Construction and Building Materials 288 (2021) 123131

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Comparative analysis of water condensate porosity using mercury

intrusion porosimetry and nitrogen and water adsorption techniques
in porous building stones
D. Benavente a,⇑, I. Such-Basañez b, A. Fernandez-Cortes c, C. Pla d, D. Cazorla-Amoros e, J.C. Cañaveras a,
S. Sanchez-Moral f
a
Department of Earth and Environmental Sciences, University of Alicante, 03690, Spain
b
Technical Research Services (SSTTI), University of Alicante, Alicante, Spain
c
Department of Biology and Geology, University of Almeria, 04120, Spain
d
Department of Civil Engineering, University of Alicante, 03690, Spain
e
Inorganic Chemistry Department, Institute of Materials Science (IUMA), University of Alicante (UA), Alicante, Spain
f
Department of Geology, National Museum of Natural Sciences (MNCN-CSIC), 28006, Spain

h i g h l i g h t s

Nitrogen adsorption technique provides the best estimation of condensate porosity.

The shape of the water isotherm depends on the pore fraction lower than 0.1 lm.

The maximum adsorbed water is closely related to the specific surface area.

a r t i c l e i n f o a b s t r a c t

Article history: Condensate porosity in porous materials has a significant influence on comfort, energy consumption, and
Received 7 September 2020 material’s strength and durability. The variation of the moisture content of the material for a given vari-
Received in revised form 14 December 2020 ation of relative humidity describes the moisture storage capacity and has to be determined experimen-
Accepted 18 March 2021
tally through the water sorption isotherm. However, the characterisation of sorption isotherm is very
Available online 31 March 2021
time-consuming, mostly for high relative humidity conditions, which may cause experimental errors
and reproducibility problems.
Keywords:
This paper aims to estimate experimental water condensate porosity using mercury intrusion
Pore structure
Stone
porosimetry and nitrogen adsorption technique considering pores smaller than 0.1 lm for a wide range
BJH of porous sedimentary rock types with different petrographic characteristics. Particularly for nitrogen
Water condensation adsorption characterisation, we interpolated the pore volume using BJH method applied to the desorp-
Durability tion branch. In the water adsorption test, condensate porosity is obtained with the maximum adsorbed
water at RH = 100%.
The ratio between water condensate porosity and total porosity in the studied porous stones is impor-
tant and varies from 2 to 38%. Nitrogen adsorption technique provides the best estimation of condensate
porosity (R2 = 0.979) and an effective estimation of water condensate porosity. The correlation between
condensate porosity using MIP is moderate (R2 = 0.892) and presents a wider dispersion for all the range
of condensate porosity. A mathematical expression that fits the shape and curvature of the water iso-
therm was also analysed in terms of pore structure. These studies are scarce for porous stones and our
results provide valuable information for these widely used construction and building material.
Ó 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).

⇑ Corresponding author.
E-mail addresses: david.benavente@ua.es (D. Benavente), ion.such@ua.es
(I. Such-Basañez), acortes@ual.es (A. Fernandez-Cortes), c.pla@ua.es (C. Pla),
cazorla@ua.es (D. Cazorla-Amoros), jc.canaveras@ua.es (J.C. Cañaveras), ssmilk@
mncn.csic.es (S. Sanchez-Moral).
1. Introduction
Porous materials in buildings and structures always contain a
certain amount of moisture that directly affects its properties, such
as gas ventilation, mechanical strength, swelling, thermal conduc-

