minerals

Article
The Role of Calcite Dissolution and Halite Thermal Expansion
as Secondary Salt Weathering Mechanisms of Calcite-Bearing
Rocks in Marine Environments
Javier Martínez-Martínez 1, * , Anna Arizzi 2 and David Benavente 3

1 Spanish Geological Survey—Higher Council for Scientific Research (IGME-CSIC), 28003 Madrid, Spain
2 Department of Mineralogy and Petrology, University of Granada, 18002 Granada, Spain; [email protected]
3 Department of Earth Sciences and the Environment, University of Alicante, 03080 Alicante, Spain;
[email protected]
* Correspondence: [email protected]

Abstract: This research focuses on the analysis of the influence of two secondary salt weathering
processes on the durability of rocks exposed to marine environments: chemical dissolution of rock
forming minerals and differential thermal expansion between halite and the hosting rock. These
processes are scarcely treated in research compared to salt crystallisation. The methodology followed
in this paper includes both in situ rock weathering monitoring and laboratory simulations. Four
different calcite-bearing rocks (a marble, a microcrystalline limestone and two different calcarenites)



were exposed during a year to a marine semiarid environment. Exposed samples show grain


detachment, crystal edge corrosion, halite efflorescences and microfissuring. Crystal edge corrosion
Citation: Martínez-Martínez, J.; was also observed after the laboratory simulation during a brine immersion test. Calcite chemical
Arizzi, A.; Benavente, D. The Role of dissolution causes a negligible porosity increase in all the studied rocks, but a significant modification
Calcite Dissolution and Halite of their pore size distribution. Laboratory simulations also demonstrate the deterioration of salt-
Thermal Expansion as Secondary Salt
saturated rocks during thermal cycles in climatic cabinet. Sharp differences between the linear
Weathering Mechanisms of
thermal expansion of both a pure halite crystal and the different studied rocks justify the registered
Calcite-Bearing Rocks in Marine
weight loss during the thermal cycles. The feedback between the chemical dissolution and differential
Environments. Minerals 2021, 11, 911.
thermal expansion, and the salt crystallisation of halite, contribute actively to the rock decay in marine
https://doi.org/10.3390/
min11080911
environments.

Academic Editor: Alexander Keywords: halite; marble; limestone; linear thermal expansion coefficient; climatic cabinet
R. Cruden

Received: 13 July 2021

Accepted: 18 August 2021 1. Introduction
Published: 23 August 2021 Rock weathering by salt crystallization is considered one of the most important pro-
cesses acting on the building stones in monuments under marine environments [1–4]. In
Publisher’s Note: MDPI stays neutral these cases, halite (NaCl) is the most frequent, if not the only, mineral phase observed
with regard to jurisdictional claims in in efflorescences and subefflorescences [4,5]. The presence of this salt in monuments is
published maps and institutional affil-
explained by means of different mechanisms for marine salt supply including capillary up-
iations.
take, saline rainwater incursion, condensation of atmospheric humidity, or dry deposition
of marine aerosol [2,4,6].
Halite can crystallise only when the environmental relative humidity is lower than
its critical deliquescence point (75.3%) [7]. This reference value is nearly independent of
Copyright: © 2021 by the authors. temperature, and the influence of other salt species is slight. In dry environments (relative
Licensee MDPI, Basel, Switzerland. humidity lower than 75.3%), sodium chloride precipitates generating salt crystallization
This article is an open access article stresses on the solid structure of the rock that can cause the failure of the weakest parts of
distributed under the terms and
the rock. However, some studies conclude that halite is relatively ineffective generating
conditions of the Creative Commons
crystallization pressures and, consequently, it generates a low level of physical damage in
Attribution (CC BY) license (https://
the built heritage [8–10]. Notwithstanding, several authors consider that halite damage is
creativecommons.org/licenses/by/
linked to other secondary weathering mechanisms such as thermal expansion [11] and/or
4.0/).

Minerals 2021, 11, 911. https://doi.org/10.3390/min11080911 https://www.mdpi.com/journal/minerals

Minerals 2021, 11, 911 2 of 15

the dissolution of the host rock, mainly in the calcite fraction [12,13]. Nevertheless, these
other two decay processes have received much less attention than the salt crystallization
effect, despite the fact that the effectivity of the last one is thrown into question.
Calcite-bearing rocks (limestones and marbles) are widely used as building materials
in both modern buildings and monuments, and their use is ubiquitous in façade claddings,
pavements, interior and exterior structures, etc. The huge interest in the use of these
rocks as building materials is justified mainly by their aesthetical properties and its good
workability. However, in outdoor environments, they can undergo significant physical
weathering especially when the presence of salty solutions in the porous system of the
rock is high. Due to this fact, special attention must be paid to all the weathering processes
acting on these building rocks in order to obtain a better understanding of the suitability of
given dimension stone for certain applications. New advances in this topic contribute to
achieving a more comprehensive knowledge of the rock decay risk, as well as to offering a
higher guarantee of durability.
The aim of this paper is to analyse the effectivity of the thermal expansion and the
chemical dissolution as secondary weathering mechanisms acting on the NaCl-CaCO3
system. This study includes both in situ monitoring and laboratory simulations. On the
one hand, the textural evolution of calcite-based rock samples (limestones, marbles and
calcarenites) was analysed after one year of direct exposure under marine conditions. On
the other hand, several tests were carried out in the laboratory in order to quantify the
response of studied rocks during both thermal shock and chemical dissolution tests. Results
will contribute to understand the real effects of the NaCl brine in the porous system of
rocks and their consequences on the decay and conservation of the built heritage in marine
environments.

2. Materials
Four different types of calcite-based rocks were selected for this study: a marble, a
massive (low-porous) limestone, and two different types of calcarenite (Figure 1). Selection
criteria attends to differences in porosity and pore-size distribution. Hand sample descrip-
tion was completed with microscope observations of thin sections under petrographic
optical microscope (Axioskop 20, Zeiss, Oberkochen, Germany). Mineralogical composi-
tion of studied rocks was analysed by powder X-ray diffraction in a Philips PW-1710/00
(Philips, Amsterdam, Netherlands) diffractometer (Cu Ka radiation with a Ni filter and a
setting of 40 kV and 40 mA). Rock porous system was characterised by means an Autopore
IV 9500 (Micromeritics, Norcross, Georgia) mercury porosimeter.
Marble sample (Mb) correspond to a homogeneous white calcite marble. Rock texture
is homeoblastic and xenoblastic, and the mean crystal size is about 740 µm, although crystal
sizes of up to 2 mm have been observed. Mineralogically, it is constituted fundamentally of
calcite (~99%) and very low quantities (2–5%) of other minerals such as quartz, muscovite,
plagioclase, pyrite, apatite, and zircon. Porosity is lower than 1%.
The grey massive limestones (Ls) constitute a dense microcrystalline rock (crystal
size of 20–40 µm) with porosity values ranging between 0.5 and 1.5%. Mineralogical
composition corresponds to 98% of calcite and low quantities of clay and dolomite. The
porous system is mainly centred on small pores (mainly fissures of ~2 µm in size) poorly
connected.
The two calcarenites show marked textural differences. One of them (Cg) corresponds
to a coarse-grained calcarenite (also named calcirrudite as the average grain size higher
than 2 mm) with a high content of algal rhodolith (several centimetres in size), and,
subordinately, briozoans and foraminifera. Lithoclast content is very low (mainly quartz).
The second calcarenite type (Cf) constitutes a fine-grained sandy calcarenite. Bioclast are
mainly foraminifera and, subordinately, fragments of briozoa, red algae and echinoderms.
Lithoclasts (tens of microns in size) are mainly composed of rock fragments of both volcanic
rocks and limestones, but some quartz grains can also be observed. Both selected varieties
have a complex porous media characterised by high porosity (16.15–24.13%). In both
Minerals 2021, 11, 911 3 of 15

