Article

Effects of Green Mussel Shells (Perna viridis) and Chitosan

Extracted from Milkfish (Chanos chanos) Scales on the
Compressive Strength of Mortar and Concrete
Bernardo Lejano, Kenneth Jae Elevado * , Lorenzo Martin Chua, Simon Rohi Cuartero, Vince Philip Fabian
and Alyanna Ysabel Rase

Department of Civil Engineering, De La Salle University, 2401 Taft Avenue, Manila 0922, Philippines;
[email protected] (B.L.); [email protected] (L.M.C.);
[email protected] (S.R.C.); [email protected] (V.P.F.);
[email protected] (A.Y.R.)
* Correspondence: [email protected]

Abstract: It is estimated that in the construction industry, cement production contributes

to 7% of global CO2 emissions. Because of this, alternative materials, including biological
resources and wastes, are being explored to determine their viability as substitutes for
conventional concrete aggregates. This study investigates the feasibility of using green
mussel shells (GMSs) as a partial cement replacement and chitosan derived from milkfish
scales as an additive in concrete. Addressing environmental concerns tied to cement
production, the research evaluates the potential of GMSs and chitosan to enhance mortar
and concrete properties. This study was conducted in two phases: phase one focused on
mortar with varying percentages of GMSs (0%, 5%, 10%, 15%, and 20%) and chitosan (0%,
0.25%, 0.50%, 0.75%, and 1%), while phase two applied the phase one results that resulted
in the highest compressive strength of concrete. The results indicate that 10% GMS and
0.25% chitosan improved mortar strength by 38.74%, although high GMS levels reduced
workability. In concrete, 10% GMS without chitosan decreased compressive strength by
up to 47% due to magnesium impurities in GMSs, verified by FTIR analysis. This study
Academic Editors: Zoltán Lakner and highlights GMSs’ and chitosan’s potential but emphasizes impurity management for its
Anita Boros application feasibility.
Received: 7 November 2024
Revised: 22 December 2024 Keywords: green mussel shells; chitosan; waste utilization in concrete; sustainable construction;
Accepted: 28 December 2024 biological wastes
Published: 31 December 2024

Citation: Lejano, B.; Elevado, K.J.;

Chua, L.M.; Cuartero, S.R.; Fabian,
V.P.; Rase, A.Y. Effects of Green Mussel 1. Introduction
Shells (Perna viridis) and Chitosan
Extracted from Milkfish (Chanos
Annually, the world produces roughly 1.6 billion tons of cement, responsible for ap-
chanos) Scales on the Compressive proximately 7% of the carbon dioxide released into the atmosphere. As such, while cement
Strength of Mortar and Concrete. is an indispensable material with which plenty of construction projects are completed, it is
Resources 2025, 14, 9. https:// also responsible for a considerable amount of pollution and copious amounts of greenhouse
doi.org/10.3390/resources14010009
gases released into the atmosphere [1]. Aside from this, cement production is considered
Copyright: © 2024 by the authors. one of the most energy-intensive in the manufacturing industry, requiring around 3.2–6.3 GJ
Licensee MDPI, Basel, Switzerland. of thermal energy per ton of clinker [2]. The aforementioned concerns have compelled the
This article is an open access article
construction industry to shift towards sustainable practices. Various studies have explored
distributed under the terms and
the use of alternative materials, such as waste products in cement, and incorporating them
conditions of the Creative Commons
Attribution (CC BY) license
in the production of concrete while adhering to established standards.
(https://creativecommons.org/ Green mussel shells (GMSs), locally referred to in the Philippines as Tahong, have
licenses/by/4.0/). garnered attention as a potential supplementary cementitious material (SCM) obtained

Resources 2025, 14, 9 https://doi.org/10.3390/resources14010009

Resources 2025, 14, 9 2 of 20

from waste. Green mussels (Perna viridis) are extensively cultivated in Southeast Asia,
including the Philippines, but the challenge of disposing of their shells has become signif-
icant. Southeast Asia generates approximately 18.75% of global shellfish waste [3,4]. In
the Philippines alone, shells constitute 40% of the 250,000 metric tons of seafood waste
produced annually, where the majority end up in landfills [5].
GMSs are rich in calcium carbonate (CaCO3), which can be converted to calcium oxide
(CaO) or lime through heating. Because of this, GMSs were found to be a potential partial
substitute for cement since 60% of cement is composed of lime [6]. This property is respon-
sible for the development of the strength and soundness of cement. Studies have shown
that GMSs can enhance the compressive strength of concrete from 21.32 MPa to 31.62 MPa
but may decrease its workability, particularly at lower water/cement ratios. However, the
use of green mussel shells as partial aggregates of concrete in high quantities was found to
have a negative effect on its overall strength [4,6,7]. The decrease in strength was attributed
to the reaction of the excess lime with the silica present in the mix. Such a reaction leads to
major concerns regarding the durability of concrete and concrete structures [8]. As the lime
reacts with the silica, the creation of ASR gel causes problems for the concrete to develop,
such as cracking. This is due to the gel created by the reaction absorbing moisture from the
atmosphere, and with the moisture absorbed, the gel slowly swells and increases its size,
putting the concrete under increased tensile stress [9]. In addition, the periostracum of the
green mussel shell contains magnesium, and previous studies found that magnesium, with
unreacted phosphate, causes the expansion of cement in concrete, leading to lower strength
as well as a higher porosity [10,11]. In a previous study, increased magnesium content
in concrete was found to increase concrete deterioration, where corrosion and concrete
peeling were observed on the concrete samples, particularly at its edges [12].
Another promising material for concrete production is chitosan, a natural polymer de-
rived from the exoskeletons of crustaceans, fish scales, insects, and fungi. In the Philippines,
milkfish (Chanos chanos) yield higher production than any other fish since they have the
ability to adapt to different cultural conditions [13,14]. The amount of fish scales produced
can become a source of chitosan. In the construction industry, chitosan, a biodegradable
and natural source, can be used in ready-mixed concrete as an admixture. Studies have
shown that chitosan can increase the fresh unit weight of concrete while decreasing its
air content. When used in concrete production, it can also increase both the early and
late stages of concrete compressive strength. Additionally, natural admixtures such as
chitosan can decrease the cost of concrete, as chitosan does not require an immense amount
of work and energy for production while also decreasing the corresponding environmental
emissions [15].
Previous studies have also shown that chitosan exhibits some efficiency as a plasticizer
in concrete. Increased performance was observed in terms of application and fluidity
of cement paste compared to Portland cement or polycarboxylate plasticizers while also
exhibiting a strong retarding effect when it comes to cement hydration. In addition, chitosan
was found to effectively lower the water content of the fresh concrete and produced a greater
28-day compressive strength at about 1.12% for the concrete with the chitosan additive
compared to the control setup of concrete without any additives and admixture. It was
also determined that the chitosan samples used, when compared to a commonly used
plasticizer, had a lower slump but a longer setting time due to water retention, as it took
around 90 min for the plasticizer to have a reduction in its slump, while the chitosan took
around 120 min before its slump was reduced [16]. Meanwhile, another study found that
chitosan-derived plasticizers increased the 28th-day compressive strength of concrete at
13.3% and 10.9% with a 0.69 water/cement ratio. The increase in compressive strength
due to the addition of chitosan may be attributed to factors such as an increase in unit
Resources 2025, 14, 9 3 of 20

