Pa e son e al. (1993) deduced he equa ion om he cha ac e isa ion o a agoni ic ish
o oli hs in he empe a u e ange o 3.2 o 30.3 ºC.
- Tho old e al. (1997) also deduced an equa ion om a agoni ic ish o oli hs in he
empe a u e ange o 18 o 25 ºC.
- Whi e e al. (1999) s udied a agoni ic ma ine molluscs in he ange o empe a u es
om 8 o 24 ºC o de i e an equa ion.
- Böhm e al. (2000): p oposed and equa ion om he e alua ion o a agoni ic sponges in
he empe a u e ange o 3 o 28 ºC.
- Zhou and Zeng (2003) pe o med expe imen s o a agoni e p ecipi a ion in he
empe a u e ange o 10 o 70 ºC o ob ain he equa ion
36
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
- Kim e al. (2007) ca ied ou expe imen s wi h ino ganic syn he ic a agoni es in he
empe a u e ange o 10 o 40 ºC o p opose hei equa ion.
- Chacko and Deines (2008) de i ed an equa ion applicable in he empe a u e ange o 0
o 130 ºC om he calcula ion o he pa i ion unc ion a ios ( o a agoni e and wa e )
om s a is ical mechanical calcula ion and a compila ion o ib a ional equency da a.
- Wang e al. (2013): deduced he equa ion a e a agoni e p ecipi a ion om seawa e
expe imen s in he empe a u e ange o 25 – 55 ºC.
- Kele e al. (2015): p oposed an equa ion om a combina ion o da a o na u al calci e
and a agoni e a e ines. The e o e, i can be used in a e ines composed by a
mix u e o a agoni e and calci e.
As one o he s udied samples consis s o a calci e – a agoni e mix u e he wo mos common
δ18O calci e – wa e ac iona ion equa ions ha e also been used (Table 3):
- Kim and O’Neil (1997): de i ed om ino ganic calci es syn hesised in labo a o y in he
ange o 10 o 40 ºC.
- Coplen (2007): p oposed he equa ion om ein calci e samples om De ils Hole
(Ne ada, USA).
37
3. Me hodology
4. RESULTS
4.1 Pape 1
Geochemis y, geo he mome y and in luence o he concen a ion o
mobile elemen s in he chemical cha ac e is ics o ca bona e-e apo i ic
he mal sys ems. The case o he Tie mas geo he mal sys em (Spain)
Mónica Blasco, Luis F. Auqué, Ma ia J. Gimeno, Pa icia Ace o, Ma ia P. As a
Chemical Geology 466, 696-709 (2017)
Impac Fac o (2017): 3.57
Qua ile and Ca ego y (2017): Q1 (19/85), Geochemis y and geophysics
DOI: 10.1016/j.chemgeo.2017.07.013
Sen : 14 Oc obe 2016
Accep ed: 17 July 2017
A ailable online: 19 July 2017
Final publica ion: 5 Sep embe 2017
Con en s lis s a ailable a ScienceDi ec
Chemical Geology
jou nal homepage: www.else ie .com/loca e/chemgeo
Geochemis y, geo he mome y and influence o he concen a ion o
mobile elemen s in he chemical cha ac e is ics o ca bona e-e apo i ic
he mal sys ems. The case o he Tie mas geo he mal sys em (Spain)
Mónica Blasco
a,⁎
, Luis F. Auqué
a
, Ma ia J. Gimeno
a
, Pa icia Ace o
a
, Ma ia P. As a
b
a
Geochemical Modelling G oup, Pe ology and Geochemis y A ea, Ea h Sciences Depa men , Uni e si y o Za agoza, Spain C/ Ped o Ce buna 12, 50009 Za agoza,
Spain.
b
En i onmen al Mic obiology Labo a o y (EML), École Poly echnique Fédé ale de Lausanne (EPFL), EPFL-ENAC-IIE-EML, S a ion 6, 1015 Lausanne, Swi ze land.
ARTICLE INFO
Keywo ds:
Geo he mal sys em
Geo he mome y
Chemical geo he mome e s
Iso opic geo he mome e s
Geo he mome ical modelling
Mobile elemen s
ABSTRACT
The Tie mas low empe a u e geo he mal sys em, hos ed in he Paleocene-Eocene ca bona es o he Jaca-
Pamplona basin, has been s udied o e alua e he geochemis y and he empe a u e o he wa e s in he deep
ese oi . These wa e s a e o chlo ide-sodium ype and eme ge wi h a empe a u e o abou 37 °C. Two hy-
d ogeochemical g oups o wa e s ha e been dis inguished: one wi h lowe sulpha e concen a ion and lowe TDS
(abou 7500 ppm) and he o he wi h highe sulpha e con en and TDS alues (close o 11,000 ppm). The e a e
also sligh diffe ences in he ese oi empe a u e es ima ed o each g oup. These empe a u es ha e been
de e mined by combining se e al geo he mome ical echniques: (1) classical chemical geo he mome e s (SiO
2
-
qua z, Na-K, K-Mg and Na-K-Ca), (2) specific geo he mome e s o ca bona e sys ems (Ca-Mg), (3) iso opic
geo he mome e s and, (4) geo he mome ical modelling.
The good ag eemen in he empe a u e ob ained by hese echniques, including he ca ionic geo he m-
ome e s which a e no usually conside ed sui able o his ype o sys ems, allows es ablishing a eliable ange o
empe a u e o 90 ± 20 °C o he low-sulpha e wa e s and 82 ± 15 °C o he high-sulpha e wa e s.
The mine al assemblage in equilib ium in he ese oi is assumed o be he same o bo h g oups o wa e s
(calci e, dolomi e, qua z, anhyd i e, albi e, K- eldspa and o he aluminosilica e phases); he e o e, he diffe -
ences ound in he ese oi empe a u e and, mos ly, in he geochemical cha ac e is ics o each g oup o wa e s
mus be due o he exis ence o wo flow pa hs, wi h sligh ly diffe en empe a u es and in ensi y o wa e - ock
in e ac ion.
Anhyd i e is a equilib ium in he ese oi sugges ing ha , al hough his sys em is hos ed in ca bona es,
e apo i es may also be p esen . The dissolu ion o hali e (and he consequen inc ease in he chlo ide con-
cen a ion) condi ions he chemical cha ac e is ics o he wa e s and he equilib ium si ua ions in he ese oi
and wa e s acqui e hei chlo ide-sodium affini y a dep h and no du ing hei ascen o he su ace.
Finally, a a ou able ec onic s uc u e o CO
2
s o age has been ecognised in he Paleocene-Eocene ca -
bona es o his a ea. The e o e, conside ing he cha ac e is ics o hese wa e s (in equilib ium wi h calci e,
dolomi e and anhyd i e in he ese oi ), he esul s o his wo k a e use ul o unde s and some o he geo-
chemical p ocesses ha migh ake place du ing he CO
2
injec ion: 1) p ecipi a ion o ca bona es and sulpha es
in he icini y o he injec ion well due o desicca ion o he wa e s and, 2) ca bona e dissolu ion and sulpha e
p ecipi a ion in he long e m.
1. In oduc ion
Geo he mal sys ems ha e always been o in e es o indus ial o
ou is ic use o hei wa e s (e.g., in g eenhouses o balneo he apy).
One o he fi s s eps in he e alua ion o he geo he mal po en ial o an
a ea is he s udy o he geochemical and iso opic cha ac e is ics o he
he mal sp ings (e.g. D'Amo e and A nó sson, 2000). These s udies
p o ide in o ma ion abou he wa e e olu ion along he hyd ological
ci cui and abou i s empe a u e in he ese oi . The gene al geo-
chemical and geo he mome ic cha ac e isa ion o he Tie mas geo-
he mal sys em is p esen ed in his pape .
The Tie mas he mal wa e s ha e been used in balneo he apy since
h p://dx.doi.o g/10.1016/j.chemgeo.2017.07.013
Recei ed 14 Oc obe 2016; Recei ed in e ised o m 19 May 2017; Accep ed 17 July 2017
⁎
Co esponding au ho a : Geochemical Modelling G oup, Pe ology and Geochemis y A ea, Ea h Sciences Depa men , Uni e si y o Za agoza, Spain.
E-mail add ess: monicabc@uniza .es (M. Blasco).
&KHPLFDO*HRORJ ²
$YDLODEOHRQOLQH-XO
(OVHYLHU%9$OOULJKWVUHVHUYHG
41
4. Resul s
Roman imes. Nowadays he sp ings a e co e ed by he wa e s im-
pounded by he Yesa dam du ing mos o he yea . Howe e , hese
sp ings become exposed equen ly du ing la e summe and many
people come o benefi om hei he apeu ic p ope ies. New p ojec s
o use hese he mal wa e s again a e being p oposed. The sp ing
empe a u e is abou 40 °C and he flow a e 200 L/s and hey a e
conside ed one o he mos impo an geo he mal sys ems in A agon o
i s geo he mal po en ial (Sánchez, 2000; Sánchez e al., 2004).
Du ing he de elopmen o he ALGECO2 p ojec , conduc ed by he
Spanish Geological Su ey (IGME), he Paleocene-Eocene ca bona e
ocks in his a ea (which is he mos easible aqui e o he Tie mas
wa e s; see below) we e conside ed a a ou able s uc u e o CO
2
geological s o age (Ley e-Be dún s uc u e, sou hwa ds Ley e Sie a;
Suá ez e al., 2014). This makes he s udy o hese wa e s a po en ial
analogue s udy o he ones expec ed o be in he p oposed CO
2
s o age,
om which he e a e no ye hyd ochemical da a (Suá ez e al., 2014;
Gaus, 2010).
Despi e he well known in e es o he sys em, i s hyd ological and
hyd ochemical ea u es a e s ill poo ly known due o he complex
geology o he zone. Thus, he aim o his wo k is o fill in his gap wi h
he geochemical cha ac e isa ion o hese wa e s and he es ima ion o
he ese oi empe a u e using classical and geo he mome ical mod-
elling echniques.
2. Geological and hyd ological se ing
The Tie mas sp ings a e loca ed in he A agonian p e-Py enees, in
he no hwes o he Za agoza p o ince (Fig. 1). They eme ge in he
no h sho e o he Yesa ese oi , which co e s he sp ings du ing mos
o he yea . Geologically, he sys em is loca ed in he Jaca-Pamplona
Basin, be ween he Bol aña an icline and he Pamplona aul , and
bounded on he no h by he Axial Zone and he Inne Ranges and on
he sou h by he Ou e Ranges (Fig. 2). The Jaca-Pamplona Basin is
elonga ed in eas -wes di ec ion, pa allel o he gene al end o he
Py enees. O e all, he s uc u e o he basin is an asymme ic syncline
dipping sou h and filled wi h Te ia y o ma ions (La asoaña e al.,
1996; Bauluz e al., 2008). The e olu ion o his basin was condi ioned
by a comp essional con ex . The Sou h Py enean zone was a o eland
basin du ing he C e aceous and a deep ench opened wes wa ds e-
cei ing sedimen s om a u bidi ic sys em. In he Middle Eocene his
basin was ans o med in a piggy back basin, wi h sou hwa ds dis-
placemen due o he p opaga ion o he Sou h Py enean Basal Th us
and, e en ually, was filled by e ia y sedimen s (Pay os e al., 1994;
Oli a e al., 1996).
The Jaca Basin has a g ea s uc u al complexi y: he e a e wo main
s uc u al ends ha gi e ise o wo aul sys ems, one wi h NNE-SSW
di ec ion, due o he eac i a ion o he a di-he cynian aul sys ems,
and he o he wi h E-W di ec ion (Fig. 1), which co esponds o he
Py eneean end (IGME, 1973).
2.1. S a ig aphy
S a ig aphically, he Jaca-Pamplona Basin is cons i u ed by T iassic
o Miocene o ma ions wi h a sedimen a y and me asedimen a y
Paleozoic basemen (Sau a and Teixell, 2006). The T iassic ocks be-
long o he Bundsands ein and Keupe Facies, wi h abou 400 m o
conglome a es, sands ones and lu i es, and 150 m o e apo i es, lu i es
and limes ones, espec i ely (Pueyo e al., 2012), al hough due o he
ole o he Keupe Facies as de achmen le el, i is difficul o de e mine
i s exac hickness. These T iassic o ma ions a e di ec ly o e laid by a
ma ine se ies deposi ed in he o eland Sou h Py eneean basin du ing
he Uppe C e aceous: he Paleocene Al eoline Limes ones, he Lowe
and Middle Eocene Gua a Limes ones and u bidi es o he Hecho
G oup (IGME, 1973; Faci, 1997). This is ollowed by a eg essi e ca -
bona e se ies in he Middle and Uppe Eocene o med in an ex e nal
pla o m and a p odel a sys em cons i u ed by he Sabiñanigo
Sands ones ( he La es Ma ls in o he a eas), he A guis-Pamplona
Ma ls and he Belsué-A a és ma ls and sands ones. These o ma ions a e
o e laid by e apo i ic ocks, which indica e he ansi ion o a pa alic
con inen al en i onmen , and a e cons i u ed by hali e, anhyd i e and
po assium sal s (syl i e and ca nalli e) uni s (e.g. Ayo a e al., 1994,
1995). The po ash uni s a e es ic ed o he depocen e and hey a e
mos ly absen in he es o loca ions (Ayo a e al., 1994); o ins ance,
in he hyd oca bon explo a ion d illing Sangüesa 1 (Fig. 1) hese e a-
po i es a e only cons i u ed by anhyd i e and hali e a dep h.
Finally, he las s age o he basin e olu ion co esponds o he al-
lu ial filling o he Jaca-Pamplona Basin ha is ep esen ed in he
Oligocene and Miocene con inen al o ma ions (Campoda be G oup
and Be nués and Uncas illo Fo ma ions; IGME, 1973; Faci, 1997).
In he con ex o his s udy, he Uppe C e aceous and he
Paleocene-Eocene o ma ions a e o special in e es as hey cons i u e
he po en ial geo he mal o ma ions (FG6 and FG7; Sánchez, 2000;
Sánchez e al., 2000, 2004) o he Tie mas he mal sp ings. The
hickness o he Uppe C e aceous is abou 200 m in he a ea and i is
cons i u ed, a i s base, by dolomi ic limes ones, ma ls and sandy
limes ones and, a he op, by he Ma bo é Sands ones (calca eni es
wi h sands ones and siliceous conglome a es in he uppe mos pa ;
IGME, 1973; Faci, 1997).
In he Paleocene-Eocene o ma ions, he Al eoline Limes ones a e
120 o 300 m hick, and consis o ca bona es and calca eni es, wi h
spa i ic o mic ospa i ic cemen , bioclas s, qua z g ains and, locally,
oncoids, ooids and in aclas s (IGME, 1973; Faci, 1997). The Gua a
Limes ones in he a ea a e abou 100 m hick and consis o bioclas ic
limes ones wi h abundan siliciclas ic ocks a he bo om ha g ade o
ma ls owa ds he op (IGME, 1973; Puigde àb egas, 1975; Faci, 1997).
Explo a o y d illing a dep hs be ween 2800 and 3700 m shows ha
hese limes ones om he Paleocene-Lowe Eocene (Al eoline and
Gua a Limes ones) a e dolomi ic a he bo om (Sánchez Guzmán and
Ga cía de la Noceda, 2005). Finally, he Hecho G oup consis s o se s o
siliciclas ic u bidi es and hemipelagic ma ls wi h calci e, illi e, chlo i e
and mino albi e and dolomi e (Bauluz e al., 2008). The mos a eni ic
pa s con ain li hic agmen s and clas s o qua z, plagioclase, K- eld-
spa and musco i e (Gup a and Picke ing, 2008). Embedded in hese
ma e ials appea he so-called ca bona ed mega-laye s (o mega- u bi-
di es), which a e hick and la e ally con inuous ca bona e-cemen ed
b eccias and calca eni es, emo ed om a pla o m and e-deposi ed in
a deep ma ine ench. Up o se en mega-laye s wi h up o 200 m o
hickness ha e been iden ified in he Jaca-Pamplona Basin (IGME,
1973; Pay os e al., 1994; Faci, 1997; Bauluz e al., 2008).
These o ma ions, conside ed as he sui able aqui e o he wa e s
s udied he e, al hough mainly cons i u ed by ca bona es, hey also
con ain siliciclas ic ocks, which will de e mine he geochemical cha -
ac e is ics o he wa e s (see below).
2.2. Hyd ogeology
Sánchez (2000) and Sánchez e al. (2000, 2004) dis inguish se e al
geo he mal o ma ions in he Py enees a ea defining hem as “geolo-
gical uni s able o s o e wa e o o he fluids a a specific empe a u e
and unde specific mobili y condi ions sui able o allow some ype o
geo he mal exploi a ion”. Two o hem, FG6 and FG7, a e loca ed in he
s udied a ea, he fi s one co esponds o he Uppe C e aceous o -
ma ions and he second is o med by he Al eoline Limes ones (Paleo-
cene), he Gua a Limes ones (Paleocene-Eocene) and he mega-
u bidi es om he Eocene Flysch. The second one is conside ed he
po en ial aqui e o he Tie mas sp ings (ITGE-DGA, 1994; Faci, 1997;
Sánchez, 2000; Sánchez e al., 2000, 2004) and o he geo he mal
sys em o Jaca-Se ablo (abou 70 km NE om Tie mas; Sánchez
Guzmán and Ga cía de la Noceda, 2005).
The Tie mas wa e s a e chlo ide-sodium/calcium-sulpha e ype
wi h a TDS ( o al dissol ed solids) highe han 10,000 ppm. O he
wa e s also hos ed in he Al eoline Limes ones show diffe en chemical
M. Blasco e al. &KHPLFDO*HRORJ ²
42
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
Fig. 1. Loca ion o he Tie mas geo he mal sys em and geological map o he a ea
(modified om Oli a-U cia e al., 2012).
Fig. 2. C oss sec ion showing he gene al s uc u e o he Jaca-Pamplona Basin and he loca ion o Tie mas Sp ings
(modified om ALGECO2 p ojec : h p://in o.igme.es/algeco2/;IGME, 2010).
M. Blasco e al. &KHPLFDO*HRORJ ²
43
4. Resul s
The e olu ion wi h he empe a u e o he sa u a ion indices o he
selec ed mine als o sample T3 ( ep esen a i e o he high-sulpha e
g oup) is shown in Fig. 6. Since he e is no aluminium da a o his
sample, i s concen a ion was fixed by imposing he K- eldspa equili-
b ium (Pang and Reed, 1998; Paland i and Reed, 2001). The esul s
show a ema kable deg ee o con e gence o he sa u a ion indices o
qua z and anhyd i e which each equilib ium a he same empe a u e,
72 and 71 °C, espec i ely. These phases a e highly eliable in geo-
he mome ical de e mina ions (Kha aka and Ma ine , 1989; Auqué,
1993; Pas o elli e al., 1999), since hey a e he modynamically well
cha ac e ised and hei sa u a ion s a es a e no affec ed by pH a ia-
ions du ing he ascen o he mal wa e s. On op o ha , hey a e in-
dependen o unce ain ies om he aluminium concen a ion o he
wa e s. Wi h espec o he es o he mine als, albi e p o ides a
empe a u e o 81 °C whils clinochlo e and dolomi e sligh ly highe
(p obably because hese las wo mine als can s ill be affec ed by some
unce ain ies due o he o de deg ee in he fi s case, and he a ia ions
in i s composi ion and c ys allini y in he second; Helgeson e al., 1978;
Paland i and Reed, 2001).
In summa y, he empe a u e ange deduced o he samples in he
low-sulpha e g oup is 101 ± 6 °C and 92 ± 20 °C o B1 and T1, e-
spec i ely, and he empe a u e ange p edic ed o sample T3 (as e-
p esen a i e o he high-sulpha e g oup) is somewha lowe ,
84 ± 13 °C.
5. Discussion
Combining he esul s ob ained wi h he a ious geo he mome ical
echniques, he empe a u e in he ese oi deduced om each g oup
is sligh ly diffe en .
Tempe a u e in he low sulpha e g oup is highe , abou 90 °C, and
al hough he esul s show a mo e widesp ead empe a u e ange han
o he high-sulpha e g oup, hey a e in a easonable unce ain y ange
( ± 20 °C; Fou nie , 1982 and Tole e al., 1993). The SiO
2
-qua z and K-
Mg geo he mome e s p edic sligh ly lowe empe a u es o sample B1
(68 and 66 °C, espec i ely), which could be due o seconda y p ocesses
(e.g. dissolu ion/p ecipi a ion) affec ing silica and magnesium con en s
(D'Amo e and A nó sson, 2000). Anhyd i e p o ides a high empe a u e
(113 °C) o sample T1 (wi h lowe sulpha e con en p obably due o
sulpha e educ ion), whils o sample B1 (wi h highe sulpha e con-
en ), anhyd i e eaches equilib ium also close o 90 °C. The e o e, i
he empe a u e indica ed by anhyd i e in sample T1 is no conside ed
ep esen a i e o he condi ions a dep h, he empe a u e ange de-
fined o he wa e s o he low sulpha e g oup in he ese oi would be
90 ± 20 °C.
