1
In-si u analy ical s udy o b icks exposed o 1
ma ine en i onmen using Hand-Held X- ay 2
luo escence spec ome y and ela ed 3
labo a o y echniques 4
5 Héc o Mo illasa*, C is ina Ga cía-Flo en inoa, Ike Ma caidaa, 6 Mai e Magu eguib, Go ka A anaa, Luis F.O. Sil ac and Juan Manuel Mada iagaa
7
8 aDepa men o Analy ical Chemis y, Facul y o Science and Technology, Uni e si y o he Basque 9 Coun y UPV/EHU, P.O. Box 644, 48080 Bilbao, Basque Coun y, Spain 10 e-mail: hec o [email p o ec ed]s11 bDepa men o Analy ical Chemis y, Facul y o Pha macy, Uni e si y o he Basque Coun y UPV/EHU,12 P.O. Box 450, 01080 Vi o ia-Gas eiz, Basque Coun y, Spain13 cResea ch G oup in En i onmen al Managemen and Sus ainabili y, Facul y o En i onmen al Sciences,14 Uni e sidad De La Cos a, Calle 58 #55-66, 080002 Ba anquilla, A lán ico, Colombia15
16 ABSTRACT 17
18 In his wo k, he deg ada ion p ocesses ha ake place in b icks exposed o ma ine 19
en i onmen s ha e been s udied. Taking in o accoun he impo ance o his building 20
ma e ial whe e he silica es p esen in he inal p oduc ac as s abilize in he po ous 21
ma e ial i sel , i is necessa y o unde s and he decay p ocesses ha occu in hese 22
agg essi e en i onmen s. As is known, he ma ine ae osol ca ies di e en ypes o sal s, 23
such as chlo ides, sul a es, ni a es, e c., p esen in su ounding en i onmen exe ing a 24
nega i e in luence on he ma e ials p oducing c acking and disin eg a ion p ocesses o 25
he ma e ial and consequen ly loss o b ick wall s abili y. Nowadays he de elopmen o 26
po able de ices is aking much mo e impo ance helping esea che s o esol e p oblems 27
in he ield in a as and easy way. In o de o ex ac as and sa is ac o y esul s abou 28
he conse a ion s a e o di e en b icks om Pun a Begoña Galle ies (Ge xo, Basque 29
Coun y, Spain), an in-si u analy ical me hodology was de eloped based on he use o 30
hand-held Ene gy Dispe si e X- ay luo escence spec ome y (HH-ED-XRF) assis ed 31
wi h o he labo a o y echniques (µ-ED-XRF and X-Ray Di ac ion) in o de o 32
co obo a e and complemen he in o ma ion ob ained in-si u. This cons uc ion 33
unde goes he in luence o ma ine ae osol, indus ial po , powe gene a ion plan s, and 34
a uel e ine y among o he s. The pa hologies isually obse able in hese b icks a e 35
disin eg a ion, b eakup and de achmen o he b icks. The p esence o de e io a ion 36
compounds in he b icks has been s udied acco ding o he o ien a ions o he b icks inside 37
he cons uc ion. 38
This is he accep ed manusc ip o he a icle ha appea ed in inal o m in Spec ochimica Ac a Pa B: A omic Spec oscopy 146 : 28-35
(2018), which has been published in inal o m a h ps://doi.o g/10.1016/j.sab.2018.04.020. © 2018 Else ie unde CC BY-NC-ND license
(h p://c ea i ecommons.o g/licenses/by-nc-nd/4.0/)
2
39
Keywo ds: B ick; in-si u analysis; ma ine en i onmen ; HH-ED-XRF, calcium
40
silica e.
41
42
43
1. In oduc ion
44
Since ancien imes, b icks a e some o he mos used ma e ials in cons uc ions. In
45
5,000 BC, he b ick appea ed as building ma e ial, and a ound 3,500 BC, he i ed b ick
46
was inally c ea ed. Thanks o he indus ializa ion in he 19 h cen u y, he use o b ick as
47
building ma e ial inc eased and acqui ed g ea impo ance, being one o he mos used
48
ma e ial o he building cons uc ions [1].
49
B icks used o cons uc ions a e made om clay, which is kneaded wi h 20-25% wa e .
50
The esul ing pas e is molded and he b icks ob ained a e d ied in he ai [2]. Al hough
51
se e al p ocesses o b icks p oduc ion exis , a ious mix u es o aw clays (mainly
52
composed o illi e-chlo i e, qua z, calci e and/o dolomi e, sodium and po assium
53
eldspa s, and i on oxides/hyd oxides) a e i ed a abou 900–1025°C in o de o ob ain
54
he inal b ick [3]. Thei cha ac e is ic eddish-o ange colou , is indica i e o he amoun
55
and ype o i on oxides and oxyhid oxides p esen in he clay used o i s manu ac u e
56
[4]. Howe e , o he chemical elemen s such as Sb, Pb, Ca, Fe and aces o Cu ha e a key
57
ole in he eddish o ange colou o he b icks [5]. In his sense, he composi ion and
58
mic os uc u e o he b icks a e some o he mos impo an cha ac e is ics o p ese e
59
hei du abili y [6, 7]. Mo eo e , he clay mus ha e a low amoun o impu i ies and
60
especially mus ha e a low con en o calcium ca bona e o be plas ic enough, and o
61
a oid he p esence o un eac ed lime a e i ing. The p esence o calcium ca bona e in
62
he b icks can cause c acks when he clay is mixed wi h wa e . Fo his eason, usually
63
he clay mus con ain calcium ca bona e in a p opo ion o less han 8-10%. Du ing i ing,
64
a se ies o mine alogical ans o ma ions ake place depending essen ially on he ini ial
65
composi ion, kiln empe a u e, hea ing g ade, i ing ime and p e alence o oxidizing o
66
educing eac ions [8-10] ede ining he mine alogical composi ion and mic os uc u e.
