Applied mineralogy in the study of historical lime mortars

8. Appendices: Published and Submi ed Wo ks
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8.Appendices
Published and Submi ed Wo ks
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8. Appendices: Published and Submi ed Wo ks
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APPENDIX I
Accu a e Mine alogical Cha ac e iza ion o Assess he
Radioca bon Da ing o His o ical Lime Mo a s
Applied Mine alogy in he S udy o His o ical Lime Mo a s
78
8. Appendices: Published and Submi ed Wo ks
79
APPENDIX I.1
Hyd o alci e and Hyd ocalumi e in Mo a Binde s om he Medie al
Cas le o Po illa (Ála a, No h Spain): Accu a e Mine alogical Con ol o
Achie e Mo e Reliable Ch onological Ages
G aciela Ponce-An ón, Luis Angel O ega, Ma ia C uz Zuluaga,
Ainhoa Alonso-Olazabal, Jose Luis Solaun
Mine als 2018; 8(8):326

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A icle Me ics
9 Jou nal Ci a ion Repo s
Ci a ions: 1
Impac Fac o
2018
5 Yea s
2.25
2.453
JCR® Rank
Classi ica ion
Qua ile
Pe cen ile
Mine alogy
12 o 29
Q2
60.345
Mining & Mine al P ocessing
6 o 19
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70.053
9 Scopus
Ci a ions: 3
Ci eSco e 2018
2.46
SJR 2018
0.427
SNIP 2018
0.966
Ci eSco e Rank
Classi ica ion
Pe cen ile
Ea h and Plane a y Sciences
(Geo echnical Enginee ing and Enginee ing
Geology)
39 o 176
78
Ea h and Plane a y Sciences
(Geology)
47 o 217
78
9 Google Academic
Ci a ions: 7
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82
mine als
A icle
Hyd o alci e and Hyd ocalumi e in Mo a Binde s
om he Medie al Cas le o Po illa (Ála a, No h
Spain): Accu a e Mine alogical Con ol o Achie e
Mo e Reliable Ch onological Ages
G aciela Ponce-An ón1,*ID , Luis Angel O ega 1ID , Ma ia C uz Zuluaga 1,
Ainhoa Alonso-Olazabal 1and Jose Luis Solaun 2ID
1Depa men o Mine alogy and Pe ology, Science and Technology Facul y, Uni e si y o he Basque
Coun y-UPV/EHU, Sa iena s/n, 48940 Leioa, Bizkaia, Spain; [email p o ec ed] (L.A.O.);
[email p o ec ed] (M.C.Z.); [email p o ec ed] (A.A.-O.)
2Depa men o Geog aphy, P ehis o y and A chaeology, Facul y o A s, Uni e si y o he Basque
Coun y-UPV/EHU, Paseo de la Uni e sidad, 5, 01006 Vi o ia-Gas eiz, Spain; [email p o ec ed]
*Co espondence: [email p o ec ed]; Tel.: +34-946-015-456
Recei ed: 8 June 2018; Accep ed: 26 July 2018; Published: 29 July 2018
!"#!$%&'(!
!"#$%&'
Abs ac :
Mo a s om di e en s a ig aphic uni s a Po illa Cas le (Ala a, No h Spain) ha e
been analyzed o mine alogical cha ac e iza ion be o e adioca bon da ing. The mo a binde a
Po illa Cas le is composed no only o neo o ma ion calci e bu also o double-laye ed hyd oxide
(LDH) mine als such as hyd o alci e and hyd ocalumi e. The mine alogy o se e al ac ions o
he binde has been analyzed o de e mine he g anulome ic dis ibu ion o mine als in he binde .
The con inuous moni o ing o mine alogy du ing he ex ac ion o di e en g ain size ac ions
has been pe o med by using a scanning elec on mic oscopy (SEM), X- ay di ac ion (XRD), and
he mog a ime ic analyses (TGA). Hyd o alci e and hyd ocalumi e-bea ing mo a binde s gi e
olde ages han expec ed since hey in oduce dead ca bon in o he sys em.
Keywo ds: mo a ; binde ; hyd o alci e; hyd ocalumi e; adioca bon da ing
1. In oduc ion
One o he main goals in building a chaeology is o de e mine he age o he s uc u es disco e ed.
In he absence o w i en eco ds o o he a chaeological e idence o es ablish he ch onology o he
building, adi ionally wooden imbe s a e used in adioca bon da ing [
1
]. Th ough his way, he
da e ob ained may poin o olde ages due o ma e ial euse o long s o age. The e o e, i is i al o
de e mine ha he his o ical emains a e no a ec ed by he use o olde cons uc ion ma e ials since
he euse o wood ma e ials leads o an in-buil age de ined as he di e ence be ween he ime when
he wood o med and he da e o he e en o in e es [2–5].
In his amewo k, mo a s can p o ide a po en ial da ing solu ion. A chaeological mo a s a e
a i icial ma e ials composed o a mix u e o lime o plas e as binde and sand o o he kinds o
o ganic o ino ganic addi i e as agg ega es. The ease o p epa a ion as well as he a ailabili y o aw
ma e ials and hei du abili y ha e con ibu ed o make mo a s ubiqui ous ma e ials a si es om
he Neoli hic pe iod onwa ds, which becomes an impo an sou ce o in o ma ion in a chaeological
si es [6,7].
A chaeological mo a s ha e been da ed by using adioca bon me hods since he 1960s as a way
o de e mine he age o his o ical/a chaeological s uc u es. As such, he applica ion o adioca bon
da ing o mo a s has been desc ibed by se e al au ho s [
8
–
21
]. Many s udies ha e used cha coal
Mine als 2018,8, 326; doi:10.3390/min8080326 www.mdpi.com/jou nal/mine als
8. Appendices: Published and Submi ed Wo ks
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ine ac ion (<2 µm), magnesium calci e was iden i ied as he main componen o all samples while
qua z, hyd o alci e [Mg6Al2(CO3)(OH)16·4(H2O)], and hyd ocalumi e
[Ca4Al2(Cl,CO3,OH)2(OH)12·4H2O] a e also p esen in mino amoun s (Figu e 5). The low in ensi y o
hyd o alci e and hyd ocalumi e e lec ions indica es no only low abundance bu also he low
deg ee o c ys alliza ion o hese mine al phases [49].
Figu e 4. Pho omic og aphs showing he ex u al he e ogenei y o his o ic lime mo a s om Po illa
Cas le. (a) Mo a wi h ock agmen s, lumps, and qua z g ains. (b) F agmen s o unbu n
limes one and angula qua z g ains. (c) Mo a wi h limes one agmen s and qua z bea ing lumps.
(d) Mo a wi h a pu e lump and cha coal agmen . Rx: ock agmen , Q z: qua z, L: lump, U:
unbu n , C: cha coal.
Figu e 5.
X- ay di ac ion pa e ns o ex ac ed binde ac ions. (
a
) Fine ac ion, (
b
) ul a ine ac ion,
and (
c
) a ge ac ion. HC: hyd ocalumi e, HT: hyd o alci e, Q z: qua z, Mg-Cal: magnesium calci e.
These LDH mine al phases a e o med as a esul o he slaking p ocess and iden i ica ion and
cha ac e iza ion is c ucial due o hei e y high abili y o ix ca bona e anions [
68
]. Du ing he
ehyd a ion p ocess, CO
32
om he pa ial washing o unbu n agmen s o limes one is ixed in he
c ys alline s uc u e o HT-like mine als. The cap u ed CO
32
in oduces dead ca bon in he sys em
and ages he adiome ic da es. A new s ep was in oduced in he ex ac ion p ocedu e in o de o
emo e he po en ial con aminan HT-like mine al phases in he ul a ine ac ion (<0.5 µm).
SEM obse a ions o ine ac ion (<2
µ
m) o he binde con i m he p esence o e y small HT-like
pa icles embedded in a calci ic ma ix (Figu e 6). I egula and hexagonal c ys als o <0.5
µ
m g ain
size, co esponding o Ca-en iched o Mg-en iched anion clays, can be obse ed in Figu e 6b. The
Ene gy Dispe si e X- ay (EDX) analyses indica e ha well- o med o euhed al c ys als co espond o
Ca-en iched HT-like pa icles (poin 1 in Figu e 7) while he i egula o anhed al c ys als co espond
o Mg-en iched HT-like pa icles (poin 2 in Figu e 7). The e o e, Ca-en iched pa icles co espond
o hyd ocalumi e and Mg-en iched pa icles o hyd o alci e. In ac , hyd o alci e is mo e likely o be
p esen as a non-well- o med phase compa ed wi h hyd ocalumi e [
44
]. The EDX analysis also shows
he p esence o silica ha has been a ibu ed o he p esence o mic oc ys alline qua z. The SEM
images o ul a ine ac ion (<0.5
µ
m) show a homogeneous ma ix composed only o hyd o alci e and
hyd ocalumi e phases o a <0.5
µ
m g ain size. The SEM-EDX analysis suppo s ha he ex ac ion o
HT-like mine als om he ine ac ion was success ul (Figu e 6c).
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Figu e 5. X- ay di ac ion pa e ns o ex ac ed binde ac ions. (a) Fine ac ion, (b) ul a ine
ac ion, and (c) a ge ac ion. HC: hyd ocalumi e, HT: hyd o alci e, Q z: qua z, Mg-Cal:
magnesium calci e.
These LDH mine al phases a e o med as a esul o he slaking p ocess and iden i ica ion and
cha ac e iza ion is c ucial due o hei e y high abili y o ix ca bona e anions [68]. Du ing he
ehyd a ion p ocess, CO32− om he pa ial washing o unbu n agmen s o limes one is ixed in he
c ys alline s uc u e o HT-like mine als. The cap u ed CO32− in oduces dead ca bon in he sys em
and ages he adiome ic da es. A new s ep was in oduced in he ex ac ion p ocedu e in o de o
emo e he po en ial con aminan HT-like mine al phases in he ul a ine ac ion (<0.5 µm).
SEM obse a ions o ine ac ion (<2 µm) o he binde con i m he p esence o e y small
HT-like pa icles embedded in a calci ic ma ix (Figu e 6). I egula and hexagonal c ys als o <0.5
µm g ain size, co esponding o Ca-en iched o Mg-en iched anion clays, can be obse ed in Figu e
6b. The Ene gy Dispe si e X- ay (EDX) analyses indica e ha well- o med o euhed al c ys als
co espond o Ca-en iched HT-like pa icles (poin 1 in Figu e 7) while he i egula o anhed al
c ys als co espond o Mg-en iched HT-like pa icles (poin 2 in Figu e 7). The e o e, Ca-en iched
pa icles co espond o hyd ocalumi e and Mg-en iched pa icles o hyd o alci e. In ac ,
hyd o alci e is mo e likely o be p esen as a non-well- o med phase compa ed wi h hyd ocalumi e
[44]. The EDX analysis also shows he p esence o silica ha has been a ibu ed o he p esence o
mic oc ys alline qua z. The SEM images o ul a ine ac ion (<0.5 µm) show a homogeneous ma ix
composed only o hyd o alci e and hyd ocalumi e phases o a <0.5 µm g ain size. The SEM-EDX
analysis suppo s ha he ex ac ion o HT-like mine als om he ine ac ion was success ul
(Figu e 6c).
Figu e 6. Scanning Elec on Mic oscopy images o binde mo a : (a,b) ine ac ion and (c) ul a ine
ac ion. Poin 1 and poin 2 indica e he pa icles analysed by EDX.
Figu e 7. Ene gy dispe si e X- ay analyses esul s o laye ed double hyd oxides (LDH) o he ine
ac ion shown in Figu e 6b. Poin 1 is Ca-en iched anion clay (i.e., hyd ocalumi e) and poin 2 is
Ca-en iched anion clay (i.e., hyd o alci e).
Pe og aphic, XRD, and SEM-EDX analyses show ha he aw ma e ial used o ob ain lime was
impu e limes one and/o pa ially dolomi ized limes one. When limes ones en iched in calcium
magnesium a e calcined, magnesium mine als should be conside ed in he mo a binde .
Figu e 6.
Scanning Elec on Mic oscopy images o binde mo a : (
a
,
b
) ine ac ion and (
c
) ul a ine
ac ion. Poin 1 and poin 2 indica e he pa icles analysed by EDX.
Mine als 2018, 8, x FOR PEER REVIEW 8 o 16
Figu e 5. X- ay di ac ion pa e ns o ex ac ed binde ac ions. (a) Fine ac ion, (b) ul a ine
ac ion, and (c) a ge ac ion. HC: hyd ocalumi e, HT: hyd o alci e, Q z: qua z, Mg-Cal:
magnesium calci e.
These LDH mine al phases a e o med as a esul o he slaking p ocess and iden i ica ion and
cha ac e iza ion is c ucial due o hei e y high abili y o ix ca bona e anions [68]. Du ing he
ehyd a ion p ocess, CO32− om he pa ial washing o unbu n agmen s o limes one is ixed in he
c ys alline s uc u e o HT-like mine als. The cap u ed CO32− in oduces dead ca bon in he sys em
and ages he adiome ic da es. A new s ep was in oduced in he ex ac ion p ocedu e in o de o
emo e he po en ial con aminan HT-like mine al phases in he ul a ine ac ion (<0.5 µm).
SEM obse a ions o ine ac ion (<2 µm) o he binde con i m he p esence o e y small
HT-like pa icles embedded in a calci ic ma ix (Figu e 6). I egula and hexagonal c ys als o <0.5
µm g ain size, co esponding o Ca-en iched o Mg-en iched anion clays, can be obse ed in Figu e
6b. The Ene gy Dispe si e X- ay (EDX) analyses indica e ha well- o med o euhed al c ys als
co espond o Ca-en iched HT-like pa icles (poin 1 in Figu e 7) while he i egula o anhed al
c ys als co espond o Mg-en iched HT-like pa icles (poin 2 in Figu e 7). The e o e, Ca-en iched
pa icles co espond o hyd ocalumi e and Mg-en iched pa icles o hyd o alci e. In ac ,
hyd o alci e is mo e likely o be p esen as a non-well- o med phase compa ed wi h hyd ocalumi e
[44]. The EDX analysis also shows he p esence o silica ha has been a ibu ed o he p esence o
mic oc ys alline qua z. The SEM images o ul a ine ac ion (<0.5 µm) show a homogeneous ma ix
composed only o hyd o alci e and hyd ocalumi e phases o a <0.5 µm g ain size. The SEM-EDX
analysis suppo s ha he ex ac ion o HT-like mine als om he ine ac ion was success ul
(Figu e 6c).
Figu e 6. Scanning Elec on Mic oscopy images o binde mo a : (a,b) ine ac ion and (c) ul a ine
ac ion. Poin 1 and poin 2 indica e he pa icles analysed by EDX.
Figu e 7. Ene gy dispe si e X- ay analyses esul s o laye ed double hyd oxides (LDH) o he ine
ac ion shown in Figu e 6b. Poin 1 is Ca-en iched anion clay (i.e., hyd ocalumi e) and poin 2 is
Ca-en iched anion clay (i.e., hyd o alci e).
Pe og aphic, XRD, and SEM-EDX analyses show ha he aw ma e ial used o ob ain lime was
impu e limes one and/o pa ially dolomi ized limes one. When limes ones en iched in calcium
magnesium a e calcined, magnesium mine als should be conside ed in he mo a binde .
Figu e 7.
Ene gy dispe si e X- ay analyses esul s o laye ed double hyd oxides (LDH) o he ine
ac ion shown in Figu e 6b. Poin 1 is Ca-en iched anion clay (i.e., hyd ocalumi e) and poin 2 is
Ca-en iched anion clay (i.e., hyd o alci e).
Pe og aphic, XRD, and SEM-EDX analyses show ha he aw ma e ial used o ob ain lime was
impu e limes one and/o pa ially dolomi ized limes one. When limes ones en iched in calcium
magnesium a e calcined, magnesium mine als should be conside ed in he mo a binde . Magnesium
oxide (MgO) is o med as well as calcium oxide (CaO) du ing he calcina ion o dolomi ic ocks due o
he dolomi ic cycle, which di e s om he ypical lime cycle (Figu e 8).
Conside ing ha he LDH mine al phases cons i u e a po en ial con aminan in adioca bon
da ing, he g ain size ac ion <0.5
µ
m (i.e., ul a ine ac ion) is ex ac ed in o de o elimina e hese
phases. XRD pa e ns o UF show signi ican inc eases o e lexions a d = 7.86 Å (11.2

2
✓
), d = 7.69 Å
(11.4

2
✓
), d = 3.83 Å (23.2

2
✓
), and d = 2.58 Å (34.4

2
✓
) co esponding o hyd o alci e and indica e a
la ge en ichmen o LDH mine al phases in he ul a ine ac ion (Figu e 5b).
As a esul o he LDH mine als phase being emo ed, he a ge ac ion (TF) co esponds o
he g ain size ac ion be ween 0.5
µ
m o 2
µ
m. An XRD pa e n o he TF ac ion shows an inc ease
in magnesium calci e e lec ions while hyd o alci e e lec ions disappea (Figu e 5c). Ne e heless,
an ex ac ion p ocedu e o he a ge ac ion has o be checked in each mo a sample. Figu e 9
shows XRD pa e ns o he a ge ac ion o se e al samples. The p esence and he in ensi y o
cha ac e is ic e lec ions o LDH mine als in some XRD pa e ns sugges di e en le els o e inemen
in he ex ac ion p ocedu e, which indica es di e en amoun s o LDH mine als in each sample. As
can be obse ed, CP-2-TF, CP-4-TF, and CP-19-TF samples exhibi low in ensi y hyd o alci e e lec ions
while CP-13-3-TF, CP-13-6-TF, CP-13-8-TF, and CP-13-10-TF samples s ill p esen signi ican LDH
mine al e lec ions.
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Magnesium oxide (MgO) is o med as well as calcium oxide (CaO) du ing he calcina ion o
dolomi ic ocks due o he dolomi ic cycle, which di e s om he ypical lime cycle (Figu e 8).
Figu e 8. Lime binde cycles. (a) lime cycle and (b) p oposal o dolomi ic lime cycle o impu e
dolos one.
Conside ing ha he LDH mine al phases cons i u e a po en ial con aminan in adioca bon
da ing, he g ain size ac ion <0.5 µm (i.e., ul a ine ac ion) is ex ac ed in o de o elimina e hese
phases. XRD pa e ns o UF show signi ican inc eases o e lexions a d = 7.86 Å (11.2° 2θ), d = 7.69 Å
(11.4° 2θ), d = 3.83 Å (23.2° 2θ), and d = 2.58 Å (34.4° 2θ) co esponding o hyd o alci e and indica e a
la ge en ichmen o LDH mine al phases in he ul a ine ac ion (Figu e 5b).
As a esul o he LDH mine als phase being emo ed, he a ge ac ion (TF) co esponds o
he g ain size ac ion be ween 0.5 µm o 2 µm. An XRD pa e n o he TF ac ion shows an inc ease
in magnesium calci e e lec ions while hyd o alci e e lec ions disappea (Figu e 5c). Ne e heless,
an ex ac ion p ocedu e o he a ge ac ion has o be checked in each mo a sample. Figu e 9
shows XRD pa e ns o he a ge ac ion o se e al samples. The p esence and he in ensi y o
cha ac e is ic e lec ions o LDH mine als in some XRD pa e ns sugges di e en le els o
e inemen in he ex ac ion p ocedu e, which indica es di e en amoun s o LDH mine als in each
sample. As can be obse ed, CP-2-TF, CP-4-TF, and CP-19-TF samples exhibi low in ensi y
hyd o alci e e lec ions while CP-13-3-TF, CP-13-6-TF, CP-13-8-TF, and CP-13-10-TF samples s ill
p esen signi ican LDH mine al e lec ions.
Table 2 summa izes he mine alogical assemblages and he semi-quan i a i e alues (exp essed
in pe cen ages) o iden i ied phases in he ul a ine (<0.5 µm) and a ge (0.5 µm o 2 µm) ac ions.
XRD esul s o a ge ac ion show he pe sis en p esence o LDH phases in small a iable amoun s
in all samples. Ne e heless, XRD analysis does no always de ec he p esence o LDH phases when
he amoun emains nea o unde he de ec ion limi . To check he ex ac ion o he a ge ac ion,
e en when he LDHs a e no de ec ed by XRD analysis, he mo-g a ime ic analysis (TGA) is
pe o med.
Figu e 8.
Lime binde cycles. (
a
)limecycleand(
b
)p oposalo dolomi iclimecycleo impu edolos one.
Mine als 2018, 8, x FOR PEER REVIEW 10 o 16
Figu e 9. X- ay di ac ion pa e ns o a ge ac ions o di e en mo a binde s. HC:
hyd ocalumi e, HT: hyd o alci e, Mg-Cal: magnesium calci e, Q z: qua z.
Table 2. Semi-quan i a i e da a esul s (%) o X- ay di ac ion analyses o a ge and ul a ine
ac ions o mo a binde s.
Sample Ta ge F ac ion (%) Ul a ine F ac ion (%)
Mg-Cal HT HC Q z To al LDHs Mg-Cal HT HC Q z To al LDHs
CP-2 88 3 6 3 9 64 12 24 - 36
CP-4 84 8 8 - 16 58 16 26 - 42
CP-13-6 62 10 28 - 38 38 28 34 - 62
CP-13-8 79 9 10 2 19 48 28 24 - 52
CP-13-10 85 4 10 1 14 55 22 23 - 45
CP-19 89 5 5 1 10 55 24 20 - 44
CP-13-3 68 13 18 1 31 61 11 28 - 39
Mg-Cal: magnesium calci e, HT: hyd o alci e, HC: hyd ocalumi e, Q z: qua z, LDHs: laye ed double
hyd oxides.
The empe a u e anges and ela i e weigh loss obse ed in TGA analysis a e eliable o he
cha ac e iza ion o hese ma e ials. The i s weigh loss below 120 °C is a ibu ed o he p esence o
adso p ion wa e in he in e -pa icle po e. The second weigh loss occu s be ween 120 and 200 °C
and is a ibu ed o he c ys alliza ion wa e o he in e laye wa e . The weigh loss be ween 200 °C
o 600 °C is a ibu ed o s uc u al OH−, which co esponds o he dehyd a ion o he Ca(OH)2 o
pu e ca bona es. Las ly, a empe a u es abo e 600 °C, he loss o CO2 akes place due o he
decomposi ion o he ca bona e [69–71]. Howe e , in he hi d decomposi ion s ep (200 °C o 600 °C)
o a ge ac ion (0.5 µm o 2 µm) om Po illa Cas le samples, he TGA cu e shows wo weigh
loss s eps (Figu e 10). These weigh losses co espond o he decomposi ion o LDH phases and a e
a ibu ed o he loss o he OH− g oups bonded o Al3+ and o Mg2+ in Mg-Al-CO3 compounds
[72,73].
The he mos-g a ime ic analyses o he a ge ac ion show wo di e en pa e ns, which a e
ep esen a i e o TGA cu es. These pa e ns a e shown in Figu e 10. The pa e n ype-A
co esponds o samples wi h li le weigh loss in he 200 °C o 600 °C ange (CP-2-TF, CP-4-TF, and
CP-19-TF) while pa e n ype-B displays a p onounced s epped weigh loss (CP-13-3-TF, CP-13-6-TF,
CP-13-8-TF, and CP-13-10-TF). Table 3 summa izes he weigh loss pe cen ages o he a ge ac ion
in each empe a u e ange. Samples show weigh loss be ween 1.5% and 2.9% due o adso bed
Figu e 9.
X- ay di ac ion pa e ns o a ge ac ions o di e en mo a binde s. HC: hyd ocalumi e,
HT: hyd o alci e, Mg-Cal: magnesium calci e, Q z: qua z.
Table 2summa izes he mine alogical assemblages and he semi-quan i a i e alues (exp essed in
pe cen ages) o iden i ied phases in he ul a ine (<0.5
µ
m) and a ge (0.5
µ
m o 2
µ
m) ac ions. XRD
esul s o a ge ac ion show he pe sis en p esence o LDH phases in small a iable amoun s in all
samples. Ne e heless, XRD analysis does no always de ec he p esence o LDH phases when he
amoun emains nea o unde he de ec ion limi . To check he ex ac ion o he a ge ac ion, e en
when he LDHs a e no de ec ed by XRD analysis, he mo-g a ime ic analysis (TGA) is pe o med.
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92
Mine als 2018,8, 326 11 o 17
Table 2.
Semi-quan i a i e da a esul s (%) o X- ay di ac ion analyses o a ge and ul a ine ac ions
o mo a binde s.
Sample Ta ge F ac ion (%) Ul a ine F ac ion (%)
Mg-Cal HT HC Q z To al LDHs Mg-Cal HT HC Q z To al LDHs
CP-2 88 3 6 3 9 64 12 24 - 36
CP-4 84 8 8 - 16 58 16 26 - 42
CP-13-6
62 10 28 - 38 38 28 34 - 62
CP-13-8
79 9 10 2 19 48 28 24 - 52
CP-13-10
85 4 10 1 14 55 22 23 - 45
CP-19 89 5 5 1 10 55 24 20 - 44
CP-13-3
68 13 18 1 31 61 11 28 - 39
Mg-Cal: magnesium calci e, HT: hyd o alci e, HC: hyd ocalumi e, Q z: qua z, LDHs: laye ed double hyd oxides.
The empe a u e anges and ela i e weigh loss obse ed in TGA analysis a e eliable o he
cha ac e iza ion o hese ma e ials. The i s weigh loss below 120

C is a ibu ed o he p esence o
adso p ion wa e in he in e -pa icle po e. The second weigh loss occu s be ween 120 and 200

C and
is a ibu ed o he c ys alliza ion wa e o he in e laye wa e . The weigh loss be ween 200

C o
600

C is a ibu ed o s uc u al OH

, which co esponds o he dehyd a ion o he Ca(OH)
2
o pu e
ca bona es. Las ly, a empe a u es abo e 600

C, he loss o CO
2
akes place due o he decomposi ion
o he ca bona e [
69
–
71
]. Howe e , in he hi d decomposi ion s ep (200

C o 600

C) o a ge ac ion
(0.5
µ
m o 2
µ
m) om Po illa Cas le samples, he TGA cu e shows wo weigh loss s eps (Figu e 10).
These weigh losses co espond o he decomposi ion o LDH phases and a e a ibu ed o he loss o
he OHg oups bonded o Al3+ and o Mg2+ in Mg-Al-CO3compounds [72,73].
Mine als 2018, 8, x FOR PEER REVIEW 11 o 16
wa e . The lowe weigh loss o wa e molecules om he in e laye space co esponds o ype-A
pa e ns and highe o ype-B pa e ns. The weigh loss be ween 200 °C and 600 °C empe a u e
ange co esponding o he dehyd oxyla ion p ocesses shows la ge a ia ions in he TG cu es.
Type-A pa e n cu es show weigh loss a ying om 10.3% o 12.8% while he weigh loss in he
ype-B pa e ns a ies om 13.6% o 19.6%. Weigh loss in dehyd oxyla ion p ocesses shows la ge
con en s o LDH mine als in he ype-B samples han in samples wi h a ype-A pa e n. When o e
600 °C, ca bona es decompose and CO2 con en anges be ween 16.3% and 23.5%. The weigh loss o
pu e calcium ca bona e decomposi ion is 44% and lowe pe cen ages o weigh loss indica e a iable
amoun s o o he compounds as LDH mine als. The e o e, mo a s wi h no o li le
s uc u ally-bound wa e (OH−) and high ca bon dioxide con en a e po en ially adequa e o
adioca bon da ing since hey e lec he absence o o he ca bona e phases apa om calci e.
The e o e, CP-2 and CP-19 a e he mos sui able mo a s o adioca bon da ing since hey display
lowe s uc u ally-bound wa e and highe ca bon dioxide con en (Table 3).
Figu e 10. The mo-g a ime ic analyses o a ge ac ions o ep esen a i e mo a binde s. (A)
Binde samples wi h li le weigh loss and (B) binde samples wi h clea s epped weigh loss in he
200 °C o 600 °C ange.
Table 3. The mo-g a ime ic analysis esul s (w %) o a ge ac ions o mo a binde s.
Sample Pa e n Type H2O(I p) H2O(I l) OH− CO32−
CP-2-TF A 1.46 1.35 10.40 23.47
CP-4-TF
A 2.86 1.82 12.8 16.28
CP-13-6-TF B 2.30 2.78 19.64 18.46
CP-13-8-TF
B 1.89 2.28 15.41 23.04
CP-13-10-TF
B 1.89 2.12 17.01 21.83
CP-19-TF A 2.54 1.41 10.31 23.29
CP-13-3-TF B 2.77 2.45 13.56 18.06
I p: in e pa icle, I l: in e laye , TF: a ge ac ion. Pa e n ype as e e ed in Figu e 10.
Since sample CP-19 shows he lowes weigh loss o s uc u ally-bound wa e co esponding o
he decomposi ion o LDH phases, i has been selec ed ins ead o sample CP-2. In o de o e i y he
con aminan po en ial o LDHs, bo h ine ac ion (pa icle size <2 µm) and a ge ac ion (pa icle
size be ween 0.5 and 2 µm) ha e been da ed (Table 4).
The esul o 14C da ing o CP-19-FF is 2180 ± 40 BP co esponding o he calenda age o Cal BC
380–160 (Figu e 11a) and he adioca bon age o CP-19-TF is 1370 ± 30 BP, which co esponds o he
calenda age o Cal AD 640–675 (Figu e 11b). The ob ained da es a e olde han expec ed since he
i s w i en ch onicle o Po illa Cas le is da ed in 1040 AD. The age in e al be ween he
Figu e 10.
The mo-g a ime ic analyses o a ge ac ions o ep esen a i e mo a binde s. (
A
) Binde
samples wi h li le weigh loss and (
B
) binde samples wi h clea s epped weigh loss in he 200

C o
600 C ange.
The he mos-g a ime ic analyses o he a ge ac ion show wo di e en pa e ns, which a e
ep esen a i e o TGA cu es. These pa e ns a e shown in Figu e 10. The pa e n ype-A co esponds
o samples wi h li le weigh loss in he 200

C o 600

C ange (CP-2-TF, CP-4-TF, and CP-19-TF) while
pa e n ype-B displays a p onounced s epped weigh loss (CP-13-3-TF, CP-13-6-TF, CP-13-8-TF, and
CP-13-10-TF). Table 3summa izes he weigh loss pe cen ages o he a ge ac ion in each empe a u e
ange. Samples show weigh loss be ween 1.5% and 2.9% due o adso bed wa e . The lowe weigh
loss o wa e molecules om he in e laye space co esponds o ype-A pa e ns and highe o
ype-B pa e ns. The weigh loss be ween 200

C and 600

C empe a u e ange co esponding o he
8. Appendices: Published and Submi ed Wo ks
93
Mine als 2018,8, 326 12 o 17
dehyd oxyla ion p ocesses shows la ge a ia ions in he TG cu es. Type-A pa e n cu es show
weigh loss a ying om 10.3% o 12.8% while he weigh loss in he ype-B pa e ns a ies om 13.6%
o 19.6%. Weigh loss in dehyd oxyla ion p ocesses shows la ge con en s o LDH mine als in he ype-B
samples han in samples wi h a ype-A pa e n. When o e 600

C, ca bona es decompose and CO
2
con en anges be ween 16.3% and 23.5%. The weigh loss o pu e calcium ca bona e decomposi ion
is 44% and lowe pe cen ages o weigh loss indica e a iable amoun s o o he compounds as LDH
mine als. The e o e, mo a s wi h no o li le s uc u ally-bound wa e (OH