https://doi.org/10.1016/j.conbuildmat.2021.123131
0950-0618/Ó 2021 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
D. Benavente, I. Such-Basañez, A. Fernandez-Cortes et al.
tivity, and durability [1–3]. Condensate water appears in both
building indoor and outdoor environments and can become critical
depending on microclimate variations and pore structure and
hygrothermal properties of the material. Water affects stone’s
strength and deformability and triggers salt and ice crystallisation,
clay swelling, the development and proliferation of microorgan-
isms, also increasing rock reactivity and the intensity of chemical
weathering processes by the presence of CO2 [4–8]. Particularly,
the presence of water can become critical inside of monuments
as building materials include indoor elements (such as stone ash-
lars, clay-based materials, stuccos) and the unique works of art
they enclose (i.e.: sculptures, paintings, frescoes) [9]. Being able
to estimate the condensate porosity of construction and building
materials can be very useful to configure and design appropriate
strategies for the conservation of sites with a valuable cultural her-
itage. In indoor environments, hazardous gases such as 222Rn, CO2,
CO, NH3 and volatile organic compounds (VOCs) can be accumu-
lated as condensate water obstructs the direct passage of gases
and reduces the gas diffusion coefficients [10–13]. For example,
the study of the natural radioactive radon gas (222Rn) is nowadays
of great human health interest because accumulates within build-
ings and consequently, is inhaled by their occupants [14].
Consequently, condensate water directly influences the build-
ing material behaviour and depends on the volume fraction of
pores with radii below 0.1 lm. At low relative humidities, vapor
water is adsorbed on the pore surface of the stone. With rising
air humidity, the number of layers of water molecules on the pore
surface increases until capillary condensation occurs in pores with
radii around 0.1 lm. Porous stones show this behaviour once the
relative humidity reaches 75–80%, where the condensate water
increases until a maximum is reached. The value of the water-
condensate porosity corresponds to the volume fraction of pores
filled by adsorbed water and becomes important in porous stones
which have pores with radii lower than 0.1 lm.
The water sorption isotherm describes the amount of conden-
sate water (expressed as a ratio Dm/m0) at different relative
humidity (RH). The maximum adsorbed water, Dm/m0,max, corre-
sponds to adsorbed water at RH = 100%. The moisture storage
capacity, sometimes referred to as the sorption capacity, repre-
sents the variation of the moisture content of the material for a
given variation of relative humidity and has to be determined
experimentally [3,15].
Several mathematical expressions for the calculation of mois-
ture content over the whole range of relative humidity values have
been proposed in the literature [16]. Künzel [17] proposed a simple
equation that fits accurately to a wide range of building porous
materials. Based on this equation, the calculation of adsorbed
water, Dm/m0(), with regard to relative humidity, RH(), can
be rewritten as follows:
ðbw  1Þ  RH
Dm=m0 ¼  Dm=m0;max ð1Þ
bw  RH
where bW(–) is an approximation coefficient. RH(–) is expressed as
a fraction of unity and Dm/m0 and bW are dimensionless. bW is
determined experimentally using a pair of values or fitting the
equation to the experimental water isotherm and a small variation
in bW causes a strong variation in shape of the water adsorption iso-
therm. The maximum adsorbed water is also referred to as the
moisture content at free saturation. The value of this parameter
for various building materials can be found in WUFI software mate-
rial database [18], although it is scarce for porous rocks. However,
the relationship between these parameters and pore structure for
most of the situations has to be experimentally obtained.
The classical method for obtaining sorption isotherm consists of
conditioning the samples in saturated salt solution under constant
relative humidity and temperature until static equilibrium is
2
Construction and Building Materials 288 (2021) 123131
achieved (mass difference lower than 0.01% in a certain period).
However, this method is very time-consuming, mostly for high rel-
ative humidity conditions, which may cause experimental errors
and reproducibility problems. In recent years, a technique initially
used in the pharmaceutical field and known as dynamic vapor
sorption has been developed [15]. This technique uses less amount
of sample and leads to shorter tests. The use of small samples lim-
its the use of this method for the characterisation of heterogenous
construction materials such as rocks and concrete. The use of
dynamic vapor sorption technique in the characterisation of por-
ous building stones is, therefore, scarce [19]. Both techniques have
been compared for construction materials but the statistical anal-
ysis was not entirely conclusive [15].
Pore structure has influence on both the shape of water adsorp-
tion–desorption curves and on the maximum adsorbed water (Dm/
m0,max). For that reason, various attempts have been performed to
model the water sorption isotherm using mercury intrusion
porosimetry (MIP) and nitrogen gas sorption at 77 K. These tech-
niques are the most widely used methods for investigation of the
porous texture of the building materials. Substantial research has
been undertaken in the comparison of the particular pore structure
parameters obtained by MIP (e.g. the specific surface area), nitro-
gen and water sorption techniques, particularly for cement-based
materials [3,20–23], although few in building stones [12]. How-
ever, the use of MIP or gas nitrogen sorption results for water
adsorption evaluation or prediction present several discrepancies
related to the fact that the pore structure parameters determined
by MIP, nitrogen gas sorption at 77 K and water sorption can differ