cases, porous system presents a main pore population centered in a narrow3 ofpore
Minerals 2021, 11, x FOR PEER REVIEW 16
size range
(0.2–1 µm for Cf and 0.08–1 µm for Cg).

Figure 1. Geographical location of the Nueva Tabarca island (A,B). Location and position of the rock samples exposed to
Figure 1. Geographical location of
the marine environment theand
(C–E) Nueva
sketchTabarca island (A,B).
of the preparation Location
of the samples (F).and position
Studied of the
lithotypes: rock samples
coarse-grained exposed to the
calcar-
marine environment (C–E) and calcarenite
enite (Cg); fine-grained sketch of(Cf);
thewhite
preparation of the
marble (Mb) samples
and grey (F).limestone
massive Studied(Ls).
lithotypes: coarse-grained calcarenite
(Cg); fine-grained calcarenite (Cf); white marble (Mb) and grey massive limestone (Ls).
Marble sample (Mb) correspond to a homogeneous white calcite marble. Rock tex-
ture is homeoblastic and xenoblastic, and the mean crystal size is about 740 µm, although
3. Methodology
crystal sizes of up to 2 mm have been observed. Mineralogically, it is constituted funda-
mentally
The of calcite (∼99%)
methodology and very
followed inlow quantities
this (2–5%) of other
study included bothminerals
in situsuch as quartz, and labora-
monitoring
muscovite, plagioclase, pyrite, apatite, and zircon. Porosity is lower than 1%.
tory simulations.
The grey massive limestones (Ls) constitute a dense microcrystalline rock (crystal
size of 20–40 µm) with porosity values ranging between 0.5 and 1.5%. Mineralogical com-
3.1. Inposition
Situ Rock Weathering
corresponds to 98%Monitoring
of calcite and low quantities of clay and dolomite. The porous
system is mainly centred
One sample of each lithology on small wasporesexposed
(mainly fissures of ~2 µm
to a marine in size) poorly
environment con-the course of
over
nected.
one year. Samples were located at the south façade of the museum building of the Nueva
The two calcarenites show marked textural differences. One of them (Cg) corre-
Tabarca Island
sponds to a(Figure 1). The
coarse-grained museum
calcarenite location
(also is in a completely
named calcirrudite flat plain
as the average and very close
grain size
to thehigher
seacoast (50 m). Due to the absence of sheltering structures, all the
than 2 mm) with a high content of algal rhodolith (several centimetres in size), and, samples present
seaward exposure.briozoans and foraminifera. Lithoclast content is very low (mainly quartz).
subordinately,
The second
The exposed calcarenite
face oftype
each(Cf)rock
constitutes
was apreviously
fine-grained sandy calcarenite.
polished, and Bioclast
the lowerare half of the
mainly foraminifera and, subordinately, fragments of briozoa, red algae and echinoderms.
sample was covered with a heat shrink-wrap in order to protect it from weathering agents
Lithoclasts (tens of microns in size) are mainly composed of rock fragments of both vol-
(Figure 1F).
canic Before
rocks sample location
and limestones, in thegrains
but some quartz Nueva Tabarca
can also museum,
be observed. rock surface was
Both selected
observed under
varieties have aa complex
Scanning Electron
porous Microscopebyinhigh
media characterised backscattering electron
porosity (16.15–24.13%). In mode (BSE-
SEM, both cases, Hitachi,
S3000N, porous system presents
Tokyo, a main
Japan). poremicroscope
The population centered
used inin athis
narrow
studyporewas
size a HITACHI
range (0.2–1 µm for Cf and 0.08–1 µm for Cg).
S-3000 N (Hitachi, Tokyo, Japan) variable pressure SEM working at low vacuum. An
Energy Dispersion Spectrometer (Bruker-XFlash 3001 EDS, Bruker, Billerica, MA, USA) is
3. Methodology
attached for chemical microanalysis and compositional mappings. SEM observations of
rocks were carried out again after a one-year exposure to marine conditions. The same
areas of the rock surface were used as checkpoints in order to compare the rock texture
before and after the one-year exposure. Non-exposed (covered) parts of the samples were
also analysed in order to corroborate that observed changes were directly related to marine
exposure.
Local climatic parameters were measured during the exposure period by means of a
weather station (Davis-Wireless Vantage PRO2, Davis Instruments Corp. Inc., Hayward,
Minerals 2021, 11, 911 4 of 15

CA, USA) which included a tipping-bucket rain gauge (Davis 7852) for rainfall measure-
ments and a 12-bit smart Sensor (Davis 7315) to measure the relative humidity and air
temperature with an accuracy of ± 0.5 ◦ C above −7 ◦ C, and ± 2% from 10% to 100%
relative humidity. The Data Acquisition System consisted of a WeatherLink (#6510USB)
data logger.

3.2. Laboratory Simulation: Differential Thermal Expansion

The linear thermal expansion coefficient (αT ) of the studied rocks was determined
by means of Thermomechanical Analysis (TMA). The equipment used is a Q400 TA In-
struments Thermomechanical Analyser (Research Support Services, Alicante University,
Alicante, Spain) that may work from −70 ◦ C to 800 ◦ C with a maximum strength of 2N.
The linear thermal expansion of a pure crystal of halite was also measured. All samples
were exposed to three heating–cooling cycles, ranging temperatures between 30 ◦ C and
70 ◦ C. Linear thermal expansion coefficient was calculated from the formula:

1 dl
αT = · (1)
l0,T dT

where l0,T is the length at a reference temperature.