weight leading to a reduction of air content. Furthermore, it has been mentioned that the
water-reducing properties of chitosan significantly increase the compressive strength of
concrete [15]. These similar studies served as a framework for this study that utilized
chitosan from milkfish scales as an admixture for concrete.
The utilization of waste products as an intervention in construction materials has been
studied broadly in the civil engineering field to help reduce its negative impact on the
environment. GMSs and fish scales are two of the most discarded wastes in the seafood
section, and studies have shown that GMS contains lime and chitosan can adsorb water.
Because of this, the feasibility of GMSs as a partial cement replacement and milkfish scales-
derived chitosan as an additive to improve the properties of concrete was investigated in
this study to optimize waste utilization within the civil engineering industry.
Various research regarding the application of GMSs and fish scales-derived chitosan
in improving the properties of concrete have been studied independently in the past. Some
studies have utilized GMSs as a partial replacement for cement and chitosan as an admix-
ture [6,15]. However, the likelihood of the availability of resources, where both materials
are applied to concrete at the same time and milkfish scales are used as a source of chitosan,
is minimal. As such, this research aids in understanding the effects of GMSs and milkfish
scales-derived chitosan on the properties of concrete, such as workability and compres-
sive strength. This study addresses certain research gaps in concrete by investigating the
simultaneous use of these biological waste materials in concrete production.

2. Materials and Methods

The study carried out a two-phase experiment, namely Phase 1 for the mortar testing,
followed by Phase 2 for the concrete testing. The experiment started with sourcing out the
seafood waste materials, GMSs, and milkfish scales. Ordinary Portland cement (OPC) was
utilized in both experiments, while aggregates varied. In particular, this study used OPC
by Republic Cement. In Phase 1, Ottawa sand was utilized following ASTM C109-20 [17],
while standard sand and gravel were procured from a local construction supplier for the
concrete phase. Figure 1 shows the research methodology, supplemented by the discussions
in the succeeding sub-parts of this article.
Tests were performed to identify their physical properties according to ASTM. The
results are presented in Table 1. Aside from this, equipment and materials such as a
Digi Mortar Mixer, 2′′ × 2′′ Phenolic Board Molds, Half Bagger Concrete Mixer, 4′′ × 8′′
Cylindrical Molds, and a Universal Testing Machine (UTM) were employed to mix, mold,
and test the mortar and concrete specimens.

Table 1. Physical properties of sand and gravel.

ASTM ASTM
Property Sand Gravel
Designation Designation
Fineness Modulus C33-18 [18] 2.41 C33-18 7.67
Moisture Content (%) C566-19 [19] 7.87 C566-19 0.39
Specific Gravity C128-22 [20] 2.62 C127-15 [21] 2.85
Absorption (%) C128 3.93 C127 0.99
Dry Unit Weight (kg/m3 ) - C29-23 [22] 1553.44
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Figure1.1.Research
Figure Researchmethodology.
methodology.
2.1. Collection and Processing of Green Mussel Shells
Table 1. Physical properties of sand and gravel.
Before mixing, GMSs were procured from Kaymig Seafood Grill and Restaurant in
Dampa Seaside Market in Pasay City, Philippines. The shells were
ASTM heated in a pan and
ASTM
Property
stirred for three hours, ensuring they Sand
were brittle enough for processing. Subsequently, Gravel
they
Designation Designation
were pulverized into consistent powdered form using a mortar and pestle or a hammer
Fineness Modulus C33-18 [18] 2.41 C33-18 7.67
until they passed through a number 50 sieve or 300-micrometer diameter opening. The
Moisture Content (%) C566-19 [19] 7.87 C566-19 0.39
ones that passed through the sieve were used in the experiment, while others underwent
Specific Gravity C128-22 [20] 2.62 C127-15 [21] 2.85
the process again. Figures 2a, 2b, and 2c show the experimental photos when the GMSs
Absorption (%) C128 3.93 C127 0.99
were heated, pulverized, and sieved, respectively.
Dry Unit Weight (kg/m3) - C29-23 [22] 1553.44

2.1. Collection and Processing of Green Mussel Shells

Before mixing, GMSs were procured from Kaymig Seafood Grill and Restaurant in
Dampa Seaside Market in Pasay City, Philippines. The shells were heated in a pan and
stirred for three hours, ensuring they were brittle enough for processing. Subsequently
they were pulverized into consistent powdered form using a mortar and pestle or a ham
mer until they passed through a number 50 sieve or 300-micrometer diameter opening
The ones that passed through the sieve were used in the experiment, while others under
went the process again. Figures 2a, 2b, and 2c show the experimental photos when the
GMSs were heated, pulverized, and sieved, respectively.
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14, 9x FOR PEER REVIEW 5 of 21
5 of 20

(a) (b) (c)

(a) (b) (c)
Figure 2. Experimental photos when (a) heating, (b) pulverizing, and (c) sieving the green mussel
Experimentalphotos
Figure 2.2.Experimental
Figure photos when
when (a)(a) heating,
heating, (b)(b) pulverizing,
pulverizing, andand (c) sieving
(c) sieving the green
the green mus-
mussel
shells.
sel shells.
shells.
2.2.2.2.
Collection of Milkfisk
Collection Scales
of Milkfisk andand
Scales Extraction of Chitosan
Extraction of Chitosan
2.2. Collection of Milkfisk Scales and Extraction of Chitosan
TheThemilkfish
milkfishscales were
scales werealsoalso
obtained
obtained from a wet
from market
a wet marketin Libertad,
in Libertad, Pasay City,City,
Pasay
The
Philippines.
Philippines.milkfish
TheThe scales
milkfish
milkfish were
scales also
were
scales obtained
cleaned
were cleaned from
using a wet market
distilled
using water
distilled in
water Libertad,
andand dried Pasay
using
dried City,
thethe
using
ovenPhilippines.
for for
oven The
24 h24and milkfish
sat sat
h and for for scales
another
another were cleaned
24 h24athroom
at room using
temperature, distilled
temperature, water
ensuring
ensuring and
improved dried
improved using
quality the of
of
quality
theoven
the for 24chitosan.
extracted
extracted h and satDemineralization
chitosan. forDemineralization
another 24 h atwas room
was temperature,
performed
performed ensuring
bybysubmerging
submerging improved
the
thedried quality
dried scalesof in
scales
the extracted chitosan. Demineralization was performed by submerging the dried scales
in aa2%
2%HClHClsolution
solutionfor for1616hhatat room
room temperature
temperature with
with a solid
a solid solvent
solvent ratioratio of (weight-
of 1:5 1:5 (weight-
in a 2% HCl solution for 16 h at room temperature with a solid solvent ratio of 1:5 (weight-
to-volume).
to-volume). TheThe residue
residue waswas washed
washed untiluntil it reached
it reached neutral
neutral pHpH andand waswas oven-dried
oven-dried for for
to-volume). The residue was washed until it reached neutral pH and was oven-dried for
12 Subsequently,
12 h. h. Subsequently, deproteinization
deproteinization waswas executed
executed by submerging
by submerging the thescalescale residue
residue in ain a
12 h. Subsequently, deproteinization was executed by submerging the scale residue in a
4% 4%NaOHNaOH solution
solution for for
20 h20athroomat room temperature
temperature withwith a solid-to-solvent
a solid-to-solvent ratio
ratio of 1:5.
of 1:5. TheThe
4% NaOH solution for 20 h at room temperature with a solid-to-solvent ratio of 1:5. The
residue
residue waswas washed
washed untiluntil it reached
it reached neutral
neutral pHpH andandwaswas oven-dried
oven-dried for for 12The
12 h. h. The
lastlast
stepstep
residue was washed until it reached neutral pH and was oven-dried for 12 h. The last step
for for extraction
extraction involved
involved submerging
submerging thethe residuefor
residue foranother
another20 20hhin inaa4% 4% NaOH
NaOH solution for
for extraction involved submerging the residue for another 20 h in a 4% NaOH solution
for deacetylation,
deacetylation,but butatat6060 ± ±5 ◦5C°Cwith
witha solid/solvent
a solid/solvent ratio of 1:10.
ratio The The
of 1:10. residue was washed
residue was
for deacetylation, but at 60 ± 5 °C with ◦ a solid/solvent ratio of 1:10. The residue was
and oven-dried
washed and oven-driedfor 4 hforat 4about 40 ± 540C.
h at about ± 5Figures 3a and
°C. Figures 3a3b display
and the deacetylation
3b display the deacety-and
washed and oven-dried for 4 h at about 40 ± 5 °C. Figures 3a and 3b display the deacety-
straining
lation of the chitosan
and straining samples,samples,
of the chitosan respectively.
respectively.
lation and straining of the chitosan samples, respectively.