67
In his way, a e i ing a 900-1025°C, kaolin is dissocia ed in o silica and alumina and
68
also in o calcium and aluminum silica e. One o he c i ical ac o s in he conse a ion
69
s a e o b icks is he con en o calcium silica e ha p o ides s abili y o he s uc u e and
70
3
esis ance o empe a u e changes. Consequen ly, he b icks i e o cooking empe a u e
71
is es ablished as one o he mos impo an s eps in he b icks cons uc ion [11, 12].
72
B icks, as all building ma e ials, can expe imen di e en chemical eac ions ha could
73
p omo e changes in hei appea ance and conse a ion s a e. B icks can su e he e ec
74
o humidi y [13,14], biocoloniza ions [15], he a ack o a mosphe ic acidic gases [16],
75
in il a ions by aqueous solu ions [17-19], he impac o ma ine ae osols [20, 21], d y and
76
we deposi ions [22-24], eeze- haw cycles [25], e c. These sou ces o de e io a ion, can
77
p omo e se e al chemical and physical p oblems as well as e lo escences o ma ion [17],
78
loss o ma e ial [26], e c.
79
In he li e a u e, he e a e many wo ks ha analyze b icks in o de o ex ac conclusions
80
abou hei conse a ion s a e [27, 28], he p o enance [29], o iginal composi ion [30],
81
he b ick composi ion in luence on decay compounds [31], e c. Mo eo e , di e en
82
echniques such as X-Ray di ac ion (XRD) [32], Raman spec oscopy [33, 1, 19],
83
in a ed spec oscopy [34, 35], Induc i ely Coupled Plasma Mass Spec ome y (ICP-
84
MS) [36], Lase abla ion Induc i ely Coupled Plasma Mass spec ome y (LA-ICP-MS)
85
combined wi h Ins umen al Neu on Ac i a ion Analysis (INAA) and X- ay
86
luo escence (XRF) [37], XRF [38] and Lase -induced b eakdown spec oscopy (LIBS)
87
[39], ha e been used o ca y ou hese ypes o analyses. In all hese case s udies, he
88
analy ical ins umen s used we e labo a o y bench op de ices and he e a e no wo ks ha
89
use hand-held/po able ins umen s o analyze b icks and o e alua e hei pa hologies.
90
Some imes he ex ac ion o samples is a c i ical s ep, mainly due o sampling es ic ions.
91
Fo his eason, he applica ion o po able de ices is aking much mo e impo ance,
92
helping esea che s o ca y ou di e en in-si u analyses ob aining sa is ac o y esul s
93
wi hou he necessi y o aking samples [40-42, 18]. Example o hese ypes o de ices
94
a e he hand-held Ene gy Dispe si e X-Ray luo escence spec ome e s (HH-ED-XRF),
95
o which i s use is being inc eased in he las yea s, because hey a e use iendly and
96
o e esul s in ew seconds o minu es [43-45]. As a consequence o his, many
97
wo ldwide scien i ic g oups a e imp o ing and de eloping new analy ical me hodologies
98
based on hese kind o de ices [46, 47].
99
In his wo k, a simple, as and non-des uc i e me hodology based on he use o a hand-
100
held Ene gy Dispe si e X- ay luo escence spec ome e (HH-ED-XRF) was applied o
101
pe o m a ield analysis o b icks om Pun a Begoña Galle ies (Ge xo, Basque Coun y,
102
Spain) which show di e en de e io a ion deg ees depending mos ly on hei loca ion in
103
4
on o he indus ial po o Bilbao and di e se ac o ies emi ing a mosphe ic pollu an s.
104
In o de o con i m and complemen conclusions ex ac ed in-si u, addi ional analyses
105
we e conduc ed in he labo a o y using mic o-ED-XRF spec ome y and X-Ray
106
di ac ion (XRD) echniques.
107
2. Expe imen al
108
2.1. Pun a Begoña Galle ies
109
110
Pun a Begoña Galle ies a e loca ed in Ge xo, close o E eaga beach, in Biscay (Basque
111
Coun y, Spain). These galle ies we e buil in 1918 by an indus ial ycoon, Ho acio
112
Eche a ie a [48]. I is one o he mos signi ica i e cons uc ion in Biscay and Basque
113
Coun y o he 20 h cen u y. Nowadays, i is abandoned and i is poo ly p ese ed (see
114
Fig. 1). The cons uc ion is composed by wo galle ies: he uppe galle y o “No hwes
115
Galle y” (NG) and he lowe galle y o “Sou hwes Galle y” (SG). The NG is o ien ed o
116
he no hwes , and he SG is o ien ed o he sou hwes . All he cons uc ion is placed in
117
on o he sea; he e is a beach in on o he NG and a leisu e po in on o he SG,
118
oge he wi h he indus ial po o Bilbao a 1-8 km and se e al ac o ies ( e ine y, powe
119
s a ion plan o liquid hyd oca bons, and me allu gical companies), emi ing acid gases
120
and me allic pa icles o he a mosphe e, a no mo e han 10 km om he building. The
121
whole building is made by di e en ma e ials such as conc e e, ce amic, mo a , cemen ,
122
limes one and b ick.