Differential thermal expansion between halite crystals and the hosting rock was
visually checked using an Environmental Scanning Electron Microscope (ESEM) (Centre for
Scientific Instrumentation, Granada University, Granada, Spain). This microscope is a low-
vacuum SEM with the ability to examine samples under a range of different environments.
The environmental chamber can be manipulated in terms of atmosphere, temperature
(−5 ◦ C to 60 ◦ C), and pressure (0 to 20 Torr). A rock sample previously filled with both
halite efflorescences and subefflorescences was tested in ESEM with variable temperature
conditions (from 3 to 50 ◦ C) in order to observe differences in thermal expansivity.
Rock damages caused by differential thermal expansion between both halite crystals
present in the porous system of rocks and the rock hosting were simulated in a climatic
cabinet. The experiments used three prismatic samples (3 cm × 3 cm × 6 cm) of the studied
rocks. Stone blocks were dried in an oven until a constant weight. Once dried, the blocks
were immersed in a saturated NaCl solution for 10 h and then they were dried under room
conditions for 14 h. The saturation-drying cycle was repeated 10 times in order to obtain
both dense halite efflorescences and subefflorescences over and inside the samples.
The cabinet used for differential thermal expansion tests was a Sanyo-FE 300H/MP/R20
(Sanyo, Santa Fe Springs, California, USA) (inner volume: 675 × 630 × 650 mm3 ), available
at the University of Oxford, with a steady thermostat and an external temperature–moisture
programmer. The cabinet was programmed with a 24-h temperature cycle. The air temper-
ature during the cycle oscillated between 20 and 70 ◦ C with an initial 7 h constant-speed
heating ramp and 9 h of constant-speed cooling. Each cycle finished with 8 h at a constant
temperature (20 ◦ C). The relative humidity within the cabinets varied between 60% (at
20 ◦ C) and 50% (at 70 ◦ C). These values were selected to avoid any damage caused by halite
crystallization in the porous system of rocks during the test. It was avoided by establishing
the relative humidity inside the climatic cabinet under 75.3.%. This value corresponds
to the critical deliquescence point for halite. Consequently, dry conditions (RH < 75.3%)
during the whole test guarantee the presence of halite inside the rock in its solid phase.
To remove the salts from the samples, they have been immersed in distilled water at
50 ◦ C to prevent damage during cleaning, and the water was changed every day. Electrical
conductivity of the water used to wash the samples was monitored to follow its degree
of saturation, since the concentration of NaCl in the solution has a significant influence
on it. Samples were considered clean when the electrical conductivity was stable around
0.3 mS/m while deionised water had a conductivity of 0.1 mS/m.
Changes in the appearance of samples were controlled visually during the experiment
and their weight loss was recorded at the end of the experiment.
Minerals 2021, 11, 911 5 of 15

3.3. Laboratory Simulation: Chemical Dissolution

The chemical dissolution experiment was carried out in a saline solution, which
represents the salt chemical weathering of studied rocks in saline environments. The
experiment used 2 cm cubes of each lithology. Calcite dissolution was carried out in a stirrer
cell, filled with a saline NaCl solution (pH of 8.44) at 25 ◦ C and a constant atmospheric CO2
concentration of 440 ppm. Under this experimental condition, only the calcite dissolution
is produced and no other salts precipitate on the calcite surface. During the experiment,
the solution was magnetically stirred at 300 rpm to ensure homogeneity. Dissolution
conditions were maintained for 72 h. This test duration was established taking into account
that, although the first isolated dissolution pits appear almost immediately (within the first
10 min of reaction) [14], the depth of these first pits is mainly around 0.3–0.6 nm and even
after several hours of dissolution, some areas of the surface show only isolated shallow
pits (~1 nm deep).
Two adjacent rock blocks (1.5 cm cubes) were obtained from each lithology. One
of them was used for characterizing the porous system of the rock in fresh conditions.
Pore size distribution was obtained in an Autopore IV 9500 (Micromeritics, Norcross,
Georgia) mercury porosimeter. Pore size interval characterization by mercury intrusion
porosimetry ranges from 0.006 to 200 µm. The other cube was used for the chemical
dissolution experiment. After the test, the appearance of the weathered rock surface was
observed under BSE-SEM. Moreover, pore size distribution of the weathered sample was
measured by MIP.

4. Results and Discussion

4.1. Rock Textural Changes after Direct Exposure to Marine Environment
Rock samples were exposed to a Mediterranean semiarid climate (“Csa” according to
Köppen–Geiger climate classification). Table 1 shows the climatic parameters measured
in the Nueva Tabarca weather station. The region is characterised by hot, dry summers
and mild, wet winters. The relative humidity is high due to the proximity of the sea, with
an average annual value of 74.3%. Annual rainfalls are low (251 mm during the studied
period) in accordance with the prevailing semiarid climate. During the summer, there
are long periods of drought, with only short and punctual rainfalls. Torrential rains are
characteristic in autumn and winter, reaching records of 66.6 mm in less than 12 h.

Table 1. Climatic data of Nueva Tabarca Island.

Temperature (◦ C) RH (%) Rainfall

Month
Mean Min Max Mean Min Max (mm)
January 12.5 4.3 20.2 78.0 36.0 96.8 45.8
February 12.6 5.5 21.1 74.9 32.1 94.8 67.5
March 13.0 6.0 21.1 78.9 34.7 97.3 74.6
April 16.9 13.2 21.2 74.0 37.5 94.4 0.0
May 19.3 13.7 23.2 81.9 41.2 95.6 3.2
Jun 23.2 18.3 29.8 80.1 36.2 94.1 0.0
July 26.1 22.8 31.6 81.9 48.3 93.8 0.2
August 26.8 23.4 30.2 78.3 50.0 90.1 4.2
September 25.0 22.2 31.1 71.5 38.4 86.5 0.0
October 21.0 16.8 24.9 72.9 38.3 92.7 4.6
November 17.9 10.3 26.6 70.5 32.5 92.1 18.2
December 12.3 3.6 19.3 75.0 34.6 94.2 11.0

At the mesoscale, weathered samples do not show any noticeable decay sign with
naked eye. Exceptionally, the shine of the polished surface of porous samples (it means, in
Cf and Cg rock blocks) has been lost at some points due to the increase in roughness associ-
ated with weathering processes. This roughness increase also causes a colour change [15],
especially visible in the dark rocks (Ls variety).
Minerals 2021, 11, 911 6 of 15

However, microscopically, there are significant textural changes in all the tested rocks.
Figure 2A–D illustrates the textural evolution of studied rocks after direct exposure to the
marine environment. Images show exactly the same area before and after the in situ test.
Remarkable differences are observed between fresh and weathered surfaces,
Minerals 2021, 11, x FOR PEER REVIEW depending
7 of 16
the developed decay patterns on the studied lithology.

