Case Studies in Construction Materials 17 (2022) e01582

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Case Studies in Construction Materials

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

Case study

Durability of a reinforced concrete structure exposed to marine

environment at the Málaga dock
Julio Emilio Torres Martín a, Nuria Rebolledo Ramos a, Servando Chinchón-Payá a,
Isabel Helices Arcila a, Antonio Silva Toledo a, Javier Sánchez Montero a, *,
Marta Llorente Sanjuán b, Sergio Agulló Soto b, Fidel Otero García b,
Leendert de Haan b
a
Instituto Eduardo Torroja de Ciencias de la Construcción (IETcc-CSIC), Calle de Serrano Galvache, 4, 28033 Madrid, Spain
b
Ingeniería y economía del transporte S.M.E. M.P., S.A (INECO), Paseo de la Habana, No 138, 28036 Madrid, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: The durability of structures in aggressive environments does not often reach the service life for
Corrosion which they were designed. This paper shows the methodology and results obtained in the eval­
Marine exposure uation of a 22-year-old breakwater’s crow wall. The results reveal that there are no degradation
Concrete
processes or expansive reactions in the concrete, nor carbonation. However, there is high chloride
NDT
Monte Carlo simulation
contamination, which has led to depassivation of the reinforcement of the entire structure, which
in turn has led to bursting and delamination of the cover in some areas. Monte Carlo analysis
shows that the chloride concentration exceeds the critical concentration given by the regulations
up to a depth of 150 mm. It is advisable immediate repair and protection of the structure given
the condition of the structure.

1. Introduction

Structures in contact with seawater commonly suffer durability problems [1–5]. Corrosion is the primary cause of shortened
reinforced concrete structure service life [6–8], prompting the need for costly maintenance and repair [9–11]. The main causes of
corrosion in reinforced concrete structures are concrete carbonation and/or chloride diffusion, mainly in marine environments. On the
other hand, the consequences of corrosion such as cracking or even spalling of the concrete cover, loss of bonding and loss of
cross-section, which can lead to brittle failure of the structures, are well known [12–20].
Is it a design issue, an on-site placing problem, or is it because a bad material selection? There are different alternatives to extend
the durability of structures such as the use of cathodic protection or the use of stainless steels [21–23].
The Dique de Levante project was carried out in 1998, entering into service in July 2001 [24]. The reinforced concrete structure
provides a height of 10 m to the breakwater. The breakwater has an approximate length of 1235 m built in 30 reinforced concrete
caissons, 20 m long. The last two caissons (29 and 30), located at the outer point of the breakwater, are perpendicular to the rest of the
caissons. The crown wall is divided into modules with an approximate length of 42.80 m and has nine buttresses, except for module 1,
which only has eight buttresses (Fig. 1).
The cement used is a CEM I - 42.5 R - SR/MR type from the GOLIAT brand. A superplasticiser was used as an additive to improve the

* javier.sanchez@csic.es
E-mail addresses: servando@ietcc.csic.es (S. Chinchón-Payá), javier.sanchez@csic.es (J. Sánchez Montero).

https://doi.org/10.1016/j.cscm.2022.e01582
Received 5 August 2022; Received in revised form 30 September 2022; Accepted 16 October 2022
Available online 17 October 2022
2214-5095/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
J.E. Torres Martín et al. Case Studies in Construction Materials 17 (2022) e01582

workability and setting performance of the concrete. The Table 1 shows the proportions for each of the modules.
The concrete cover was measured by means of a cover meter (Pachometer) at a total of 2980 points, with an average value of
75 mm ± 9 mm.
Components of modules 01, 04, 08, 11, 15, 19, 23, 27, 28 and 29 have been selected for analysis. In each module, the facing and the
two buttresses that compose it have been selected. The exposure class according to EN 206 are XS1 + XA2 in both the port side and the
seaside.
The objective of the present study is to assess the service life of the structure 22 years after its construction. The methodology
selected for this study and the most relevant results are described below. Information not shown in the article can be found in an
additional document of supplementary material.

2. Methodology

2.1. In-situ testing

A potential corrosion mapping (Ecorr) of all the elements defined above was performed using a Gecor 10 in-situ corrosion equipment
[25,26]. The mapping mesh size was 1 × 1 m2, which allowed inspecting the surface of the selected elements in the batches. A
Cu/CuSO4 electrode was used following the UNE 112083 standard. Values more positive than − 274 mV will indicate a low probability
of corrosion (shown in green in the figures), whereas values more negative than − 424 mV (shown in red in the figures) mean high
probability of corrosion.
Resistivity (ρ) is measured at the same time as corrosion potential. Values below 100 Ωm have been considered to imply a high risk
of corrosion, while values above 1000 Ωm imply a low risk of corrosion [27–29].

Fig. 1. Image of the breakwater and the crown wall.