123
2.2. In-si u analyses
124
125
The in-si u analyses we e ca ied ou in bo h galle ies by means o HH-ED-XRF. Fo his
126
pu pose, se en a eas om he No hwes Galle y (coded samples NG1-NG7) and
127
addi ional se en om he Sou hwes Galle y (coded samples SG1-SG7) we e selec ed
128
(see Fig. 1). As can be obse ed in Fig. 1, b icks show a be e o wo se conse a ion s a e
129
depending on he o ien a ion.
130
2.3. Ins umen a ion
131
The in-si u elemen al analysis o he b icks was ca ied ou using an XMET5100 (Ox o d
132
Ins umen s, UK) hand-held ene gy dispe si e X-Ray luo escence spec ome e (HH-
133
ED-XRF). The ins umen is equipped wi h an Rh ube wo king a a maximum ol age o
134
45 kV. The spo size o he emi ed X-Ray beam is 9 mm. The analyze includes a Pel ie -
135
5
cooled silicon d i de ec o (SDD) o high esolu ion ha is able o p o ide an ene ge ic
136
esolu ion o 150 eV (calcula ed o he Mn Kα line). The analyze con ains a PDA o
137
con ol he spec ome e and also o sa e he spec a and semi-quan i a i e in o ma ion.
138
To de e mine he p esence o he hea ies elemen s (Z>Ti) he ol age and cu en o he
139
X-Ray ube was se a 40 kV and 15 µA espec i ely and he spec a we e acqui ed du ing
140
100 seconds ( eal ime) in o de o imp o e he limi o de ec ion o he iden i ica ion o
141
ace elemen s. Addi ionally, o emo e he B emss ahlung and possible B agg
142
di ac ion peaks, a 500 µm Al il e was used. In o de o imp o e he de ec ion o he
143
ligh e elemen s (Z<Ti), addi ional measu emen s we e pe o med wi hou he Al il e
144
and a lowe ol age (13 kV) and highe cu en (40 µA) du ing 70 seconds. In o de o
145
de e mine possible con ibu ions om de ec o ma e ials and possible con amina ions o
146
he XRF analyze window, 20 epe i i e spec a o an ins umen al blank (a PTFE block)
147
we e acqui ed be o e each measu emen s ba ch. Fo he epe i i e measu emen s, he
148
same spec al condi ions ( ol age, cu en , il e and es ime) as hose used o he
149
analysis o he b icks we e conside ed. Al hough he so wa e is based on he use o
150
Fundamen al Pa ame e s quan i ica ion me hods, in his wo k, he ne coun s o Kα lines
151
o each de ec ed elemen in he spec um we e conside ed ollowing a no maliza ion
152
p ocess. See elsewhe e o u he de ails [43]. To ex ac ep esen a i e esul s, en
153
measu emen s (9 mm a ea each one) we e pe o med andomly dis ibu ed on se en a eas
154
om he NG (NG1-NG7) and on addi ional se en om he SG (SG1-SG7). In o de o
155
e alua e he elemen al composi ion o he b icks wi hou ex ac ing any sample, semi-
156
quan i a i e in o ma ion gi en by he HH-ED-XRF was a oided. Ins ead o ha , a
157
speci ic spec al da a ea men based on he no maliza ion o he ne coun s o each
158
de ec ed elemen was conduc ed [43]. Fo all he de ec ed elemen s, ne coun s associa ed
159
wi h Kα line we e conside ed, excep o Pb o which Lβ line was used. Conside ing ha
160
Fe is a majo elemen which showed an almos cons an concen a ion in all he measu ed
161
a eas, i s Fe Kα line was used o no malize he ne coun s o ligh elemen s (Z≤20) in he
162
spec a. Fo he hea ies elemen s (Z ≥ 26), he ne coun s o hei Kα lines we e
163
no malized agains he ne coun s o he Comp on line (incohe en sca e ing). This
164
no maliza ion p ocess was done in o de o co ec possible ma ix e ec s and a ia ions
165
in he posi ioning o he measu ing sampling in e ace. In o de o a oid spec al
166
in e e ences be ween he As K1 and Pb L1 lines, Kβ1 (11.7 keV) and Pb Lβ1 (12.6 keV)
167
lines we e conside ed o As and Pb espec i ely.
168
6
In o de o ex ac mo e conclusions, he elemen al composi ion was also s udied in he
169
labo a o y by using he M4 TORNADO Ene gy Dispe si e X- ay Fluo escence
170
spec ome e (B uke Nano GmbH, Be lin, Ge many). This ins umen is equipped wi h
171
a mic o- ocus side window Rh X- ay ube powe ed by a low-powe HV gene a o and
172
cooled by ai . The spec al acquisi ions in his wo k we e pe o med a he maximum
173
ol age (50 kV) and cu en (600 μA) ha he X- ay sou ce allows. This equipmen can
174
wo k using polycapilla lenses, which allow pe o ming bo h single poin measu emen s
175
down o 25 μm o la e al/spa ial esolu ion, and Hype Maps o de e mine he dis ibu ion
176
o each elemen de ec ed in he collec ed agmen s. A XFlash® silicon d i de ec o wi h
177
30 mm2 sensi i e a ea and ene gy esolu ion o 145 eV o Mn-Kα was used o
178
luo escence adia ion de ec ion. In o de o imp o e he de ec ion o he ligh es elemen s
179
(Z<11), il e s we e no used and measu emen s we e acqui ed unde acuum (20 mba ).