The good ag eemen o he esul s ob ained wi h chemical geo-
he mome e s and geochemical modelling o he wa e s o he high-
sulpha e g oup sugges s ha he effec s o seconda y p ocesses a e no
impo an and a lowe empe a u e in he ese oi is indica ed,
82 ± 15 °C.
A ema kable finding is ha equilib ium wi h albi e and K- eldspa
in he ese oi is e idenced wi h he geo he mome ical modelling and
he chemical geo he mome e s. This is no a common si ua ion in low
empe a u e ca bona e-e apo i ic sys ems. This equilib ium has been
iden ified in some o he “complex”ca bona e-e apo i ic sys em in
which wa e s we e also in con ac wi h me asedimen a y ocks (Ma ini
e al., 2000), whils o he au ho s epo ed equilib ium wi h espec o
albi e bu no wi h espec o K- eldspa in simila geo he mal sys ems
(e.g. López-Chicano e al., 2001; Bosche i e al., 2005). The possible
explana ion o his equilib ium in a ca bona e-e apo i ic sys ems is
ha he aqui e o ma ions con ain a significan amoun o de i al
ma e ial, as indica ed by López-Chicano e al. (2001), allowing he
wa e s o each he equilib ium wi h phases like albi e, K- eldspa and
o he aluminosilica e phases, as also e idenced he e in he geo he -
mome ical modelling.
Despi e he composi ional diffe ences, he wa e s o bo h g oups
seem o ha e eached he equilib ium wi h he same mine al assem-
blage in he ese oi (calci e, dolomi e, qua z, anhyd i e, albi e, K-
eldspa and o he aluminosilica e phases) and a qui e simila em-
pe a u es. The e o e, he composi ional diffe ences be ween he g oups
mus be due o diffe en ex en o eac ion wi h he e apo i ic mine als
and/o o he pa icipa ion o addi ional eac ions along he flow pa hs
(as eflec ed in he Na/Cl and Ca/SO
4
a ios).
One o he main conclusions is ha he equilib ium o hese he mal
wa e s wi h espec o anhyd i e in he ese oi implies hey mus
acqui e he chlo ide-sodium/calcium-sulpha e composi ion a dep h
and no whils ascending o su ace, o he wise, his equilib ium would
no exis . Howe e , wi h he a ailable da a, i is no possible o ce -
ainly de e mine i he e apo i ic ocks in con ac wi h he wa e s in he
ese oi a e hose o he Keupe acies o hose o he Eocene-
Oligocene limi .
Al hough he deg ee o knowledge o his sys em is no enough o
quan i y he diffe en in ensi y in he wa e - ock in e ac ion p ocesses,
wo ele an issues can be discussed om hese esul s: 1) he influence
o hali e dissolu ion in he chemical cha ac e is ics o he wa e s; and 2)
he implica ions ha he chemical cha ac e o hese wa e s could ha e
o CO
2
s o age in he ese oi o ma ions.
5.1. The influence o hali e dissolu ion in he chemical cha ac e is ics o he
wa e s
The chemical cha ac e is ics o a wa e in equilib ium wi h a se o
mine als a e condi ioned by he empe a u e and he p essu e a which
his equilib ium is a ained; bu hey also depend on he concen a ion
o elemen s no con olled by mine al equilib ia such as chlo ide o
sulpha e, he mobile elemen s o Micha d (1987). The influence o
mobile elemen s, especially chlo ide, was ecognised long ago by
Helgeson (1970) and chlo ide has been conside ed as an independen
mas e a iable in de e mining he wa e composi ion in ock-buffe ed
sys ems (Hano , 2001). This impo ance has been e ified in a ious
ypes o geo he mal sys ems (Micha d, 1987; Micha d and Bas ide,
1988; Micha d e al., 1996; Chiodini e al., 1991), in low empe a u e
g oundwa e s in c ys alline sys ems (G imaud e al., 1990; T o ignon
e al., 1999) and in saline wa e s in sedimen a y basins (Hano , 1994,
1996, 2001).
The influence o he mobile elemen s a e especially impo an in
ca bona e-e apo i ic geo he mal sys ems because he wa e s a e likely
o be in con ac wi h hali e and i s dissolu ion will condi ion he
chemis y o he wa e s in equilib ium wi h a specific mine al se . This
influence has been es ed in he Tie mas he mal wa e s using he e-
ac ion-pa h capabili ies o PHREEQC (Pa khu s and Appelo, 2013).
The wa e composi ion in equilib ium wi h he iden ified se o
mine als was econs uc ed o ep esen he wa e in he ese oi be-
o e hali e dissolu ion s a s. To do ha , equimola amoun s o chlo ide
and sodium we e sub ac ed om he solu ion, down o Cl
−
= 0 mol/L,
while main aining he o he mine al equilib ia (albi e, K- eldspa ,
qua z, anhyd i e, calci e and dolomi e) a he ese oi empe a u e
(82 °C in he case o he high-sulpha e g oup and 95 °C in he case o he
low-sulpha e g oup). F om his heo e ical solu ion, he effec s o in-
c easing he concen a ions o chlo ide (and Na, h ough hali e dis-
solu ion) on he es o he chemical componen s con olled by he
imposed mine al equilib ia, can be discussed. The esul s ob ained o
all he samples a e simila and he e o e, only hose om T3 a e shown
in Fig. 7.
The heo e ical e olu ion o he concen a ion o he majo elemen s
in sample T3 is plo ed in Fig. 7a o d agains chlo ide unde he si-
ua ion o equilib ium wi h he es o he mine al se . The concen a-
ion o all hese majo elemen s (Na, K, Ca, Mg and sulpha e), al hough
con olled by ha equilib ium si ua ion a a cons an empe a u e, in-
c eases wi h sodium and chlo ide (excep o silica whose concen a-
ions is almos cons an , Fig. 7b).
Dissol ed sulpha e inc eases wi h chlo ide con en s (Fig. 7d) as
M. Blasco e al. &KHPLFDO*HRORJ ²
50
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
anhyd i e solubili y is enhanced by he inc ease o salini y and, he e-
o e, by hali e dissolu ion:
+→++
+− +
−
N
aCl CaSO Na Cl Ca SO
hal anh() 4( ) 24
2(1)
The inc ease in dissol ed sodium p omo es, in u n, he displace-
men o he albi e-K- eldspa equilib ium eac ion owa ds he le , in-
c easing he amoun o dissol ed po assium (Fig. 7c):
+↔ +
+−+
N
aAlSi O K KAlSi O Na
alb K eld38( ) 38( ) (2)
And he inc ease o dissol ed calcium p omo es he displacemen o
he calci e-dolomi e equilib ium eac ion owa ds he le , inc easing
he concen a ions o dissol ed magnesium (Fig. 7b):
+↔ +
+
+
2
CaCO Mg CaMg CO Ca()
calc dol3( ) 232( ) 2
(3)
The wo las panels in Fig. 7 (e and ) show he e olu ion o he
Fig. 7. Va ia ion o he concen a ion o majo elemen s (Na, Mg, Ca, Si, K and SO
4
, panels a o d) and o he a ios Ca/Mg and Na/K (as o al elemen concen a ions; panels e and ) in
sample T3 wi h he a ia ion o he dissol ed chlo ide in he wa e s a 82 °C and main aining he mine al equilib ia ha exis in he ese oi (albi e, K- eldspa , qua z, anhyd i e, calci e
and dolomi e). The g ey do s in all he plo s ep esen he chemical composi ion o sample T3.
M. Blasco e al. &KHPLFDO*HRORJ ²
51
4. Resul s
elemen al a ios Ca/Mg and Na/K. The co esponding ac i i y a ios
s ay cons an unde he specific empe a u e in he calcula ions as hey
a e con olled by he calci e-dolomi e and albi e-K- eldspa equilib ia,
espec i ely ( eac ions 2 and 3); howe e , he elemen al a ios show a
diffe en beha iou . The Na/K elemen al a io is also cons an and nea
he co esponding ac i i y a io (aNa
+
/aK
+
= 185) because hese
elemen s a e almos unaffec ed by complexing and he ee ion ac i i y
coefficien s mu ually cancel ou (Chiodini e al., 1991). The Ca/Mg
elemen al a io, howe e , is diffe en om he ac i i y a io (aCa
2+
/
aMg
2+
= 1.59) and sligh ly inc eases wi h Cl
−
concen a ions (Fig. 7e;
no e he e ical scale) as hese elemen s a e mo e and diffe en ially
affec ed by he effec o complexa ion and ac i i y coefficien calcula-
ions, which cause a de ia ion be ween he o al con en s and he ac-
i i ies (Chiodini e al., 1991).
These esul s indica e ha al hough he chemis y o he wa e s is
mainly con olled by mine al equilib ia a a gi en empe a u e, he
concen a ion o mobile elemen s a e, he e o e, an impo an a iable
in he con ol o he wa e composi ion. In he case s udied he e, he
mobile elemen pa icipa ing in he con ol o he sys em is chlo ide.
None heless, in o he sys ems in which sulpha e is no con olled by
equilib ium wi h anhyd i e o gypsum, he concen a ion o his com-
ponen may ha e an influence in he con olled elemen s o he wa e s.
5.2. Effec s o he chemical cha ac e is ics o he wa e in a u u e CO
2
s o age
Du ing he ALGECO2 p ojec (IGME, 2010), a a ou able ec onic
and sedimen a y s uc u e o CO
2
s o age was iden ified in he s udied
a ea ( he Ley e-Be dún s uc u e; Suá ez e al., 2014) in he Paleocene-
Eocene ca bona e ocks, which p obably is he aqui e o he Tie mas
he mal wa e s. I he ea u es o he wa e s in ha s uc u e a e simila
o hose deduced in he he mal wa e s, hen some impo an conclu-
sions abou some plausible p ocesses effec i e du ing he CO
2
injec ion
could be d awn. Fo example, in he icini y o he injec ion well, he
desicca ion o he saline wa e s in con ac wi h d y CO
2
could easily
induce he p ecipi a ion o ca bona es and sulpha es (Gaus, 2010;
Gimeno e al., 2011; Gu ié ez e al., 2011) as he wa e s a dep h a e in
equilib ium wi h calci e, dolomi e and anhyd i e. In he long e m,
injec ion o CO
2
will p omo e he acidifica ion o he saline g ound-
wa e s, which will lead o he dissolu ion o ca bona e mine als (calci e
and dolomi e). In his con ex , p ecipi a ion o sulpha es (gypsum o
anhyd i e) may be igge ed as he wa e s a e in equilib ium wi h an-
hyd i e (e.g. wi h high concen a ions o dissol ed sulpha e). A simila
si ua ion has been ound in he Spanish es si e o CO
2
geological
s o age, loca ed a Hon omin (Bu gos), in a limes one ese oi , also
wi h sulpha e- ich saline g oundwa e s in equilib ium wi h gypsum/
anhyd i e (Ga cia-Rios e al., 2014).
These p ocesses in ol ing ca bona e and sulpha e mine als a e ki-
ne ically as and hei effec s on he po osi y and pe meabili y o he
ese oi ocks o in he well en i onmen should be e alua ed in u u e
and mo e de ailed si e selec ion s udies.
6. Conclusions
Two hyd ogeochemical g oups o wa e s ha e been iden ified in
Tie mas sp ings: a g oup wi h TDS abou 7500 ppm and low sulpha e
con en s (low-sulpha e g oup) and o he wi h TDS close o 11,000 ppm
and highe sulpha e con en s (high-sulpha e g oup).
The empe a u e o he wa e s in he ese oi has been de e mined
by combining a ious chemical and iso opic geo he mome e s wi h
geo he mome ical modelling, and a eliable ange o empe a u es has
been es ablished. The empe a u es p edic ed o he wa e s a e also
sligh ly diffe en o each g oup; being 90 ± 20 °C o he low-sulpha e
g oup and sligh ly lowe 82 ± 15 °C o he high-sulpha e one.
I is ema kable he good esul s ob ained wi h some ca ionic geo-
he mome e s, such as he Na/K geo he mome e , in a geo he mal
sys em o low empe a u e and hos ed in ca bona e-e apo i ic ocks
like he s udied he e. This unusual si ua ion may be a ibu ed o he
p esence o de i al ocks (silica e mine als) in he ca bona e-e apo i ic
aqui e , which p o ides o equilib ium be ween albi e and K- eldspa
as ound in he geo he mome ical modelling.
The wo wa e g oups a e in equilib ium wi h he same mine al
assemblage in he ese oi (calci e, dolomi e, qua z, anhyd i e, albi e,
K- eldspa and o he aluminosilica e phases). Howe e , hey show
sligh diffe ences in he empe a u e a dep h and in he concen a ion
o some chemical elemen s, which sugges s ha each g oup o wa e s
could ep esen a diffe en flow pa h wi h diffe en ypes and/o in-
ensi ies o wa e - ock in e ac ion p ocesses.
The influence o hali e dissolu ion has also been e alua ed and he
esul s indica e ha apa om empe a u e, chlo ide con en s o he
he mal wa e s ha e a significan influence on he concen a ions o
SO
4
, Na, K, Ca and Mg measu ed in hese wa e s. As demons a ed in
he simula ions p esen ed he e, i hali e dissolu ion had occu ed
du ing he ascen o he he mal wa e s (wi hou he influence o he
mine al equilib ia a dep h) hei chemical cha ac e is ics would be
diffe en . These esul s, along wi h he ac ha anhyd i e is included in
he mine al assemblage in equilib ium in he ese oi , indica e ha he
wa e s should be in con ac wi h an e apo i ic acies in he ese oi
and no du ing hei ascen o su ace.
Finally, as a a ou able s uc u e o CO
2
s o age has ecen ly been
iden ified in he Paleocene-Eocene ca bona es, he p obable aqui e o
he Tie mas geo he mal sys em, he g oundwa e s s udied he e could be
used as analogues o he wa e s in ha si e. The e o e, he esul s o his
s udy a e use ul o unde s anding he main p ocesses ela ed o he
CO
2
injec ion and mixing wi h his ype o wa e . Nea he injec ion
wells, he wa e s will desicca e causing he p ecipi a ion o calci e,
dolomi e and anhyd i e, since he wa e s a e in equilib ium wi h e-
spec o hese phases in he ese oi , affec ing he po osi y and pe -
meabili y o he ocks. And in he long e m, he wa e will acidi y
leading o he ca bona e dissolu ion and sulpha e p ecipi a ion.
Acknowledgemen s
M. Blasco is wo king in his s udy hanks o a schola ship om he
Minis y o Educa ion, Cul u e and Spo s o Spain, o he T aining o
Uni e si y Teache s ( e . FPU14/01523). This s udy o ms pa o he
ac i i ies o he Geochemical Modelling G oup (Uni e si y o Za agoza;
A agón Go e nmen ). The commen s o D . M.H. Reed and an anon-
ymous e iewe ha e con ibu ed o imp o e he wo k and a e g a e-
ully app ecia ed.
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modelling o Äspö g oundwa e s: a sensi i i y s udy o he modynamic equilib ium
cons an s. Appl. Geochem. 14, 907–916.
T uesdell, A.H., 1974. Oxygen iso ope ac i i ies and concen a ions in aqueous sal so-
lu ions a ele a ed empe a u es: consequences o iso ope geochemis y. Ea h
Plane . Sci. Le . 23, 387–396.
T uesdell, A.H., 1976. Geochemical echniques in explo a ion. Summa y o sec ion III. In:
P oceedings o he Second Uni ed Na ions Symposium on he De elopmen and Use
o Geo he mal Resou ces. San F ancisco, Cali o nia, pp. iii-xxix.
U illa, R., Pie e, C., O í, F., Rosell, L., Inglés, M., Pueyo, J.J., 1987. Es udio Iso ópico de
los Sul a os en Fo maciones E apo í icas Mesozoicas y Te cia ias Con inen ales. II
Cong eso de Geoquímica de España, So ia, pp. 91–94.
Wang, J., Jin, M., Jia, B., Kang, F., 2015. Hyd ochemical cha ac e is ics and geo he -
mome y applica ions o he mal g oundwa e in no he n Jinan, Shandong, China.
Geo he mics 57, 185–195.
Zeebe, R.E., 2010. A new alue o he s able oxygen iso ope ac iona ion be ween dis-
sol ed sul a e ion and wa e . Geochim. Cosmochim. Ac a 74, 818–828.
Zheng, Y.F., 1999. Oxygen iso ope ac iona ion in ca bona e and sul a e mine als.
Geochem. J. 33, 109–126.
M. Blasco e al. &KHPLFDO*HRORJ ²
54
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
4.2 Pape 2
Low empe a u e geo he mal sys ems in ca bona e-e apo i ic ocks:
Mine al equilib ia assump ions and geo he mome ical calcula ions.
Insigh s om he A nedillo he mal wa e s (Spain)
Mónica Blasco, Ma ía J. Gimeno, Luis F. Auqué
Science o The To al En i onmen 615, 526-539 (2018)
Impac Fac o (2017): 4.61
Qua ile and Ca ego y (2017): Q1 (27/241), En i onmen al Sciences
DOI: 10.1016/j.sci o en .2017.09.269
Sen : 22 Augus 2017
Accep ed: 25 Sep embe 2017
A ailable online: 5 Oc obe 2017
Final publica ion: 15 Feb ua y 2018
55
4. Resul s
Low empe a u e geo he mal sys ems in ca bona e-e apo i ic ocks:
Mine al equilib ia assump ions and geo he mome ical calcula ions.
Insigh s om he A nedillo he mal wa e s (Spain)
Mónica Blasco ⁎, Ma ía J. Gimeno, Luis F. Auqué
Geochemical Modelling G oup, Pe ology and Geochemis y A ea, Ea h Sciences Depa men , Uni e si y o Za agoza, Spain C/ Ped o Ce buna 12, 50009 Za agoza, Spain
HIGHLIGHTS
•Mine al equilib ia in low empe a u e
geo he mal sys ems a e discussed.
•Consequences on some geo he mome ical
me hods a e add essed.
•The o de deg ee o he dolomi e p esen in
he aqui e is calcula ed.
•A low empe a u e geo he mal sys em
hos ed in ca bona e ocks is used as an
example.
GRAPHICAL ABSTRACT
abs ac a icle in o
A icle his o y:
Recei ed 22 Augus 2017
Recei ed in e ised o m 24 Sep embe 2017
Accep ed 25 Sep embe 2017
A ailable online xxxx
Edi o : D. Ba celo
Geo he mome ical calcula ions in low-medium empe a u e geo he mal sys ems hos ed in ca bona e-
e apo i ic ocks a e complica ed because 1) some o he classical chemical geo he mome e s a e, usually, inad-
equa e (since hey we e de eloped o highe empe a u e sys ems wi h di e en mine al-wa e equilib ia a
dep h) and 2) he chemical geo he mome e s calib a ed o hese sys ems (based on he Ca and Mg o SO
4
and F con en s) a e no ee o p oblems ei he . The case s udy o he A nedillo he mal sys em, a ca bona e-
e apo i ic sys em o low empe a u e, will be used o deal wi h hese p oblems h ough he combina ion o se -
e al geo he mome ical echniques (chemical and iso opic geo he mome e s and geochemical modelling).
The ese oi empe a u e o he A nedillo geo he mal sys em has been es ablished o be in he ange o 87 ± 13 °C
being he wa e s in equilib ium wi h espec o calci e, dolomi e, anhyd i e, qua z, albi e, K- eldspa and o he alu-
minosilica es. Anhyd i e and qua z equilib ia a e highly eliable o s ablish he ese oi empe a u e. Addi ionally,
he anhyd i e equilib ium explains he cohe en esul s ob ained wi h he δ
18
O anhyd i e –wa e geo he mome e .
The equilib ium wi h espec o eldspa s and o he aluminosilica es is unusual in ca bona e-e apo i ic sys ems and
i is p obably ela ed o he p esence o de i al ma e ial in he aqui e .
The iden ifica ion o he expec ed equilib ia wi h calci e and dolomi e p esen s an in e es ing p oblem associa ed
o dolomi e. Va iable o de deg ees o dolomi e can be ound in na u al sys ems and his ac a ec s he associ-
a ed equilib ium empe a u e in he geo he mome ical modelling and also he esul s om he Ca-Mg
geo he mome e . To a oid his unce ain y, he o de deg ee o he dolomi e p esen in he A nedillo ese oi
has been de e mined and he esul s indica e 18.4% o o de ed dolomi e and 81.6% o diso de ed dolomi e.
Keywo ds:
Low empe a u e geo he mal sys em
Geochemical modelling
Geo he mome y
Mine al equilib ia
Dolomi e o de /diso de deg ee
Science o he To al En i onmen 615 (2018) 526–539
⁎Co esponding au ho .
E-mail add ess: monicabc@uniza .es (M. Blasco).
h ps://doi.o g/10.1016/j.sci o en .2017.09.269
0048-9697/© 2017 Else ie B.V. All igh s ese ed.
Con en s lis s a ailable a ScienceDi ec
Science o he To al En i onmen
jou nal homepage: www.else ie .com/loca e/sci o en
57
4. Resul s
O e all, he esul s sugges ha his mul i- echnique app oach is e y use ul o sol e some o he p oblems asso-
cia ed o he s udy o ca bona e-e apo i ic geo he mal sys ems.
© 2017 Else ie B.V. All igh s ese ed.