(A)

(B)

Figure 2. Cont.
Minerals 2021, 11, 911
Minerals 2021, 11, x FOR PEER REVIEW 8 of 16 7 of 15

(C)

(D)

Figure 2.Figure 2. (A) Textural

(A) Textural evolution
evolution of Mbof Mb sample
sample (calcitemarble)
(calcite marble) after
afterdirect exposure
direct exposure to marine environment.
to marine Images A’Images A0
environment.
0 and B’ correspond to the weathered aspect of A and B. Images C and D are surface details obtained in the red squares of
and B correspond to the weathered aspect of A and B. Images C and D are surface details obtained in the red squares of
A’ and B’, respectively. (B) Textural evolution of Ls sample (microcrystalline limestone) after direct exposure to marine
A0 and Benvironment.
0 , respectively. (B) Textural evolution of Ls sample (microcrystalline limestone) after direct exposure to marine
Images E’ and F’ correspond to the weathered aspect of E and F. Arrow in E’ shows the apparition of new
factures.
environment. Image G
Images E’isand
a surface detail obtained
F’ correspond in the
to the red squareaspect
weathered of F’. Image H is aF.surface
of E and Arrow detail
in E’ofshows
the weathered surface of new
the apparition
0
factures. Image G is a surface detail obtained in the red square of F . Image H is a surface detail of the weathered surface
of Ls sample. (C) Textural evolution of Cf sample (fine-grained calcarenite) after direct exposure to marine environment.
Images I0 and J0 correspond to the weathered aspect of I and J. Stars in I0 and J0 indicate examples of grain detachment.
Images K and L correspond to surface details of the weathered surface of Cf sample. (D) Textural evolution of Cg sample
(coarse-grained calcarenite) after direct exposure to marine environment. Images M0 and N0 correspond to the weathered
aspect of M and N. Stars in M0 and N0 indicate examples of grain detachment. Arrow in N’ shows the apparition of new
factures. Images O and P correspond to surface details of the weathered surface of Cg sample.
Minerals 2021, 11, 911 8 of 15

Marble (Mb sample, Figure 2A) shows chemical corrosion of crystal edges and intra-
crystalline line defects (cleavage planes) (Figure 2A, image D). Martínez-Martínez et al. [16]
observed similar dissolution patterns in marbles chemically weathered in brine immersion.
Corrosion of samples occurs preferentially on the crystal edges rather than in the interior,
due to two main reasons. On the one hand, calcite dissolution occurs by the creation of
both shallow and deep pits at the surface [14]. The formation of these pits, especially the
deep ones, is likely driven by line defects, contributing to the more intense dissolution of
these planes. On the other hand, inter-crystalline cracks constitute moisture flow paths
where the contact rock-brine is more prolonged. Evidence of these preferential ways for
penetration and evaporation of moisture to and from the inner rock is the presence of saline
efflorescences (halite crystals) growing throughout inter-crystalline contacts (Figure 2A,
image C).
Microweathering signs on the surface of the massive limestone sample (Ls, Figure 2B)
are very similar to those observed on Mb surface but adapted to the microcrystalline
texture of Ls rock. The most characteristic decay pattern is the corrosion of crystal edges
(Figure 2B, image H). This chemical dissolution is much more intense in calcite than in
the dolomite crystals included in the rock mass (dark minerals in Figure 2B, image G).
The higher chemical stability of dolomite than calcite has been deeply studied [17,18]. Ls
also show calcite veins with high crystal size (up to 0.4 mm) around which cracks are
developed during weathering (white arrow in image E0 , Figure 2B). These cracks result
from the coalescence of previous intercrystalline microcracks formed because of widening
of intercrystalline contacts.
The two calcarenites (Cf and Cg; Figure 2C,D, respectively) develop similar decay pro-
cesses. In both cases, grain detachment (examples marked with white stars in photographs
I0 , J0 , M0 and N0 , Figure 2C,D) and the appearance of efflorescences and subefflorescences
(white areas and white crystals in photographs K, L, O and P, Figure 2C,D) are the main
weathering signs after one year of direct exposure. Intragranular microcracks also appeared
in a few points in Cg (white arrow in image N0 , Figure 2D).
These results are compatible with the decay patterns and weathering processes ob-
served in the rock blocks of the cultural heritage of the Nueva Tabarca Island. Both porous
limestones (Cf and Cg) are extensively used in the local buildings [5]. Salt subefflorescences
and grain detachment are the main weathering processes observed in porous limestones
(Cf and Cg), resulting in larger decay forms such as differential erosion or honeycomb
patterns [5]. After 244 years of exposure, the erosion rates measured in the building stone
blocks of the monuments vary between 0.11 and 0.28 mm/year. Despite the submillimetric
range of these rates, they are slightly overestimated, taking into account the material loss
observed in these rocks under SEM after one year of direct exposure. This fact can be
explained because stone decay behaves most often as a non-linear system, and rock weath-
ering degrees do not change proportionally to time [19]. The so-called “catastrophic decay”
seems to be particularly common in sandstones [20], but are also found in limestones [21].
All these weathering patterns developed in marine conditions are mainly due to the
presence of halite (in its crystalline form or in the brine) in the porous system of the rock.
The location of the tested samples on the upper part of the building indicate that salt supply
is carried out by sea-spray deposition [1,4]. Once marine aerosol has been deposited on
the stone surface, halite is dissolved, and the dissolution penetrates towards the inside of
the stone. This process will be more important in those rocks with a higher proportion
of micropores (radius lower than 1 µm) because they are the responsible for the moisture
adsorption and condensation processes. However, a low penetration depth of the brine
inside the rock is expected, leaving a wet layer closer to the stone surface. Then, wind-
enhanced evaporation of the saline solution induces the formation of subefflorescence,
resulting in granular disintegration [9]. The cyclic repetition of this wet–dry process
supposes a continuous supply and flow of salty solution to the rock, favoring the chemical
dissolution of soluble minerals (calcite).
als 2021, 11, x FOR PEER REVIEW 10 of 16

