pISSN 2093-2332 eISSN 2287-5638

J. Korea Soc. Waste Manag., Vol. 37, No. 5, pp. 327-334, July 2020
https://doi.org/10.9786/kswm.2020.37.5.327 Original Paper

Evaluating Remediation Efficiency of Functional Oyster Shell Powder

for Organically Enriched Sediment

Md Akhte Khirul·Beom-Geun Kim·Daechul Cho*·Sung-Hyun Kwon**,†

Department of Ocean System Engineering, College of Marine Science, Gyeongsang National University
*Department of Energy and Environmental Engineering, Soonchunhyang University
**Department of Marine Environmental Engineering, Gyeongsang National University
(Received 10 April 2020 : Revised 29 June 2020 : Accepted 1 July 2020)

Abstract

Eutrophication is a serious environmental issue in coastal areas, caused by increased nutrient concentration from external
sources. Nutrients could augment in the bottom sediment and be released into overlying water, acting as an internal nutrient
source. Converted oyster shell powders were used to evaluate the suppression of nutrients release from bottom sediments.
Two kinds of oyster shell powder were applied into the sediment in the individual column with the control column. The
natural oyster shell powder (NOSP) was composed of calcium carbonate and the functional oyster shell powder (FOSP)
was composed of calcium peroxide. In the column where FOSP was applied, pH was increased due to hydrolysis of calcium
peroxide in the overlying water. The concentration of dissolved oxygen in the FOSP-treated columns was higher than that
of the control column. The FOSP could suppress the release of ammonia nitrogen and phosphates from the sediment into
the overlying water. It was proven that FOSP can effectively adsorb phosphates from organically enriched sediments.
Overall, the application of FOSP could effectively control nutrient release from the sediment to overlying water and help
reduce the eutrophication in the coastal areas.

Key Words : Marine sediment, Eutrophication, Remediation, Phosphate, Oyster shell powder, Nitrification

I. Introduction matter keeps on the bottom water and consumes dis-

solved oxygen. Under reduced condition, generates
The extensive eutrophication of coastal area is a most nutrients to overlying water from sediment for the
serious problem. Marine eutrophication has been increased degeneration of organic matter2). Consequently, NH4+-N
due to agricultural, industrial wastewater, aquaculture and PO43-P are an important contributor to the enhance-
activities etc. Nutrients are deposited into sediments and ment of hypoxia. It may reason, the dissolved oxygen
its released into water by the existing organic matter depletion in the water caused by its oxidation resulting in
decomposition in the sediment1). Several coastal regions the digression of marine ecosystems. On the contrary,
in South Korea has a lot of problems such as blue tide, the depletion of oxygen is an enormous effect on aquatic
raw scum, the wideness of smelly gas and eutrophica- organisms and occasionally occur economic losses to
tion. In consequence, input nutrients contain organic aquaculture activities. So, it is necessary to cut down the
sulfide concentration in the sediments wherein sustain
healthy ecosystems and keep up effective aquaculture
First author : Md Akhte Khirul, Ph.D. student, Gyeongsang activities.
National University
The southeastern coastal area in Korea is one of the
Co-author : Beom-Geun Kim, Master’s student, Gyeongsang
National University, Daechul Cho, Prof., Soonchunhyang most productive oyster farming water in the world and it
University contribute a large part of the local economy. Though,
†
Corresponding author : Sung-Hyun Kwon, Prof., Gyeongsang
National University, shkwon@gnu.ac.kr, 055-772-9132 annually about 250,000 tons of waste oyster shells are