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Table 1
Concrete mix proportions of the modules of the crown wall.
N cement [Kg/m3 ] Sand [Kg/m3 ] Gravel 15 [Kg/m3 ] Gravel 25 [Kg/m3 ] Water [l/m3 ] w/c Additive [Kg/m3 ]

2 300 797 414 774 150 0,50 5,84

3 300 714 329 618 150 0,50 6,11
4 308 706 341 636 154 0,50 4,80
5 302 869 412 776 151 0,50 4,21
6 304 868 401 787 151 0,50 4,05
7 300 675 333 619 147 0,49 4,09
8 320 849 415 774 153 0,48 2,40
9 330 820 417 775 164 0,50 1,38
10 330 809 417 776 166 0,50 1,36
11 337 623 334 627 173 0,51 1,39
12 330 798 412 777 171 0,52 1,35
13 324 826 407 691 158 0,49 1,12
14 342 776 407 765 166 0,50 1,34
15 320 788 393 742 165 0,52 1,34
16 343 857 408 974 170 0,50 1,35
17 330 833 400 765 170 0,52 1,37
18 330 856 378 754 165 0,50 1,39
19 330 857 381 750 168 0,51 1,38
20 332 847 383 753 155 0,47 1,39
21 339 909 426 749 171 0,50 1,39
22 334 860 385 737 162 0,49 1,53
23 330 866 380 747 170 0,51 1,38
24 346 913 398 718 178 0,52 1,63
25 336 887 389 763 173 0,51 1,38
26 330 859 375 747 170 0,52 1,40
27 330 859 375 745 170 0,51 1,40
28 329 378 749 170 170 0,52 1,37
29 330 846 382 745 170 0,51 1,33

Corrosion rate (Icorr) has been measured employing the Current Modulated Confinement Method [26]. The interpretation of the
corrosion rate measurements is performed based on the UNE 112072 standard.
The depth of carbonation has been determined by colorimetric tests according to UNE 112011 standard.
The last technique that has been performed in-situ is the ultrasonic velocity measurement (UT or UPV). The equipment used was the
PUNDIT7, a portable model PC1012, from CNSFARNELL. The indirect method has been applied with a separation of 10 cm between
probes. The ultrasonic velocity qualitatively classifies the quality of the tested concrete [30]. After proper calibration, with this
technique it is also possible to distinguish internal defects according to the loss of velocity in the inspected area. This methodology is
defined in the UNE EN 12504–4 standard.

2.2. Sampling plan for the field survey

Modules Nº 01, 04, 08, 08, 11, 15, 19, 23, 27, 28 and 29 have been inspected. In each module, one facing has been selected, on both
the interior and exterior sides, and the two buttresses that delimit the facing.

Fig. 2. Location of coring zone in module 1.

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2.3. Laboratory tests

A total of 41 cores of 120 mm diameter and an approximate length of 300 mm were extracted. Four cores were extracted in each
module except in module 19 where one more was extracted from the buttress. The cores were extracted at a height of approximately
1 m in the buttress (C), the inner face (P1) and the outer face (E). A core was also extracted in the inner face at a height of 3 m (P2).
Fig. 2 shows an example of the location of the cores in one of the modules.

2.4. Tests description

All concrete core probes were subjected to the following essays:

(i) Visual inspection and photographic report,

(ii) Chloride profile according to UNE EN 12390–11 and total chloride content according to UNE EN 14629
(iii) Water Penetration Depth under Pressure according to UNE EN 12390–8
(iv) Density and Water Accessible Porosity according to UNE 83980
(v) Ultrasonic Pulse Velocity according to UNE EN 12504–4
(vi) Electrical Resistivity of concrete according to UNE 83988–1
(vii) Mercury Intrusion Porosimetry according to ASTM D4404
(viii) X-ray Diffraction
(ix) Scanning Electron Microscopy with Secondary Electrons (SEM) and Backscattered Scanning Electron Microscopy (BSE).

A general scheme with the distribution of the tests performed on the concrete cores is shown in Fig. 3.

3. Results

3.1. In-situ test results

3.1.1. Visual inspection

In the elements inspected, several pathologies were found randomly distributed within each module and along practically the
entire length of the crown wall, in different degrees of affection. Cracking caused by corrosion of the reinforcement has been observed
with different opening sizes, from 0.2 mm to more than 15.0 mm. Cracking can also be observed in map sizes between 0.2 and 0.3 mm
which could be due to several causes such as: (a) shrinkage or (b) expansive reactions of the concrete.
Corrosion of the reinforcement has produced the detachment of the cover in some areas. A significant decrease in the reinforcement
cross-section, lack of concrete-steel bonding and the appearance of rust stains and white efflorescence have also been observed, see
Fig. 4.

3.1.2. Corrosion potential mapping

Fig. 5 shows the corrosion potential mapping in a facing of module 8 that has been placed over a photograph as an orthomosaic. The

Fig. 3. Scheme of work and tests conducted on the extracted cores.

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orange area indicates there is a probability of corrosion greater than 10% and the red color show the areas with a probability of
corrosion greater than 90 %. Except in very specific cases, it is observed that the studied elements show very negative corrosion
potentials (between − 300 and − 500 mV vs. Cu/CuSO4) which represent a high probability of corrosion. There is no significant dif­
ference between the elements directly exposed to seawater (exterior facing) and the interior elements.

3.1.3. Resistivity mapping of concrete cover

Fig. 6 shows the resistivity mapping of the concrete cover in a facing of module 8, which has been placed on a photograph of the
same facing as an orthomosaic. In green are represented the areas with low probability of corrosion with resistivity values higher than
500 Ω m, in orange are represented the areas with medium probability of corrosion with resistivity values between 100 and 500 Ω m,
while in red are represented the areas with high probability of corrosion with resistivity values lower than 100 Ω m. In general, it has
been observed that the outer faces have lower resistivities due to the high humidity caused by direct contact with seawater or the effect
of waves.

3.1.4. Corrosion rate (Icorr)

Fig. 7 shows the corrosion rate values recorded in the different measurement points of each of the modules. As can be seen, all the
points, regardless of the module, show corrosion rate values higher than 0.1 µA/cm2 (lower limit considered for the steel depassivation
threshold [31–33]). In fact, most of them are above 1.0 µA/cm2, which indicates that the structure presents a high corrosion with
section losses due to corrosion higher than 0.01 mm/year [34,35].

