Barbachi& al./ Appl. J. Envir. Eng. Sci.

5 N°2(2019) 153-161

Physico-chemical analysis of mussel shells for use in civil

engineering

M.Barbachi(a), M. El Biriane(a), M. Bouabaz(b), K. Boudjellal(b)

(a)
Laboratory of Mechanic, Proceeding of Energy and Environment (LMPEE), ENSA of Ibn Zohr University, BP
1136 Agadir, Morocco.
(b)
Laboratory LMGHU of the University 20 Août 1955, Skikda, Algeria.

Corresponding author,E-mail :m.barbachi@uiz.ac.ma

Received 24Apr2019, Revised 16Jun2019, Accepted 21Jun 2019

Abstract
This paper studies the physicochemical characterization of granulates obtained from the grinding of
mussel shells of Souss Massa region in Morocco. Its main objective is to valorize these shell waste
as aggregates in the formulation of concrete or mortar. Physical characterizations of different
aggregates were carried out, including shells, to more particularly determine the measurement of
bulk density, the apparent particle density, and compactness of shells. A geometric characterization
through a particle size analysis was also performed. The obtained parameters were compared to
those of dune sand and quarry sand. Furthermore, a study on the chemical characterization on these
shells was conducted using X-Ray Diffraction (XRD). The obtained results show that the mussel
shell aggregates are mainly composed of CaCO3 with acceptable chloride and Sulphur contents for
the concrete formulation.

Keywords: Mussel shells; Chemical analysis, X-Ray Diffraction (XRD); Valorization of shells.

1. Introduction
This study is conducted as a contribution to shell waste recovery for use as a construction material.
The objective is to characterize the Physico-chemical properties of aggregates obtained from a
marine shell grinding process in the SOUSS MASSA region, Morocco, in order to be used as a
substitute for the concrete components or a cement material additive.
Several scientific studies have been carried out in this field. In fact, shell by-products have been
used as a partial substitute for cement, sand or gravel for mortars and concrete[1-7].

153
Barbachi& al./ Appl. J. Envir. Eng. Sci. 5 N°2(2019) 153-161

2. Experimental program and results

2.1. Sample preparation:
The mussel shells used are collected from the CAP GHIR site in the Souss Massa region
(Morocco). They are washed with tap water to remove all impurities (Figure 1). The sample is then
dried in an oven at 105°C until it reaches a constant weight.

Figure 1.Mussel Shell sample

2.2. Particle size analysis:

After drying the sample, the seashells were crushed in a jaw mill Mono ball type, cylindrical jar,
agate balls (Ø20m) (Figure2). The resulting sample has a mass of 370 g. The particle size analysis
was then carried out through the following shaking sieves: 0.125 - 0.25 - 0.50 - 1.00 - 2.00 - 4.00
mm, according to EN 12620 standards. The retained mass of different sieves was measured (Figure
3). Table 1 summarizes the obtained results.

Figure2. Centrifugal ball mill

154
Barbachi& al./ Appl. J. Envir. Eng. Sci. 5 N°2(2019) 153-161

Figure 3.Mass retained from different sieves

Table1:Particle size analysis sample after grinding

Sieve size (mm) Cumulative mass Cumulative Cumulative mass Percent passing
retained (g) percent passing(g) (%)
retained(%)
1.250 0 0 370 100
1.00 211,27 57,1 158,73 42,9
0.710 233,84 63,2 136,16 36,8
0.500 250,86 67,8 119,14 32,2
0.355 266,4 72 103,6 28
0.250 284,53 76,9 85,47 23,1
0.180 296,555 80,15 73,445 19,85
0.125 313,76 84,8 56,24 15,2
< 0.125 323,75 87,5 46,25 12,5

From the analysis of table 1, the particle size distribution curve of the sea shell sample is
established (figure4).

mussel shell particle size

distribution curve
100
percentage passing (%)

80

60

40

20

0
0,1 1
particle size (mm)

Figure 4.Particle size curve of mussel shell sample

155
Barbachi& al./ Appl. J. Envir. Eng. Sci. 5 N°2(2019) 153-161

2.3. Fineness modulus

The fineness of sands is usually characterized by the fineness modulus (FM). This index number is
equal to the sum of the cumulative percentages retained on the standard sieves 0.125 – 0.25 – 0.50
– 1.00 – 2.00 – 4.00 mm divided by 100 in accordance with EN 12620 standards. When the
fineness modulus is lower, the sand is finer. A high fineness modulus characterizes coarse sand.
For concrete, this value should be in the range of 1.8 to 3.2. It is calculated using the following
formula:

The application of the previous formula gives a fineness modulus in the range of 2.86. Hence, it is
good sand for concrete formulation.