1. In oduc ion
The s udy o he chemical and iso opic composi ion o he mal wa-
e s allows iden i ying he wa e - ock in e ac ion p ocesses in ol ed
in hei e olu ion, de e mining he possible seconda y p ocesses ha
could a ec hem du ing hei ascen o su ace (e.g. mine al
eequilib ium o mixing) and es ablishing he ese oi empe a u e
by geo he mome ical me hods. This cha ac e isa ion is he fi s s ep
o e alua e he geo he mal po en ial o an a ea (e.g. D'Amo e and
A nó sson, 2000). Nowadays, he use o geo he mal ene gy is di e si y-
ingand he echnical ad ances make possible o ob ain elec ical ene gy
om wa e s o lowe empe a u e. Addi ionally, one o he possibili ies
conside ed o he CO
2
geological s o age is he use o deep saline aqui-
e s, usually ho , hos ed in sedimen a y ocks (e.g. Auqué e al., 2009,
and e e ences he ein). These deep s o ages a e inaccessible o hei
s udy in an ini ial s age and, he e o e, he in o ma ion ob ained om
low o medium empe a u e he mal sys ems wi h simila hyd ogeo-
chemical cha ac e is ics becomes a sui able and e y con enien sou ce
o in o ma ion.
The empe a u e in he deep ese oi s can be de e mined by se e -
al chemical and iso opic geo he mome e s and by geo he mome ical
modelling. Howe e , hese echniques p esen some p oblems in he
case o ca bona e-e apo i ic aqui e s. The classical ca ionic
geo he mome e s (based on he equilib ium wi h aluminosilica e
phases) a e use ul in sys ems wi h high empe a u e o wi h hos
ocks like g ani es o basal s inwhich hewa e s ha e eached he equi-
lib ium wi h a ious aluminosilica es such as albi e o K- eldspa (e.g.
A nò sson e al., 1983; As a e al., 2012; Auqué e al., 1997; Buil e al.,
2006; Choi e al., 2005; D'Amo e e al., 1987; Fouillac and Micha d,
1981; Fou nie , 1981, 1977; Giggenbach e al., 1983; Giggenbach,
1988; Kha aka and Ma ine , 1989; Ma ine e al., 2006; Mu lu and
Güleç, 1998; S e ánsson and A nó sson, 2000, among much o he s).
These equilib ia a e no likely o ha e been a ained in ca bona e-
e apo i ic sys ems and hey may p o ide e oneous esul s (Chiodini
e al., 1995; Ka imi and Moo e, 2008; Le e e al., 2002; López-Chicano
e al., 2001; Sonney and Vua az, 2010) al hough,in some cases, hesilica
and some ca ionic geo he mome e s ha e p o ided good esul s (e.g.
Apolla o e al., 2012; Blasco e al., 2017; Fe nández e al., 1988;
Gökgöz and Ta kan, 2006; Micha d and Bas ide, 1988; Mohammadi
e al., 2010; Pas o elli e al., 1999; Wang e al., 2015).
The mo e sui able geo he mome e s a e, ob iously, hose de eloped
o his kind o sys ems, ha is, he Ca-Mg and SO
4
-F geo he mome e s,
ini ially p oposed by Ma ini e al. (1986) and e iewedbyChiodini e al.
(1995) a e wa ds. Howe e , e en hese migh ha e p oblems since he
o me can be a ec ed by he unce ain ies in he he modynamic p op-
e ies o dolomi e (due o non-s oichiome y o o de /diso de deg ee;
Chiodini e al., 1995; F ondini, 2008; Helgeson e al., 1978; Ma ini,
2006; Paland i and Reed, 2001) and he la e will only be sui able i
he wa e s a e in equilib ium wi h anhyd i e (o gypsum) and fluo i e
(Chiodini e al., 1995) which is no always he case.
The iso opic geo he mome y is ano he possible echnique al-
hough i may also be p oblema ic. Fo example, he δ
18
O exchange be-
ween CO
2
and H
2
O is easily modified du ing he ascen o he wa e s o
su ace since he kine ics o he exchange eac ion is as and he iso o-
pic eequilib ium akes place e en a low empe a u es (D'Amo e and
A nó sson, 2000). O he common iso opic geo he mome e is he δ
18
O
SO
4
-H
2
O, bu adi ionally i s calib a ions a e based in he HSO
4
-H
2
Oex-
change, and he HSO
4
is no p esen in neu al o basic wa e s
(Bosche i, 2013). Some new calib a ions ha e been ecen ly p oposed
ying o sol e his p oblem, al hough hey a e no widely used ye .
Finally, he geo he mome ical modelling (o mul icomponen sol-
u e geo he mome y; e.g. Spyche e al., 2014) is e y use ul since i al-
lows de e mining he ese oi empe a u e by s udying he sa u a ion
s a es o a as numbe o mine als, p o iding impo an in o ma ion
abou he p obable mine al se he wa e s a e in equilib ium wi h in
he ese oi . Addi ionally i allows e alua ing he seconda y p ocesses
(e.g. mixing, degasifica ion o mine al eequilib ium) ha could a ec
he wa e s du ing hei ascen o su ace (As a e al., 2010; Auqué
e al., 2009; Micha d and Fouillac, 1980; Micha d and Roekens, 1983;
Micha d e al., 1986a; Paland i and Reed, 2001; Pang and Reed, 1998;
Reed and Spyche , 1984; Tole e al., 1993). Ne e heless, his echnique
also shows some p oblems associa ed o he unce ain ies in he mine -
al solubili y o some mine als (Paland i and Reed, 2001).
The s udy o he low-medium empe a u e geo he mal sys em o
A nedillo will be used 1) o es all he men ioned geo he mome ical
echniques, in o de o imp o e hei knowledge o hei use in u he
s udies; and 2) o cha ac e ise hyd ogeochemically his na u al he mal
sys em o a u u e exploi a ion o i s geo he mal po en ial.
2. Geological and hyd ogeological se ing
The A nedillo he mal wa e s eme ge nea he Cidacos Ri e , in he
A nedillo illage (La Rioja, Spain). Geologically, hey a e loca ed in he
NW o he Ibe ian Chain, in he con ac be ween he eas e n Came os
Range and he e ia y Eb o Basin (Fig. 1;Coloma e al., 1997; Sánchez
and Coloma, 1998).
The Came os Range, cons i u ed mainly by Mesozoic o ma ions, is
bounded by wo con inen al basins and wo Palaeozoic elie s: he
Eb o and Due o basins in he no h and he sou h, espec i ely; and
he Demanda and Moncayo Ranges a he eas and wes (Gil e al.,
2002). The T iassic is ep esen ed by Bun sands ein (sands ones, sil -
s ones and b eccias su ounding he Demanda Range), Muschelkalk
(mainly dolos ones, al hough he ou c ops in he a ea a e sca ce) and
Keupe acies (gypsum/anhyd i e, ma ls and clays) which is hede ach-
men le el o he e ia y h us ing (Coloma, 1998; Gil e al., 2002).
The ma ine Ju assic o ma ions (up o Kimme idgian, Uppe Ju as-
sic) a e he ones ound in he es o he Ibe ian Chain (Coloma, 1998;
Gil e al., 2002; Goy e al., 1976), consis ingo dolos onesandlimes ones
wi h some in e cala ions o ma ls: Imon (dolos ones), Co es de Tajuña
(dolomi ic b eccias wi h anhyd i e), Cue as Lab adas (limes ones and
dolos ones), Ce o del Pez (ma ls), Ba ahona (bioclas ic limes ones),
Tu miel (ma ls and limes ones), Chel a (limes ones), Aldealpozo
(blacklimes ones)andTo ecilla(limes oneswi hco als). These o ma-
ions a e mainly cons i u ed by ca bona es bu some e igenous de-
posi s a e also p esen (Goy e al., 1976). These T iassic and ma ine
Ju assic o ma ions cons i u e he p e- i sequence.
A i ing p ocess ook place a he end o he Ju assic and du ing he
C e aceous, esul ing in he o ma ion o he Came os Basin. The co e-
sponding o ma ions a e known as he syn- i sequence, which is con-
s i u ed by con inen al sedimen s om he Uppe Ju assic (Ti honian)
o he Lowe C e aceous (Albian) (Coloma, 1998; Gil e al., 2002; Mas
e al., 1993). These con inen alsedimen s ha e been adi ionally di id-
ed in o fi e g oups (Tische , 1965): Te a, Oncala, U bión (flu ial sedi-
men s consis ing o lu i es and sands ones), Enciso and Oli án
(lacus ine sedimen s cons i u ed by limes ones, ma ls and limoli es).
TheUppe C e aceouscons i u es he pos - i sequenceandconsis s
o ca bona es om he U gon Facies, he U illas Sands ones and he ca -
bona e sedimen a ion a he end o his pe iod (Gil e al., 2002).
Du ing he Te ia y he ec onic in e sion esul edin he elie o he
Came os Range and he o ma ion o he e ia y basins, which we e
527M. Blasco e al. / Science o he To al En i onmen 615 (2018) 526–539
58
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
filled wi h de i al ma e ial mainly om he Paleogene and
Neogene. Comp essi e s uc u es we e gene a ed wi h E-W o NW-SE
di ec ion, being he Came os h us one o he mos impo an , which
makes he Mesozoic se ies h us o e he e ia y o ma ions o he
Eb o Basin (Coloma, 1998; Gil e al., 2002). Finally, he Qua e na y is
cons i u ed by allu ial and collu ial deposi s due o he glacis – e ace
sys ems de eloped om he Came os Range o he Eb o Ri e (Coloma,
1998).
The ca bona e o ma ions o he p e- i sequence (Fig. 2) cons i u e
he main aqui e in his a ea. These o ma ions a e di ided in h ee
g oups, wo pe meable ones sepa a ed by o he less pe meable:
1) Imón, Co es de Tajuña and Cue as Lab adas Fo ma ions ( he fi s
pe meable g oup); 2) Ce o del Pez, Ba ahona and Tu miel Fo ma ions
( he in e media e impe meable g oup); and 3) Chel a, Aldealpozo
and To ecilla Fo ma ions ( he second pe meable g oup). Due o he
g ea ac u a ion a ec ing hem, hese o ma ions a e in e connec ed
Fig. 1. Geological map o he A nedillo a ea and loca ion o he geo he mal sp ings (modified om Gil e al., 2002). A–B indica es he loca ion o he c oss sec ion shown in Fig. 2.
Fig. 2. SW-NE c oss sec ion (A–B, in Fig. 1) showing he gene al ec onic s uc u e o he A nedillo geo he mal sys em modified o m ALGECO2 P ojec ; IGME, 2010). The g ey a ows
ep esen he flow di ec ion.
528 M. Blasco e al. / Science o he To al En i onmen 615 (2018) 526–539
59
4. Resul s
discussed along his wo k, allow de e mining ha he empe a u e
ange o he A nedillo he mal wa e s in he ese oi is 87 ± 13 °C.
Mo eo e , he good con e gence o he sa u a ion index o he consid-
e ed mine al phases in he line o SI = 0 (Fig. 7) indica es ha hese
he mal wa e s ha e no been a ec ed by a significan mixing p ocess.
A mixing p ocess would modi y he empe a u e esul s since he
con e gence poin would be shi ed o unde sa u a ed alues (Pang
and Reed, 1998).
The dep h o he ese oi o hese he mal wa e s can be app oxi-
ma ed using he empe a u e es ima ed o hem. Assuming ha he
he mal g adien in he Came os Range is 18 °C/km (as de e mined in
he Cas il ío oil well; Fig. 1;Fe nández e al., 1998), and he mean
Fig. 6. E olu ion wi h empe a u e o he sa u a ion indices o he mine als supposed o be in equilib ium wi h he wa e samples AR1 and AR2 in he ese oi . This calcula ion has been
pe o med by using he LLNL he modynamic da abase and p io o he econs uc ion o he ese oi cha ac e is ics. The dolomi e used is he diso de ed dolomi e and he albi e is he
low empe a u e albi e.
Fig. 7. E olu ion wi h empe a u e o he sa u a ion indices o he mine als supposed o be in equilib ium wi h he wa e samples AR1 and AR2 a e he econs uc ion o he ese oi
cha ac e is ics by adding CO
2
. The esul s ob ained wi h wo di e en he modynamic da abases, LLNL and WATEQ4F, a e shown. In he case o heLLNL da abase he diso de ed dolomi e
and low empe a u e albi e ha e been used. In he case o he WATEQ4F he he modynamic da a o he pa ially o de ed dolomi e om Hyeong and Capuano (2001) and albi e, K-
eldspa and py ophylli e om Micha d (1983) ha e been added o he da abase.
535M. Blasco e al. / Science o he To al En i onmen 615 (2018) 526–539
66
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
su ace empe a u e in Spain is 16 °C (Chamo o e al., 2014), he ese -
oi should be loca ed a abou 4000 m dep h, coinciden wi h hedep h
o he Ju assic ocks ha cons i u e he aqui e o hese wa e s (Fig. 2).
O e all, his esul ein o ces he eliabili y o he geo he mome ical
esul s.
Finally, as men ioned a he beginning o his discussion, some com-
men sa eneeded wi h espec o hep oblemsassocia ed o hecalci e-
dolomi e equilib ium. This equilib ium is expec ed o be a ained by
he wa e s a dep h in sys ems hos ed in ca bona e ocks (like he one
s udied he e) due o he high empe a u es and he long esidence
ime. Howe e , his equilib ium is no always easy o e i y in
geo he mome ical modelling due o he ou gassing o he wa e s and
he subsequen modifica ion o he sa u a ion s a es o ca bona e
phases (as shown in Sec ion 4.3.3). An addi ional complica ion is ha ,
while he he modynamic da a o calci e a e qui e well defined, he do-
lomi e solubili y is condi ioned by i s deg ee o o de which in he end
a ec s he equilib ium empe a u e o his phase (e.g. F ondini, 2008;
Hyeong and Capuano, 2001; Vespasiano e al., 2014).
The esul s ound o he A nedillo sys em indica e ha he empe -
a u e ob ained o he ully diso de ed dolomi e used in he LLNL da a-
base is oo high wi h espec o he one ob ained wi h calci e (Table 6)
while he pa ially-o de ed dolomi e p oposed by Hyeong and
Capuano (2001) and in oduced in he WATEQ4F da abase (calcula ed
o be 11% o o de ed dolomi e, see below) gi es a mo e simila empe -
a u e al hough s ill a ew deg ees highe (Table 6). The influence o he
o de deg ee o dolomi e in geo he mome ical calcula ions is e iden
and he esul s sugges ha he dolomi e in he A nedillo ese oi
should be o highe o de deg ee han he dolomi es used in he
modelling.
To delimi his issue some addi ional calcula ions on he o de o he
dolomi e ha e been done as p oposed by Vespasiano e al. (2014) o
aqui e s in dolomi ic ocks a ec ed by me amo phism. In his case, as-
suming ha dolomi e should be in equilib ium wi h calci e a 87 °C in
heA nedillo aqui e , he co espondingdeg ee o o de has been de e -
mined. F om he esul s ob ained in he specia ion –solubili y calcula-
ions, a logK = 1.1237 ( o he dissolu ion eac ion: CaMg(CO
3
)
2
+2H
+
=Ca
2+
+Mg
2+
+2HCO
3
) has beencalcula ed o hedolomi e
a 87 °C. This logK yields he Gibbs ee ene gy o he eac ion (Eq. (1)).
Wi h ha alue and wi h he Gibbs ee ene gy o o ma ion o he spe-
cies (Ca
2+
,Mg
2+
and HCO
3
-
)
1
, he Gibbs ee ene gy o o ma ion (ΔG
)
o he dolomi e a 87 °C can be ob ained (Eq. (2)):
logK ¼−ΔGR
2:303RT ð1Þ
ΔGR¼XΔG p oduc s−XΔG eac an s ð2Þ
whe e R is he cons an o he ideal gases and T he empe a u e in K.
The alue ob ained is ΔG
,A n
=−519.06 Kcal. Knowing he ΔG
alue
o he o de ed dolomi e (ΔG
,o d
=−520.298 Kcal)
1
and he diso -
de ed dolomi e (ΔG
,dis
=−518.362 Kcal)
1
(all a 87 °C), he p opo ion
o o de and diso de dolomi e p esen in he dolomi e om A nedillo
can be de e mined using he ollowing equa ion (Ande son and
C e a , 1993):
ΔG ;A n ¼Xo d ΔG ;o d þXdis ΔG ;dis
þRT Xo d ln Xo d þXdis ln Xdis
ðÞð3Þ
whe e X
o d
is he mola a io o heo de ed dolomi e and X
dis
he mola
a io o he diso de ed dolomi e.
The esul is ha he dolomi e p esen in he aqui e o he A nedillo
he malsys em is cons i u ed by 18.4% o o de ed dolomi eand81.6% o
diso de ed dolomi e, which is a pa ially-diso de ed dolomi e bu wi h
a highe o de deg ee han he dolomi e ob ained by Hyeong and
Capuano (2001). This is consis en wi h he in e p e a ion done om
he esul s o he geo he mome ical modelling.
Goinga s ep o wa d, om he alues o o de and diso de ob ained
and using he Eq. (3), he ΔG
,A n
, and he e o e he logK, a di e en
empe a u es can also be calcula ed (Eqs. (2) and (1)). The esul s a
s anda d condi ions (25 °C) o he logK o he A nedillo dolomi e is
3.55 o he dissolu ion eac ion CaMg(CO
3
)
2
+2H
+
=Ca
2+
+Mg
2+
+2HCO
3
. The co esponding alues o he o de ed and diso de ed do-
lomi e a e 4.01 and 2.61, espec i ely.
Fig. 8 shows he calci e/dolomi e equilib ia in a log (aCa
2+
/aMg
2+
)
s empe a u e plo o di e en dolomi es: he ully o de ed and
ully diso de ed dolomi es, he A nedillo dolomi e and some o he
pa ially-o de ed dolomi es om he li e a u e deduced om na u al
sys emsas he e a e no expe imen al da a o dolomi es o in e media e
o de . The ully o de ed and ullydiso de ed dolomi es ha e been aken
om he LLNL he modynamic da abase. Da a om na u al g oundwa-
e sys ems om s udies whe e calci e-dolomi e equilib ium has been
e ified in a wide ange o empe a u es ha e also been included.
Hyeong and Capuano (2001) s udied he equilib ium si ua ion be ween
calci e and dolomi e in he g oundwa e s o he Oligocene F io Fo ma-
ion in he Texas Gul Coas , be ween 40 and 150 °C, and he o de has
been calcula ed o be 11%. Busby e al. (1991) also s udied he calci e-
dolomi e equilib ium in he g oundwa e s o he Ca boni e ous Madi-
son Aqui e , be ween 10 and 100 °C, and he o de has been calcula ed
o be 23.5%. Finally, da a om Vespasiano e al. (2014) co esponding
o a dolomi e in he T iassic ocks a ec ed by a low-g ade me amo -
phism in Calab ia (I aly) ha e also been included (o de o 22%).
The log (aCa
2+
/aMg
2+
) o he di e en dolomi es a di e en em-
pe a u es has been calcula ed om he logK a hose empe a u es and
using he Eq. (4) ( he calci e da a was aken om he LLNL he mody-
namic da abase).
log aCa2þ
aMg2þ
!
¼2logKcalci e−logKdolomi e ð4Þ
The compa ison shown in Fig. 8 e idences he g ea impo ance o
he o de /diso de deg ee o dolomi e in he geo he mome ical de e -
mina ionsas small changes can yield o ep esen a i e di e ences in he
equilib ium empe a u e o his phase.
The p oblem s ands on he di ficul ies o know he o de deg ee o
he dolomi e p esen in a specific aqui e since in g oundwa e sys ems
hos ed in sedimen a y ocks calci e-dolomi e equilib ium usually in-
ol e Ca- o Fe- ich pa ially o de ed dolomi es (Ca pen e , 1980;
Helgeson e al., 1978; Hyeong and Capuano, 2001; Land, 1985; Reede ,
2000) ha emain wi h a iable diso de deg ee o hund eds o mil-
lions o yea s o bu ial diagenesis (Kaczma ek and Duncan, 2011;
Table 6
Tempe a u es (°C) a which he mine al phases conside ed each equilib ium in he sam-
ples AR1 and AR2 and calcula ed wi h he LLNLand WATEQ4F da abases. In he case o he
LLNL da abase, he dolomi e and albi e conside ed a e he ully diso de ed dolomi e and
he low empe a u e albi e, espec i ely. In he case o he WATEQ4F, he he modynamic
da a co espond o he dolomi e deduced by Hyeong and Capuano (2001) and he albi e,
K- eldspa and py ophylli e ha e been aken om Micha d (1983).