(a)(a) (b)
(b)
Figure 3. Experimental photos of (a) deacetylation of chitosan samples and (b) straining of chitosan
samples for drying.
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Resources 2025, 14, 9 6 of 20

Figure 3. Experimental photos of (a) deacetylation of chitosan samples and (b) straining of chitosan
samples for drying.
The characterization of the chitosan involved determining its percentage yield and
The characterization
Fourier of the Radiation
Transform Infrared chitosan involved determining
(FTIR) graph. its percentage
The percentage yield
yield was and
determined
Fourier Transform
to show Infrared
how much Radiation
chitosan (FTIR)
yielded graph.
from The scales
the fish percentage
usingyield was determined
the formula presented in
to show how much
Equation (1): chitosan yielded from the fish scales using the formula presented in
Equation (1):
Yield (%) = (Amount of chitosan obtained)/(Amount of fish scales used) × 100%, (1)
Yield (%) = (Amount of chitosan obtained)/(Amount of fish scales used) × 100%, (1)
The FTIR
The FTIR helped
helped determine
determine the different
the different functional
functional groups
groups or compounds
or compounds present
present in in
the chitin,
the chitin, whichwhich
aidedaided in determining
in determining whatwhat specific
specific component
component or group
or group might
might affectaffect
the the
properties of the mortar and concrete produced.
properties of the mortar and concrete produced.

2.3. Processing
2.3. Processing and Testing
and Testing of Mortar
of Mortar Mix Mix
In theInfirst
the phase
first phase
of theofstudy,
the study, the design
the mix mix design
of theofmortar
the mortar
was was developed
developed usingusing
ASTM ASTM
C109-20C109-20
[17]. [17]. The design
The mix mix design ofmortar
of the the mortar
per 1per 1 cubic
cubic meter
meter is presented
is presented in Table 2.
in Table
The different ratios of GMSs as partial cement replacement and chitosan
2. The different ratios of GMSs as partial cement replacement and chitosan as an additive as an additive
werewere
also also considered
considered in theinprocess.
the process. The GMS/cement
The GMS/cement weightweight
ratiosratios
were were 0%,10%,
0%, 5%, 5%, 10%,
15%, and 20%, while the chitosan/mixture weight ratios were 0%, 0.25%, 0.50%, 0.75%, and
15%, and 20%, while the chitosan/mixture weight ratios were 0%, 0.25%, 0.50%, 0.75%,
1%. With
and 1%. With this,
this, aa total
total of
of25
25cases
caseswere
wereproduced.
produced.Each
Eachcase
casehad
had5 cube
5 cube specimens,
specimens, which
had a size of 2 ′′ × 2′′ , for a total of 125 specimens produced in Phase 1.
which had a size of 2” × 2”, for a total of 125 specimens produced in Phase 1.
Table 2. Mix design of mortar mix per 1 cubic meter.
Table 2. Mix design of mortar mix per 1 cubic meter.
Material
Material Amount
Amount
Cement
Cement 635.7
635.7 kgkg
Sand
Sand 1748.1 kgkg
1748.1
Water 307.7 L
Water 307.7 L

All mortar specimens

All mortar werewere
specimens mixed usingusing
mixed a Digi Mortar
a Digi Mixer
Mortar by Tinius
Mixer Olsen.
by Tinius The The
Olsen.
specimens werewere
specimens curedcured
underwater for 28for
underwater days before
28 days beingbeing
before subjected to thetocompressive
subjected the compressive
strength
strength test. Figures
test. Figures 4a and4a4band 4b show
show the curing
the curing and testing
and testing of mortar
of mortar specimens,
specimens, respec-
respec-
tively.
tively. The The compressive
compressive strength
strength waswas computed
computed usingthe
using theresulting
resulting maximum
maximum load load in
inUTM
UTMover
overthethesurface
surfacearea
areaofofthe
theface
faceofofthe
thespecimen
specimenthat
thatwas
wassubjected
subjectedtotoloading.
loading.

(a) (b)

Figure 4. Mortar
Figure samples
4. Mortar subjected
samples to (a) to
subjected curing and (b)
(a) curing testing.
and (b) testing.
Resources 2025, 14, 9 7 of 20

2.4. Processing and Testing of Concrete Mix

The second phase of the study focused on the mixing and compressive strength
testing of concrete specimens while adhering to ASTM C192-14 [23] and ASTM C39-21 [24],
respectively. The cases considered were the setups that resulted in the highest compressive
strength for the GMS-only setup, the chitosan-only setup, and the combination of the
GMS and chitosan setup from the first phase (mortar). The ACI mix design for concrete
was utilized to ensure the mixture of each setup. These were subjected to controlled
water/cement ratios of 0.4, 0.5, and 0.6, resulting in 12 cases, including the controlled setup.
Each case had 5 cylindrical specimens, with a size of 4′′ × 8′′ , for a total of 60 concrete
specimens for Phase 1. A half-bagger concrete mixer by Saturn was used for the mixing of
all concrete specimens.
After mixing the concrete aggregates in a half-bagger concrete mixer, a slump test was
performed on fresh concrete following ASTM C143-12 [25] prior to molding to determine
its workability. The specimens were cured underwater for 28 days before they were tested
to determine their compressive strength.

3. Results
3.1. Chitosan and GMS Analysis
3.1.1. Percentage Yield
Equation (1) was used in determining the chitosan yield. The weight of the milkfish
scales used to extract the chitosan totaled 10,379 g, while the extracted chitosan totaled
about 2103 g.
A resulting percentage yield of 20.26% was obtained, which is within the acceptable
range for milkfish scales of around 20–30% [26,27]. The value falling at the lower range
of acceptance may be attributed to the extra weight of contaminants, as the study used
milkfish scales that were already waste materials compared to previous studies that sourced
fresh scales.