) and high ca bon dioxide
con en a e po en ially adequa e o adioca bon da ing since hey e lec he absence o o he ca bona e
phases apa om calci e. The e o e, CP-2 and CP-19 a e he mos sui able mo a s o adioca bon
da ing since hey display lowe s uc u ally-bound wa e and highe ca bon dioxide con en (Table 3).
Table 3. The mo-g a ime ic analysis esul s (w %) o a ge ac ions o mo a binde s.
Sample Pa e n Type H2O(I p) H2O(I l) OHCO32
CP-2-TF A 1.46 1.35 10.40 23.47
CP-4-TF A 2.86 1.82 12.8 16.28
CP-13-6-TF B 2.30 2.78 19.64 18.46
CP-13-8-TF B 1.89 2.28 15.41 23.04
CP-13-10-TF B 1.89 2.12 17.01 21.83
CP-19-TF A 2.54 1.41 10.31 23.29
CP-13-3-TF B 2.77 2.45 13.56 18.06
I p: in e pa icle, I l: in e laye , TF: a ge ac ion. Pa e n ype as e e ed in Figu e 10.
Since sample CP-19 shows he lowes weigh loss o s uc u ally-bound wa e co esponding o
he decomposi ion o LDH phases, i has been selec ed ins ead o sample CP-2. In o de o e i y he
con aminan po en ial o LDHs, bo h ine ac ion (pa icle size <2
µ
m) and a ge ac ion (pa icle
size be ween 0.5 and 2 µm) ha e been da ed (Table 4).
Table 4. Resul s o AMS 14C da es o di e en g ain-size ac ions o mo a binde .
Lab Code Sample Binde G ain-Size Con en ional Age 13CCalib a e Age (95.4%)
BETA375404 CP-19-TF 0.5–2 µm 1370 ±30 BP 16.5 Cal AD 640–675
BETA343295 CP-19-FF <2 µm 2180 ±40 BP 21.3 Cal BC 380–160
TF: a ge ac ion, FF: ine ac ion.
The esul o
14
C da ing o CP-19-FF is 2180
±
40 BP co esponding o he calenda age o Cal
BC 380–160 (Figu e 11a) and he adioca bon age o CP-19-TF is 1370
±
30 BP, which co esponds
o he calenda age o Cal AD 640–675 (Figu e 11b). The ob ained da es a e olde han expec ed
since he i s w i en ch onicle o Po illa Cas le is da ed in 1040 AD. The age in e al be ween he
a chaeological age and adioca bon ages o he a ge ac ion e lec s he pe sis en p esence o dead
ca bon con amina ion ela ed wi h he CO32anion o hyd o alci e and hyd ocalumi e.
Applied Mine alogy in he S udy o His o ical Lime Mo a s
94
Mine als 2018,8, 326 13 o 17
Mine als 2018, 8, x FOR PEER REVIEW 12 o 16
a chaeological age and adioca bon ages o he a ge ac ion e lec s he pe sis en p esence o dead
ca bon con amina ion ela ed wi h he CO32−anion o hyd o alci e and hyd ocalumi e.
Figu e 11. Calib a ed 14C da es o wo ac ion-sizes o he same lime mo a om Po illa Cas le, (a)
ine ac ion (FF), and (b) a ge ac ion (TF) ob ained wi h OxCal 4.1.7 [63] and In Cal09
a mosphe ic da a [64].
Table 4. Resul s o AMS 14C da es o di e en g ain-size ac ions o mo a binde .
Lab Code Sample Binde G ain-Size Con en ional Age δ13C Calib a e Age (95.4%)
BETA375404 CP-19-TF 0.5–2 µm 1370 ± 30 BP −16.5 Cal AD 640–675
BETA343295 CP-19-FF <2 µm 2180 ± 40 BP −21.3 Cal BC 380–160
TF: a ge ac ion, FF: ine ac ion.
The mine alogical composi ion o ca bona e phases o he mo a binde and he g anulome ic
dis ibu ion has de e mined he pa icle size o be ex ac ed o adioca bon da ing. The selec ion o
ine-g ain size ac ion (<2 µm) is only use ul when he mo a binde is o med solely by calci e, e.g.,
O ega e al. [28]. In con as , when he binde includes hyd o alci e and hyd ocalumi e besides
neo- o ma ion calci e, as in Po illa Cas le, which de e mines he g anulome ic dis ibu ion o
ca bona e mine als is essen ial in selec ing e ec i e h esholds. Once he g anulome ic dis ibu ion
is de e mined, he mos sui able p econdi ioning me hod should be es ablished o each sample in
o de o isola e he adequa e ac ion o adioca bon da ing. The e o e, da ing o mo a s wi hou a
comp ehensi e mine alogical s udy can lead o meaningless esul s.
5. Conclusions
Po illa Cas le mo a s a e o med by calci ic binde and qua z, limes one agmen s, some
pa ially dolomi ized, and unbu n limes one emains as agg ega es. The p esence o hyd o alci e
and hyd ocalumi e in he ine g ain ac ion o binde indica es he use o impu e limes one and/o
pa ially dolomi ized limes ones in he lime p oduc ion. These aw ma e ials p o ide magnesium
and aluminium ions and unde hype -alkaline condi ions lead o he o ma ion o LDHs phases
du ing he slaking p ocess.
The con inuous mine alogical con ol o he ex ac ion p ocedu e allows a be e mine alogical
cha ac e iza ion o he ines g ain ac ions (<2 µm) o he binde . Only he s udy o hese ac ions
allows he iden i ica ion o hyd o alci e and hyd ocalumi e in lime mo a s. In his con ibu ion,
addi ional s eps in he ex ac ion p ocess o emo e small g ain size pa icles en iched in LDHs has
been pe o med making he ob ained adioca bon da es close o he a chaeological ages.
The occu ence o hyd o alci e and hyd ocalumi e mainly in he g ain size is smalle han 0.5
µm in he Po illa Cas le mo a s, which adds dead ca bon o he sys em and explains olde ages
han expec ed. The e o e, hyd o alci e and hyd ocalumi e cons i u e c ucial con aminan mine al
phases in mo a da ing issues.
Mine alogical s udies a e essen ial o selec he samples o da ing and ejec unsui able samples
since hey allow he mine alogical na u e o he con aminan s and he g ain size dis ibu ion wi hin
Figu e 11.
Calib a ed
14
C da es o wo ac ion-sizes o he same lime mo a om Po illa Cas le, (
a
) ine
ac ion (FF), and (
b
) a ge ac ion (TF) ob ained wi h OxCal 4.1.7 [
63
] and In Cal09 a mosphe ic
da a [64].
The mine alogical composi ion o ca bona e phases o he mo a binde and he g anulome ic
dis ibu ion has de e mined he pa icle size o be ex ac ed o adioca bon da ing. The selec ion o
ine-g ain size ac ion (<2
µ
m) is only use ul when he mo a binde is o med solely by calci e, e.g.,
O ega e al. [
28
]. In con as , when he binde includes hyd o alci e and hyd ocalumi e besides
neo- o ma ion calci e, as in Po illa Cas le, which de e mines he g anulome ic dis ibu ion o
ca bona e mine als is essen ial in selec ing e ec i e h esholds. Once he g anulome ic dis ibu ion
is de e mined, he mos sui able p econdi ioning me hod should be es ablished o each sample in
o de o isola e he adequa e ac ion o adioca bon da ing. The e o e, da ing o mo a s wi hou a
comp ehensi e mine alogical s udy can lead o meaningless esul s.
5. Conclusions
Po illa Cas le mo a s a e o med by calci ic binde and qua z, limes one agmen s, some
pa ially dolomi ized, and unbu n limes one emains as agg ega es. The p esence o hyd o alci e
and hyd ocalumi e in he ine g ain ac ion o binde indica es he use o impu e limes one and/o
pa ially dolomi ized limes ones in he lime p oduc ion. These aw ma e ials p o ide magnesium and
aluminium ions and unde hype -alkaline condi ions lead o he o ma ion o LDHs phases du ing he
slaking p ocess.
The con inuous mine alogical con ol o he ex ac ion p ocedu e allows a be e mine alogical
cha ac e iza ion o he ines g ain ac ions (<2
µ
m) o he binde . Only he s udy o hese ac ions
allows he iden i ica ion o hyd o alci e and hyd ocalumi e in lime mo a s. In his con ibu ion,
addi ional s eps in he ex ac ion p ocess o emo e small g ain size pa icles en iched in LDHs has
been pe o med making he ob ained adioca bon da es close o he a chaeological ages.
The occu ence o hyd o alci e and hyd ocalumi e mainly in he g ain size is smalle han 0.5
µ
m
in he Po illa Cas le mo a s, which adds dead ca bon o he sys em and explains olde ages han
expec ed. The e o e, hyd o alci e and hyd ocalumi e cons i u e c ucial con aminan mine al phases in
mo a da ing issues.
Mine alogical s udies a e essen ial o selec he samples o da ing and ejec unsui able samples
since hey allow he mine alogical na u e o he con aminan s and he g ain size dis ibu ion wi hin
he binde o be de e mined. Mine alogical s udies o he binde ha e o de elop ailo ed pu i ica ion
p ocedu es o each sample.
Au ho Con ibu ions:
L.A.O. and M.C.Z. concei ed and designed he expe imen s; J.L.S., G.P-A. and L.A.O.
selec ed a chaeological ma e ials, G.P.-A. pe o med he expe imen s; G.P.-A., L.A.O. and M.C.Z. analyzed he
da a; A.A.-O. con ibu ed o he discussion; G.P.-A., L.A.O. and M.C.Z. w o e he pape .
Funding:
This esea ch was possible hanks o he inancial suppo o SAI13/106 esea ch p ojec o Basque
Coun y Go e nmen .
8. Appendices: Published and Submi ed Wo ks
95

Mine als 2018,8, 326 14 o 17
Acknowledgmen s:
The au ho s would like o hank he anonymous e e ees o hei commen s and sugges ions
on he manusc ip . GPA also acknowledges he PhD esea ch g an o he Basque Coun y Go e nmen
(2015-1-02-35). They also would like o hank Pe e Smi h o e iewing he use o English in he manusc ip .
Con lic s o In e es : The au ho s decla e no con lic o in e es .
Re e ences
1.
Schi e , M. Radioca bon Da ing and he “Old Wood” P oblem: The Case o he Hohokam Ch onology; Else ie :
New Yo k, NY, USA, 1986; Volume 13, pp. 13–30.
2. Mc Fadgen, B.G. Da ing New Zealand a chaeology by adioca bon. N. Z. J. Sci. 1982,25, 379–392.
3.
Ga in, D.G. Es ima ion o inbuil age in adioca bon ages o soil cha coal o i e his o y s udies. Radioca bon
2001,43, 27–44. [C ossRe ]
4. Bowman, S. Radioca bon Da ing; B i ish Museum P ess: London, UK, 1990.
5.
Taylo , R.; Ba -Yose , O. Radioca bon Da ing: An A chaeological Pe spec i e; Le Coas P ess: Walnu C eek, CA,
USA, 2014.
6.
Boa e o, E.; Poduska, K.M. Ma e ials science challenges in adioca bon da ing: The case o a chaeological
plas e s. J. Ma e . 2013,65, 481–488. [C ossRe ]
7.
Kinge y, D.W.; Pamela, B.V.; Ma ha, P. The Beginnings o Py o echnology, Pa II: P oduc ion and Use o Lime and
Gypsum Plas e in he P e-Po e y Neoli hic Nea Eas ; Taylo and F ancis: New Yo k, NY, USA, 1988; Volume
15, pp. 219–243.
8.
Labey ie, J.; Delib ias, G. Da ing o old mo a by Ca bon-14 me hod. Na u e
1964
,201, 742–743. [C ossRe ]
9.
S ui e , M.; Smi h, C.S. Radioca bon Da ing o Ancien Mo a and Plas e , P oceedings o he 6 h In e na ional
14
C Con e ence, Mon eal, Canada, 8–15 Sep embe 1965; Cha e s, R.M., Olson, C.A., Eds.; Clea inghouse o
Fede al Scien i ic and Technical In o ma ion: Sp ing ield, IL, USA; pp. 338–343.
10.
Pachiaudi, C.; Ma echal, J.; Van S ydonck, M.; Dupas, M.; Daucho dehon, M. Iso opic ac iona ion o
ca bon du ing CO2abso p ion by mo a . Radioca bon 1986,28, 691–697. [C ossRe ]
11.
Ambe s, J. S able ca bon iso ope a ios and hei ele ance o he de e mina ion o accu a e adioca bon
da es o lime mo a s. J. A chaeol. Sci. 1987,14, 569–576. [C ossRe ]
12. Bax e , M.S.; Wal on, A. Radioca bon da ing o mo a s. Na u e 1970,225, 937–938. [C ossRe ][PubMed]
13.
Folk, R.L.; Valas o, S.J. Success ul echnique o da ing o lime mo a by ca bon-14. J. Field A chaeol.
1976
,3,
203–208. [C ossRe ]
14.
Van S ydonck, M.; Dupas, M.; Daucho -Dehon, M. Radioca bon da ing o old mo a s,
14
C and A chaeology,
P oceedings; Mook, W.G., Wa e bolk, H.T., Eds.; PACT: Phnom Penh, Cambodia, 1983; pp. 337–343.
15.
Van S ydonck, M.; Dupas, M.; Daucho dehon, M.; Pachiaudi, C.; Ma echal, J. The in luence o con amina ing
( ossil) ca bona e and he a ia ions o del a-C-13 in mo a da ing. Radioca bon
1986
,28, 702–710. [C ossRe ]
16.
Van S ydonck, M.J.Y.; Van de Bo g, K.; De Jong, A.F.M.; Keppens, E. Radioca bon da ing o lime ac ions
and o ganic ma e ial om buildings. Radioca bon 1992,34, 873–879. [C ossRe ]
17.
Lind oos, A.; Heinemeie , J.; Ringbom, Å.; B askén, M.; S einbjö nsdó i , Á. Mo a da ing using AMS
14
C
and sequen ial dissolu ion: Examples om medie al, non-hyd aulic lime mo a s om he Åland Islands,
SW Finland. Radioca bon 2007,49, 47–67. [C ossRe ]
18.
Sonninen, E.; Jungne , H. An imp o emen in p epa a ion o mo a o adioca bon da ing. Radioca bon
2001,43, 271–273. [C ossRe ]
19.
Hale, J.; Heinemeie , J.; Lancas e , L.; Lind oos, A.; Ringbom, Å. Da ing ancien mo a . Am. Sci.
2003
,91,
130–137. [C ossRe ]
20.
Naw ocka, D.; Michniewicz, J.; Pawly a, J.; Pazdu , A. Applica ion o adioca bon me hod o da ing o lime
mo a s. Geoch onome ia 2005,24, 109–115.
21.
Heinemeie , J.; Jungne , H.G.; Lind oos, A.; Ringbom, S.; on Konow, T.; Rud, N. AMS
14
C da ing o lime
mo a . Nucl. Ins um. Me hods Phys. Res. Sec . B Beam In e ac . Ma e . A oms 1997,123, 487–495. [C ossRe ]
22.
Tubbs, L.E.; Kinde , T.N. The use o AMS o he da ing o lime mo a s. Nucl. Ins um. Me hods Phys. Res.
Sec . B Beam In e ac . Ma e . A oms. 1990,52, 438. [C ossRe ]
23.
To olo, M.; Maei , A.M.; Chadwick, J.R.; Boa e o, E. Cha ac e iza ion o con ex s o adioca bon da ing:
Resul s om he ea ly I on Age a Tell es-Sa i/Ga h, Is ael. Radioca bon 2012,54, 371–390. [C ossRe ]
Applied Mine alogy in he S udy o His o ical Lime Mo a s
96
Mine als 2018,8, 326 15 o 17
24.
Assche , Y.; Lehmann, G.; Rosen, S.A.; Weine , S.; Boa e o, E. Absolu e da ing o he la e b onze o i on age
ansi ion and he appea ance o philis ine cul u e in qubu el-walaydah, sou he n Le an . Radioca bon
2015
,
57, 77–97. [C ossRe ]
25.
Rod iguez-Na a o, C.; Hansen, E.; Ginell, W.S. Calcium hyd oxide c ys al e olu ion upon aging o lime
pu y. J. Am. Ce am. Soc. 1998,81, 3032–3034. [C ossRe ]
26.
Boyn on, R.S. Chemis y and Technology o Lime and Limes one; John Wiley & Sons, Inc.: New Yo k, NY,
USA, 1980.
27.
Zou idakis, N.M.; Saliege, J.F.; Pe son, A.; Filippakis, S.E. Radioca bon da ing o mo a s om ancien g eek
palaces. A chaeome y 1987,29, 60–68. [C ossRe ]
28.
O ega, L.A.; Zuluaga, M.C.; Alonso-Olazabal, A.; Mu elaga, X.; Insaus i, M.; Ibañez-E xebe ia, A. His o ic
lime-mo a
14
C da ing o San a Ma ía la Real (Za au z, no he n Spain): Ex ac ion o sui able g ain size o
eliable 14C da ing. Radioca bon 2012,54, 23–36. [C ossRe ]
29.
Ma zaioli, F.; Lub i o, C.; Nonni, S.; Passa iello, I.; Capano, M.; Te asi, F. Mo a adioca bon da ing:
P elimina y accu acy e alua ion o a no el me hodology. Anal. Chem.
2011
,83, 2038–2045. [C ossRe ]
[PubMed]
30.
Ma zaioli, F.; Nonni, S.; Passa iello, I.; Capano, M.; Ricci, P.; Lub i o, C.; De Cesa e, N.; E amo, G.; Qui ós
Cas illo, J.A.; Te asi, F. Accele a o mass spec ome y
14
C da ing o lime mo a s: Me hodological aspec s
and ield s udy applica ions a CIRCE (I aly). Nucl. Ins um. Me hods Phys. Res. Sec . B Beam In e ac .
Ma e . A oms 2013,294, 246–251. [C ossRe ]
31.
Folk, R.L.; Valas o, S. Success ul Technique o Da ing o Lime Mo a by Ca bon-14. J. Field A chaeol.
1976
,
3, 203–208. [C ossRe ]
32.
Gosla , T.; Naw ocka, D.; Cze nik, J. Fo amini e ous limes one in C-14 da ing o mo a . Radioca bon
2009
,51,
987–993. [C ossRe ]
33.
Heinemeie , J.; Ringbom, A.; Lind oos, A.; S einbjo nsdo i , A.E. Success ul AMS
14
C da ing o
non-hyd aulic lime mo a s om he medie al chu ches o he Aland Islands, Finland. Radioca bon
2010
,52,
171–204. [C ossRe ]
34.
Al-Bashai eh, K. Plas e and mo a adioca bon da ing o Naba ean and Islamic s uc u es, Sou h Jo dan.
A chaeome y 2013,55, 329–354. [C ossRe ]
35.
Ringbom, A.; Lind oos, A.; Heinemeie , J.; Sonck-Koo a, P. 19 yea s o mo a da ing: Lea ning om
expe ience. Radioca bon 2014,56, 619–635. [C ossRe ]
36.
Nonni, S.; Ma zaioli, F.; Secco, M.; Passa iello, I.; Capano, M.; Lub i o, C.; Migna di, S.; Tonghini, C.;
Te asi, F. 14C mo a da ing: The case o he medie al shayza ci adel, Sy ia. Radioca bon 2013,55, 514–525.
[C ossRe ]
37.
Pesce, G.; Qua a, G.; Calcagnile, L.; D’Elia, M.; Ca aciocchi, P.; Las ico, C.; Guas ella, R. Radioca bon
da ing o lumps om ae ial lime mo a s and plas e s: Me hodological issues and esul s om San Nicolòo
Capodimon e chu ch (Camogli, Genoa, I aly). Radioca bon 2009,51, 867–872. [C ossRe ]
38.
Pesce, G.L.A.; Ball, R.J.; Qua a, G.; Calcagnile, L. Iden i ica ion, ex ac ion, and p epa a ion o eliable lime
samples o
14
C da ing o plas e s and mo a s wi h he “pu e lime lumps” echnique. Radioca bon
2012
,54,
933–942. [C ossRe ]
39.
Be u o, D.T.; Vecchia ini, R.; Gio dani, M. Solid p oduc s and a e-limi ing s ep in he he mal hal
decomposi ion o na u al dolomi e in a CO
2
(g) a mosphe e. The mochim. Ac a
2003
,405, 183–194. [C ossRe ]
40. Scho k, J. Dolomi ic Lime in he US. J. A chi . Conse . 2012,18, 7–25. [C ossRe ]
41.
Kuzel, H.-J.; Baie , H. Hyd a ion o calcium alumina e cemen s in he p esence o calcium ca bona e. Eu . J.
Mine al. 1996, 129–142. [C ossRe ]
42.
E ans, D.G.; Slade, R.C.T. S uc u al aspec s o laye ed double hyd oxides. In Laye ed Double Hyd oxides;
Duan, X., E ans, D.G., Eds.; Sp inge : Be lin/Heidelbe g, Ge many, 2006; pp. 1–87.
43.
Fo ano, C.; Hibino, T.; Le oux, F.; Ta io -Guého, C. Chap e 13.1 laye ed double hyd oxides. De . Clay Sci.
2006,1, 1021–1095.
44.
Guo, Q.; Rea don, E.J. Calcined dolomi e: Al e na i e o lime o minimizing undesi able elemen leachabili y
om ly ash. Ind. Eng. Chem. Res. 2012,51, 9106–9116. [C ossRe ]
45.
Miya a, S.; Okada, A. Syn hesis o hyd o alci e-like compounds and hei physico-chemical
p ope ies—The sys ems Mg
2+
-Al
3+
-SO
42
- and Mg
2+
-Al
3+
-C O
42
.Clays Clay Min.
1977
,25, 14–18.
[C ossRe ]
8. Appendices: Published and Submi ed Wo ks
97
Mine als 2018,8, 326 16 o 17
46.
Miya a, S. Physico-chemical p ope ies o syn he ic hyd o alci es in ela ion o composi ion. Clays Clay Min.
1980,28, 50–56. [C ossRe ]
47.
Miya a, S. Anion-exchange p ope ies o hyd o alci e-like compounds. Clays Clay Min.
1983
,31, 305–311.
[C ossRe ]
48.
Reichle, W.T. Syn hesis o anionic clay mine als (mixed me al hyd oxides, hyd o alci e). Solid S a e Ionics
1986,22, 135–141. [C ossRe ]
49.
Ca ani, F.; T i i ò, F.; Vacca i, A. Hyd o alci e ype anionic clays, p epa a ion, p ope ies and applica ions.
Ca al. Today 1991,11, 173–301. [C ossRe ]
50.
Mills, S.J.; Ch is y, A.G.; Génin, J.-M.R.; Kameda, T.; Colombo, F. Nomencla u e o he hyd o alci e
supe g oup: Na u al laye ed double hyd oxides. Mine al. Mag. 2012,76, 1289–1336. [C ossRe ]
51.
Ku us, B.; Gacsi, A.; Pallagi, A.; Palinko, I.; Pein le , G.; Sipos, P. A comp ehensi e s udy on he dominan
o ma ion o he dissol ed Ca(OH)
2
(aq) in s ongly alkaline solu ions sa u a ed by Ca(ii). RSC Ad .
2016
,6,
45231–45240. [C ossRe ]
52.
Pallagi, A.; Tasi, A.; Gácsi, A.; Csá i, M.; Pálinkó, I.; Pein le , G.; Sipos, P. The solubili y o Ca(OH)
2
in
ex emely concen a ed NaOH solu ions a 25 C. Cen . Eu . J. Chem. 2012,10, 332–337. [C ossRe ]
53.
Rea don, E.J.; Della Valle, S. Anion seques e ing by he o ma ion o anionic clays: Lime ea men o ly ash
slu ies. En i on. Sci. Technol. 1997,31, 1218–1223. [C ossRe ]
54.
Rosenbe g, S.P.; A ms ong, L. Laye ed double hyd oxides in he Baye p ocess: Pas , p esen and u u e.
In Essen ial Readings in Ligh Me als; Sp inge : Be lin, Ge many, 2005; pp. 157–161.
55.
Sipos, P. The s uc u e o Al (III) in s ongly alkaline alumina e solu ions—A e iew. J. Mol. Liq.
2009
,146,
1–14. [C ossRe ]
56.
Gácsi, A.; Ku us, B.; Kónya, Z.; Kuko ecz, Á.; Pálinkó, I.; Sipos, P. Es ima ion o he solubili y p oduc o
hyd ocalumi e-hyd oxide, a laye ed double hyd oxide wi h he o mula o [Ca
2
Al(OH)
6
]OH
·
nH
2
O. J. Phys.
Chem. Solids 2016,98, 167–173. [C ossRe ]
57.
A ioli, G.; Secco, M.; Addis, A.; Bello o, M. 5 Role o hyd o alci e- ype laye ed double hyd oxides in
delayed pozzolanic eac ions and hei bea ing on mo a da ing. In Cemen i ious Ma e ials: Composi ion,
P ope ies, Applica ion; Wal e de G uy e : Be lin, Ge many, 2017.
58.
Siedel, H.; Michalski, S.; Ull ich, B. Cha ac e isa ion o dolomi ic lime mo a s om he Benedic ine
monas e y in Riesa, Saxony (Ge many). In His o ic Mo a s; Sp inge : Do d ech , The Ne he lands, 2012;
pp. 115–124.
59.
B andon, C.J.; Hohl elde , R.L.; Jackson, M.D.; Oleson, J.P. Building o E e ni y: The His o y and Technology o
Roman Conc e e Enginee ing in he Sea; Oxbow Books: Ox o d, UK; Philadelphia, PA, USA, 2014.
60.
Massazza, F. Pozzolana and pozzolanic cemen s. In Lea’s Chemis y o Cemen and Conc e e, 4 h ed.; Hewle , P.,
Ed.; Else ie -Bu e wo h-Heinemann: Ox o d, UK, 1998; pp. 471–635.
61.
Sag edo, I. Na a a: Cas illos que De endie on el Reino (Tomo III) La Na a a Occiden al, la F on e a del Ma Ála a,
Bizkaia, el Du anguesado, Guipuzkoa; PAMIELA: Pamplona, Spain, 2007.
62.
Solaun, J.L.; Azcá a e, A. El cas illo de Po illa (Zamb ana, Ala a). O igen y signi icado de una o aleza
plenomedie al en e i o io ala és (siglos XI-XII). Munibe An opol.-A keol. 2016,67, 167–183.
63.
Ramsey, C.B.; Sco , M.; an de Plich , H. Calib a ion o a chaeological and en i onmen al e es ial
samples in he ime ange 26–50 ka cal BP. Radioca bon 2013,55, 2021–2027. [C ossRe ]
64.
Reime , P.J.; Ba d, E.; Bayliss, A.; Beck, J.W.; Blackwell, P.G.; Ramsey, C.B.; Buck, C.E.; Cheng, H.;
Edwa ds, R.L.; F ied ich, M.; e al. In Cal13 and ma ine13 adioca bon age calib a ion cu es 0–50,000 yea s
cal BP. Radioca bon 2013,55, 1869–1887. [C ossRe ]
65.
Casadio, F.; Chia i, G.; Simon, S. E alua ion o binde /agg ega e a ios in a chaeological lime mo a s
wi h ca bona e agg ega e: A compa a i e assessmen o chemical, mechanical and mic oscopic app oaches.
A chaeome y 2005,47, 671–689. [C ossRe ]
66.
Wa ken in, B.P.; Maeda, T. Physical and mechanical cha ac e is ics o andisols. In Soils wi h Va iable Cha ge;
Theng, B.K.G., Ed.; New Zealand Socie y o Soil Science: Lowe Hu , New Zealand, 1980; pp. 281–302.
67. Langmui , D. Aqueous En i onmen al Geochemis y; P en ice Hall: London, UK, 1997.
68.
G o e , K.; Koma neni, S.; Ka suki, H. Syn he ic hyd o alci e- ype and hyd ocalumi e- ype laye ed double
hyd oxides o a sena e up ake. Appl. Clay Sci. 2010,48, 631–637. [C ossRe ]
69.
Bakolas, A.; Biscon in, G.; Mo opoulou, A.; Zend i, E. Cha ac e iza ion o s uc u al byzan ine mo a s by
he mog a ime ic analysis. The mochim. Ac a 1998,321, 151–160. [C ossRe ]
Applied Mine alogy in he S udy o His o ical Lime Mo a s
98
Mine als 2018,8, 326 17 o 17
70.
Paama, L.; Pi känen, I.; Rönkkömäki, H.; Pe ämäki, P. The mal and in a ed spec oscopic cha ac e iza ion
o his o ical mo a s. The mochim. Ac a 1998,320, 127–133. [C ossRe ]
71.
Mo opoulou, A.; Bakolas, A.; Anagnos opoulou, S. Composi e ma e ials in ancien s uc u es. Cem. Conc .
Compos. 2005,27, 295–300. [C ossRe ]
72.
Yang, W.; Kim, Y.; Liu, P.K.T.; Sahimi, M.; Tso sis, T.T. A s udy by in si u echniques o he he mal e olu ion
o he s uc u e o a Mg-Al-CO3laye ed double hyd oxide. Chem. Eng. Sci. 2002,57, 2945–2953. [C ossRe ]
73.
León, M.; Díaz, E.; Bennici, S.; Vega, A.; O dóñez, S.; Au oux, A. Adso p ion o CO
2
on hyd o alci e-de i ed
mixed oxides: So p ion mechanisms and consequences o adso p ion i e e sibili y. Ind. Eng. Chem. Res.
2010,49, 3663–3671. [C ossRe ]
©
2018 by he au ho s. Licensee MDPI, Basel, Swi ze land. This a icle is an open access
a icle dis ibu ed unde he e ms and condi ions o he C ea i e Commons A ibu ion
(CC BY) license (h p://c ea i ecommons.o g/licenses/by/4.0/).
8. Appendices: Published and Submi ed Wo ks
99
Applied Mine alogy in he S udy o His o ical Lime Mo a s
106
Fig. 3. Loca ion o s udied samples in he Towe Keep a I ulegi Cas le (modi ied om Ponce-An ón
e al., 2019).
Table 1. Lis o sample ac ions analysed by X- ay di ac ion (XRD), he mog amime ic analyses
(TGA) and ca hodoluminiscence (CL). Sample Code [i.e. CI-T-9B.1]: CI: I ulegi Cas le, T: Towe , 9:
Numbe o sample, B: g ain-size (B: 46-75 µm g ain-size window, T: 0.5-2 µm g ain-size window);
.1: The inal numbe in he sample code co esponds o he numbe o he CO2 ac ion ob ained by
sequen ial solu ion.
Bulk mo a
Bulk mo a ac ion
(46-75 µm)
CO
2
ac ion o
Bulk mo a ac ion
Binde mo a ac ion
(0.5-2 µm)
CO
2
ac ion o
Binde mo a ac ion
CI-T-9B
CI-T-9B.1
CI-T-9T.1
CI-T-9T.2
CI-T-9
CI-T-9B.2
CI-T-9T
CI-T-9B.3
CI-T-10B.1
CI-T-10T.1
CI-T-10T.2
CI-T-10
CI-T-10B
CI-T-10B.2
CI-T-10T
CI-T-10B.3
CI-T-13B.1
CI-T-13T.1
CI-T-13T.2
CI-T-13
CI-T-13B
CI-T-13B.2
CI-T-13T
CI-T-13B.3
3.2. Sample p epa a ion
In o de o isola e he neo o med calci e om he mo a binde , wo sample p epa a ion
p ocedu es we e pe o med. Bo h sample p epa a ions aim o a oid con amina ion due o
ca bona ed agg ega es and/o unbu ned limes one elic s p esen in he mo a . One o he
sample p epa a ions was based on he se ling o mo a binde and he o he on he sie ing o
c ushed mo a (Fig.4). Selec ed p epa a ion p oduc s om each p ocedu e we e hyd olysed
by a sequen ial dissolu ion p ocess (Fig.5).
The elemen a y p inciples o he p ocedu es a e widely desc ibed and de ailed in O ega
e al. (2012b) and Ponce-An ón e al. (2018) o sample p epa a ion by he se ling p ocess
and in Lind oos e al. (2007) and Heinemeie e al. (2010) o sample p epa a ion by he
sie ing p ocess and a sequen ial dissolu ion p ocess.
Be o e ca ying ou bo h p ocesses, he uppe su ace o all mo a samples was emo ed
using a sc ape o elimina e he o ganic coa ing o ino ganic c us s o med by a mosphe ic
exposu e and a oid addi ional con amina ion p oblems.