significantly [24].
This paper aims to estimate experimental water condensate
porosity using mercury intrusion porosimetry and nitrogen
adsorption technique considering the pore range filled by water
when determining water sorption, i.e., r < 0.1 lm. For this purpose,
we use thirty sedimentary rocks types with different petrographic
characteristics. Pore structure characterisation is described in
terms of porosity, pore size distribution, specific surface area and
pore volume, using mercury intrusion porosimetry, nitrogen gas
adsorption at 77 K and water adsorption techniques, and the
helium pycnometry. We discuss the calculation of pore volume
for pores smaller than 0.1 lm obtained from each technique, which
is considered the condensable volume fraction. Finally, we analyse
the mathematical expressions that fits the shape and curvature of
the water isotherm in terms of pore structure, with an emphasis on
the condensable volume fraction and specific surface area.
2. Material and methods
2.1. Materials
In this study, we use thirty sedimentary rocks, which are
employed as building materials or found in the Spanish built her-
itage. They present different petrophysical and petrographic char-
acteristics. These building stones can be classified as (C) clastic
limestones or biocalcarenites with a variable amount of intrabasi-
nal bioclasts and extrabasinal terrigenous components, and differ-
ent types of fabric and not fabric selective porosity; (L) limestones
composed mostly of calcite particles (skeletal and non-skeletal
grains) with calcite cement and/or micrite; and (S) siliciclastic
sandstones mainly composed of quartz grains and other silicate
minerals. Table SS1 of the Supplementary Materials section sum-
marizes the nature of the clasts, type of porosity, cement and
matrix type, and stone classification according to [25–30].
C1 and C2 are well-sorted biocalcarenites or sandy fossiliferous
limestones that contain planktonic foraminifera (mainly Globigeri-
nae) and quartz, feldspar, mica and dolomite grains [31–34].
D. Benavente, I. Such-Basañez, A. Fernandez-Cortes et al.
Foraminiferś shells, ranging in size from 0.2 to 0.5 mm, are gener-
ally filled by glauconitic and/or siliceous cement. The terrigenous
fraction is comprised of quartz, feldspars, micas, dolostones and
other rock fragments. These stones show interparticle and intra-
particle as well as channel porosity. Calcite cement is scarce and
consists of equant–equicrystalline mosaics of calcite spar. C1 and
C2 have been widely used in the built heritage, named as Piedra
Bateig [35].
C3 is also a well-sorted biocalcarenite rich in foraminifers
(mainly Globigerinae) ranging in size from 0.2 to 0.5 mm. As in
C1 and C2 foraminifers’ shells are generally filled by glauconitic
and/or siliceous cement and the terrigenous fraction is comprised
of quartz, feldspars, micas, dolostone and other rock fragments.
Both interparticle and intraparticle porosity vary. The most abun-
dant type of cement present in these stones is equant-
equicrystalline mosaics of calcite spar. This stone has been widely
used in the built heritage, named as Almorqui Stone [33].
C4 is a biomicrite that contain planktonic foraminifers (mainly
Globigerinae), ranging in size from 0.1 to 0.2 mm. The terrigenous
fraction (10%) is mainly comprised of quartz, feldspars and micas.
The main porosity types are intraparticle and vug.
Samples from C5 to C24 were extracted from the Roman
Necropolis of Carmona (Seville), which represents one of the most
significant burial sites in Southern Spain used during the first and
second centuries A.D. [4,8,36]. Samples were taken in different
tombs and constructions along with 100,000 m2 of the Necropolis.
These stones show a grain-supported texture with moderate to
poor sorting and are composed of variable amounts of carbonate
intrabasinal grains (mainly bioclasts) (40–85%) and non-
carbonate extrabasinal grains (15–60%). They can be classified as
biocalcarenites (carbonate intrarenites, sandy biosparites or
packed grainstones) or hybrid arenites depending on the relative
abundance of their framework components.
Bioclasts mainly consist of reworked fragments of molluscs
shells, and variable content of benthic foraminifera, echinoderms,
red algae, bryozoan and gastropods. Extraclasts, consist mainly of
siliciclastic (terrigenous) grains, predominantly monocrystalline
quartz, although polycrystalline quartz, chert, feldspars are also
recognized. Intrabasinal non-carbonate grains as glauconite
peloids or ferruginous grains are also present in variable amounts.
The degree of cementation is small. Equant spar calcite cement
predominates although Fe-rich cement, typically as amorphous
masses or coatings are observed. Matrix is relatively abundant
and consists of a generally poorly cohesive mixture of carbonate
mud (micrite) and clays (smectites, illites) [4,8].
These stones show relatively high porosity. The predominant
porosity type is interparticle in most of the samples, but also pre-
sent other fabric selective porosity types, such as intraparticle (clo-
sely related to foraminifera content), moldic (especially abundant
in C11, C12, C14, C18 and C22) and not fabric selective (vug, frac-
ture) (abundant in C8, C10 and C15).
L25 is an unsorted biosparite with fragments of bryozoans, red
algae, echinoderms, foraminifers and molluscs. This stone usually
shows a banded structure with layers of different amounts of inter-
particle porosity. Quartz, feldspar, rock fragment and chert com-
prise 5 ± 5% of the stone. The interparticle and intraparticle
porosity are abundant. Cement, mainly drusy calcite spar, in this
stone is scarce. L25 have been used in the built heritage, named
as Oasis Yellow commercial marble.
L26 is a coarse biosparrudite that mainly contains fragments of
bryozoans and red algae. Some plates of echinoderms and frag-
ments of molluscs are also present. It contains traces of detrital
quartz. Interparticle porosity is very abundant. The intraparticle