3.1.5. Ultrasonic velocity measurements

Fig. 8 shows the Ultrasonic Velocity values for all the elements studied for each module. Many of the values are close to 4000 m/s,
however, at some points values below 3000 m/s have been obtained. These points are randomly distributed in the different elements
within each module and throughout the structure. These low values may be related to delaminations in the concrete cover, caused in
turn by corrosion of the reinforcement.

3.1.6. Measurements of the carbonation front of the concrete cover

Carbonation front measurements were carried out on each of the connection pits for electrochemical measurements. There is no
significant carbonation depth at any of the measured points (average values of less than 10 mm) with the carbonation front being far
away from the reinforcement in all cases.

3.2. Results of laboratory tests

3.2.1. Chloride profiles

The most superficial 13–15 cm of the concrete core were used for chloride profiling. All the profiles obtained are shown as
additional content of this publication. The profiles were fitted to Fick’s second law [23,36]. The fit is performed under the assumptions

Fig. 4. Detachment of cover, efflorescence, loss of section and cracking of internal facing.

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Fig. 5. Graphical representation of the corrosion potential on the orthomosaic of module 08.

that the surface concentration (Cs) and diffusion coefficient (Dns) are constant.
( [ ])
x
Cx = Ci + (Cs − Ci ) 1 − erf √̅̅̅̅̅̅̅̅̅̅̅̅̅ (1)
Dns • t

Where Cx is the chloride content corresponding to depth x after time t; Cs is the calculated chloride content corresponding to the
exposed concrete surface; Ci is the initial chloride content; x is the depth from each analysis point to the surface; Dns is the diffusion
coefficient in non-steady state; t is the age of the structure.
Table 2 shows the parameters obtained in the fits of all the chloride profiles in the cores. In the column corresponding to the
diffusion coefficient, the cases in which the fit has a value of R2 < 0.95 have been marked with an asterisk. These values correspond to
cores that have surface cracks and therefore chloride transport has not occurred solely by diffusion. In all subsequent analyses these
results have been eliminated, in accordance with the standards.
Fig. 9 shows in a box-and-whisker plot the values of the diffusion coefficient grouped according to the type of element of the
structure. The average diffusion coefficient values obtained in the interior faces present similar values, around 4⋅10-8 – 6⋅10-8 cm2/s,
while in the buttresses and the exterior face the average diffusion value increases to around 7⋅10-8 cm2/s.
Fig. 9 right shows in a box-and-whisker plot the values of the diffusion coefficient as a function of the modulus in which the cores are
located. Modulus 11 and 28 are not represented since there is only one diffusion coefficient value valid for each modulus. This figure
shows that all the modules have an average diffusion coefficient between 5⋅10-8 and 7–10-8 cm2/s with a dispersion that is independent
of the module.
Fig. 10 left shows a box-and-whisker plot for surface concentration as a function of core location. There is no clear ranking or trend,
although there is a higher mean value in the upper face. Fig. 10 right shows the surface chloride concentration in each module. As in the
previous case, the data obtained do not show a significant difference between modules. In other words, the behavior of the structure
with respect to the durability parameters can be considered as the same population.

3.2.2. Depth of water penetration under pressure

Fig. 11 left shows the box-and-whisker plot for the penetration depth to water at medium pressure. Fig. 11 right shows the dis­
tribution of water penetration depth at medium pressure as a function of modulus. No significant differences are observed in the values
obtained as a function of the modules studied, although this value seems to increase as we move towards the final modules. Many of the

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Fig. 6. Graphical representation of the resistivity of the overburden concrete on the orthomosaic of module 08.

Fig. 7. Corrosion rate values for each of the elements of the modules studied.

values obtained are greater than 30 mm, exceeding the threshold established in Spanish regulations.

3.2.3. Density and porosity accessible to water

Fig. 12 shows the box-and-whisker plot for water porosity and Fig. 13 shows the corresponding plot for bulk density. The density
results obtained are very homogeneous throughout the dock, with no dependence on the location of the core tested. In the case of the
porosity accessible to water, there is a clear difference between the cores of the first modules M1 and M4; the modules from M8 to M27
and, finally, modules 28 and 29, with a higher porosity, which places it in a medium porosity. The porosity results obtained from
modules M1 to M27, in most cases, are in low porosity according to CEB-FIB Bulletin 243.

3.2.4. Ultrasonic velocity

Fig. 14 shows a box and whiskers figure for the ultrasonic velocity values as a function of sample location. The values obtained are
within a range classified as excellent. However, it can be observed how the M28 and M29 modules show values related to poorer
quality or more deteriorated concretes.

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Fig. 8. Ultrasound velocity values measured in each of the modules studied.

Table 2
Initial chloride concentration (Ci), surface chloride concentration (Cs) and diffusion coefficient in non-steady state (Dns).
Module Core Name Ci (%cem) Cs (%cem) Dns•10-8 (cm2/s)