8. Appendices: Published and Submi ed Wo ks
107
Fig. 4. Sample p epa a ion p ocedu es o mo a adioca bon da ing. (a) Sample p epa a ion by he
se ling p ocess (modi ied om Ponce-An ón e al., 2018). CF: coa se ac ion, FF: ine ac ion,
UF: ul a ine ac ion, TF: a ge ac ion. Selec ed ac ion co esponds o he 0.5-2 µm g ain-size
window (b) Sample p epa a ion by he sie ing p ocess. Selec ed ac ion co esponds o he 46-75 µm
g ain-size window.
3.2.1. Sample p epa a ion p ocedu e by a se ling p ocess
Sample p epa a ion p ocedu e by he se ling p ocess was pe o med in he Clay Mine als
Labo a o y a he Uni e si y o he Basque Coun y (UPV/EHU) (Leioa, Spain). The
p ocedu e is based on a pa icle- ac iona ion echnique used in soil and clay mine alogical
s udies (Lai d and Dowdy, 1994; Soukup e al., 2008). Mo a samples we e i s manually
disagg ega ed o a oid mechanical c umbling, p e en ing he homogeniza ion o he g ain
size dis ibu ion and he o ma ion o po en ial con amina ing small g ain-size pa icles o
ca bona ed agg ega es (de G oo , 2004). The o ganic componen s ound embedded in he
mo a we e picked ou , emo ed and p ese ed sepa a ely. The ea e , o imp o e gen le
sample disagg ega ion he ul asonic ba h o we samples was used p ese ing he o iginal
g ain-size. Di e en g ain-size ac ions we e ex ac ed by di e en ial se ling o he pa icles
in ul apu e wa e bu e ed a pH = 8 by adding pu e NH4OH (Fig.4a). The 0.5-2 µm g ain-
size ac ion o mo a binde was selec ed o pe o m sample hyd olysis by sequen ial
dissolu ion o adioca bon da ing. Ex ac ion p ocedu e is epea ed un il su icien binde is
ob ained o chemical-mine alogical and AMS analyses. Samples ob ained by he se ling
p epa a ion p ocedu e ha e been named wi h a “T” a he end (Table 1).
3.2.2. Sample p epa a ion p ocedu e by a sie ing p ocess
Sample p epa a ion p ocedu e by he sie ing p ocess was pe o med in he Geology and
Mine alogy Labo a o y a Åbo Akademi Uni e si y (Tu ku, Finland). Mo a samples we e
co e ed wi h a plas ic ilm and c ushed wi h plie s while d y. The c ushed ma e ial was
sie ed in a sie e se ies wi h dec easing mesh size anging be ween 20 and 500 µm
(Fig.4b).The 46-75 µm g ain-size ac ion o bulk mo a was lushed wi h ul apu e wa e
and selec ed o pe o m sample hyd olysis by sequen ial dissolu ion o adioca bon da ing.
Samples ob ained by he se ling p epa a ion p ocedu e ha e been named wi h a “B” a he
end (Table 1).
3.2.3. Sample hyd olysis by sequen ial dissolu ion
Be ween 38 and 44 mg o sample ob ained by he se ling p ocess (0.5-2 µm g ain-size
window) and 80 mg o sample ob ained by he sie ing p ocess (46-75 µm g ain-size
windows) we e used o sample hyd olysis by sequen ial dissolu ion (Fig.5). P epa a ion
p oduc s om each p ocedu e we e diges ed in 5 ml o 85% phospho ic acid (H3PO4) a oom
empe a u e ( om 20 o 25°C). The CO2 gene a ed by he chemical eac ion was isola ed in
se e al ac ions. The ime o dissolu ion o each ac ion a ies un il a minimum o 0.2 mg
Applied Mine alogy in he S udy o His o ical Lime Mo a s
108
o C is eached in he ial. Fo samples ob ained by he se ling p ocess he i s wo
successi e CO2 ac ions (a o al o six CO2 ac ions) we e isola ed, and o samples ob ained
by sie ing he i s h ee successi e CO2 ac ions (a o al o nine CO2 ac ions) we e
isola ed. The isola ed CO2 ac ions we e used o adioca bon da ing.
Fig. 5. P epa a ion line o sample hyd olysis by sequen ial dissolu ion (modi ied om Ringbom e al.,
2014).
3.3. Me hods
Hand sample obse a ions we e ca ied ou by means o a Dino-Li e P emie
AM7013MZT digi al handheld mic oscope p o ided wi h a Mic o ouch II senso o be e
obse a ion o o ganic componen s embedded in he mo a . Magni ica ion wo king dis ance
was up o 200x and bo h measu emen s, acquisi ion and calib a ions we e ca ied ou using
DinoCap u e 2.0 so wa e.
A Nikon Eclipse LV100POL mic oscope equipped wi h a DS F-11digi al came a and DS
L2 came a con ol uni was used o he pe og aphic s udies o mo a s. Mine alogical and
mic o ex u al cha ac e is ics o samples we e analysed on polished hin-sec ions using bo h
plane and c ossed-pola ized ligh modes.
The mine alogical composi ion o samples was de e mined by means o X- ay di ac ion
(XRD) using a Philips X’Pe di ac ome e (Mal e n PANaly ical, Almelo, The
Ne he lands) in polyc ys alline powde samples. The di ac ome e was p o ided wi h a
monoch oma ic Cu-kα1 X- adia ion ope a ing a 40 kV and 20 mA. The da a collec ion was
made by a con inuous scan in he ange 5-70º 2θ, a an acquisi ion a e o 0.02° pe second.
Mine al phases iden i ica ion was ca ied ou wi h X’Pe HighSco e Plus 3.0 so wa e by
PANaly ical.
The mog a ime ic analysis (TGA) we e ca ied ou in a TA SDT 2960 TG-DSC
he mog a ime ic analyse (TA Ins umen s, New Cas le, DE, USA) by hea ing 10 mg o
powde sample a 10°C min-1 om oom empe a u e ( om 20 o 25°C) o 900 °C unde ai
a mosphe e in a P c ucible.
Ca hodoluminescence (CL) was pe o med in powde sample by using a Technosyn Cold
Ca hode uni –luminescence 8200 MK II a ached o an Olympus BH–II mic oscope equipped
wi h an Olympus Camedia C 7070 came a.
The ca bona ion es was ca ied ou o he isual assessmen o he mo a ca bona ion
deg ee using a phenolph halein indica o solu ion (2% in e hanol).
Radioca bon da ing o samples was pe o med by means o Accele a o Mass
Spec ome y (AMS) in he Labo a o y o Ion Beam Physics ETH (Zu ich, Swi ze land)
(Synal, 2013; Synal e al., 2007) ollowing he p ocedu e desc ibed by Hajdas (2008). A
cha coal agmen ound embedded in he mo a was also da ed in he Aa hus AMS Cen e
(AARAMS), Aa hus Uni e si y (Aa hus, Denma k). Cha coal was p e- ea ed by he acid-
alkali-acid (AAA) me hod p io o con e sion o CO2 (Bi d e al., 1999). The 14C ages a e
8. Appendices: Published and Submi ed Wo ks
109
epo ed in con en ional adioca bon yea s BP (Be o e P esen = AD 1950) acco ding o he
in e na ional con en ion (S ui e and Polach, 1977). Calcula ed 14C ages we e co ec ed o
na u al iso opic ac iona ion based on he 14C/13C a io measu emen o be equi alen o he
s anda d δ13C alue o -25‰ VPDB. The con en ional 14C ages we e calib a ed o calenda
ages using he In Cal13 a mosphe ic calib a ion cu e (Reime e al., 2013) by means o
OxCal 4.2.3 calib a ion so wa e (B onk Ramsey, 2017). The p obabili y me hod was used
o calcula e he calib a ed age anges and will be epo ed a he 95.4 % con idence le el (2σ).
The epo ed δ13C alues a e AMS de i ed alues.
Collagen om a oo h ound embedded in he mo a was ex ac ed o adioca bon
da ing using p e-cleaned ul a- il e s o he Millipo e Amicon Ul a-4 ype wi h MW=30 kDa
a he AARAMS (B own e al., 1988).
4. Resul s and Discussion
Mac oscopically all mo a samples showed a he e ogeneous ex u e wi h small cha coal
agmen s dispe sed in he binde -ma ix (Fig.6a). Small bone agmen s (Figs. 6b and c) and
an animal oo h (Fig.7) isible o he naked eye we e also ound in Sample CI-T-13. The oo h
was iden i ied as a lowe igh i s o second mola (M1, M2) o a sheep/goa (J. Ro es, pe s.
comm., Janua y 2019).
Fig. 6. O ganic agmen s embedded in he I ulegi Cas le lime mo a s. (a) Rep esen a i e cha coal
agmen . (b) and (c) bone agmen om he Sample CI-T-13.
Fig. 7. (a) Animal oo h embedded in he Sample CI-T-13. Images o he di e en aces o he oo h
ound embedded in he mo a binde ma ix: (b) Occlusal ace. (c) Apical ace. (d) Buccal ace.
(e) Lingual ace. ( ) Mesial ace. (g) Dis al ace.
Applied Mine alogy in he S udy o His o ical Lime Mo a s
110
Fig. 8. Thin sec ion pho omic og aphs in c oss-pola ized ligh , XPL and plane-pola ized ligh , PPL.
The mos ep esen a i e ex u es showing he he e ogeneous binde ma ix-suppo ed ex u e o
his o ic lime mo a s om I ulegi Cas le. (a) Subangula sands one agmen (XPL). (b) B yozoan
agmen (XPL). (c) Sands one agg ega e showing mic ocline c ys als (XPL). (d) Mic ocline c ys al
embedded in he binde -ma ix (XPL). (e) Lime lumps embedded in he binde -ma ix (XPL).
( ) Rounded ce amic agmen embedded in he binde -ma ix (XPL). (g) Cha coal agmen (PPL).
(h) Seconda y calci e c ys als illing ca i ies (XPL). Q z: qua z, Rx: Rock agmen , Fsl: ossil;
Mc: mic ocline, L: Lump, C: ce amic, Ch: cha coal.
8. Appendices: Published and Submi ed Wo ks
111
Thin sec ions o a chaeological mo a s we e subjec ed o pe og aphic analyses unde
pola ized-ligh mic oscopy in o de o obse e he o e all mo a ex u e and o iden i y he
binde and agg ega es na u e. All samples show a he e ogeneous binde ma ix-suppo ed
ex u e. All mo a s a e composed by a mic i ic calci e binde and angula o subangula
qua z g ains and he e ome ic agmen s o sands ones, ma ls and calca eni es as agg ega es
(Fig. 8). Bioclas agmen s (e.g. echinode m pla es, o amini e s and molluscs) and angula
mic ocline c ys als (K- eldspa ) a e obse ed sca e ed in he binde -ma ix as a esul o
c ushing he ocks used as agg ega es, (Fig. 8a, b, c and d). Lumps < 1 mm in size, ounded
ce amic agmen s < 5 mm in size and cha coal agmen s a e also obse ed dispe sed in he
binde -ma ix (Fig. 8e, , g). The use o lime lumps o mo a adioca bon da ing (Lind oos e
al., 2007; Lind oos e al., 2014; Lind oos e al., 2018; Pesce e al., 2009; Pesce e al., 2012;
Van S ydonck e al., 1992) was no possible in I ulegi Cas le mo a s. The lime lumps we e
no su icien ly abundan o la ge enough o achie e he equi ed amoun o sample o ensu e
a eliable adioca bon da e. Addi ionally, seconda y calci e c ys als ha e been obse ed illing
ca i ies, pa icula ly in Sample CI-T-9 (Fig. 8h). Sample CI-T-13 shows sca ce and small
bone agmen s as was also obse ed mac oscopically (Fig. 9).
Fig. 9. Thin sec ion pho omic og aphs o bone agmen s in Sample CI-T-13. (a) in c ossed-pola ized
ligh (b) in plane pola ized ligh . (c) on he le in c ossed-pola ized ligh and on he igh in plane
pola ized ligh . Bx: bone agmen .
To check sample alkalini y, he ca bona ion es was also ca ied ou o assess he mo a
ca bona ion deg ee isually since alkaline samples a e p oblema ic o mo a adioca bon
da ing (Lich enbe ge e al., 2015). Acco ding o he es esul s, samples we e ully-
ca bona ed since hey emained colou less a e eac ing wi h he phenolph halein, indica ing
a non-alkaline pH and he e o e he absence o po landi e in he binde .
Table 1 summa izes he sample ac ions ob ained bo h by he sie ing p ocess (46-75 µm
g ain-size window named wi h a B) and se ling p ocess (0.5-2 µm g ain-size window named
wi h a T). Ca bona ion es was pe o med in all sample ac ions be o e analyzing hem by
means o X- ay di ac ion (XRD), he mog a ime ic analyses (TGA), ca hodoluminescence
analysis (CL) and AMS analysis.
Calci e and qua z we e he main mine al phases iden i ied by XRD in all ex ac ed
ac ions while K- eldspa and plagioclase we e iden i ied in mino amoun s in samples
CI-T-9B, CI-T-10B and CI-T-13B and as aces in Sample CI-T-9T (Fig. 10, Table 2). T aces
o illi e-like phyllosilica es we e also p esen in Samples CI-T-9B, CI-T-10B and CI-T-13B
and in mino amoun s in Samples CI-T-9T, CI-T-10T and CI-T-13T.
Samples in he 46-75 µm g ain-size window show highe amoun s o qua z, K- eldspa
and plagioclase compa ed wi h samples in he 0.5-2 µm g ain-size window. K- eldspa s and
plagioclases come om he ock agmen s used as agg ega es (Fig. 8c). The la ge amoun o
hese phases indica es he p esence o agg ega e emains in he 46-75 µm g ain-size window.
Agg ega e emains could be a ibu ed o he small agg ega e agmen s mixed wi h he lime

Applied Mine alogy in he S udy o His o ical Lime Mo a s
112
pu y in he mixing p ocess and o he agg ega e agmen s esul ing om bulk mo a
c ushing in he sample p epa a ion by sie ing.
Mo eo e , i should be no ed ha laye ed double hyd oxide phases (LDHs) we e no
iden i ied by XRD in ei he o he g ain-size windows. LDHs ha e a high CO32- anion cap u e
capaci y due o hei ion-exchange p ope ies ha could imp o e he ca bona ion esis ance o
mo a (Ma e al., 2019; Miya a, 1983). Ne e heless, he iden i ica ion o LDHs in samples
o adioca bon da ing is essen ial. The high CO32- a ini y o LDHs makes hem a po en ially
con amina ing mine al phase g oup in mo a adioca bon da ing since hey could inco po a e
CO32- om he agg ega es and in oduce dead ca bon in o he sys em, hus ageing adioca bon
da es (G o e e al., 2010; Miya a, 1983; Ponce-An ón e al., 2018).
Fig. 10. X- ay di ac ion pa e ns o he ep esen a i e samples ob ained by sie ing and se ling
p ocesses (a) sample ob ained by sie ing (46-75 µm g ain-size window), (b) sample ob ained by
se ling (0.5-2 µm g ain-size window). Q z: qua z, Cal:Calci e; Plg: plagioclase, K-Fsp: po assium
eldspa , Fsp: eldspa s s.l., Phy: illi e-like phyllosilica es.
Fig. 11. The mo-g a ime ic analyses (TGA) o he di e en bulk mo a ac ions and binde
ac ions ob ained by sie ing (46-75 µm g ain-size window) and by se ling (0.5-2 µm g ain-size
window), espec i ely.
The mog a ime ic analyses (TGA) o s udied ac ions show a con inuous
he mog a ime ic p o ile wi h ou main weigh losses (Fig.11). Ini ial weigh loss akes
place be ween oom empe a u e ( om 20 o 25°C) and 120 ºC due o he p esence o
adso p ion wa e (in e -pa icle wa e ) while he second weigh loss be ween 120 ºC and
8. Appendices: Published and Submi ed Wo ks
113
200 ºC was a ibu ed o he c ys alliza ion wa e (in e laye wa e ). The hi d weigh loss
be ween 200 ºC and 600ºC co esponds o dehyd oxyla ion esul ing om he loss o he
s uc u al hyd oxyl g oups (OH-). The ou h and mos impo an weigh loss occu s a
empe a u es abo e 600 ºC when he CO2 is los due o he ca bona es decomposi ion
(Bakolas e al., 1998; Mo opoulou e al., 2005; Paama e al., 1998).
Samples in he 0.5-2 µm g ain-size window (CI-T-9T, CI-T-10T and CI-T-13T) show a
o al weigh loss a ying om 22% o 26.1%, while samples in he 46-75 µm g ain-size
window (CI-T-9B, CI-T-10B and CI-T-13B) om 25.4% o 27.1%. The p esence o he
phyllosilica es iden i ied by XRD was con i med by TGA. The weigh loss in he empe a u e
ange o 400 ºC o 550 ºC in he he mog a ime ic cu e is associa ed wi h phyllosilica e
dehyd oxyla ion and a ies wi h s uc u e and composi ion (Cheng and Heida i, 2017; D i s
and McCa y, 2007; G im, 1962). Wa e - e en ion capaci y o phyllosilica es has led o a high
weigh loss o he adso p ion wa e and in e laye wa e a ying om 7.1% o 8.7% in
samples in he 0.5-2 µm g ain-size window, while he weigh loss in he 46-75 µm g ain-size
window anges om 2.4% o 3.5%. Abo e 600 ºC, he weigh loss ela ed o ca bona es
decomposi ion anges be ween 7.4% and 12.11% o samples in he 0.5-2 µm g ain-size
window and om 18.9% o 21.9% o samples in he 46-75 µm g ain-size window.
LDHs ha e no been iden i ied by XRD because hey could be unde he de ec ion limi
o he analy ical me hod. Ne e heless, he TGA con i ms he absence o LDHs in all s udied
samples. The wo con inuous weigh losses be ween 200 and 500 ºC ela ed o OH- g oups
loss bonded o Al3+ and o Mg2+ co esponding o he LDHs he mal decomposi ion we e no
obse ed (Ficicila and Dogu, 2006; León e al., 2010; Ma e al., 2019; Yang e al., 2002).
Fig. 12. Ca hodoluminescence (CL) pho omic og aphs o bulk mo a ac ions and binde mo a
ac ions. (a) Sample CI-T-9B. (b) Sample CI-T-10B. (c) Sample CI-T-13B. (d) Sample CI-T-9T.
(e) Sample CI-T-10T. ( ) Sample CI-T-13T. Blue: qua z o K- eldspa . G eenish-yellow: plagioclase.
Tile- ed: binde calci e. Red-o ange: ca bona ed agg ega es o geogenic o igin
The CL analyses suppo he mine alogical composi ion de e mined by XRD and e i ied
by TGA. Calci ic mo a binde s o ac ions ob ained by se ling and sie ing show a ile- ed
o da k b own luminescence colou in CL (Fig. 12). G ains wi h a b igh ed-o ange
luminescence colou associa ed wi h ca bona ed agg ega es o geogenic o igin a e obse ed in
he 46-75 µm bulk mo a ac ion samples (Fig.12a, b and c) while in he 0.5-2 µm binde
ac ion samples hey a e no obse ed (Fig. 12d, e and ). The blue luminescence o
K- eldspa di e s om he g eenish-yellow colou o plagioclases (Gö ze e al., 2000) bu
blue luminescence can also be ela ed o qua z g ains. Samples CI-T-10T and CI-T-13T show
Applied Mine alogy in he S udy o His o ical Lime Mo a s
114
a sca ce p esence o e en absence o ca bona ed agg ega es, qua z, K- eldspa and
plagioclase g ains.
The use o CL mic oscopy alone is no su icien o mine al de e mina ion (Pagel e al.,
2000). Colou obse a ion in CL makes mine alogical in e p e a ion di icul since di e ences
in luminescence colou s can also be a esul o small a ia ions in he composi ion o a
mine al (Ma shall, 1988). Ne e heless, CL was use ul o iden i y he ca bona ed agg ega e
emains (b igh o ange luminescence) since by XRD and TGA he calci e om ca bona ed
agg ega es (geogenic calci e) canno be di e en ia ed om he neo o med calci e. The CL
analyses show he p esence o geogenic calci e in he bulk mo a ac ion samples in he
46-75 µm g ain-size window ob ained by sie ing bu no in he binde ac ion samples in he
0.5-2 µm g ain-size window ob ained by se ling. The p esence o geogenic calci e
(ca bona ed agg ega es) in samples in he 46-75 µm g ain-size window would explain he
highe ca bona e con en in he TGA analyses (Fig. 11). Geogenic calci e con ibu es o
sample con amina ion since du ing sample hyd olysis i inco po a es geological ca bon in o
he sys em esul ing in an ageing o adioca bon da es.
Table 2. Resul s o he mine alogical composi ion o bulk mo a ac ions and binde mo a ac ions
de e mined by X- ay di ac ion. Cal: calci e, Qz: qua z, Fsp: eldspa s s.l.; Phy: illi e-like
phyllosilica es ****: p edominan compounds; ***: high p opo ion; **: medium p opo ion; *: low
p opo ion; : ace; -: unde ec ed.
Sample
Mine alogy
CI-T-9B
CI-T-10B
CI-T-13B
CI-T-9T
CI-T-10T
CI-T-13T
Size ac ion 46-75 µm
Size ac ion 0.5-2 µm
Cal
***
***
***
****
****
****
Qz
**
**
**
*
*
*
Fsp
*
*
*
-
-
Phy
*
*
*
Bulk mo a ac ions (46-75 µm g ain-size window) and binde mo a ac ions
(0.5-2 µm) we e hyd olysed and h ee and wo CO2 ac ions we e ob ained, espec i ely
(Table 2, Fig. 5). Each isola ed CO2 ac ion was analysed by AMS o adioca bon da ing. A
o al o i een AMS 14C measu emen s om h ee mo a samples om he Towe Keep o
he I ulegi Cas le we e pe o med, six om bulk mo a ac ions ob ained by se ling and
nine om mo a binde ac ions ob ained by sie ing.
Fig. 13. 14C age p o iles o ob ained ac ions om h ee mo a samples om he Towe Keep a
I ulegi Cas le. G ey ba s along he abscissas show he ela i e size o each CO2 inc emen .
F: dissolu ion p og ess (scale 0 o 1 ins ead o 0 o 100%).
The 14C age p o iles a e named as B-p o iles o samples in he 46-75 µm g ain-size
window and T-p o iles o samples in he 0.5-2 µm g ain-size window (Fig. 13). The
B-p o iles show a e ical end whe eas T-p o iles display a mo e ho izon al end. The 14C
age p o iles wi h mo e ho izon al ends indica e less con amina ion in he samples
8. Appendices: Published and Submi ed Wo ks
115
(Heinemeie e al., 2010; Lind oos e al., 2007). Since he T-p o iles a e la e han he
B-p o iles i would show ha mo e con aminan s we e emo ed by se ling han by sie ing, as
was obse ed by CL analyses (Fig. 12).
Table 3 and Figu e 14 show he ob ained adioca bon da ing esul s in con en ional
adioca bon ages (BP), calib a ed in o calenda ages (AD) and epo ed a he 95.4 %
con idence le el (2σ).
Fig. 14. Calenda calib a ion o AMS 14C da es o bulk mo a ac ions, binde mo a ac ions and a
cha coal agmen . In ed, he mili a y campaign o Abd Al-Rahman III in 924. In blue, he di e en
epai s ca ied ou in he Towe Keep and he decade o cas le de ence eno a ion. Sample code
explana ion in Table 1.
Seconda y calci e obse ed wi hin he mo a could explain he eju ena ed da es
(Fig. 8h). P esence o po landi e (Ca(OH)2) would indica e he alkaline na u e o he sample
which would eac wi h he mo e ecen a mosphe ic ca bon dioxide o ming seconda y
calci e ha would yield eju ena ed adioca bon da es. Ne e heless po landi e was no
de ec ed in he alkalini y es no iden i ied by XRD. Fu he mo e, na u al me eo ic wa e
inco po a es a mosphe ic CO2, leading o a dec ease in pH and he acidi ica ion o wa e .
Applied Mine alogy in he S udy o His o ical Lime Mo a s
122

8. Appendices: Published and Submi ed Wo ks
123
APPENDIX II.1
Mine alogical, Tex u al and Physical Cha ac e isa ion o De e mine
De e io a ion Suscep ibili y o I ulegi Cas le Lime Mo a s (Na a e,
Spain)
G aciela Ponce-An ón, Anna A izzi, Ma ia C uz Zuluaga, Giuseppe Cul one,
Luis Angel O ega, Juan xo Agi e Mauleon
Ma e ials 2019; 12(4):584
Applied Mine alogy in he S udy o His o ical Lime Mo a s
124
8. Appendices: Published and Submi ed Wo ks
125
A icle Me ics
9 Jou nal Ci a ion Repo s
Ci a ions: 3
Impac Fac o
2018
5 Yea s
2.972
3.532
JCR® Rank
Classi ica ion
Qua ile
Pe cen ile
Ma e ials Science
Mul idisciplina y
102 o 293
Q2
65.358
9 Scopus
Ci a ions: 2
Ci eSco e 2018
3.26
SJR 2018
0.686
SNIP 2018
1.200
Ci eSco e Rank
Classi ica ion
Pe cen ile
Ma e ials Science
(Gene al Ma e ials Science)
97 o 438
77
9 Google Academic
Ci a ions: 3
Applied Mine alogy in he S udy o His o ical Lime Mo a s
126
ma e ials
A icle
Mine alogical, Tex u al and Physical Cha ac e isa ion
o De e mine De e io a ion Suscep ibili y o I ulegi
Cas le Lime Mo a s (Na a e, Spain)
G aciela Ponce-An ón1,* , Anna A izzi 2, Ma ia C uz Zuluaga 1, Giuseppe Cul one 2,
Luis Angel O ega 1and Juan xo Agi e Mauleon 3
1Depa men o Mine alogy and Pe ology, Facul y o Science and Technology, Uni e si y o he Basque
Coun y-UPV/EHU, Sa iena s/n, 48940 Leioa, Bizkaia, Spain; [email p o ec ed] (M.C.Z.);
[email p o ec ed] (L.A.O.)
2Depa men o Mine alogy and Pe ology, Facul y o Sciences, Uni e si y o G anada,
A da. Fuen enue a s/n, 18002 G anada, Spain; a izzina@ug .es (A.A.); cul one@ug .es (G.C.)
3A anzadi Socie y o Sciences, Zo oagagaina 11, 20014 Donos ia-San Sebas ián, Gipuzkoa, Spain;
[email p o ec ed]
*Co espondence: [email p o ec ed]; Tel.: +34-946-015-456
Recei ed: 29 Janua y 2019; Accep ed: 12 Feb ua y 2019; Published: 15 Feb ua y 2019
!"#!$%&'(!
!"#$%&'
Abs ac :
A chaeological lime mo a s om he Towe Keep and Wes pe ime e wall o I ulegi Cas le
(Na a e, Spain) we e analysed o de e mine suscep ibili y o de e io a ion. Chemical, mine alogical,
ex u al and physical cha ac e isa ion was pe o med by di e en es s and mul ianalysis echniques
in o de o de e mine he in insic ea u es o he o iginal his o ical mo a s a he cas le. Samples om
he Towe Keep a e mo e p one o de e io a e compa ed wi h he Wes pe ime e wall due o high
wa e abso p ion capaci y and high po osi y. A high deg ee o po e in e connec ion, high deso p ion
index and he p esence o high po e olume in he 0.01 o 1
µ
m size ange a ec he mo a du abili y
since po es e ain wa e longe inside he mo a . Local en i onmen condi ions wi h pe sis en
annual ain all, high humidi y and empe a u e a ia ions con ibu e o he decay p ocess o he
o iginal mo a . Cha ac e isa ion o his o ical mo a s no only allows be e unde s anding o
suscep ibili y o de e io a ion bu also helps he design o compa ible and du able epai mo a o
u u e in e en ions on his o ical he i age. Compa ibili y o new ma e ials wi h he his o ical mo a
will be ensu ed by s udying mo a cha ac e is ics and p ope ies.
Keywo ds:
lime mo a ; mine alogy; ex u e; du abili y; de e io a ion; hyd ic beha iou ; po e sys em
1. In oduc ion
The p ese a ion o buil he i age equi es sui able ma e ials and echniques o enable e ec i e
es o a ion in e en ions [
1
]. The cha ac e isa ion o o iginal his o ical mo a s is an impo an s ep
be o e ca ying ou any epai in e en ions since he cha ac e is ics o he new mo a mus be as
simila as possible o hose o he ancien mo a [
2
]. Di e ences in he ma e ial p ope ies lead o
a lack o compa ibili y be ween he new and o iginal mo a educing hei du abili y [
3
]. Se e al
au ho s ha e ca ied ou chemical, mine alogical and physical analyses p io o he o mula ion o
epai mo a s [
4
–
7
]. Compa a i e s udies using di e en limes and addi i es also ha e been ca ied
ou [
8
–
10
]. In addi ion, he ma e ial is exposed o di e en en i onmen al condi ions o de e mine
how hey a ec he mo a p ope ies and which ac o s a e in ol ed in hei decay [
11
–
15
]. S udies o
he epai ma e ial p ope ies a e pe o med in o de o selec he mos sui able mo a mix u e o
es o a ion wo k [16].
Ma e ials 2019,12, 584; doi:10.3390/ma12040584 www.mdpi.com/jou nal/ma e ials
8. Appendices: Published and Submi ed Wo ks
127

Ma e ials 2019,12, 584 2 o 17
En i onmen al ac o s condi ion ma e ial de e io a ion p ocesses [
11
,
17
]. Wa e , in liquid o
apou o m (e.g., as humidi y), a ou s he i e e sible phenomenon o decay, gi ing place o
di e en physical, chemical and biological de e io a ion p ocesses [
18
,
19
]. Chemical deg ada ion o
mo a s akes place mainly due o hyd olysis, hyd a ion o oxida ion p ocesses. Volume inc ease
wi hin he po es, by such p ocesses as c ys alliza ion o wa e in o ice o swelling o some clay mine als,
leads o physical deg ada ion o he ma e ial [
20
]. Fu he mo e, wa e can inco po a e dissol ed sal s
in o he ma e ial ha may c ys allize a e wa e e apo a ion, as well as gaseous species such as CO
2
ha can dissol e he calca eous ma e ials unde speci ic condi ions [21].
Du abili y o ma e ials does no only depend on he en i onmen al ac o s bu also on hei
in insic mine alogical and ex u al ea u es [
22
,
23
]. The po e sys em plays an impo an ole in
mo a du abili y since wea he ing p ocesses o en depend on he ci cula ion o wa e inside he po es,
accele a ing he physical, chemical and biological de e io a ion [
24
]. S udies on hyd ic beha iou
ha e been ca ied ou o unde s and wa e de e io a ion mechanisms in building ma e ials since he
pa ame e s associa ed wi h luid up ake and anspo inside he po es di ec ly in luence ma e ial
de e io a ion [
3
,
5
]. Wa e ci cula ion h ough he ma e ial is also condi ioned by he p esence o
aniso opies and he in e connec ion deg ee be ween he po es [17,25].
No only compa ibili y bu also au hen ici y o he es o a ion ma e ial wi h he o iginal mo a
is one o he main goals in he i age conse a ion. Achie ing aes he ic ea u es in e ms o isual
appea ance (e.g., ex u e and colou ) is ano he impo an equi emen in he es o a ion p ocess [
2
,
26
].
Colou is a senso ial pe cep ion be ween he objec , he ligh ing and he obse e , so isual a ia ions in
colou be ween es o ed and o iginal ma e ials is an issue o in e es in es o a ion [
27
,
28
]. In addi ion
o chemical, mine alogical, physical and aes he ic cha ac e isa ion, he wo kabili y is ano he impo an
ea u e o conside in mo a o mula ion [26].
I ulegi Cas le (Na a e, no he n Spain) was buil in a de ensible si e. Geog aphically he cas le is
loca ed in a mid-la i ude clima e zone wi h a suboceanic wes coas al ma i ime clima e [
29
]. Regional
clima e is cha ac e ised by a mode a ely wa m clima e wi h cool summe s and abundan ain all well
dis ibu ed h oughou he yea , al hough wi h wo d y mon hs.
The aim o his s udy is o assess he hyd ic beha iou s o lime-based a chaeological mo a s
om I ulegi Cas le in o de o es ablish hei suscep ibili y o de e io a ion. Taking in o accoun he
clima ic condi ions o which his o ical mo a s a e exposed, knowledge o chemical, mine alogical and
physical p ope ies will allow he o mula ion o an adequa e epai mo a o ensu e he compa ibili y
and au hen ici y o he es o a ion ma e ial wi h he o iginal mo a .
2. A chaeological Backg ound
The medie al a chaeological si e o I ulegi Cas le is on he eas e n bo de o he Pamplona Basin
(Figu e 1). I is a ock cas le on I ulegi Moun ain in he eas o A angu en moun ain ange (Na a e,
Spain). The his o ical s a egic emplacemen o he cas le allowed isual con ol o he Na a e
kingdom capi al and he ou es o he pass o e he Py enees along he Izagaondoa alley.
The walled a chaeological si e is cha ac e ised by a ec angula loo 39 m
⇥
15 m in size wi h
an a ea o app oxima ely 460 m
2
. Wi hin he cas le s uc u es, mo a s om he Towe Keep and
he Wes pe ime e wall we e s udied. The Towe Keep p esen s pseudoisodom bonding wi h high
quali y ashla s. The absence o composi ional di e ences in he owe ashla s indica es ha all he
s uc u e was buil in he same cons uc ion pe iod [
30
]. Ne e heless impo an eno a ions in he
de ensi e elemen s o he cas le we e unde aken as a esul o he cons uc i e echniques de eloped
o e ime. The emodelling o he Towe Keep esul ed in he disman ling o he sou h ou e wall and
he o iginal ec angula loo was ans o med in o he cu en polygonal loo wi h a e ex-shaped
s uc u e. This emodelling inc eased he loo a ea om 90 m
2
o 105 m
2
. The wes pe ime e wall
shows lowe -quali y i egula bonding and has a e age dimensions o 1.25 m wid h and 11.35 m
leng h (Figu e 2). A con inuous se lemen sequence om he La e B onze Age o he La e Middle
Ages has been ecognised in he a chaeological si e. Howe e , he ea lies o i ica ion building is
Applied Mine alogy in he S udy o His o ical Lime Mo a s
128
Ma e ials 2019,12, 584 3 o 17
unknown since no documen a y da a abou he i s building pe iod o he cas le exis . The oldes
men ions o I ulegi Cas le a e da ed in he second hal o he 12 h cen u y and beginning o he 13 h
cen u y.
The cas le
was demolished a he end o he 15 h cen u y and cu en ly only uins emain
s anding [30,31].
Ma e ials 2019, 12, x FOR PEER REVIEW 3 o 17
unknown since no documen a y da a abou he i s building pe iod o he cas le exis . The oldes
men ions o I ulegi Cas le a e da ed in he second hal o he 12 h cen u y and beginning o he 13 h
cen u y. The cas le was demolished a he end o he 15 h cen u y and cu en ly only uins emain
s anding [30,31].
Figu e 1. Geog aphic loca ion o I ulegi Cas le (Na a e, Spain).
Figu e 2. Loca ion o s udied samples in he Towe Keep and Wes pe ime e wall a I ulegi Cas le.
3. Ma e ials and Me hods
3.1. Ma e ials
Eigh a chaeological mo a samples, se en om he Towe Keep and one om he Wes
pe ime e wall a I ulegi Cas le (Na a e, Spain) we e collec ed and analysed (Table 1 and Figu e 2).
While he Towe Keep s uc u e is s ill unconsolida ed, he Wes pe ime e wall was consolida ed in
2017 bu he sample co esponding o his wall was collec ed be o e he consolida ion o he cas le
Figu e 1. Geog aphic loca ion o I ulegi Cas le (Na a e, Spain).
Ma e ials 2019, 12, x FOR PEER REVIEW 3 o 17
unknown since no documen a y da a abou he i s building pe iod o he cas le exis . The oldes
men ions o I ulegi Cas le a e da ed in he second hal o he 12 h cen u y and beginning o he 13 h
cen u y. The cas le was demolished a he end o he 15 h cen u y and cu en ly only uins emain
s anding [30,31].
Figu e 1. Geog aphic loca ion o I ulegi Cas le (Na a e, Spain).
Figu e 2. Loca ion o s udied samples in he Towe Keep and Wes pe ime e wall a I ulegi Cas le.
3. Ma e ials and Me hods
3.1. Ma e ials
Eigh a chaeological mo a samples, se en om he Towe Keep and one om he Wes
pe ime e wall a I ulegi Cas le (Na a e, Spain) we e collec ed and analysed (Table 1 and Figu e 2).
While he Towe Keep s uc u e is s ill unconsolida ed, he Wes pe ime e wall was consolida ed in
2017 bu he sample co esponding o his wall was collec ed be o e he consolida ion o he cas le
Figu e 2. Loca ion o s udied samples in he Towe Keep and Wes pe ime e wall a I ulegi Cas le.
3. Ma e ials and Me hods
3.1. Ma e ials
Eigh a chaeological mo a samples, se en om he Towe Keep and one om he Wes pe ime e
wall a I ulegi Cas le (Na a e, Spain) we e collec ed and analysed (Table 1and Figu e 2). While he
Towe Keep s uc u e is s ill unconsolida ed, he Wes pe ime e wall was consolida ed in 2017
bu he sample co esponding o his wall was collec ed be o e he consolida ion o he cas le
8. Appendices: Published and Submi ed Wo ks
129
Ma e ials 2019,12, 584 4 o 17
uins. Conside ing he s udied mo a s co espond o a chaeological ma e ials, sample selec ion
was de e mined on he basis o he minimum olume equi ed o pe o m he capilla y es s.
Table 1. S udied samples om di e en s uc u es a I ulegi Cas le.
A chaeological S uc u e Sample
Wes pe ime e wall CI-M-3
Towe Keep
CI-T-8
CI-T-9
CI-T-10
CI-T-11
CI-T-12
Towe Keep ex ension CI-TE-8
CI-TE-9
3.2. Me hods
Di e en analy ical echniques and es s we e pe o med o de e mine he mine alogy, chemis y,
ex u e and physical p ope ies o he collec ed a chaeological mo a s.
3.2.1. Mine alogical, Chemical and Pe og aphic Cha ac e isa ion
The mine alogical composi ion o samples was de e mined by means o X- ay di ac ion (XRD)
using a Philips X’Pe di ac ome e (Leioa, Spain) equipped wi h a monoc oma ic Cu-k
↵1
X- adia ion
ope a ing a 40 kV and 20 mA. The da a collec ion on he powde sample was pe o med by a
con inuous scan in he ange om 5 o 70