porosity is related to bryozoans. Cement is scarce and mainly con-
sists of drusy calcite spar. This stone has been used as building
materials (Cream Spain commercial marble).
3
Construction and Building Materials 288 (2021) 123131
L27 is an oolitic limestone where oolites are densely packed and
poorly sorted [37]. Some big fragments of bioclastic limestone
(limeclasts) can be observed. The ooids cores are formed by fossil
remains. Mineralogy is mainly calcite (99%). Other, accessory, min-
erals can be also observed (mainly oxides). Pores are generally con-
fined to the gaps between oolites (interparticle porosity), although
the majority of these spaces are filled with microcrystalline
cement.
S28 is a well-sorted quartzarenite that consists of monocrys-
talline quartz grains with rare feldspars, metamorphic rock frag-
ments, chert and muscovite grains. Primary interparticle porosity
has been partially filled by silica crystallization, which forms fre-
quent overgrowths on quartz grains [38].
S29 and S30 can be classified as subarkoses or lithic arkoses.
They present a high concentration of quartz, while feldspars, cal-
cite and phyllosilicates (mostly chlorite and muscovite) appear in
smaller amounts. The quartz crystals are angular to subrounded
in shape. Feldspars usually are partially altered to sericite. Phyl-
losilicates and an interparticle calcareous matrix appear in sparse,
unevenly distributed amounts. Sandstones S29 and S30 have been
also used in the built heritage, named as Piedra Tarifa Dorada and
Piedra Tarifa Gris, respectively [33,39].
Table SS2 of the Supplementary Materials section shows the
displays the mineralogical composition of the studied rocks, which
is concordance with the petrographic characterization. Major min-
eralogical composition was obtained using by powder Xray diffrac-
tion of the randomly oriented samples and the qualitative search-
matching procedure was based on the ICDD-PDF2 database. Clay
fraction was performed using orientated aggregates (air-dried, sol-
vated with ethylene–glycol and heated at 550 0C).
2.2. Methods
Pore structure characterisation was described in terms of poros-
ity, pore size distribution, specific surface area (SSA) and pore vol-
ume, using mercury intrusion porosimetry (MIP), nitrogen gas
adsorption at 77 K and water adsorption techniques, and helium
pycnometry.
Total porosity, PT, is the fraction of the volume of voids over the
bulk material volume and is calculated from bulk and grain densi-
ties. Bulk density, qb (g/cm3), was determined as the ratio of dry
weight to the volume of the sample. Grain or real density, qr
(g/cm3), was obtained using an AccuPyc 1330 Helium pycnometer.
Before the characterisation of the porous rocks with MIP,
helium pycnometry, and water adsorption, rock specimens were
cut in regular samples of approximately 1 cm3 and were dried at
60 0C for 24 h.
Connected porosity, Pc, only considers connected voids. Con-
nected porosity and mean throat-pore radius, rM, were obtained
from mercury intrusion porosimetry (MIP) measurements with
an Autopore IV 9500 Micrometrics mercury porosimeter in the
pore radius interval of 0.002–200 lm. MIP is based on the assump-
tion that non-wetting liquid will only intrude pores under pressure
and that pores have cylindrical geometry. Accordingly, Washburn
equation was used to determine pore radius from the applied pres-
sure. However, the MIP pore size distributions often overestimate
the portion of small pores due the ink-bottle effect, where the large
pores are accessible through the smaller ones or through the very
narrow pore throats [1,3].
Gas adsorption analysis was performed by measuring the Nitro-
gen adsorption–desorption isotherm at 77 K in an automatic volu-
metric gas sorption apparatus Autosorb-6B by Quantachrome.
Samples were vacuum degassed at 150 °C for 4 h in a Masterprep
(Quantachrome) degassing unit by means of a rotatory oil pump.
This temperature was chosen in order to prevent sample modifica-
tion by clay dehydroxylation at higher temperatures under vac-
D. Benavente, I. Such-Basañez, A. Fernandez-Cortes et al.
uum. Rocks do not usually present high nitrogen uptakes and this
fact can present a problem when low nitrogen volumes are to be
measured. In this study, the amount of sample was chosen to be
as high as possible (about 1 g or higher). This brings the measure-
ment of the nitrogen uptake well into the measuring range of the
pressure transducers used in volumetric adsorption equipment,
making the measurements highly reliable. From the nitrogen
adsorption isotherms at 77 K several pore structure parameters
can be obtained. Nitrogen adsorption isotherms are commonly pre-
sented as dry mass normalized VSTP adsorbed (volume of gas at
standard pressure and temperature in cm3/g) vs. relative pressure,
P/P0. IUPAC (International Union of Pure and Applied Chemistry)
usually recommends using moles adsorbed (mmol/g) vs. P/P0
[40]. In this paper, nitrogen adsorption isotherms will be expressed
as volume of liquid nitrogen vs. P/P0 in order to show a closer
match with MIP and water sorption measurements. To do so, the
molar volume of N2 behaving as an ideal gas (22400 cm3/mol),
molar mass of N2 molecule (28 g/mol) and density of N2 as a liquid
at 77 K (0.808 g/cm3) were considered.
Specific surface area, SSA, was calculated by using the BET
(Brunauer-Emmet-Teller) model over a relative pressure range of
0.05–0.30 on the adsorption branch of the isotherm. In the BET
method, the amount adsorbed in a monolayer is determined and
from it SSA is derived [41].
Total pore volume adsorbed at a given relative pressure
expressed as a liquid is often a measure of total volume of pores
up to a given pore size. Pore size and relative pressure are related
through the Kelvin equation, which is modified to consider the sta-
tistical thickness of the adsorbed layer. This relation calculates that
pores with sizes smaller than 0.1 lm would be filled at a relative
pressure of P/P0 = 0.9991. At this relative pressure, where pores