3.1.2. Chitosan FTIR Analysis

Figure 5 displays the FTIR spectra of the chitosan utilized in the study, which was
compared to the commercial chitosan at 400–4000 cm−1 [28]. The key peaks shown in
the graph correspond to the verification of the properties. The peak at ~3370.92 cm−1
indicates N-H and O-H bonds, suggesting the presence of aliphatic amines and alcohols,
which has a retardation effect on the water evaporation on concrete, explaining the increase
of workability [29]. On the other hand, the peak at ~2974.51 cm−1 confirms the amino
polysaccharide structure that is typical of chitosan. Peaks at 1641.65–1337.17 cm−1 reveal
residual N-acetyl groups from chitin deacetylation, while the 1035.55 cm−1 peak shows a
C-O-C bridge. These peaks are common in the samples of other papers that were processed
using FTIR analysis, confirming that the chitosan used in the study is the compound
itself [28].
Chemically processed chitosan with its corresponding chemical compounds has lots
of uses, especially in the fields of medicine and materials science. In a study conducted
by Ke et al., the material properties of chitosan were reviewed as an antimicrobial agent,
which was used as a food additive or preservative, a component in cosmetics, and hydrogel
films in pharmaceutical applications [30]. In terms of material science, chitosan is used
as an additive for concrete in some studies, although not in its pure form, but rather as a
compound that involves its structure. It can also serve as chitin nanofibers and nanocrystals
in cement, protection of Bacillus pseudofirmus bacteria for a self-healing concrete, anti-
corrosive coating for reinforced concrete, and a superplasticizer for concrete [15,31–33].
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14,x9FOR PEER REVIEW 8 of
8 of2120

Figure 5. FTIR spectra of dried chitosan samples.

Chemically processed chitosan with its corresponding chemical compounds has lots
of uses, especially in the fields of medicine and materials science. In a study conducted by
Ke et al., the material properties of chitosan were reviewed as an antimicrobial agent,
which was used as a food additive or preservative, a component in cosmetics, and hydro-
gel films in pharmaceutical applications [30]. In terms of material science, chitosan is used
as an additive for concrete in some studies, although not in its pure form, but rather as a
compound that involves its structure. It can also serve as chitin nanofibers and nanocrys-
tals in cement, protection of Bacillus pseudofirmus bacteria for a self-healing concrete,
anti-corrosive coating for reinforced concrete, and a superplasticizer for concrete [15,31–
33].
FTIRspectra
Figure5.5.FTIR
Figure spectraofofdried
driedchitosan
chitosansamples.
samples.

3.1.3. GMS FTIR Analysis

Chemically processed chitosan with its corresponding chemical compounds has lots
Figure 6 displays
displaysthetheFTIR
FTIRspectra
spectra forfor
thethe GMSsGMSs used in this
used in study, which
this study, were were
which com-
of uses, especially in the fields of medicine and materials science. In a study conducted2+by 1
pared to thetoFTIR
compared the spectra of limestone
FTIR spectra and CaCO
of limestone 3 with
and and3without
CaCO with andMg2without
⁺ at 400–4000
Mg cm⁻ at
Ke et al., the −material
1
properties of chitosan were reviewed as an antimicrobial agent,
[34,35]. The
400–4000 cmGMSa graph
[34,35]. Theshows
GMSa similar
graphpeaks
showscompared
similar peaksto both graphs to
compared of both
the related
graphslit-
of
which was used as a food additive or preservative, a component in cosmetics, and hydro-
erature
the at around
related literature 2356.35 cm−1,2356.35
at around cm−the
indicating 1 , indicating
possible presence of dolomite,
the possible presence of a limestone
dolomite,
gel films in pharmaceutical applications [30]. In terms of material science, chitosan is used
arich in CaCO
limestone 3 and
rich in Magnesium Carbonate. The
CaCO and Magnesium peaks atThe
Carbonate. 1472.17,
peaks860.32, and 712.39
at 1472.17, 860.32,cm−1
and
as an additive for concrete3in some studies, although not in its pure form, but rather as a
in Figure
712.39 cm−51show the presence
in Figure 5 show the of presence
CaCO3 with of CaCOlow magnesium
with low content
magnesium [34]. Lastly,
content the
[34].
compound that involves its structure. − 1
It can also serve3as chitin nanofibers and nanocrys-
peak atthe
Lastly, 1082.95
peak cm−1 can be
at 1082.95 cm attributed
can beto the presence
attributed of presence
to the magnesium cations, which
of magnesium is an
cations,
tals in cement, protection of Bacillus pseudofirmus bacteria for a self-healing concrete,
impurity
which thatimpurity
is an can leadthat
to lower 28-day
can lead compressive
to lower 28-daystrength compared
compressive to its
strength 7-day com-
compared to
anti-corrosive coating for reinforced concrete, and a superplasticizer for concrete [15,31–
pressive
its 7-day strength,
compressive which expands
strength, the cement
which expands andthealso increases
cement the increases
and also rate of deterioration
the rate of
33].
[7,10,12,35]. [7,10,12,35].
deterioration
3.1.3. GMS FTIR Analysis
Figure 6 displays the FTIR spectra for the GMSs used in this study, which were com-
pared to the FTIR spectra of limestone and CaCO3 with and without Mg2⁺ at 400–4000 cm⁻1
[34,35]. The GMSa graph shows similar peaks compared to both graphs of the related lit-
erature at around 2356.35 cm−1, indicating the possible presence of dolomite, a limestone
rich in CaCO3 and Magnesium Carbonate. The peaks at 1472.17, 860.32, and 712.39 cm−1
in Figure 5 show the presence of CaCO3 with low magnesium content [34]. Lastly, the
peak at 1082.95 cm−1 can be attributed to the presence of magnesium cations, which is an
impurity that can lead to lower 28-day compressive strength compared to its 7-day com-
pressive strength, which expands the cement and also increases the rate of deterioration
[7,10,12,35].

Figure 6. FTIR spectra of GMS samples.

Figure 6. FTIR spectra of GMS samples.
3.2. Mortar Results and Analysis
3.2.1. Flow Table Test
Figure 7 shows the comparison of the different values in the flow table test for the
mortar samples at different additive percentages based on the weight of the mixture
of chitosan. It is shown that the flow of the controlled setup was 140.88 mm, and the
chitosan-only setup had a maximum flow of 142.73 mm with 0.50% chitosan additive,
which increased by 1.31%. However, with 0.25% chitosan additive, a decrease in flow was
observed with a 14.66% difference. This low flow value can be attributed to the retardation
of the cement hydration while mixing the mortar sample, as the flow table test was instantly
conducted after following the ASTM C109-20 [17] procedure for mixing. As the workability
is dependent
Figure on theofoverall
6. FTIR spectra mix design of the mortar samples, it cannot be compared to
GMS samples.
 creased by 1.31%. However, with 0.25% chitosan additive, a decrease in flow was ob-
creased by 1.31%. However, with 0.25% chitosan additive, a decrease in flow was ob-
served with a 14.66% difference. This low flow value can be attributed to the retardation
served with a 14.66% difference. This low flow value can be attributed to the retardation
of the cement hydration while mixing the mortar sample, as the flow table test was in-
Resources 2025, 14, 9 of the cement hydration while mixing the mortar sample, as the flow table test was 9 ofin-
20
stantly conducted after following the ASTM C109-20 [17] procedure for mixing. As the
stantly conducted after following the ASTM C109-20 [17] procedure for mixing. As the
workability is dependent on the overall mix design of the mortar samples, it cannot be
workability is dependent on the overall mix design of the mortar samples, it cannot be
compared
different to different
andstudies, and other studies initially measured
settingthe setting timesamples
of their
comparedstudies,
to different other studies
studies, initially
and other measured
studies initially the
measured time
the of their
setting time of their
samples
before before determining
determining the workability
the workability by
by using by using
theusing the
flow tableflow table test.
test.table test.
samples before determining the workability the flow

Figure
Figure 7.
7. Flow
Flow table
table test
test results
results of
of samples
samples with
with varying
varying chitosan
chitosan additives.
additives.
Figure 7. Flow table test results of samples with varying chitosan additives.