Module 1 M1C5 0.191 3.033 6.695

M1C5P1 0.150 2.907 5.641
M1C5P2 0.132 4.149 4.768
M1C6E 0.150 2.319 3.850
Module 4 M4C3 0.115 1.741 10.657
M4C3P1 0.271 1.370 23.060*
M4C3P2 0.186 3.117 5.030
M4C4E 0.216 3.099 6.622
Module 8 M8C6 0.190 1.430 12.681*
M8C6P1 0.197 3.035 3.669
M8C6P2 0.088 3.686 5.025
M8C7E 0.097 4.603 8.013
Module 11 M11C2 0.115 0.923 6.342*
M11C2P1 0.123 0.864 9.513*
M11C2P2 0.115 1.873 10.487
M11C3E 0.223 4.400 13.414*
Module 15 M15C5 0.088 2.832 7.058
M15C5P1 0.207 1.155 9.657
M15C5P2 0.296 3.454 2.498
M15C6E 0.106 3.238 12.684*
Module 19 M19C6S 0.115 2.915 10.611
M19C6E 0.106 2.043 6.874
M19C6P1 0.215 2.991 6.135*
M19C6P2 0.168 3.381 2.892
M19C7E 0.208 3.883 6.220
Module 23 M23C3 0.141 3.799 11.439*
M23C3P1 0.513 1.785 12.684*
M23C3P2 0.216 3.312 3.049*
M23C3E 0.339 2.551 12.681*
Module 27 M27C7 0.106 2.305 13.647*
M27C7P1 0.286 2.248 5.301
M27C7P2 0.097 3.064 6.093
M27C8E 0.097 2.569 24.295*
Module 28 M28C2 0.231 4.410 2.832
M28P1 0.206 8.18 12.680*
M28E 0.514 12.00 10.660*
M28L 0.419 1.950 8.755*
Module 29 M29C3 0.303 3.680 2.811
M29P1 0.282 1.420 4.392*
M29E 0.420 1.860 12.680*
M29L 0.381 1.990 9.677
*
Values corresponding to a fit with R2 < 0.95

3.2.5. Electrical resistivity

Fig. 15 shows a box-and-whisker plot for the electrical resistivity values as a function of sample location. The electrical resistivity
was measured on the slice extracted in the central area of the core, about 13–14 cm from the surface, after saturation under vacuum.
For this purpose, the direct method was used as indicated in the UNE 83988–1 standard. The electrical resistivity of saturated concrete

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Fig. 9. Left: Box-and-whisker plot of the non-steady-state diffusion coefficients as a function of the element under study (C: buttress; E: Sea side or
exterior facing; P1: Interior side facing, lower zone; P2: Interior side facing, upper zone). Right: Box-and-whisker plot of the non-steady-state
diffusion coefficients as a function of the module studied.

Fig. 10. Left: Box-and-whisker plot of surface concentration as a function of the studied element (C: buttress; E: seaward or exterior side facing; P1:
interior side facing, lower zone; P2: interior side facing, upper zone). Right: Box-and-whisker plot of surface concentration as a function of the
module studied.

Fig. 11. Left: Box-and-whisker plot for mean penetration as a function of the element under study (C: buttress; E: Sea side or exterior facing; P1:
Interior side facing, lower zone; P2: Interior side facing, upper zone). Right: Box-and-whisker plot for mean penetration as a function of the
module studied.

is related to its porosity and, therefore, to its capacity for penetration of aggressive agents through it [29,37]. This parameter, in
concretes made with type I cement, is between 50 and 200 Ω•m. Most of the concretes studied are within this range.

3.2.6. X-ray diffraction

All the X-ray diffraction analyses show similar results. It can be observed that the analyzed concretes are composed of dolomitic
aggregate (calcium and magnesium carbonate). A little calcite also appears, but given the small amount of calcite it may be due to the

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Fig. 12. Left: Box-and-whisker plot for porosity to water as a function of the studied element (C: buttress; E: Facing seaward or exterior side; P1:
Facing interior side, lower zone; P2: Facing interior side, upper zone). Right: Box-and-whisker plot for water porosity as a function of the mod­
ule studied.

Fig. 13. Left: Box-and-whisker plot for bulk density as a function of the studied element (C: buttress; E: Sea side or exterior facing; P1: Interior side
facing, lower zone; P2: Interior side facing, upper zone). Right: Box-and-whisker plot for density as a function of the module studied.

Fig. 14. Left: Box-and-whisker plot for ultrasonic velocity as a function of the element under study (C: buttress; E: Sea side or exterior facing; P1:
Interior side facing, lower zone; P2: Interior side facing, upper zone). Right: Box-and-whisker plot for ultrasonic velocity as a function of the
studied module.

carbonation of the portlandite. Only one of the samples contains a small amount of brucite. This compound may appear as a conse­
quence of dolomite degradation or it may also have been formed by cation exchange with the portlandite since these concretes are in
direct contact with seawater, which has a large amount of magnesium salts that can react.

3.2.7. Porosimetry by mercury intrusion

The average values obtained from the samples analyzed are 0.0344 µm for pore diameter, 2.40 g/ml for density and 10.2% for total

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Fig. 15. Left: Box-and-whisker plot for resistivity as a function of the study element (C: buttress; E: Sea side or exterior facing; P1: Interior side
facing, lower zone; P2: Interior side facing, upper zone). Right: Box-and-whisker plot for resistivity as a function of the module studied.

porosity, which correspond to medium permeability concretes.

3.2.8. Scanning electron microscopy with secondary electrons (SEM)

All the samples analyzed show similar contents, with a large amount of portlandite on the surface and, to a lesser extent, calcium
carbonate, portlandite and ettringite crystals. The general aspect is quite good since no fissures can be seen in the paste or in the
aggregates. There is no trace of the characteristic gel of alkali-silica reaction, nor of efflorescent salts such as sodium or potassium
sulfates. No other pathology associated with concrete degradation has been observed.

3.2.9. Back scattered electron microscopy (BSE)

The general appearance of the aggregates, as well as the surrounding cementitious paste and the interface they form with it, is good.
There are no cracks or signs of reaction gels that could indicate that there has been a deterioration reaction of the aggregates due to an
aggregate-alkali reaction. The aggregates are dolomitic and present a good aspect, without cracks advancing from the interior and
affecting the cementitious paste. The interface does not appear degraded and no neoformed products are observed, neither in the pores
of the paste nor in the aggregate interface.