have a radius of 0.1 lm, the statistical thickness calculated by de
Boer and generalized Halsey equations [41] is below 0.002 and
0.003 lm, respectively. That means that the statistical thickness
is<2–3% of the pore size and therefore we consider that its influ-
ence can be considered negligible on the value of calculated pore
size.
BJH (Barret–Joyner–Halenda) is a pore size distribution calcula-
tion method often used in nitrogen gas adsorption isotherm anal-
ysis. This method is based on the Kelvin equation and its validity
is restricted to mesopores (size 1–25 nm in radius according to
the IUPAC classification, [42] and larger pores (macropores). BJH
is usually applied to the desorption branch of the isotherm as this
data are in true equilibrium while adsorption data are often con-
sidered as being in metastable equilibrium [41].
In this work, we calculated the pore volume for pores smaller
than 0.1 lm by the interpolation of the adsorbed amount at
P/P0 = 0.9991 using (1) BJH method applied to the desorption
branch and (2) the statistical thickness calculated by the de Boer
equation. This is referred to as vp, N2 (cm3/g) where pore volume
is expressed as a liquid.
The water adsorption curve (static method) was determined at
long exposure time and constant temperature (isothermal equilib-
rium conditions 22.5 ± 0.5 °C). Humidity was controlled by selected
aqueous saturated salt solutions: H2O (100%); KH2PO4 (96%); KNO3
(93%); KCl (85%); NaCl (75%); K2CO32H2O (43%); CaCl26H2O (29%)
and Si-gel (7%). The elapsed time to reach equilibrium depended on
relative humidity: approximately a day for low relative humidity
conditions and a week for each high relative humidity. The mass
of the samples was weighed by means of electronic scales with
the accuracy of 0.001 g. The adsorption curve was plotted as the
mass of water adsorbed per unit of dry sample, Dm/m0, versus rel-
ative humidity, RH. The maximum adsorbed water, Dm/m0,max,
was calculated as the mass of water adsorbed per unit of dry sam-
ple at RH = 100%. The maximum adsorbed water can be also
referred to gravimetric water content.
4
Construction and Building Materials 288 (2021) 123131
Condensate porosity, Pcond, is different for each technique. Thus,
for MIP, the calculated mercury condensate porosity, Pcond,Hg, is
estimated considering the connected porosity for pore radius lower
than 0.1 lm, i.e. in the pore interval 0.002–0.1 lm. For nitrogen
adsorption characterisation, nitrogen condensate porosity, Pcond,
3
N2, is calculated from vP (cm /g) and bulk density of the adsorbent
(rock) as Pcond,N2 = vpqb. Water condensate porosity, Pcond,H2O, con-
siders the maximum adsorbed water, Dm/m0, and bulk and water
densities, as Pcond,H2O = Dm/m0qb/qw.
3. Results and discussion
3.1. Pore structure characterisation
Fig. 1 shows the water and nitrogen isotherms and MIP pores
size distributions for five representative types of rocks according
to the degree of sorting, whereas Fig. SS1 of the Supplementary
Materials section displays the curves of the all tested porous rocks.
Moreover, Fig. 1 also compares pore size distributions obtained
using MIP and BJH method applied to the desorption branch.
Table 1 shows the maximum adsorbed water achieved in the water
isotherm (Dm/m0,max); pore volume adsorbed in pores smaller
than 0.1 lm (vP,N2) and SSA obtained with N2 adsorption; con-
nected porosity (PC) and mean radius (rM) with MIP; and bulk
(qb) and grain (qr) densities, as well as the calculated total
porosity.
The studied porous stones exhibit different petrographic and
pore structure characteristics. By observing their nitrogen adsorp-
tion isotherms at 77 K, we can conclude that they mainly present
meso- and macropores according to IUPAC classification [42].
MIP characterisation reports that porous stones studied in this
work show a high total porosity in the range of 10 to 35% and a
polymodal pore size distribution (Fig. SS1). Connected porosities
of the studied stones are higher than 10% and they have well-
established pore connectivity [38,43].
The petrographic characteristics of stones, including grain size
distribution, type of cement and cement/matrix ratio (Table SS1),
considerably affect the pore structure and, therefore, the pore size
distribution and porosity. Stones with coarser grains (bioclasts,
extraclasts) display large pores (for example, L25 and L26) which
are not completely filled with cement. The most important types
of cements in the carbonate stones are drusy calcite spar, which
is mainly comprised of prismatic calcite, and equant-
equicrystalline mosaics of calcite spar. The latter fills the interpar-
ticle porosity with equant crystals of calcite. In sandstones, the
syntaxial silica cement is abundant. These types of cements reduce
porosity in the stones and provide excellent resistance properties
to be used as construction a building material [32]. In general,
low cement/matrix ratio leads to unsorted stones, with a pore pop-
ulation with small pore sizes.
Various types of pore size distributions are observed that range
from sorted rocks, which show a unimodal pore population, to
poorly sorted and unsorted rocks (Fig. 1): (1) main peak or pore
population is close or smaller than 0.1 lm (C1, C3, C4, L27, S29,
S30); (2) main peak in the interval of 0.1–1 lm (C2, C8); (3) main
peak with pores larger than 1 lm (C10, L26, S28); (4) unsorted
pore distribution with significant pore volume in pores smaller
than 0.1 lm (C13, C16, C18, C22); and (5) unsorted pore distribu-
tion with low pore volume in pores smaller than 0.1 lm (C5, C6,
C7, C9, C11, C12, C14, C15, C17,C19, C20, C21, C23, C24, L25).
In the studied rocks, closed porosity is negligible, and the frac-
tion of large pores is reflected in the total porosity values, which
are always slightly higher than the connected porosity (Table 1).
For example, C21, C11, C20, L25 and L26 are formed by large grains
D. Benavente, I. Such-Basañez, A. Fernandez-Cortes et al. Construction and Building Materials 288 (2021) 123131