The setup
The setup that
that contains
contains only
only GMSs
GMSs hadhad aa maximum
maximumflow flowof
of 157.78
157.78mmmmwithwithaa 15%
15%
The setup that contains only GMSs had a maximum flow of 157.78 mm with a 15%
GMS
GMS partial cement
cement replacement, which increased by 12% in comparison to the flowthe
replacement, which increased by 12% in comparison to the flow of of
GMS partial cement replacement, which increased by 12% in comparison to the flow of
control
the mixture.
control On On
mixture. the the
other hand,
other the the
hand, 10%10%
GMS partial
GMS cement
partial replacement
cement replacement generated
gener-
the control mixture. On the other hand, the 10% GMS partial cement replacement gener-
the lowest
ated increase
the lowest in the
increase inflow of the
the flow of GMS-only
the GMS-onlysetups, withwith
setups, a 5.41% difference
a 5.41% from
difference the
from
ated the lowest increase in the flow of the GMS-only setups, with a 5.41% difference from
control
the setup.
control With
setup. With a 5%
a 5% GMS
GMSpartial
partialcement
cementreplacement,
replacement,thethe flow
flow had decreased by by
the control setup. With a 5% GMS partial cement replacement, the flow had decreased by
5.03%. These results are illustrated in Figure
5.03%. These results are illustrated in Figure 8.
5.03%. These results are illustrated in Figure 8.

Figure 8. Flow table results of mortar samples with varying GMSs as partial cement replacement.

Figure 9 shows the flow table results of mortar samples with varying GMS percentages
as a cement replacement and chitosan as an additive percentage. When GMSs and chitosan
were combined, the maximum value of flow for mortar samples was found to be 176.65 mm,
which was a 25.39% increase from the control sample. In contrast to the initial presumptions
of the study, the flow values indicate that the addition of GMSs in mortar mixtures enhances
the overall workability of the mortar samples. This improvement may be significant in the
construction industry since it can lead to more efficient construction processes in terms
of easier handling, placement, and finishing of mortar. Furthermore, these advantages
are particularly important for masonry construction and plastering in hot climates, such
 presumptions of the study, the flow values indicate that the addition of GMSs in mortar
mixtures enhances the overall workability of the mortar samples. This improvement may
be significant in the construction industry since it can lead to more efficient construction
Resources 2025, 14, 9 10 of 20
processes in terms of easier handling, placement, and finishing of mortar. Furthermore,
these advantages are particularly important for masonry construction and plastering in
hot
as inclimates, such as in
the Philippines, tothe Philippines,
mitigate to mitigate
challenges posed bychallenges posedand
rapid drying by rapid drying
difficult and
working
difficult working
conditions [36]. conditions [36].

9. Flow
Figure 9.
Figure Flow table
tableresults
resultsofofmortar
mortarsamples with
samples varying
with GMS
varying percentages
GMS as cement
percentages replacement
as cement replace-
and chitosan as additive percentage.
ment and chitosan as additive percentage.
3.2.2. Compressive Strength Test of Mortar Samples
3.2.2. Compressive Strength Test of Mortar Samples
Figure 10 shows the corresponding compressive strength of the mortar samples. It
Figure 10 shows the corresponding compressive strength of the mortar samples. It is
is shown that the controlled setup produced an average strength of 10.17 MPa, while the
shown
highest that the controlled
average produced for setup
the produced an average
chitosan-only strength of
setups produced 10.17 MPa,
a strength whileMPa,
of 14.79 the
highest average produced for the chitosan-only setups produced a strength of
which came from the 0.25% mix. The compressive strength of the 0.25% chitosan additive 14.79 MPa,
which
had ancame from
increase ofthe 0.25%
45.43% mix. Theto
compared compressive strength
the controlled setup.ofOn
thethe
0.25% chitosan
other additive
hand, the GMS-
had an increase of 45.43% compared to the controlled setup. On the other
only setups produced the highest average compressive strength of 12.80 MPa, which hand, the GMS- is
only
Resources 2025, 14, x FOR PEER REVIEW setups produced the highest average compressive strength of 12.80 MPa,
from the 10% setup, as shown in Figure 9. Compared to the control setup, the compressive which
11 of is
21
from the of
strength 10%10%setup,
GMSasasshown
a CRPinisFigure
higher9.by
Compared
25.86%. to the control setup, the compressive
strength of 10% GMS as a CRP is higher by 25.86%.

Figure10.
Figure Compressivestrength
10.Compressive strengthof
ofmortar
mortarsamples
samplesat
atvarying
varyingchitosan
chitosanadditive
additivepercentages
percentagesafter
after
28days
28 daysof
ofcuring
curingperiod.
period.

Figure 11 illustrates the compressive strength of mortar samples with varying GMSs
Figure 11 illustrates the compressive strength of mortar samples with varying GMSs
as partial cement replacement. Similar to the study by Lejano [6], the partial cement re-
as partial cement replacement. Similar to the study by Lejano [6], the partial cement re-
placement percentage of GMSs that generated the highest increase in compressive strength
placement percentage of GMSs that generated the highest increase in compressive
was 10%. However, concrete specimens were utilized in the experiment. It must also be
strength was 10%. However, concrete specimens were utilized in the experiment. It must
noted that further increase of the GMS replacement, at a certain point, leads to lower com-
also be noted that further increase of the GMS replacement, at a certain point, leads to
lower compressive strength due to excess lime. According to Lejano [4], excess lime con-
tent during the lime-silica reaction may affect the soundness of concrete. Due to a higher
content of GMSs, the creation of alkali–silica reaction (ASR) gel due to the reaction of lime
with silica will cause cracking and swelling in the concrete. According to Figueira [8], this
 Figure 11 illustrates the compressive strength of mortar samples with varying GMSs
as partial cement replacement. Similar to the study by Lejano [6], the partial cement re-
Resources 2025, 14, 9 placement percentage of GMSs that generated the highest increase in compressive 11 of 20
strength was 10%. However, concrete specimens were utilized in the experiment. It must
also be noted that further increase of the GMS replacement, at a certain point, leads to
pressive
lower strength due
compressive to excess
strength due lime. According
to excess to Lejano to
lime. According [4],Lejano
excess[4],
lime content
excess limeduring
con-
tent during the lime-silica reaction may affect the soundness of concrete. Due to a higherof
the lime-silica reaction may affect the soundness of concrete. Due to a higher content
GMSs, of
content theGMSs,
creation
theofcreation
alkali–silica reaction (ASR)
of alkali–silica gel (ASR)
reaction due togel
thedue
reaction
to theofreaction
lime with silica
of lime
will cause cracking and swelling in the concrete. According to Figueira [8],
with silica will cause cracking and swelling in the concrete. According to Figueira [8], thisthis causes
major major
causes concerns, including
concerns, reduced
including strength
reduced and microstructural
strength weaknesses,
and microstructural reducingre-
weaknesses, its
overall durability.
ducing its overall durability.

Figure11.
Figure Compressivestrength
11.Compressive strength of
of mortar
mortar samples
samples with
with varying
varying GMS
GMSreplacements
replacementsafter
after2828days
daysof
curing period.
of curing period.