327
328 Md Akhte Khirul·Beom-Geun Kim·Daechul Cho·Sung-Hyun Kwon

produced and most of the shells left untreated for long lected in the mariculture sea area of Tongyeong bay, in
time3). These oyster shells are consisting of 97% cal- the southern part of Korea. The sediment sample was
cium carbonate4). In fact, huge amounts of oyster shell collected from 0 to 15 cm below the sediment-water
dumped into public water and reclaimed lands near the interface using a grab sampler. The collected sediments
seaside, causing odor problems because of the environ- were packed in airtight polyethylene bags and stored at
mental degradation5). Thus, recycling of waste oyster 4oC. Seawater samples were collected from 0.5-1.0 m
shells has appeared as an essential issue in the maricul- depth below the surface water. The sediment samples
ture area. It is this important to find way to use oyster were strained to remove debris and pebbles, followed by
shell which is reduce environmental problems. Several homogenized before column packing and sediment char-
studies on the application of oyster shells as a materials acterization.
filter in the food and chemical industries4), construction
materials6-7), soil conditioner8), sludge conditioner9), cement 2. Preparation of natural and functional oyster shell
clinker10), catalyst11), desulphurization sorbents12) and fil- powders (NOSP and FOSP)
tering medium13) etc. Some of the waste oyster shells are
used for chicken feed and limestones in fertilizer14). The The oyster shells are consisting of 97% calcium car-
Korean government has led to the investment of a fertil- bonate4). Natural Oyster shell powder dried in a drying
izer plant to enhance recycling of oyster shells15). oven was ground for fine formation by using mortar. The
The purpose of the study are (1) the effects of pH, DO fine oyster shell powder passed through the 0.85 mm
on the release of nutrients into overlying water from sed- sieve. One part of shell powder was sonicated with dis-
iments, (2) to develop converting waste oyster shells and tilled water for 60 min (powder: water (w/w) = 1 : 2)
to examined the remediation ability of functional oyster using an ultrasonicator (T18, Ultra-turrax, USA). The
shell powders application to organically enriched sedi- dried powder was milled and then oxidized with hydro-
ment-water column in terms of suppressing NH4+-N, gen peroxide. The re-milled powder was used for exper-
PO43-P concentration and sediment oxygen demand to iments, which is called functional oyster shell powder, as
reduce eutrophication. oxygen releasing compound16). The involving chemical
reactions are shown in Eqs. (1), (2) and (3).
II. Materials and Methods CaCO3 CaO + CO2 (1)

1. Sample collection and study area CaO + H2O Ca(OH)2 (2)

Ca(OH)2 + H2O2 CaO2 + 2H2O (3)

In this study, marine sediment and water were col-

Fig. 1. The process of preparing functional oyster shell powder (FOSP).

 Evaluation of the Remediation Efficiency of Functional Oyster Shell Powder Application to Organically Enriched Sediment 329