2
✓
, a an acquisi ion a e o 0.02

pe second. Mine al phase
iden i ica ions we e pe o med wi h X’Pe HighSco e Plus 3.0 so wa e by PANaly ical (Leioa, Spain).
Chemical composi ion o majo elemen s in bulk mo a was es ablished by means o X- ay
Fluo escence (XRF) in powde sample. Measu emen s we e aken by Wa eleng h Dispe si e X- ay
Fluo escence (WDXRF) using a PANaly ical Axios Ad anced PW4400 XRF spec ome e (4 kW Rh
anode SST-mAX X- ay ube, Leioa, Spain). Fused beads we e ob ained a e hea ing a sample and
li hium bo a e lux (Spec omel A12, Me ck, Leioa, Spain) mix u e in app oxima e 20:1 p opo ions a
~1200

C o 3 min in P /Au c ucibles using a PANaly ical Pe l’X3 usion machine. De ec ion lowe
limi s o majo elemen s a e in he ange o 0.01 w %. The loss on igni ion (LOI) has been calcula ed
a e hea ing a powde sample o bulk mo a a 1050 C o one hou .
The mo a ex u e and na u e o componen s we e de e mined in polished hin sec ions using a
Nikon Eclipse LV100POL mic oscope (Leioa, Spain) equipped wi h DS F-I1 digi al came a and a DS
L-2 con ol uni .
3.2.2. Cha ac e isa ion o Po e Sys em and Hyd ic Beha iou
Me cu y in usion po osime y (MIP) was used o de e mine he po e size dis ibu ion and he
open po osi y (P
MIP
) by a Po emas e -60 GT (Quan ach ome Ins umen s, Alican e, Spain), wi h a
maximum injec ion p essu e o 414 MPa, measu ing he po e diame e ange om app oxima ely 0.003
o 360
µ
m. Mo a sample agmen s abou 1 cm
3
we e o en-d ied o 24 h a 60

C be o e he analysis.
To ob ain a comple e ision o he po e sys em, hyd ic es s (HT) we e ca ied ou in samples
o 3 cm
3
in size; p e iously o en-d ied a 80

C o 24 h. Measu emen s we e aken unde
con olled he mo-hyg ome ic condi ions a 25

C and 50% ela i e humidi y. The es measu emen s
we e pe o med on no mo e han wo o h ee samples pe mo a ype, since samples a e
a chaeological ma e ials.
The ee (A
b
) and o ced (A
, unde acuum) wa e abso p ion alues and abso p ion coe icien
(C
a
) we e de e mined ollowing he UNE-EN 13755 [
32
] s anda d. The deg ee o in e connec ion
Applied Mine alogy in he S udy o His o ical Lime Mo a s
130
Ma e ials 2019,12, 584 5 o 17
be ween he po es (A
x
)[
33
] and he sa u a ion coe icien (S) [
34
] we e also de e mined. These hyd ic
pa ame e s we e calcula ed as ollows
Ab=MLM0
M0·100 (1)
whe e M0is he mass o he d ied sample and MLis he mass o he sample sa u a ed unde wa e a
a mosphe ic p essu e (un il cons an mass is eached):
A =MsM0
M0·100 (2)
Ax=A Ab
A ·100 (3)
Ca=Ab
p (4)
whe e M
S
is he mass o he sample sa u a ed wi h wa e unde acuum. The abso p ion coe icien
(C
a
) is de e mined as he slope o he cu e ep esen ing he weigh inc ease as a unc ion o he squa e
oo o ime 4 min a e he beginning o he es :
S=M48h M0
MSM0·100, (5)
whe e M48h is he mass o he sample a e 48 h imme sion in wa e a a mosphe ic p essu e.
D ying index (D
i
) is de ined as he de ini e in eg al o he d ying cu e om he beginning (
0
) o
he end (
) imes o he es in which M
ep esen s a dec easing wa e weigh con en s a ing om
he sa u a ion alues (unde acuum) as a unc ion o ime. The D
i
was measu ed acco ding o he
NORMAL 29/88 [35]:
Di=R
0 (M )d
MS· (6)
The capilla i y coe icien (C
c
) and he capilla i y heigh (H
c
) o samples we e calcula ed acco ding
o he UNE-EN 1925 [36] s anda d:
Cc=M M0
A·p , (7)
whe e M
is he amoun o wa e abso bed a ime and A is he su ace o he sample in con ac wi h
he wa e :
Hc=h
p (8)
whe e h is he heigh o wa e ise by capilla i y a ime .
Finally, UNE-EN 1936 [
37
] s anda d was used o de e mine he open po osi y (P
HT
) and skele al
(⇢Hsk) and bulk (⇢Hb) densi ies as ollows
PHT =MsM0
MsMH·100 (9)
⇢Hsk =M0
M0MH(10)
⇢Hb =M0
MsMH, (11)
whe e MHis he mass o he sample sa u a ed wi h wa e unde acuum and weigh ed in wa e .
8. Appendices: Published and Submi ed Wo ks
131
Ma e ials 2019,12, 584 12 o 17
Ma e ials 2019, 12, x FOR PEER REVIEW 12 o 17
Figu e 6. Hyd ic beha iou s o I ulegi Cas le lime mo a s. (a) F ee wa e abso p ion, o ced wa e
abso p ion and d ying cu es. Weigh a ia ion (ΔM/M) e sus ime (in hou s). (b) Capilla y up ake
cu es: Weigh a ia ion (ΔM/S) e sus ime (in hou s) and (c) capilla i y on cu es. Heigh (in
mm) e sus ime (in hou s).
Rega ding capilla y up ake cu es, samples abso b wa e quickly a he beginning o he es
and as samples become sa u a ed in wa e he eloci y o capilla y ise dec eases and s abilizes
eaching an equilib ium alue (Figu e 6b), ollowing he mos common capilla y ise end ound o
lime mo a s [5]. The nonlineal cu es showing wo sec ions wi h di e en slopes a e due o he
p esence o wo main amilies o po es in he mo a s [48] as MIP analysis e ealed (0.01 µm < < 1
Figu e 6.
Hyd ic beha iou s o I ulegi Cas le lime mo a s. (
a
) F ee wa e abso p ion, o ced wa e
abso p ion and d ying cu es. Weigh a ia ion (
D
M/M) e sus ime (in hou s). (
b
) Capilla y up ake
cu es: Weigh a ia ion (
D
M/S) e sus ime (in hou s) and (
c
) capilla i y on cu es. Heigh (in mm)
e sus ime (in hou s).
Rega ding capilla y up ake cu es, samples abso b wa e quickly a he beginning o he es and
as samples become sa u a ed in wa e he eloci y o capilla y ise dec eases and s abilizes eaching
an equilib ium alue (Figu e 6b), ollowing he mos common capilla y ise end ound o lime
Applied Mine alogy in he S udy o His o ical Lime Mo a s
138

Ma e ials 2019,12, 584 13 o 17
mo a s [
5
]. The nonlineal cu es showing wo sec ions wi h di e en slopes a e due o he p esence
o wo main amilies o po es in he mo a s [
48
] as MIP analysis e ealed (0.01
µ
m< <1
µ
m and
1
µ
m< <10
µ
m). Samples CI-T-10 and CI-TE-8 ha e high capilla i y coe icien (C
C
) alues because
hey abso b wa e as e han samples CI-M-3 and CI-TE-9, which indeed show lowe C
C
alues
(Table 4). The capilla y on eached he op o all samples a e 48 h excep in Sample CI-TE-9
whe e wa e did no each he op un il 216 h (nine days) a e he beginning o he es (Figu e 6c).
Howe e ,
his isual
sa u a ion does no coincide in ime wi h he eal sa u a ion ha occu s a e
400 h
(
~16 days
) (Figu e 6b,c). This delay con i ms he p esence o wo amilies o po es, which a e
illed a di e en eloci ies by wa e (smalle po es a e illed i s ). Sa u a ion is achie ed when all
connec ed po es a e illed.
Samples CI-M-3 and CI-T-11 show he highes alues o bo h bulk (
⇢Hb
) and skele al (
⇢Hsk
)
densi y (Table 4). Di e ences be ween skele al and bulk densi ies a e ela ed o he po osi y o mo a s.
This di e ence is g ea e in he mo e po ous samples (CI-T-9, CI-T-10, CI-TE-8 and CI-TE-9).
4.3. Nondes uc i e Tes s
Table 5summa izes he ul asound measu emen s in mo a samples. Conside ing lime mo a as
an ideal wo-phase media o agg ega e embedded in a calci ic ma ix, V
p
alues depend on he wa e
eloci y bo h in he ma ix and he agg ega es, since ul asonic wa e p opaga ion is di e en in each
phase. The V
p
dec eases conside ably when he wa e p opaga es om an agg ega e o he ma ix [
49
].
No ela ionship be ween he V
p
and agg ega e size has no been ound p obably because agg ega es
ac as a homogeneous s uc u e conside ing size a cons an pa ame e [
50
]. Howe e , agg ega e
mine alogy is impo an in ul asonic wa e p opaga ion eloci y [51]. In ac , wa es p opaga e mo e
quickly h ough calci e (app oxima ely 6660 m/s) han h ough qua z (app oxima ely 5800 m/s) [
52
].
The e o e, P-wa e eloci y is di ec ly ela ed o he pe og aphic cha ac e is ic o he mo a . V
p
alues
dec ease in all mo a samples due o he p esence o a la ge amoun o siliceous agg ega es, excep in
Sample CI-M-3, which con ains he lowes amoun o agg ega es. Po osi y also a ec s he ul asonic
wa e p opaga ion eloci y since when he wa e p opaga es om a solid (agg ega es o ma ix) h ough
a gaseous medium (po es) he ul asonic wa e p opaga ion eloci y dec eases [
15
]. Ul asound da a,
indeed, a e in ag eemen wi h he abo e-men ioned po osi y esul s (Tables 4and 5). The p esence
o small c acks also a ec s V
p
, causing a all in eloci y [
53
], as in samples CI-T-11, CI-T-12, CI-TE-8
and CI-TE-9.
Table 5.
Resul s o ul asonic wa e p opaga ion h ough lime mo a s om I ulegi Cas le. V
P1
,V
P2
and V
P3
(in m/s): P-wa e eloci y in h ee o hogonal di ec ions;
D
M
p
: o al aniso opy coe icien
o P-wa es.
CI-M-3 CI-T-8 CI-T-9 CI-T-10 CI-T-11 CI-T-12 CI-TE-8 CI-TE-9
VP1 1815.48 186.75 178.77 130.80 158.19 150.49 178.77 151.83
VP2 1828.91 197.60 340.66 134.20 159.79 169.49 191.62 183.43
VP3 1820.90 197.60 358.70 132.78 197.37 157.36 203.82 177.51
DM 0.52 5.49 48.88 2.01 11.43 7.92 9.58 15.87
The o al aniso opy coe icien o P-wa es (
D
M
p
) con i ms he ex u al homogenei y o CI-M-3
sample and he ex u al he e ogenei y o he es o he samples. Sample CI-M-3 ga e he lowes
D
M
p
alue and sample CI-T-9 he highes (Table 5).
The ch oma ic pa ame e s o each mo a a e summa ised in Table 6. Colo ime ic analyses
showed ha he ligh ness alue (L*) was lowe o samples CI-M-3, CI-T-9, CI-T-10 and CI-T-11, while
samples CI-T-12, CI-TE-8 and CI-TE-9 show he highe L* alues. The ch oma ic axes (a* and b*)
alues end owa ds o he ligh g ey ield due o a luminosi y alue close o 80. The a* alues a e e y
simila in all samples excep o Sample CI-M-3 which p esen s he highes alues. Samples CI-T-12
8. Appendices: Published and Submi ed Wo ks
139
Ma e ials 2019,12, 584 14 o 17
and CI-TE-9 ha e he lowes b* alues. Lowe L* is due o he p esence o agg ega es, phyllosilica e
phases and i on oxides, as pe og aphic and XRD analyses indica e.
Table 6.
Ch oma ic pa ame e s o mo a samples. Ligh ness (L*), ch oma ic coo dina es (a* and b*),
ch oma (C*), hue angle (H).
CI-M-3 CI-T-8 CI-T-9 CI-T-10 CI-T-11 CI-T-12 CI-TE-8 CI-TE-9
L* 72.31 78.31 76.76 73.69 73.41 80.79 80.55 80.24
a* 3.22 2.36 2.35 2.95 2.38 2.15 2.81 2.04
b* 13.79 11.83 11.26 14.67 12.8 9.63 12.86 9.76
C* 14.16 12.07 11.51 14.96 13.02 9.86 13.17 9.97
H 76.85 78.71 78.06 78.63 79.46 77.45 77.82 78.22
Acco ding o he measu ed pa ame e s, samples CI-T-9, CI-T-10, CI-TE-8 and CI-TE-9
(Sou h-Sou heas ace o he Towe Keep) p esen he highes ee wa e abso p ion alues (
Ab> 25%
),
high po osi y alues (P
HT
and P
MIP
> 40%) wi h good po e in e connec ion (lowes A
x
alues),
a ou ing he inco po a ion o dissol ed sal s and gaseous species such as CO
2
in o he ma e ial ha
could de e io a e he mo a . Samples CI-T-11 and CI-T-12 (Sou hwes wall o he Towe Keep) display
he wo s po e in e connec ion (highe A
x
alues) and d y mo e slowly (highe D
i
alues), indica ing a
longe wa e e en ion also a ec ing mo a du abili y. Only sample CI-M-3 om he Wes pe ime e
wall shows less po en ial o de e io a ion due o he low ee wa e abso p ion alues (A
b
< 19%),
as d ying and lowe po osi y (PHT and PMIP ~32%).
Addi ionally, en i onmen al ac o s condi ion mo a du abili y due o he p esence o wa e
bo h as humidi y (wa e apou ) and as ain all (liquid wa e ). The clima ic condi ions a I ulegi
Cas le a ou mo a de e io a ion since he a e age annual p ecipi a ion is a ound 858 mm and in
10 mon hs
ain all is abo e 50 mm. The annual a e age humidi y is ~76% bu in summe pe iods he
humidi y is highe han he a e age alues. Mo eo e , he a e age empe a u e is 11.8

C bu he
absolu e a e age minimum and maximum empe a u es a e

12.4

C and 39.9

C, espec i ely [
54
].
The wide a ia ion be ween absolu e maximum and minimum empe a u e oge he wi h he high
humidi y a ou he physical wea he ing o mo a s. Ma e ial exposu e o empe a u e a ia ions
leads o he mal expansion and empe a u es below eezing esul in os wedging causing c acking
o mo a s. Addi ionally, he pe sis en ain all a ou s dissol ed sal s and CO
2
inco po a ion in o he
mo a s p oducing c ys al g ow h and ca bona e species dissolu ion, espec i ely.
5. Conclusions and Pe spec i es
The mine alogical, chemical and physical p ope ies o eigh a chaeological lime mo a samples
om I ulegi Cas le we e de e mined o enable an unde s anding o hei suscep ibili y o de e io a ion.
High po e olume in he 0.01 o 1
µ
m size ange is one o he easons o he du abili y p oblems
ha he s udied mo a s migh su e in he u u e, since smalle po es e ain wa e longe and d y
mo e slowly. Rela ed wi h hei po e sys em, samples om he Towe Keep show high suscep ibili y o
de e io a ion compa ed wi h he Wes pe ime e wall sample. Samples om he sou h-sou heas ace o
he Towe Keep show highe wa e abso p ion capaci y and po osi y (wi h good po e in e connec ion),
while samples om he Sou hwes wall p esen he wo s po e in e connec ion and d y mo e slowly.
No only do he in insic ea u es o he o iginal mo a s o I ulegi Cas le, bu also he local
en i onmen al exposu e condi ions, a ec mo a de e io a ion. The pe sis en ain all du ing he yea ,
high humidi y and empe a u e a ia ions in his a ea ce ainly con ibu e o wea he ing p ocesses in
he o iginal mo a s. To design du able and compa ible epai ma e ial o his cas le, o iginal mo a
cha ac e is ics and en i onmen al condi ions should be aken in o accoun .
Conside ing ha he s udied mo a s a e a chaeological medie al mo a s, di e ences in
he physical p ope ies among nea by samples would no necessa ily indica e di e en mo a
Applied Mine alogy in he S udy o His o ical Lime Mo a s
140
Ma e ials 2019,12, 584 15 o 17
manu ac u ing p ocesses bu could ins ead co espond o he ypical he e ogenei y o his ype
o ma e ial.
This s udy was able o de e mine he chemical-mine alogical cha ac e is ics and physical
p ope ies o he o iginal his o ical mo a s a I ulegi Cas le, wi h posi i e implica ions o he design
o compa ible and du able epai mo a in u u e in e en ions. I will be essen ial o selec he
mos app op ia e mo a composi ion o ensu e a sa is ac o y and long-las ing epai in e en ion.
Compa ibili y, du abili y, au hen ici y and e e sibili y o he epai ma e ials a e indeed c ucial
equi emen s in any es o a ion wo k o be ca ied ou in he u u e in his cas le.
In he u u e, addi ional decay es s, including sal c ys alliza ion, we and d y cycles, ain all
exposu e and eeze- haw cycles, should be ca ied ou o assess he de e io a ion p ocesses due o
en i onmen al agen s in he a ea.
Au ho Con ibu ions:
Concep ualiza ion, G.P.-A., A.A., G.C., M.C.Z. and L.A.O.; Da a Cu a ion, G.P.-A.;
W i ing-O iginal D a P epa a ion, G.P.-A.; W i ing—Re iew & Edi ing, G.P.-A., M.C.Z., A.A. and G.C.; Funding
Acquisi ion, A.A., G.C., L.A.O. and J.A.M. All au ho s ead and app o ed he inal manusc ip .
Funding:
This s udy was possible hanks o he inancial suppo o Jun a de Andalucía Resea ch G oup RNM179
and Resea ch P ojec MAT2016-75889-R.
Acknowledgmen s:
G.P.-A. acknowledges he PhD esea ch g an o he Basque Go e nmen [2015-1-02-35].
The au ho s would like o hank Pe e Smi h o e iewing he use o English in he manusc ip .
Con lic s o In e es : The au ho s decla e no con lic s o in e es .
Re e ences
1.
ICOMOS Decla a ion o Ams e dam-1975. A ailable online: h ps://www.icomos.o g/en/and/169- he-
decla a ion-o -ams e dam (accessed on 14 Feb ua y 2019).
2.
Schue emans, L.; Cize , Ö.; Janssens, E.; Se é, G.; Balen, K.V. Cha ac e iza ion o epai mo a s o he
assessmen o hei compa ibili y in es o a ion p ojec s: Resea ch and p ac ice. Cons . Build. Ma e .
2011
,25,
4338–4350. [C ossRe ]
3.
G oo , C.; Ashall, G.J.; Hughes, J.J.; Ba os, P.J. Cha ac e isa ion o old mo a s wi h espec o hei epai :
A s a e o he a . Rilem Rep. 2007,28, 1.
4.
Hughes, J.J.; Cu hbe , S.J. The pe og aphy and mic os uc u e o medie al lime mo a s om he wes
o Sco land: Implica ions o he o mula ion o epai and eplacemen mo a s. Ma e . S uc .
2000
,33,
594–600. [C ossRe ]
5.
A izzi, A.; Cul one, G. The wa e ans e p ope ies and d ying sh inkage o ae ial lime-based mo a s:
An assessmen
o hei quali y as epai ende ing ma e ials. En i on. Ea h Sci.
2014
,71, 1699–1710.
[C ossRe ]
6.
Mo illas, H.; Vazquez, P.; Magu egui, M.; Ma caida, I.; Sil a, L.F.O. Composi ion and po osi y s udy o
o iginal and es o a ion ma e ials included in a coas al his o ical cons uc ion. Cons . Build. Ma e .
2018
,
178, 384–392. [C ossRe ]
7.
Noguei a, R.; Fe ei a Pin o, A.P.; Gomes, A. Design and beha io o adi ional lime-based plas e s and
ende s. Re iew and c i ical app aisal o s eng hs and weaknesses. Cem. Conc . Compos.
2018
,89, 192–204.
[C ossRe ]
8.
A izzi, A.; Cul one, G. The di e ence in beha iou be ween calci ic and dolomi ic lime mo a s se unde
d y condi ions: The ela ionship be ween ex u al and physical–mechanical p ope ies. Cem. Conc . Res.
2012,42, 818–826. [C ossRe ]
9.
A izzi, A.; Cul one, G. Ae ial lime-based mo a s blended wi h a pozzolanic addi i e and di e en
admix u es: A mine alogical, ex u al and physical-mechanical s udy. Cons . Build. Ma e .
2012
,31,
135–143. [C ossRe ]
10.
Sil a, B.A.; Fe ei a Pin o, A.P.; Gomes, A. Na u al hyd aulic lime e sus cemen o blended lime mo a s
o es o a ion wo ks. Cons . Build. Ma e . 2015,94, 346–360. [C ossRe ]
11.
Cha ola, A.; Kwia kowski, D.; Lö endahl, R. S one de e io a ion in his o ic buildings and monumen s.
In P oceedings o he 10 h In e na ional Cong ess on De e io a ion and Conse a ion o S one, S ockholm,
Sweden, 27 June–2 July 2004.
8. Appendices: Published and Submi ed Wo ks
141
Ma e ials 2019,12, 584 16 o 17
12.
Cul one, G.; Sebas ian, E. Labo a o y simula ion showing he in luence o sal e lo escence on he
wea he ing o composi e building ma e ials. En i on. Geol. 2008,56, 729–740. [C ossRe ]
13.
Izagui e, A.; Lanas, J.; Ál a ez, J.I. Ageing o lime mo a s wi h admix u es: Du abili y and s eng h
assessmen . Cem. Conc . Res. 2010,40, 1081–1095. [C ossRe ]
14.
A izzi, A.; Viles, H.; Cul one, G. Expe imen al es ing o he du abili y o lime-based mo a s used o
ende ing his o ic buildings. Cons . Build. Ma e . 2012,28, 807–818. [C ossRe ]
15.
A izzi, A.; Hue ga, G.M.; Sebas ián, E.; Cul one, G. Mine alogical, ex u al and physical-mechanical s udy
o hyd aulic lime mo a s cu ed unde di e en mois u e condi ions. Ma e . Cons ucc. 2015.[C ossRe ]
16.
Lanas, J.; Al a ez-Galindo, J.I. Mason y epai lime-based mo a s: ac o s a ec ing he mechanical beha io .
Cem. Conc . Res. 2003,33, 1867–1876. [C ossRe ]
17.
Cha ola, A.E.; Lanzza ini, L. Ma e ial Deg ada ion Caused by Acid Rain. In ACS Symposium; Baboian, R.,
Ed.; Ame ican Chemical Socie y: Washing on, DC, USA, 1986; pp. 250–258.
18.
Kühnel, R.A. D i ing o ces o ock deg ada ion. In P o ec ion and Conse a ion o he Cul u al He i age o he
Medi e anean Ci ies; Galan, E., Zezza, F., Eds.; Swe s & Zei linge : Lisse, The Ne he lands, 2002; pp. 11–17.
19.
Veniale, F.; Se i, M.; Lodola, S. Diagnosing s one decay in buil he i age. Fac s and pe spec i es.
Ma e . Cons ucc. 2008,58, 11–32. [C ossRe ]
20.
Esbe , R.; Mon o o, M.; O daz, J. Rock as a cons uc ion ma e ial du abili y de e io a ion and conse a ion.
Ma e . Cons ucc. 1991,41, 61–73. [C ossRe ]
21.
Winkle , E.M. Wea he ing and wea he ing a es o na u al s one. En i on. Geol. Wa e Sci.
1987
,9, 85–92.
[C ossRe ]
22.
O dóñez, S.; Fo , R.; Del Cu a, M.G. Po e size dis ibu ion and he du abili y o a po ous limes one. Q. J.
Eng. Geol. Hyd ogeol. 1997,30, 221–230. [C ossRe ]
23.
Tö ök, Á.; Vásá helyi, B. The in luence o ab ic and wa e con en on selec ed ock mechanical pa ame e s
o a e ine, examples om Hunga y. Eng. Geol. 2010,115, 237–245. [C ossRe ]
24.
Molina, E.; Cul one, G.; Sebas ián, E.; Alonso, F.J.; Ca izo, L.; Gisbe , J.; Buj, O. The po e sys em o
sedimen a y ocks as a key ac o in he du abili y o building ma e ials. Eng. Geol.
2011
,118, 110–121.
[C ossRe ]
25. Hall, C.; Ho , W.D. Wa e T anspo in B ick, S one and Conc e e; Taylo & F ancis: London, UK, 2002.
26.
Van Balen, K.; Hend ickx, R. P ese a ion o wo kmanship o wo kmanship o p ese a ion. In P oceedings
o he 6 h In e na ional Con e ence on S uc u al Analysis o His o ical Cons uc ions: P ese ing Sa e y and
Signi icance, Ba h, UK, 2–4 July 2008; pp. 3–12.
27.
Lozano, R.D. El Colo y su Medición: Con Una In oducción a la Óp ica Fisiológica y al Es udio de la Visión;
Amé icalee S.R.L.: Buenos Ai es, A gen ina, 1978.
28.
López, A.; Guzmán, G.A.; Di Sa li, A.R. Colo s abili y in mo a s and conc e es. Pa 1: S udy on a chi ec u al
mo a s. Cons . Build. Ma e . 2016,120, 617–622. [C ossRe ]
29.
Peel, M.C.; Finlayson, B.L.; McMahon, T.A. Upda ed wo ld map o he Köppen-Geige clima e classi ica ion.
Hyd ol. Ea h Sys . Sci. 2007,11, 1633–1644. [C ossRe ]
30.
Buces Cabello, J.; Mo aza Ba ea, A.; Agi e Mauleon, J.; Pescado Med ano, A.; Lego bu u A zamendi, M.
Un encla e es a égico en la Cuenca de Pamplona: el cas illo medie al de I ulegi (Lakidain, Na a a).
Balance de los abajos a queológicos (2007–2012). A ailable online: h p://www.a anzadi.eus/wp-con en /
iles_m /1390899077I ulegi.pd (accessed on 14 Feb ua y 2019).
31. Ma inena Ruiz, J.J. Na a a Cas illos y Palacios; Caja de Aho os de Na a a: Pamplona, Spain, 1980.
32.
UNE-EN 13755, Na u al S one Tes Me hods De e mina ion o Wa e Abso p ion a A mosphe ic P essu e; AENOR:
Mad id, Spain, 2008.
33.
Cul one, G.; De La To e, M.J.; Sebas ián, E.; Cazalla, O. E alua ion o b icks du abili y using des uc i e
and nondes uc i e me hods (DT and NDT). Ma e . Cons ucc. 2003,53, 41–59. [C ossRe ]
34.
RILEM. Recommended es o measu e he de e io a ion o s one and o assess he di e ences o ea men
me hods. Ma e . S uc . 1980,13, 175–253. [C ossRe ]
35. NORMAL 29/88, Misu a Dell’indice di Asciugamen o (D ying Index); CNR-ICR: Rome, I aly, 1988.
36.
UNE-EN 1925, Na u al S one Tes Me hods. De e mina ion o Wa e Abso p ioncoe icien by Capilla i y; AENOR:
Mad id, Spain, 2000.
37.
UNE-EN 1936, Na u al S one Tes Me hods. De e mina ion o Real Densi y and Appa en Densi y, and o To al and
Open Po osi y; AENOR: Mad id, Spain, 2007.
Applied Mine alogy in he S udy o His o ical Lime Mo a s
142
Ma e ials 2019,12, 584 17 o 17
38.
ASTM D 2845-05, S anda d Me hod o Labo a o y De e mina ion o Pulse Veloci ies and Ul asonic Elas ic Cons an s
o Rock; ASTM In e na ional S anda ds Wo ldwide: Wes Conshohocken, PA, USA, 2005.
39.
Guyade , J.; Denis, A. Wa e p opaga ion in aniso opic ocks unde s ess e alua ion o he quali y o sla es.
Bull. In . Assoc. Eng. Geol. 1986,33, 49–55. [C ossRe ]
40.
UNE-EN 15886, Conse a ion o Cul u al P ope y. Tes Me hods. Colou Measu emen o Su aces; AENOR:
Mad id, Spain, 2011.
41.
Valdeón, L.; Esbe , R.M.; G ossi, C.M. Hyd ic p ope ies o some Spanish building s ones: a pe ophysical
in e p e a ion. Ma e . Issues A A chaeol. 1993,3, 911–916. [C ossRe ]
42.
Alejand e Sánchez, F.J. His o ia, Ca ac e ización y Res au ación de Mo e os; Uni e sidad de Se illa: Se illa,
Spain, 2002.
43.
Bena en e, D. Why po e size is impo an in he de e io a ion o po ous s ones used in he buil he i age.
Macla 2011,15, 41–42.
44. Sche e , G.W. Theo y o D ying. J. Am. Ce am. Soc. 1990,73, 3–14. [C ossRe ]
45.
Rod iguez-Na a o, C. Técnicas de análisis del sis ema po oso de un ma e ial pé eo o namen al.
In Cuade nos Tecnicos "Tecnicas de Diagnos ico Aplicadas a la Conse acion de los Ma e iales de Cons uccion
en los Edi icios His o icos"; Ins i u o Andaluz del Pa imonio His ó ico: Se illa, Spain, 1996; Volume 2,
pp. 51–65.
46.
Cul one, G.; Madkou , F. E alua ion o he e ec i eness o ea men p oduc s in imp o ing he quali y o
ce amics used in new and his o ical buildings. J. Cul . He i . 2013,14, 304–310. [C ossRe ]
47. Ki k, R.E.; O hme , D.F. Encyclopedia o Chemical Technology; Wiley: New Yo k, NY, USA, 2004.
48.
Beck, K.; Al-Mukh a , M.; Rozenbaum, O.; Rau u eau, M. Cha ac e iza ion, wa e ans e p ope ies and
de e io a ion in u eau: building ma e ial in he Loi e alley-F ance. Build. En i on.
2003
,38, 1151–1162.
[C ossRe ]
49.
A izzi, A.; Ma ínez-Ma ínez, J.; Cul one, G. Ul asonic wa e p opaga ion h ough lime mo a s:
An al e na i e and non-des uc i e ool o ex u al cha ac e iza ion. Ma e . S uc .
2013
,46, 1321–1335.
[C ossRe ]
50.
Philippidis, T.P.; Aggelis, D.G. Expe imen al s udy o wa e dispe sion and a enua ion in conc e e. Ul asonics
2005,43, 584–595. [C ossRe ][PubMed]
51.
Schön, J.H. Physical P ope ies o Rocks: Fundamen als and P inciples o Pe ophysics; Pe gamon: Ox o d,
UK, 1996.
52.
Ca michael, R.S. P ac ical Handbook o Physical P ope ies o Rocks and Mine als; CRC p ess: Boca Ra on, FL,
USA, 1989.
53.
Molina, E.; Bena en e, D.; Sebas ian, E.; Cul one, G. The in luence o ock ab ic in he du abili y o wo
sands ones used in he Andalusian A chi ec u al He i age (Mon o o and Ronda, Spain). Eng. Geol.
2015
,197,
67–81. [C ossRe ]
54.
Beo egi GN. A ailable online: h p://me eo.na a a.es/clima ologia/sel ichaclima.c m?IDEs acion=12&
ipo=AUTO (accessed on 17 Janua y 2019).
©
2019 by he au ho s. Licensee MDPI, Basel, Swi ze land. This a icle is an open access
a icle dis ibu ed unde he e ms and condi ions o he C ea i e Commons A ibu ion
(CC BY) license (h p://c ea i ecommons.o g/licenses/by/4.0/).
8. Appendices: Published and Submi ed Wo ks
143

