ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. 2007; 2: 460467

Published online 21 August 2007 in Wiley InterScience
(www.interscience.wiley.com) DOI:10.1002/apj.082
Research Article
A preliminary study of processing seafood shells for
eutrophication control
J. A. Currie,
1
N. R. Harrison,
1
L. Wang,
1
M. I. Jones
1
* and M. S. Brooks
2
1
Department of Chemical and Materials Engineering, University of Auckland, Auckland, New Zealand
2
Department of Process Engineering and Applied Science, Dalhousie University, Halifax NS B3J 2X4, Canada
Received 23 November 2006; Revised 13 February 2007; Accepted 23 February 2007
ABSTRACT: Shells from the seafood processing industry in New Zealand are currently an under-utilized waste
resource. In this study we investigate the processing conditions required for the creation of calcium oxide (lime) from
green-lipped mussel (Perna canaliculus) and pacic oyster (Crassostrea gigas) shells. Lime is commonly used in
wastewater treatment for the removal of phosphorous compounds from water, thus providing a means of eutrophication
control. Mussel and oyster shells were processed in a horizontal tube furnace at various temperatures (650800

C)
in both air and nitrogen environments. From X-ray diffraction (XRD) and weight-loss measurements, the extent of
limestone calcination was found to increase with increasing furnace temperature for both shell species and furnace
atmospheres. Analysis showed that the lime was present as a layer on the surface of the shell particles. From scanning
electron microscope (SEM) images, signicant changes in the surface morphology of the raw shells were observed
as a result of heat treatment in both air and nitrogen atmospheres. Preliminary testing of shells heat-treated in both
air and nitrogen atmospheres indicated that both types of shell removed about 90% of phosphates in water within
30 min, whereas up to 40% of phosphates were removed with untreated shells. Our results for heat-treated oyster shell
differ slightly with studies in the literature, which report an absence of compositional and structural changes in an air
atmosphere. 2007 Curtin University of Technology and John Wiley & Sons, Ltd.
KEYWORDS: shells; pyrolysis; heat treatment; phosphate; lime
INTRODUCTION
Shellsh farming in New Zealand is a well-established
industry; the two commercial species of interest are the
green lipped mussel (Perna canaliculus) and pacic
oyster (Crassostrea gigas). Figures from the Ministry
of New Zealand Fisheries indicate that the annual crop
of mussels alone is around 67 000 tonnes. Processed
shellsh are often sold without their shells, creating
large volumes of shell waste.
Shell disposal can be problematic due to current
environmental regulations in New Zealand, which limit
the disposal of shells back to the sea. The use of
landlls is limited by the fee that is charged on a per
volume basis and the requirement of some sites that
shells are free of organic matter. Traditional alternatives
to landll include producing low-value products from
shells such as aggregates for driveways and pathways.
An alternative solution is to use heat processing to
convert the shells to lime (calcium oxide) for use in
*Correspondence to: M. I. Jones, Department of Chemical and
Materials Engineering, University of Auckland, Private Bag 92019,
Auckland, New Zealand. E-mail: mark.jones@auckland.ac.nz
water treatment as a phosphate removal agent (Kwon
et al ., 2004; Lee et al ., 2005). Waterways with high
phosphate levels are a problem in New Zealand: around
90% of lakes in the North Island are considered
eutrophic (Taylor and Smith, 1997).
In this study we investigate lime formation from
mussel and oyster shells and use the treated shells to
perform preliminary phosphate-removal tests on water.
MATERIALS AND METHODS
Materials
Shells from green-lipped mussels (P. canaliculus) and
the pacic oyster (C. gigas) were obtained from
Coromandel-based shellsh processors owned by San-
fords, a New Zealand seafood company. These were
stored in a freezer. Prior to use, the frozen shells were
thawed and scrubbed clean. The shells were then dried
in an oven, crushed in a ring mill and sieved. Crushed
shell particles with size range of 300600 m were
used for experiments.
2007 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacic Journal of Chemical Engineering PROCESSING SEAFOOD SHELLS FOR EUTROPHICATION CONTROL 461
Heat treatment and pyrolysis
A horizontal tube furnace was used for the treatment of
crushed shells at 650, 750 and 800