Figure 12 shows the compressive strength results of mortar samples when GMSs
Figure 12 shows the compressive strength results of mortar samples when GMSs are
are utilized as a CRP with chitosan as an additive. The mix of both chitosan and GMSs
utilized as a CRP with chitosan as an additive. The mix of both chitosan and GMSs12pro-
Resources 2025, 14, x FOR PEER REVIEW
produced the highest value of 14.11 MPa, which came from the mix of 10% GMS andof1% 21
duced the highest value of 14.11 MPa, which came from the mix of 10% GMS and 1%
chitosan. The compressive strength of this mixture had a 38.74% increase compared to
chitosan. The compressive strength of this mixture had a 38.74% increase compared to the
the control setup. Aside from this, when 10% GMS was mixed with 1% chitosan, a 10.23%
control
increasesetup. Aside fromstrength
this, when 10% GMS was mixedtowith 1% chitosan, a 10.23%of
increase in compressive
in compressive strength was
was observed
observed compared
compared to the
the compressive
compressive strength
strength of
10% GMS
10% GMS alone.
alone.

Figure 12.
Figure Compressivestrength
12. Compressive strengthofofmortar
mortar samples
samples with
with varying
varying GMSGMS percentages
percentages as cement
as cement re-
replacement and chitosan as additive percentages after 28 days of curing period.
placement and chitosan as additive percentages after 28 days of curing period.

Considering that the mortar mix with 10% GMS and 1% chitosan produced the highest
Considering that the mortar mix with 10% GMS and 1% chitosan produced the high-
compressive strength among the mixes in Phase 1, this proportion was carried over to
est compressive strength among the mixes in Phase 1, this proportion was carried over to
Phase 2 of the experiment to compare the workability and compressive strength of the
Phase 2 of the experiment to compare the workability and compressive strength of the
said materials in concrete. Table 3 presents the mix design used in preparing the concrete
specimens, with a 0.4 water/cement ratio.

Table 3. Mix design (per cubic meter) for 0.4 water/cement ratio for control and 10% GMS with 1%
Resources 2025, 14, 9 12 of 20

said materials in concrete. Table 3 presents the mix design used in preparing the concrete
specimens, with a 0.4 water/cement ratio.

Table 3. Mix design (per cubic meter) for 0.4 water/cement ratio for control and 10% GMS with 1%
chitosan setups.

0% GMS and 0% Chitosan 10% GMS and 1%

Material
(Control) Chitosan
Cement, kg 512.50 461.25
GMS, kg 0 51.25
Water, kg 186.27 186.27
Gravel, kg 1029.28 1029.28
Sand, kg 679.61 679.61
Chitosan, kg 0 24.08

3.2.3. ANOVA Results of Mortar Specimens

Prior to conducting ANOVA, the experimental results were plotted in a Box and
Whisker plot. Figures 13a, 13b, 13c, 13d, and 13e present the Box and Whisker plots
representing the experimental data of 0%, 5%, 10%, 15%, and 20% GMS replacement,
respectively, with varying amounts of chitosan. Based on the Box and Whisker plot of each
group, a total of 9 out of 125 mortar samples were found to be outliers. These outliers were
removed in the corresponding data set moving forward.
In confirming the validity of the compressive strength results for the ANOVA, the
Shapiro–Wilk and Fligner–Killeen tests were used before starting the analysis. Table 4
shows the summary of F-values and p-values of the different variables to determine the
applicability of ANOVA.

Table 4. Confirmation of the normality and homoscedasticity of the results.

Variable F-Value p-Value

Chitosan 0.968 0.4287
GMS 14.477 2.32 × 10−9
Chitosan/GMS 2.081 0.0148

Based on the results shown in Table 4, with a computed p-value of 0.2048 for the
Shapiro–Wilk normality test and 0.6863 p-value for the Fligner–Killeen test, the data follows
normality and homoscedasticity and, as such, ANOVA can be performed and interpreted.
As shown in Table 5, the GMS and Chitosan/GMS setups yielded p-values of less than
the significance level of 0.05, which indicates a significant difference between the strength
of the setups compared to the control setup. On the other hand, the chitosan setup yielded
a p-value of 0.4287, which is greater than the significance level. This would mean that there
is no significant difference between the compressive strength of the chitosan-only samples
and the controlled setup.

Table 5. ANOVA of mortar compressive strength.

Test Test Statistic p-Value

Shapiro–Wilk normality test W = 0.98551 0.2048
Fligner–Killeen test of homogeneity of variances X2 = 20.183 0.6863
Resources 2025, 14, x FOR PEER REVIEW 13 of 21
Resources 2025, 14, 9 13 of 20

(a) (b)

(c) (d)

(e)

Figure
Figure13.
13.Box
Boxand
andWhisker
Whiskerplots
plotsfor
forPhase
Phase1 1considering
considering(a)(a)0%
0%GMS,
GMS,(b)
(b)5%
5%GMS,
GMS,(c)(c)10%
10%GMS,
GMS,
(d)15%
(d) 15%GMS,
GMS,and
and(e)
(e)20%
20%GMS.
GMS.

3.3. In
Concrete Results
confirming and
the Analysis
validity of the compressive strength results for the ANOVA, the
3.3.1. Slump Test
Shapiro–Wilk and Fligner–Killeen tests were used before starting the analysis. Table 4
showsFigure 14 showsofthe
the summary comparison
F-values of the different
and p-values of the values obtained
different from
variables tothe slump test
determine theof
the concrete of
applicability samples.
ANOVA. From the figure, it can be observed that the slump of the control setup
at 0.40, 0.50, and 0.60 water/cement ratios is 85 mm, 155 mm, and 160 mm, respectively.
Comparing
Table this setup
4. Confirmation to the
of the 0% GMS
normality and and 0.25% C setup,
homoscedasticity it can
of the be seen that there was an
results.
increase of 10 mm in the slump for all of the mixes. In the 10% GMS and 0% C setup, a
Variable F-Value p-Value
decrease in the slump, when compared to the control setup, was observed, with a 25 mm
Chitosan 0.968 0.4287
Resources 2025, 14, 9 14 of 20

decrease in the 0.40 and 0.50 water/cement ratio mixes, while the 0.60 water/cement
ratio sample had a 5 mm decrease in its slump. The 10% GMS and 1% C setup, when
compared to the 10% GMS and 0% C setup, exhibited a 25 mm increase in the slump of the
0.40 w/c ratio mix, resulting in an equal slump with the 0.40 w/c ratio mix of the control
setup. A 50 mm slump increase was observed from both the 0.50 w/c ratio mix and the
0.60 water/cement mix. However, only the 0.40 w/c ratio setups corresponded to the target
slump of 75 mm to 100 mm in the mix design of concrete. The effect of utilizing GMSs as a
CRP on the workability of concrete was observed to have decreased, similar to the study by
Lejano [6]. Moreover, in accordance with the study by Lv [16], due to the ability of chitosan
to adsorb water, the workability increased when 0.25% C is compared to the control15setup
Resources 2025, 14, x FOR PEER REVIEW of 21
and when 10% GMS and 1% C is compared to 10% GMS and 0% C.

Figure14.
Figure 14.Slump
Slumptest
testresults
resultsofofconcrete
concretesamples.
samples.