Fig. 1. MIP and BJH pores size distributions (first column), and nitrogen (second column) and water (third column) isotherms of five representative types of stones according
to the degree of sorting.

5
D. Benavente, I. Such-Basañez, A. Fernandez-Cortes et al. Construction and Building Materials 288 (2021) 123131

Table 1
Bulk (qb) and grain (qr) densities; total (PT) and connected (PC) porosities; pore mean radius obtained with MIP (rM); specific surface area (SSA); pore volume (vP,N2); and the
maximum adsorbed water (Dm/m0,max) for the studied porous rocks.

Ref. qb qr PT PC rM SSA vP,N2 Dm/m0,max

(g/cm3) (g/cm3) (%) (%) (lm) (m2/g) (cm3/g) (-)
C1 2.21 2.64 16.25 14.31 0.08 10.22 0.022 0.023
C2 2.16 2.70 20.05 18.65 0.33 9.97 0.037 0.032
C3 2.17 2.79 22.15 19.86 0.18 10.17 0.035 0.038
C4 1.95 2.67 27.09 26.02 0.35 13.14 0.035 0.036
C5 1.83 2.74 33.38 32.90 8.25 2.72 0.012 0.012
C6 2.01 2.76 27.12 24.56 7.88 2.48 0.007 0.007
C7 2.16 2.79 22.76 19.62 2.76 1.55 0.009 0.007
C8 2.32 2.79 17.01 16.62 0.69 1.60 0.013 0.012
C9 2.01 2.77 27.31 24.76 1.50 1.55 0.007 0.008
C10 1.79 2.68 33.17 32.13 22.00 2.23 0.011 0.011
C11 2.02 2.74 26.07 21.67 6.66 3.24 0.017 0.013
C12 2.07 2.76 24.93 20.84 5.88 3.69 0.014 0.010
C13 2.45 2.74 10.51 8.37 0.31 2.24 0.007 0.006
C14 1.83 2.76 33.80 30.17 8.77 1.13 0.012 0.008
C15 1.89 2.71 30.15 28.76 129.77 2.90 0.01 0.012
C16 1.94 2.85 31.85 29.16 28.73 2.69 0.021 0.022
C17 1.83 2.75 33.54 31.05 90.08 2.80 0.011 0.012
C18 2.03 2.73 25.76 24.00 21.51 5.08 0.016 0.017
C19 2.04 2.71 24.76 21.32 4.96 3.00 0.01 0.009
C20 1.86 2.69 30.60 26.37 13.24 1.62 0.007 0.009
C21 2.09 2.73 23.41 18.57 16.92 2.05 0.008 0.013
C22 1.97 2.74 28.14 25.77 32.23 4.09 0.013 0.016
C23 2.03 2.74 26.04 25.48 32.81 2.10 0.011 0.014
C24 1.81 2.77 34.75 31.69 77.57 3.44 0.012 0.012
L25 2.18 2.78 21.29 17.79 28.69 0.82 0.007 0.008
L26 2.18 2.74 20.19 16.32 34.18 0.83 0.0005 0.002
L27 2.51 2.79 10.03 9.36 6.36 0.62 0.012 0.014
S28 2.27 2.66 14.62 13.48 2.43 2.36 0.01 0.006
S29 2.12 2.75 22.87 21.43 0.17 9.93 0.031 0.029
S30 2.52 2.88 12.39 11.78 0.38 4.95 0.02 0.017

or bioclasts, and therefore, by large pore radius that mercury intru-
sion porosimetry technique cannot measure.
Nitrogen adsorption isotherms at 77 K of rocks measured in this
work would be classified as Type II isotherms, showing H3 hystere-
sis loops according to the IUPAC classification [40]. Type II iso-
therms are typical of solids showing low or no microporosity
(<1nm in radius according to the IUPAC classification [42]) and a
certain amount of mesopores in the range of 1–25 nm in radius.
Finally, at high pressures, the shape of this isotherm is the result
of unrestricted monolayer-multilayer adsorption up to high P/P0,
typically present in macroporous adsorbents.
SSA values calculated from nitrogen adsorption isotherms of the
studied rocks range from 0.6 to 14 m2/g, where the highest values
are found in rocks whose main peak in the MIP pore size distribu-
tion is close to or smaller than 0.1 lm.
3.2. Condensate porosity
Fig. 1 and SS1 show the water adsorption curve (third column)
of the porous materials at different relative humidities. The pres-
ence of a bend at a relative humidity of about 75–80% is the result
of the capillary water condensation for this type of mesoporous
materials. The adsorbed water in the range 0–75% is lower than
25% of the total adsorbed water.
Table 2 shows the maximum adsorbed water and the approxi-
mation coefficient bW, which strongly depends on the pore fraction
lower than 0.1 lm. On the one hand, the maximum adsorbed water
accounts all the pore space below this pore size, both during the
formation of monolayers of adsorbed water at low relative humid-
ity and during the capillary water condensation. Larger pores are
not active for capillary water condensation and their contribution
to maximum adsorbed water is negligible.
On the other hand, the shape and curvature of the water iso-
therm depend on the adsorbed water previous to capillary conden-
sation. With rising air humidity, the number of layers of water
molecules on the pore surface increases until capillary condensa-
tion occurs and the adsorbed water increases abruptly until the
maximum adsorbed water is reached at RH = 100%. The adsorbed
water at low RH for porous rocks with large pores is negligible
and it only becomes significant at high RH, if capillary condensa-
tion takes place. In this situation, bW presents low values that
range from 1.010 to 1.050 for the studied rocks. However, in rocks
with small pores (r < 0.1 lm) the number of layers of water mole-
cules on the pore surface gradually increases with RH values. When
capillary condensation occurs, the adsorbed water increases
smoothly compared to rocks with large pores. Consequently, the
shape of the water isotherm leads to higher bW values (Table 2).
Water isotherm, Dm/m0,max and bW values (Tables 1 and 2) are
not clearly related to the mineralogical composition (Table SS2).
Most of the studied stones are composed of calcite and quartz, with
a variable number of feldspars and dolomite. However, the pres-
ence of clay minerals strongly influences the water adsorption
capacity (Dm/m0,max). Water vapor at ambient temperature shows
a great affinity for oxygen groups (i.e., hydroxyls) present at the
surface of clay minerals. Thus, C3 containing the highest amount
of clay mineral, also presents the highest Dm/m0,max value. The
presence of clay minerals explains why Dm/m0,max is higher in
C3 than C2 when they present similar MIP pore size distributions
or S29 or C1 having smaller pores.
Generally, the shape of isotherms and values of the adsorbed
water at RH = 100% and nitrogen adsorbed in pores r < 0.1 lm
are similar and reflect the adsorption process that occurs in these
types of porous materials (Figure SS1).
Table 2 and Fig. 2 compare the condensate porosity calculated
from water isotherms with that calculated from nitrogen adsorp-
tion isotherms and MIP. The best correlation with Pcond,H2O is
reached using nitrogen adsorption technique, both presenting very
similar values (R2 = 0.979). In other words, pore volume obtained