C. In this work, raw

shells are those that were not treated in the furnace, heat
treatment refers to the situation where heat is applied in
an air atmosphere and pyrolysis where heat is applied
in a nitrogen atmosphere. Shell samples (10 g) were
placed in the cold furnace and the heat source turned
on. Once the desired treatment temperature was reached,
samples were left for 1 h in the furnace. Samples
were then removed from the furnace and allowed to
cool. For the pyrolysis treatments the furnace was rst
evacuated before allowing nitrogen to return the furnace
to atmospheric pressure. A nitrogen ow of 0.2 l/min
was used to ush the furnace during the pyrolysis
treatments.
Characterisation methods
X-ray diffraction (XRD)
X-ray diffraction (XRD) analyses were performed using
a Bruker D8 Advance X-ray diffractometer operating
with a 40-kV Cu K X-ray source. Scans were carried
out in the 2 range 20 to 70

with a 0.02

-step size
and a 1-s step time. All gures with XRD spectra have
intensity (arbitrary units) plotted against 2.
Scanning electron microscopy (SEM)
Scanning electron microscope (SEM) studies were per-
formed using an FEI Quanta 200 FEG environmen-
tal scanning electron microscope (5 kV accelerating
voltage). Samples were sputter-coated with a plasma-
applied platinum coating to prevent charging.
Phosphate removal experiments
Preliminary tests were conducted to assess the phos-
phate removal rate from water with added shells. For
each test, 2 l of phosphate solution (30 mg/l) was dosed
with 10 g of crushed shells. Experiments were car-
ried out in a stirred vessel to ensure adequate mixing.
Water samples were taken every 20 min and measured
for phosphate content using a Perkin Elmer Lamda 35
UV/Vis Spectrometer at 880 nm (APHA Ascorbic Acid
method).
RESULTS AND DISCUSSION
The XRD spectra of crushed raw shells (Fig. 1) show
that the crystalline component of the untreated mussel
shell is aragonite, whereas the crystalline component
of the untreated oyster shell is calcite. Both aragonite
and calcite are different mineral forms of calcium
carbonate. The heat treatment of mussel shells at 650,
Aragonite
0
50
100
150
200
250
20 30 40 50
(a)
(b)
60
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Calcite
0
100
200
300
400
500
600
700
800
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Figure 1. XRDspectra for crushed rawshells: (a) mussel and
(b) oyster. XRD spectral peaks corresponding to aragonite
and calcite are labelled with symbols, as indicated.
750 and 800

C results in the formation of lime (calcium

oxide); this is shown in the XRD spectra in Fig. 2.
In addition, calcite was detected; this is not present
in the raw mussel shell. Pyrolysis of mussel shells at
650 and 800

C also results in the formation of calcite,

although the formation of lime was not detected at
650

C (Fig. 3). The heat treatment of oyster shells at

650, 750 and 800

C also resulted in the formation of

lime (Fig. 4). Lime was also formed during pyrolysis
of the oyster shell (results not shown).
From the XRD results (Figs 2 and 4), an increase in
the furnace temperature results in an increase in lime
content. This is detected by the relative increase in the
height of the diffraction peaks associated with lime.
The increase in lime content with furnace temperature
is supported by weight loss measurements, where the
sample weight is measured before and after heat treat-
ment/pyrolysis. The lime content can be calculated from
Eqn (1) with the assumption that all the weight loss is
due to the evolution of carbon dioxide; results are shown
in Fig. 5.
CaCO
3(s)