Mine al phase AR1 AR2
LLNL WATEQ4F LLNL WATEQ4F
Calci e 87 87 87 87
Dolomi e 106 92 107 92
Qua z 90 97 88 94
Anhyd i e 81 88 80 87
Albi e 79 85 94 99
K- eldspa 80 78 93 91
Py ophylli e 91 90 106 106
1
The alues o ΔG
o he di e en species needed o calcula e he ΔG
o he dolomi e
in he A nedillo sys em and he alues o ΔG
,o d
and ΔG
,dis
a he empe a u e o in e es ,
ha e been ob ained om h p://geopig3.la.asu.edu:8080/GEOPIG/pigop 1.h ml
536 M. Blasco e al. / Science o he To al En i onmen 615 (2018) 526–539
67
4. Resul s
Lumsden and Chimahusky, 1980; Spe be e al., 1984). The e o e his
ype o calcula ions is no only use ul in dolomi ic aqui e s a ec ed by
me amo phism (as applied by Vespasiano e al., 2014) bu also in sedi-
men a y/diagene ic ca bona e o ca bona e-e apo i ic aqui e s.
In summa y, wi h espec o hecalci e-dolomi e equilib ium unce -
ain ies, i is impo an o keep in mind ha al hough he conside a ion
o he ully diso de ed dolomi e will p o ide, a leas , a maximum em-
pe a u e o hewa e sin hedeep ese oi , a ca e ulapp oach,like he
one done in his wo k, is needed o in e p e and imp o e he esul s o
he geo he mome ical calcula ions based on he calci e-dolomi e
equilib ia.
6. Conclusion
In his s udy a mul i- echnique app oach o de e mine he empe a-
u e in he ese oi o ca bona e-e apo i ic and low empe a u e
he malsys ems is applied o as udy casein LaRioja (Spain). This me h-
odology and i s applica ion o a specific case has esul ed o be e y
help ul o deal wi h some o he p oblems ha he geo he mome ical
calcula ions p esen in his kind o sys ems.
The in eg a ion o he esul s ob ained wi h chemical
geo he mome e s, iso opic geo he mome e s and geochemical model-
ling has gi en a ese oi empe a u e o he A nedillo he mal sys em
o 87 ± 13 °C. A his empe a u e he wa e s a e in equilib ium wi h e-
spec o calci e, dolomi e, anhyd i e, qua z, albi e, K- eldspa and o he
aluminosilica es. Conside ing he geo he mal g adien in he s udied
a ea, he app oxima e dep h o he ese oi seems o be a abou
4000m dep h,whichiscoinciden wi h hedep ho hesugges edaqui-
e o ma ions.
I is also ema kable he cohe en esul s ob ained wi h he Na-K
geo he mome e since i is conside ed inadequa e o his ype o sys-
ems. Howe e he p esence o a significan amoun o de i al ma e ial
in he ca bona e aqui e seems o be enough o allow he wa e eaching
he equilib ium wi h espec he phases in which i is based (albi e and
K- eldspa ).
Finally, he e ec s o he he modynamic unce ain ies ela ed o do-
lomi e ha e been e alua ed and he o de deg ee o he dolomi e p es-
en in he ese oi o he A nedillo he mal wa e s has been
de e mined, esul ing in 18.4% o o de ed dolomi e and 81.6% o diso -
de ed dolomi e, wi h a log K = 3.55 a s anda d condi ions ( o he e-
ac ion CaMg(CO
3
)
2
+2H
+
=Ca
2+
+Mg
2+
+2HCO
3
).
The need o his kind o calcula ions and o he in eg a ion o all he
geo he mome ical echniques is p oposed he e as a me hodological
p ocedu e o be used in simila kind o s udies.
Acknowledgemen
M. Blasco has wo ked in his s udy hanks o a schola ship om he
Minis y o Educa ion, Cul u e and Spo s o Spain, o he T aining o
Uni e si y Teache s ( e . FPU14/01523). This s udy o ms pa o heac-
i i ies o he Geochemical Modelling G oup (Uni e si y o Za agoza;
A agón Go e nmen ).
We hank he s a o heA nedillo spa o allowing us o sample and
hei help du ing he sampling campaign. We a e also g a e ul o
Gio anni Vespasiano o his guidelines in he he modynamic calcula-
ions. The echnical assis ance o En ique Oli e , om he Ea h Science
Depa men o he Uni e si y o Za agoza, is also hank ul. The com-
men s o wo anonymous e iewe s a e g a e ully acknowledged.
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70
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
4.3 Pape 3
Geochemical e olu ion o he mal wa e s in ca bona e – e apo i ic
sys ems: he igge ing e ec o hali e dissolu ion in he
dedolomi isa ion and albi isa ion p ocesses
Mónica Blasco, Luis F. Auqué, Ma ía J. Gimeno
Jou nal o Hyd ology 570, 623-636 (2019)
Impac Fac o (2017): 3.727
Qua ile and Ca ego y (2017): Q1 (7/128), Enginee ing Ci il; Wa e Resou ces;Q1
(27/189),Geosciences.
DOI: 10.1016/j.jhyd ol.2019.01.013
Sen : 30 Augus 2018
Accep ed: 12 Janua y 2019
A ailable online: 16 Janua y 2019
Final publica ion: Ma ch 2019
71
4. Resul s
Con en s lis s a ailable a ScienceDi ec
Jou nal o Hyd ology
jou nal homepage: www.else ie .com/loca e/jhyd ol
Resea ch pape s
Geochemical e olu ion o he mal wa e s in ca bona e –e apo i ic sys ems:
The igge ing effec o hali e dissolu ion in he dedolomi isa ion and
albi isa ion p ocesses
Mónica Blasco
⁎
, Luis F. Auqué, Ma ía J. Gimeno
Geochemical Modelling G oup, Pe ology and Geochemis y A ea, Ea h Sciences Depa men , Uni e si y o Za agoza, Spain C/ Ped o Ce buna 12, 50009 Za agoza, Spain
ARTICLE INFO
This manusc ip was handled by Huaming Guo,
Edi o -in-Chie , wi h he assis ance o P osun
Bha acha ya, Associa e Edi o
Keywo ds:
Geo he mal sys em
Geo he mome y
Geochemical modelling
Dedolomi isa ion
Albi isa ion
Hali e dissolu ion igge ing effec s
ABSTRACT
The Fi e o and A nedillo geo he mal sys ems a e loca ed in he NW pa o he Ibe ian Range (No he n Spain).
The geo he mal ese oi is hos ed in he Lowe Ju assic ca bona es, in con ac wi h he e apo i ic Keupe
Facies. The mal wa e s a e o chlo ide-sodium ype wi h discha ge empe a u e o abou 45 °C and nea neu al
pH. The A nedillo wa e s a e mo e saline wi h highe Na, Cl and sulpha e con en s, bu lowe Ca and Mg han he
Fi e o wa e s. All wa e s ha e a ained mine al equilib ium a dep h wi h calci e, dolomi e, anhyd i e, qua z,
albi e, K- eldspa and o he aluminosilica es, excep o he Fi e o wa e s, which ha e no eached he equili-
b ium wi h he aluminosilica es. The calcula ed ese oi empe a u e is 81 ± 11 °C in Fi e o and 87 ± 13 °C in
A nedillo. In o de o iden i y he easons o he diffe ences ound be ween he wo sys ems some in e se and
o wa d geochemical calcula ions we e pe o med and he main wa e - ock in e ac ion p ocesses esponsible o
he chemical e olu ion o hese wa e s ha e been e alua ed.
Hali e dissolu ion has been ound o be he igge ing ac o o he wo mos impo an geochemical p o-
cesses in he sys em: a) albi isa ion p ocess, due o he common ion effec (Na); and b) dedolomi isa ion p ocess,
associa ed wi h he salini y inc ease, which enhance he dissolu ion o anhyd i e and, in u n, p oduces he
p ecipi a ion o calci e (common ion effec , Ca) and he concomi an dissolu ion o dolomi e.
Hali e dissolu ion may be an impo an d i ing o ce in he geochemical e olu ion o g oundwa e sys ems in
con ac wi h ca bona es and e apo i es, whe e equilib ium wi h K- eldspa , albi e and anhyd i e has al eady
been a ained. The e olu ion o he p ocesses a pH, empe a u e and salini y anges wide han hose in he
Fi e o-A nedillo sys em has been heo e ically examined wi h addi ional eac ion-pa h simula ions, in o de o
gene alise he geochemical beha iou o hese p ocesses in o he en i onmen s.
1. In oduc ion
Fi e o and A nedillo a e wo small illages in Na a a and La Rioja
egions (Spain) espec i ely, which ha e well known spas unc ioning
o a long ime (e.g. Gu ié ez, 1801; Mezquí iz, 2004) o i s medicinal
and he apeu ic benefi s. A nedillo is abou 35 Km NW o Fi e o, and
he wa e s ha eme ge in bo h illages belong o he same ca bona e-
e apo i ic ese oi . The discha ge empe a u e o he he mal wa e s
a bo h si es is simila , bu hei chemis y is diffe en .
The hyd ogeochemical cha ac e isa ion o hese he mal wa e s
s a ed wi h he s udy o he A nedillo sys em (Blasco e al., 2018) and
i is comple ed in his pape wi h he cha ac e isa ion o he Fi e o
he mal wa e s. Mo eo e , ollowing he same me hodology as o he
A nedillo wa e s, he empe a u e in he ese oi o he Fi e o sys em
has been de e mined by using he chemical and iso opic
geo he mome e s and he geo he mome ical modelling. The use o
classical chemical geo he mome e s (ca ionic geo he mome e s and
silica geo he mome e s) in low- empe a u e and ca bona e-e apo i ic
sys ems is a he con o e sial, since hey we e de eloped o be used in
wa e s o highe empe a u e and wi h a diffe en mine al assemblage
in con ac o he wa e s in he ese oi . Howe e , al hough no com-
ple ely ee o unce ain ies o limi a ions, he e a e some chemical
geo he mome e s specifically calib a ed o his ype o sys ems (Ca-Mg
and SO
4
-F; Chiodini e al., 1995). These issues we e ho oughly ea ed
in he p e ious s udy on he A nedillo wa e s (Blasco e al., 2018) and,
he e o e, only some obse a ions a e included he e. In any case, as
bo h sys ems belong o he same ese oi , he s udy o he Fi e o
he mal wa e s will imp o e he gene al unde s anding in he pa icu-
la i ies o he use o hese geo he mome e s (as explained in Blasco
e al., 2017).
h ps://doi.o g/10.1016/j.jhyd ol.2019.01.013
Recei ed 30 Augus 2018; Recei ed in e ised o m 4 Janua y 2019; Accep ed 12 Janua y 2019
⁎
Co esponding au ho .
E-mail add ess: monicabc@uniza .es (M. Blasco).
-RXUQDORI+ GURORJ ²
$YDLODEOHRQOLQH-DQXDU
(OVHYLHU%9$OOULJKWVUHVHUYHG
73
4. Resul s
Finally, he geochemical cha ac e isa ion o he whole sys em al-
lows assessing, by mass balance and eac ion pa hs calcula ions, he
main eac ions (and hei ex en ) ha condi ion he e olu ion o hese
he mal wa e s. This e alua ion has e idenced he impo an ole
played by hali e dissolu ion in he geochemical e olu ion o his ype o
sys ems h ough i s effec s on se e al wa e -mine al equilib ia.
2. Geology and hyd ogeology
The Fi e o and A nedillo he mal sp ings a e loca ed in he NW o
he Ibe ian Chain, in he con ac be ween he eas e n Came os Range
and he e ia y Eb o Basin (Fig. 1;Coloma e al., 1997a,b; Sánchez and
Coloma, 1998). These sp ings a e aligned in a NW-SE h us ha se-
pa a es he a o emen ioned wo uni s (Albe , 1979; Auqué e al.,
1988). They a e loca ed in he Fi e o (Na a a, Spain) and A nedillo (La
Rioja, Spain) illages, espec i ely, which a e sepa a ed by abou
35 km.
The Came os Range, cons i u ed mainly by Mesozoic ocks, is lim-
i ed by wo con inen al basins and wo Paleozoic elie s (Fig. 1): he
Eb o and Due o basins in he no h and he sou h, espec i ely; and he
Demanda and Moncayo Ranges a he eas and wes (Gil e al., 2002).
The o ma ions o his a ea ange om he Paleozoic up o he Qua-
e na y. The T iassic and he ma ine Ju assic ca bona e ocks (up o
Kimme idgian) cons i u e he p e- i sequence, and hey a e e-
p esen ed by he o ma ions no mally ound in he Ibe ian Chain
(Coloma, 1998; Gil e al., 2002; Goy e al., 1976). A he end o he
Ju assic and du ing he C e aceous ime a i ing p ocess esul ed in he
c ea ion o he Came os Basin and he sedimen a ion o his pe iod
cons i u es he syn- i sequence. These a e con inen al sedimen s om
Uppe Ju assic o Uppe C e aceous (Ti honian o Lowe Albian;
Coloma, 1998; Gil e al., 2002; Mas e al., 1993) and hey a e con-
s i u ed by an in e cala ion o flu ial and lacus ine sedimen s. Finally,
he pos - i sequence is cons i u ed by he Uppe C e aceous ca bona es
(U gon Facies) and sands ones (U illas Fo ma ion) and he ca bona es
o he La e C e aceous (San a Ma ía de la Hoyas, Pico en es, Muñecas,
Ho ezuelos, Hon o ia Pina , Bu go de Osma, San o Domingo de Silos
and San ibañez del Val Fo ma ions; Gil e al., 2002, 2004). The Ca-
me os Range elie and he e ia y basin we e c ea ed du ing he e -
ia y ec onic in e sion when E-W and NW-SE comp essi e s uc u es,
such as he Came os h us , we e gene a ed (Coloma, 1998; Gil e al.,
2002).
The geo he mal ese oi associa ed wi h hese he mal wa e s is
loca ed in he Ju assic ca bona es o he p e- i sequence. Based on
hei pe meabili y, hese ma e ials ha e been di ided in h ee g oups,
wo pe meable ones sepa a ed by o he less pe meable (Coloma e al.,
1995; Sánchez and Coloma, 1998; Sánchez e al., 1999), al hough hey
a e in e connec ed due o he in ense ac u a ion:
1) G oup 1 ( he fi s pe meable g oup): Imón (dolos ones), Co es de
Tajuña (dolomi ic ca nioles) and Cue as Lab adas (limes ones and
dolos ones) Fo ma ions.
2) G oup 2 ( he in e media e less pe meable g oup): Ce o del Pez
(ma ls), Ba ahona (bioclas ics limes ones) and Tu miel (ma ls and
limes ones) Fo ma ions.
3) G oup 3 ( he second pe meable g oup): Chel a (limes ones),
Aldealpozo (black limes ones) and To ecilla (limes ones wi h
co als) Fo ma ions.
Fig. 1. Loca ion o he A nedillo and he Fi e o geo he mal sp ings and geological map o he a ea (modified om Blasco e al. 2018).
M. Blasco e al. -RXUQDORI+ GURORJ ²
74
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
All hese o ma ions cons i u e he egional d ainage le el o he
Ibe ian Chain, al hough he main flow occu s h ough he ma e ials o
he fi s pe meable g oup (Coloma e al., 1995; Sánchez and Coloma,
1998; Sánchez e al., 1999).
The echa ge occu s h ough he ou c ops o Ju assic ocks and he
syn- i sequence and om he infil a ion om i e s (Coloma e al.,
1995; Sánchez e al., 1999). Then, he ascen o he he mal wa e s o
su ace akes place h ough he Came os h us (Coloma, 1998; Coloma
e al., 1996;Fig. 1). The discha ges a e associa ed wi h he Keupe a-
cies and he Lowe Ju assic o ma ions (Auqué e al., 1988; Coloma,
1998; Coloma e al., 1996). The he mal wa e s a e o chlo ide-sodium
ype and he discha ge empe a u e is close o 50 °C in bo h cases,
howe e , he flow a e is highe in Fi e o (abou 50 L/s) han in A -
nedillo (up o 20 L/s; Coloma e al., 1998, 1997b, 1995; Sánchez and
Coloma, 1998).
3. Me hodology
3.1. Field sampling and analyses
A sampling campaign was conduc ed in Oc obe 2015 and ou
wa e samples we e aken and analysed. Two o hem we e collec ed in
A nedillo, one inside he A nedillo spa (AR1) and he o he in a sp ing
in a pool buil in he Cidacos Ri e (AR2). The o he wo samples we e
aken in Fi e o in wo diffe en spas, one in he Beque spa (F1) and he
o he in he Pala ox spa (F2).
The field sampling p ocedu es and analy ical me hodology we e
desc ibed in de ail in Blasco e al. (2018). B iefly, empe a u e, pH and
elec ical conduc i i y we e de e mined in si u in all hese samples;
alkalini y was de e mined by i a ion wi h H
2
SO
4
0.02 N and endpoin
moni o ing by pH-me e , chlo ide and fluo ide by selec i e elec odes
and sulpha es by colo ime y. The majo ca ions (Ca, Na, K, Mg, S and
Si) we e analysed by ICP-OES, he mino ca ions by ICP-MS and he
iso opes (δ
18
O, δ
2
H, δ
13
C, and δ
34
S and
18
O in dissol ed sulpha es) by
CF-IRMS.
3.2. Geo he mome e s
The use o chemical and iso opic geo he mome e s o de e mining
he ese oi empe a u e o a he mal sys em can be conside ed com-
plemen a y o he geo he mome ical modelling and h ough he
combina ion o he h ee echniques he empe a u e is mo e p ecisely
es ablished. The cha ac e is ics o he chemical and iso opic geo-
he mome e s used he e and hei applica ion o hese he mal wa e s
we e de ailed in Blasco e al. (2018), so he e only he mos ele an
in o ma ion is highligh ed.
3.2.1. Chemical geo he mome e s
Chemical geo he mome e s a e he classical echnique used o de-
e mining he ese oi empe a u e o he mal wa e s. They consis o
empi ic o expe imen al calib a ions based on chemical he e ogeneous
eac ions which depend on empe a u e and con ol he elemen al
con en s dissol ed in wa e s (e.g. Ma ini, 2004; T uesdell, 1976). The e
a e some geo he mome e s ha ha e been specifically calib a ed o
ca bona e-e apo i ic and low empe a u e he mal sys ems and hey
ha e been used in his s udy: he Ca-Mg and he SO
4
-F geo he m-
ome e s (Chiodini e al. 1995).
Howe e , mos o he exis ing geo he mome e s (ca ionic and silica
geo he mome e s) ha e been calib a ed o wa e s o high empe a u e
(> 180 °C) and hos ed in diffe en ocks han he ones p esen in he
s udied a ea (e.g. A nò sson e al., 1983; As a e al., 2010; Auqué e al.,
1997; Buil e al., 2006; Choi e al., 2005; DAmo e e al., 1987; Fouillac
and Micha d, 1981; Fou nie , 1981, 1977; Giggenbach e al., 1983;
Giggenbach, 1988; Kha aka and Ma ine , 1989; Ma ine e al., 2006;
Mu lu and Güleç, 1998; S e ánsson and A nó sson, 2000). These geo-
he mome e s ha e p o ided cohe en esul s in some sys ems simila
o he ones s udied he e (e.g. Apolla o e al., 2012; Blasco e al., 2018,
2017; Fe nández e al., 1988; Gökgöz and Ta kan, 2006; Micha d and
Bas ide, 1988; Mohammadi e al., 2010; Pas o elli e al., 1999; Wang
e al., 2015) and, he e o e, hei applicabili y in he Fi e o –A nedillo
geo he mal sys em is es ed. Classical chemical geo he mome e s and
calib a ions used in his s udy a e: SiO
2
-qua z (calib a ions: Fou nie ,
1977; Micha d, 1979; T uesdell, 1976), SiO
2
-chalcedony (calib a ions:
A nò sson e al., 1983; Fou nie , 1977) Na-K (calib a ions: Fou nie ,
1977; Giggenbach, 1988; Ve ma and San oyo, 1997), K-Mg
(Giggenbach e al., 1983 calib a ion) and Na-K-Ca (Fou nie and
T uesdell, 1973 calib a ion).
3.2.2. Iso opic geo he mome e s
Iso opic geo he mome e s a e simila o chemical geo he mome e s
as hey consis o eac ions dependen on empe a u e, howe e hey
a e based on he iso opic equilib ium be ween wo species. The iso opic
geo he mome e s used in his s udy a e he ones based on he δ
18
O
exchange be ween wa e s and sulpha e. The adi ional calib a ions o
his geo he mome e a e based on he δ
18
O HSO
4
-H
2
O exchange and
he calib a ions used he e a e hose om F iedman and O’Neil (1977)
and Seal e al. (2000). Howe e as iso opic equilib ium in wa e s o
neu al pH is supposed o be con olled by he δ
18
OSO
42-
–H
2
O ex-
change (Bosche i, 2013), addi ional calib a ions based on his as-
sump ion ha e also been used (Halas and Plu a, 2000; Zeebe, 2010).
Finally, he calib a ion based on δ
18
O CaSO
4
-H
2
O exchange (Bosche i
e al., 2011) p o ides good esul s in sys ems o e sa u a ed o in
equilib ium wi h anhyd i e (e.g. Awaleh e al., 2015; Bosche i, 2013;
Bosche i e al., 2011) and i has also been used he e.
3.3. Geochemical modelling
The geochemical calcula ions ha e been pe o med by using he
PHREEQC geochemical code (Pa khu s and Appelo, 2013) and he
WATEQ4F he modynamic da abase (Ball and No ds om, 2001) wi h
some addi ional he modynamic da a which a e de ailed below:
•py ophylli e, laumon i e, albi e, K- eldspa and chalcedony da a
om Micha d (1983). These da a ha e been selec ed because hey
ha e p o ided good esul s in geo he mal sys ems p e iously (e.g.