3. Experimental incubation 5. Sediment Oxygen Demand (SOD)

For laboratory-scale experiments was conducted in a Before measurements, the distilled water was filtering
3-L transparent column (100 cm height × 6 cm diame- with glass microfiber filter paper (GF/C,What man, UK)
ter). 300 gm sediment was added into the column to a and aerated 8 h in a dark place. 2 grams sediment sam-
height of 20 cm from the bottom. Functional oyster shell ple was placed into different BOD bottles. Then, the bot-
powder (FOSP) and natural oyster shell powder (NOSP) tles were filled with the aerated water. The dissolved
were added in the sediment (0.5% w/w) and mixed to be oxygen was continuous measured every 30 min in the
fully homogenized each column. While another column overlying water for a total duration of 5 h with a DO
prepared as control by the same quantity of natural sed- meter (YSI 550A, USA). Mathematically, the incuba-
iment. 2-L of filtered seawater was slowly added to the tion SOD rate can be formulated as following method18):
column to avoid resuspension of sediment. The columns
dC 1 100
were roofed by aluminum foil and stood in room tem- SOD = -------  V   -----  -------------------- (4)
dt  M 100 – W
perature (22ºC ± 2ºC). The overlying water samples
analysis were conducted on the days of 0, 3, 9, 12, 15 where dC/dt denotes change of DO (mg O2/L) per
and sediment samples were analyzed before and at the time, and M is weight of a sample.
end of the experiments. Overlying water samples were
collected from three layers in the experimental col- III. Results and Discussion
umns: top, middle and bottom layer from the sediment
surface by the distance of 70, 35, and 15 cm, respec- 1. Effects of oyster shell powder on pH
tively.
The pH of the control, NOSP applied column and
4. Analysis of Physicochemical Property and Chemical FOSP applied column were 6.9-7.5, 7.0-7.9, and 7.2-8.1
Analysis for sediments and 7.6-7.8, 7.6-7.9, 7.6-8.0 for overlying
waters, respectively (Fig. 2). The FOSP applied column
Before analyzed, the water and sediment were sepa- pH was higher than NOSP applied column with control.
rated from the column and sediment was fully to be Because FOSP component is calcium peroxide which is
homogenized. The pH and oxidation-reduction potential generate hydroxide. On the other hand, NOSP compo-
(ORP) were measured using a multifunctional meter nent is calcium carbonate which is low soluble in water.
(Orion 3 star, USA). Dissolved oxygen of the overlying Generally, organically enriched sediment pH is weakly
water was measured with a DO meter (YSI 550A, acidic condition due to organic matter decomposition
USA). The supernatant pore water was collected from and generate organic acid. So, appropriate amount of
the sediment by centrifugation (2000 rpm, 20 min). Before FOSP application will not affect the pH value in the sed-
analysis, the supernatant and overlying water samples iment water column.
were filtered by microfiber filter (47 mm, GF/C). The
NO3N, NO2 -N and NH4+-N concentration were ana- 2. Effects of oyster shell powder on dissolved oxygen
lyzed by potassium persulfate oxidation assays, indophe- and sediment oxygen demand
nol blue method, N-(1-naphthyl)- ethylenediamine
adsorption spectrophotometry and cadmium-copper col- The organic matter mineralization in the sediments
umn reduction method respectively according to the fol- consumes much amounts of oxygen, which is increase
lowing previously described17). Phosphate (PO43-P) was anoxia problem in the coastal area. The deficiency of
measured using the ascorbic acid reduction method. oxygen in the water is a potential risk to aquatic ecosys-
For all experiments, overlying water and sediment were tems, as a result release harmful gas and increases degree
conducted in triplicate and the average result were of eutrophication. In this study, the concentration of DO
used. of the control, NOSP applied column and FOSP applied
column were 6.7-5.2, 6.7-6.2, and 6.7-6.6 mg/L in the
330 Md Akhte Khirul·Beom-Geun Kim·Daechul Cho·Sung-Hyun Kwon

Fig. 2. variation of pH in the overlying water (A) and Fig. 3. Variation of DO in the overlying water (A) and
sediment (B) by addition of NOSP, FOSP (0.5% w/w) and sediment oxygen demand (B) by addition of NOSP, FOSP
control for 15 days. (0.5% w/w) and control for 15 days.

overlying water respectively (Fig. 3A). FOSP applied phates etc. As a result, depletion of oxygen in the control
column dissolved oxygen concentration was higher than column overlying water (Fig. 3B). Sediment oxygen
that of the NOSP applied column with control in the demand (SOD) is a main cause of DO concentration. On
overlying water. Because FOSP component is calcium the other hand, FOSP applied column SOD was slightly
peroxide which is slowly generate oxygen and increas- increased which indicates increased DO level in the
ing the DO level in the overlying water. overlying water and reduce the nutrients release from
Sediment oxygen demand is a sink of oxygen, which sediments to overlying water compared to others exper-
is defined as the oxygen consumption rate due to decom- imental column.
position of settled organic matter, chemically or biologi-
cally in the sediment17). SOD has been found to contribute 3. Effects of oyster shell powder on nitrogen release
significantly to oxygen depletion. As shown in fig 3B,
the concentration of SOD of the control, NOSP applied The transition and transportation of nitrogen concen-
column and FOSP applied column were 0.04 ~ 0.09, tration at the sediment water interface is complicated,
0.03 ~ 0.07 and 0.03 -0.05 mg/g in the sediment respec- containing the interconversion of different nitrogen spe-
tively. This experimental result showed that, control col- cies. Some environmental factors may impact on nitro-
umn SOD was highly increased under experimental gen release from sediments such as DO, pH, redox
period. Because highly degradation of organic matter in potential etc19). Nitrification-denitrification, ammonifica-
the control column sediment, which was release of nutri- tion, and dissimilatory nitrate reduction to ammonium
ents, such as nitrogen, ammonium, phosphorus, phos- (DNRA) action are important role in interconversion
 Evaluation of the Remediation Efficiency of Functional Oyster Shell Powder Application to Organically Enriched Sediment 331