4.2.
Minerals 2021, 11, 911 Rock Weathering during Thermal Cycles 9 of 15
Figure 3 illustrates the comparison between the linear thermal expansion of the dif-
ferent studied rocks and a pure crystal of halite. The linear thermal expansion coefficient
(αT) of studied rocks range between 0.90 × 10−6 °C−1 (marble, Mb) and 7.72 × 10−6 °C−1 (fine-
Chemical dissolution and halite subefflorescences act mainly as weathering agents
grained sandy(in calcarenite,
contraposition Cf). The halite agents),
to erosion sample shows
causinga the
noticeable higher thermal
initial weakness ex- surface, and
of the rock
pansivity thantherefore
rocks. This different behaviour during heating was visually
increasing the efficiency of the subsequent erosive process. Previous checked by studies
means of an Environmental Scanning Electron Microscope (ESEM) (Figure 4). During
conclude that, in the semiarid Mediterranean climate, wind-driven rain is revealed as the the
test, a pore partially filled with
main erosion halite
process crystalsdue
especially wastoobserved during
its torrential the heating
character [5]. process.
As the temperature rises from 3 °C to 50 °C (image sequence from A to D in Figure 4), the
expansion of 4.2.
the crystal length is during
Rock Weathering observed, while
Thermal the walls of the hosting pore remain
Cycles
unchanging. Figure 3 illustrates the comparison between the linear thermal expansion of the
Previous different
studies [11] point
studied out and
rocks that aifpure
the pores
crystalofofahalite.
stone become
The linearfilled withexpansion
thermal halite, coefficient
the mismatch(α inT )the coefficient of thermal expansion
of studied rocks range between 0.90 × 10 can be
− 6 destructive.
◦ − 1 Given than
C (marble, Mb) and 7.72 the × 10−6 ◦ C−1
thermal stress(fine-grained
of halite is roughly equal to the
sandy calcarenite, product
Cf). E·Δαsample
The halite T·ΔT, where
showsEaisnoticeable
the Young higher thermal
modulus (35 GPa for halite)
expansivity thanand the thermal
rocks. expansion
This different mismatch
behaviour between
during heatingstonewasand salt checked by
visually
(ΔαT) is 30 × 10means
−6 °C−1 approximately, this is about 1 MPa per degree change in temperature.
of an Environmental Scanning Electron Microscope (ESEM) (Figure 4). During the
According to this
test,result,
a porethe changefilled
partially in temperature
with halitefrom day to
crystals was night could generate
observed during the stress
heating process.
exceeding theAs tensile strength of stone ◦
(frequently ◦
lower than 10 MPa in this rock
the temperature rises from 3 C to 50 C (image sequence from A to D in Figure 4), the types,
[22]) This theoretical
expansion damage
of theiscrystal
effective whenispores
length are full
observed, of salt,
while the and
wallsitsofeffectiveness
the hosting pore remain
decreases progressively
unchanging. as the salt filling degree decreases.

Figure
Figure 3. Linear 3. Linear
thermal thermal
expansion of expansion of studied
the different the different
rocks studied rocks
and a pure and of
crystal a pure crystal
halite. of halite. Cg: calcarenite;
Cg: coarse-grained
coarse-grained calcarenite; Cf: fine-grained calcarenite;
Cf: fine-grained calcarenite; Ls: massive limestone; Mb: marble. Ls: massive limestone; Mb: marble.

Previous studies [11] point out that if the pores of a stone become filled with halite, the
mismatch in the coefficient of thermal expansion can be destructive. Given than the thermal
stress of halite is roughly equal to the product E·∆αT ·∆T, where E is the Young modulus
(35 GPa for halite) and the thermal expansion mismatch between stone and salt (∆αT ) is
30 × 10−6 ◦ C−1 approximately, this is about 1 MPa per degree change in temperature.
According to this result, the change in temperature from day to night could generate
stress exceeding the tensile strength of stone (frequently lower than 10 MPa in this rock
types, [22]) This theoretical damage is effective when pores are full of salt, and its effective-
ness decreases progressively as the salt filling degree decreases.
Hence, differential thermal expansion can justify (or at least can contribute to justify-
ing) some of the weathering patterns observed during the direct exposure of rocks to the
marine semiarid conditions, such as the grain detachment in areas with subeffloresnces, as
well as the widening and development of microcracks in Ls and Cg (images E0 and N0 in
Figure 2B,D, respectively).
Minerals
Minerals 2021,
2021, 11,
11, x911
FOR PEER REVIEW 11
10 of
of 16
15

Figure 4.
Figure Thermalexpansion
4. Thermal expansionofof halite
halite crystals
crystals inside
inside a pore
a pore during
during the heating
the heating process.
process. Photographs
Photographs taken taken with
with an an
Envi-
Environmental
ronmental Scanning
Scanning Electron
Electron Microscope
Microscope (ESEM).
(ESEM). Images Images (A–D)
(A), (B), illustrate
(C) and the evolution
(D) illustrate of the crystal
the evolution of the morphology
crystal mor-
phology during
during the theprocess
heating heatingfrom
process
coldfrom
(image at 3 ◦ C)
coldA,(image A,toatwarm
3 °C) to warm conditions
conditions at 50 ◦D,
(image D,(image C).at 50 °C).

The real
Hence, effectiveness
differential of this
thermal weathering
expansion can process
justify (orwas checked
at least by means of
can contribute to the lab-
justify-
oratory
ing) some simulation in the climatic
of the weathering patterns cabinet.
observed Table 2 shows
during the weight
the direct exposure lossofmeasured
rocks to the in
each rock
marine sampleconditions,
semiarid after the test.
suchMoreover,
as the grain mean weight increment
detachment in areas withper rock variety was
subeffloresnces,
also
as calculated
well with respect
as the widening to the initial weight.
and development Results show
of microcracks that Cg
in Ls and thermal
(imagesexpansion
E’ and N’ of
halite present as both efflorescences
in Figure 2B and 2D, respectively). and subefflorescences in the porous system of rocks
is anTheeffective weathering process.
real effectiveness It is especially
of this weathering aggressive
process was checkedin porous rocks of
by means (weight loss
the labor-
up to 2% after the test), while the weight loss measured in massive
atory simulation in the climatic cabinet. Table 2 shows the weight loss measured in each varieties (Ls and Mb)
is almost
rock sample zero. In the
after fact,test.
Ls and Mb register
Moreover, meana weight
slight increment
incrementinper therock
sample weight
variety was even
also
after the cleaning
calculated process
with respect in distilled
to the water.Results
initial weight. This increment
show thatcan be explained
thermal expansion due to the
of halite
remaining
present of small
as both quantities of
efflorescences andsalts in the tortuous pore
subefflorescences in the network.
porous system of rocks is an
Two reasons explain the lower durability of
effective weathering process. It is especially aggressive in porous Cf and Cg during
rocks the cabinetloss
(weight test.
upOn to
2% after the test), while the weight loss measured in massive varieties (Ls and Mb) is Cg
the one hand, they are much more porous than Mb and Ls (porosity values of Cf and al-
rage between
most 16 and
zero. In fact, Ls 24%,
and Mb whilst they are
register around
a slight 1% for Ls
increment in and Mb). Porosity
the sample weightcontrols
even after the
amount of salt crystallised inside the rock. The higher the rock capacity to contain salts, the
the cleaning process in distilled water. This increment can be explained due to the remain-
higher the thermal stresses generated during heating processes when pores are completely
ing of small quantities of salts in the tortuous pore network.
filled with halite.
Table 2. Weights measured in each Onrock
thesample
other hand,
beforethe
andmechanical properties
after the thermal cyclesof
in rocks
climaticarecabinet.
a key factor
Three for rock (A,
samples durabil-
B and C) per rock variety were tested. Mean weight increment (%) per rock variety is also calculated with respect to theWhen
ity due to the fact that strength is the material’s resistance to weathering processes.
initial weight. the tensile strength of a rock is lower than or similar to the thermal stresses generated dur-
ing thermal dilation of halite inside pores, rock tends to suffer disintegration, detachment
Sample and fracturation
Initial State at the outer
After layers
Salt of the block [11,23]. InAfter
Saturation
Cabinet
this sense, TestCg are softer
Cf and
than Mb and Ls. According to previous works,With Cf and Salts After Saltstrength
Cg compressive Removing ranges
A between 34.119.69 and 44.22 MPa34.66 [5], whilst the mean 34.66 value for Ls is around34.11 110.10 MPa and
Weight (g) B 89.41 34.46 MPa for Mb [16]. 34.98 34.98 34.48
Ls
C 24.86 25.29 25.28 24.85
Mean Weight increment (%) 1.69 1.61 0.02
Minerals 2021, 11, 911 11 of 15