As a e al., 2012; Auqué e al., 1998; Micha d and Roekens, 1983;
Micha d e al., 1989, 1986) and hei eliabili y in his sys em was
p o en by Blasco e al. (2018); and
•dolomi e da a om Blasco e al. (2018), which was calcula ed om
he da a o he A nedillo geo he mal sys em. This is a pa ially o -
de ed dolomi e which consis s o 18.4% o o de ed dolomi e and
81.6% o diso de ed dolomi e.
3.3.1. Specia ion-solubili y calcula ions
These calcula ions p o ide he dis ibu ion o he diffe en species in
he wa e , de e mining hei concen a ions and ac i i ies. They also
gi e he sa u a ion s a es o wa e s wi h espec o he mine al phases
and he pa ial p essu e o gasses (e.g. pCO
2
). The sa u a ion s a e (SI) is
he loga i hm o he a io be ween he ionic ac i i y p oduc (IAP) and
he equilib ium cons an o he mine al eac ion a he indica ed em-
pe a u e (K(T)):
⎜
⎟
=⎛
⎝
⎞
⎠
SI log IAP
KT() (1)
When SI = 0 he solu ion is in equilib ium wi h he mine al phase, a
posi i e alue indica es o e sa u a ion and a nega i e alue unde -
sa u a ion. These de e mina ions will be he basic pa o he geo he -
mome ical modelling.
3.3.2. Geo he mome ical modelling
As men ioned abo e, in o de o compa e he esul s, he
M. Blasco e al. -RXUQDORI+ GURORJ ²
75
4. Resul s
and Pé ez del Villa , 2011) and e en in b ines du ing bu ial diagenesis
(e.g. Budai e al., 1984; S oessell e al., 1987; Woo and Moo e, 1996 and
e e ences he ein).
Albi isa ion p ocesses (like he K- eldspa albi isa ion deduced in
his s udy) a e usually de eloped in g oundwa e sys ems a empe a-
u es highe han 60 °C (e.g. Aagaa d e al., 1990) bu hey ha e also
been obse ed in he mal wa e s a simila empe a u es (a ound 85 °C)
and salini ies (TDS abou 8000 ppm) o he ones s udied he e (Blasco
e al., 2017) o , mo e o en, in mo e saline o ma ion o in e s i ial
wa e s in sedimen a y basins a highe empe a u es (e.g. Aagaa d
e al., 1990; Dias Lima and De Ros, 2002; Egebe g and Aagaa d, 1989;
Hano , 1996; Saigal e al., 1988 and e e ences he ein). Tha is, he
wo main p ocesses iden ified in his sys em can ake place in o he
si ua ions and unde diffe en pH (pCO
2
), empe a u e and salini y
condi ions.
In o de o make hese findings mo e gene al, some addi ional si-
mula ions ha e been pe o med o assess he effec s o diffe en phy-
sicochemical condi ions on he main p ocesses iden ified (dedolomi i-
sa ion and albi isa ion). Fo his, sample F1 has been conside ed as he
ini ial solu ion and i has been o ced o dissol e up o 2000 mmol/L o
hali e (ionic s eng h close o 2). Then he a ious condi ions con-
side ed ha e been 1) a a ia ion o pH be ween 6 and 8, since his is he
mos common ange o pH in na u al sys ems, and 2) a ange o em-
pe a u e om 25 o 200 °C. The LLNL da abase (using low_albi e and
he same dolomi e as in he WATEQ4F da abase) has been used o ca y
ou his calcula ion because he WATEQ4F da abase was de eloped o
be used up o 100 °C and a highe empe a u es he esul s should be
ca e ully conside ed (Ball and No ds om, 2001), while empe a u e
ange o he LLNL da abase is up 300 °C (Johnson e al., 2000).
The mos impo an esul s a e shown in Table 7,Fig. 7 and Figu e
S2 (in he Supplemen a y Ma e ial;Fig. 7 con ains he esul s ob ained
a pH = 6 and he esul s ob ained a pH = 7 and pH = 8 a e in he
Supplemen a y Ma e ial since hey a e almos he same as hose o
pH = 6). Albi isa ion and dedolomi isa ion p ocesses, along wi h an-
hyd i e dissolu ion, a e mo e in ense as salini y inc eases in all he si-
mula ions. Dolomi e dissolu ion and calci e p ecipi a ion, ha is, he
dedolomi isa ion p ocess, is mo e in ense a lowe empe a u es (Fig. 7a
and Figu e S2a-b) as i was also poin ed ou by Esco cia e al. (2013).
The effec o pH is o mino impo ance and almos impe cep ible in
Fig. 7a and Figu e S2a-b, and while dolomi e dissolu ion is almos he
same wi h he inc ease o pH, he calci e p ecipi a ion is somewha
highe being mos impo an a highe empe a u es (Table 7). The
dissolu ion o anhyd i e is mo e in ense a low empe a u es and i is
almos unaffec ed by he a ia ion o he pH (Fig. 7b, Figu e S2c-d,
Table 7). Finally, he albi isa ion p ocess displays he opposi e beha-
iou (Table 7,Fig. 7c and Figu e S2 e- ): he amoun o albi e p e-
cipi a ed is always he same as he amoun o dissol ed K- eldspa being
mo e in ense a highe empe a u es and no affec ed by he pH a -
ia ions.
Conside ing all hese esul s i is clea ha hali e dissolu ion and,
he e o e, he inc ease o he salini y o he wa e s, can be a ele an
con olling ac o o he hyd ochemical e olu ion o he wa e s. Hali e
dissolu ion inc eases he Na dissol ed con en s and by he ion-common
effec he albi isa ion p ocess akes place (Eq. (2)):
+→ +
−++
K
AlSi O Na NaAlSi O K
K eld alb38( ) 38( ) (2)
On he o he hand, anhyd i e solubili y is highly influenced by he
salini y o he wa e s due o he sal ing-in effec (Langmui , 1997), in
he way ha he inc ease in he salini y will lead o a highe solubili y
o anhyd i e (e.g. Li and Duan, 2011; Raines and Dewe s, 1997).
The e o e, hali e dissolu ion enhances anhyd i e dissolu ion (Eq. (3)):
Fig. 6. Changes in he elemen al con en s in he Fi e o wa e s, wi h Cl
-
= 45.6 mmol/L, when 46 mmol/L o hali e a e dissol ed ( ep esen ed by he inc ease in he
Cl
-
concen a ion).
M. Blasco e al. -RXUQDORI+ GURORJ ²
82
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
+→+++
+− + −
N
aCl CaSO Na Cl Ca SO
hal anh() 4( ) 24
2(3)
Anhyd i e dissolu ion inc eases he calcium con en o he wa e s
(as shown in Eq. (3)) and, gi en ha wa e s a e in equilib ium wi h
espec o calci e, he excess o Ca will p oduce he o e sa u a ion o
calci e and, he e o e, i s p ecipi a ion (common-ion effec ; Eq. (4)):
+→ +
+
Ca HCO CaCO H
calc33() (4)
A he same ime calci e p ecipi a ion leads o a dec ease in calcium
and HCO
3
–
in he solu ion (Eq. (4)) and o an inc ease in he H
+
and he
pCO
2
which igge s he dissolu ion o dolomi e (dedolomi isa ion
p ocess; Eq. (5)):
+→ +
++
CaMg CO Ca CaCO Mg() 2
dol calc32( ) 23( ) 2(5)
This dedolomi isa ion p ocess, igge ed by anhyd i e (o gypsum)
dissolu ion, has been epo ed in o he ca bona e aqui e s, con aining
dolos ones and in con ac wi h anhyd i e o gypsum (Appelo and
Pos ma, 2005; Auqué e al., 2009; Back e al., 1983; Capaccioni e al.,
2001; Ca denal e al., 1994; Choi e al., 2012; Deike, 1990; F ondini,
2008; Leybou ne e al., 2009; López-Chicano e al., 2001; Plumme ,
1977; Plumme e al., 1990; P ado-Pé ez and Pé ez del Villa , 2011;
Sacks e al., 1995). Howe e , in he case p esen ed he e, al hough an-
hyd i e dissolu ion is he di ec igge ing eac ion o he dedolomi i-
sa ion, he p ocess ac ually esponsible o i is he dissolu ion o hali e.
Hali e dissolu ion keeps he dedolomi isa ion p ocess ongoing e en
when he wa e s each he equilib ium wi h anhyd i e (o gypsum).
Finally, he dissolu ion o hali e also igge s he albi isa ion p ocess
and, al hough his had p e iously been iden ified in diagene ic en-
i onmen s (Egebe g and Aagaa d, 1989; Hano , 1996; Saigal e al.,
1988), he esul s shown in his pape indica e ha his p ocess is also
easible in g oundwa e ( he mal) sys ems a lowe empe a u es and
salini ies.
O e all, hese esul s a e also ele an o he geological CO
2
s o age
in saline aqui e s o , e en, o enhanced geo he mal sys ems (EGS)
whe e saline wa e s, ini ially in equilib ium wi h he ese oi ocks,
a e usually in ol ed. The e olu ion o he dedolomi isa ion p ocesses
has been iden ified as a c i ical poin in assessing ca bona e o ma ions
o po en ial CO
2
s o age (e.g. Auqué e al., 2009; P ado-Pé ez and
Pé ez del Villa , 2011 and e e ences he ein). And albi isa ion p o-
cesses ha e been iden ified in CO
2
–b ine– ock in e ac ion expe imen s
a in si u P–T condi ions o he pilo CO
2
s o age si e a Ke zin in
Ge many (Fische e al., 2010) and in he expe imen s wi h hyd o-
he mal Na-Cl solu ions on ac u e su aces in he geo he mal ese oi
o he Uppe Rhine G aben (Schmid e al., 2017). The e o e, he e o-
lu ion and consequences o he p ocesses iden ified in his pape should
be u he explo ed.
5. Conclusions
The sp ing wa e s o he Fi e o-A nedillo geo he mal sys em a e
loca ed in he locali ies o he same name and sepa a ed abou 35 km.
They a e hos ed in ca bona e-e apo i ic ma e ials and hey a e o
chlo ide-sodium ype wi h nea neu al pH and discha ge empe a u e
o abou 45 °C. The main diffe ences be ween hese wa e s a e he
highe salini y o hose eme ging in A nedillo, he sligh ly highe Ca
and Mg con en s in Fi e o and he calcula ed ese oi empe a u e
(81 ± 11 °C in Fi e o and 87 ± 13 °C in A nedillo). All hese oge he
wi h he mine al equilib ia in he ese oi indica e ha , al hough he
wa e s belong o he same geo he mal ese oi , hey e ol e along
diffe en flow pa hs wi h diffe en in ensi ies o wa e - ock in e ac ion
p ocesses which would jus i y a mo e e ol ed s age o he A nedillo
sys em compa ed o he Fi e o he mal wa e s.
Mass-balance and eac ion pa h calcula ion ha e been used o assess
he main eac ions esponsible o he chemical diffe ences and e olu-
ion o hese wa e s and he esul s indica e ha he igge ing p ocess
is he hali e dissolu ion, which leads o an albi isa ion p ocess and o
he dissolu ion o anhyd i e, which, in u n, igge s he calci e p e-
cipi a ion and he dolomi e dissolu ion (dedolomi isa ion p ocess). The
p ocesses iden ified in his sys em (dedolomi isa ion and albi isa ion)
ha e been iden ified in diffe en en i onmen s unde diffe en condi-
ions o empe a u e, pH and/o salini ies, and how hese pa ame e s
affec hem has also been e alua ed in his pape . The ex ension o hese
p ocesses is highe as he salini y o he wa e s inc eases. Howe e , he
effec o pH (assessed be ween 6 and 8) is almos negligible in e ms o
he mass ans e s o he in ol ed phases. Tempe a u e also causes
significan a ia ions in a way ha he dedolomi isa ion and anhyd i e
dissolu ion a e highe a low empe a u es and he albi isa ion is mo e
in ense a high empe a u es.
These calcula ions ha e e idenced he impo ance ha he changes
in he salini y o he wa e s ( h ough hali e dissolu ion) ha e o e he
geochemical e olu ion o wa e s due o i s effec in he wa e -mine al
equilib ia a ained. Hali e dissolu ion has been p o en o igge a de-
dolomi isa ion p ocess e en when he wa e s ha e eached he equili-
b ium wi h espec o anhyd i e, calci e and dolomi e. Mo eo e i has
been shown ha hese p ocesses a e mo e gene al han wha was
known up o da e and dese e u u e s udies, mainly conside ing hei
easibili y in pa icula ly ele an si ua ions such as he enhanced
geo he mal sys ems and he geological CO
2
s o age si es.
Acknowledgemen s
M. Blasco has wo ked in his s udy hanks o a schola ship om he
Minis y o Science, Inno a ion and Uni e si ies o Spain, o he
T aining o Uni e si y Teache s ( e . FPU14/01523). This s udy o ms
pa o he ac i i ies o he Geochemical Modelling G oup (Uni e si y o
Za agoza; A agón Go e nmen ).
We a e g a e ul o he s affo he Fi e o and A nedillo spas o hei
disposi ion and assis ance du ing he sampling campaign. The echnical
assis ance o En ique Oli e , om he Ea h Sciences Depa men o he
Uni e si y o Za agoza, is acknowledged. The commen s om wo
anonymous e iewe s a e also app ecia ed.
Appendix A. Supplemen a y da a
Supplemen a y da a o his a icle can be ound online a h ps://
doi.o g/10.1016/j.jhyd ol.2019.01.013.
Table 7
To al mass ans e s ob ained in he eac ion-pa h calcula ion when 2000 mmol/L o hali e a e dissol ed a pH o 6, 7 and 8 and empe a u es o 25, 100 and 200 °C.
The esul s a e exp essed in mmol/L (posi i e alues mean p ecipi a ion and nega i e alues mean dissolu ion).
pH = 6 pH = 7 pH = 8
25 °C 100 °C 200 °C 25 °C 100 °C 200 °C 25 °C 100 °C 200 °C
Calci e 48.9 5.2 0.5 51.2 5.6 0.6 51.3 5.6 0.8
Dolomi e –23.4 −2.9 −0.4 −26.6 −2.8 −0.4 −26.3 −2.8 −0.4
Anhyd i e −61.3 −21.5 −4.9 −63 −21.7 −4.9 −63 −21.7 −4.9
Albi e 1.9 16 77 1.9 16 77 1.9 16 77
K-Feldspa −1.9 −16 −77 −1.9 −16 −77 −1.9 −16 −77
M. Blasco e al. -RXUQDORI+ GURORJ ²
83
4. Resul s
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Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
4.4 Pape 4
Mine al equilib ia and he modynamic unce ain ies in he
geo he mome ical cha ac e isa ion o ca bona e geo he mal sys ems
o low empe a u e. The case o he Alhama-Ja aba sys em (Spain)
Mónica Blasco, Luis F. Auqué, Ma ía J. Gimeno, Pa icia Ace o, Ja ie Gómez, Ma ia P. As a
Geo he mics 78, 170-182 (2019)
Impac Fac o (2017): 2.693
Qua ile and Ca ego y (2017): Q2 (57/189), Geosciences; Q2(47/97),Ene gy&Fuels.
DOI: 10.1016/j.geo he mics.2018.11.004
Sen : 11 May 2018
Accep ed; 19 No embe 2018
A ailable online: 22 Decembe 2018
Final publica ion: Ma ch 2019
87
4. Resul s
Con en s lis s a ailable a ScienceDi ec
Geo he mics
jou nal homepage: www.else ie .com/loca e/geo he mics
Mine al equilib ia and he modynamic unce ain ies in he
geo he mome ical cha ac e isa ion o ca bona e geo he mal sys ems o low
empe a u e. The case o he Alhama-Ja aba sys em (Spain)
Mónica Blasco
a,⁎
, Luis F. Auqué
a
, Ma ía J. Gimeno
a
, Pa icia Ace o
a
, Ja ie Gómez
a
,
Ma ia P. As a
b
a
Geochemical Modelling G oup. Pe ology and Geochemis y A ea, Ea h Science Depa men , Uni e si y o Za agoza, Spain C/ Ped o Ce buna 12, 50009, Za agoza,
Spain
b
En i onmen al Mic obiology Labo a o y (EML), École Poly echnique Fédé ale de Lausanne (EPFL). EPFL-ENAC-IIE-EML. S a ion 6, 1015, Lausanne, Swi ze land
ARTICLE INFO
Keywo ds:
Low empe a u e geo he mal sys em
Geo he mome y
Geo he mome ical modelling
Calci e-dolomi e equilib ium
Ca bona e aqui e
ABSTRACT
Geo he mome ical cha ac e isa ion o low- empe a u e, ca bona e-e apo i ic geo he mal sys ems is usually
hampe ed by he lack o app op ia e mine al equilib ia o success ully use mos o he classical geo he mome e s
and/o by he he modynamic unce ain ies affec ing some o he mos p obable mine al equilib ia in low
empe a u e condi ions. This si ua ion is u he hinde ed i he he mal wa e s a e addi ionally affec ed by
seconda y p ocesses (e.g., CO
2
loss) du ing hei ascen o su ace.
All hese p oblems clus e oge he in he low- empe a u e Alhama-Ja aba he mal sys em, hos ed in ca -
bona e ocks, wi h sp ing empe a u es abou 30 °C and wa e s o Ca-Mg−HCO
3
/SO
4
ype. This sys em, one o
he la ges na u ally flowing (600 L/s) low empe a u e he mal sys ems in Eu ope, is used in his pape as a
sui able ame o assess he p oblems in he applica ion o chemical geo he mome ical echniques (classical
geo he mome e s and geo he mome ical modelling) and o p o ide a me hodology ha could be used in his
ype o geo he mal sys em o in po en ial CO
2
s o age si es in simila aqui e s.
The esul s ob ained ha e shown ha he effec s o he seconda y p ocesses can be a oided by selec ing he samples
unaffec ed by such p ocesses and, he e o e, ep esen a i e o he condi ions a dep h, o by applying exis ing
me hodologies o econs uc he o iginal composi ion, as is usually done o medium o high empe a u e sys ems.
The effec i e mine al equilib ia a dep h depend on he empe a u e, he esidence ime and he specific li-
hological/mine alogical cha ac e is ics o he sys em s udied. In he p esen case, he mine al equilib ia on which
classical ca ion geo he mome e s a e based ha e no been a ained. The low p opo ion o e apo i ic mine als in
he hos ing aqui e p e en s he sys em om eaching anhyd i e equilib ium, o he wise common in ca bona e-
e apo i ic sys ems and necessa y o he specific SO
4
-F geo he mome e o he specially eliable qua z (o chal-
cedony) – anhyd i e equilib ium in he geo he mome ical modelling o hese geo he mal sys ems.
Unde hese ci cums ances, he empe a u e es ima ion mus ely on qua z (o chalcedony), clay mine als
and, especially, calci e and dolomi e. Howe e , clay mine als and dolomi e p esen impo an he modynamic
unce ain ies ela ed o possible a ia ions in composi ion o c ys allini y deg ee o clays and o de /diso de
deg ee o dolomi e. To deal wi h hese p oblems, a sensi i i y analysis o he he modynamic da a o clay
mine als has been ca ied ou , compa ing he esul s ob ained when conside ing diffe en solubili y da a. The
unce ain ies associa ed wi h dolomi e ha e been add essed by e iewing he solubili y da a a ailable o do-
lomi es wi h diffe en o de deg ees and pe o ming specific calcula ions o he o de deg ee o he dolomi e in
he aqui e . This app oach can be used o find he mos adequa e dolomi e he modynamic da a o he sys em
unde conside a ion, including medium-high empe a u e geo he mal sys ems.
Finally, he empe a u e es ima ion o he Alhama-Ja aba wa e s in he deep ese oi has been ob ained om
simul aneous equilib ia o qua z, calci e, pa ially diso de ed dolomi e and some aluminosilica e phases. The
ob ained alue o 51 ± 14 °C is wi hin he unce ain y ange no mally affec ing his ype o es ima ions and is
cohe en wi h independen es ima ions om geophysical da a.
h ps://doi.o g/10.1016/j.geo he mics.2018.11.004
Recei ed 11 May 2018; Recei ed in e ised o m 8 No embe 2018; Accep ed 19 No embe 2018
⁎
Co esponding au ho a : Geochemical Modelling G oup. Pe ology and Geochemis y A ea, Ea h Sciences Depa men , Uni e si y o Za agoza, Spain.
E-mail add ess: monicabc@uniza .es (M. Blasco).
*HRWKHUPLFV²
(OVHYLHU/WG$OOULJKWVUHVHUYHG
89
4. Resul s
1. In oduc ion
A wide a ie y o geo he mome ical echniques a e a ailable o
e alua e he ese oi empe a u e o he mal wa e s: a ious chemical
and iso opic solu e geo he mome e s and he geo he mome ical mod-
elling (o mul icomponen solu e geo he mome y; e.g. Spyche e al.,
2014). Howe e , no all o hem a e always applicable o all he mal
sys ems and hey should be ca e ully selec ed acco ding o he diffe en
equilib ia expec ed a dep h.