3.3.2.
3.3.2.Compressive
CompressiveStrength
StrengthTest
TestofofConcrete
ConcreteSamples
Samples
Figure 15 shows the corresponding compressive
Figure 15 shows the corresponding compressive strength of the
strength of concrete samples.
the concrete The
samples.
compressive strength values obtained by the control setup were 36.62
The compressive strength values obtained by the control setup were 36.62 MPa, 33.45 MPa, 33.45 MPa, and
22.90
MPa,MPa and for 0.40,
22.90 MPa 0.50,
forand 0.60
0.40, w/c
0.50, ratios,
and 0.60 respectively. Correspondingly,
w/c ratios, respectively. the decreasing
Correspondingly, the
compressive strength of the concrete samples as the w/c ratios increased
decreasing compressive strength of the concrete samples as the w/c ratios increased was expected due
was
to the decrease
expected due toofthecement in the
decrease mixture.in The
of cement results corroborate
the mixture. The resultsthe theory that
corroborate theexcess
theory
water in the concrete mixture produces greater voids among the aggregates.
that excess water in the concrete mixture produces greater voids among the aggregates. Furthermore,
these voids are these
Furthermore, filled voids
with air
areonce
filledthe moisture
with air onceevaporates, resulting
the moisture in concrete
evaporates, specimens
resulting in con-
that are more porous. As such, a decrease in compressive strength was
crete specimens that are more porous. As such, a decrease in compressive strength was observed.
Comparing the control setup with 0.25% chitosan as an additive percentage and a 0%
observed.
GMS cement replacement, there was an increase for all the samples, with the 0.40 w/c ratio
having a value of 41.03 MPa with a percent increase of 12%, the 0.50 w/c ratio having a
value of 34.93 MPa with a percent increase of 4%, and the 0.60 w/c ratio having a value of
25.73 MPa with a percent increase of 12%. These compressive strength increase rates are
also similar to the 28th-day compressive strength increase rates due to chitosan-derived
plasticizers mentioned by Arslan [15] at 13.3% and 10.9% with a 0.69 water/cement ratio.
The compressive strength increase due to the addition of chitosan may be attributed to
factors such as an increase in unit weight leading to a reduction of air content. Furthermore,
it has been mentioned that the water-reducing properties of chitosan significantly increase
the compressive strength of concrete.
 expected due to the decrease of cement in the mixture. The results corroborate the theory
that excess water in the concrete mixture produces greater voids among the aggregates.
Furthermore, these voids are filled with air once the moisture evaporates, resulting in con-
Resources 2025, 14, 9 15 ofwas
20
crete specimens that are more porous. As such, a decrease in compressive strength
observed.

Figure15.
Figure 15.Compressive
Compressivestrength
strengthofofconcrete
concretesamples
samplesafter
after2828days
daysofofcuring
curingperiod.
period.

However,
Comparing a noticeable
the controldecrease in compressive
setup with 0.25% chitosan strength can be observed
as an additive percentagein and
the 10%
a 0%
GMS and 0% chitosan samples, with the 0.40, 0.50, and 0.60 water/cement ratios
GMS cement replacement, there was an increase for all the samples, with the 0.40 w/c ratio producing
values
havingofa32.27
valueMPa, 17.70MPa
of 41.03 MPa, anda13.30
with MPa,
percent respectively.
increase of 12%,These compressive
the 0.50 w/c ratio strength
having a
values, when compared to the control setup, resulted in a percent decrease
value of 34.93 MPa with a percent increase of 4%, and the 0.60 w/c ratio having a valueof 12% for theof
0.40 w/c
25.73 MParatio mix,
with a percent
a percent decrease
increase of 47%
of 12%. for compressive
These the 0.50 w/cstrength
ratio mix, and a rates
increase percentare
decrease of 42% for the 0.60 w/c ratio mix. The compressive strength decreased
also similar to the 28th-day compressive strength increase rates due to chitosan-derived further
when 10% GMS
plasticizers was added
mentioned with 1%
by Arslan [15]chitosan
at 13.3%additive,
and 10.9%with thea0.40,
with 0.69 0.50, and 0.60 w/c
water/cement ratio.
ratio samples having a compressive strength of 27.19 MPa, 10.84 MPa, and 7.12 MPa,
respectively, with percent decreases of 26%, 68%, and 69%, respectively.
Compared to the study conducted by Lejano [6], there is a notable difference in
the compressive strength values. As for the 0.40 and 0.50 w/c ratio with the 10% GMS
replacement, the compressive strength values were 31.62 MPa and 23.27 MPa. With
these values, when compared to the resulting compressive strengths of 32.27 MPa and
17.70 MPa, a 2.06% decrease and 23.94% increase were observed, respectively. Furthermore,
a decrease in compressive strength due to GMS cement replacement contradicts findings
from other studies.
Upon performing FTIR analysis, the GMSs used as a partial replacement for the
concrete specimens were found to have the presence of magnesium cations. Magnesium,
which can be found at the periostracum of the GMSs [11] and can be eliminated with the
use of heat, can cause the expansion of the cement in concrete. In addition, the decrease in
the compressive strength of the concrete mixture incorporated with GMSs can be attributed
to this [10] since, according to a study conducted by Li [7], magnesium content in concrete
will yield a decrease in compressive strength due to the rapid expansion of the cement
which will result to a lower 28-day compressive strength compared to its 7-day compressive
strength. This may explain the contradictions with regard to the results from the study
conducted by Lejano [6]. However, while the magnesium content from the samples of that
study is unknown, further factors, such as the lack of heat in processing the GMS, may
also attributed to these conflicting results. As such, it is important for future studies to
determine the chemical compositions of the materials being substituted to the conventional
concrete aggregates, if possible.

3.3.3. ANOVA Results of Concrete Specimens

Prior to conducting ANOVA, the experimental results were plotted in a Box and
Whisker plot. Figures 16a and 16b present the Box and Whisker plots for the 0% and
Resources 2025, 14, 9 16 of 20

10% GMS replacement, respectively, with varying amounts of chitosan and water/cement
ratios. Based on the Box and Whisker plot for each group, only 1 out of 60 concrete
samples was found to be an outlier, which was determined in the data set of 10% GMS
Resources 2025, 14, x FOR PEER REVIEW 17 of 21
and 0% chitosan with a 0.4 water/cement ratio. This data point was removed in the
corresponding data set moving forward.

(a)

(b)

Figure 16.
Figure 16. Box
Box and
andWhisker
Whiskerplots
plotsfor
forPhase
Phase2 2considering
considering
(a)(a)
0%0% GMS
GMS andand
(b)(b)
10%10% GMS,
GMS, withwith var-
varying
chitosan content
ying chitosan and water/cement
content ratiosratios
and water/cement (w/c).
(w/c).

Table
Table 66 summarizes
summarizesthe theresults
resultsobtained
obtainedfromfrom thethe ANOVA
ANOVA statistical
statistical analysis
analysis of
of the
the concrete
concrete specimens
specimens having
having 0% GMS
0% GMS and and
0.25%0.25% chitosan,
chitosan, considering
considering the different
the different wa-
water/cement ratios. The resulting p-values of the chitosan (0.00176) and
ter/cement ratios. The resulting p-values of the chitosan (0.00176) and water/cement ratio water/cement
ratio
(3.45 (3.45 10−13lower
× 10−13×) were ) werethan
lowerthethan the value
critical criticalofvalue of 0.05
0.05 for a 95%forconfidence
a 95% confidence level.
level. Hence,
Hence, the analysis shows that both chitosan and water/cement ratios are significant
the analysis shows that both chitosan and water/cement ratios are significant factors that factors
that
affectaffect the compressive
the compressive strength
strength of concrete.
of concrete.

Table 6. ANOVA test results for 0% GMS and 0.25% chitosan.

Variable F-Value p-Value

Chitosan 12.15 0.00176
w/c 105.20 3.45 × 1013

Another variable measured in this study was the effect of chitosan on the compres-
sive strength of concrete, which is presented in Table 7. The table shows the ANOVA sta-
Resources 2025, 14, 9 17 of 20

Table 6. ANOVA test results for 0% GMS and 0.25% chitosan.