Table 2. Weights measured in each rock sample before and after the thermal cycles in climatic cabinet. Three samples (A, B
and C) per rock variety were tested. Mean weight increment (%) per rock variety is also calculated with respect to the initial
weight.

After Cabinet Test

Sample Initial State After Salt Saturation
With Salts After Salt Removing
A 34.1 34.66 34.66 34.11
Weight (g) B 34.46 34.98 34.98 34.48
Ls
C 24.86 25.29 25.28 24.85
Mean Weight increment (%) 1.69 1.61 0.02
A 38.91 41.88 41.01 38.13
Weight (g) B 44.85 47.68 46.55 43.97
Cf
C 42.69 45.55 44.6 41.89
Mean Weight increment (%) 6.88 4.55 −1.95
A 54.03 58.98 57.84 53.15
Weight (g) B 49.66 54.5 53.58 49.02
Cg
C 50.07 54.89 53.78 49.2
Mean Weight increment (%) 9.51 7.45 −1.55
A 48.96 48.98 48.98 48.97
Weight (g) B 47.51 47.5 47.5 47.5
Mb
C 52.81 52.84 52.84 52.82
Mean Weight increment (%) 0.02 002 0.01

4.3. Rock Weathering during Brine Immersion Test

Figure 5 illustrates the weathered surface of the rocks tested in the brine immersion
test. Observations corroborate the preferential chemical corrosion of crystal edges and
intra-crystalline line defects, rather than discontinuity-free crystal areas. The solubility
of calcite is higher in NaCl solutions than in pure water [24]. Calcite solubility increases
about 2% with 1 mmol of dissolved NaCl and about 10% with 10 mmols [25]. At the same
time, the presence of sodium chloride in solution also accelerates the dissolution of calcite.
Nevertheless, calcite dissolution in basic media (brines) is much less aggressive than in
acid solutions, common in meteoric waters in polluted air environments [26].
The resulting weathered textures of Mb and Ls are very similar to those observed after
the direct exposure of samples to the marine environment, confirming that the chemical
dissolution of calcite minerals acts as an effective weathering agent during rock exposure
under marine conditions.
Mineral corrosion modifies the characteristics of the porous system of rocks, increasing
in most of the cases the pore connection, and lastly favouring the effectiveness of posterior
weathering agents. Figure 6 shows the MIP curves obtained in the fresh and weathered
rock samples before and after the brine immersion test, respectively. For all the rocks, the
porosity is higher in the weathered samples than in the fresh ones. Even if this porosity
increase, in absolute values, is almost negligible (less than 1%) in relative values, it doubles
the initial porous content of some of the rocks (Ls, for example). Changes in the pore size
distribution are related to: (1) the appearance of new pore families (pore family centred in
0.1 µm in Ls); (2) the increase in volume of some pore families (pore family of 2–10 µm in
Mb; or pore family centred in 100 µm in Ls); (3) displacement of the MIP curve to the right
(towards bigger pore radii; Cf and Cg curves, for example); (4) displacement of the MIP
curve to the left (i.e., towards smaller pore radii; Cf curve).
Minerals 2021, 11, 911 12 of 15
Minerals 2021, 11, x FOR PEER REVIEW 13 of 16

Figure5.
Figure 5. Weathered
Weatheredsurface
surfaceof
ofthe
therocks
rockstested
testedin
inthe
thebrine
brineimmersion
immersiontest.
test.Photographs
Photographstaken
takenwith
with
a Scanning Electron Microscope.
a Scanning Electron Microscope.

The resulting
Angeli weathered
et al. [27] analysed textures
the evolutionof MbofandMIPLscurves
are very
aftersimilar to those observed
salt crystallization tests,
after the direct
registering fiveexposure of samples
possible cases for the toevolution
the marineofenvironment,
the MIP curves confirming that the chem-
after weathering tests.
ical dissolution
Their conclusions of cannot
calcite minerals
be completelyacts astransferred
an effectiveto weathering
the discussionagentof during rock expo-
our results due
sure
to theunder marine
fact that theyconditions.
consider the presence of salt crystals in the porous system of rocks.
Mineral
However, the corrosion modifies used
general reasoning the characteristics
by Angeli et al.of the porous
explains system
most of theof modifications
rocks, increas-
ing in most
observed in of
thetheMIPcases the pore
curves afterconnection, and lastlytest.
the brine immersion favouring
Firstly,the
theeffectiveness
apparition of ofnew
pos-
pore
teriorfamilies
weatheringis related to the
agents. dissolution
Figure 6 showsof crystal
the edges, obtained
MIP curves creating ainnew the pore
freshnet
andwithout
weath-
connection to the previous
ered rock samples before and porous
after the system. This situation
brine immersion test, can be only seen
respectively. in the
For all massive
rocks,
crystalline
the porosity low-porous
is higher inrocks, such as Lssamples
the weathered samples. than in the fresh ones. Even if this porosity
Secondly,
increase, when the
in absolute edgeisdissolution
values, occurs(less
almost negligible in porous
than 1%)rocks, two situations
in relative values, can be
it dou-
observed. On the
bles the initial one hand,
porous a new
content micropore
of some of thenet (dissolved
rocks (Ls, forinter-crystalline
example). Changes discontinuities)
in the pore
is connected
size to theare
distribution previous
relatedporous
to: (1) system. In this case,
the appearance the MIP
of new porecurve shifts
families to lower
(pore values
family cen-
(displacement to the left) due to the fact that new small entries to
tred in 0.1 µm in Ls); (2) the increase in volume of some pore families (pore family of 2– the pores are created.
This
10 µmsituation
in Mb; could
or porebefamily
interpreted
centred as in
an100
exaggeration
µm in Ls);of (3)the ink bottle phenomenon.
displacement of the MIP curve On
the other
to the hand,
right the dissolved
(towards bigger poreedges constitute
radii; Cf andtheCgentry to for
curves, pre-existing
example);chambers. In this
(4) displacement
case,
of thethe
MIPdissolution
curve to the process widens
left (i.e., towards the smaller
pore entry,
poreand theCfMIP
radii; curve shifts to bigger
curve).
values (displacement to the right).
Finally, a global pore wall dissolution (including both pore chamber and entries) can
occur in all the porous system of the sample. In this case, an increase in the pore volume is
registered in the MIP curve as well as a slight displacement to bigger pore sizes.
According to the above reasoning, chemical dissolution of massive crystalline rocks
in a brine immersion tend to create new pore families associated with the dissolution of
crystal edges. This new family can either increase the connectivity of the pre-existent
porous system (Mb) or create a new pore net without connection with previous pores (Ls).
 Minerals 2021, 11, 911 13 of 15

In the case of porous rocks (Cf and Cg), chemical dissolution causes the widening of pore
s 2021, 11, x FOR PEER REVIEW entries as well as the creation of new micropores that increase the ink
14 bottle
of 16 character of
the porous system.