180
The acuum was achie ed wi h a diaph agm pump MV 10 N VARIO-B. The li e ime
181
used o each single poin measu emen was 200 seconds. Two ideo-mic oscopes we e
182
used o ocus he a ea unde s udy, a low magni ica ion (1 cm2 a eas) one o he
183
explo a ion o he sample and a highe magni ica ion one (1 mm2 a eas) o he inal
184
ocusing. In o de o ob ain he Hype Maps, he Kα line o each elemen was used a e a
185
p e ious elemen al assigna ion and decon olu ion o he spec al in o ma ion using he
186
M4 TORNADO so wa e (B uke Nano GmbH, Be lin, Ge many).
187
Finally, XRD analyses we e pe o med wi h a powde di ac ome e PANaly ical X´Pe
188
PRO, equipped wi h a coppe ube (λCuKαmedia= 1.5418 Å, λCuKα1= 1.54060 Å, λCuKα2=
189
1.54439 Å), e ical goniome e (B agg-B en ano geome y), p og ammable di e gence
190
ape u e, au oma ic in e change o samples, seconda y monoch oma o om g aphi e and
191
PixCel de ec o . The measu emen condi ions we e 40 kV and 40 mA, wi h an angula
192
ange (2θ) scanned be ween 5 and 70°. Fo he da a ea men o he di ac og ams and
193
he iden i ica ion o he p esen mine al phases, he speci ic so wa e X`Pe HighSco e
194
(PANaly ical) in combina ion wi h he speci ic powde di ac ion ile da abase
195
(In e na ional Cen e o Di ac ion Da a - ICDD, Pennsyl ania, USA) was used.
196
197
7
198
Fig. 1. Pun a Begoña Galle ies (Ge xo, Basque Coun y, no h o Spain) and he analyzed
199
b ick a eas om hei No hwes and Sou hwes Galle ies (NG and SG).
200
201
202
3. Resul s and discussion
203
204
3.1. HH-ED-XRF analyses
205
To simpli y he isualiza ion o he no malized a eas ela ed o he a e age o he 10
206
spec al measu emen s om each s udied a ea, hey a e p esen ed as a ba g aph (see Fig.
207
2). In Table S1 om Appendix, he no malized coun s o all he elemen s de ec ed in he
208
measu ed a eas a e p esen ed as he a e age o he en epe i i e measu emen s on each
209
a ea oge he wi h hei espec i e s anda d de ia ions. Among all he de ec ed elemen s,
210
Cl, B and S can be p esen in he b ick coming om he ma ine ae osol [48-50]. The
211
las elemen could be also na u ally p esen in he b icks. As i has been explained in he
212
8
expe imen al sec ion, o a oid alse posi i es he backg ound o e ed by he ins umen
213
(ins umen al blank) was e alua ed. This issue can be conside ed o special in e es
214
conside ing he in e e ence caused by he Rh L coming om he ube in he Cl K line.
215
The no malized coun s o Cl, B and S o all he a eas in he NG and SG a e qui e simila
216
(see Fig. 2A), al hough a li le bi highe alues we e egis e ed in some measu ed a eas
217
om he SG.
218
In all he analyzed a eas, S was also de ec ed. The p esence o his elemen in he b icks
219
could sugges he possible p esence o sul a es. These compounds can be p esen in he
220
b icks due o he in luence o in il a ion wa e s ich in sul a es o as a consequence o
221
he impac o a mosphe ic SOx. Calcium ca bona e ha can be p esen on hem can eac
222
wi h he sul a es in he i s case and wi h he H2SO4 coming om he a mosphe ic SOx.
223
S no malized coun s alues a e highe in he SG han in he NG, excep o he case o
224
NG1 and NG7 a eas.
225
Apa om elemen s ha can be p esen in he b icks due o he in luence o he
226
su ounding a mosphe e, hose ela ed wi h he o iginal composi ion we e also e alua ed.
227
In Fig. 2B, he no malized coun s o hese kind o elemen s (Al, Si, K, Ca and Fe) a e
228
p esen ed. The no malized coun s o Al and Si a e qui e simila excep o he NG7 a ea,
229
whe e a li le bi highe alues we e egis e ed. The p esence o bo h elemen s in he
230
b icks is ela ed wi h he con en o silica es and aluminosilica es on hem. The esul s
231
ob ained o K a e qui e simila , e ealing simila no malized coun s alues in all he
232
a eas, excep in he NG1 a ea, which shows highe alues han he es o he a eas.
233
Acco ding o Ca, he highes alues we e egis e ed in he SG, al hough in he NG high
234
alues we e also ob ained o he NG1 and NG7 a eas, as i happened o Ca. As has been
235
p e iously men ioned, he p esence o Fe is qui e simila in all he measu ed a eas. This
236
elemen is ela ed wi h he p esence o i on oxides and oxy-hyd oxides in he b icks,
237
compounds ha gi e he cha ac e is ic o ange- ed colo o he analyzed b icks.