2.4. Sand equivalent test

The sand equivalent (SE) test determines the cleanliness of an aggregate by measuring the clay
fraction of the material. The test consists of separating the sand from the clayey or fine materials,
which flocculate up to the upper part of the specimen (the higher the SE value, the cleaner the
sand) (Figure 5). The test is carried out in accordance with EN 933-8 standard. The SE value is
calculated using the following equation:

Where, h1: Height of flocculated material

h2: Height of sediment

:
Figure 5. Principle of sand equivalent test

Table 2 provides the sand quality according to the ES value.

156
Barbachi& al./ Appl. J. Envir. Eng. Sci. 5 N°2(2019) 153-161

Table2:Sand cleanliness according to the SE value

SE < 65 Clayey sand: to be rejected for use in concrete
65 ≤SE< 75 Slightly clayey sand: suitable for common quality concrete
75 ≤ SE< 85 Clean sand with a low percentage of fine clays: perfectly
suitable for quality concretes
SE ≥ 85 Very clean sand: risk of a plasticity deficiency.

As a result, the sand equivalent value of the seashell sample is given by the following formula:

The resulting SE value is around 85%. Therefore, very clean sand is obtained from the grinding of
seashells. This is probably due to the calcareous nature and the washing process of the shells.

2.5. Methylene Blue Test:

The methylene blue test is performed on the 0/2 mm granular fraction of common sands or on
fillers (0/0.125 mm) contained in high fillers sand. The test is carried according to the EN 933-9
standards. It is used to identify the existence of clay particles and to determine their characteristics.
The blue methylene value (MB) of sand is the quantity in grams of methylene blue absorbed by a
kilogram of the 0/2 mm fraction of the sand.
A solution of methylene blue is added gradually in successive doses to a suspension of the sample
and verified after each addition by performing a spot test on a filter paper to detect the presence of
free dye.
After confirmation of the presence of free dye, the value of methylene blue (MB) is calculated and
expressed in grams of dye absorbed per kilogram of the tested granular fraction (0/2 mm) using the
following equation:

MB=10
Where M1 is the mass of the sample in grams and V1 is total volume of the injected solution in
milliliters.
The obtained value of MB is 0.23. The material is therefore quite sensitive to water.

2.6. Chemical analysis:

2.6.1. Methodology and results
Chemical analysis of the shells was performed using the X-ray diffraction (XRD) method. The
spectra obtained using this technique are shown in Figure 6.

157
Barbachi& al./ Appl. J. Envir. Eng. Sci. 5 N°2(2019) 153-161

158
Barbachi& al./ Appl. J. Envir. Eng. Sci. 5 N°2(2019) 153-161

Figure 6.XRD pattern of mussel shell sample

Based on the spectrum analysis, the mineralogical composition of the sample can be determined. The
obtained results are summarised in the following table 3.

Table 3: Chemical composition of mussel shell sample (unit %)

Organic matter moisture content CaCO3 SiO2
5.07 0.674 94.42 1.22

Na Mg Al S Cl Ca Fe Zn Br Sr Zr Cd
1,622 0,208 0,031 0,141 0,247 77,029 0,020 0,003 0,025 0,262 0,001 0,067

2.6.2. Discussion and results Analysis:

According to the chemical analysis of the shell sample, it can be noted that the shell of the mussel
is mainly composed of calcium carbonate CaCO3 (94.42%). The other components are organic
matter and other minerals with trivial amounts.

Several authors confirm this result concerning the chemical composition of shells (Scallop, Mussel,
Oyster...). According to W. Yang and al. and Martínez-Garcíaand al, the main components of bio-
shells are calcium carbonate which is generally about 95% by weight and less than 5% by weight
of organic matter[8-9].

159
Barbachi& al./ Appl. J. Envir. Eng. Sci. 5 N°2(2019) 153-161

In the same context, Hamester et al.[10] have investigated the chemical composition of oyster,
mussel and commercial limestone. They obtained the results presented in Table 4. The results show
that seashells have a similar composition to natural limestone.
Table4 : Chemical composition of seashells and commercial limestone[10]
components Mussel( %) Oyster(%) CaCO3(%)
CaO 95.7 98.2 99.1
K2O 0.5 -- 0.4
SiO2 0.9 -- --
SrO 0.4 -- --
Fe2O3 0.7 -- --
SO3 0.7 0.7 --
MgO 0.6 -- --
Al2O3 0.4 -- --
The aggregates resulting from the grinding of the shells contain 0.247% chloride. These values are
higher than those obtained by Lertwattanaruk et al.[11](between 0.01 and 0.02%).However, the
results obtained by Martínez-García and al. reveal a chloride content in the range of 0.28% to
0.51%. The presence of chlorides in the concrete in an uncontrolled amount contributes to tosteel
reinforcement corrosion and reduces the load-bearing capacity of the structural elements. They also
contribute to the perturbation of cement curing and the hardening of concrete.
The chloride ions content is limited for many reinforced concrete products. The NF EN 206-1
standard states the maximum content of Chloride ions per mass of cement following the use of
concrete. This maximum content is 0.20% for concretes containing steel pre-stressed
reinforcement, and 0.40% for those containing steel reinforcement and 1% for concretes with no
steel reinforcement[12].
Considering a reinforced concrete designed with a cement content of 350 Kg/m3, the maximum
chloride content would be 0.4%*350=1.4kg chloride which is equivalent to a 566 Kg shell mass
sample. This was calculated without including the amount of chloride contained in the other
components of the concrete.
The sulphur content of the shell sample is about 0.141%.This value is acceptable for concrete
formulation. Aggregates may contain minor amounts of sulphates and sulphides up to a total
sulphur content of 0.4 % by mass. The sulphate content (SO3) must be less than 0.2%. By
oxidising, the sulphurs compounds of aggregates can be transformed into sulphates, which may
generate swelling phenomena. Therefore, it is necessary to limit the sulphur content to prevent this
risk. Sulphates can disrupt the setting and actions of admixtures [13].
The presence of organic matter is one of the factors that influence negatively the mechanical
properties of concrete. The organic matter contained in the matrix of mussel shells consists of
polysaccharides, proteins and glycoproteins [8]. The organic matter content of mussel shell sample
is about 5%, which is higher than the results obtained by Martínez-García and al. (less than 2.5%).
This difference is explained by the shell treatment temperature. In fact, Martínez-García and al.