In he case o low empe a u e he mal sys ems hos ed in ca bona e
ocks, a se ies o p oblems a ise when applying he geo he mome ical
echniques due o h ee main easons: 1) he low empe a u es usually
make difficul he a ainmen o he mine al and/o iso opic equilib ia;
2) he mine al se p esen in he ese oi is usually mo e limi ed
(mainly calci e and dolomi e) han in o he ype o geo he mal sys ems;
and 3) he he modynamic p ope ies o dolomi e and clays a e un-
ce ain.
An addi ional complica ion in he e alua ion o he ese oi em-
pe a u e in any he mal sys em is he p esence o seconda y p ocesses
du ing he ising o he he mal wa e s o su ace (e.g. mixing wi h
colde and shallowe wa e s, e-equilib ium p ocesses h ough mine al-
wa e eac ions and/o CO
2
ou gassing).
The wo k p esen ed in his pape is ocused on he use and e a-
lua ion o se e al geo he mome ical ools in o de o calcula e he
ese oi empe a u e o he geo he mal sys em o Alhama de A agón –
Ja aba ( om now on, Alhama–Ja aba). The cha ac e is ics o his
he mal sys em p o ide he oppo uni y o deal wi h almos all he
a o emen ioned complexi ies (Tena e al., 1995;Auqué e al., 2009;
Blasco e al., 2016): 1) he ese oi is hos ed mainly in ca bona e ocks
(limes ones and dolos ones), 2) he empe a u e is, a p io i, low and 3)
he e a e diffe en seconda y p ocesses (mixing, CO
2
ou gassing) a -
ec ing he chemis y o some o he wa e s. The e a e o he easons
why he s udy o his sys em p esen s a special in e es . One is he
impo ance o he sys em as a na u al esou ce wi h e y high flow a es
(550 L/s in Alhama and 600 L/s in Ja aba; IGME, 1980;De Toledo and
A qued, 1990;Sánchez e al., 2004) compa able o hose ound in he
a ea conside ed he Eu ope’s la ges na u ally flowing he mal sys em
in Budapes (discha ge o ca. 580 L/s; Goldscheide e al., 2010 and
e e ences he ein). The o he eason is ela ed o i s special geological
and hyd ogeochemical ea u es which ha e gi en i he conside a ion o
a na u al analogue o he CO
2
geological s o age (Auqué e al., 2009).
In summa y, his s udy gi es a sui able na u al ame o es di -
e en geo he mome ical echniques and he associa ed unce ain ies
in low empe a u e sys ems hos ed in ca bona e ocks. F om his, a
gene al me hodology can be es ablished o be applied in his ype o
geo he mal sys ems and e en in he cha ac e isa ion o some po en ial
CO
2
s o age si es in simila aqui e s.
2. Geological, hyd ogeological and hyd ogeochemical se ing
The Alhama de A agón and Ja aba sp ings (NE Spain, Fig. 1) belong
o one o he main he mal sys ems in Spain. The e a e se e al he mal
eso s and wa e bo ling plan s in he a ea a p esen . The Ja aba
he mal complex, close o he Mesa Ri e , consis s o 14 ca alogued
sp ings flowing a an ele a ion o 737 m.a.s.l. and he Alhama he mal
complex, loca ed close o he Jalón Ri e bank, is o med by a dozen o
ca alogued sp ings flowing a an ele a ion o 660 m. Apa om hese
well-known sp ing complexes, he e a e ano he wo mino ho sp ings
Fig. 1. Loca ion o he Alhama de A agón and Ja aba geo he mal sys ems in he geological map (modified o m Sánchez e al., 2004) and a c oss sec ion showing he
main s uc u al and li hological cha ac e is ics o he a ea s udied (modified om he ALGECO2 p ojec ; IGME, 2010).
M. Blasco e al. *HRWKHUPLFV²
90
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
in he nea by a ea, Embid and Deza sp ings (Tena e al., 1995;Sanz and
Yelamos, 1998;Sánchez e al., 2004;Auqué e al., 2009;Fig. 1), which
ha e no been included in his s udy.
Geologically, he Alhama-Ja aba he mal sys em is loca ed on he
bo de o he Wes e n Ibe ian Range and he e ia y Almazán Basin
(Fig. 1). The e a e wo main aqui e s in his a ea: 1) he Solo io aqui e ,
hos ed in he Ju assic ca bona e o ma ions; and 2) he Alhama aqui e ,
hos ed in he Uppe C e aceous ca bona e ocks. The hyd ological
model o he egion is no comple ely clea , bu he mos accep ed
hypo hesis s a es ha he e a e wo possible echa ge a eas loca ed 1)
in he Solo io Range wi h a flow di ec ion SW-NE owa ds Ja aba and
Alhama (Fig. 1) and 2) in he icini y o Deza, wi h a NW-SE flow di-
ec ion owa ds Embid and Alhama (Fig. 1;IGME, 1980,1987;De
Toledo and A qued, 1990;Sanz and Yelamos, 1998;Sánchez e al.,
2004). The ac ha he ocks in he Solo io echa ge a ea a e mainly
Ju assic and ha all he he mal sp ings a e associa ed wi h he Uppe
C e aceous o ma ions (Sánchez e al., 2004) sugges s ha bo h aqui e s
could be connec ed and ha hei eme gence would be ela ed o he
p esence o e ical o nea e ical laye s ha allow a apid ascen o
he wa e om dep h (Sánchez e al., 2004).
The mine alogy o he Ju assic and C e aceous ca bona e ocks is
qui e simila . The ocks a e mainly dolos ones and limes ones wi h
dispe sed anhyd i e/gypsum in e cala ions (Meléndez e al., 1985;
Alonso e al., 1993;Au ell e al., 2002). The C e aceous o ma ions a e
locally affec ed by a silicifica ion p ocesses wi h de elopmen o au-
higenic qua z c ys als (Meléndez e al., 1985) and he e a e also in-
e cala ions o e igenous ocks, mainly a he base o he U illas
Fo ma ion, consis ing o sands ones, clays ones, sil s ones, dolomi ic
sil s ones, dolomi ic ma ls, limes ones and dolomi ic limes ones, wi h a
mine alogy comp ising calci e, dolomi e, qua z, K- eldspa , li hic
agmen s and clay mine als (IGME, 1991).
The iso ope δ
18
Oandδ
2
H da a a ailable (IGME, 1982,1994;Sanz
and Yelamos, 1998;Pinuaga e al., 2004) indica e a clea me eo ic
o igin. The i ium da a a ailable a e also om he a o emen ioned
wo ks and hey show he absence o i ium o le els close o he de-
ec ion limi (≈ 1 TU) in he ho es sp ings. The mos common in-
e p e a ion o hese esul s is ha he he mal g oundwa e s ha e
esidence imes longe han 50 yea s and ha some o hem a e affec ed
by mino mixing wi h shallow mode n wa e s (Cla k and F i z, 1997).
3. Me hodology
3.1. Field sampling and analysis
Six and nine sp ings we e sampled in he Alhama and Ja aba
he mal si es, espec i ely. Field sampling p ocedu es and analy ical
me hodology we e mos ly as desc ibed by Auqué e al. (2009). B iefly,
a each sampling poin , empe a u e, pH and conduc i i y we e de-
e mined in si u and sepa a ed samples o anion and ca ion analysis
we e aken in 1 N HCl p e-washed polye hylene bo les. Samples o
ca ion analysis we e fil e ed h ough 0.1 μm and acidified o pH less
han 1 wi h ul apu e HNO
3
. Anions we e de e mined wi hin 24 h a e
collec ion. To al alkalini y was de e mined by i a ion wi h a Me le
i a o wi h an end-poin elec ode. Chlo ide and fluo ide concen a-
ions we e de e mined by a selec i e ion analyse equipmen , using he
selec i e elec odes o chlo ide ORION 94-17B and fluo ide ORION 94-
09. Sulpha e was de e mined by colo ime y using a modifica ion o he
Neme h me hod (Neme h, 1963). Po assium concen a ions we e ana-
lysed by Flame Pho ome y and aluminium concen a ions we e de-
e mined by Elec o he mal A omisa ion A omic Abso p ion Spec o-
me y wi h Zeeman-effec backg ound co ec ion. Induc i ely Coupled
Plasma-A omic Emission Spec ome y was used o he analysis o he
es o he elemen s (Ca, Mg, Na, Li, and Si). The a e age analy ical
e o was es ima ed < 5% o alkalini y, chlo ide, fluo ide, sulpha e,
Table 1
Calib a ions used in his wo k o he diffe en classical geo he mome e s. Geo he mome ical unc ions p o ide he empe a u e alues in deg ees Celsius. The
concen a ion uni s co esponding o he diffe en exp essions a e also indica ed (usually mg/L o mol/L).
Geo he mome e Au ho s o calib a ion Exp ession Uni s
SiO
2
-qua z Micha d (1979)
=T273.15
log SiO
1322
0.435 ( 2)
mol/L
Fou nie and Po e (1982)
=T273.15
log SiO
1309
5.19 ( 2)
mg/L
Na-K Giggenbach (1988)
=
+
()
T273.15
log Na K
1390
1.75
mg/L
Fou nie (1979)
=
+
()
T273.15
log Na K
1217
1.483
mg/L
Na-K-Ca
1
Fou nie and T uesdell (1973)
=
+ + +
()
T273.15
log Na Klog Ca Na
1647
2.06 2.47
mg//L
Ca-K Fou nie and T uesdell (1973)
2
=
+
()
T273.15
log Ca K
2920
3.02 2
mol/L
Micha d (1990)
=
+
()
T273.15
log Ca K
3030
3.94 2
mol/L
K-Mg Giggenbach e al. (1983)
=T273.15
log KMg
4410
13.95 2
mg/L
Na-Li Fouillac and Micha d, 1981
=
+
()
T273.15
log Na Li
1000
0.33
mol/L
Li Fouillac and Micha d, 1981
=
+
T273.15
log Li
2258
1.44 ( )
mol/L
Mg-Li Kha aka and Ma ine , 1988 =
+
T273.15
log Mg Li
2200
5.47
mg/L
Ca-Mg
3
Chiodini e al. (1995) =
+
()
T273.15
log Ca Mg log eq
979.8
3.1170 )0.07003
mol/L
1
β = 4/3 should be used i he empe a u e ob ained is lowe han 100 °C; i he empe a u e ob ained, using ha alue o β, is highe han 100 °C, i should be
ecalcula ed conside ing β = 1/3. Mg-co ec ion p oposed by Fou nie and Po e (1979) o he Na-K-Ca geo he mome e canno be applied o he s udied sp ings,
acco ding o he c i e ia indica ed by hose au ho s.
2
De i ed om Fou nie and T uesdell (1973) in Micha d (1990).
3
Σeq is he summa ion (in eq/L) o he majo dissol ed species.
M. Blasco e al. *HRWKHUPLFV²
91
4. Resul s
doing so, Al concen a ions in he wa e s would be highe han he
measu ed ones and ha he e is a lack o con e gence o he SI alues
o he es o he aluminosilica e phases, which is wo se han he
p e ious esul s (compa e he esul s in Fig. 5 and Figu e S2). Simila
si ua ions ha e been ob ained when imposing equilib ia wi h o he
aluminosilica e phases (e.g. kaolini e, musco i e; Pang and Reed, 1998)
in he calcula ions (no shown), sugges ing ha dissol ed aluminium in
he wa e s s udied is no meaning ully affec ed by seconda y p ocesses
(e.g. eequilib ia wi h espec o Al-bea ing phases) du ing he ascen o
he he mal wa e s.
O e all, a alue o 51 ± 14 °C is indica ed om he equilib ia wi h
espec o qua z, calci e, dolomi e (Dolomi e_H&C, pa ially dis-
o de ed; Hyeong and Capuano, 2001), py ophylli e, pa agoni e and low
c ys alline kaolini e, as he mos p obable empe a u e ange a dep h
in he Alhama-Ja aba he mal sys em. This ange akes in o accoun he
he modynamic unce ain ies o he key mine als and encloses he
empe a u e alues deduced by he qua z geo he mome e .
5. Discussion
The combina ion o diffe en geo he mome ical app oaches and
sensi i i y analysis o he modynamic da a has allowed defining a
p obable empe a u e ange o he Alhama-Ja aba he mal wa e s in
he aqui e a dep h.
The esul s p esen ed he e suppo he expec ed unsui abili y o
mos ca ionic geo he mome e s o he es ima ion o he ese oi
empe a u es in low empe a u e en i onmen s and/o in ca bona e-
e apo i ic ese oi s (Henley e al., 1984;D´Amo e e al., 1987;
Minissale and Duchi, 1988;Mu lu and Güleç, 1998;López-Chicano
e al., 2001;Le e e al., 2002;Ka imi and Moo e, 2008;Sonney and
Vua az, 2010). The applica ion o hese classical geo he mome e s o
he Alhama-Ja aba he mal wa e s leads o empe a u es ei he oo
high (compa ed wi h he combined esul s o o he me hodologies) o
oo low (below sp ing empe a u e). The ques ion ha a ises he e is
why hese geo he mome e s ha e p o ided cohe en esul s in o he
simila low empe a u e sys ems hos ed in ca bona e–e apo i ic ocks
and no in his pa icula one. Blasco e al. (2017, 2018) ha e s udied
some examples o his si ua ion and hey indica e ha he good esul s
ound in hose sys ems a e condi ioned by he exis ence o de i al ocks
in he ca bona e–e apo i ic ese oi , allowing he wa e s o each
equilib ium wi h espec o he phases on which hese geo he mome e s
a e based. In his case, hei unsui abili y, despi e he p esence o some
de i al o ma ions in he aqui e , seems o be ela ed o he sho e
esidence ime o he wa e s o he less homogeneous dis ibu ion o
his specific mine alogy.
The SO
4
-F chemical geo he mome e , based on he anhyd i e–-
fluo i e equilib ia, was de eloped specifically o ca bona e–e apo i ic
sys ems; howe e , i is no always applicable in hem as fluo i e is no a
common mine al in hese aqui e s (e.g. Blasco e al., 2017,2018). This
is also he si ua ion in he Alhama–Ja aba sys em and he e o e his
geo he mome e canno be applied he e. Addi ionally, dispe sed an-
hyd i e has been iden ified in he aqui e s udied al hough in a clea
unde sa u a ion s a e ha p oduces i s dissolu ion and he associa ed
dedolomi isa ion p ocess ha con ols he geochemical e olu ion o
hese he mal wa e s (Auqué e al., 2009). The disequilib ium o he
wa e s wi h espec o anhyd i e p e en s he use o one o he mos
eliable equilib ia in he geo he mome ical modelling o his ype o
sys em, which is he equilib ium qua z/chalcedony–anhyd i e (see
below).
The esul s ob ained wi h he Ca-Mg geo he mome e (Ma ini e al.,
1986;Chiodini e al., 1995), also de eloped o ca bona e–e apo i ic
ocks, ange be ween 63 and 78 °C, bu he unce ain ies ela ed o he
c ys allini y and solubili y o dolomi e p e en i om ob aining a un-
equi ocal es ima ion o he ese oi empe a u e. As al eady ex-
plained, his is one o he main difficul ies in he geo he mome ical
calcula ions de eloped o his ype o ca bona e sys em and i
cons i u es a majo limi a ion o hei applica ion o na u al sys ems. In
o de o a oid hese unce ain ies, a ious dolomi es ha e been used
he e in he geo he mome ical modelling and he mos consis en esul
(i.e. he bes con e gence be ween calci e and dolomi e owa ds SI = 0)
has been ob ained conside ing he dolomi e p o ided by Hyeong and
Capuano (2001), which indica es ha he dolomi e p esen in he e-
se oi o he Alhama-Ja aba he mal wa e s should be o a simila
o de as Dolomi e_H&C, which is 11%.
To explo e he impo ance o he o de o dolomi e on he classical
geo he mome ical esul s, log (aCa
2+
/aMg
2+
) alues ha e been cal-
cula ed om Eq. (2) o he diffe en dolomi es included in he WA-
TEQ4F and LLNL da abases, and also o o he dolomi es p esen in
na u al sys ems, a diffe en empe a u es. As shown in Fig. 6, he e is a
wide a iabili y field o log (aCa
2+
/aMg
2+
) alues (and, he e o e, o
possible es ima ed empe a u es) depending on he ype o dolomi e
assumed in he calcula ions. The a e age log (aCa
2+
/aMg
2+
) alues
calcula ed wi h PHREEQC a e e y simila o Alhama and Ja aba
he mal wa e s (a ound 0.16; when conside ing he sample wi hou
mixing in Ja aba) and his alue co esponds o ese oi empe a u es
abou 77 °C when conside ing he ully-diso de ed dolomi e (Fig. 6).
The p esence o his ype o dolomi e is qui e imp obable in old ocks
om he Ju assic-C e aceous, bu , in any case, his empe a u e can be
conside ed as a maximum es ima e (Blasco e . al., 2018). On he o he
hand, he calcula ions indica e he impossibili y o occu ence o a
ully-o de ed dolomi e in equilib ium wi h he wa e s s udied (which
would imply alues o log (aCa
2+
/aMg
2+
) abo e 1.2; see Fig. 6). In
ag eemen wi h he esul s o he geo he mome ical modelling, he
mos consis en esul is he one ob ained when his calcula ion is
ca ied ou conside ing he pa ially o de ed dolomi e wi h an o de
deg ee o 11% (dolomi e_H&C). Finally, ollowing he me hodology
sugges ed by Blasco e al. (2018) o deal wi h hese unce ain ies, he
app oxima e o de deg ee o he dolomi e p esen in his sys em was
calcula ed conside ing samples ZA-27, om Ja aba, and ZA-40, om
Alhama. The o de deg ee ob ained o he dolomi e in he ese oi o
his he mal sys em is simila o bo h samples: 11.3% in he case o
Ja aba and 14.7% in he case o Alhama, as expec ed close o he alue
o he dolomi e s udied by Hyeong and Capuano (2001).
Qua z equilib ium in he geo he mome ical simula ions (and
qua z geo he mome e esul s) p o ides easonable alues, in he
Fig. 6. Log (aCa
2+
/aMg
2+
) s. empe a u e plo o he calci e–dolomi e
equilib ium using diffe en dolomi es, om 25 o 150 °C. The equilib ia wi h
espec o calci e and ully-diso de ed dolomi e and wi h espec o calci e and
ully-o de ed dolomi e, ha e been calcula ed wi h he he modynamic da a in
he LLNL da abase. The equilib ia wi h espec o calci e and some pa ially
o de ed dolomi es p esen in na u al sys ems a e also shown (see ex ). The log
(aCa
2+
/aMg
2+
) a e age alue (0.146) calcula ed wi h PHREEQC o he
Ja aba and Alhama he mal wa e s is also ep esen ed as a ho izon al g ey line.
M. Blasco e al. *HRWKHUPLFV²
98
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
lowe ange o he es ima ed empe a u e (51 ± 14 °C).
Qua z (o chalcedony) – anhyd i e equilib ium has been shown o
be a eliable indica ion o he ese oi empe a u e (e.g. Pas o elli
e al., 1999;Le e e al., 2002;Alçiçek e al., 2016,2017;Blasco e al.,
2017,2018). Un o una ely, as men ioned abo e, his equilib ium is no
applicable o his sys em because anhyd i e equilib ium is no eached.
Fo o he key mine als (K- eldspa and aluminosilica e phases), he
es ima ed ese oi empe a u e ange in geo he mome ical simula-
ions depends s ongly on he he modynamic da a selec ed and Al
concen a ion. Howe e , using easonable solubili y “end-membe s” o
hese mine als (co e ing diffe ences due o he deg ee o c ys allini y,
pa icle size effec s o he o de /diso de phenomena), a ela i ely
na ow empe a u e ange o ± 20 °C can be ob ained, in ag eemen
wi h one o he sca ce ea lie unce ain y es ima ions o geo he mo-
me ical modelling, ca ied ou by Tole e al. (1993).
Taking in o accoun all he geo he mome ical echniques applied in
his s udy and he usual unce ain ies conside ed in he empe a u es
ob ained wi h classical geo he mome e s ( ± 5 o ± 10 °C and may be
g ea e han 20 °C; Fou nie , 1982), o geochemical modelling
( ± 20 °C; Tole e al., 1993), he empe a u e es ima e o 51 ± 14 °C
o he Alhama-Ja aba he mal wa e s can be conside ed qui e p ob-
able. This common empe a u e ange a dep h o he Alhama and
Ja aba he mal wa e s would be in ag eemen wi h he idea ha hei
o igin is om he same aqui e .
Fu he mo e, he esul s o he s udies ca ied ou in he con ex o
he ALGECO2 p ojec (IGME, 2010) in he a ea o he Almazán Basin,
indica e ha he ca bona e aqui e eaches a dep h o abou 1200 m.
The geo he mal g adien o he Almazán Basin is abou 30 °C/Km
(Fe nández e al., 1998) and, hus, conside ing an a e age ai em-
pe a u e o abou 14–15 °C in his a ea (López e al., 2007), he es i-
ma ed empe a u e a hese dep hs would be 52 °C, in close ag eemen
wi h he a e age empe a u e ob ained om he combined echniques
used in his s udy.