4. Discussion

The results obtained, both in-situ and on the cores, are discussed below. The discussion has focused on the study of the parameters
influencing the service life of the structure, like the analysis of the corrosion rate and chloride concentration, on the analysis of the
concrete microstructure and the corrosion index.

4.1. Concrete analysis

The visual inspection of the structure shows the appearance of: (a) concrete cover detachments, corrosion cracking, significant
reduction of the reinforcement section, lack of concrete-steel bonding and appearance of rust stains and white efflorescence; (b) map
cracking, delamination and heterogeneous covers. The first pathologies are related to the important corrosion degradation suffered by
the structure due to the presence of chloride ions, while the second deteriorations are commonly related to deficient curing and
placing. These defects have been detected in the in-situ ultrasonic measurements, where it was possible to distinguish the areas of the
concrete without defects from the areas in which there are cracks or delaminations, whether visible or not.
On the other hand, the heterogeneity observed in the durable parameters: Chloride Diffusion Coefficient, Pressurized Water
Permeability and Electrical Resistivity is derived from the degradation or cracking of the cover. At the time of analysis, it is therefore
not possible to establish populations by element type, modulus or environmental exposure.
The ultrasonic values inside the cores show values corresponding to an excellent concrete quality.
Regarding the presence of other pathologies in the concrete, the X-Ray Diffraction analysis did not show any anomaly and allowed
the identification of the dolomitic aggregate. Likewise, the Scanning Electron Microscopy and Backscattered Electron Microscopy
analyses show a good general appearance, no cracks in the paste or aggregates and no other pathology associated with the degradation
of the concrete was observed.

4.2. Electrochemical parameters measured in-situ. Corrosion rate

Corrosion potential and resistivity mappings performed in-situ on elements of the 10 chosen modules, distributed along the length
of the crown wall, show that the entire structure is at high risk of corrosion. These corrosion probability values have been quantified by
measuring the in-situ corrosion rate. It has been observed that, regardless of the module, element and orientation, all points of the

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structure are depassivated, i.e., with active corrosion which is established for corrosion rate values higher than 0.1 µA/cm2. Therefore,
the corrosion rate confirms the corrosion probability map of the structure obtained by the other electrochemical techniques.
Fig. 16 shows the histogram of accumulated frequencies for the corrosion rate, representing on the abscissa axis this parameter in
logarithmic scale in µA/cm2. Since the corrosion rate cannot be negative values, it has been fitted to a log-normal distribution [1.06;
1.30]. Fig. 16 shows the degree of agreement between the values obtained (bar diagram) and the adjustment made (blue curve). Some
characteristics of this distribution are:
(a) The average value of corrosion rate is 2.9 µA/cm2, which implies that the average loss of reinforcement radius is higher than
0.03 mm/year.
(b) 90 % of the values obtained are higher than 0.6 µA/cm2, which corresponds to a decrease in the reinforcement radius of
approximately 0.007 mm/year.
(c) 90 % of the values obtained are lower than 15 µA/cm2, which corresponds to a decrease in the reinforcement radius of
approximately 0.17 mm/year.
Additionally, it should be taken into consideration that chloride corrosion leads to pitting corrosion, which causes a localization of
such corrosion with a significant impact on the mechanical behavior of the reinforcement [12,15,16,34]. Taking into account that the
pitting factor can take values between 3 and 20, if a value of 10 is considered [38,39], this implies that on average in the structure the
rebars suffer a decrease in their radius of 0.3 mm/year, with extreme values varying between 0.07 and 1.7 mm/year.

4.3. Chloride concentration in the structure

As mentioned above, there is no carbonation in the structure. Therefore, the main cause of reinforcement corrosion is due to the
presence of chlorides. Starting from the chloride profiles, which its fit has a value of R2 > 0.95, Fig. 17 shows all the profiles grouped in
a box and whiskers diagram. According to this figure, it is necessary to exceed 100 mm depth for the average chloride concentration to
be below the threshold value of 0.6%cem given by the regulations in Spain [40].
Considering the profile fits with an R2 value > 0.95, Fig. 18 shows the relationship between the Diffusion Coefficient and surface
concentration. There is no clear correlation between the two parameters and there is no grouping according to the modulus or location
of the core.
Considering that both parameters can vary independently, they have been fitted to different distributions, considering the most
appropriate for each parameter. Fig. 19 left shows the histogram and the fit of the Diffusion Coefficient values to a Lognormal dis­
tribution [− 16.69; 0.443], which assumes that the mean of the distribution is for a value of Dns = 5.67–10-8 cm2/s and the 90%
confidence interval is [2.7–10-8 - 11.7–10-8 cm2/s]. Fig. 19 right shows the histogram and the fit of the surface concentration values to a
Weibull distribution [3.91; 3.30], which assumes that the mean of the distribution is for a value of Cs = 3.0 % cement weight and the 90
% confidence interval is [1.5–4.4%cem].

4.3.1. Monte Carlo model

In order to take into account the variability of both the Diffusion Coefficient and the surface concentration of chlorides, a Monte
Carlo simulation has been used to consider all possible scenarios that can be reached in the structure [41–43]. We performed 100,000
simulations in which Dns and CS were varied randomly and independently, following the distributions to which the experimental data
were fitted (see Fig. 19). For each pair of values and taking into account Eq. 1, a chloride concentration profile has been obtained
considering the age of the structure at the time of the study, t = 22 years. To discuss these results, the chloride content has been
analyzed considering different depths or concrete covers: 5, 10 and 15 cm.
Fig. 20 shows the probability distribution for the chloride concentration at a depth of 5 cm. The results obtained follow a Weibull
distribution [329; 1.83], which means that approximately 97.5 % of the values are higher than the critical concentration. In other
words, any reinforcement located within a 5 cm cover has a probability greater than 97.5 % of being depassivated or, in other words,
with active corrosion.