Applied Mine alogy in he S udy o His o ical Lime Mo a s
144
8. Appendices: Published and Submi ed Wo ks
145
APPENDIX II.2
Lime mo a s om Amaiu Cas le (Na a e, Spain): mine alogical and
physical cha ac e iza ion o assess hei du abili y
G aciela Ponce-An ón, Anna A izzi, Ma ia C uz Zuluaga, Giuseppe Cul one,
Luis Angel O ega, Juan xo Agi e Mauleon
Submi ed o Cons uc ion and Building Ma e ials
Applied Mine alogy in he S udy o His o ical Lime Mo a s
146
8. Appendices: Published and Submi ed Wo ks
147
Lime mo a s om Amaiu Cas le (Na a e, Spain):
mine alogical and physical cha ac e iza ion o assess hei
du abili y
Abs ac : Mine alogical, chemical and physical cha ac e iza ions we e pe o med on he
a chaeological lime mo a s om di e en s uc u es a Amaiu Cas le (Na a e, Spain) in
o de o de e mine hei du abili y. Samples om he sou h-eas o he illing mo a and 16 h
cen u y bas ion and he samples om he sou h-eas o he 17 h cen u y bas ion may decay
mo e easily. The high po osi y and wa e abso p ion capaci y, he poo in e connec ion o
po es and he di icul y o d ying a e he main ac o s in ol ed in hei de e io a ion. A
sou h-eas sample om he 16 h cen u y bas ion was also suscep ible o de e io a ion and
could be ela ed o he epai s pe o med du ing he 16 h cen u y as desc ibed in w i en
sou ces. Wa e abso p ion capaci y o mo a s om he cis e n could a ec he p ese a ion o
he emains o he cis e n aul . Mine alogical cha ac e iza ion allowed an app oach o he
echnological knowledge used in he mo a manu ac u ing p ocess a Amaiu Cas le.
Hyd o alci e and hyd omagnesi e iden i ied in he mo a binde suppo he use o he
adi ional ho -mixing me hod in he mo a manu ac u e. The ho -mixing me hod would be
ad an ageous in he damp and cold clima e condi ions p e ailing in he egion whe e Amaiu
Cas le is loca ed.
Keywo ds: lime mo a ; de e io a ion; hyd ic beha iou ; hyd omagnesi e; hyd o alci e; ho -
mixed mo a
1. In oduc ion
Knowledge o he composi ion and beha iou o his o ical mo a s has imp o ed since
he i s s udies a he end o he 19 h cen u y [1]. Chemical and mine alogical
cha ac e iza ions o hese ma e ials ha e been inc easing since he app o al o he Venice
Cha e in 1964 [2] and he ounda ion o he In e na ional Council on Monumen s and Si es
(ICOMOS) in 1975.
Mine alogical, chemical and physical cha ac e iza ion o his o ical mo a s is essen ial o
assess compa ibili y be ween he o iginal and epai mo a s in es o a ion p ojec s [3, 4] and
hus ensu e a chi ec u al he i age conse a ion [5].
Knowledge o he hyd ic beha iou o po ous ma e ials such as mo a s is essen ial o
assess hei du abili y o e ime. Wa e is one o he mos ha m ul agen s and i s low h ough
a po ous sys em plays an impo an ole in building ma e ial de e io a ion [6, 7]. Fu he mo e,
he clima e condi ions no only in luence he mo a ha dening p ocess bu also condi ioned
he wa e p esence in he mo a a ec ing he mo a du abili y [8, 9].
Mine alogical, chemical and physical cha ac e iza ion and hyd ic beha iou s udies ha e
been pe o med o e alua e he du abili y o his o ical mo a s and/o o ensu e he quali y o
epai mo a s used in he his o ical buildings [10-14].
P e ious s udies poin o he use o he adi ional ho -mixing me hod in he mo a
manu ac u e a Amaiu Cas le (Na a e Spain) [15]. The combina ion o chemical-
mine alogical analyses and physical p ope ies in he s udy o his o ical mo a s a e use ul o
in es iga e he adi ional ho -mixing me hod and he di e en building phases o di e en
pe iods a he cas le.
The p esen s udy aims o cha ac e ize mine alogical, chemical and physical ea u es o
his o ical lime mo a s om Amaiu Cas le o assess hei du abili y. The s udy o he po e
Applied Mine alogy in he S udy o His o ical Lime Mo a s
154
Fig. 4. Pho omic og aphs o he mos ep esen a i e mic o ex u al ea u es o he lime mo a s om
Amaiu Cas le. (a) He e ogeneous binde ma ix-suppo ed ex u e wi h angula o subangula dolos one
agmen s embedded in a mic i ic calci e ma ix. (b) Mo a wi h a sub ounded ce amic agmen .
(c) Sands one agg ega e in a mo a wi h high po osi y. (d) La ge dolos one agg ega e in a mo a wi h low
po osi y. (e) Mo a wi h a lime lump. ( ) Mo a wi h Mg- ich spo s and hyd omagnesi e c ys als.
(g) Hyd omagnesi e c ys als illing he binde po es and dolos one uggy po es. (h) Mic oc acks wi h
seconda y calci e inside. Reac ion zone in he dolomi ic agg ega es is shown in all pho omic og aphs.
B: binde . C: ce amic agmen . SCal: seconda y calci e. Ck: mic oc ack. DRx: dolos one.
HMgs: hyd omagnesi e. L: lime lump. Mg-SP: Mg- ich spo . P: po e. Qz: qua z. R: eac ion zone.
SRx: sands one. VP: uggy po osi y.

8. Appendices: Published and Submi ed Wo ks
155
4.4. Cha ac e iza ion o Po e Sys em and Hyd ic Beha iou
Mo a s show a complex po e sys em since hey a e composed o bo h po ous binde and
di e en po ous agg ega es [45]. Wa e cons i u es an impo an deg ada ion agen o
building ma e ials since i s ci cula ion and e en ion wi hin he po ous ma e ials causes hei
de e io a ion and in some cases i e e sible damage. The e o e, mo a cha ac e iza ion
h ough he po ous sys em is essen ial since he po osi y and po e size dis ibu ion a ec he
wa e ci cula ion wi hin he ma e ial [46, 47].
Me cu y in usion po osime y (MIP) was used o e alua e he po e size dis ibu ion o
he mo a s. Table 4 summa ises he ob ained MIP alues. The highes po osi y alues
(PMIP) we e measu ed in Samples CA-B1-4 and CA-B2-3 (45% and 37.8%, espec i ely),
whe eas he lowes alue we e measu ed in Sample CA-R-8 and Sample CA-B1-13 (26.3%
and 27.7%, espec i ely).
Table 4. Hyd ic pa ame e s and po osi y alues o he lime mo a s om Amaiu Cas le. Ab: F ee
wa e abso p ion (%). A : o ced wa e abso p ion (%). Ax: deg ee o po e in e connec ion (%).
S: Sa u a ion coe icien (%). Ca: abso p ion coe icien (g/min0.5). Di: d ying index. ρHb: bulk densi y
(g/cm3). ρHsk: skele al densi y (g/cm3). Cc: capilla i y coe icien (g/cm2 min0.5). Hc: Heigh o he wa e
le el du ing capilla y up ake (mm s−0.5). PHT and PMIP: open po osi y (%) de e mined by hyd ic es s
(HT) and me cu y in usion po osime y (MIP), espec i ely.
Rega ding he po e size dis ibu ion (Fig.5), all samples show a amily o small po es o
0.01 < < 1 µm connec ed o a amily o la ge po es o 1 < < 10 µm, showing a g ea e
olume o po es o 0.1 < < 1 µm cha ac e is ic o he ma ix o lime mo a s [48, 49].
Samples CA-B1-2 and CA-B2-1 a e also cha ac e ized by a amily o la ge po es o
10 < < 100 µm. The bimodal po e size dis ibu ion wi h wo main peaks si ua ed a a ound
0.1 µm and a a ound 1 µm is cha ac e is ic in mos o samples, excep o Samples CA-M2-1
and CA-B2-3 ha show a nea ly unimodal po e size dis ibu ion wi h a main peak a a ound 1
µm. The Samples CA-B1-4 and CA-B2-3 no only s and ou o he highes PMIP alues bu
also o , espec i ely, a ma ked bimodal and unimodal po e size dis ibu ion (Fig. 5).
The amily o smalle po es is ela ed o he agg ega es po osi y, al hough some
dolos one agmen s show sca ce la ge po es, whe eas he la ge po e amily is ela ed o he
binde po osi y (Fig. 4). Fu he mo e, he po osi y and he po e dis ibu ion could ha e been
modi ied due o de e io a ion, which would explain he highe po osi y alues and a la ge
po e size.
The s udy o he hyd ic p ope ies is also o g ea impo ance o e alua e he po e sys em
and o assess he suscep ibili y o mo a s o de e io a ion. Hyd ic es s (HT) we e pe o med
o a be e s udy o he po e sys em and o e alua e he hyd ic beha iou o samples (Fig. 6
and Table 4).
CA-M2-1
CA-M2-3
CA-AL-2
CA-AL-6
CA-R-1
CA-R-7
CA-R-8
CA-R-9
CA-B1-2
CA-B1-4
CA-B1-11
CA-B1-13
CA-B2-1
CA-B2-3
Ab
24.10
19.38
20.40
18.90
15.80
29.58
22.63
15.18
18.61
31.59
16.49
16.34
17.99
17.58
A
25.05
20.04
20.96
19.24
16.30
31.54
25.22
16.28
19.27
33.13
19.59
17.98
22.60
17.75
Ax
3.81
3.30
2.67
1.76
3.06
6.22
10.28
6.75
3.40
4.65
15.85
9.11
20.41
1.00
S
91.95
93.40
94.46
96.92
96.37
90.25
87.76
92.16
91.84
91.16
72.91
90.65
78.78
96.00
Ca
12.05
9.69
10.20
9.45
7.90
14.79
11.32
7.59
9.31
15.79
8.24
8.17
8.99
8.79
Di
0.246
0.249
0.248
0.249
0.251
0.244
0.247
0.251
0.249
0.240
0.248
0.249
0.247
0.249
Hb
1.57
1.68
1.68
1.73
1.79
1.34
1.52
1.79
1.72
1.34
1.63
1.64
1.49
1.72
Hsk
2.59
2.54
2.59
2.59
2.53
2.31
2.47
2.52
2.58
2.40
2.39
2.33
2.26
2.48
Cc
0.040
0.024
0.022
0.030
0.010
0.023
0.021
0.014
0.028
0.028
0.022
0.020
0.017
0.029
Hc
0.81
0.65
0.65
0.65
0.58
0.65
0.97
0.65
0.78
0.97
1.16
0.97
1.03
1.18
PTH
39.3
33.8
35.1
33.3
29.2
42.2
38.4
29.1
33.2
44.3
31.9
29.6
33.8
30.5
PMIP
34.1
31.4
31.6
-
31
-
26.3
-
31
45
-
27.7
29.2
37.8
Applied Mine alogy in he S udy o His o ical Lime Mo a s
156
The deg ee o po e in e connec ion alues (Ax) was lowes in Samples CA-AL-2,
CA-AL-6 and CA-B2-3 (< 3%), indica ing a be e po e in e connec ion ha a ou s wa e
low hough he mo a . In con as , Samples CA-R-8, CA-B1-11, CA-B1-13 and CA-B2-1
show he highes Ax alues (> 9%), which indica es g ea e di icul y o wa e o low due o
wo se po e in e connec ion. Conside ing he lowes Ax alues o he samples om each
s uc u e (Table 4), Sample CA-AL-6, Sample CA-M2-3 ( om he sou h-wes ) and Samples
CA-R-1, CA-B1-2, CA-B1-4 and CA-B2-3 ( om he sou h-eas ) show he lowe Ax alues.
Samples wi h be e po e in e connec ion a e hose ha display a highe sa u a ion coe icien
(S), since S alues a e ela ed o he Ax pa ame e .
Rega ding he d ying cu e, a he beginning o he es he d ying a e is cons an .
Cu es close o he e ical co espond o he samples ha d y as e (Fig. 6a). Once he
c i ical mois u e con en is eached he d ying a e dec eases and po e size and po e
in e connec ion a e he ac o s con olling he d ying eloci y [50]. Samples wi h highes
d ying index alues (Di > 0.248) d y mo e slowly and he po ous sys em emains ull o wa e
o longe . Samples CA-R-1 and CA-R-9 s and ou o aking he longes o d y (Di = 0.251)
while Sample CA-B1-4 o d ying as e (Di = 0.240).
Fig. 5. Po e size dis ibu ion cu es o lime mo a s om Amaiu Cas le ob ained by me cu y
in usion po osime y. (a) CA-M2-1, (b) CA-M2-3, (c) CA-AL-2, (d) CA-R-1, (e) CA-R-8,
( ) CA-B1-2, (g) CA-B1-4, (h) CA-B1-13, (i) CA-B2-1, (j) CA-B2-3. Accessible po e adius (in µm)
s. inc emen al po e olume (in cm3/g) is ep esen ed.
8. Appendices: Published and Submi ed Wo ks
157
Fig. 6. Hyd ic beha iou o he lime mo a s om Amaiu Cas le. (a) F ee wa e abso p ion, o ced
wa e abso p ion and d ying cu es. Weigh a ia ion (ΔM/M) e sus ime (in hou s). (b) Capilla i y
cu es. Weigh a ia ion (ΔM/S) e sus ime (in hou s) and (c) capilla i y on cu es. Heigh (in
mm) e sus ime (in hou s).
Applied Mine alogy in he S udy o His o ical Lime Mo a s
158
Capilla y up ake cu es (Fig. 6b) show he ypical capilla y ise end o lime mo a s
cha ac e ized by wo di e en slopes [51, 52]. The i s sha p slope is ela ed o apid wa e
abso p ion a he beginning o he es . F om 24 h o he es , he abso p ion eloci y
dec eased and he wa e up ake became slow and con inuous leading o a mo e linea slope
un il sa u a ion a 250 h. Capilla y on o all samples also eached he op a e 24 h
(Fig. 6c). The wo slopes in he capilla y up ake cu e and he ime-lag be ween isual and
eal sa u a ion con i ms he wo main po e amilies (0.01 < < 1 µm and 1 < < 10 µm)
de ec ed by MIP analysis in which he amily o smalle po es sa u a es be o e he amily o
la ge po es [51]. The wa e amoun abso bed by capilla i y was highe in Samples CA-Al-6
and CA-R-7 while Samples CA-R-1 and CA-B1-2 abso bed he leas amoun o wa e .
Capilla i y wa e up ake was as e in Samples CA-M2-1, CA-B1-2, CA-B1-4, CA-B2-3 and
CA-AL-6, which showed a highe capilla i y coe icien (CC) (> 0.025 g/cm2 min0.5) while
Samples CA-R-1 and CA-R-9 displayed he slowes alues (< 0.015 g/cm2 min0.5) (Table 4).
Mic oc acks in Samples CA-M2-1 CA-AL-6 and CA-B2-3 (Fig. 3h) could ha e a ou ed he
capilla i y wa e up ake.
Open po osi y alues om he hyd ic es s (PH) we e highes in Samples CA-B1-4 and
CA-R-7 (44.33% and 42.17%, espec i ely) and lowes in sou h-wes illing mo a s (Sample
CA-R-1 wi h 29.17% and Sample CA-R-9 wi h 29.11%). Conside ing he highe PH alues o
he samples om each s uc u e (Table 4), he highes PH alues we e ob ained o mo a s
om he sou h-eas medie al wall and bas ions (Samples CA-M2-1, CA-B1-2, CA-B1-4 and
CA-B2-1), sou h-wes illing mo a s (Samples CA-R-7 and CA-R-8) and mo a om he
lune e aul (Sample CA-AL-2).
The g ea es amoun o wa e was abso bed by he samples wi h he highes PH alues
(Table 4 and Fig. 6a). Samples CA-M2-1, CA-B1-4, CA-R-7, CA-R-8 and CA-Al-2 showed
he highes alues (> 20%) o ee wa e abso p ion (Ab) and o ced wa e abso p ion (A ) and
we e he as es abso bing he wa e (high Ca alues in Table 4). Sample CA-B2-1 also
abso bed a la ge amoun o wa e by o ced abso p ion.
The PH alues we e simila o he alues ob ained by me cu y in usion po osime y
(PMIP). Ne e heless, he sligh di e ences be ween bo h po osi ies a e caused by he wo
di e en luids used and he di e en exe ed p essu es (wa e a a mosphe ic p essu e in he
HT and me cu y a 414 MPa in MIP analysis). Samples wi h he highes open po osi y alues
show he g ea es di e ence be ween skele al and bulk densi ies (ρHsk and ρHb, espec i ely)
(Table 4).
4.5. Ul asonic Pulse Veloci y Tes
Ul asonic pulse eloci y es is a non-des uc i e es ha allows o e alua e ea u es
conce ning he po osi y and aniso opies in he mo a [53]. Table 5 summa izes alues o he
p opaga ion eloci y o ul asonic p ima y wa es (Vp) and s uc u al aniso opy (ΔM).
Table 5. Resul s o he ul asonic pulse eloci y es in he lime mo a s om Amaiu Cas le. VP1, VP2
and VP3: P-wa e eloci y in he h ee o hogonal di ec ions (in m/s). ΔVp: A e age alue o he
P-wa e eloci ies. σVp: s anda d de ia ion. ΔM: s uc u al aniso opy (%).
CA-M2-1
CA-M2-3
CA-AL-2
CA-AL-6
CA-R-1
CA-R-7
CA-R-8
CA-R-9
CA-B1-2
CA-B1-4
CA-B1-11
CA-B1-13
CA-B2-1
CA-B2-3
V
P1
157.61
237.70
188.17
190.22
279.28
225.16
257.58
271.60
244.27
213.06
233.90
239.13
223.77
210.42
V
P2
160.40
244.09
204.82
211.18
295.77
253.73
277.31
285.09
248.06
224.49
250.03
253.77
229.39
216.81
V
P3
170.27
250
193.18
193.71
290.18
230.26
272.73
277.31
264.46
215,95
235.49
239.90
244.19
219.03
ΔV
p
162.76
243.93
195.39
198.37
288.41
236.38
269.21
278
252.26
217.83
239.81
244.27
232.45
215.42
σVp
6.65
6.15
8.54
11.23
8.39
15.24
10.33
6.77
10.73
5.94
8.87
8.24
10.54
4.47
ΔM
4.67
3.78
5.44
6.04
4.67
6.95
6.34
3.42
4.68
3.25
3.64
3.12
5.49
3.44
8. Appendices: Published and Submi ed Wo ks
159
P-wa e eloci y could a y acco ding o he mine alogy, ex u e and po osi y o he
ma e ial [47, 54]. All s udied samples show he same mine alogy wi h sligh a ia ions, hus
he ex u e and po osi y will be he main ac o s ha a ec he Vp alues. While he a ia ion
in he eloci y o he P-wa es is no ela ed o he size o agg ega es, he high calca eous
agg ega e con en a ou s he inc ease in eloci y [55-57]. The highe Vp alues we e
measu ed in samples wi h a la ge amoun o agg ega es (Samples CA-R-1 and CA-R-9,
co esponding o illing mo a s om he SE a ea), whe eas he lowe alues we e ob ained in
he mo a s wi h he lowes agg ega es con en (Samples CA-AL-2 and CA-AL-6 om he
cis e n) (Figs. 2 g-h and i, espec i ely). P opaga ion eloci y o ul asonic pulses is also
a ec ed by he po osi y, wi h he Vp alue dec easing wi h highe po osi y [9, 57].
Acco dingly, he lowes Vp alues we e de ec ed in he samples wi h he highes po osi y
alues as measu ed in MIP analysis and hyd ic es s (Table 4), and obse ed in he
pe og aphic s udy (Figs. 4c and d). Besides, he small-scale aniso opies wi hin he ma e ial
such as mic oc acks no only a ec he wa e ci cula ion bu also dec ease he Vp alues [58,
59]. Thus, he high equency o mic oc acks in Sample CA-M2-1 (Fig. 4h) could explain he
lowes Vp alue measu ed in his sample (Table 5). S uc u al aniso opy (ΔM) con i ms he
he e ogeneous mo a ex u e o all mo a s. The la ge size o agg ega es om he sou h-wes
illing mo a samples (Samples CA-R-7 and CA-R-8) explains he high ΔM alues.
4.5. Colo ime y
Compa ibili y be ween he epai mo a and he o iginal mo a in e ms o isual
appea ance is also an impo an equi emen o conside in es o a ion wo k [4, 60]. The
colou o mo a s was e alua ed by non-des uc i e colo ime ic analyses using he CIELAB
(CIE 1976 L*a*b*) colou space sys em p oposed by he In e na ional Commission on
Illumina ion (CIE). Ch oma ic pa ame e s o each mo a sample a e summa ised in Table 6.
The ligh ness (L*) alues a ound 80 and he alues measu ed o he ch oma ic axes (a* and
b*) indica ed samples wi h a endency owa d o he ligh g ey ield. The lowe L* alues
we e measu ed in Samples CA-AL-6, CA-R-8, CA-B1-4, CA-B2-1 and CA-B2-3. The a* and
b* alues a e simila in all samples, al hough Samples CA-M2-1 and samples om he cis e n
(CA-AL-2, CA-AL-6) and om he 17 h cen u y bas ion (CA-B2-1 and CA-B2-3) show
highe alues. The high ch oma ic axes alues and he low L* alues o samples om he
17 h cen u y bas ion a e explained by he p esence o ce amic agmen s in he mo a .
Table 6. Ch oma ic pa ame e s o his o ic lime mo a samples om Amaiu Cas le. L*: Ligh ness, a*
and b*: ch oma ic coo dina es, C*: ch oma, H: hue angle.
The wo ks and epai s ca ied ou in he cas le o e ime as a esul o he con lic s in he
egion ep esen an addi ional complexi y in he s udy o mo a s. In he Gene al A chi es o
Simancas, di e en epai s a e documen ed, including a epai in he sou h-eas s uc u e o
he 16 h cen u y bas ion [17, 61, 62], he a ea whe e Sample CA-B1-4 was loca ed. I could
explain he clea ly di e en hyd ic pa ame e s and po osi y alues o his sample om he es
(Table 4).
CA-M2-1
CA-M2-3
CA-AL-2
CA-AL-6
CA-R-1
CA-R-7
CA-R-8
CA-R-9
CA-B1-2
CA-B1-4
CA-B1-11
CA-B1-13
CA-B2-1
CA-B2-3
L*
80.70
83.60
82.05
77.41
80.10
85.19
77.92
80.83
81.02
84.37
83.14
79.24
79.42
73.70
a*
2.75
1.70
1.806
2.00
1.46
2.05
1.81
1.32
2.00
1.47
2.18
2.52
2.49
3.89
b*
12.06
8.76
10.76
10.94
7.87
9.02
8.37
8.76
9.99
7.76
9.77
9.56
10.44
13.99
C*
12.37
8.93
10.91
11.13
8.00
9.26
8.56
8.86
10.19
7.90
10.02
9.89
10.73
14.52
H
77.25
79.10
80.48
79.63
79.63
77.04
77.83
81.49
78.62
79.20
77.45
75.22
76.59
74.46