Figure
Figure 6. 6. MIPobtained
MIP curves curves obtained in the
in the fresh andfresh and weathered
weathered rock before
rock samples samples before
and after and after the
the brine brine test.
immersion
immersion test.
5. Conclusions
Angeli et al. [27] analysed the evolution of MIP curves after salt crystallization tests,
The results obtained from this paper demonstrate that mineral dissolution and differ-
registering five possible cases for the evolution of the MIP curves after weathering tests.
ential thermal expansion between both halite and hosting rock are active mechanisms of
Their conclusions cannot beof
deterioration completely
calcite-based transferred to the to
rocks exposed discussion of our resultsThese
marine environments. due toconclusions are
the fact that they consider the presence of salt crystals in the porous system
based on the analysis of the behaviour of four different litotypes (a marble, of rocks. How-a limestone and
ever, the generaltworeasoning used
calcarenites) by Angeli
during et al. explains most
both environmental directofexposure
the modifications ob- simulations.
and laboratory
served in the MIP curves after the brine immersion test. Firstly, the apparition
Weathered samples after direct exposure do not show noticeable decay signs at of new pore
families is related to the dissolution
mesoscale, but grain of crystal edges,
detachment, creating
crystal edge a new pore net
corrosion, without
halite con-
efflorescences and mi-
nection to the previous porous system. This situation can be only seen in massive
crofissuring were observed under Scanning Electron Microscope. Although all these decay crystal-
line low-porous rocks, such
patterns cannotas Ls
be samples.
justified exclusively to the halite–rock interaction due to the fact that
Secondly,other
whenmeteorological
the edge dissolutionevents occurs
act on in theporous rocks, two
rock samples situations
during direct can be
exposure, results ob-
observed. On the one hand, a new micropore net (dissolved inter-crystalline
tained from laboratory simulations demonstrate that they can explain most of the rock discontinui-
ties) is connected to the previous porous system. In this case, the MIP curve shifts to lower
pathologies.
values (displacement to the left)
Laboratory due to the fact
measurements thatthat
prove new small
halite entries
crystals to the
have pores arehigher thermal
a noticeably
created. This situation
expansivity could be interpreted
than studied rocks. as anLinear
exaggeration
thermalofexpansion
the ink bottle phenom-
coefficient (αT ) of halite is
enon. On the other × 10−6the
38.89 hand, ◦ Cdissolved
−1 , while this
edges constitute
coefficient the entry
in studied to pre-existing
rocks range between 0.90 × 10−6 ◦ C−1
cham-
bers. In this case, the dissolution
(marble, Mb) and 7.72 × 10−
process 6 ◦ C−1 the
widens pore entry,sandy
(fine-grained and the MIP curve
calcarenite, Cf).shifts
This difference can
to bigger values (displacement
justify (or at leasttocan thecontribute
right). to justifying) some of the weathering patterns observed
Finally, a global
duringpore wall dissolution
the direct exposure of (including
rocks to theboth pore chamber
marine semiaridand entries) can
conditions, such as the grain
occur in all thedetachment
porous system of the
in areas sample.
with In this case, an
subefflorescences, asincrease
well as thein the pore volume
widening and development of
is registered inmicrocracks.
the MIP curve as well as a slight displacement to bigger pore sizes.
According to the Theabove reasoning, chemical
real effectiveness of thermal dissolution
expansivity of massive
of halitecrystalline
present asrocks
both efflorescences
and subefflorescences
in a brine immersion tend to create new waspore
demonstrated by meanswith
families associated of rock monitoringof
the dissolution during thermal
cycles
crystal edges. This newin afamily
climatic
cancabinet. Halite expansivity
either increase the connectivity is especially dangerouspo-
of the pre-existent in porous rocks,
rous system (Mb) causing weight
or create losses
a new up net
pore to 2% after the
without test.
connection with previous pores (Ls).
In the case of porous rocks (Cf and Cg), chemical dissolution causes the widening of pore
entries as well as the creation of new micropores that increase the ink bottle character of
the porous system.
Minerals 2021, 11, 911 14 of 15

Weathered samples after the brine immersion test show preferential chemical corro-
sion of crystal edges and intra-crystalline line defects, similar to those observed after the
direct exposure of samples to the marine environment. Mineral corrosion modifies the char-
acteristics of the porous system of rocks, increasing in most of the cases the pore connection
and lastly favouring the effectiveness of posterior weathering agents. The comparison of
mercury intrusion porosimetry (MIP) curves of fresh and weathered samples corroborates
the modification of the pore size distribution, mainly focused on: (1) the appearance of
new pore families; (2) an increase in the volume of some pore families; (3) the displacement
of the MIP curve to bigger sizes due to the dissolution of pore entries; (4) the displacement
of the MIP curve to smaller values, related to the creation of new small entries to the pores.