6. Conclusions
The wa e s o he low empe a u e Alhama-Ja aba geo he mal
sys em, hos ed in ca bona e ocks and one o he la ges na u ally
flowing he mal sys ems in Eu ope, ha e been cha ac e ised in his
s udy, and a ious chemical geo he mome ical echniques ha e been
es ed.
The he mal wa e s in he Ja aba sp ings a e o Ca-Mg−HCO
3
ype
whils hey a e mo e SO
4
-Cl ype in Alhama. The ange o eme ging
empe a u es in he Alhama sp ings is qui e na ow, be ween 30 and
32.4 °C, while in Ja aba he empe a u es ange be ween 21 and 32 °C,
due o he effec s o mixing wi h shallowe and coole wa e s. Va iable
CO
2
-ou gasssing p ocesses affec diffe en sp ings a bo h si es, p o-
mo ing changes in he pH alues o he wa e s. In summa y, he
Alhama-Ja aba sys em, as a whole, b ings oge he almos all d aw-
backs and possible difficul ies o he applica ion o he geo he mo-
me ical me hods in his ype o low empe a u e geo he mal sys em:
p oblems ela ed o he exis ence o seconda y p ocesses du ing he
ascen o he he mal wa e s and p oblems ela ed o he effec i e mi-
ne al equilib ia in he ese oi a low empe a u es.
The effec s o he seconda y p ocesses iden ified can be minimised
wi h 1) a ca e ul selec ion o he adequa e samples o he geo he -
mome ical calcula ions (e.g. disca ding hose samples affec ed by
mixing) and/o 2) using he econs uc ion me hodologies a ailable
when applying he mul icomponen geo he mome ical me hods (e.g.
adding CO
2
o e e se he effec s o CO
2
-ou gassing du ing he ascen o
he he mal wa e s).
The mine alogical/li hological cha ac e is ics o he aqui e im-
po an ly cons ain he mine al equilib ia a dep h and, he e o e, he
esul s ob ained wi h he classical geo he mome e s o wi h he mul-
icomponen geo he mome y. Ca ion geo he mome e s ha e been
success ully used in some ca bona e-e apo i ic geo he mal sys ems
wi h p esence o de i ial ocks in he aqui e . These de i al ocks a e
also p esen in he Alhama-Ja aba sys em bu he lowe esidence imes,
he lowe empe a u e a dep h and/o he mo e dispe se dis ibu ion o
siliciclas ic ma e ials in he aqui e p e en he wa e s om a aining
he mine al equilib ia on which hese geo he mome e s a e based (e.g.
albi e and K- eldspa ). This has also been confi med in he esul s o he
geo he mome ical modelling.
The aqui e s udied is domina ed by ca bona es wi h only a sligh
e apo i ic cha ac e eflec ed by he low abundance o gypsum/anhy-
d i e in he ocks and by he disequilib ium o he wa e s wi h espec
o hese phases. Due o his disequilib ium, he SO
4
–F geo he mome e
(specifically de eloped o ca bona e-e apo i ic geo he mal sys ems)
and he equilib ium qua z (o chalcedony)–anhyd i e (one o he mos
eliable equilib ia in he geo he mome ical modelling), canno be used
o his sys em.
The e o e, he only possible mine al equilib ia a ailable o he
geo he mome ical calcula ions in sys ems like he one p esen ed he e
a e silica polymo phs, calci e, dolomi e and clay mine als. A e e al-
ua ing he esul s ob ained wi h diffe en silica phases, he SiO
2
-qua z
geo he mome e appea s o p o ide consis en esul s in he sys em
s udied. The e alua ion o he dolomi e and clay mine al equilib ia,
howe e , shows impo an unce ain ies in he solubili y alues a ail-
able ela ed o deg ee o c ys allini y, pa icle size effec s and/o he
o de /diso de phenomena.
Al hough he wa e s a e in equilib ium wi h espec o calci e and
dolomi e, he unce ain ies associa ed wi h he o de deg ee o dolo-
mi e affec he Ca-Mg geo he mome e and he e alua ion o his
equilib ium by geo he mome ical modelling. To deal wi h hese un-
ce ain ies a possible s a egy is he one applied in his pape , consis ing
o e alua ing he esul s ob ained wi h diffe en dolomi es (wi h he Ca-
Mg geo he mome e and he geochemical modelling).
Finally, clay mine al equilib ia in he geo he mome ical modelling
p o ide consis en esul s wi hin a easonable unce ain y ange, as
long as p ope sensi i i y analysis is pe o med in o de o e alua e he
effec s o he he modynamic da a selec ed.
By applying all hese me hods, he ese oi empe a u e o he
Alhama-Ja aba sys em has been es ablished o be 51 ± 14 °C, wi h
wa e s in equilib ium wi h qua z, calci e, pa ially-o de ed dolomi e
and some aluminosilica e phases. This empe a u e is in close ag ee-
men wi h ha deduced om he esul s o geophysical s udies in he
a ea.
Acknowledgemen s
M. Blasco has wo ked on his s udy hanks o a schola ship om he
Minis y o Educa ion, Cul u e and Spo s o Spain, o he T aining o
Uni e si y Teache s ( e . FPU14/01523). This s udy o ms pa o he
ac i i ies o he Geochemical Modelling G oup (Uni e si y o Za agoza;
A agón Go e nmen ). The echnical assis ance o En ique Oli e , om
he Ea h Sciences Depa men o he Uni e si y o Za agoza, is also
acknowledged. The commen s and sugges ions o D . N. Spyche and o
wo anonymous e iewe s ha e con ibu ed o imp o e he wo k and
a e g a e ully app ecia ed.
Appendix A. Supplemen a y da a
Supplemen a y da a associa ed wi h his a icle can be ound, in he
online e sion, a h ps://doi.o g/10.1016/j.geo he mics.2018.11.004.
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Geo he mal Cong ess 2010 25–29.
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M. Blasco e al. *HRWKHUPLFV²
101
4. Resul s
4.5 Pape 5
Cha ac e isa ion o ecen a agoni e a e ine deposi s associa ed o
he Fi e o he mal wa e s (Spain) I: s able iso opes equilib ium
e alua ion
Mónica Blasco, Luis F. Auqué, Ma ía J. Gimeno, Ma ía P. As a, Juan Mandado
Sedimen a y Geology
Impac Fac o (2017): 2.575
Qua ile and Ca ego y (2017): Q1 (9/47), Geology
Sen : 02 May 2019
Cu en ly unde e iew
103
4. Resul s
Cha ac e isa ion o ecen a agoni e a e ine deposi s
associa ed o he Fi e o he mal wa e s (Spain) I: s able
iso opes equilib ium e alua ion
Unde e iew in Sedimen a y Geology
Mónica Blascoa,*, Luis F. Auquéa, Ma ía J. Gimenoa, Ma ía P. As ab, Juan Mandadoa
a Geochemical Modelling G oup. Pe ology and Geochemis y A ea, Ea h Sciences
Depa men , Uni e si y o Za agoza, Spain C/ Ped o Ce buna 12, 50009 Za agoza, Spain.
b Ins i u des Ciences de la Te e (ISTe e). Uni e si e G enoble Alpes - CNRS. 1381 Rue de la
Piscine, 38610, Giè es (F ance)
* Co esponding au ho : Geochemical Modelling G oup. Pe ology and Geochemis y A ea,
Ea h Sciences Depa men , Uni e si y o Za agoza, Spain. e-mail: monicabc@uniza .es; Tel.:
+34 976761071; Fax: +34 976761106
Abs ac
The a agoni e a e ine deposi s o he Fi e o he mal sp ings, wi h a p opo ion o a agoni e
highe han 98 % in mos o he samples, a e s udied in his pape . The main objec i e is o
imp o e he gene al unde s anding o he a agoni e p ecipi a ion since he deposi s o almos
pu e a agoni e a e e y sca ce. The s udy has been ocus on ob aining a comple e mine alogical
and iso opic cha ac e isa ion o hese solids, including he e alua ion o he δ18O and 13C
ac iona ion du ing hei p ecipi a ion, as a aluable in o ma ion o paleoclima e and
paleoen i onmen al s udies.
The Fi e o he mal wa e s, om which hese solids p ecipi a e, a e o chlo ide-sodium ype,
wi h sp ing empe a u e abou 45 ºC and nea neu al pH. One a e ine sample o almos pu e
a agoni e (98 %) was aken om a pipe discha ging he exceeding wa e om he cooling pool
inside he spa. The wa e empe a u e was abou 40 ºC and i su e ed an impo an p ocess o
CO2 loss, as sugges ed by he geochemical calcula ions and by he δ13C alues measu ed in he
a e ines and he wa e s. This CO2 ou gassing is he igge ing ac o o he o e sa u a ion
and concomi an p ecipi a ion o ca bona e phases, and he empe a u e seems o be he main
ac o con olling he p ecipi a ion o a agoni e o calci e in di e en p opo ions. This
empe a u e e ec has been checked by s udying ano he a e ine sample wi h a highe
p opo ion o calci e (40%), p ecipi a ed in ano he pipe a he end o all he spa ci cui whe e
he wa e discha ges a a iable empe a u es, om 33 o 40 ºC.
105
4. Resul s
Va ious δ18O iso ope ac iona ion equa ions o a agoni e and o calci e we e used o e alua e
he da a in he a e ine samples. The esul s indica e ha he p ecipi a ion ook place close o
equilib ium acco ding o some o hese equa ions and he calcula ed empe a u e i s e y well
wi h he measu ed one; mo eo e , no di e ences ha e been ound be ween he calci e–wa e
and a agoni e–wa e oxygen ac iona ion. The ac ha he equilib ium is main ained du ing
p ecipi a ion in a na u al sys em wi h an impo an CO2 loss is qui e su p ising. Howe e , i can
be explained by an oxygen iso opic equilib ium be ween dissol ed HCO3- and wa e and a di ec
ans e o he HCO3- iso ope signal o he p ecipi a ing ca bona e wi hou ac iona ion due o
he as CO2 loss and p ecipi a ion. This would esul in a δ18O equilib ium be ween a e ines
and wa e and, he e o e, accu a e empe a u e esul s could be expec ed using he δ18O
ac iona ion equa ions.
The empe a u e–δ18O alues o he a agoni e deposi s in Fi e o i wi h he a ailable da a in
o he a agoni e a e ines om he li e a u e (always wi h a agoni e p opo ions highe han 90
%). O e all, hey de ine a ac iona ion equa ion o na u al a agoni e in he empe a u e ange
o 23 o 80 ºC nea he expe imen al equa ion o Kim e al. (2007), sugges ing ha he exis ence
o equilib ium, o appa en equilib ium, si ua ions is no uncommon.
Keywo ds: geo he mal sys em; a e ine; a agoni e; s able iso ope; iso ope equilib ium
1. In oduc ion
The Fi e o he mal sp ings (Na a a egion, Spain) a e qui e well known and hei wa e s a e
used in wo spas in he illage o hei medicinal and he apeu ic p ope ies. They ha e been
s udied by di e en au ho s (e.g. Blasco e al., 2019, Auqué e al., 1989, 1988, Coloma e al.,
1998, 1997a, 1996, 1995; Fe nández e al., 1988) ob aining he empe a u e in he deep
ese oi , a comple e chemical and iso opic cha ac e isa ion o he hyd ogeochemical sys em
and a good knowledge o he main p ocesses con olling he e olu ion o he wa e s.
Despi e his b oad cha ac e isa ion o he he mal wa e s, he a e ines p ecipi a ing om hem
a e s ill almos uns udied. Tha is why he i s objec i e o his esea ch is he in-dep h s udy o
hese a e ines1. The ac ha some o he Fi e o a e ines consis o almos pu e a agoni e
1 The e minology ha will be used he e is he one p oposed by Fo d and Pedley (1996) in which he e m
a e ine is used o e e o he ca bona es p ecipi a ed om he mal (ho ) wa e s, while he e m u a is
ese ed o he ca bona es p ecipi a ed om cold wa e s (e.g. i e s).
106
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
(wi h less han 2 % o calci e) makes his sys em e en mo e in e es ing because he e a e e y
ew s udies abou pu e o almos pu e a agoni e a e ines o u as, as mos o hem a e
mix u es o calci e and a agoni e and hey a e s udied as a whole. The e o e, he s udy o he
a agoni e a e ine will help o imp o e he gene al unde s anding o he a agoni e p ecipi a ion
p ocess and, he s udy o ano he mo e calci e- ich a e ine (60% o calci e) p ecipi a ed om
he same he mal wa e s will se e o compa a i e pu poses and o e alua e he main
con olling ac o s esponsible o he p ecipi a ing mine al phases.
The he mal sp ings in he Fi e o spa a e cu en ly con olled o hei use in he balneo he apic
acili ies and he a e ines s udied he e a e gene a ed inside wa e discha ging pipes; howe e ,
hei s udy will s ill be use ul o he objec i es o his wo k as i has al eady been done by o he
au ho s such as As a e al. (2017) in a e ines collec ed in he acili ies o o he spas,
Rod íguez-Be igue e e al. (2018) in u as p ecipi a ed in a pipe used o i iga ion o A enas e
al. (2018) in a u a gene a ed in a pipe ha di e ed wa e om a i e .
The s udy and cha ac e isa ion o he Fi e o a agoni e a e ines will be add essed om wo
di e en poin s o iew which will be p esen ed and discussed in wo complemen a y pape s:
one dealing wi h he mine alogical and iso opic cha ac e isa ion o he a e ines ( he p esen
pape ) and he o he which will add ess hei ex u al and geochemical cha ac e isa ion, oge he
wi h he dis ibu ion coe icien s o some ace elemen s.
The ele ance o he iso ope cha ac e isa ion o hese solids lies on he ac ha he s able δ18O
iso ope signa u e o a e ines, u as and speleo hems p ecipi a ed unde equilib ium condi ions
depends on he empe a u e and, he e o e, i can be used o paleon i onmen al and
paleoclima ic econs uc ions (e.g. And ews, 2006; Capezzuoli e al., 2014; Fo d and Pedley,
1996; Fouke e al., 2000; Ga ne e al., 2004; Jones and Renau , 2010; Kele e al., 2011, 2008;
Lachnie , 2015; Liu e al., 2006, 2010; Osáca e al., 2016, 2013; Pedley, 2009; Pen ecos , 2005)
by using empi ical and expe imen al empe a u e-dependan equa ions assumed o ep esen he
iso opic equilib ium be ween a e ine and wa e . Howe e , he paleo he mome ical
in e p e a ion o he s able iso opes in ca bona es is no always s aigh o wa d due o se e al
easons: 1) he iso opic signa u e o he old a e ines pa en al wa e is unknown; 2) he
equilib ium is no always a ained, o main ained, du ing he a e ine p ecipi a ion due o he
kine ic iso ope e ec s ela ed o CO2 ou gassing and high p ecipi a ion a es (e. g. Fouke e al.,
2000; Kele e al., 2008; 2011; among o he s); and 3) he ep esen a i eness o hose equa ions
wi h espec o he eal equilib ium is no always wa an ied (e.g. Kele e al., 2015; Lachnie ,
2015). All hese di icul ies make he s udy o ac i ely p ecipi a ing a e ines an in e es ing
subjec ha will help o in e p e he iso ope composi ion in old a e ines.
107
4. Resul s
i s loca ion hei chemical cha ac e is ics would be e y simila o he main sp ing (F1) excep
o a empe a u e o 40 ºC.
Table 2. Chemical and iso opic analyses o he Fi e o he mal wa e ha sp ings in he Becque spa (F1;
whose chemical composi ion is cons an o e ime) and he chemical analysis o a wa e sample aken a
he exi o a discha ging pipe om he spa (FWNP). TDS (calcula ed using PHREEQC) and dissol ed
elemen s a e exp essed in ppm.
F1 FWNP
Tempe a u e (°C) 45.50 33
TDS 4820.2 4423
pH 6.86 7.72
HCO3- 174.02 125
Cl- 1610 1505
SO4- 1376 1290
Ca 469 441
Mg 92.10 80.8
Na 981 920
K 30.20 30.3
S 11.10 10.3
SiO2 23.75
Fe 0.13
δ18O in H2O (SMOW) -8.7
δ2H in H2O (SMOW) -63.9
δ13C in DIC (PDB) -8.42
The δ18O and δ2H alues in F1 (-8.7 and -63.9, espec i ely; Table 2) sugges a me eo ic o igin
o he he mal wa e since hey a e close o he Global Me eo ic Wa e Line (δ2H = 8 δ18O + 10;
C aig, 1961) and he Spanish Me eo ic Wa e Line calcula ed om he da a o he Spanish
Ne wo k o he con ol o he iso opes in he ain all (δ2H = 8 δ18O + 9.27; Díaz-Teijei o e al.,
2009). The δ13C alue in he dissol ed ino ganic ca bon o he he mal wa e is -8.4% (Table 2)
and i sugges s ha , a e in il a ion h ough he soils (deg ada ion o C3− ype plan s esul s in
δ13C alues o abou -23‰; Cla k and F i z, 1997), he he mal wa e in e ac s wi h ca bona e
ocks in he aqui e (wi h δ13C alues a ound 0‰; Cla k and F i z, 1997; Figu e 4).
Some specia ion-solubili y calcula ions we e ca ied ou wi h he PHREEQC geochemical code
(Pa khu s and Appelo, 2013) and he WATEQ4F he modynamic da abase. The main esul s
ela ed o he ca bona e sys em show ha calci e and a agoni e a e in equilib ium o close o
equilib ium a sp ing empe a u e in F1 (sa u a ion s a es o 0.14 and 0.01, espec i ely) and
wi h a high log pCO2, -1.58, whils hese mine als a e mo e o e sa u a ed (0.7 and 0.54,
114
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
espec i ely) in he wa e sample FWNP due o an impo an CO2 ou gassing du ing he
ci cula ion o he wa e s h ough he pipe gi ing a log pCO2 o -2.7. The amoun o CO2
ou gassing and calcium ca bona e p ecipi a ion can be calcula ed by a simple mass balance
be ween he wo wa e s and he esul s indica e ha he e a e 0.614 mmol/L o CO2 loss which
leads o he p ecipi a ion o 0.71 mmol/L o calcium ca bona e. The e o e, calcium ca bona e
was p ecipi a ing in he momen o he wa e sampling in he new pipe, indica ing ha he CO2
ou gassing is he igge ing ac o o he ca bona e p ecipi a ion, p omo ed by he high pCO2
and he high empe a u e o he wa e s a he sp ing (CO2 solubili y is lowe a highe
empe a u es, acili a ing he degassing o he a mosphe e).
This ou gassing p ocess mus ha e also aken place in he wa e ci cula ing h ough he old pipe
o p omo e he p ecipi a ion o he a agoni e a e ine. The sou ce wa e was he same he mal
sp ing F1, whose composi ional cha ac e s show mino a ia ions wi h ime (e.g. Auqué e al.,
1989; Blasco e al., 2019). The e o e simila equilib ium condi ions wi h espec o calci e and
o a agoni e should p e ail a he momen o eme gence and CO2 degassing would be necessa y
o igge he p ecipi a ion o ca bona es (o he wise, as he solubili y o hese mine als inc ease
wi h he dec ease o empe a u e he wa e s, ini ially in equilib ium in he sp ing, would ha e
su e ed he opposi e e ec in he cooling pool, he unde sa u a ion wi h espec o he
ca bona es).
4.2. Main cha ac e is ics o he a e ines
The a e ine samples consis o an al e na ion o clea and eddish bands (Figu e 3b). Each
band is also cons i u ed by a hin lamina ion ba ely dis inguishable a a glance bu e iden when
s udying he hin sec ion unde he pe og aphic mic oscope. This lamina ion is no ela ed o
empo al (o clima ic) a ia ions bu o he in e mi en discha ge h ough he pipes and
he e o e, hey a e condi ioned by he a ailabili y o wa e , as also desc ibed by Rod íguez-
Be igue e e al. (2018) in o he human induced a e ines.
Al hough bo h a e ines look simila , hei mine alogy is qui e di e en . The X – Ray
Di ac ion analyses o wo clea and wo eddish bands o sample FTOP ( om he old pipe)
indica e a p opo ion o a agoni e highe han 98 % wi h mino amoun s o calci e, and his is
common o bo h ypes o bands. The mine alogical esul s o sample FTNP ( om he new pipe;
Figu e 3a) indica e a highe p opo ion o calci e (abou 60 %) and much less a agoni e (40 %),
as an a e age om one clea and one eddish band.
115
4. Resul s
Figu e 3. Panel a) New pipe a i s discha ge poin on he Cidacos i e , whe e a e ine FTNP is
p ecipi a ing. Panel b) FTOP and FTNP a e ine samples whe e he al e na ion be ween clea and
eddish bands can be seen. Panel c) Pho og aph aken wi h a pe og aphic mic oscope whe e he ib ous-
adial ex u e wi h an shaped agg ega es can be seen (FTOP). Panel d) FESEM image o he FTOP
a e ine showing he a agoni ic bands (on he igh and le o he image) and a calci e in e laye in
be ween. Some dispe se calci e c ys al in he a agoni e can also be app ecia ed. Panel e) FESEM image o
he FTOP a e ine wi h a de ail o an a agoni e needle wi h i on oxy-hyd oxides g owing on i . Panel )
FESEM image o he FTNP a e ine whe e abundan calci e c ys als can be iden i ied while a agoni e
needles a e less common.