Fig. 16. Corrosion rate in the crown wall. Statistical study.

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Fig. 17. Chloride concentration profile in a box-and-whisker plot.

Fig. 21 shows the probability distribution for the chloride concentration at a depth of 10 cm. The results obtained follow a Weibull
distribution [2.07; 0.816], which means that approximately 59 % of the values are higher than the critical concentration. In other
words, any reinforcement located within a 10 cm cover has a 59 % probability of being depassivated.
Fig. 22 shows the probability distribution for the chloride concentration at a depth of 15 cm. The results obtained in this case follow
a Weibull distribution [1.25; 0.29], which means that approximately 8% of the values are higher than the critical concentration. In
other words, it is necessary to be at a depth of 15 cm for the probability that the reinforcement is corroded to be approximately 8 %, or
in other words, that 92 % of the reinforcement is passive. If seen from the point of view of a traditional repair, it would be necessary to
remove at least the first 15 cm of the structure to ensure that the chloride concentration is no higher than the critical value.

4.4. Corrosion index calculation

The calculation of the corrosion index (CI) is deduced from the aggressiveness indicator of the environment (AE) to which the
structure is exposed and from the Corrosion Damage Indicators (CDI) by performing its arithmetic mean. The CI allows to know, from
the data obtained in-situ in the structure, the moment in which an intervention or repair of the structure is necessary [44].
Fig. 23 shows the calculation of the Corrosion Index for the studied modules. As can be seen, all the modules studied, regardless of
their structural typology, present values between 3 and 4, related to a high Corrosion Index. The evaluation carried out indicates that,
after 20 years of construction, all the elements studied are in an advanced state of corrosion of the reinforced concrete due to the
presence of chloride ions. This advanced state of deterioration does not allow distinguishing areas with greater or lesser deterioration,
nor the different elements within the same modules. An urgent rehabilitation with the intervention of the entire structure should be
carried out.

5. Conclusions

This work shows the evaluation of a structure exposed to a marine environment such as a breakwater’s crown wall. From the first
visual inspection, the presence of corrosion of the reinforcement was detected, even causing the detachment of the concrete cover or
internal damages that were detected in the ultrasonic inspection. Carbonation was ruled out; in all the analyses performed, the depth of
carbonation is negligible.
The chemical analysis of the concrete has ruled out any other type of degradation other than that produced by corrosion of the
reinforcement. No deterioration of the concrete related to expansive reactions was found.
The Corrosion Potential and Resistivity mapping carried out in-situ showed that most of the structure is at high risk of corrosion.
These values have been confirmed by measuring corrosion rates higher than 0.10 µA/cm2, the lower limit considered for the steel
depassivation threshold. Ninety percent of the measured values are above 0.6 µA/cm2, indicating that the structure presents high
corrosion with corrosion radius losses above 0.070 mm/year.
Chloride profiles and analysis of data obtained with the aid of a Monte Carlo simulation show concretes heavily contaminated by
chlorides at very high depths of up to approximately 150 mm. These high chloride concentrations in the concrete are responsible for
the corrosion occurring throughout the structure.
The corrosion index calculation places the structure at a high corrosion index and immediate intervention is recommended
throughout the structure.

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Fig. 18. Comparison of surface concentration and diffusion coefficient, ordered values by diffusion coefficient.

Fig. 19. Left: Histogram of the Diffusion Coefficient. Fit to a lognormal distribution. Right: Histogram of surface concentration. Fit to a Weibull
distribution.

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Fig. 20. Monte Carlo simulation result. Probability distribution. Estimated chloride concentration for a depth of 5 cm at the current time.

Fig. 21. Monte Carlo simulation result. Probability distribution. Estimated chloride concentration for a depth of 10 cm at the current time.

Fig. 22. Monte Carlo simulation result. Probability distribution. Estimated chloride concentration for a depth of 15 cm at the current time.

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Fig. 23. Corrosion index for the modules studied.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Data availability

Data will be made available on request.

Acknowledgments

The authors would like to thank Francisco J. Martín Prez, Head of Infrastructure Division of the Málaga Port Authority for the
commissioning of the study.

Appendix A. Supporting information

Supplementary data associated with this article can be found in the online version at doi:10.1016/j.cscm.2022.e01582.