238
The no malized coun s o Ti, V, C , Mn, Ni, Cu, Zn and Pb a e p esen ed in Fig. 2C. Ti,
239
V, C and Mn show in e e ence once wi h each o he ’s. Thus, hese in e e ences could
240
al e he conclusions ha can be ex ac ed analyzing he no malized coun s. Lea ing aside
241
his obse a ion, he no malized coun s o each elemen is simila in all he analyzed
242
a eas, sugges ing ha he main con ibu ion o hese me als come om he na u al aw
243
ma e ial i sel . This endency was no obse ed o Pb. In his case, highe no malized
244
9
coun s we e ob ained in he a eas om NG han in a eas om SG; pa icula ly, his
245
elemen was no iden i ied in he SG2 a ea. This obse a ion could sugges a possible
246
deposi ion o Pb coming om he su ounding a mosphe e, especially in he b icks om
247
he NG a ea. I is necessa y o ema k ha he e a e me allu gical indus ies om he
248
me opoli an Bilbao, no a away om he Galle ies, and hey con ibu e o emissions o
249
me allic pa icles, being possible hei subsequen d y deposi ion [22, 23, 45].
250
Finally, o he es o he de ec ed elemen s (see Fig. 2D) he ob ained alues we e simila
251
in all he measu ed a eas excep o Z and Sn. The no malized coun s o Z a e simila
252
in all he a eas, excep in NG7 a ea, whe e he e is no p esence o his elemen . Finally,
253
i is necessa y o ema k ha Sn was de ec ed in all he NG a eas bu only in ew a eas
254
om he SG was de ec ed (SG5 and SG7)
255
256
257
Fig. 2. Ba cha s ep esen ing he loga i hm o he no malized a eas ela ed o he a e age
258
o he 10 spec al measu emen s ob ained wi h HH-ED-XRF on each measu ed a ea
259
oge he wi h hei e o ba s o A) S, Cl, B and S ; B) Al, Si, K, Ca, Fe; C) Ti, Ni, Cu,
260
Zn, Pb and D) Rb, Y, Z and Sn.
261
3.2. P incipal Componen Analysis (PCA) o in-si u ED-XRF esul s
262
In o de o ex ac addi ional conclusions, he da a ma ix (no malized coun s o NG and
263
SG a eas, 14 a eas x 10 analysis each) was subjec ed o P incipal Componen Analysis
264
16
Acknowledgemen s
429
This wo k has been unded by he Spanish Minis y o Economy, Indus y and
430
Compe i i eness and he Eu opean Regional De elopmen Fund (ERDF/FEDER),
431
h ough he p ojec MADyLIN (G an No. BIA2017-87063-P, AEI-EU/FEDER) and by
432
he coope a ion ag eemen be ween he Uni e si y o he Basque Coun y (UPV/EHU)
433
and he Ci y Council o Ge xo (OTRI2014-0639). Technical suppo p o ided by Gene al
434
X- ay Se ice o he SGIKe (UPV/EHU, Minis y o Economy and Compe i i eness o
435
Spain, Basque Go e nmen , ERDF and Eu opean Social Fund) is also g a e ully
436
acknowledged.
437
438
Appendix A. Supplemen a y da a
439
Supplemen a y da a o his a icle can be ound online a DOI:..
440
441
442
443
Re e ences
444
[1] M. Magu egui, A. Sa mien o, R. Esc ibano, I. Ma inez-A ka azo, K. Cas o, J.M.
445
Mada iaga, Raman spec oscopy a e accele a ed ageing es s o assess he o igin o some
446
decayed p oduc s ound in eal his o ical b icks a ec ed by u ban pollu ed a mosphe es,
447
Anal. Bioanal. Chem. 395 (2009) 2119-2129.
448
[2] A. Angiolani, In oducción a la química Indus ial. Fundamen os químicos y
449
ecnológicos. Edi . And es Bello. San iago de Chile, Chile, 1960.
450
[3] A. Viani, K. So i iadis, A. Len, P. Šašek, R. Še čík, Assessmen o i ing condi ions
451
in old Fi ed-clay b icks: The con ibu ion o X- ay powde di ac ion wi h he Rie eld
452
me hod and small angle neu on sca e ing, Ma e . Cha ac . 116 (2016) 33-43.
453
[4] R. K eimeye , Some No es on he Fi ing Colo o Clay B icks, Appl. Clay Sci. 2
454
(1987) 175-183.
455
17
[5] P. Holakooei, A mul i-spec oscopic app oach o he cha ac e iza ion o ea ly glaze
456
opaci ie s: S udies on an Achaemenid glazed b ick ound a Susa, sou h-wes e n I an
457
(mid- i s millennium BC), Spec ochim. Ac a A 116 (2013) 49-56.
458
[6] G. Cul one, I. Sid aba, E. Sebas ián, Mine alogical and physical cha ac e iza ion o
459
he b icks used in he cons uc ion o he “T iangul bas ion”, Riga (La ia), Appl.Clay
460
Sci. 28 (2005) 297–308.
461
[7] K. Ele , G. Cul one, C. Rod iguez Na a o, E. Sebas ián, Du abili y o b icks used
462
in he conse a ion o his o ic buildings—in luence o composi ion and mic os uc u e,
463
J. Cul . He i . 4 (2003) 91–99.
464
[8] R. Fo , M. Al a ez de Bue go, M.C. López de Azcona, F. Minga o, M.J. Va as, J.
465
So iano, Ca ac e ización de la Fáb ica de Lad illo del Palacio del In an e Don Luis,
466
Boadilla del Mon e, Mad id, Bol. Soc. Esp. Ce am. Vid io 43 (2004) 578-582.