Author Contributions: Conceptualization, collecting, processing and analyzing the samples, inter-
preting the results and writing the original draft, J.M.-M.; methodology and interpreting the results,
A.A.; interpreting results and finalizing the paper, D.B. All authors have read and agreed to the
published version of the manuscript.
Funding: Experimental tests in the cabinet carried out at the University of Oxford were financially
supported by the European Commission under the Marie Curie program (FP7-PEOPLE-2012-IEF
call, research project “NaturaLime”). This research has been supported by the Spanish Government
(MICINN) (PID2020-116896RB-C21 and PID2020-116896RB-C22).
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Cardell, C.; Delalieux, F.; Roumpopoulos, K.; Moropoulou, A.; Auger, F.; Van Grieken, R. Salt-induced decay in calcareous stone
monuments and buildings in a marine environment in SW France. Constr. Build. Mater. 2003, 17, 165–179. [CrossRef]
2. Andriani, G.F.; Walsh, N. The effects of wetting and drying, and marine salt crystallization on calcarenite rocks used as building
material in historic monuments. Geol. Soc. Lond. Spec. Publ. 2007, 271, 179–188. [CrossRef]
3. Rothert, E.; Eggers, T.; Cassar, J.; Ruedrich, J.; Fitzner, B.; Siegesmund, S. Stone properties and weathering induced by salt
crystallization of Maltese Globigerina Limestone. In Building Stone Decay: From Diagnosis to Conservation; Prikryl, R., Smith, B.J.,
Eds.; Geological Society: London, UK, 2015; pp. 189–198.
4. Stefanis, N.A.; Theoulakis, P.; Pilinis, C. Dry deposition effect of marine aerosol to the building stone of the medieval city of
Rhodes, Greece. Build. Environ. 2009, 44, 260–270. [CrossRef]
5. Martínez-Martínez, J.; Benavente, D.; Jiménez-Gutiérrez, S.; García-del-Cura, M.A.; Ordóñez, S. Stone weathering under
Mediterranean semiarid climate in the fortress of Nueva Tabarca island (Spain). Build. Environ. 2017, 121, 262–276. [CrossRef]
6. Colston, B.J.; Watt, D.S.; Munro, H.L. Environmentally-induced stone decay: The cumulative effects of crystallization–hydration
cycles on a Lincolnshire oopelsparite limestone. J. Cult. Herit. 2001, 2, 297–307. [CrossRef]
7. Grossi, C.M.; Brimblecombe, P.; Menéndez, B.; Benavente, D.; Harris, I.; Déqué, M. Climatology of salt transitions and implications
for stone weathering. Sci. Total. Environ. 2011, 409, 2577–2585. [CrossRef]
8. Goudie, A.S.; Viles, H.A. Salt Weathering Hazards; John Wiley: Chichester, UK, 1997; p. 241.
9. Rodriguez-Navarro, C.; Doehne, E.; Sebastián, E. Origins of honeycomb weathering: The role of salts and wind. GSA Bull. 1999,
111, 1250–1255. [CrossRef]
10. Doehne, E. Salt weathering: A selective review. In Natural Stone, Weathering Phenomena, Conservation Strategies and Case Studies;
Siegesmund, S., Weisss, T., Vollbrecht, A., Eds.; Geological Society Special Publication: London, UK, 2002; p. 256.
11. Scherer, G.W.; Flatt, R.; Wheeler, G. Materials science research for the conservation of sculpture and monuments. MRS Bull. 2001,
26, 44–50. [CrossRef]
12. Benavente, D.; Sanchez-Moral, S.; Fernández-Cortes, A.; Canaveras, J.C.; Elez, J.; Saiz-Jimenez, C. Salt damage and microclimate
in the Postumius Tomb, Roman Necropolis of Carmona, Spain. Environ. Earth Sci. 2011, 63, 1529–1543. [CrossRef]
13. Benavente, D.; Brimblecombe, P.; Grossi, C.M. Termodynamic calculations for the salt crystallisation damage in porous built
heritage using PHREEQC. Environ. Earth Sci. 2015, 74, 2297–2313. [CrossRef]
14. Liang, Y.; Baer, D.R. Anisotropic dissolution at the CaCO3 {104}–water interface. Surf. Sci. 1997, 373, 275–287. [CrossRef]
15. Benavente, D.; Martínez-Verdú, F.; Bernabéu, A.; Viqueira, V.; Fort, R.; García del Cura, M.A.; Illueca, C.; Ordóñez, S. Influence of
Surface roughness on color changes in builing stones. Color Res. Appl. 2002, 28, 343–351. [CrossRef]
16. Martínez-Martínez, J.; Benavente, D.; Pérez-Huerta, A.; Cueto, N.; García-del-Cura, M.A. Changes on the Surface properties of
foliated marbles at different cutting orientations. Constr. Build. Mater. 2019, 222, 493–499. [CrossRef]
17. Liu, A.; Yuan, D.; Dreybrodt, W. Comparative study of dissolution rate-determining mechanisms of limestone and dolomite.
Environ. Geol. 2005, 49, 274–279. [CrossRef]
Minerals 2021, 11, 911 15 of 15

18. Luttge, A.; Winkler, U.; Lasaga, A.C. An interferometric study of the dolomite dissolution: A new conceptual model for mineral
dissolution. Geochim. Cosmochim. Acta 2003, 67, 1099–1116. [CrossRef]
19. Viles, H.A. Can Stone decay be chaotic? In Stone Decay in the Architectural Environment; Turkington, A.V., Ed.; Geological Society
of America, Special Publication: Boulder, CO, USA, 2005; p. 390.
20. Smith, B.J.; Gomez-Heras, M.; McCabe, S. Understanding the decay of stone-built cultural heritage. Prog. Phys. Geog. 2008, 32,
361–439. [CrossRef]
21. Smith, B.J.; Gomez-Heras, M.; Viles, H.A. Underlying Issues on the Selection Use and Conservation of Building Limestone; Geological
Society, Special Publication: London, UK, 2010; p. 331.
22. Martínez-Martínez, J.; Corbí, H.; Martín-Rojas, I.; Baeza-Carratalá, J.F.; Giannetti, A. Stratigraphy, petrophysical characterization
and 3D geological modelling of the historical quarry of Nueva Tabarca island (western Mediterranean): Implications on heritage
conservation. Eng. Geol. 2017, 231, 88–99. [CrossRef]
23. Benavente, D.; Cueto, N.; Martínez-Martínez, J.; García-del-Cura, M.A.; Cañaveras, J.C. The influence of petrophysical properties
on the salt weathering of porous building rocks. Environ. Earth Sci. 2007, 52, 215–224. [CrossRef]
24. Millero, F.J.; Milne, P.J.; Thurmond, V.L. The solubility of calcite, strontianite and witherite in NaCl solutions at 25 ◦ C. Geochim.
Cosmochim. Acta 1984, 48, 1141–1143. [CrossRef]
25. Sanchez-Moral, S.; Soler, V.; Canaveras, J.C.; Sanz-Rubio, E.; Van Grieken, R.; Gysels, K. Inorganic deterioration affecting the
Altamira Cave, N Spain: Quantitative approach to wall-corrosion (solutional etching) processes induced by visitors. Sci. Total.
Environ. 1999, 244, 67–84. [CrossRef]
26. Arvidson, R.S.; Ertan, I.E.; Amonette, J.E.; Luttge, A. Variation in calcite dissolution rates: A fundamental problem? Geochim.
Cosmochim. Acta 2003, 67, 1623–1634. [CrossRef]
27. Angeli, M.; Benavente, D.; Bigas, J.P.; Menéndez, B.; Hébert, R.; David, C. Modification of the porous network by salt crystallization
in experimentally weathered sedimentary stones. Mater. Struct. 2008, 41, 1091–1108. [CrossRef]