References

[1] M. Otieno, J. Ikotun, Y. Ballim, Experimental investigations on the influence of cover depth and concrete quality on time to cover cracking due to carbonation-
induced corrosion of steel in RC structures in an urban, inland environment, Constr. Build. Materi. 198 (2019) 172–181, https://doi.org/10.1016/j.
conbuildmat.2018.11.215.
[2] M.B. Otieno, H.D. Beushausen, M.G. Alexander, Modelling corrosion propagation in reinforced concrete structures – a critical review, Cem. Concr. Compos. 33
(2) (2011) 240–245, https://doi.org/10.1016/j.cemconcomp.2010.11.002.
[3] R.E. Melchers, C.Q. Li, Reinforcement corrosion initiation and activation times in concrete structures exposed to severe marine environments, Cem. Concr.
Compos. 39 (11) (2009) 1068–1076, https://doi.org/10.1016/j.cemconres.2009.07.003.
[4] M.G. Sohail, R. Kahraman, N.G. Ozerkan, N.A. Alnuaimi, B. Gencturk, M. Dawood, A. Belarbi, Reinforced concrete degradation in the harsh climates of the
Arabian Gulf: field study on 30-to-50-year-old structures, J. Perform. Constr. Facil. 32 (5) (2018) 1–12, https://doi.org/10.1061/(asce)cf.1943-5509.0001204.
[5] M.G. Sohail, M. Salih, N. Al Nuaimi, R. Kahraman, Corrosion performance of mild steel and epoxy coated rebar in concrete under simulated harsh environment,
Int. J. Build. Pathol. Adapt. 37 (5) (2019) 657–678, https://doi.org/10.1108/IJBPA-12-2018-0099.
[6] J. Xia, T. Li, J.-X. Fang, W. Jin, Numerical simulation of steel corrosion in chloride contaminated concrete, Constr. Build. Mater. 228 (2019), 116745, https://
doi.org/10.1016/j.conbuildmat.2019.116745.
[7] B. Hou, X. Li, X. Ma, C. Du, D. Zhang, M. Zheng, W. Xu, D. Lu, F. Ma, The cost of corrosion in China, Npj Mater. Degrad. 1 (1) (2017) 4, https://doi.org/10.1038/
s41529-017-0005-2.
[8] L. Schueremans, D. Van Gemert, S. Giessler, Chloride penetration in RC-structures in marine environment – Long term assessment of a preventive hydrophobic
treatment, Constr. Build. Mater. 21 (6) (2007) 1238–1249, https://doi.org/10.1016/j.conbuildmat.2006.05.006.