116
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
The de ailed mine alogical examina ion o FTOP allowed iden i ying addi ional ele an
cha ac e is ics o he a agoni ic a e ines: 1) he pe og aphic mic oscope showed a ib ous-
adial, an-shaped ex u e in he a agoni e (Figu e 3c) which, in he FESEM, is seen as
elonga ed p isms o needles agg ega ed o ming bushes (Figu e 3d); 2) he p esence o dispe se
calci e in all he bands is mainly associa ed o he hin in e laye s be ween clea and eddish
a agoni e bands, whils he e is no a p e e en ial dis ibu ion o calci e o a agoni e in he FTNP
a e ine (Figu es 3d and 3 ); 3) lump agg ega es o amo phous oxy-hyd oxides ha e been
iden i ied on he a agoni e needles in he eddish bands (Figu e 3e) and hey p obably a e he
esponsible o he colou o he bands despi e hei low con en (uniden i ied by XRD and
cohe en wi h he low dissol ed Fe in wa e s; Table 2).
Examina ion o hin sec ions and de ailed FESEM obse a ions show no e idence o mic obial
ac i i y (e.g. bio ilms o ex acellula polyme ic subs ances, EPS) in he a e ines. These
e idences a e no usually p ese ed in old a e ines (Jones and Renau , 1995; Peng and Jones,
2012) bu gi en ha he samples s udied he e a e om a p esen deposi , he lack o hem
sugges s an abiogenic o igin (Jones, 2017a).
Iso opic de e mina ions o δ18O and δ13C in he ca bona es we e made in he a e ine sample
FTNP (whole sample) and in 6 subsamples o FTOP, in h ee eddish bands (FTOP-D1, D2,
D3), and in h ee clea bands (FTOP-C1, C2 C3; Table 3). The esul s show ha he δ18O alues
a e simila in all he bands o he a agoni e a e ine and also in he calci e-a agoni e a e ine
be ween 17.719 and 17.927 ‰ s. V-SMOW.
Table 3. Iso opic da a o a e ine samples: he da k bands (FTOP-D) and he clea bands (FTOP-C) o
sample FTOP, and he whole sample o a e ine FTNP.
δ13C (PDB) δ18O (PDB) δ18O (SMOW)
FTOP-D1 0.536 -12.623 17.896
FTOP-D2 0.544 -12.795 17.719
FTOP-D3 0.364 -12.754 17.761
FTOP-C1 0.859 -12.393 17.927
FTOP-C2 0.803 -12.683 17.834
FTOP-C3 0.794 -12.737 17.778
FTNP 0.87 -12.617 17.854
Wi h espec o he δ13C alues (‰ s V-PDB), hey a e highe in he clea bands (FTOP-C) and
in he sample FTNP, abou 0.8 ‰, han in he eddish bands, be ween 0.36 ‰ and 0.54 ‰
(Table 3). A mo e de ailed desc ip ion o he al e na ing clea and eddish bands and hei
geochemical cha ac e isa ion will be discussed in he second pape abou he ace elemen
con en s in he a e ine deposi s.
117
4. Resul s
5. Discussion
The e a e wo main issues o discuss he e. The i s one e e s o he di e en mine alogical
composi ion o he wo s udied a e ine samples (di e en amoun s o a agoni e and calci e)
and he second e e s o hei iso opic composi ion and hei possible use as paleoen i onmen al
indica o s.
5.1. Mine alogy
The e a e se e al classical s udies on he main ac o s con olling calci e o a agoni e
p ecipi a ion in geological na u al samples and in labo a o y expe imen s (Folk, 1994; Fouke e
al., 2000; Jones, 2017b; Pen ecos , 2005; and e e ences he ein). These ac o s a e: empe a u e,
Mg/Ca a io in he wa e , dissol ed s on ium con en , CO2 con en and degassing, and he
biological in luence. Excep o he las ac o , ha will no be discussed he e since no e idence
o biological e ec s ha e been ound in he s udied a e ines, an e alua ion o he in luence o
he o he con olling ac o s in p esen ed nex .
Tempe a u e and magnesium concen a ion ha e been conside ed he mos impo an ac o s
con olling he mine alogy o he p ecipi a ed ca bona es. Gene ally speaking, a agoni e is
conside ed o p ecipi a e a highe empe a u es han calci e; o example, Folk (1994) obse ed
ha a agoni e p ecipi a es i he empe a u e is highe han 40 ºC i espec i e o he wa e
composi ion, and calci e would p ecipi a e i he empe a u e o he wa e is lowe han 40ºC
and i is Ca- ich. Fouke e al. (2000), in he same line, indica ed ha i he empe a u e is highe
han 44 ºC only a agoni e p ecipi a es, i he empe a u e is lowe han 30 ºC only calci e does,
and when i is be ween 30 and 43 ºC bo h mine al phases p ecipi a e oge he . Howe e ,
a agoni e is no always a ou ed o e calci e a his “c i ical empe a u e” o abou 40 ºC; o
example, calci e has been ound o p ecipi a e in Ege szalók (Hunga y) a a empe a u e o
abou 70 ºC (Kele e al., 2008) and in No h Island (New Zealand), whe e he wa e empe a u e
is highe han 90 ºC (Jones e al., 1996; see also he e iew by Jones, 2017b).
Rega ding he magnesium concen a ion in he wa e s, Fischbeck and Mülle (1971) s a ed ha
he a agoni e p ecipi a ion is signi ican i he Mg/Ca a io is highe han 2.9; Folk (1994)
epo ed ha a agoni e would p ecipi a e i he Mg/Ca a io o he wa e is highe han 1:1 no
ma e he wa e empe a u e; and AlKha ib and Eisenhaue (2017) indica ed ha any Mg/Ca
a io highe han 2:1 will assu e a agoni e p ecipi a ion e en a empe a u es o only 12.5 ºC.
Fu he mo e, in some lakes in he G ea Plains o No h Ame ica, he e apo a ion p oduces high
Mg/Ca a ios ha igge he p ecipi a ion o a agoni e despi e a empe a u e o he wa e lowe
han 30 ºC (Las , 1989; Las e al., 1998).
In he case o he sample FTOP, he empe a u e o he pa en al wa e is 40 ºC and he
composi ion is assumed o be he same as he he mal wa e F1, wi h a e y low Mg/Ca a io o
118
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
0.32. Acco ding o he p e ious au ho s, he wa e empe a u e would a ou he a agoni e
p ecipi a ion, despi e he low Mg/Ca which would allow he p ecipi a ion o some mino
amoun s o calci e. This is exac ly wha has been obse ed and, he e o e, he hin calci e in e -
laye s be ween he a agoni e bands seem o ep esen in e -discha ge pe iods, when he
emaining wa e would p obably ha e a empe a u e lowe han 40 ºC. In he case o he sample
FTNP, he Mg/Ca a io in he pa en al wa e (FWNP) is 0.27, e y simila o he F1 sample, bu
he empe a u e o he wa e discha ged h ough he pipe a ies be ween 40 and 33 ºC which
would explain he highe p opo ion o calci e. So, in hese a e ines empe a u e seems o be
he main con ol o he mine alogy.
O he con olling ac o s may play a ole, addi ionally o, o in e played wi h, empe a u e
(Jones, 2017b). Some au ho s a gue ha he S con en in he wa e s a ou s a agoni e
p ecipi a ion and inhibi s calci e g ow h bu o he s s a e ha he highe S concen a ions in
a agoni e, in compa ison o calci e, a e only due o he pa i ion coe icien s, which a e highe in
a agoni e (S inco po a es easie in a agoni e la ice han in calci e). The ac ha he wo
a e ine samples FTOP and FTNP ha e p ecipi a ed om a e y simila wa e wi h simila S
con en (Table 2) and one o hem is almos pu e a agoni e and he o he has 60 % o calci e,
suppo s he hypo hesis ha he dissol ed con en o S is no an impo an con olling ac o o
he mine alogical phase, a leas in ou sys em.
Finally, ega ding he impo ance o CO2 con en and ou gassing a e some au ho s epo ed ha
a agoni e p ecipi a ion is a ou ed by high CO2 con en s and degassing a es as i is common in
he mal sp ings (Cha e z e al., 1991; Jones, 2017b; Ki ano, 1963). As s a ed abo e, CO2
ou gassing is he igge ing ac o o he ca bona e p ecipi a ion in he s udied a e ines, since
he sp ing wa e s a e in equilib ium, o nea equilib ium, wi h espec o a agoni e and calci e.
Howe e , di e ences in he a e o CO2 ou gassing may also p omo e a ia ions in he
o e sa u a ion deg ee and, in u n, in he p ecipi a ed ca bona e phase (Jones and Peng, 2016;
Jones, 2017b). The a e ines s udied he e p ecipi a e inside inclined pipes whe e an impo an
ou gassing a e is expec ed. Bu di e ences may a ise by a ia ions in he discha ge and/o in
he dis ance o he p ecipi a es om he sp ing.
In he case o he pu e a agoni e a e ine FTOP, p ecipi a ed om wa e s a nea ly cons an
empe a u es (40 ºC), he possible a ia ions in he ou gassing a e do no seem o induce
impo an mine alogical changes. Only he hin calci e in e -laye s be ween he a agoni e bands,
which is in e p e ed as ep esen ing in e -discha ge pe iods, could be ela ed o wa e
empe a u es lowe han 40 ºC o pe iods o lowe discha ge and lowe CO2 ou gassing a e.
The FTNP a e ine, loca ed a he away om he sou ce he mal wa e s han he FTOP
deposi s, is associa ed wi h a wide ange o wa e empe a u es (33-40 ºC) and wi h mo e
119
4. Resul s
a iable discha ge egimes. In he momen o he sampling o FWNP, he wa e empe a u e was
33 ºC (Table 2) and he discha ge was low. Highe discha ges, wa e empe a u es and, mos
p obably, CO2 ou gassing a es, occu in his pipe du ing he spa ac i i y. The e o e, coupled
changes in empe a u e and CO2 ou gassing a es may also be he cause o he highe
p opo ions o calci e in his deposi , al hough mo e de ailed s udies would be necessa y o
cla i y his hypo hesis
5.2. S able iso opes
5.2.1.
13C
The δ13C alues o a e ines a e conside ed o e lec he o igin o he CO2 in he sou ce wa e
in he classi ica ion scheme o Pen ecos (2005) which includes wo main a e ine ypes,
he mogene and me eogene. The mogene a e ines a e hose in which he CO2 has a deep
o igin (magma ic o om deca bona a ion p ocesses) and he δ13C alues ange om -1 o +10
‰. T a e ines a e conside ed as me eogene i he CO2 has a shallow o igin, mainly me eo ic,
and hey can be di ided in ambien and supe ambien (o he mome eogene). The ambien
me eogene a e ines a e o med a ambien empe a u es (wa e s ha e no su e ed a hea ing
p ocess) and hey display δ13C alues anging om -12 o -3 ‰. The supe ambien me eogene
a e ines p ecipi a e om wa m wa e s (wa e s hea ed h ough deep ci cula ion and eme ging
as ho sp ings) and ha e δ13C alues anging om -12 o +2 ‰.The δ13C da a in he s udied
a e ines ange om 0.36 o 0.87 ‰ (Table 3) and, he e o e, hey could be classi ied as
supe ambien me eogene o he mome eogene a e ines.
Howe e , he sou ce o CO2 can only be p ope ly assessed om he δ13C alues in a e ines
whe e seconda y modi ica ions (e.g. CO2 ou gassing) o he iso opic ca ie a e minimised (e.g.
close o he sp ing o i ice; Kele e al., 2011; Jones and Peng, 2016 and e e ences he ein) and
his is no exac ly he case he e. Fi e o a e ines ha e p ecipi a ed a e CO2 degassing o he
he mal wa e s (see abo e) and, he e o e, hei δ13C alues would e lec he δ13C in he
dissol ed CO2 in he momen o he a e ine p ecipi a ion. In o de o be e check he meaning
o he alues analysed in he a e ines, he δ13C in he CO2 in he p ecipi a ion momen and in
he sp ing condi ions, p e ious o he CO2 ou gassing, ha e been calcula ed.
As p e iously done by o he au ho s (e.g. Jones and Peng, 2016; Kele e al., 2011, 2008;
Minissale, 2004; Sie al a e al., 2010), he δ13C in he a e ine can be used o es ima e he
δ13C in he dissol ed CO2 in he momen o he a e ine p ecipi a ion, by using he equa ion
p oposed by Panichi and Tongio gi (1976; Table 4). Applying his equa ion o all he a e ine
samples (a agoni e and calci e−a agoni e), he δ13CCO2 ob ained ange om -10 o -9.5 ‰.
Howe e , since his equa ion does no ake in o accoun he δ13C dependency on empe a u e,
120
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
he calcula ions we e epea ed wi h he equa ions p oposed by Romanek e al. (1992; Table 4)
o he δ13C ac iona ion be ween a agoni e (o calci e) and CO2.
Table 4. F ac iona ion equa ions o he δ13C in CO2 es ima ion om δ13C in he ca bona e o δ13C in
HCO3 dissol ed.
Au ho Equa ion
CaCO3-CO2
Panichi and Tongio gi (1979) 1.210.5
Romanek e al. (1992)1 1013.880.13
Romanek e al. (1992)1 1011.980.12
HCO3-CO2
Mook e al. (1974)2 109.5221024.1
Zhang e al. (1995)1 100.095410.41
Sza an (1997)1 100.114110.78
1 Tempe a u e (T) is in ºC
2 Tempe a u e (T) is in kel in
The δ13CCO2 alues ob ained o he FTOP samples (a agoni e), assuming a p ecipi a ion
empe a u e o 40 ºC, we e om -8.3 o -7.8 ‰. Fo sample FTNP, he p ecipi a ion
empe a u es conside ed o he calcula ion we e be ween 33 and 40 ºC (possible ange o he
ci cula ing wa e s) and he alues ob ained we e be ween -7.2 and -6.3 ‰. In summa y,
conside ing all he esul s ob ained wi h he equa ions p oposed by Romanek e al. (1992) he
δ13C in he dissol ed CO2 when he a e ine p ecipi a ed was in he ange o -8.3 o -6.3 ‰.
These alues we e hen compa ed wi h he δ13C in he CO2 calcula ed in he eme gence sp ing
(wa e sample F1). This las alue was heo e ically app oxima ed om he δ13C analysed in he
DIC (dissol ed ino ganic ca bon) assuming ha he DIC mainly co esponds o HCO3- ( he pH
alue o he sp ing wa e is nea 7; Table 2) and using he equa ions p oposed by Mook e al.
(1974), Zhang e al. (1995) and Sza an (1997) o he δ13C ac iona ion be ween HCO3 and CO2
(Table 4). A good ag eemen a ound -15 ‰ was ob ained among all hese equa ions.
Two main conclusions can be ex ac ed om hese esul s:
Fi s , he δ13C alue calcula ed o he CO2 a sp ing condi ions, and he
hyd ogeological and hyd ogeochemical cha ac e s o he Fi e o geo he mal sys em
(Blasco e al, 2019), suppo he classi ica ion o he a e ines as he mome eogene,
de i ed om wa e s hea ed by a deep ci cula ion bu wi hou an “endogenous” δ13C
componen (Pen ecos , 2005). In his scheme, ca bon dissol ed om he ca bona e
ocks in he aqui e (wi h δ13C alues usually be ween -1 and 5‰; Figu e 4) would
in luence he δ13C alues o he wa e s (and a e ines) shi ing hem owa ds
iso opically hea ie alues han hose in he echa ge wa e s (Figu e 4).
121
4. Resul s
Second, he δ13C alues calcula ed o he CO2 a sp ing condi ion (-15 ‰) a e mo e
nega i e han in he momen o he a e ine p ecipi a ion (-8.3 o -6.3 ‰). These
numbe s would be consis en wi h he a o emen ioned exis ence o a CO2 ou gassing
p ocess ( esul ing in he δ13C en ichmen in he CO2 o he wa e s) as he igge o he
a e ine p ecipi a ion.
Figu e 4. δ13C composi ion o he Fi e o he mal wa e and he a e ine p ecipi a ed om i ( he
a e ine ep esen a ion include all he bands o FTOP sample and he FNTP sample, since he alues a e
be ween 0.9 and 0.3). The iso opic alues o he possible δ13C sou ces a e shown in he uppe pa o he
g aph. The equa ions desc ibed by Romanek e al. (1992) ha e been used o he calcula ion o he
iso opic heo e ical signa u e o DIC. Figu e modi ied om Delgado and Reyes (2004) and Reyes e al.
(1998).
5.2.2.
18O
As men ioned abo e, al hough wi h some unce ain ies ela ed o he possible equilib ium
si ua ions be ween he solids and hei pa en al wa e s, he use o δ18O in a agoni e (o calci e)
o paleoclima ic and paleon i onmen al econs uc ions is a e y use ul ool. The e a e some
examples in na u al sys ems o a e ine p ecipi a ion unde , o close o, equilib ium condi ions
wi h espec o some o he ac iona ion equa ions (A enas e al., 2018; As a e al., 2017;
Cha e z e al., 1991; Coplen, 2007; Ga ne e al., 2004; Kele e al., 2015; Lachnie e al., 2012;
Li e al., 2011, 2012, Osáca e al., 2013, 2016; Wang e al., 2014; Yan e al., 2012). Bu he e
a e also examples whe e equilib ium is no main ained du ing p ecipi a ion (As a e al., 2017;
Coplen, 2007; Demény e al., 2010; Fouke e al., 2000; F iedman, 1970; Kele e al., 2015, 2011,
2008, Lojen e al., 2009, 2004; Wang e al., 2014; Yan e al., 2012; Za dla e al., 2017).
The s udy o an ac i e p ecipi a ion sys em, like he one p esen ed he e, p o ides he possibili y
o compa e he empe a u e esul s ob ained om he applica ion o he δ18O “equilib ium”
122
Geochemical cha ac e isa ion o low empe a u e ca bona e geo he mal sys ems
ac iona ion equa ions and he empe a u e ac ually measu ed in he pa en al wa e . This will
gi e a be e knowledge o he p ocesses a ec ing he iso opic equilib ium and will help o
in e p e he iso opic signa u e o old a e ines.
To do ha , se e al equa ions (sec ion 3.3) ha e been applied o δ18O equilib ium be ween he
a agoni es om sample FTOP ( he 6 subsamples) and he equi alen o hei pa en al wa e , F1
wi h 40 ºC. Fo compa a i e pu poses, some o he a agoni e and calci e equilib ium equa ions
(sec ion 3.3) ha e been used o he sample FTNP (cons i u ed by a mix u e o calci e and
a agoni e) and he wa e F1 (a 40 ºC) because, un o una ely, he e is no iso opic in o ma ion
om i s own pa en al wa e FWNP.
All ac iona ion equa ions used he e ha e been ep esen ed in Figu e 5. Panel a shows he
equa ions o a agoni e and panel b shows he equa ions o calci e (o o a mix u e o calci e
and a agoni e). The iso opic alues o he s udied a e ines a hei p ecipi a ion empe a u es
a e also shown: six open ci cles o he a agoni e a e ine in Figu e 5a, and a g ey ec angle
ep esen ing he calci e-a agoni e a e ine and he in e al be ween 33 – 40 ºC ha co e s he
empe a u e a ia ion o he wa e ci cula ing h ough he pipe, in Figu es 5a and b. As i can be
seen, all he a e ine samples all in he “equilib ium window” de ined by he a ea co e ed by
all he ac iona ion equa ions, sugges ing ha hey ha e p ecipi a ed unde o close o iso ope
equilib ium (e.g. Lachnie ; 2015). Howe e , his o e all “equilib ium” si ua ion is ansla ed o
a ela i ely wide ange o possible empe a u es co e ed by he whole se o conside ed
equa ions (Table 5).
Rega ding he pu e a agoni e a e ine FTOP, he e a e wo equa ions ha p o ide disc epan
empe a u es (Table 5): 1) he one p oposed by Zhou and Zheng (2003) which gi es a
empe a u e abou 30 ºC (p obably due o he exis ing con o e sy abou he expe imen al
condi ions o i s de e mina ion; Ho i a and Clay on, 2007; Kim and O’Neil, 2005; Lécuye e
al., 2012; Wang e al., 2013) and 2) he empi ical equa ion om Kele e al. (2015), which
p o ides a empe a u e o almos 48 ºC, which is highe han he possible pa en al wa e
(p obably due o he ac ha he i ing o his equa ion was s ongly in luenced by i e samples
wi h e y high ac iona ion o unclea o igin; Kele e al. 2015). In bo h cases he esul s should
be used wi h cau ion and hey would no be aken in o accoun in he discussion below. The
empe a u e ob ained using he es o he equa ions, ega dless i hey we e calib a ed using
biogenic o ino ganic a agoni es, is abou 40 ºC which is he empe a u e a which he
p ecipi a ion ac ually akes place. These coinciden esul s could be expec ed as he equa ions
used he e a e wi hin he unce ain y ange de ined by Kim e al. (2007) in hei calib a ion (±
0.46 ‰, see Figu e 5 in Kim e al., 2007).
123
4. Resul s