160
Barbachi& al./ Appl. J. Envir. Eng. Sci. 5 N°2(2019) 153-161

have treated the mussel shells at a temperature of around 132° for 32 min to ensure better
disinfection their safe handling and storage[8].

3. Conclusion
This study was carried out to characterize the physicochemical properties of a sample of mussel
shell aggregates. This has led to the following conclusions:
 The sand obtained after grinding is standard clean sand.
 Shell aggregates are mainly made of calcium carbonate CaCO3, which is one of
the main components of the cement manufacturing process.
 Shell aggregates have acceptable chloride and sulphur contents according to
standards requirements.
Consequently, the use of mussel shell-based aggregates is promising for its use as a partial
substitute for cement and aggregates in the production of an eco-material.

References
1. H. Othman, B. Hisham, A. Bakar, M. M. Don, M. Azmi, et M. Johari, « Cockle Shell Ash Replacement
for Cement and Filler in Concrete », Malaysian J. Civ. Eng., vol. 25, 2 (2013) 201-211.
2. K. Muthusamy, N. a Sabri, E. Resources, et L. T. Razak, « Cockle Shell: A Potential Partial Coarse
Aggregate Replacement In Concrete », Int. J. Sci. Environ. Technol., vol. 1, 4 (2012) 260-267.
3. M. Olivia, A. A. Mifshella, et L. Darmayanti, « Mechanical properties of seashell concrete », Procedia
Eng., vol. 125 (2015) 760-764.
4. D. H. Nguyen, M. Boutouil, N. Sebaibi, L. Leleyter, et F. Baraud, « Valorization of seashell by-products
in pervious concrete pavers », Constr. Build. Mater., 49 (2016) 151-160.
5. E. I. Yang, S. T. Yi, et Y. M. Leem, « Effect of oyster shell substituted for fine aggregate on concrete
characteristics: Part I. Fundamental properties », Cem. Concr. Res., vol. 35, 11 (2005) 2175-2182.
6. H. Cuadrado, N. Sebaibi, M. Boutouil, et B. Boudart, « Properties of concretes incorporating crushed
queen scallops for artificial reefs », Proc. RECIF Conf. Artif. reefs from Mater. to Ecosyst, (2015).
7. C. P. Woon, P. N. Shek, M. M. Tahir, et A. B. H. Kueh, « Compressive Strength of Ground Waste
Seashells in Cement Mortars for Masonry and Plastering », Appl. Mech. Mater., vol. 727-728 (2015)
167-170.
8. C. Martínez-García, B. González-Fonteboa, F. Martínez-Abella, et D. Carro- López, « Performance of
mussel shell as aggregate in plain concrete », Constr. Build. Mater., vol. 139 (2017) 570-583.
9. W. Yang, N. Kashani, X. W. Li, G. P. Zhang, et M. A. Meyers, « Structural characterization and
mechanical behavior of a bivalve shell (Saxidomus purpuratus) », Mater. Sci. Eng. C, vol. 31, 4 (2011)
724-729.
10. M. R. R. Hamester, P. S. Balzer, et D. Becker, « Characterization of Calcium Carbonate Obtained from
Oyster and Mussel Shells and Incorporation in Polypropylene », Mater. Res., vol. 15, 2 (2012) 204-208.
11. P. Lertwattanaruk, N. Makul, et C. Siripattarapravat, « Utilization of ground waste seashells in cement
mortars for masonry and plastering », J. Environ. Manage., 111 (2012) 133-141.
12. C. Page, « NF EN 206-1 Béton », vol. 1, 2004 (2010) 1-81.
13. C. Béton, « Les constituants des bétons et des mortiers » (2005).

161