467
[9] M. Magge i, Phase Analysis and i s Signi icance o Technology and O igin, J.S.
468
Olin, A.D. F anklin (Eds.), A chaeological Ce amics, Smi hsonian Ins i u ion P ess,
469
Washing on D.C (1982), pp. 121-133.
470
[10] L. Ma i an, L. Noda i, C. Mazzoli, A. Milano, U. Russo, In luence o i ing
471
condi ions on ce amic p oduc s: expe imen al s udy on clay ich in o ganic ma e , Appl.
472
Clay Sci. 31 (2006) 1-15.
473
[11] B. Bauluz, M.J. Mayayo, A. Yus e, C. Fe nandez-Nie o, J.M. Gonzalez Lopez, TEM
474
s udy o mine al ans o ma ions in i ed ca bona ed clays: ele ance o b ick making,
475
Clay Mine . 39 (2004) 333–344.
476
[12] G. Cul one, E. Sebas ián, K. Ele , M.J. de la To e, O. Cazalla, C. Rod iguez-
477
Na a o, In luence o mine alogy and i ing empe a u e on he po osi y o b icks, J. Eu .
478
Ce am. Soc. 24 (2004) 547–564.
479
[13] H. Mo illas, M. Magu egui, O. Gómez-Lase na, J. T ebolazabala, J.M. Mada iaga,
480
Cha ac e isa ion and diagnosis o he conse a ion s a e o cemen i ious ma e ials
481
exposed o he open ai in XIX cen u y ligh houses loca ed on he coas o he Basque
482
Coun y: The case o Igueldo ligh house, San Sebas ian, No h o Spain, J. Raman
483
Spec osc. 43 (2012) 1630-1636.
484
18
[14] H. Mo illas, M. Magu egui, O. Gómez-Lase na, J. T ebolazabala, J.M. Mada iaga,
485
Could ma ine ae osol con ibu e o de e io a e building ma e ials om in e io a eas o
486
ligh houses? An answe om he analy ical chemis y poin o iew, J. Raman Spec osc.
487
44 (2013) 1700–1710.
488
[15] H. Mo illas, M. Magu egui, I. Ma caida, J. T ebolazabala, I. Salcedo, J.M.
489
Mada iaga, Cha ac e iza ion o he main colonize and biogenic pigmen s p esen in he
490
ed bio ilm om La Galea Fo ess sands one by means o mic oscopic obse a ions and
491
Raman Imaging, Mic ochem. J. 121 (2015) 48–55.
492
[16] A. Sa mien o, M. Magu egui, I. Ma inez-A ka azo, M. Angulo, K. Cas o, M.A.
493
Olazabal, L.A. Fe nandez, M.D. Rod iguez-Laso, A.M. Mujika, J. Gomez, J.M.
494
Mada iaga, Raman spec oscopy as a ool o diagnose he impac s o combus ion and
495
g eenhouse acid gases on p ope ies o Buil He i age, J. Raman Spec osc. 39 (2008)
496
1042-1049.
497
[17] H. Mo illas, M. Magu egui, J. T ebolazabala, J.M. Mada iaga, Na u e and o igin o
498
whi e e lo escence on b icks, a i icial s ones and join mo a s o mode n houses
499
e alua ed by po able Raman spec oscopy and labo a o y analyses, Spec ochim. Ac a A
500
136 (2015) 1195-1203.
501
[18] H. Mo illas, J. Ga cía-Galan, M. Magu egui, C. Ga cía-Flo en ino, I. Ma caida, J.A.
502
Ca e o, J.M. Mada iaga, In-si u mul ianaly ical me hodology o e alua e he
503
conse a ion s a e o he en ance a ch o La Galea Fo ess (Ge xo, no h o Spain),
504
Mic ochem. J. 128 (2016) 288-296.
505
[19] M. Magu egui, A. Sa mien o, I. Ma ínez-A ka azo, M. Angulo, K. Cas o, G. A ana,
506
N. E xeba ia, J.M. Mada iaga, Analy ical diagnosis me hodology o e alua e ni a e
507
impac on his o ical building ma e ials, Anal. Bioanal. Chem. 391 (2008) 1361–1370.
508
[20] H. Mo illas, M. Magu egui, C. Pa is, L. Bello -Gu le , P. Colomban, J.M.
509
Mada iaga, The ole o ma ine ae osol in he o ma ion o (double) sul a e/ni a e sal s in
510
plas e s, Mic ochem. J. 123 (2015) 148-157.
511
[21] H. Mo illas, J. Ga cía-Galán, M. Magu egui, I. Ma caida, C. Ga cía-Flo en ino, J.A.
512
Ca e o, J.M. Mada iaga, Assessmen o ma ine and u ban-indus ial en i onmen s
513
19
in luence on buil he i age sands one using X- ay luo escence spec oscopy and
514
complemen a y echniques, Spec ochim. Ac a B. 123 (2016) 76-88.
515
[22] H. Mo illas, M. Magu egui, C. Ga cía-Flo en ino, I. Ma caida, J.M. Mada iaga,
516
S udy o pa icula e ma e om P ima y/Seconda y Ma ine Ae osol and an h opogenic
517
sou ces collec ed by a sel -made passi e sample o he e alua ion o he d y deposi ion
518
impac on Buil He i age, Sci. To al En i on. 550 (2016) 285-296.
519
[23] H. Mo illas, I. Ma caida, C. Ga cía-Flo en ino, M. Magu egui, G. A ana, J.M.