6
D. Benavente, I. Such-Basañez, A. Fernandez-Cortes et al. Construction and Building Materials 288 (2021) 123131

Table 2
Approximation coefficient (bW), condensate porosity calculated from mercury
intrusion porosimetry (Pcond,MIP), water (Pcond,H2O) and nitrogen (Pcond,N2) adsorption
isotherms for the studied porous stones.

Reference bW Pcond,MIP Pcond,H2O Pcond,N2

(–) (%) (%) (%)
C1 1.10 8.77 5.03 4.87
C2 1.05 5.29 6.81 7.99
C3 1.09 8.03 8.32 7.59
C4 1.06 4.74 7.02 6.82
C5 1.07 2.07 2.16 2.19
C6 1.04 1.55 1.44 1.41
C7 1.07 2.16 1.53 1.94
C8 1.06 1.38 2.82 3.01
C9 1.06 2.14 1.60 1.41
C10 1.05 1.34 2.05 1.97
C11 1.02 1.62 2.69 3.44
C12 1.09 1.97 2.05 2.90
C13 1.08 3.30 1.51 1.72
C14 1.06 1.68 1.49 2.19
C15 1.05 1.53 2.22 1.89
C16 1.04 4.23 4.35 4.07
C17 1.04 1.36 2.25 2.01
C18 1.07 2.74 3.41 3.25
C19 1.07 2.19 1.76 2.04
C20 1.06 1.44 1.70 1.30
C21 1.03 0.75 2.64 1.67
C22 1.05 2.45 3.18 2.56
C23 1.04 2.59 2.80 2.23
C24 1.07 1.57 2.25 2.17
L25 1.02 1.19 1.75 1.53
L26 1.04 0.05 0.39 0.11
L27 1.01 5.67 3.59 3.02
S28 1.07 1.41 1.27 2.27
S29 1.12 5.19 6.15 6.58
S30 1.05 4.23 4.35 5.04