Applied Mine alogy in he S udy o His o ical Lime Mo a s
160
4.6. En i onmen al conside a ions
En i onmen al ac o s such as ela i e humidi y, ain all and empe a u e also a ec
mo a du abili y. Geog aphically, Amaiu Cas le is loca ed in he Oceanic ma i ime wes
coas clima e zone (C b in he Köppen-Geige clima e classi ica ion) [63, 64].
Annual a e age ela i e humidi y in he a ea o he cas le is 83.4%, eaching alues
abo e 86% in some mon hs. The a e age annual p ecipi a ion is a ound 2040 mm, wi h
ain all abo e 90 mm h oughou all mon hs o he yea and eaching abo e 200 mm in he
we es mon hs [65, 66]. A ela i e humidi y alues be ween 65% and 95%, he wa e apou
and wa e liquid coexis leading o he con inuous p esence o wa e wi hin he po e sys em
[45]. Howe e , besides mois ening he mo a , he me eo ic wa e could also inco po a e
soluble CO2 and sal s inside he po es. While dissol ed CO2 a ou s he pa ial dissolu ion o
ca bona es, he olume inc ease due o he c ys alliza ion o seconda y ca bona es and/o
soluble sal s wi hin he po es esul s in mechanical s ess con ibu ing o he mo a
de e io a ion [67-69].
Fu he mo e, mo a s a Amaiu Cas le a e exposed o con inuous empe a u e a ia ions
since, e en i he annual a e age empe a u e is 12.9 ºC, he annual absolu e a e age
minimum empe a u e eaches -19 ºC and he annual absolu e a e age maximum empe a u e
41 ºC [65]. Con inued empe a u e a ia ions o e ime may lead o he c acking o mo a
since he he mal expansion p oduced by he c ys allisa ion o wa e in o ice in colde pe iods
also esul s in a mechanical s ess [70].
E en i he cold and we local en i onmen al condi ions a Amaiu Cas le could ha e
been ad an ageous o he ho -mixing me hod, since i was commonly used in cold-wea he
wo k [40], he high humidi y, he con inuous ain all and he empe a u e a ia ion o e a
b oad ange o he a ea con ibu e o he cu en wea he ing o Amaiu Cas le lime mo a s.
Conside ing he samples om each di e en s uc u e, he high po osi y, high wa e
abso p ion capaci y and poo po e in e connec ion (high Ax) o Samples CA-M2-1, CA-AL-2,
CA-R-7, CA-R-8 and CA-B2-1 a ou mo a decay since hei o uous po e sys em hinde s
he wa e low ou wa d. Al hough Samples CA-B1-4 d ies he as es (low Di), i s high
po osi y and wa e abso p ion capaci y could also a ec he du abili y. Sample CA-AL-6 is
mo e suscep ible o de e io a ion by capilla i y since i no only abso bs a g ea e amoun o
wa e by capilla i y bu also up akes he wa e as e . Fu he mo e, Samples CA-B1-11 and
CA-B1-13 ook longe o d y (high Di) and show poo po e in e connec ion (high Ax), which
leads o wa e e en ion inside o longe , a ou ing mo a decay.
5. Conclusions
Mine alogical, chemical and physical cha ac e iza ion pe o med in he p esen s udy has
con ibu ed o a be e unde s anding o he his o ic lime mo a s om Amaiu Cas le and he
esul s achie ed ha e been able o add ess speci ic goals:
Suscep ibili y o mo a de e io a ion
Samples om he 14 h-15 h cen u y wall show e y simila mine alogical, chemical and
ex u al cha ac e is ics, bu he high p esence o mic oc acks in he sou h-eas sample poin o
i s wo s conse a ion.
The poo po e in e connec ion o samples om he SW s uc u e o he 16 h cen u y
bas ion and he SE samples o he 17 h cen u y diamond-shaped s uc u e makes hem mo e
suscep ible o decay since wa e is e ained longe .
The sou h-eas sample om he 16 h cen u y bas ion could be ela ed o he epai s
pe o med du ing he 16 h cen u y as he hyd ic pa ame e s and po osi y alues a e clea ly
di e en ia ed in compa ison wi h he es o he samples.
8. Appendices: Published and Submi ed Wo ks
161
The wa e abso p ion capaci y o samples om he lune e and ba el aul base could
a ec he p ese a ion o he only cis e n aul emains cu en ly p ese ed.
Filling mo a shows a di e en hyd ic beha iou and po e sys em be ween he sou h-eas
and sou h-wes a ea. Filling mo a s om he sou h-wes a ea a e mo e suscep ible o
de e io a ion no only because hey show a highe po osi y and wa e abso p ion capaci y bu
also due o he poo in e connec ion o po es and he di icul y in d ying.
En i onmen al condi ions a Amaiu Cas le (high humidi y, con inuous ain all and he
empe a u e a ia ion o e a b oad ange) also a ou he wea he ing o mo a s. On he o he
hand, he high humidi y condi ions could ha e a o ed he hyd omagnesi e c ys alliza ion in
he binde .
App oach o echnological knowledge
Mine alogical and ex u al cha ac e iza ion has also allowed an explo a ion o he
echnological knowledge used in he mo a manu ac u ing p ocess.
Filling mo a shows la ge agg ega es, p obably used o s abilize he mo a olume and
o imp o e he long- e m s eng h. Di e ences in agg ega e size and in he physical ea u es
be ween he illing mo a om he sou h-wes a ea and he sou h-eas sugges a leas wo
di e en illing pe iods.
Selec ion o angula ca bona ed agg ega es would ha e imp o ed he mechanical s eng h
o he mo a .
P esence o hyd o alci e and hyd omagnesi e in he mo a binde would also ha e
a ou ed he mo a s eng h.
Iden i ica ion o hyd omagnesi e in he p esen s udy suppo he use o he adi ional
ho -mixing me hod in he mo a manu ac u e a Amaiu Cas le, a me hod ha migh ha e
been app op ia e o he damp and cold a ea in which he cas le is loca ed.
Con ibu ion o he i age conse a ion and u u e pe spec i es
The p esen s udy ep esen s a aluable e e ence o he sui able o mula ion o a
compa ible epai mo a ha ensu es he a chi ec u al he i age conse a ion in u u e
es o a ion wo ks a Amaiu Cas le.
Ha sh en i onmen al ac o s in he s udied a ea make i necessa y o pe o m u u e decay
es s o a be e assessmen o his o ic lime mo a de e io a ion.
The di e en s uc u es om di e en pe iods a Amaiu Cas le, due o changes in he
de ences o he building, esul ed in mo a s wi h di e en ex u al cha ac e is ics.
E olu ion in he Amaiu Cas le de ences led o he cons uc ion o di e en s uc u es in
di e en pe iods esul ing in mo a s wi h di e en ex u al cha ac e is ics. Fu u e s udies on
he mechanical p ope ies will be able o ob ain a be e unde s anding o changes in mo a
manu ac u e acco ding o he e olu ion o he de ensi e s uc u es.
Acknowledgmen s
This s udy was suppo ed by he GIC18/133 Resea ch G oup o he Uni e si y o he
Basque Coun y (UPV/EHU) and o Jun a de Andalucía Resea ch G oup RNM179 and
Resea ch P ojec MAT2016-75889-R. G.P.-A. acknowledges he PhD esea ch g an o he
Basque Go e nmen [2015-1-02-35]. The au ho s also would like o hank Pe e Smi h o
e iewing he use o English in he manusc ip .
Applied Mine alogy in he S udy o His o ical Lime Mo a s
162
Re e ences
[1] W. Wallace, On ancien mo a s, Chemical News 11 (1865) 185-186.
[2] Venice, Cha e , In e na ional Cha e o he Conse a ion and Res o a ion o Monumen s and
Si es. A ailable online: h p://icomos.o g/cha e s/ enice_e.pd (accessed on 27 Ma ch 2020).
(1964).
[3] C. G oo , G.J. Ashall, J.J. Hughes, P.J. Ba os, Cha ac e isa ion o old mo a s wi h espec o hei
epai : A s a e o he a , RILEM REPORT 28 (2007) 1.
[4] L. Schue emans, Ö. Cize , E. Janssens, G. Se é, K.V. Balen, Cha ac e iza ion o epai mo a s o
he assessmen o hei compa ibili y in es o a ion p ojec s: Resea ch and p ac ice, Cons uc ion
and Building Ma e ials 25(12) (2011) 4338-4350.
[5] ICOMOS, Decla a ion o Ams e dam. A ailable online: h ps://www.icomos.o g/en/and/169-
hedecla a ion-o -ams e dam (accessed on 10 Janua y 2020). (1975).
[6] N.S. Ma ys, C.F. Fe a is, Capilla y anspo in mo a s and conc e e Cemen and Conc e e
Resea ch 27(5) (1997) 747-760.
[7] R.P.J. Van Hees, L. Binda, I. Papayianni, E. Toumbaka i, Cha ac e isa ion and damage analysis o
old mo a s, Ma e ials and s uc u es 37 (2004) 644-648.
[8] C. Bo ges, A. San os Sil a, R. Veiga, Du abili y o ancien lime mo a s in humid en i onmen ,
Cons uc ion and Building Ma e ials 66 (2014) 606-620.
[9] A. A izzi, G.M. Hue ga, E. Sebas ián, G. Cul one, Mine alogical, ex u al and physical-
mechanical s udy o hyd aulic lime mo a s cu ed unde di e en mois u e condi ions, Ma e iales
de cons ucción 65(318) (2015).
[10] J.J. Hughes, S.J. Cu hbe , The pe og aphy and mic os uc u e o medie al lime mo a s om he
wes o Sco land: Implica ions o he o mula ion o epai and eplacemen mo a s, Ma e ials
and S uc u es 33(9) (2000) 594-600.
[11] I. Papayianni, V. Pach a, M. S e anidou, Analysis o ancien mo a s and design o compa ible
epai mo a s: The case s udy o Odeion o he a chaeological si e o Dion. , Cons uc ion and
Building Ma e ials 40 (2013) 84-92.
[12] H. Mo illas, P. Vazquez, M. Magu egui, I. Ma caida, L.F.O. Sil a, Composi ion and po osi y
s udy o o iginal and es o a ion ma e ials included in a coas al his o ical cons uc ion,
Cons uc ion and Building Ma e ials 178 (2018) 384-392.
[13] G. Bo soi, A.S. Sil a, P. Menezes, A. Candeias, J. Mi ão, Analy ical cha ac e iza ion o ancien
mo a s om he a chaeological oman si e o Pisões (Beja, Po ugal), Cons uc ion and Building
Ma e ials 204 (2019) 597-608.
[14] G. Ponce-An ón, A. A izzi, M.C. Zuluaga, G. Cul one, L.A. O ega, J. Agi e Mauleon,
Mine alogical, Tex u al and Physical Cha ac e isa ion o De e mine De e io a ion Suscep ibili y
o I ulegi Cas le Lime Mo a s (Na a e, Spain), Ma e ials 12(4) (2019) 584.
[15] G. Ponce-An ón, M.C. Zuluaga, L.A. O ega, J.A. Mauleon, Mul i-analy ical app oach o
chemical-mine alogical cha ac e iza ion o eac ion ims in he lime mo a s om Amaiu Cas le
(Na a e, Spain), Mic ochemical Jou nal 152 (2020) 104303.
[16] I. Sag edo, Na a a. Cas illos que de endie on el eino (Tomo I) de Lagua dia a Foix, y del
Moncayo al Goie i, Pamiela Ed., Pamplona, 2006.
[17] I. Sag edo, El cas illo de Amaiu a a és de la his o ia de Na a a, Pamiela Ed., Pamplona, 2009.
[18] R.L. Folk, A compa ison cha o isual pe cen age es ima ion, Jou nal o Sedimen a y Resea ch
21(1) (1951) 32-33.
[19] UNE-EN 13755 Na u al s one es me hods de e mina ion o wa e abso p ion a a mosphe ic
p essu e, 2008., AENOR, Mad id.
[20] G. Cul one, M.J. De La To e, E. Sebas ián, O. Cazalla, E alua ion o b icks du abili y using
des uc i e and nondes uc i e me hods (DT and NDT), Ma e iales de Cons uccion 53(269)
(2003) 41-59.
[21] RILEM, Recommended es o measu e he de e io a ion o s one and o assess he di e ences o
ea men me hods., Ma e ials and S uc u es 13 (1980) 175-253.
[22] UNE-EN 1936, Na u al s one es me hods. De e mina ion o eal densi y and appa en densi y,
and o o al and open po osi y, 2007., AENOR, Mad id.
[23] NORMAL 29/88, Misu a dell'indice di asciugamen o (d ying index), 1988., CNR-ICR, Rome.
8. Appendices: Published and Submi ed Wo ks
163
[24] UNE-EN 1925, Na u al s one es me hods. De e mina ion o wa e abso p ioncoe icien by
capilla i y, 2000., AENOR, Mad id.
[25] ASTM D 2845-05, S anda d me hod o labo a o y de e mina ion o pulse eloci ies and
ul asonic elas ic cons an s o ock, 2005., ASTM In e na ional S anda ds Wo ldwide,
Pennsyl ania.
[26] J. Guyade , A. Denis, Wa e p opaga ion in aniso opic ocks unde s ess e alua ion o he
quali y o sla es, Bulle in o he In e na ional Associa ion o Enginee ing Geology - Bulle in de
l'Associa ion In e na ionale de Géologie de l'Ingénieu 33(1) (1986) 49-55.
[27] UNE-EN 15886, Conse a ion o cul u al p ope y. Tes me hods. Colou measu emen o
su aces, 2011., AENOR, Mad id
[28] G. Ponce-An ón, L.A. O ega, M.C. Zuluaga, A. Alonso-Olazabal, J.L. Solaun, Hyd o alci e and
Hyd ocalumi e in Mo a Binde s om he Medie al Cas le o Po illa (Ála a, No h Spain):
Accu a e Mine alogical Con ol o Achie e Mo e Reliable Ch onological Ages, Mine als 8(8)
(2018) 326.
[29] A. A izzi, G. Cul one, The di e ence in beha iou be ween calci ic and dolomi ic lime mo a s
se unde d y condi ions: The ela ionship be ween ex u al and physical–mechanical p ope ies,
Cemen and Conc e e Resea ch 42(6) (2012) 818-826.
[30] A. Diekamp, J. Konze , P.W. Mi wald, Magnesian lime mo a s–Iden i ica ion o magnesium
phases in medie al mo a s and plas e s wi h imaging echniques, 12 h Eu osemina on
Mic oscopy Applied o Building Ma e ials, Do mund, Ge many, 2009, pp. 15-19.
[31] A.R. San os, M. do Rosa io Veiga, A.S. Sil a, J. de B i o, J.I. Ál a ez, E olu ion o he
mic os uc u e o lime based mo a s and in luence on he mechanical beha iou : he ole o he
agg ega es, Cons uc ion and Building Ma e ials 187 (2018) 907-922.
[32] J. Lanas, J.I. Al a ez-Galindo, Mason y epai lime-based mo a s: ac o s a ec ing he
mechanical beha io , Cemen and Conc e e Resea ch 33(11) (2003) 1867-1876.
[33] G. Cul one, E. Sebas ian, M.O. Hue as, Du abili y o mason y sys ems: A labo a o y s udy,
Cons uc ion and Building Ma e ials 21(1) (2007) 40-51.
[34] A. A izzi, J. Ma ínez Ma ínez, G. Cul one, D. Bena en e, Mechanical e olu ion o lime
mo a s du ing he ca bona ion p ocess, Key Enginee ing Ma e ials, T ans Tech
Publica ions2011, pp. 483-486.
[35] A. A izzi, G. Cul one, The in luence o agg ega e ex u e, mo phology and g ading on he
ca bona ion o non-hyd aulic (ae ial) lime-based mo a s, Qua e ly Jou nal o Enginee ing
Geology and Hyd ogeology 46(4) (2013) 507-520.
[36] M. S e anidou, I. Papayianni, The ole o agg ega es on he s uc u e and p ope ies o lime
mo a s, Cemen and Conc e e Composi es 27(9-10) (2005) 914-919.
[37] M. Back, M. Baue , H. S anjek, S. Pei e , Seques a ion o CO2 a e eac ion wi h alkaline ea h
me al oxides CaO and MgO, Applied Geochemis y 26(7) (2011 ) 1097-1107.
[38] R.M. Dheilly, A. Bougue a, B. Beaudoin, J. Tudo, M. Queneudec, Hyd omagnesi e de elopmen
in magnesian lime mo a s, Ma e ials Science and Enginee ing A268 (1999) 127–131.
[39] A. Fo s e , Ho -lime mo a s: a cu en pe spec i e, Jou nal o A chi ec u al Conse a ion 10(3)
(2004) 7-27.
[40] A. Hen y, J. S ewa , P ac ical building conse a ion: Mo a s, ende s & plas e s, P ac ical
Building Conse a ion. English He i age, Su ey 2011.
[41] N. Copsey, Ho mixed lime and adi ional mo a s : a p ac ical guide o hei use in conse a ion
and epai , The C owood P ess, Ramsbu y, Ma lbo ough, 2019.
[42] M. Zajac, S.K. B emse h, M. Whi ehead, M. Ben Haha, E ec o CaMg(CO3)2 on hyd a e
assemblages and mechanical p ope ies o hyd a ed cemen pas es a 40°C and 60°C, Cemen and
Conc e e Resea ch 65 (2014) 21-29.
[43] A. Machne , M. Zajac, M. Ben Haha, K.O. Kjellsen, M.R. Geike , K. De Wee d , Limi a ions o
he hyd o alci e o ma ion in Po land composi e cemen pas es con aining dolomi e and
me akaolin, Cemen and Conc e e Resea ch 105 (2018) 1-17.
[44] J. Lanas, J.I. Al a ez, Dolomi ic limes: e olu ion o he slaking p ocess unde di e en
condi ions, The mochimica Ac a 423(1-2) (2004) 1-12.
[45] M. Thomson, J.E. Lindq is , J. Elsen, C.J.W.P. G oo , 2.5. Po osi y o mo a s, in: C. G oo , G.
Ashall, J. Hughes (Eds.) Cha ac e isa ion o Old Mo a s wi h Respec o hei Repai -S a e o he
A . Repo o RILEM Technical Commi ee 167-COM, 2007, pp. 77-106.
Applied Mine alogy in he S udy o His o ical Lime Mo a s
170

Con en s lis s a ailable a ScienceDi ec
Mic ochemical Jou nal
jou nal homepage: www.else ie .com/loca e/mic oc
Mul i-analy ical app oach o chemical-mine alogical cha ac e iza ion o
eac ion ims in he lime mo a s om Amaiu Cas le (Na a e, Spain)
G aciela Ponce-An ón
a,⁎
, Ma ia C uz Zuluaga
a
, Luis Angel O ega
a
, Juan xo Agi e Mauleon
b
a
Depa men o Mine alogy and Pe ology, Science and Technology Facul y, Uni e si y o he Basque Coun y (UPV/EHU), Spain
b
A anzadi Socie y o Sciences, Spain
ARTICLE INFO
Keywo ds:
Reac ion im
Dedolomi iza ion
Lime mo a
Hyd o alci e
Ho -mixed mo a s
ABSTRACT
This wo k p esen s a chemical-mine alogical s udy o a chaeological lime mo a s om Amaiu Cas le (Na a e,
Spain) da ed be ween he 14 h and 17 h cen u ies. The s udy ocuses on he analysis o he eac ion zone
obse ed a ound he dolomi ic agg ega es o lime mo a s by means o op ical mic oscopy, scanning elec on
mic oscopy wi h X- ay mic oanalysis, mic o-Raman spec oscopy and X- ay diff ac ion. Mul i-analy ical analysis
show ha he eac ion zone is composed o wo eac ion ims and a halo o med as esul o he dedolomi iza ion
o dolomi ic mo a agg ega es in a s ongly alkaline medium. The mine alogical esul s sugges mo a s cu ed a
a ound 60 °C, poin ing o a adi ional ho -mixing manu ac u e me hod.
1. In oduc ion
Mo a s a e a i icial ma e ials composed by a mix u e o ino ganic
binde , agg ega es and some o ganic o ino ganic addi i es ha o m a
bonding ma e ial in he mason y. In basic mo a manu ac u e he
calcium ca bona e (CaCO
3
) o he limes one used as aw ma e ial is
hea ed in he calcina ion p ocess o p oduce quicklime (CaO). In he
slaking p ocess wa e is added o calcium oxide o p oduce po landi e
(Ca(OH)
2
). The slaked lime and agg ega es a e mixed wi h wa e o
make mo e wo kable pu y. In he ca bona ion p ocess he calcium
hyd oxide in he pu y eac s wi h a mosphe ic ca bon dioxide (CO
2
) o
o m calcium ca bona e again.
Ne e heless, du ing mo a manu ac u e o he eac ions could ake
place be ween he diffe en mo a componen s [1,2]. Alkali-agg ega e
eac ions (AAR) can ake place du ing manu ac u e o mo a . AAR is a
gene al e m e e ing o all eac ions occu ing be ween binde alkalis
and agg ega es. AAR occu s when, in he highly alkaline medium, some
agg ega e mine al phases eac wi h he alkaline hyd oxides p esen in
he hyd a ed lime pu y. The na u e, size and amoun o agg ega es,
alkali con en s, empe a u e and pH de e mine he AAR eac ion speed
[3]. Ne e heless, he scien i ic communi y s ill does no ully unde -
s and he mechanisms in ol ed [3]. In ensi e esea ch has been ca ied
ou on AAR since i was i s epo ed in he 1940s [4–12]. Alkali-silica
eac ion (ASR) and alkali-ca bona e eac ion (ACR) ha e been de-
sc ibed wi hin he AAR [13]. ASR in ol es he eac ion o silica p esen
in he siliceous limes one agg ega es wi h he alkalis p esen in he
binde esul ing in an expansi e gel. Howe e , ACR akes place when
a gillaceous dolomi ic limes one agg ega es eac wi h he binde alkali
[3].
Se e al au ho s ha e desc ibed ACR in mo a s and conc e es since
i was i s ecognized in he 1950s [5,14–19]. Wi hin ACR, a dedolo-
mi iza ion eac ion could ake place. Dedolomi iza ion in ol es he
pa ial dissolu ion o dolomi e o ming a eac ion zone a ound he edge
o dolomi ic agg ega es [20,21]. Fo ma ion o eac ion zones su -
ounding mo a agg ega es has been desc ibed by se e al au ho s
[18,22–28].
The aim o his wo k was o s udy he eac ion zone in he dolomi ic
agg ega es o Amaiu Cas le (Na a e) lime mo a s, and he alkali-ag-
g ega e eac ions in ol ed. A mul i-analy ical s udy was ca ied ou o
chemical, mine alogical and ex u al cha ac e iza ion by means o op ical
mic oscopy, Raman spec oscopy, X- ay diff ac ion and scanning elec on
mic oscopy coupled wi h elec on-dispe si e spec oscopy. In his way, he
s udy is able o con ibu e knowledge o he manu ac u ing p ocess o lime
mo a s be ween he14 h and 17 h cen u ies.
2. Ma e ials and me hods
2.1. Samples
A chaeological lime mo a samples om Amaiu Cas le (Na a e
Spain) we e analyzed in o de o s udy he eac ion zone in dolomi ic
agg ega es. The mo a s belong o s uc u es buil in diffe en pe iods: a
wall be ween he 14 h and15 h cen u ies, a 16 h cen u y bas ion and
illings, and a second bas ion da ed in he 17 h cen u y (Fig. 1).
h ps://doi.o g/10.1016/j.mic oc.2019.104303
Recei ed 13 May 2019; Recei ed in e ised o m 3 Oc obe 2019; Accep ed 3 Oc obe 2019
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8. Appendices: Published and Submi ed Wo ks
171
2.2. Digi al and op ical mic oscopy
Mac oscopic high- esolu ion analysis was ca ied ou on he po-
lished su ace o bulk mo a using a Dino-Li e P emie AM7013MZT
digi al handheld mic oscope equipped wi h a Mic o ouch II senso wi h
adjus able pola ize wi h up o 200×magni ica ion wo king dis ance.
Measu emen and calib a ion we e made wi h DinoCap u e 2.0 so -
wa e.
Pe og aphic s udies we e pe o med on polished hin-sec ions by
pola izing mic oscopy using a Nikon Eclipse LV100POL mic oscope
equipped wi h a DS F-11digi al came a and DS L2 came a con ol uni .
Sample mic o ex u al cha ac e is ics we e analyzed using bo h ans-
mi ed and e lec ed pola ized ligh modes.
2.3. Raman mic ospec oscopy
Mic o-Raman analyses we e pe o med by means o Renishaw inVia
con ocal mic oRaman spec ome e (Renishaw, Glouces e shi e, UK)
coupled o a DMLM Leica mic oscope p o ided wi h 5×,20×, 50×and
100×long wo king dis ance lenses using 785 nm (NIR) exci a ion
lase . Lase was se a low powe (no mo e han 1 mW a he sample) in
o de o a oid he mal pho odecomposi ion. Da a acquisi ion was ca -
ied ou using Renishaw's Wi eTM 3.2 so wa e package. The in e -
p e a ion o Raman esul s was ca ied ou by compa ison o acqui ed
Raman spec a wi h Raman spec a o pu e s anda d compounds col-
lec ed in he e-VISNICH dispe si e Raman da abase. In o de o ob ain
Raman mapping, he S eamLine echnique was used. Spec a we e
acqui ed be ween 1000 and 1120 cm
−1
wi h a 1 cm
−1
esolu ion wi h
a50×objec i e and a good signal-noise a io. In e nal calib a ions and
daily calib a ion wi h a silicon chip ensu ed measu emen quali y.
2.4. X- ay powde diff ac ion
The X- ay diff ac ion (XRD) analysis was pe o med on a powde
polyc ys alline sample by means o Philips X'Pe diff ac ome e
(Mal e n PANaly ical, Almelo, The Ne he lands) equipped wi h a
monoch oma ic Cu-ka1 X- adia ion. The ope a ing condi ions we e
40 kV and 20 mA. A con inuous scan in he ange om 5° o 70° 2θwas
pe o med o he da a collec ion, a an acquisi ion a e o 0.02° pe
second. Mine al phase iden i ica ion was made by X'Pe HighSco e Plus
3.0 so wa e by PANaly ical (Mal e n PANaly ical, Almelo, The
Ne he lands) using he expe imen al pa e ns o ICDD and ICSD di -
ac ion da abases.
2.5. Scanning elec on mic oscopy
Scanning elec on mic oscopy and ene gy-dispe si e X- ay spec o-
scopic (SEM–EDX) analyses we e ca ied ou on polished hin sec ions
by means o a JEOL JSM-7000F Scho ky- ype ield emission scanning
elec on mic oscope (JEOL, Tokyo, Japan) equipped wi h an INCA EDX
X-sigh Se ies Si (Li) Ox o d pen aFET mic oanalysis sys em. The back-
sca e ed elec on (BSE) esolu ion was 3 nm a 15 kV and 10 mm
wo king dis ance. Ene gy dispe si e X- ay spec oscopic mapping
measu emen s we e pe o med using an EVO 40 scanning elec on
mic oscope (Ca l Zeiss STS, Ge many) coupled o an X-Max ene gy-
dispe si e X- ay spec ome e (Ox o d Ins umen s, Abingdon,
Ox o dshi e, UK). The EDX analyses we e ca ied ou using a wo king
dis ance o 8–10 mm, an I P obe o 400 pA, an accele a ion po en ial o
20 kV and 10 scans. Samples we e ca bon-coa ed o elimina e cha ging
effec s. SEM-EDS measu emen s we e ca ied ou o de e mine he
elemen al dis ibu ion images in he c oss-sec ion o he eac ion zone.
The XRD, SEM-EDX and Raman mic ospec oscopy analyses we e
pe o med in he Ma e ials and Su ace Uni and he Raman-LASPEA
labo a o y a he Ad anced Resea ch Facili ies (SGIke ) o he
Uni e si y o he Basque Coun y (UPV/EHU).
3. Resul s
3.1. Digi al and op ical mic oscopy
Ca bona ed agg ega es o mo a la ge han 2 cm in size showed a
p onounced eac ion zone isible e en a mac oscopic scale. Digi al
mic oscopy obse a ions o bulk mo a polished su aces enabled
be e obse a ion o la ge-size agg ega e eac ion zones (Fig. 2a).
Obse ed mac oscopic ea u es we e imp o ed by he pe og aphic
s udy allowing he obse a ion o he mo a mic o ex u al cha ac e -
is ics. Mic oscopically, mo a s showed he e ogeneous ex u e.
Embedded in a mic i ic calci e ma ix, he ca bona ed agg ega es con-
sis ed o angula ine-g ained dolos one agmen s wi h uggy po osi y
(Fig. 2b and c). Obse ed dolos ones a e seconda y dolos ones o med
by he geological p ocess o dolomi iza ion in which he eplacemen o
CaCO
3
by CaMg(CO
3
)
2
ake place [29]. Besides, he pe og aphic s udy
allowed a be e obse a ion o he eac ion zone o dolomi ic ag-
g ega es (Fig. 2d).
3.2. Raman mic ospec oscopy
Lime mo a s we e analyzed by Raman spec oscopy [30,31] and
measu emen s we e pe o med on a polished su ace (Fig. 3a). Fig. 3b
shows he eco ded Raman spec a wi h he highes in ensi ies o he
main calci e and dolomi e bands; 1087 cm
−1
and 1098 cm
−1
, espec-
i ely [32,33]. The main bands o calci e and dolomi e o e lap due o
he ela i e shi o only 11 cm
−1
, bu he 1 cm
−1
spec al esolu ion
used has allowed he wo in ensi ies o be diffe en ia ed and mapped
independen ly. Dolomi e was de ec ed in he unal e ed agg ega e and
in some zones wi hin he binde (Fig. 3c) whe eas calci e was mainly
ound in he mo a binde and in he eac ion zone, and sca cely wi hin
he unal e ed agg ega e (Fig. 3d).
3.3. X- ay diff ac ion
XRD analyses iden i ied diffe en mine al phases in he mo a
(Fig. 4). Agg ega es a e mainly composed o dolomi e [CaMg(CO
3
)
2
]
and aces o calci e [CaCO
3
] which is in acco dance wi h he pe o-
g aphic s udies (Fig. 4a). To cha ac e ize binde , a< 2 µm ac ion was
ex ac ed ollowing he p ocedu e desc ibed by O ega e al. [34] and
Ponce An on e al. [2]. Magnesium calci e [(Ca,Mg)CO
3
] was iden i ied
as he p incipal componen o mo a binde bu hyd o alci e
[Mg
6
Al
2
(CO
3
)(OH)
16
•4(H
2
O)] and py oau i e [Mg
6
Fe
2
(CO
3
)
(OH)
16
•4H
2
O] phases we e also p esen in mino amoun s (Fig. 4b).
Hyd o alci e and py oau i e belong o laye ed double hyd oxide phases
(LDHs) cha ac e ized by a b uci e-like s uc u e occu ing as clay-sized
c ys als wi h a gene al o mula [M
2+
(1- x)
M
3+x
(OH)
2
]
x+
(A
n-1
)
x/n
•yH
2
O
whe e M
2+
and M
3+
a e di- and i alen ca ions, and A
n-1
is a cha ge-
balancing anion [35–39].
The XRD pa e n shows asymme ic and b oad peaks a ∼11 °2θ
and ∼23 °2θindica ing low c ys allini y and also sugges ing a p obable
o e lapping o e lec ion. Hyd o alci e was iden i ied by he cha -
ac e is ic basal e lec ions d
003
= 7.61 Å a 11.63 °2θand d
006
=3.81Å
a 23.33 °2θ; whe eas py oau i e was iden i ied acco ding o
d
003
= 7.7 Å a 11.38 °2θand d
006
= 3.92 Å a 22.67 °2θ. In addi ion,
he e lec ions a 23.15 °2θco espond o he cha ac e is ic basal plane
d
012
= 3.84 Å o calci e. XRD esul s ag ee wi h he pe og aphic and
Raman s udies.
3.4. Scanning elec on mic oscopy
Scanning elec on mic oscopy esul s on polished hin sec ions
showed a sequence o diffe en eac ion zones (∼100 µm wid h) wi hin
coa se agg ega e (Figs. 5,6a, 7aand8a.). Se e al sec o s can be dis-
inguished in he eac ion zone acco ding o ex u al cha ac e is ics.
The eac ion sec o s a e dis ibu ed as ollows: an inne na ow eac ion
G. Ponce-An ón, e al. 0LFURFKHPLFDO-RXUQDO

Applied Mine alogy in he S udy o His o ical Lime Mo a s
172
im in con ac wi h he unal e ed dolomi ic agg ega e, a hicke eac-
ion im in he ou e ma gin o he agg ega e and a halo wi hin he
binde in con ac wi h he ou e pa o he agg ega e (Fig. 5). A hicke
eac ion im is cha ac e ized by a pseudomo phic ex u e composed o
da k and b igh spo s. Expansion c acks we e no obse ed.
EDX analyses we e pe o med in o de o cha ac e ize eac ion
sec o s. Table 1 summa izes he majo elemen semi-quan i a i e e-
sul s. The eac ion zone is mainly composed o MgO and CaO bu MgO
concen a ion dec eases om he inne o ou e zones o he agg ega e
while he CaO concen a ion inc eases. MgO con en anges be ween
33.5 o 1.2% whe eas CaO a ies om 65.5 o 98% showing a p o-
nounced CaO en ichmen in he eac ion halo. Na
2
O, P
2
O
5
, TiO
2
and
MnO appea in mino amoun s (<0.2%). The SiO
2
(15.4%), Al
2
O3
(1.1%), FeO (0.8%) and K
2
O (0.3%) con en s inc ease no ably in he
inne na ow im. Howe e , he highes FeO con en s a e in he hicke
eac ion im (1.6%).
Elemen al maps we e p oduced in o de o obse e elemen dis-
ibu ion in he eac ion sec o s. Elemen al mapping shows ca bon,
oxygen, magnesium, calcium, aluminum and silicon spa ial dis ibu ion
in he agg ega e, agg ega e-binde in e ace ( eac ion zone) and binde
(Figs. 6 and 7). In he agg ega e/binde in e ace C and Ca concen a-
ions inc ease (Figs. 6band7b, c) whe eas O and Mg concen a ion
dec eases (Figs. 6c, d and 7d, e). The whi ish halo clea ly s ands ou
owing o he en ichmen in Ca whe eas he maximum concen a ion o
Mg is p esen in he agg ega es (Fig. 7c and e). Al hough Al and Si
concen a ions a e e y low, he Si is sligh ly highe in he inne na ow
im (Fig. 7 and g). Howe e , by dec easing he Si esolu ion on he
elemen al dis ibu ion map, bo h pixel size and in ensi y inc ease, al-
lowing he inne na ow im o be dis inguished mo e clea ly (Fig. 7h).
Fig. 8 shows elemen al mapping semi-quan i a i e esul s exp essed as
absolu e w %. C and Ca show he highes concen a ions (83% and
71%, espec i ely) while O and Mg display lowe concen a ions (58%
and 21%, espec i ely). The Si and Al concen a ion is less han 12%.
When semiquan i a i e alues a e exp essed as absolu e w % and a e
less han 25% he elemen dis ibu ion is no clea ly obse ed (Fig. 8b,
c, d, e). The e o e, o a be e obse a ion o he elemen dis ibu ion,
ela i e w % alues we e used o Mg, Al and Si elemen s (Fig. 8e, , and
g). Al and Mg p esence in elemen al mapping o binde e i ies he
Fig. 1. Geog aphic loca ion o Amaiu Cas le (Na a e, Spain). S udied samples came om he highligh ed s uc u es on he a chaeological plan. In blue, 14 h–15 h
cen u ies wall; in g een 16 h cen u y bas ion; and in eddish 17 h cen u y bas ion.
G. Ponce-An ón, e al. 0LFURFKHPLFDO-RXUQDO

8. Appendices: Published and Submi ed Wo ks
173
LDHs p esence as iden i ied by XRD analysis. Hexagonal c ys als g ea e
han 1 µm wi hin he binde ac ion also e i y he LDHs p esence
(Fig. 9a and b). Mg, Al and Fe ob ained by EDX (Fig. 9c) sugges he
p esence o hyd o alci e and py oau i e, as was iden i ied by XRD
(Fig. 4). The silica con en can be a ibu ed o mic oc ys alline qua z.
4. Discussion
Chemical-mine alogical esul s show ims and halo o ma ion wi h a
ma ked Mg loss and Ca inc ease poin ing o chemical eac ions due o
dedolomi iza ion o dolomi ic agg ega es (Figs. 3c, 6d, 7e, 8eand
Table 1).
Se e al au ho s ha e s udied he dedolomi iza ion eac ion me-
chanism [20,21,40,41] and also he de elopmen o eac ion zones
a ound dolomi e agg ega es [18,22–28]. Two elemen a y eac ions
occu in he dedolomi iza ion p ocess: he i s wi hin he agg ega e
gi ing ise o a eac ion im (Eq. (1) and Eq. (2)) and he second wi hin
he binde o ming a ca bona e halo (Eq. (3)). Reac ion im o ma ion
akes place as ollows:
+ +CaMg(CO ) Ca(OH) 2CaCO Mg(OH)
32 2 3 2
(1)
Dolomi e [CaMg(CO
3
)
2
] eac s wi h po landi e [Ca(OH)
2
] o gen-
e a e calci e [CaCO
3
] and b uci e [Mg(OH)
2
]. Once calci e and b uci e
p ecipi a e, a eac ion im on he edge o he dolomi e agg ega e is
o med (Fig. 5). Dissolu ion o dolomi e is in luenced by empe a u e
and alkaline medium [20,21]. Unlike limes one, dolos ones a e un-
s able in alkaline en i onmen s [13]. Thus, in alkaline en i onmen s,
dolomi e eac s wi h hyd oxyl ions [OH
−
] o o m calci e, b uci e and
ca bona e ions [CO
32−
] as ollows:
+++CaMg CO OH CaCO Mg OH CO()2 ()
32 323
2
(2)
Ca bona e halos a e o med wi hin he binde in con ac wi h he
ou e pa o he dolomi ic agg ega e by he ca bona ion o lime pu y.
A halo is no o med by he pu y ca bona ion bias o he eac ion wi h
a mosphe ic ca bon dioxide bu due o he eac ion be ween dolomi ic
agg ega e and alkalis leading o in si u calci e p ecipi a ion [11]. Fo he
halo o ma ion, he CO
32−
libe a ed by dedolomi iza ion eac ion
Fig. 2. A chaeological mo a samples showing eac ion zones a he edge o he dolomi ic agg ega e: (a) s e eomic oscopic image o he eac ion zone; (b) mo a
pho omic og aph; (c) mo a pho omic og aph showing uggy po osi y; (d) de ail o he agg ega e eac ion zone. A = agg ega e, B = binde , R = im, VP = uggy
po osi y.
Fig. 3. Op ical and chemical esul s o agg ega e edge Raman analysis: (a)
op ical mic oscopy image; (b) Raman spec a o he mapped a eas wi h he
highes in ensi ies o he 1098 cm
-1
dolomi e band and he 1087 cm
-1
calci e
band; (c) Raman mic oscopy map showing dolomi e dis ibu ion; (d) Raman
mic oscopy map showing calci e dis ibu ion.
G. Ponce-An ón, e al. 0LFURFKHPLFDO-RXUQDO
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Applied Mine alogy in he S udy o His o ical Lime Mo a s
174
mig a es in o he lime pu y and eac s wi h po landi e o p oduce
calci e and OH
−
[42] as ollows:
+ +CO Ca OH OH CaCO() 2
3
22 3
(3)
Reac ion ims and ca bona e halo o ma ion do no p oduce ex-
pansion bu a o he high alkaline en i onmen [18,19]. Besides,
wa e dissocia es in a e e sible eac ion in which bo h hyd ogen ions
(H
+
)andOH
−
a e gene a ed. Wi h a highe pH, as e dedolomi iza-
ion eac ions ake place [26,42].
Al hough calci e and b uci e a e o med as dedolomi iza ion p o-
duc s (Eq. (1) and Eq. (2)), b uci e could no be iden i ied by XRD since
he small size o he eac ion im did no allow he ex ac ion o a e-
p esen a i e powde sample wi hou agg ega e and ma ix con amina-
ion. Howe e , da k and b igh spo s obse ed in BSE a he hicke
eac ion im (Fig. 5) could be iden i ied as b uci e and calci e, espec-
i ely, o ming a pseudomo phic ex u e [18]. Mo eo e , he elemen al
mapping o Ca and Mg concen a ions also sugges s he p esence o
b uci e since Ca concen a ion dec eases in da k spo s while Mg con-
cen a ion inc eases (Figs. 7cand8c, ). EDX analysis shows Ca en-
ichmen in he halo in acco dance wi h Eq. (3) (Table 1 and Fig. 7c).
The siliceous na ow im can be explained as esul o an alkali-
silica e eac ion (ASSR) (Figs. 5 and 7g, h). The ASSR is a speci ic ype
o alkali-silica eac ion (ASR) ha occu s mo e slowly [3]. In an ASR,
silica in siliceous agg ega es eac s wi h alkali solu ion o ming an
uns able silica gel (ASR-gel) which abso bs wa e and expands causing
he o ma ion o c acks [6,19]. Howe e , when he phyllosilica es
wi hin agg ega es eac wi h he alkaline solu ion, ASSR occu s e-
sul ing in small amoun o silica e gel (ASSR-gel) [3,18,43]. Phyllosi-
lica es appea sca e ed in dolos ones as impu i ies and in con ac wi h
an alkaline medium eac and b eak down [13]. Unlike ASR-gel com-
posed o alkalis, calcium, silica and wa e , he ASSR-gel is composed o
alkalis (po assium), silica, aluminum and i on [44].
To o m he siliceous na ow im, he ASSR-gel eac s wi h b uci e
o o m non-expansi e Mg-silica e-gel ha in u n eac s wi h b uci e o
o m “chlo i e-like” phases [19,23,25]. Nei he phyllosilica es om he
dolomi ic agg ega e no eac ion p oduc s in he siliceous na ow im
could be iden i ied by XRD due o he sca ce amoun o impu i ies in
agg ega es and he small size o he im, espec i ely. Howe e , he Si,
Al, Fe and K con en s o he siliceous na ow im (Table 1) sugges he
p esence o “chlo i e-like” phases in he im as well as phyllosilica es in
he dolomi ic agg ega e. Acco ding o chemical esul s, chlo i e
[(Mg,Fe)
5
Al(Si
3
Al)O
10
(OH)
8
] and illi e [K(Al,Mg,Fe)
2
(Si,Al)
4
O
10
(OH)
2
]
a e he expec ed phyllosilica es in dolos one agg ega es.
Highe Si concen a ion in he na ow im can be ela ed o he
p esence o magnesium silica e hyd a e (M–S–H) phases as eac ion
p oduc s. M–S–H phases (sho o (MgO)
x
–(SiO
2
)
y
–(H
2
O)
z
) show a
laye ed s uc u e simila o phyllosilica es [45–48]. The c ys alline
s uc u e o M-S-H syn he ic phases has been ela ed o he poo ly-
c ys alline ioc ahed al (2:1 o 1:1) phyllosilica es c ys alline s uc-
u es [49] and ha e also been associa ed wi h sepioli e
[Mg
4
Si
6
O
15
(OH)
2
•6H
2
O] [45]. Like phyllosilica es, M–S–H phases a e
s able in an alkaline en i onmen a pH up o 10 [46,49–51].
Fig. 4. X- ay diff ac ion pa e ns o mo a componen s: (a) mo a dolomi ic agg ega e spec um; (b) mo a binde ac ion less han 2 µm spec um.
Dol = dolomi e, Cal = calci e, Q z = qua z, HT = hyd o alci e, P = py oau i e.
Fig. 5. SEM-BSE image o lime mo a polished hin-sec ion. Diffe en eac ion
zones a e obse ed. A = agg ega e, B = binde , NRR = na ow eac ion im,
TRR = hick eac ion im, H = halo. .
Fig. 6. SEM-BSE image and elemen al mapping o eac ion zone o dolomi ic
agg ega e: (a) BSE image; (b) SEM-EDS dis ibu ion image o calcium; (c) SEM-
EDS dis ibu ion image o oxygen; (d) SEM-EDS dis ibu ion image o mag-
nesium.
G. Ponce-An ón, e al. 0LFURFKHPLFDO-RXUQDO
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8. Appendices: Published and Submi ed Wo ks
175