CaO
(s)
+CO
2(g)
(1)
Shell samples with higher levels of lime also appear
visually lighter than samples treated at lower temper-
atures (Fig. 6). It should be noted that the calculated
2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 460467
DOI: 10.1002/apj
462 J. A. CURRIE ET AL. Asia-Pacic Journal of Chemical Engineering
Calcite
Lime
0
50
100
150
200
250
300 (a)
(b)
(c)
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Calcite
Lime
0
50
100
150
200
250
300
350
400
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Calcite
Lime
0
100
200
300
400
500
600
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Figure 2. XRD spectra of mussel shell samples heat-treated
at: (a) 650

C, (b) 750

C and (c) 800

C. XRD spectral peaks

for calcite and lime are labelled with symbols, as indicated.
lime content of the samples in Fig. 5 do not account for
the presence of organic compounds in the raw shells.
Therefore these gures may be slightly high due to the
additional weight loss from the burning of the organics.
The organic content of the shells was not determined
in this study, but subsequent work has shown that the
organic content of mussel shell can be estimated at
67 wt%.
The SEM micrographs of the raw shells (Fig. 7) show
that despite sieving, nes adhered to both the mussel
and oyster particles. Upon pyrolysis at 650

C (Fig. 8),
both mussel and oyster shell particles show signs of
having undergone sintering, being rounder and having
less dened edges than the raw shell surface particles.
20 30
(a)
(b)
40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Calcite
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Calcite
20 30 40 50 60
Lime
Figure 3. XRD spectra of mussel shell samples pyrolysed at:
(a) 650

C and (b) 800

C. XRD spectral peaks for calcite and

lime are labelled with symbols, as indicated.
There are similar morphological changes that occur
for both mussel and oyster shell particles at particular
furnace temperatures during both pyrolysis and heat
treatment. For brevity, we will only present SEM
micrographs of heat-treated oyster shell processed at
different furnace temperatures (Fig. 9). From Fig. 9 we
can see that sintering of the particles occurs, resulting
in the coarsening of particles and densication of the
sample. At higher processing temperatures there is an
increase in grain size. Although the SEM images do not
give information about the composition of the samples,
they do indicate that there are structural changes that
occur to the samples during heat treatment.
From the XRD analysis, it is clear that lime has been
produced from heat-treating and pyrolysing both the
mussel and oyster shells. To gauge the effectiveness
of the treated samples to remove phosphates from
water, preliminary tests were conducted and the results
compared to that achieved with raw shells. These results
are shown in Fig. 10.
From our tests, the raw shells were able to remove up
to around 40% of the phosphates from water, whereas
both the pyrolysed and heat-treated shells demonstrate
around 90% of phosphate removal. In addition, most of
the phosphate removal occurred within the rst 30 min
of the experiments.
2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 460467
DOI: 10.1002/apj
Asia-Pacic Journal of Chemical Engineering PROCESSING SEAFOOD SHELLS FOR EUTROPHICATION CONTROL 463
Calcite
Lime
0
100
200
300
400
500
20
(a)
(b)
(c)
30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Calcite
Lime
0
100
200
300
400
500
600
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Calcite
Lime
0
50
100
150
200
250
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Figure 4. XRD spectra of oyster shell samples heat-
treated at: (a) 650

C, (b) 750

C and (c) 800

C. XRD
spectral peaks for calcite and lime are labelled with
symbols, as indicated.
Figure 5. Lime content (expressed as a percentage of total
shell weight) vs furnace temperature for mussel and oyster
shell (heat-treated and pyrolysed). This gure is available in
colour online at www.apjChemEng.com.
Given that XRD analysis has shown lime present in
the pyrolysed and heat-treated shells used in the phos-
phate removal experiments, the mechanism for phos-
phate removal from water can be demonstrated with the
following equilibria (Tchobanoglous and Burton, 1991),
where the hydroxyapatite, Ca
10
(PO
4
)
6
(OH)
2
, precipi-
tates out the soluble phosphates:
Ca(OH)
2
+H
2
CO
3