520
Mada iaga, Mic o-Raman and SEM-EDS analyses o e alua e he na u e o sal clus e s
521
p esen in seconda y ma ine ae osol, Sci. To al. En i on. 615 (2018) 691-697.
522
[24] H. Mo illas, I. Ma caida, M. Magu egui, J.A. Ca e o, J.M. Mada iaga, The in luence
523
o ainwa e composi ion on he conse a ion s a e o cemen i ious building ma e ials,
524
Sci. To al En i on. 542 (2016) 716-727.
525
[25] E.M. Pe ez-Monse a , F. Agua, R. Fo , M. Al a ez de Bue go, J.F. Conde, M.
526
Ga cía-He as, E ec o manu ac u ing me hods on he decay o ce amic ma e ials: A case
527
s udy o b icks in mode n a chi ec u e o Mad id (Spain), Appl. Clay Sci. 135 (2016) 136-
528
149.
529
[26] B. Lubelli, R.P.J an Hees, C.J.W.P. G oo , The ole o sea sal s in he occu ence
530
o di e en damage mechanisms and decay pa e ns on b ick mason y, Cons . Build.
531
Ma e . 18 (2004) 119-224.
532
[27] P. Aloise, M. Ricca, M.F. La Russa, S.A. Ru olo, C.M. Bel io e, G. Padele i, G.M.
533
C isci, Diagnos ic analysis o s one ma e ials om unde wa e exca a ions: he case s udy
534
o he Roman a chaeological si e o Baia (Naples, I aly), Appl. Phys. A-Ma e . 114 (2014)
535
655-662.
536
[28] A.A. El-Midany, H.M. Mahmoud, Mine alogical, physical and chemical
537
cha ac e is ics o his o ic b ick-made s uc u es, Mine . Pe ol. 109 (2015) 733-739.
538
[29] L. Bonizzoni, A. Galli, M. Gondola, M. Ma ini, Compa ison be ween XRF, TXRF,
539
and PXRF analyses o p o enance classifica ion o a chaeological b icks, X-Ray
540
Spec om.42 (2013) 262-267.
541
[30] J. Chen, M. Yan, J. Su, B. Li, J. Sun, The kiln coa ing o ma ion mechanism o MgO-
542
FeAl2O4 b ick, Ce am. In . 42 (2016) 569-575.
543
20
[31] J-H. Chen, D-F. Liu, M-W. Yan, P. Jiang, B. Li, J-L. Sun, In luence o
544
Mic os uc u e on Fo ma ion o De e io a ion Laye in Pe iclase-He cyni e B icks,
545
Re ac . Ind. Ce am. 57 (2016) 267-272.
546
[32] S. Belgacem, H. Galai, H. Tiss, Quali a i e and quan i a i e in es iga ion o pos -
547
mo em cemen e ac o y: The case o magnesia-spinel b icks, Ce am. In . 42 (2016)
548
19147-19155.
549
[33] J.M. Alia, H.G.M. Edwa ds, F.J. Ga cía-Na a o, J. Pa as-A men e os, C.J.
550
Sanchez-Jimenez, Applica ion o FT-Raman spec oscopy o quali y con ol in b ick
551
clays i ing p ocess, Talan a 50 (1999) 291-298.
552
[34] V.Z. Abd akhimo , E.S. Abd akhimo a, Phase Composi ion and Po osi y S uc u e
553
o Ce amic B icks Mo e Than 100 Yea s Old: Ca holic Chu ch, I e skiy Monas e y, and
554
Chu ch o he Na i i y in Sama a Oblas , Glass Ce am. 73 (2016) 111-114.
555
[35] N.A. Pé ez, L. Bucio, E. Lima, E. So o, C. Cedillo, Iden i ica ion o allophane and
556
o he semi-c ys alline and amo phous phases on p e-Hispanic Mexican adobe ea h b icks
557
om Cholula, Mexico, Mic ochem. J. 126 (2016) 349-358.
558
[36] D.N. Phillips, Vanadium s aining in i ed clay b icks, B i . Ce am. T. 102 (2003)
559
257-260.
560
[37] N. Scheid, S. Becke , M. Duecking, G. Hampel, J. Volke K an z, P. Wa zke, P. Weis, S.
561
Zaune , Fo ensic in es iga ion o b ick s ones using ins umen al neu on ac i a ion
562
analysis (INAA), lase abla ion-induc i ely coupled plasma-mass spec ome y (LA-ICP-
563
MS) and X- ay luo escence analysis (XRF), Appl. Radia . Iso opes, 67 (2009) 2128-
564
2132.
565
[38] L. Bonizzoni, ED-XRF analysis o Cul u al He i age: is quan i a i e e alua ion
566
always essen ial?, J. Phys. Con . Se . 630 (2015) 012001/1-012001/9.
567
[39] S.S. Rai, N. K. Rai, A.K. Rai, U.C. Cha opadhyaya, Ra e ea h elemen s analysis in
568
a chaeological po e y by lase induced b eakdown spec oscopy, Spec oscopy Le e s
569
49 (2016) 57-62.
570
[40] C. Ga cía-Flo en ino, M. Magu egui, H. Mo illas, U. Balziskue a, A. Azka a e, G.
571
A ana, J.M. Mada iaga, Po able and Raman imaging use ulness o de ec decaying on
572
21
mo a s om Pun a Begoña Galle ies (Ge xo, No h o Spain), J. Raman. Spec osc. 47
573
(2016) 1458–1466.