at r = 0.1 lm from the desorption curve using the BJH method can
be used for the calculation of the maximum adsorbed water and
condensate porosity. The correlation with condensate porosity
using MIP is only moderate (R2 = 0.892) and presents a wider dis-
persion for all the range of condensate porosity.
This can be attributed to the fact that water and nitrogen iso-
therms are based on the same physical adsorption process for
these types of porous materials N2 physisorption and water vapor
adsorption are based on a gas–solid interaction and subsequent
surface enrichment occurs through the interacting potential of
the solid walls of the adsorbent and the gas adsorbate (N2 or water
vapor).
Nitrogen adsorption at 77 K is usually selected as a way of mea-
suring surface properties of an adsorbent without the presence of
unwanted specific interactions with the adsorbate, nitrogen in this
case, and therefore giving a measure of pure physisorption. This is
possible as nitrogen is a non-polar gas at a very low temperature
but even so, the nitrogen molecule possesses a small quadrupole
moment which could give rise to a certain degree of specific inter-
action in small micropores and surface groups, and some research-
ers are recommending the use of Ar at 87 K for adsorption in order
to reduce even further the degree of adsorbate-adsorbent interac-
tion [40,44]. Water vapor at ambient temperature, however, will
show a great affinity for oxygen groups present at the surface of
materials (hydroxyls, for instance) [45–46]. This will give rise to
adsorption isotherms where both phenomena (physisorption and
probably some chemisorption-or specific interaction) will simulta-
neously occur. But it is important to note that both techniques are
based on the same or very similar physical phenomenon and
explains the nearly identical values obtained using both
techniques.
The adsorption phenomenon is able to analyse the surface of
the material with the advantage over other techniques that no lim-
7
Fig. 2. Relationship between condensate porosity calculated from water and
nitrogen adsorption isotherm (a) and (b) MIP, as well as specific surface area,
SSA, for the studied porous rocks.
itation on adsorption by narrow neck pores occurs, even though it
is well known that these narrow neck pores will have an influence
on the desorption process and on the shape of the hysteresis loop.
Contrary, the MIP technique is based on the intrusion of a non-
wetting liquid by applying high pressures, which differs from the
physical adsorption process of the water or nitrogen isotherm.
The model relating pressure and pore size (Washburn’s equation)
makes geometric assumptions about the pores, usually supposed
to be straight parallel pores (quite a simplifying view), and narrow
pore entrances have a great influence on the shape of the intrusion
and pore size distribution curves. In addition, mercury cannot
intrude in pores smaller than 3–4 nm in diameter and this has to
be achieved at very high pressures. Gas adsorption, however, can
analyse pores in the micropore range (<2nm) which, when present,
have a great influence on parameters such as condensate porosity
and surface area that cannot be analysed by mercury porosimetry.
Despite these discrepancies, the pore size distributions calculated
with MIP and BJH method in the 0.001–0.1 lm pore range present
similarities (Fig. 1) and the estimation of condensate porosity from
MIP can also be considered adequate as shown in previous studies
[4,8,16,47–51].
D. Benavente, I. Such-Basañez, A. Fernandez-Cortes et al.
The percentage of porosity occupied by water condensation can
be significant for porous rocks with small pores, which can directly
affect their properties. This percentage can be calculated as the
ratio between water condensate porosity and total porosity (Tables
1 and 2). The percentage of the occupied porosity calculated in this
manner varies from 2 to 38% of the connected porosity.
Table 1 and Fig. 2c indicate that porous stones with high specific
surface area, SSA, display high values of maximum adsorbed water,
Dm/m0,max. SSA is directly related to porosity and inversely related
to pore size [38,47,52–53] as occurs in the water adsorption and
condensation processes and can be seen as a valuable indicator
for water condensation capacity. Thus, a building material with
high values of the specific surface area and condensate pore vol-
ume will show a high capacity and susceptibility of water conden-
sation and retention into the material. As a consequence, it will be
prone to deterioration by salt and ice crystallisation, chemical
deterioration or the development of microorganisms; its strength
and insulation capacity will be reduced; and the ventilation of
indoor gases, as the natural-radioactive radon gas, will be
decreased.
4. Conclusions
In this study, we provide an effective estimation of water con-
densate porosity. For this propose, we analyze the experimental
water condensate porosity and compare to the calculated conden-
sate porosity using mercury intrusion porosimetry (MIP) and nitro-
gen and water adsorption for a wide range of carbonate
sedimentary rock types with different petrographic characteristics.
Condensate porosity is obtained with the maximum adsorbed
water at RH = 100% in the water adsorption test. For nitrogen
adsorption characterisation, we interpolated the pore volume
using BJH method applied to the desorption branch and the statis-
tical thickness.
The best estimation of condensate porosity (R2 = 0.9787) is
reached using nitrogen adsorption technique. These results reveal
that the use of the BJH method applied to the desorption branch
method to interpolate the volume of pores with r < 0.1 lm accu-
rately represents the water condensate porosity. The correlation
between condensate porosity using MIP is moderate
(R2 = 0.8916) and presents a wider dispersion for all the range of
condensate porosity studied. This deviation can be attributed to
the differences in the physical process in which both techniques
are based. Moreover, compared to MIP, nitrogen adsorption tech-
nique is recommended from a practical point of view because is
cheaper, Hg-free and can be obtained quickly in the laboratory.
The equation that fits the shape and curvature of the water iso-
therm shows that the maximum adsorbed water and the approxi-
mation coefficient (bW), strongly depend on the pore volume
fraction lower than 0.1 lm. Thus, rocks with small pores (r < 0.1
lm) present higher values of maximum adsorbed water (conden-
sate porosity) and the bW coefficient.
Results establish that the maximum adsorbed water is closely
related to the specific surface area as well as that the ratio between
water condensate porosity and total porosity in the studied porous
rocks varies from 2 to 38%. Accordingly, this volume fraction can be
significant and can affect comfort, energy consumption, and mate-
rial’s strength and durability.
CRediT authorship contribution statement
D. Benavente: Conceptualization, Methodology, Validation,
Writing - original draft, Supervision. I. Such-Basañez: Methodol-
ogy, Validation, Writing - review & editing. A. Fernandez-Cortes:
Investigation, Visualization. C. Pla: Investigation, Visualization. D.
8
Construction and Building Materials 288 (2021) 123131
Cazorla-Amoros: Validation, Investigation. J.C. Cañaveras: Valida-
tion, Investigation. S. Sanchez-Moral: Validation, Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported by the Spanish Ministry of Science,
Innovation and Universities [grant number RTI2018-099052-B-
I00] and Regional Governments of Comunidad Valenciana (Spain)
[grant number AICO/2020/175] and Madrid (Spain) [Top Heritage,
grant number S2018/NMT-4372].
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.conbuildmat.2021.123131.
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