CaCO
3
+2H
2
O (2)
Ca(OH)
2
+Ca(HCO
3
)
2

2CaCO
3
+2H
2
O (3)
10Ca
2+
+6PO
4
3
+2OH

Ca
10
(PO
4
)
6
(OH)
2
(4)
At the end of the phosphate removal experiments,
the formation of a gelatinous-looking sludge was
observed suspended in the phosphate solution and
a build-up of scum formed on the surface of the
solution. Figure 11 is an SEM micrograph of a dried
sludge sample from phosphate removal experiments
Figure 6. Heat-treated shells. Mussel shells (top) and oyster shells (bottom).
Treatment temperatures from left to right: 650, 750 and 800

C.
2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 460467
DOI: 10.1002/apj
464 J. A. CURRIE ET AL. Asia-Pacic Journal of Chemical Engineering
(a)
(b)
Figure 7. SEM micrographs of raw shell particle
surface: (a) mussel shell and (b) oyster shell.
using heat-treated oyster shell originally heated to a
temperature of 800

C. XRD analysis (Fig. 12) indicates

that this sludge is comprised of mostly calcite and
that traces of hydroxyapatite may also be present. As
would be expected, the presence of hydroxyapatite
is difcult to conrm from the XRD analysis owing
to the small quantity of hydroxyapatite that would
form, given the amount of available phosphate in
solution. Characterisation of a dried scum sample by
SEM and XRD (Figs 13 and 14) shows that the scum
comprises of calcite in the form of distinct crystals,
this is different from the calcite morphology present
in the raw oyster shell (Fig. 7(b)) and in the sludge
(Fig. 11). It is likely, given the morphology of the
calcite, that the scum results from an equilibrium
reaction involving dissolution of carbon dioxide, which
is available from the atmosphere, to form calcium
carbonate. The corresponding mechanism would be as
(a)
(b)
Figure 8. SEM micrographs of shells pyrolysed
at 650

C: (a) mussel shell and (b) oyster shell.

follows:
CaO +H
2
O

Ca(OH)
2
(5)
Ca(OH)
2
+CO
2

CaCO
3
+H
2
O (6)
A sample of used oyster shell (previously heat-
treated at 800

C) was taken from phosphate removal

2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 460467
DOI: 10.1002/apj
Asia-Pacic Journal of Chemical Engineering PROCESSING SEAFOOD SHELLS FOR EUTROPHICATION CONTROL 465
(a) (b)
(c)
Figure 9. SEM micrographs of oyster shell particles heat-treated at: (a) 650

C, (b) 750

C and
(c) 800

C. The images are shown at low and high magnications.

experiments and analysed by XRD. The XRD result
(Fig. 15) shows that calcite and traces of calcium
phosphate are present. This indicates that the lime
originally present as a layer on the surface of the
heat-treated shell has eroded, leaving the calcite core
exposed. In future work, we will investigate parameters
for increasing the layer of lime formed on the shell
particles to increase the overall lime production.
Our work shows that shell-lime is effective in phos-
phate removal with crushed raw shells also able to
remove phosphates, but to a lesser extent. With lime
not present in the raw shells, it is likely that adsorption
is an important mechanism for phosphate removal. In a
study of the adsorption kinetics of phosphate removal
(Namasivayam et al ., 2005), the authors found that
oyster shell powder (produced from raw shells using
high pressure steam at 234

C) removed phosphates to
a comparable, though slightly lower, level to the cal-
cium carbonate powder. In that study, the initial pH
of the solution had no effect on phosphate removal
by adsorption; this differs from what we would expect
when lime is used Eqns (2)(4). Namasivayam et al .
(Namasivayam et al ., 2005) reported that raw oyster
shells did not remove any phosphates, however, from
2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 460467
DOI: 10.1002/apj
466 J. A. CURRIE ET AL. Asia-Pacic Journal of Chemical Engineering
our current work and the work done by others (Kwon
et al ., 2004; Lee et al ., 2005), we see that phosphate
removal can occur. Namasivayam et al . (Namasivayam
et al ., 2005) do not specify whether the raw shells
were crushed and this may explain the different results,
particularly as surface area is an important parameter
for adsorption.
In the work on crushed oyster shell waste by Kwon
et al . (Kwon et al ., 2004), the best phosphate removal
(98%) was achieved using oyster shell pyrolysed at
750