16
J.E. Torres Martín et al. Case Studies in Construction Materials 17 (2022) e01582

[9] D.V. Val, M.G. Stewart, Life-cycle cost analysis of reinforced concrete structures in marine environments, Struct. Saf. 25 (4) (2003) 343–362, https://doi.org/
10.1016/S0167-4730(03)00014-6.
[10] W. Zhu, R. François, Q. Fang, D. Zhang, Influence of long-term chloride diffusion in concrete and the resulting corrosion of reinforcement on the serviceability of
RC beams, Cem. Concr. Compos. 71 (2016) 144–152, https://doi.org/10.1016/j.cemconcomp.2016.05.003.
[11] J. Wei, C.-G. Wang, X. Wei, X. Mu, X.-Y. He, J.-H. Dong, W. Ke, Corrosion evolution of steel reinforced concrete under simulated tidal and immersion zones of
marine environment, Acta Metall. Sin. 32 (7) (2019) 900–912.
[12] J. Sanchez, J. Fullea, C. Andrade, Corrosion-induced brittle failure in reinforcing steel, Theor. Appl. Fract. Mech. 92 (Supplement C) (2017) 229–232, https://
doi.org/10.1016/j.tafmec.2017.08.006.
[13] J. Sanchez, J. Fullea, C. Andrade, C. Alonso, Stress corrosion cracking mechanism of prestressing steels in bicarbonate solutions, Corros. Sci. 49 (11) (2007)
4069–4080, https://doi.org/10.1016/j.corsci.2007.05.025.
[14] J. Sanchez, J. Fullea, C. Andrade, Fracto-surface mobility mechanism in high-strength steel wires, Eng. Fract. Mech. 186 (Supplement C) (2017) 410–422,
https://doi.org/10.1016/j.engfracmech.2017.11.003.
[15] L. Franceschini, F. Vecchi, F. Tondolo, B. Belletti, J. Sánchez Montero, Mechanical behaviour of corroded strands under chloride attack: a new constitutive law,
Constr. Build. Mater. 316 (2022), 125872, https://doi.org/10.1016/j.conbuildmat.2021.125872.
[16] F. Vecchi, L. Franceschini, F. Tondolo, B. Belletti, J. Sánchez Montero, P. Minetola, Corrosion morphology of prestressing steel strands in naturally corroded PC
beams, Constr. Build. Mater. (2021) 296, https://doi.org/10.1016/j.conbuildmat.2021.123720.
[17] L. Franceschini, F. Vecchi, F. Tondolo, B. Belletti, J.S. Montero, P. Minetola, in: C. Pellegrino, F. Faleschini, M.A. Zanini, J.C. Matos, J.R. Casas, A. Strauss (Eds.),
Variability in Section Loss and Maximum Pit Depth of Corroded Prestressing Wires BT - Proceedings of the 1st Conference of the European Association on
Quality Control of Bridges and Structures, Springer International Publishing, 2022, pp. 491–498.
[18] B. Belletti, F. Vecchi, C. Bandini, C. Andrade, J.S. Montero, Numerical evaluation of the corrosion effects in prestressed concrete beams without shear
reinforcement, Structural Concrete 21 (2020), doi:〈https://doi.org/10.1002/suco.201900283〉.
[19] B. Belletti, J. Rodríguez, C. Andrade, L. Franceschini, J. Sánchez Montero, F. Vecchi, Experimental tests on shear capacity of naturally corroded prestressed
beams, Struct. Concr. (2020), https://doi.org/10.1002/suco.202000205.
[20] Vecchi, F., Belletti, B., Franceschini, L., Andrade, C., Rodriguez, J., Montero, S.J. 2021. Flexural Tests on Prestressed Beams Exposed to Natural Chloride Action
(Fib (ed.); December 0, pp. 205–212). In: Proceedings of the fib CACRCS DAYS 2020.
[21] P. Pedeferri, Cathodic protection and cathodic prevention, Constr. Build. Mater. 10 (5) (1996) 391–402, https://doi.org/10.1016/0950-0618(95)00017-8.
[22] A. Pachón-Montaño, J. Sánchez-Montero, C. Andrade, J. Fullea, E. Moreno, V. Matres, Threshold concentration of chlorides in concrete for stainless steel
reinforcement: Classic austenitic and new duplex stainless steel, Constr. Build. Mater. 186 (2018) 495–502, https://doi.org/10.1016/j.
conbuildmat.2018.07.081.
[23] K. Li, P. Wang, Q. Li, Z. Fan, Durability assessment of concrete structures in HZM sea link project for service life of 120 years, Mater. Struct. 49 (9) (2016)
3785–3800, https://doi.org/10.1617/s11527-015-0754-8.
[24] Gómez de la Fuente, J. P, Remodelacion del puerto de Malaga, Revista de Obras Publicas 3 (411) (2001) 67.
[25] Ø. Vennesland, M. Raupach, C. Andrade, Recommendation of Rilem TC 154-EMC: “electrochemical techniques for measuring corrosion in
concrete”—measurements with embedded probes, Mater. Struct. 40 (8) (2007) 745–758, https://doi.org/10.1617/s11527-006-9219-4.
[26] C. Andrade, J. Sanchez, J. Fullea, N. Rebolledo, F. Tavares, On-site corrosion rate measurements: 3D simulation and representative values, Mater. Corros. 63
(12) (2012) 1154–1164, https://doi.org/10.1002/maco.201206775.
[27] R.B. Polder, Test methods for on site measurement of resistivity of concrete. RILEM TC-154 technical recommendation, Constr. Build. Mater. 15 (2–3) (2000)
125–131.
[28] A.J. Garzon, J. Sanchez, C. Andrade, N. Rebolledo, E. Menéndez, J. Fullea, Modification of four point method to measure the concrete electrical resistivity in
presence of reinforcing bars, Cem. Concr. Compos. 53 (2014) 249–257, https://doi.org/10.1016/j.cemconcomp.2014.07.013.
[29] J. Sanchez, C. Andrade, J. Torres, N. Rebolledo, J. Fullea, Determination of reinforced concrete durability with on-site resistivity measurements, Mater. Struct.
50 (41) (2017) 1–9, https://doi.org/10.1617/s11527-016-0884-7.
[30] S. Chinchón-Payá, J. Torres, N. Rebolledo, J. Sánchez, Evaluación del estado de elementos estructurales del Mercado de Legazpi: Ataque por sulfatos al
hormigón y corrosión de las armaduras, Informes de La Constr. (2021), e380, https://doi.org/10.3989/ic.76737.
[31] AENOR, 2011. UNE 112072: Laboratory measurement of corrosion speed using the polarization resistance technique polarización.
[32] ASTM2020. ASTM G 59–97: Standard practice for conducting potentiodynamic polarization resistance measurements.
[33] ASTM, 2015. ASTM G102–89: Standard practice for calculation of corrosion rates and related information from electrochemical measurements.
[34] J.A. Morales, J. Torres, N. Rebolledo, J. Sánchez, Experimental and statistical analysis of the corrosion in tendons in contact with water, Front. Mater. 6 (167)
(2019), https://doi.org/10.3389/fmats.2019.00167.
[35] E. Garcia, J. Torres, N. Rebolledo, R. Arrabal, J. Sanchez, Corrosion of steel rebars in anoxic environments. Part II: pit growth rate and mechanical strength,
Materials 14 (2021), https://doi.org/10.3390/ma14102547.
[36] T. Luping, J. Gulikers, On the mathematics of time-dependent apparent chloride diffusion coefficient in concrete, Cem. Concr. Res. 37 (4) (2007) 589–595,
https://doi.org/10.1016/j.cemconres.2007.01.006.
[37] C. Andrade, R. d’Andrea, N. Rebolledo, Chloride ion penetration in concrete: the reaction factor in the electrical resistivity model, Cem. Concr. Compos. 47 (0)
(2014) 41–46, https://doi.org/10.1016/j.cemconcomp.2013.09.022.
[38] M.G. Alvarez, J.R. Galvele, The mechanism of pitting of high purity iron in NaCl solutions, Corros. Sci. 24 (1) (1984) 27–48, https://doi.org/10.1016/0010-
938X(84)90133-1.
[39] D.A. Horner, B.J. Connolly, S. Zhou, L. Crocker, A. Turnbull, Novel images of the evolution of stress corrosion cracks from corrosion pits, Corros. Sci. 53 (11)
(2011) 3466–3485, https://doi.org/10.1016/j.corsci.2011.05.050.
[40] López, D.I., Alonso, M.C., Perdrix, C.A., Castellote, M., 2004. Potentiostatic determination of chloride threshold values for rebar depassivation: Experimental
and statistical study. https://doi.org/10.1016/j.electacta.2004.01.034.
[41] M.H. Kalos, P.A. Whitlock, Monte Carlo Methods (second), John Wiley & Sons, Ltd, 2008, https://doi.org/10.1002/9783527626212.fmatter.
[42] S. Chinchón-Payá, J.E. Torres Martín, A. Silva Toledo, J. Sánchez Montero, Quantification of chlorides and sulphates on concrete surfaces using portable X-ray
fluorescence. Optimization of the measurement method using Monte Carlo simulation, Materials 14 (2021), https://doi.org/10.3390/ma14247892.
[43] S. Chinchón-Payá, J.E. Torres Martín, N.R. Ramos, J.S. Montero, Use of a handheld x-ray fluorescence analyser to quantify chloride ions in situ: a case study of
structural repair, Materials 14 (3) (2021) 1–11, https://doi.org/10.3390/ma14030571.
[44] Contecvet, M. ,2000. Manual de usuario para la evaluación de la vida residual de estructuras de Hormigón. Manual Para La Evaluación de Estructuras Afectadas
Por Corrosión. Grupo Español.

17