Variable F-Value p-Value

Chitosan 12.15 0.00176
w/c 105.20 3.45 × 1013

Another variable measured in this study was the effect of chitosan on the compres-
sive strength of concrete, which is presented in Table 7. The table shows the ANOVA
statistical analysis of the concrete specimens with 10% GMS and 0% chitosan at varying
water/cement ratios. Similarly, the resulting p-values of the GMS composition (1.26 × 10−9 )
and water/cement ratio (6.51 × 10−11 ) at lower critical values for a 95% confidence level
signify that both GMS and water/cement ratios are significant factors that affect the com-
pressive strength of concrete.

Table 7. ANOVA test results for 10% GMS and 0% chitosan.

Variable F-Value p-Value

GMS 83.99 1.26 × 10−9
w/c 65.98 6.51 × 10−11

The ANOVA statistical analysis of the concrete specimens having 10% GMS and 1%
chitosan at different water/cement ratios is presented in Table 8. The resulting p-values
of the chitosan composition (4.47 × 10−9 ) and water/cement ratio (2 × 10−16 ) were lower
than the critical value of 0.05 for a 95% confidence level. Consequently, the analysis shows
that chitosan and water/cement ratios are significant factors that affect the compressive
strength of concrete, given its composition.

Table 8. ANOVA test results for 10% GMS and 1% chitosan.

Variable F-Value p-Value

Chitosan 73.91 4.47 × 10−9
w/c 306.72 2.00 × 10−16

Table 9 presents the Duncan Post Hoc Test for the concrete specimens. The variables
0% and 0.25% in relation to chitosan highlight the effect of chitosan on compressive strength.
A positive difference of 2.91 MPa indicates that adding chitosan to the concrete mix in-
creases the compressive strength of the samples. This is also evident in the fact that the
0.25% chitosan replacement yields significantly larger compressive strength compared to
the 0% replacement.

Table 9. Duncan Post Hoc Test for concrete compressive strength.

Setup Variable Difference (MPa) p-Value

0% GMS 0% and 0.25% Chitosan 2.91 0.0018
0% Chitosan 0% and 10% GMS −10.28 1.3 × 10−9
10% GMS 0% and 1% Chitosan −5.66 4.5 × 10−9

Moreover, 0% and 10% GMS variables in Table 9 present the effect GMSs have on
concrete. The obtained difference was −10.28 MPa, which signifies a negative influence
on the compressive strength of the concrete samples. Correspondingly, the 10% GMS
replacement was observed to have a lower compressive strength as compared to the
0% replacement. As such, a higher GMS percentage generally yields significantly lower
Resources 2025, 14, 9 18 of 20

compressive strength for this setup. Similarly, the interaction between chitosan and GMSs
did not produce positive results, as highlighted by the negative difference of −5.66 MPa.
This analysis supports the data presented earlier, as a 1.00% chitosan composition with 10%
GMS produced significantly lower compressive strength compared to the 0% replacement.

4. Conclusions and Recommendations

This study identified the most desirable setup for achieving the highest compressive
strength using ground mussel shell (GMS) as a partial cement replacement and chitosan
derived from milkfish scales as an additive. A two-phase design was utilized in conduct-
ing the experiment, specifically using mortar and concrete specimens for a cost-effective
sampling strategy.
In phase one, varying percentages of GMSs (0–20% at 5% increments) and chitosan
(0–1% at 0.25% increments) were tested both individually and in combination. Results
showed that 10% GMS cement replacement improved mortar compressive strength by
25.86%, and further increasing the GMS levels reduced the resulting strength due to
adverse chemical reactions like ASR gel formation. Chitosan-only setups achieved the
highest strength, with a 0.25% chitosan additive increasing the strength by 45.43%, though
reducing flow by 14.66%. Based on the results in Phase 1, a combination of 10% GMS and
1% chitosan increased workability by 11.78% and compressive strength by 38.74%.
In Phase 2, chitosan enhanced both workability and compressive strength in concrete,
while GMSs showed contrasting effects. A 10% GMS replacement alone in concrete reduced
compressive strength by 12%, 47%, and 42% at varying water/cement ratios of 0.4, 0.5, and
0.6. When combined with 1% chitosan, this mix with 10% GMS decreased strength even
further by 16%, 39%, and 46% at 0.4, 0.5, and 0.6 water/cement ratios, respectively, com-
pared to the control mix. This was attributed to magnesium impurities in GMSs identified
by FTIR analysis. These impurities likely caused cement expansion, accelerating deteriora-
tion. Additionally, the study found an inverse relationship between compressive strength
and workability: as workability improved, compressive strength tended to decrease in
concrete. These results were not in line with the initial hypothesis of the study, where a
decrease in concrete compressive strength was obtained mainly due to the presence of
magnesium impurities in the GMS samples. Furthermore, the results for both mortar and
concrete samples differ from each other because the mortar specimens used a constant
water/cement ratio in the design mix, as opposed to the setups of the concrete that used
different w/c ratios for each setup. It was imperative to vary the water/cement ratios for
Phase 2 to investigate the potential effects of GMSs and chitosan on the overall workability
of concrete. The experimental results have shown that higher water/cement ratios result in
lower concrete compressive strengths.
To further enhance this study, it is recommended to examine the differences in proper-
ties of green mussel shells from different sources, as well as seasons, as this could have a
significant impact on the compressive strength of the samples. Such investigations could
help determine the variability in quality and effectiveness of the shells based on their
origin and the time of year they are harvested, potentially identifying optimal conditions
for their use in the concrete mix. In addition, exploring various extraction methods for
chitosan and processing methods for GMSs is recommended. Comparative studies on
these methods could identify more efficient, cost-effective, or environmentally sustainable
techniques for obtaining and preparing these materials. These comparative studies can be
supplemented with economic analyses, such as cost–benefit analyses and life cycle cost
analyses. Verification of green mussel shells processed through equipment, such as Fourier
Transform Infrared Spectroscopy (FTIR) or energy-dispersive X-ray spectroscopy (EDX), is
also recommended to ensure impurities, such as magnesium cations, are absent. Determin-
Resources 2025, 14, 9 19 of 20

ing the optimal processing time for GMSs, along with exploring other effective processing
methods, would further enhance the efficacy of these materials in concrete applications.

Author Contributions: B.L.: supervision, project administration, formal analysis, and conceptu-
alization. K.J.E.: writing—review and editing, supervision, project administration, data curation,
and conceptualization. L.M.C.: writing—original draft, visualization, validation, methodology, in-
vestigation, formal analysis, data curation, and conceptualization. S.R.C.: writing—original draft,
visualization, validation, methodology, investigation, formal analysis, data curation, and concep-
tualization. V.P.F.: writing—original draft, visualization, validation, methodology, investigation,
formal analysis, data curation, and conceptualization. A.Y.R.: writing—original draft, visualization,
validation, methodology, investigation, formal analysis, data curation, and conceptualization. All
authors have read and agreed to the published version of the manuscript.

Funding: This research received no external funding.

Data Availability Statement: The original contributions presented in the study are included in the
article; further inquiries can be directed to the corresponding author.

Acknowledgments: The authors would like to acknowledge the Department of Civil Engineering of De
La Salle University, Manila, Pasay City National Science High School, and the Department of Science
and Technology-Science Education Institute for all their support in making this research possible.

Conflicts of Interest: The authors declare no conflicts of interest.

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