Amo phous M-S-H o ma ion ha e been also iden i ied du ing he hy-
d a ion o binde ma e ials wi h a high con en in MgO [45]. Howe e ,
i was no possible o con i m he p esence o M-S-H phases in he
s udied mo a s.
Hyd o alci e ims ha e also been desc ibed su ounding dolomi ic
agg ega es [19,52,53]. In iew o he esul s o he elemen al mapping,
he absence o aluminum in he eac ion zone does no indica e he
p esence o hyd o alci e. Howe e , elemen al mapping shows Al and
Mg concen a ions in he binde sugges ing a p esence o hyd o alci e in
he binde (Fig. 8 , g). In ac , hyd o alci e and py oau i e we e also
iden i ied in he binde by XRD (Fig. 4). Hexagonal pla e-like c ys als
cha ac e is ic o hyd o alci e and py oau i e LDH phases we e obse ed
by SEM, con i ming he elemen al mapping and XRD esul s (Fig. 9a
and b). Addi ionally, he silica in he binde (Fig. 7g, h and 9c) can
p oceed om phyllosilica e b eakdown [26] leading o mic oc ys alline
qua z, which was he only silica e phase iden i ied by XRD (Fig. 4b).
Hyd o alci e could be o med in he mo a manu ac u e du ing he
slaking p ocess [2]. The Mg(OH)
2
and CO
32−
eleased om
dedolomi iza ion eac ions (Eqs. (1) and (2)) and he alumina e ions [Al
(OH)
4−
] eleased om phyllosilica e b eakdown can mig a e in o he
lime pu y and eac o ming hyd o alci e [26,52,54]. Besides, he lime
could also con ain MgO and Al
2
O
3
when impu e limes one and/o
pa ially dolomi ized limes ones ha e been used in lime p oduc ion,
and when hey ehyd a e and eac hey o m hyd o alci e [2,55–57].
Fu he mo e, he LDHs a e cha ac e ized by a high capaci y o cap u e
CO
32−
anions due o hei ion-exchange p ope ies [35]. Besides, he
high CO
32−
affini y o LDHs makes i possible o inco po a e he dead
ca bon om he CO
32−
o agg ega es [35,58]. The e o e, he hyd o-
alci e LDH phase cons i u es a po en ially con amina ing mine al phase
in adioca bon da ing o he mo a binde [2].
Hyd a ed calcium alumina e phases (AFm) wi h gene al o mula
[Ca
2
(Al,Fe)(OH)
6
]•X•xH2O whe e X is a mono alen o hal o a di a-
len anion [52,59] we e no iden i ied in s udied mo a s since he
hyd o alci e mine al phase is he modynamically mo e s able [60]. The
o ma ion o hyd o alci e has been desc ibed in dolomi ic mo a s cu ed
a 60 °C [52,53]. The p esence o hyd o alci e in he s udied mo a s
Fig. 7. De ailed SEM-BSE image and elemen al mapping o eac ion zone: (a) BSE image; (b) SEM-EDS dis ibu ion image o ca bon; (c) SEM-EDS dis ibu ion image
o calcium; (d) SEM-EDS dis ibu ion image o oxygen; (e) SEM-EDS dis ibu ion image o magnesium; ( ) SEM-EDS dis ibu ion image o aluminium; (g) SEM-EDS
dis ibu ion image o silicon; (h) SEM-EDS highe magni ica ion image o silicon dis ibu ion.
Fig. 8. De ailed SEM-BSE image and semiquan i a i e elemen al mapping o eac ion zone wi h pe cen ages indica ed on a colou scale: (a) SEM-BSE image; (b)–(e)
absolu e w % o ca bon, calcium, oxygen and magnesium, espec i ely; ( )-(h) ela i e w % o magnesium, aluminium and silicon, espec i ely.
G. Ponce-An ón, e al. 0LFURFKHPLFDO-RXUQDO
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Applied Mine alogy in he S udy o His o ical Lime Mo a s
176
poin s o mo a s cu ed a a ound 60 °C, sugges ing he adi ional ho -
mixing me hod in mo a manu ac u e. In he ho -mixing me hod,
quicklime (CaO) is mixed wi h he agg ega es and slaked o use i la e
when i is s ill ho [61,62]. Quicklime is highly eac i e in con ac wi h
wa e esul ing in a s ong exo he mic eac ion [63] leading o em-
pe a u es ha may each 200 °C when i is slaked wi h a li le wa e and
d op below 100 °C as mo e wa e is added un il slaking inishes a
a ound 58 °C [62]. The e o e, he ho -mixing me hod leads o bo h
po landi e and hyd oxyl ion o ma ion du ing he slaking (Eq. (4) and
Eq. (5), espec i ely) a o ing he dedolomi iza ion eac ions acco ding
o Eq. (1) and Eq. (2), espec i ely.
+CaO H OàCa(OH)
2 2
(4)
++
+
CaO H OàCa 2OH
2
2
(5)
Ho -mixed mo a p oduc ion was ela i ely cheap and quick o
manu ac u e since quicklime could be used sho ly a e i was p o-
duced, hus also educing s o age p oblems [63,64]. Ho -mixed mo a s
had excellen wo kabili y and we e commonly used o ounda ion
wo ks and co e illing p incipally in cold-wea he o win e wo k
[61,63]. These cha ac e is ics would be ad an ageous in he ypically
cold and we clima e condi ions in he egion whe e Amaiu Cas le is
loca ed [65]. Besides, he cheap and quick ho -mixed mo a manu-
ac u e would be app op ia e in he cons uc ion and modi ica ion o
Amaiu Cas le s uc u es in con lic i e pe iods.
5. Conclusions
A combina ion o op ical mic oscopy, mic o-Raman spec oscopy,
X- ay diff ac ion and scanning elec on mic oscopy wi h X- ay mic o-
analysis was able o cha ac e ize he eac ion zone o dolomi ic ag-
g ega es in Amaiu Cas le his o ic mo a s.
Chemical, mine alogical and ex u al a ia ions in he dolomi ic
agg ega e eac ion zone show he p esence o wo eac ion ims wi hin
he agg ega e and a halo wi hin he binde .
Rims and halo we e o med due o an alkali-agg ega e eac ion
(AAR) leading o dedolomi iza ion o dolomi ic mo a agg ega es in a
s ongly alkaline medium, al hough an alkali silica e eac ion (ASSR)
was also in ol ed.
Nei he AFm no M-S-H phases we e de ec ed in he s udied mo a
lime binde bu hyd o alci e and py oau i e we e iden i ied.
The p esence o hyd o alci e and py oau i e ad ises agains he use
o lime binde s om Amaiu Cas le o adioca bon da ing.
Mo a chemical and mine alogical cha ac e is ics poin o he use
o he adi ional ho -mixing me hod in he mo a manu ac u e a
Amaiu Cas le.
Decla a ion o Compe ing In e es
Au ho s decla e ha hey ha e no con lic o in e es .
Acknowledgmen s
The au ho s would like o hank he anonymous e e ee o hei
commen s and sugges ions on he manusc ip . The s udy was suppo ed
by he IT1193-19 Resea ch G oup o he Basque Coun y Go e nmen .
G.P.-A. also acknowledges a PhD esea ch g an om he Basque
Coun y Go e nmen [PRE-2015-1-0235]. The au ho s would like o
hank Pe e Smi h o e iewing he use o English in he manusc ip .
Re e ences
[1] D.T. Be u o, R. Vecchia ini, M. Gio dani, Solid p oduc s and a e-limi ing s ep in
he he mal hal decomposi ion o na u al dolomi e in a CO2 (g) a mosphe e,
The mochim. Ac a 405 (2003) 183–194.
[2] G. Ponce-An ón, L.A. O ega, M.C. Zuluaga, A.Alonso Olazabal, J.L. Solaun,
Hyd o alci e and hyd ocalumi e in Mo a Binde s om he Medie al Cas le o
Po illa (Ála a, No h Spain): accu a e mine alogical con ol o achie e mo e eli-
able ch onological ages, Mine als 8 (2018) 326.
[3] J.M.M.da Fonseca, V.K.B. de Souza, D.G.C.da Sil a, D.L.da Sil a, E.C.B. Mon ei o,
Alkali-agg ega e eac ion: de ini ion, in luence and con ol, Eng. Appl. Sci. 3
(2018) 12.
[4] T.E. S a on, Expansion o conc e e h ough eac ion be ween cemen and agg ega e,
P oc. Am. Soc. Ci il Eng. 66 (1940) 1781–1811.
[5] J.E. Gillo , Alkali-agg ega e eac ions in conc e e, Eng. Geol. 9 (1975) 303–326.
[6] L.D. Glasse , N. Ka aoka, The chemis y o ‘alkali-agg ega e' eac ion, Cem. Conc .
Res. 11 (1981) 1–9.
[7] S. Diamond, Alkali agg ega e eac ions in conc e e: an anno a ed bibliog aphy
1939–1991, Documen SHRP-C/UPW-92-601, S a egic Highway Resea ch
P og am, Na ional Resea ch Council, Washing on, DC, 1992.
[8] E.J. Lee, H.M. Clowes, Alkali-Agg ega e Reac ion 1977-1992, A De ini i e
Bibliog aphy, BCA Re : CIS/B8, B i ish Cemen Associa ion, Slough (la e
C ow ho ne), U.K, 1992.
[9] A.B. Poole, The alkali–silica eac ions in conc e e, in: S. NR (Ed.), In oduc ion o
Alkali Agg ega e Reac ion in Conc e e, Blackie & London, UK, 1992, pp. 1–28.
[10] B. Fou nie , M.-A. Bé ubé, Alkali-agg ega e eac ion in conc e e: a e iew o basic
concep s and enginee ing implica ions, Can. J. Ci . Eng. 27 (2000) 167–191.
[11] l. Sims, A. Poole, Alkali–agg ega e eac i i y, in: J. Newman, C. Ban Seng (Eds.),
Table 1
Chemical analysis esul s ob ained by EDX o majo elemen s exp essed as oxides in w %.
Analysis Zone Na
2
OMgO CaO Al
2
O
3
SiO
2
FeO K
2
OP
2
O
5
TiO
2
MnO
Poin 1 - Agg ega e 0.10 33.51 65.45 0.20 0.38 0.02 0.06 0.09 0.19
Poin 2 - Na ow im 18.58 63.55 1.11 15.40 0.83 0.29 0.04 0.04 0.17
Poin 3 - Thicke im 4.14 91.44 0.26 2.08 1.57 0.09 0.17 0.17 0.09
Poin 4 - Halo 0.12 1.19 98.03 0.03 0.42 0.06 0.01 0.14
Fig. 9. Mo a binde SEM-EDX esul s: (a) and (b) Seconda y elec on SEM images showing LDHs hexagonal c ys als; (c) EDX spec um o he ma ked a ea.
G. Ponce-An ón, e al. 0LFURFKHPLFDO-RXUQDO

8. Appendices: Published and Submi ed Wo ks
177
Ad anced Conc e e Technology – Conc e e P ope ies, Else ie , Ox o d, U.K, 2003,
pp. 1–37.
[12] G.E. Bligh , M.G Alexande , Alkali-Agg ega e Reac ion and S uc u al Damage o
Conc e e: Enginee ing Assessmen , Repai and Managemen , CRC P ess, 2011.
[13] F.H. Sh ime , P og ess in he E alua ion o Alkali-Agg ega e Reac ion in Conc e e
Cons uc ion in he Paci ic No hwes 2209-K Geological Su ey Bulle in, Uni ed
S a es and Canada. U. S, 2005, p. 11.
[14] E.G. Swenson, A eac i e agg ega e unde ec ed by ASTM es s, ASTM Bull. 226
(1957) 48–51.
[15] E.G. Swenson, J.E. Gillo , Cha ac e is ics o Kings on ca bona e ock eac ion,
Highway Res. Boa d Bull. 275 (1960).
[16] D.W. Hadley, Alkali eac i i y o ca bona e ocks-expansion and dedolomi iza ion,
Highway Resea ch Boa d P oceedings, 40 1961.
[17] M.-S. Tang, Z. Liu, Y.-N. Lu, S.-F. Han, Alkali-ca bona e eac ion and pH alue, Il
Cemen o 88 (1991) 141–150.
[18] T. Ka ayama, How o iden i y ca bona e ock eac ions in conc e e, Ma e . Cha ac .
53 (2004) 85–104.
[19] T. Ka ayama, The so-called alkali-ca bona e eac ion (ACR) — i s mine alogical and
geochemical de ails, wi h special e e ence o ASR, Cem. Conc . Res. 40 (2010)
643–675.
[20] S. Galı
, C. Ayo a, P. Al onso, E. Taule , M. Lab ado , Kine ics o dolomi e–-
po landi e eac ion: applica ion o po land cemen conc e e, Cem. Conc . Res. 31
(2001) 933–939.
[21] E. Ga cı
a, P. Al onso, E. Taule , S. Galı
, Su ace al e a ion o dolomi e in dedolo-
mi iza ion eac ion in alkaline media, Cem. Conc . Res. 33 (2003) 1449–1456.
[22] R.E. Bisque, J. Lemish, Chemical cha ac e is ics o some ca bona e agg ega e as
ela ed o du abili y o conc e e, Highway Resea ch Boa d Bulle in (1958).
[23] D.W. Hadley, Alkali eac i i y o dolomi ic ca bona e ocks, Highway Resea ch
Reco d 45 (1964).
[24] H.N. Walke , Reac ion p oduc s in expansion es specimens o ca bona e agg ega e,
T ansp. Res. Rec. 525 (1974) 28–37.
[25] A.B. Poole, P. So i opoulos, Reac ions be ween dolomi ic agg ega e and alkali po e
luids in conc e e, Q. J. Eng. Geol. Hyd ogeol. 13 (1980) 281–287.
[26] G.-L. Gan, P.G. Sp y, A.M. Cody, Rim o ma ion on iowa highway conc e e dolomi e
agg ega e: he effec s o dedolomi iza ion eac ions, En i on. Eng. Geosci. (1996)
59–72 II.
[27] T. Ka ayama, T. D imalas, J.H. Ideke , B. Fou nie , Rim- o ming dolomi ic ag-
g ega e in conc e e s uc u es in Saudi A abia - is dedolomi iza ion equal o he so-
called alkali-ca bona e eac ion? 14 h In e na ional Con e ence on Alkali Agg ega e
Reac ions (ICAAR), Aus in, Texas, 2012.
[28] S. K ama , V. Zala , M. U ose ic, W. Kö ne , A. Mauko, B. Mi ič, J. Lux,
A. Mladeno ić, Mine alogical and mic os uc u al s udies o mo a s om he ba h
complex o he Roman illa us ica nea Mošnje (Slo enia), Ma e . Cha ac . 62
(2011) 1042–1057.
[29] J.S. Boggs, Pe ology o Sedimen a y Rocks, second ed., Camb idge Uni e si y
P ess, Camb idge, 2009.
[30] S. Ma inez-Rami ez, S. Sanchez-Co es, J.V. Ga cia-Ramos, C. Domingo, C. Fo es,
M.T. Blanco-Va ela, Mic o-Raman spec oscopy applied o dep h p o iles o ca -
bona es o med in lime mo a , Cem. Conc . Res. 33 (2003) 2063–2068.
[31] T. Schmid, P. Da iz, Chemical imaging o his o ical mo a s by Raman mic oscopy,
Cons . Build. Ma e . 114 (2016) 506–516.
[32] J. Sun, Z. Wu, H. Cheng, Z. Zhang, R.L. F os , A Raman spec oscopic compa ison o
calci e and dolomi e, Spec ochim. Ac a Pa A 117 (2014) 158–162.
[33] S. Gunaseka an, G. Anbalagan, S. Pandi, Raman and in a ed spec a o ca bona es
o calci e s uc u e, J. Raman Spec osc. 37 (2006) 892–899.
[34] L.A. O ega, M.C. Zuluaga, A. Alonso-Olazabal, X. Mu elaga, M. Insaus i, A. Ibañez-
E xebe ia, His o ic lime-mo a 14C da ing o San a Ma ía la Real (Za au z,
no he n Spain): ex ac ion o sui able g ain size o eliable 14C da ing,
Radioca bon 54 (2012) 23–36.
[35] S. Miya a, Anion-exchange p ope ies o hyd o alci e-like compounds, Clays Clay
Mine . 31 (1983) 305–311.
[36] M. Meyn, K. Beneke, G. Lagaly, Anion-exchange eac ions o laye ed double hy-
d oxides, Ino g. Chem. 29 (1990) 5201–5207.
[37] K. Rozo , U. Be ne , C. Ta io -Gueho, F. Le oux, G. Renaudin, D. Kulik,
L.W. Diamond, Syn hesis and cha ac e iza ion o he LDH hyd o alci e–py oau i e
solid-solu ion se ies, Cem. Conc . Res. 40 (2010) 1248–1254.
[38] S.J. Mills, A.G. Ch is y, J.-M.R. Génin, T. Kameda, F. Colombo, Nomencla u e o he
hyd o alci e supe g oup: na u al laye ed double hyd oxides, Mine al. Mag. 76
(2012) 1289–1336.
[39] D.G. E ans, R.C.T. Slade, S uc u al aspec s o laye ed double hyd oxides, in:
X. Duan, D.G. E ans (Eds.), Laye ed Double Hyd oxides, Sp inge Be lin Heidelbe g,
Be lin, Heidelbe g, 2006, pp. 1–87.
[40] E. Busenbe g, L.N. Plumme , The kine ics o dissolu ion o dolomi e in CO2-H2O
sys ems a 1.5 o 60°C C and 0 o 1a m PCO2, Geochim, Cosmochim. Ac a 282
(1982) 45–78.
[41] X. Zhang, F.P. Glasse , K.L. Sc i ene , Reac ion kine ics o dolomi e and po landi e,
Cem. Conc . Res. 66 (2014) 11–18.
[42] T. P inčič, P. Š uko nik, S. Pejo nik, G. De Schu e , V. Bokan Bosiljko ,
Obse a ions on dedolomi iza ion o ca bona e conc e e agg ega es, implica ions
o ACR and expansion, Cem. Conc . Res. 54 (2013) 151–160.
[43] D.W. Hobbs, Alkali-Silica Reac ion in Conc e e, Thomas Tel o d, London, 1988.
[44] J. Smel z, J. Fa e , Dedolomi iza ion and Alkali Reac ions in Ohio-sou ced
Dols one Agg ega es (No. FHWA/OH-2017-9), Dep a men o T anspo a ion,
Ohio, 2017.
[45] D.R.M. B ew, F.P. Glasse , Syn hesis and cha ac e isa ion o magnesium silica e
hyd a e gels, Cem. Conc . Res. 35 (2005) 85–98.
[46] D. Nied, K. Enema k-Rasmussen, E. L'Hopi al, J. Skibs ed, B. Lo henbach, P ope ies
o magnesium silica e hyd a es (M-S-H), Cem. Conc . Res. 79 (2016) 323–332.
[47] C. Roosz, S. G angeon, P. Blanc, V. Mon ouillou , B. Lo henbach, P. Henocq,
E. Giffau , P. Vieilla d, S. Gabo eau, C ys al s uc u e o magnesium silica e hy-
d a es (M–S–H): he ela ion wi h 2:1 Mg–Si phyllosilica es, Cem. Conc . Res. 73
(2015) 228–237.
[48] S.A. Walling, H. Kinoshi a, S.A. Be nal, N.C. Collie , J.L. P o is, S uc u e and
p ope ies o binde gels o med in he sys em Mg(OH)2–SiO2–H2O o im-
mobilisa ion o Magnox sludge, Dal on T ans. 44 (2015) 8126–8137.
[49] E. Be na d, B. Lo henbach, C. Cau-Di -Coumes, C. Chlique, A. Dauzè es, I. Pocha d,
Magnesium and calcium silica e hyd a es, pa I: in es iga ion o he possible
magnesium inco po a ion in calcium silica e hyd a e (C-S-H) and o he calcium in
magnesium silica e hyd a e (M-S-H), Appl. Geochem. 89 (2018) 229–242.
[50] E. Be na d, B. Lo henbach, F. Le Goff, I. Pocha d, A. Dauzè es, Effec o magnesium
on calcium silica e hyd a e (C-S-H), Cem. Conc . Res. 97 (2017) 61–72.
[51] E. Be na d, B. Lo henbach, D. Ren sch, I. Pocha d, A. Dauzè es, Fo ma ion o
magnesium silica e hyd a es (M-S-H), Phys. Chem. Ea h, Pa s A/B/C 99 (2017)
142–157.
[52] M. Zajac, S.K. B emse h, M. Whi ehead, M. Ben Haha, Effec o CaMg(CO3)2 on
hyd a e assemblages and mechanical p ope ies o hyd a ed cemen pas es a 40°C
and 60°C, Cem. Conc . Res. 65 (2014) 21–29.
[53] A. Machne , M. Zajac, M. Ben Haha, K.O. Kjellsen, M.R. Geike , K. De Wee d ,
Limi a ions o he hyd o alci e o ma ion in Po land composi e cemen pas es
con aining dolomi e and me akaolin, Cem. Conc . Res. 105 (2018) 1–17.
[54] P. Sipos, The s uc u e o Al(III) in s ongly alkaline alumina e solu ions — a e-
iew, J. Mol. Liq. 146 (2009) 1–14.
[55] S. Miya a, A. Okada, Syn hesis o hyd o alci e-like compounds and hei physico-
chemical p ope ies- he sys ems Mg2+-Al3+-SO4 2- and Mg2+-Al3+-C O4 2,
Clays Clay Mine . 25 (1977) 14–18.
[56] S. Miya a, Physico-chemical p ope ies o syn he ic hyd o alci es in ela ion o
composi ion, Clays Clay Mine . 28 (1980) 50–56.
[57] J. Scho k, Dolomi ic lime in he US, J. A ch. Conse a. 18 (2012) 7–25.
[58] K. G o e , S. Koma neni, H. Ka suki, Syn he ic hyd o alci e- ype and hyd o-
calumi e- ype laye ed double hyd oxides o a sena e up ake, Appl. Clay Sci. 48
(2010) 631–637.
[59] H.F.W. Taylo , Cemen Chemes y, Thomas Tel o d, London, 1997.
[60] Z. Maciej, M. Ben Haha, Hyd a ion o limes one and dolomi e cemen , 14 h
In e na ional Cong ess on he Chemis y o Cemen , Beijing, China, 2015.
[61] E. He i age, P ac ical Building Conse a ion: Mo a s, Rende s & Plas e s, Ashga e,
Su ey, 2011.
[62] N. Copsey, Ho Mixed Lime and T adi ional Mo a s: A P ac ical Guide o Thei Use
in Conse a ion and Repai , The C owood P ess, Ramsbu y, Ma lbo ough, 2019.
[63] A. Fo s e , Ho -lime mo a s: a cu en pe spec i e, J. A ch. Conse . 10 (2004)
7–27.
[64] J. Válek, T. Ma as, Expe imen al s udy o ho mixed mo a s in compa ison wi h
lime pu y and hyd a e mo a s, His o ic Mo a s, Sp inge Ne he lands, Do d ech ,
2012, pp. 269–281.
[65] A izkun. A ailable online:h p://me eo.na a a.es/clima ologia/sel ichaclima.c m?
IDEs acion=66& ipo=MAN(accessed on 3 May 2019).
G. Ponce-An ón, e al. 0LFURFKHPLFDO-RXUQDO

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8. Appendices: Published and Submi ed Wo ks
179
APPENDIX III.2
Pe og aphic and chemical-mine alogical cha ac e iza ion o mo a s om
he cis e n a Amaiu Cas le (Na a e, Spain)
G aciela Ponce-An ón, Ma ia C uz Zuluaga, Luis Angel O ega, Juan xo Agi e Mauleon
Mine als 2020; 10(4):311
Mine als 2020,10, 311 5 o 16
Mic o-Ramananalyseswe epe o medusingaRenishawinViacon ocalmic oRamanspec ome e
(Renishaw inVia, Glouces e shi e, UK). Spec a we e acqui ed be ween 1000 and 1120 cm
1
wi h
a 1 cm esolu ion and he da a acquisi ion was ca ied ou using Renishaw’s Wi eTM 3.2 so wa e
package (Renishaw, Glouces e shi e, UK). Raman spec a o pu e s anda d compounds collec ed in he
e-VISNICH dispe si e Raman da abase we e used o in e p e he esul s.
Fou ie ans o m in a ed spec oscopy (FTIR) by he po assium b omide pelle echnique was
ca ied ou o de e mine he na u e o he o ganic compounds using a JASCO 4200 FTIR spec ome e
(JASCO INTERNATIONAL CO., Hachioji, Tokyo, Japan) and acqui ing spec a be ween 400 and
4000 cm1.
To imp o e he FTIR signal o he o ganic componen s, an ex ac ion was conduc ed using 200
µ
L
o dichlo ome hane o ganic sol en .
Hyd aulici y Index (HI) (Equa ion (1)) and Cemen a ion Index (CI) (Equa ion (2)) alues we e
calcula ed o assess he hyd aulici y o he binde acco ding o Boyn on o mula [
24
,
25
]. Indices we e
calcula ed as below:
HI =SiO2+Al2O3
CaO +MgO , (1)
CI =2.8SiO2+1.1Al2O3+0.7Fe2O3
CaO +1.4MgO . (2)
4. Resul s
4.1. Pe og aphic and Chemical–Mine alogical Cha ac e iza ion
Mac oscopically, a di↵e ence in he na u e o agg ega es was obse ed be ween he plas e
(Figu e 3a), mo a s om he ank (Figu e 3b–d), and he mo a s om he aul (Figu e 3e, ).
Sample CA-AL-2 om he lune e o he aul and Samples CA-AL-5 and CA-AL-6 om he base o he
ba el aul (s uc u al mo a s) show ca bona ed agg ega es, whe eas Samples CA-AL-7, CA-AL-8 and
CA-AL-9 (s uc u al mo a s), and Sample CA-AL-1 (plas e ) show siliceous agg ega es. Mo a s om
he ank also show inc easing agg ega e g ading, om s uc u al mo a s (inne pa ; Samples CA-AL-7,
CA-AL-8, and CA-AL-9) o he plas e (ou e pa ; Sample CA-AL-1) (Figu e 3).
!
Figu e 3.
Mac oscopic ex u e o he lime mo a s om he Amaiu Cas le cis e n. (
a
) CA-AL-2, plas e
sample. (
b
) CA-AL-8a, (
c
) CA-AL-8b, and (
d
) CA-AL-7, samples om he ank mo a s. (
e
) CA-AL-2
and (
) CA-AL-5, mo a s om he aul . Mo a s om he ank show an inc ease in agg ega e g ading
om he inne pa (d) o he ou e pa (a).
Mic oscopically, all samples show a he e ogeneous binde ma ix-suppo ed ex u e wi h
agg ega es embedded in a mic i ic calci e ma ix. Pe og aphic obse a ions o mo a iden i ied he
ca bona ed agg ega es o samples om he aul as poo ly so ed ine-g ained dolos one agmen s
wi h angula o subangula shape (Figu e 4a). The g ain sizes o agg ega es om he aul base
(Samples CA-AL-5 and CA-AL-6) ange om 0.2 mm up o 3 mm, whe eas agg ega es om he lune e
8. Appendices: Published and Submi ed Wo ks
187