C for 1 h. The authors reported that oyster shell

heat-treated in air at 750

C achieved a 68% removal

of phosphates and that raw oyster shell achieved only
around 10% removal. It is interesting that the authors
Figure 10. Graph of phosphate removal vs time obtained
with raw and heat-treated/pyrolysed shells. The raw shell
particles were sieved to be between 3875 m and all other
samples to between 300600 m. This gure is available in
colour online at www.apjChemEng.com.
Figure 11. SEM micrograph of dried suspended
sludge obtained at the end of phosphate removal
experiments using oyster shell (originally heat-
treated at 800

C).
0
100
200
300
400
500
600
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
yCalcite
Hydroxyapatite
Figure 12. XRD spectrum for dried suspended sludge
obtained at the end of phosphate removal experiments
using oyster shell (originally heat-treated at 800

C).
Figure 13. SEM micrograph of dried surface
scum obtained at the end of phosphate removal
experiments using oyster shell (originally heat-
treated at 800

C).
0
100
200
300
400
500
600
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
yCalcite
Figure 14. XRD spectrum for surface scum collected
during phosphate removal efciency of shells. All peaks are
associated with calcite, a mineral formof calciumcarbonate.
2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 460467
DOI: 10.1002/apj
Asia-Pacic Journal of Chemical Engineering PROCESSING SEAFOOD SHELLS FOR EUTROPHICATION CONTROL 467
0
50
100
150
200
250
300
20 30 40 50 60 70
2-theta (degrees)
I
n
t
e
n
s
i
t
y
Calcite
Calcium Phosphate
Figure 15. XRD spectrum for used oyster shell (originally
heat-treated at 800

C), obtained at the end of phosphate

removal experiments.
XRD results for the heat-treated sample at 750

C
did not detect the presence of lime only calcium
carbonate, which was also present in the raw oyster
shell. In addition, the corresponding SEM micrograph
showed no discernable difference between raw oyster
shell and the sample that was heat-treated at 750

C,
unlike our results (Figs 7 and 9). It is possible that
differences in the heating regime or the particle size of
the crushed shells could explain the differing results, as
these are not specied by Kwon et al . (Kwon et al .,
2004); further work investigating the effect of these
parameters on lime formation is required to better
understand this process.
CONCLUSIONS
We have demonstrated that it is possible to convert both
mussel and oyster shells into lime (calcium oxide) by
crushing the shells and applying heat in either a nitrogen
or air atmosphere. Temperatures of 750 and 800

C
were most successful in producing lime. Preliminary
tests indicate that shell-derived lime can remove around
90% of phosphate from solution and that raw shells
(comprised of calcium carbonate) can achieve up to
around 40% removal.
Acknowledgements
The authors would like to thank the following tech-
nicians in the Department of Chemical and Materi-
als Engineering, University of Auckland for their help
with this work: Alec Asadov, Catherine Hobbis, Allan
Clendinning and Laura Liang.
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Lee CW, Kwon HC, Jeon HP, Koopman B. Phosphate recovery
from water as hydroxyapatite with activated oystershell. Mater.
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Taylor R, Smith I. The State of New Zealands Environment. GP
Publications: Wellington, 1997.
Tchobanoglous G, Burton FL. Wastewater Engineering: Treatment,
Disposal and Reuse. McGraw Hill Book Company: Singapore,
1991.
Namasivayam C, Sakoda A, Suzuki M. Removal of phosphate by
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2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 460467
DOI: 10.1002/apj