574
[41] J.M. Mada iaga, M. Magu egui, S. Fdez O iz-De Vallejuelo, U. Knuu inen, K.
575
Cas o, I. Ma inez-A ka azo, A. Giakoumaki, A. Pi a ch, In si u analysis wi h po able
576
Raman and ED-XRF spec ome e s o he diagnosis o he o ma ion o e lo escence on
577
walls and wall pain ings o he Insula IX 3 (Pompeii, I aly), J. Raman Spec osc. 45 (2014)
578
1059-1067.
579
[42] J.M. Mada iaga, M. Magu egui, K. Cas o, U. Knuu inen, I. Ma inez-A ka azo,
580
Po able Raman, DRIFTS, and XRF analysis o diagnose he conse a ion s a e o wo
581
wall pain ing panels om Pompeii deposi ed in he Naples Na ional A chaeological
582
Museum (I aly), App. Spec osc. 70 (2016) 137-146.
583
[43] C. Ga cía-Flo en ino, M. Magu egui, H. Mo illas, I. Ma caida, J.M. Mada iaga, A
584
as in si u non-in asi e app oach o classi y mo a s om a cons uc ion o high
585
his o ical alue, Mic ochem. J. 133 (2017) 104-113.
586
[44] I. Ma caida, M. Magu egui, S. Fdez-O iz de Vallejuelo, H. Mo illas, N. P ie o-
587
Taboada, M. Vene anda, K. Cas o, J.M. Mada iaga, In si u X- ay luo escence-based
588
me hod o di e en ia e among ed och e pigmen s and yellow och e pigmen s he mally
589
ans o med o ed pigmen s o wall pain ings om Pompeii, Anal. Bioanal. Chem. 409
590
(2017) 3853-3860.
591
[45] H. Mo illas, M. Magu egui, C. Ga cía-Flo en ino, J.A. Ca e o, I. Salcedo, J.M.
592
Mada iaga, The cauli lowe -like black c us s on sands ones: A na u al passi e sample o
593
e alua e he su ounding en i onmen al pollu ion, En i on. Res. 147 (2016) 218-232.
594
[46] S. Pessanha, M. Al es, J.M. Sampaio, J.P. San os, M.L. Ca alho, M. Gue a, A
595
no el po able ene gy dispe si e X- ay luo escence spec ome e wi h iaxial geome y,
596
J. Ins . 12 (2017) P01014/1-P01014/13.
597
[47] S. Pessanha, A. Samouco, R. Adão, M.L. Ca alho, J.P. San os, P. Ama o, De ec ion
598
limi s e alua ion o a po able ene gy dispe si e X- ay luo escence se up using di e en
599
il e combina ions, X- ay Spec om. 46 (2017) 102-106.
600
[48] B. Es o nés Lasa, in Ho acio Eche a ie a Ma u i, Auñamendi Eusko En ziklopedia,
601
Euskomedia undazioa, Donos i, 2008.
602
22
[49] S-H. Zhang, G-P. Yang, H-H. Zhang, J. Yang, Spa ial a ia ion o biogenic sul u in
603
he sou h Yellow Sea and he Eas China Sea du ing summe and i s con ibu ion o
604
a mosphe ic sul a e ae osol, Sci. To al. En i on. 488-489 (2016) 157-167.
605
[50] K. Ballschmi e , Pa e n and sou ces o na u ally p oduced o ganohalogens in he
606
ma ine en i onmen : biogenic o ma ion o o ganohalogens, Chemosphe e 52 (2003)
607
313-324.
608
[51] F. Mo eno, S.A.G. Vilela, A.S.G. An unes, C.A.S. Al es, Capilla y- ising sal
609
pollu ion and g ani ic s one e osi e decay in he pa ish chu ch o To e de Monco o (NE
610
Po ugal)-implica ions o conse a ion s a egy, J.Cul . He i . 7 (2006) 56-66.
611
[52] M. Magu egui, R. Tagliapie a, M. Angulo, I. Ma inez-A ka azo, K. Cas o, J.M.
612
Mada iaga, A. B ooke , Iden i ica ion o his o ical b icks deg ada ion p oduc s by means
613
o Combined Raman spec oscopy and scanning elec on mic oscopy, in Conse a ion
614
Science 2007 Publishe : A che ype, UK, London, Edi o s: J.H. Townsend, L. Toniolo, F.
615
Capi elli, pp. 212-219.
616
617
618
FIGURE CAPTIONS
619
620
Fig.1. Pun a Begoña Galle ies (Ge xo, Basque Coun y, no h o Spain) and he analyzed
621
b ick a eas om hei No hwes and Sou hwes Galle ies.
622
Fig.2. Ba cha s wi h no malized a eas ela ed o he a e age o he 10 spec al
623
measu emen s ob ained wi h HH-ED-XRF and hei e o ba s o A) S, Cl, B and S ; B)
624
Al, Si, K, Ca ,Fe ; C) Ti, Ni, Cu, Zn, Pb and D) Rb, Y, Z and Sn.
625
Fig.3. Co ela ion g aph o he Ca and S no malized coun s and analyzed a eas.
626
Fig.4. μ-ED-XRF imaging o one o he analyzed b ick obse ing he elemen al
627
dis ibu ion o di e en elemen s. (Fo in e p e a ion o he e e ences o colo in his
628
igu e legend, he eade is e e ed o he web e sion o his a icle).
629
630