Mine als 2020,10, 311 6 o 16
(CA-AL-2) each 8 mm in size. Dolos one agg ega es show a p onounced eac ion zone (Figu e 4a).
Sca ce ce amic agmen s can also be obse ed dispe sed in he binde ma ix.
Figu e 4.
Pho omic og aphs showing he mos ep esen a i e mic o ex u es o he lime mo a s om
Amaiu Cas le cis e n. (
a
), (
b
)-le , (
c
) and (
d
)-le : plane pola ized ligh mode (PPL). (
b
)- igh , (
d
)- igh ,
(
e
,
): c ossed-pola ized ligh mode (XPL). C: ce amic; DRx: dolos one; L: lime lump; PhRx: phylli e; PL:
pigmen ed laye ; QRx: qua zi e; Qz: qua z; R: eac ion zone; ScRx: Schis ; S Rx: sub olcanic ock.
The na u e o he agg ega es om he cis e n ank mo a s is he same in bo h s uc u al mo a s
(Samples CA-AL-7, CA-AL-8, and CA-AL-9) and plas e (Samples CA-AL-1). Mo a s a e mainly
composed o subangula o ounded ce amic agmen s (s.l.), and he siliceous agg ega es obse ed
mac oscopically ha e been iden i ied as well- ounded qua z g ains and phylli e, schis , qua zi e,
sands one, and sub olcanic ocks (Figu e 4b–e). Dolos one agmen s we e also obse ed in mino
amoun s, and also some cha coal agmen s we e dispe sed in he binde ma ix. He e ome ic lime
lumps up o 4 mm we e also obse ed (Figu e 4e).
The g ain size o agg ega es dec eases and agg ega e so ing inc eases om he inne laye o
he s uc u al mo a (Sample CA-AL-7) o he ou e pa (CA-AL-8 and CA-AL-9). Sample CA-AL-7
shows e y poo ly so ed agg ega es om 0.7 mm o 2 cm in size. The ou e pa o Sample CA-AL-8
(CA-AL-8a) is e y simila o Sample CA-AL-9, wi h smalle and mo e so ed agg ega es han he
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188
Mine als 2020,10, 311 7 o 16
inne pa o Sample CA-AL-8 (CA-AL-8b). Bo h Subsample CA-AL-8b and Sample CA-AL-9 show
mode a ely so ed agg ega es anging om 0.2 mm up o 3 mm in g ain size, whe eas Subsample
CA-AL-8a shows be e so ed agg ega es om 0.1 o 1.3 mm in size.
Sample CA-AL-1 co esponding o he plas e mo a consis s o wo di↵e en laye s (Figu e 4 ).
The inne laye o he plas e is also composed by he well- ounded and so ed ce amic and polygenic
ock agg ega es, as obse ed in he s uc u al mo a s o he cis e n, which a e up o 0.3 mm in size.
The ou e laye o he plas e is a eddish pigmen ed laye a ound 0.15 mm hick showing a sca ce
amoun o mica-like phyllosilica es and qua z g ains.
Binde /agg ega e a ios we e de ined by he compa ison o he cha o olume pe cen age
es ima ion [
26
]. Samples show a binde /agg ega e a io be ween 1:2 and 1:1, excep o Sample
CA-AL-7, which shows a binde /agg ega e a io o 1:1 and he inne laye o plas e , which shows a
binde /agg ega es a io o 2:1.
To de e mine he composi ion o he mo a binde s, Sample CA-AL-2 om he aul lune e,
Sample CA-AL-9 om he s uc u al mo a s o he ank, and bo h inne and pigmen ed laye s o
plas e (Sample CA-AL-1) we e selec ed o X- ay di↵ ac ion (XRD) analysis.
A binde ac ion <2
µ
m o Samples CA-AL-2 and CA-AL-9 was ex ac ed in o de o a oid he
in e e ence o he agg ega e composi ion ollowing he p ocedu es desc ibed by O ega e al. [
27
]and
Ponce-An on e al. [
28
]. The small amoun o Sample CA-AL-1 om he plas e made i impossible
o ex ac he binde ac ion <2
µ
m, and hus he bulk ac ion o bo h inne and pigmen ed laye s
was analysed. Fo he analysis o he inne laye , he agg ega es obse able wi h he naked eye
we e emo ed.
The XRD esul s a e shown in Figu e 5. All samples a e mainly composed o magnesium calci e
[(Ca, Mg)CO
3
], and in mino amoun s, hyd o alci e [Mg
6
Al
2
(CO
3
)(OH)
16·
4(H
2
O)] was also de ec ed
in all samples, excep in he pigmen ed laye whe e only aces we e de ec ed. Qua z [SiO
2
] and
illi e-like phyllosilica es we e de ec ed in samples om he cis e n ank in bo h s uc u al and plas e
mo a s. Re lec ion peaks a 7.03 Å and 3.51 Å allowed o de ec small amoun s o he amesi e mine al
phase [Mg
2
Al
2
SiO
5
(OH)
4
] in Sample CA-AL-9 and in he inne laye o he plas e . Hema i e [Fe
2
O
3
]
was also iden i ied in he pigmen ed ou e mos laye o he plas e .
Figu e 5.
X- ay di↵ ac ion pa e ns o he lime mo a s om Amaiu Cas le cis e n. (
a
) Binde ac ion
<2
µ
m om he lune e. (
b
) Binde ac ion <2
µ
m om he s uc u al mo a o he ank. (
c
) Bulk
ac ion om he inne laye o he plas e mo a . (
d
) Bulk ac ion om he pigmen ed laye o he
plas e mo a . Ame: amesi e, Hem: hema i e, HT: hyd o alci e; Mg-cal: magnesium calci e, Phy:
phyllosilica es s.l., Qz: qua z.
8. Appendices: Published and Submi ed Wo ks
189
Mine als 2020,10, 311 8 o 16
Bo h hyd o alci e and amesi e ha e been he Mg-hyd a ed phases de ec ed by XRD. Hyd o alci e
is a laye ed double hyd oxide phase (LDHs) [
29
], whe eas amesi e is a magnesium aluminosilica e
hyd a e phase (M-A-S-H).
To con i m he p esence o he Mg-hyd a ed phases de ec ed by XRD, he binde ac ion <2
µ
m
o Samples CA-AL-2 ( aul mo a ) and CA-AL-9 ( ank mo a ) we e analysed by he mog a ime ic
analysis (TGA). The TGA esul s a e shown in Figu e 6.
Figu e 6.
The mog a ime ic analyses o he binde ac ion <2
µ
m om he aul mo a (Sample
CA-AL-2 in black) and ank mo a (Sample CA-AL-9 in g een).
Sample CA-AL-2 shows a o al weigh loss o 38.14%, whe eas Sample CA-AL-9 shows a o al
weigh loss o 28.17%. Since he o al weigh loss o pu e calcium ca bona e is 44%, hese lowe weigh
losses indica e he p esence o o he mine al phases in he binde as indica ed by he XRD esul s
(Figu e 5).
The TGA cu es show ou main weigh loss egions. The i s weigh loss (<120

C) and he
second weigh loss (120 o 200

C) a e a ibu ed o he adso p ion wa e and poo ly bonded in e laye
wa e , espec i ely. The hi d weigh loss (200 o 600

C) is a ibu ed o dehyd a ion caused by he loss
o hyd oxyl g oups (OH

). The las ou h weigh loss (600 o 800

C) is ela ed o he decomposi ion o
he ca bona es [
30
–
32
]. No weigh loss is obse ed o e 800

C. Conside ing he DSC cu e, be ween
200 and 600

C, wo endo he mic peaks a e obse ed in bo h Sample CA-AL-2 and Sample CA-AL-9.
These wo endo he mic peaks co espond o he hyd o alci e (LDHs), which decomposes in wo
s eps in his ange o empe a u es [
33
,
34
]. Ne e heless, he second endo he mic peak be ween
450 and 600

C can also be ela ed o he decomposi ion o he amesi e (M-A-S-H) and illi e-like
phyllosilica es [
35
–
38
] p esen in Sample CA-AL-9, and he e o e, hey appea o o e lap. Be ween 800
and 900

C, an endo he mic peak is only de ec ed in Sample CA-AL-9, con i ming he p esence o
amesi e and illi e in he ank mo a sample, since he b eakdown o bo h phases akes place in his
empe a u e ange [35–37].
X- ay luo escence was pe o med o de e mine he chemical composi ion o he binde ac ion
<2
µ
m o Samples CA-AL-2 and CA-AL-9. Chemical esul s o bo h aul and ank mo a s (Samples
CA-AL-2 and CA-AL-9, espec i ely) we e used o calcula e he Hyd aulici y Index (HI) and
Cemen a ion Index (CI) in o de o assess and compa e he hyd aulici y deg ee o binde s om
he aul and ank (Table 2). Hyd aulici y is classi ied as weak (HI =0.1–0.2, CI =0.3–0.5), mode a e
(HI =0.2–0.4, CI =0.5–0.7), and eminen (HI <0.4, CI =0.7–1.1) [
24
,
25
]. Acco ding o he HI and CI
alues, he mo a binde om he cis e n ank is eminen ly hyd aulic, whe eas he mo a binde om
he aul is weakly hyd aulic.
Applied Mine alogy in he S udy o His o ical Lime Mo a s
190
Mine als 2020,10, 311 9 o 16
Table 2.
Semiquan i a i e esul s o he majo elemen s o he binde ac ion <2
µ
m in powde samples
om he lune e o he ba el aul and ank samples de e mined by X- ay luo escence, he hyd aulici y
index (HI), and he cemen a ion index (CI). Chemical esul s a e exp essed as oxides in w %. I on
con en is exp essed as o al Fe2O3 . LOI: loss on igni ion (%).
Sample S uc u e MgO Al2O3SiO2K2O CaO TiO2MnO Fe2O3 LOI HI CI
CA-AL-2 Lune e 6.16 2.43 5.55 0.23 44.73 0.20 0.05 2.40 38.14 0.20 0.37
CA-AL-9 Tank 6.70 8.15 21.12 1.08 29.20 0.35 0.15 4.88 28.17 0.95 1.85
4.2. S udy o he Pigmen ed Laye o Plas e
Scanningelec onmic oscopy(SEM)waspe o medonSampleCA-AL-1 o be e cha ac e iza ion
o he plas e . SEM obse a ions show ha he pigmen ed laye o plas e is less po ous han he inne
laye and ha he con ac su ace be ween bo h laye s is ough (Figu e 7).
Figu e 7.
SEM image o he cis e n plas e . A: pigmen ed laye ; B: inne laye . Rough con ac su ace
in ed.
The ou e mos pigmen ed laye o he plas e was also analysed by Raman spec oscopy and
Fou ie ans o m in a ed spec oscopy (FTIR) in o de o de e mine whe he any o he ype o
addi i e was used in he manu ac u e. Raman spec oscopy con i med ha he pigmen ed laye o
plas e is mainly composed o a mix u e o calci e and hema i e (Figu e 8a).
Raman spec a show in ense bands a 282 cm
1
, 712 cm
1
, and 1087 cm
1
a ibu ed o calci e and
less in ense bands a 226 cm
1
, 294 cm
1
, and 410 cm
1
a ibu ed o hema i e [
39
,
40
]. B oad bands
a 355 and 464 cm
1
ela ed o qua z a e also obse ed. The b oad band iden i ied in he egion o
1150–1450 cm
1
is a ibu ed o an o ganic compound, bu due o he low quali y o he spec um,
i was di icul o iden i y (Figu e 8b).
In a ed spec oscopy (FTIR) analysis was pe o med in o de o iden i y he o ganic compound
de ec ed by Raman spec oscopy. FTIR spec a show bands a 2864 cm
1
, 2514 cm
1
, 1794 cm
1
,
1428 cm
1
, 871 cm
1
, and 711 cm
1
a ibu ed o calci e and bands a 1027 cm
1
, 642 cm
1
and
528 cm
1
a ibu ed o he hema i e ( ed ea h pigmen ) (Figu e 9a) [
41
–
43
]. Ne e heless, he s ong
abso p ion o he ino ganic phases hides he signal o he o ganic compound, hinde ing i s iden i ica ion.
To imp o e he FTIR signal o he o ganic componen , an ex ac ion was conduc ed using 200
µ
L o
dichlo ome hane. The esul ed supe na an was e apo a ed on a po assium b omide disk o be hen
analysed. The in ense bands de ec ed a 2955 cm
1
, 2916 cm
1
, 2848 cm
1
, 1736 cm
1
, and 1472 cm
1
we e a ibu ed o beeswax o ganic compound (Figu e 9b) [43].
8. Appendices: Published and Submi ed Wo ks
191
Mine als 2020,10, 311 10 o 16
Figu e 8.
Raman spec oscopy o he bulk ac ion o he pigmen ed laye o he cis e n plas e .
(
a
) Raman spec a showing he highes in ensi ies bands o calci e, hema i e, and qua z. (
b
) Raman
spec a showing an o ganic compound in he egion o 1150–1450 cm
1
. Calci e bands a 282 cm
1
,
712 cm
1
, and 1087 cm
1
; hema i e bands a 226 cm
1
, 294 cm
1
, and 410 cm
1
; qua z bands a
355 cm1and 464 cm1.
Figu e 9.
Fou ie ans o m in a ed spec oscopy (FTIR) analysis o he pigmen ed laye o he cis e n
plas e . (
a
) FTIR spec a showing he highes in ensi ies bands o calci e and hema i e ( ed ea h).
(
b
) FTIR spec a showing he highes in ensi ies bands o he o ganic compound iden i ied as beeswax.
Calci e bands a 2864 cm
1
, 2514 cm
1
, 1794 cm
1
, 1428 cm
1
, 871 cm
1
, and 711 cm
1
; hema i e ( ed
ea h) bands a 1027 cm
1
, 642 cm
1
, and 528 cm
1
. Beeswax bands a 2955 cm
1
, 2916 cm
1
, 2848 cm
1
,
1736 cm1, and 1472 cm1.
5. Discussion
Pe ologicals udysugges saca e ulp ocessinbo h hemo a manu ac u eandmo a applica ion
echnique o he cis e n cons uc ion acco ding o he speci ic cha ac e is ics needed o his s uc u e.
The impe meabili y o he cis e n ank is an essen ial equi emen o app op ia e wa e s o age.
Mo a impe meabili y is s ic ly ela ed o mo a hyd aulici y, which is a ou ed by he use o
silico-aluminous agg ega es wo king as eac i e ma e ials in he mix u e [
8
,
10
–
13
]. The use o
silico-aluminous ocks and ce amic agmen s as agg ega es in he ank mo a manu ac u e, ins ead
o he ca bona ed agg ega es used o he aul mo a s, indica es a delibe a e selec ion o agg ega es
in o de o con e hyd aulici y o he mo a o ob ain wa e p oo mo a s. Fu he mo e, he use o
silico-aluminous agg ega es adds g ea e cohesion and mechanical s eng h o he mo a [44,45].
The aw ma e ials ha we e used as agg ega es o manu ac u e bo h he lime mo a s om he
aul and cis e n ank co espond o he su ounding geological ma e ials. No only he selec ion
o agg ega es was impo an bu also he agg ega e so ing. The g ain size o agg ega es in he
Applied Mine alogy in he S udy o His o ical Lime Mo a s
192

Mine als 2020,10, 311 11 o 16
ank mo a s becomes smalle and be e so ed om he i s laye o he s uc u al mo a owa d
he ou e mos pigmen ed laye o he plas e . Besides, agg ega e size also con ibu es o ma e ial
eac i i y, since he smalle he size, he highe he speci ic su ace a ea and hus he highe he eac ion
a e [
8
,
46
–
48
]. Fu he mo e, mo a po osi y is lowe in mo a s wi h be e -so ed agg ega es since
hey p oduce a be e -packed sys em [49–52].
Themine alogical analyses allowed iden i ying addi i es in he pigmen edlaye . TheXRD, Raman,
and FTIR analyses indica e ha hema i e was used as an ino ganic addi i e, which led o he eddish
colou o he pigmen ed laye (Figu es 5,8and 9). Hema i e would no be ela ed o ce amic agmen s,
since hey we e no obse ed ei he in he pe og aphic s udy o by XRD (Figu es 4 and 5d). The e o e,
he hema i e may ha e been delibe a ely added. FTIR analyses allowed iden i ying he beeswax as
he o ganic addi i e in he pigmen ed laye (Figu e 9). Beeswax was he mos common na u al wax
used as an o ganic addi i e o p o ide impe meabili y and sealing p ope y o he ma e ials [
53
].
Since o ganic compounds a e mo e suscep ible o deg ada ion han ino ganic compounds, knowledge
o he composi ion o ancien addi i es is essen ial o app op ia e in e en ions on a chaeological
s uc u es [53,54].
The e o e, o ensu e he impe meabili y o he cis e n ank, a mul ilaye applica ion o di↵e en
mo a s was pe o med using silico-aluminous agg ega es and dec easing hei g ain size om he i s
laye o he s uc u al mo a owa d he inne laye and applying a inal plas e wi h a beeswax-bea ing
pigmen ed laye (Figu e 10).
Figu e 10.
Schema ic image o he mul ilaye applica ion echnique o mo a s in Amaiu Cas le
cis e n. The cis e n ank is shown in g een, he aul lune e is shown in blue, he ba el aul is shown
in yellow, and he 14 h–15 h cen u ies wall is shown in black.
Fu he mo e, he eac ion zones obse ed in dolomi ic agg ega es esul ed om he
dedolomi iza ion o dolomi ic agg ega es, and he p esence o hyd o alci e in he binde has been
ela ed o he use o he adi ional ho -mixing me hod in mo a manu ac u e [
23
]. In he manu ac u e
o cis e n ank mo a s, he use o his adi ional ho -mixing me hod would also be expec ed since
eac ion zones we e no only obse ed a he edge o he dolomi ic agg ega es, bu hey also s and ou
in he ce amic agmen s and some silico-aluminous agg ega es (Figu e 4a–d).
8. Appendices: Published and Submi ed Wo ks
193
Mine als 2020,10, 311 12 o 16
Qua z and phyllosilica es a e a ibu ed o he ce amic agmen s and silico-aluminous ocks
used as agg ega es, whe eas magnesium calci e, hyd o alci e, and amesi e a e mine al phases o med
du ing mo a manu ac u e (Figu e 5). Magnesium calci e is o med in he se ing o mo a as a esul
o he lime cycle [
24
,
55
], and hyd o alci e is a ca bona ed mine al o med du ing he slaking p ocess in
he p esence o a ailable magnesium con en [28].
Hyd o alci e has been iden i ied in all analysed mo a binde s (Figu e 5). Magnesium eleased
om he dedolomi iza ion p ocess, leading o he o ma ion o he eac ion zone in he edge o dolomi ic
agg ega es, and he aluminium eleased om he b eakdown o phyllosilica es a ou s he o ma ion
o hyd o alci e [
23
,
56
–
58
]. Ne e heless, some amoun o magnesium and aluminium can also come
om he lime used o he mo a manu ac u e when impu e limes ones o pa ially dolomi ized
limes ones ha e been used as he aw ma e ial o lime p oduc ion [
28
,
59
]. The e o e, he p esence o
hyd o alci e and he absence o dolomi ic agg ega es in he pigmen ed laye o plas e (Figu es 4and 5)
would indica e he use o impu e limes ones o pa ially dolomi ized limes ones o he p oduc ion o
lime o he cis e n cons uc ion.
The aluminosilica e phases p esen in he silico-aluminous agg ega es o he ank mo a s a e
highly eac i e ma e ials ha in he p esence o alkalis eac wi h wa e , o ming a wide amily o
hyd a ion p oduc s ha induce hyd aulic p ope ies o he mo a s [
8
,
15
,
46
]. Reac ion zones obse ed
in he edge o he silico-aluminous agg ega es sugges he de elopmen o his eac ion (Figu e 4b–d).
The eac ion be ween aluminosilica e phases and an alkaline solu ion is known as an alkali-silica e
eac ion (ASSR), which is a speci ic ype o alkali-silica eac ion (ASR) [60–62].
Amesi e has been he only aluminosilica e hyd a ed phase de ec ed in he ank mo a s.
This mine al phase has also been desc ibed in some mo a s wi h pozzolanic agg ega es [
48
,
63
].
Amesi e is a magnesium aluminosilica e hyd a e (M-A-S-H) phase, and al hough i is chemically
ela ed o chlo i es, i displays a simila s uc u e o se pen ine wi h al e na ing e ahed al and
ioc ahed al laye s [
37
]. The amesi e has only been de ec ed in samples con aining silico-aluminous
agg ega es, indica ing ha i would ha e o med as a esul o he eac ion be ween he aluminosilica e
phases and he pu y alkalis.
Magnesium silica e hyd a e (M-S-H) phases ha e been desc ibed du ing he hyd a ion o
MgO-bea ing lime ma e ials and o med by he eac ion be ween magnesium and silica e ions [
64
–
66
].
TheM-S-Hphasesshowalaye eds uc u eandha ebeen ela ed opoo lyc ys allinephyllosilica es[
64
,
66
–
69
]. The eac ion zone o he dolomi ic agg ega es o he s uc u al mo a s om Amaiu Cas le
showed he p esence o M-S-H phases, which a e sugges ed as a esul o an ASSR, al hough he
p esence o he M-S-H phases could no be con i med [
23
]. Acco ding o Mackenzie and Bowden [
37
],
amesi e is o med by he subs i u ion o he Si
4+
in he e ahed al laye s and he Mg
2+
in he oc ahed al
laye s by he Al
3+
. The e o e, he amesi e de ec ed in he mo a s om he cis e n ank could also ha e
been o med as a esul o he ASSR, since he kine ic o ma ion o M-A-S-H phases has been desc ibed
as simila o M-S-H phases, inco po a ing aluminium in o he s uc u e [63,70].
Besides, he phases o med as a esul o he eac ion be ween he aluminosilica e phases o he
silico-aluminous agg ega es and he pu y alkalis con ibu e o dec easing he po osi y and he e o e
a ou he wa e p oo ing o he cis e n ank [45,71–73].
The s udy o bo h s uc u al and plas e mo a s om Amaiu Cas le cis e n show pa e ns/ ules in
he mo a manu ac u e acco ding o he speci ic cons uc ion equi emen s, dis inguishing wo kinds
o mo a s wi h agg ega es o di↵e en na u e. Mo a s om he cis e n ank acqui ed hyd aulici y by
he addi ion o silico-aluminous ocks and ce amic agmen s as agg ega es.
6. Conclusions
The s udy o he mo a s om he Amaiu Cas le cis e n has allowed assessing he knowledge
o he mo a manu ac u ing p ocess and he mo a applica ion echniques o ensu e he s uc u e
wa e p oo ing necessa y o he co ec s o age o wa e .
Applied Mine alogy in he S udy o His o ical Lime Mo a s
194
Mine als 2020,10, 311 13 o 16
The cis e n shows h ee ypes o lime mo a s wi h di↵e en composi ional cha ac e is ics ela ed
o he speci ic unc ion wi hin he s uc u e: s uc u al mo a s om he ba el aul , s uc u al mo a s
om he ank, and plas e .
The na u e o he agg ega es used in he manu ac u e o cis e n mo a s was di↵e en , acco ding o
speci ic cons uc ion equi emen s. Ca bona ed agg ega es we e used in he aul mo a and silicious
and silico-aluminous agg ega es in he ank mo a s and plas e , sugges ing he speci ic selec ion o
aw ma e ials.
The aw ma e ials o he su ounding geological ma e ials we e used o he manu ac u e o he
lime mo a s o he cis e n o he Amaiu Cas le.
To con e hyd aulici y o he mo a s o he cis e n ank and achie e he wa e p oo ing o he
s uc u e, ce amic agmen s and silico-aluminous ocks we e used as agg ega es in he manu ac u e.
Besides, he eac ion zones on he edge o silico-aluminous ocks and ce amic agg ega es esul ed
om an alkali silica e eac ion (ASSR) ha a ou ed he o ma ion o amesi e, he magnesium
aluminosilica e hyd a ed (M-A-S-H) phase de ec ed in he binde o he ank mo a s.
A mul ilaye ing applica ion echnique was pe o med in he cons uc ion o he cis e n ank.
Two/ h ee laye s ha e been di↵e en ia ed in he s uc u al mo a om he ank, wi h a dec ease in
g ain size and an imp o emen in so ing o agg ega es om he inne pa o he ou e pa . The plas e
is o med by wo laye s: an inne laye and an ou e pigmen ed laye .
The pigmen ed laye o plas e is composed by wo ypes o addi i es. Hema i e was iden i ied
as an ino ganic addi i e gi ing ise o he eddish colou o he laye . Addi ionally, beeswax was
iden i ied as an o ganic addi i e used o con e impe meabili y o he pigmen ed laye .
The p esence o hyd o alci e and he absence o dolomi ic agg ega es in he pigmen ed laye
poin o he use o impu e limes ones o pa ially dolomi ized limes ones as he aw ma e ial o he
p oduc ion o lime a Amaiu Cas le.
Au ho Con ibu ions:
Concep ualiza ion, G.P.-A., M.C.Z. and L.A.O.; Da a Cu a ion, G.P.-A. and M.C.Z.;
W i ing—O iginal D a P epa a ion, G.P.-A.; W i ing—Re iew and Edi ing, G.P.-A., M.C.Z.; Funding Acquisi ion,
L.A.O. and J.A.M. All au ho s ha e ead and ag eed o he published e sion o he manusc ip .
Funding: This esea ch was unded by he IT1193-13 p ojec o he Basque Go e nmen .
Acknowledgmen s:
G.P.-A. acknowledges he PhD esea ch g an o he Basque Go e nmen 2015-1-02-35.
The au ho s would like o hank Pe e Smi h o e iewing he use o English in he manusc ip .
Con lic s o In e es : The au ho s decla e no con lic o in e es .
Re e ences
1.
Cadogan, G. Wa e managemen in Minoan C e e, G eece: The wo cis e ns o one Middle B onze Age
se lemen . Wa e Sci. Technol. Wa e Supply 2007,7, 103–112. [C ossRe ]
2.
Angelakis, A.N.; Spy idakis, D.S. Wa e supply and was ewa e managemen aspec s in Ancien G eece.
Wa e Sci. Technol. Wa e Supply 2010,10, 618–628. [C ossRe ]
3.
Angelakis, A.N.; Mays, L.W.; Kou soyiannis, D.; Mamassis, N. E olu ion o Wa e Supply h ough he Millennia;
IWA Publishing: London, UK, 2012.
4.
Ca ion,A.; Fo mnes,A. Unde g oundmedie al wa e dis ibu ion ne wo kin a Spanish own. Tunn. Unde g .
Space Technol. 2016,51, 90–97. [C ossRe ]
5.
Mays, L.; An oniou, G.P.; Angelakis, A.N. His o y o Wa e Cis e ns: Legacies and Lessons. Wa e
2013
,5,
1916–1940. [C ossRe ]
6.
Van Hees, R.P.J.; Binda, L.; Papayianni, I.; Toumbaka i, E. Cha ac e isa ion and damage analysis o old
mo a s. Ma e . S uc . 2004,37, 644–648. [C ossRe ]
7.
S e anidou, M.; Pach a, V.; Konopissi, S.; Ka kadelidou, F.; Papayianni, I. Analysis and cha ac e iza ion o
hyd aulic mo a s om ancien cis e ns and ba hs in G eece. Ma e . S uc . 2014,47, 571–580. [C ossRe ]
8.
Rizzo, G.; E coli, L.; Megna, B.; Pa lapiano, M. Cha ac e iza ion o mo a s om ancien and adi ional
wa e supply sys ems in Sicily. J. The m. Anal. Calo im. 2008,92, 323–330. [C ossRe ]
8. Appendices: Published and Submi ed Wo ks
195
Mine als 2020,10, 311 14 o 16
9.
Hen y, A.; S ewa , J. P ac ical Building Conse a ion: Mo a s, Rende s & Plas e s; P ac ical Building
Conse a ion Se ies; English He i age: Su ey, UK, 2011.
10.
Ba onio, G.; Binda, L. S udy o he pozzolanici y o some b icks and clays. Cons . Build. Ma e .
1997
,11,
41–46. [C ossRe ]
11.
Ba onio, G.; Binda, L.; Lomba dini, N. The ole o b ick pebbles and dus in conglome a es based on hyd a ed
lime and c ushed b icks. Cons . Build. Ma e . 1997,11, 33–40. [C ossRe ]
12.
S e anidou, M.; Papayianni, I. The ole o agg ega es on he s uc u e and p ope ies o lime mo a s.
Cem. Conc . Compos. 2005,27, 914–919. [C ossRe ]
13.
A izzi, A.; Cul one, G. Ae ial lime-based mo a s blended wi h a pozzolanic addi i e and di↵e en
admix u es: A mine alogical, ex u al and physical-mechanical s udy. Cons . Build. Ma e .
2012
,31, 135–143.
[C ossRe ]
14.
Mi iello, D.; Bloise, A.; C isci, G.M.; De Luca, R.; De Nig is, B.; Ma ellone, A.; Osannac, M.;
Paced, R.; Peccia, A.; Ruggie i, N. New composi ional da a on ancien mo a s and plas e s om
Pompeii (Campania-Sou he n I aly): A chaeome ic esul s and conside a ions abou hei ime e olu ion.
Ma e . Cha ac . 2018,146, 189–203. [C ossRe ]
15.
Walke , R.; Pa
í
a, S. Physical p ope ies and eac i i y o pozzolans, and hei in luence on he p ope ies o
lime–pozzolan pas es. Ma e . S uc . 2011,44, 1139–1150. [C ossRe ]
16.
Bonazza, A.; Cian elli, C.; Sa della, A.; Pecchioni, E.; Fa oni, O.; Na ali, I.; Sabbioni, C. Cha ac e iza ion o
hyd aulic mo a s om a chaeological complexes in Pe a. Pe iod. Mine al. 2014,82, 459.
17.
Rampazzi, L.; Colombini, M.P.; Con i, C.; Co i, C.; Llu e as-Teno io, A.; Sansone i, A.; Zanaboni, M.
Technology o medie al mo a s: An in es iga ion in o he use o o ganic addi i es. A chaeome y
2016
,58,
115–130. [C ossRe ]
18.
Gal
á
nP
é
ez, E.; Ga c
í
a de Domingo, A.; Cab a Gil, A.; Ganz
á
lez Las a, J.; Ma inez To es, L.M.;
Pesque a P
é
ez, A. Memo ia Hoja 66-III (Maya de Baz
á
n). In Mapa Geol
ó
gico de Na a a. E. 1:25000;
Dipu ación Fo al de Na a a: Na a a, Spain, 2002.
19.
Juch, D.; K ausse, H.F.; Mülle , D.; Requad , H.; Scha e , D.; Sole, J.; Villalobos, L. Memo ia Hoja 66 (Maya
del Baz an). In Mapa Geol
ó
gico de España, E. 1:50.000, 1s ed.; Segunda Se ie; MAGNA: Magna D i e Au o a,
ON, Canada, 1974.
20.
AGN. Royal and Gene al A chi e o Na a e. In Rena Pape s; 15/3, 52, Box 33055: 1516; Go e nmen o
Na a e: Pamplona, Spain, 1995.
21.
Sag edo, I. El cas illo de Amaiu a T a
é
s de la His o ia de Na a a; Edi o ial Pamiela A gi ale xea: Pamplona,
Spain, 2009.
22.
Sag edo, I. Na a a. In Cas illos que De endie on el Reino (Tomo I) de Lagua dia a Foix, y del Moncayo al Goie i;
Edi o ial Pamiela A gi ale xea: Pamplona, Spain, 2006.
23.
Ponce-An
ó
n, G.; Zuluaga, M.C.; O ega, L.A.; Mauleon, J.A. Mul i-analy ical app oach o
chemical-mine alogical cha ac e iza ion o eac ion ims in he lime mo a s om Amaiu Cas le (Na a e,
Spain). Mic ochem. J. 2020,152, 104303. [C ossRe ]
24.
Boyn on, R.S. Chemis y and Technology o Lime and Limes one; John Wiley & Sons, Inc.: New Yo k, NY,
USA, 1980.
25. Vica , L.J. Mo a s and Cemen s; Donhead Publishing: Sha esbu y, UK, 1997.
26. Folk, R.L. A compa ison cha o isual pe cen age es ima ion. J. Sedimen . Res. 1951,21, 32–33.
27.
O ega, L.A.; Zuluaga, M.C.; Alonso-Olazabal, A.; Mu elaga, X.; Insaus i, M.; Ibañez-E xebe ia, A. His o ic
lime-mo a 14C da ing o San a Ma
í
a la Real (Za au z, no he n Spain): Ex ac ion o sui able g ain size o
eliable 14C da ing. Radioca bon 2012,54, 23–36. [C ossRe ]
28.
Ponce-An
ó
n, G.; O ega, L.A.; Zuluaga, M.C.; Alonso-Olazabal, A.; Solaun, J.L. Hyd o alci e and
Hyd ocalumi e in Mo a Binde s om he Medie al Cas le o Po illa (
Á
la a, No h Spain): Accu a e
Mine alogical Con ol o Achie e Mo e Reliable Ch onological Ages. Mine als 2018,8, 326. [C ossRe ]
29.
Mills,S.J.; Ch is y,A.G.; G
é
nin,J.-M.R.; Kameda, T.; Colombo,F. Nomencla u eo hehyd o alci esupe g oup:
Na u al laye ed double hyd oxides. Mine al. Mag. 2012,76, 1289–1336. [C ossRe ]
30.
Bakolas, A.; Biscon in, G.; Mo opoulou, A.; Zend i, E. Cha ac e iza ion o s uc u al byzan ine mo a s by
he mog a ime ic analysis. The mochim. Ac a 1998,321, 151–160. [C ossRe ]
31.
Paama, L.; Pi känen, I.; Rönkkömäki, H.; Pe ämäki, P. The mal and in a ed spec oscopic cha ac e iza ion o
his o ical mo a s. The mochim. Ac a 1998,320, 127–133. [C ossRe ]
Applied Mine alogy in he S udy o His o ical Lime Mo a s
196
Bo om igh , masons manu ac u ing a mo a . A de ail om Cons uc ion du Temple de
Jé usalem pa o d e de Salomon., In: An iqui és judaïques de Fla ius Josèphe. Biblio hèque
Na ionale de F ance, Pa is. Ms 247, ol.163 . Jean Fouque , 1470-1475.

This PhD hesis has been accomplished wi h he esea ch g an om he Basque Coun y Go e nmen
PRE-2015-1-0235 in he Depa men o Mine alogy and Pe ology o he Uni e si y o he Basque
Coun y (UPV/EHU) unde he supe ision o D Ma ia C uz Zuluaga and D Luis Angel O ega.
The conse a ion and es o a ion o monumen s mus ha e ecou se o all he
sciences and echniques which can con ibu e o he s udy and sa egua ding o
he a chi ec u al he i age.
A icle 2. Venice Cha e , 1964