Fig. 4. Variation of NH4+-N concentration in the overlying

Fig. 5. Variation of NO3-N concentration in the overlying
water (A) and sediment (B) by addition of NOSP, FOSP
water (A) and sediment (B) by addition of NOSP, FOSP
(0.5% w/w) and control for 15 days.
(0.5% w/w) and control for 15 days.

process. Under oxic condition, nitrification take place water was decreased in the all experimental columns.
spontaneously and NO3-N concentration becomes On the other hand, the concentration of NO3−-N was
higher. But under the anoxic condition, denitrification decreased in the overlying water and pore water of the
was occurred, and nitrification restrained. In this experi- all experimental column until 15 days experimental
ment, the concentration of nitrogen nutrients such as period (Fig. 5). However, the NO3−-N concentration in
NH4+-N, NO2-N, NO3-N release from sediment to the overlying water and pore water of the FOSP applied
water were monitored by the effect of oyster shell pow- column was higher than that of the other column. As
der with control, where the sediment performed the lead show in the fig 4 and 5, the concentration of NO3−-N
as a source. It was observed that, before the process, showed a mirror image of NH4+-N due to the diagenetic
NH4+-N concentration equilibrium in the overlying water reactions. The NH4+-N concentration in the main form of
at all experimental column (Fig. 4). The concentration of inorganic nitrogen released into overlying water from
NH4+-N was rapidly increased with in the first 12 days sediments. This experimental result may relate to the
and the reached equilibrium in the NOSP applied col- mineralization into NH4+-N of organic nitrogen. It was
umn with control. On the other hand, FOSP applied col- proved that, high pH may change the sediment proper-
umn NH4+-N concentration was gradually increased until ties and high dissolved oxygen concentration can inhibit
experimental period in the overlying water. Therefore, NH4+-N release from sediments20-21). In general, the
the NH4+-N concentration of the overlying water in the NH4+-N release rate decreased with the increasing pH. In
FOSP applied column decreased compared to others col- this experimental column, FOSP applied column sedi-
umn. The concentration of NH4+-N in the sediment pore ment and water pH was comparatively higher than oth-
332 Md Akhte Khirul·Beom-Geun Kim·Daechul Cho·Sung-Hyun Kwon

ers column. On the other hand, the DO concentration

was decreased from 0 to 6 days in all column. After 6
days, FOSP applied column DO was increased due to
the oxygen releasing ability from peroxide. But NOSP
applied column DO was slightly increased and control
column DO was gradually decreased until experimental
period. Moreover, enough oxygen could help to catalyze
nitrification and denitrification processes22), so FOSP
applied column ammonium nitrogen concentration de-
creased and nitrate concentration increased compared to
others column. The concentration of nitrite nitrogen is
very low and continuously decreased, which became
negligible23). In summary, the nitrogen transformation
result indicates that the FOSP was blocked ammonium
release from sediment and increased NO3−-N in the over-
lying water compared to others column. This may be due
to decrease the nitrification rate and increase dissimila-
tory nitrate reduction to ammonium in the control and
NOSP applied column because the dissolved oxygen
concentration was lower than FOSP applied column.

4. Effects of oyster shell powder on Phosphorus release

The phosphorus release from sediments into overly- Fig. 6. Variation of PO43-P concentration in the overlying
ing water are affected by different environmental factors water (A) and sediment (B) by addition of NOSP, FOSP
(0.5% w/w) and control for 15 days.
including pH, oxidation reduction potential, tempera-
ture, physical process, intensity of light etc24). Under
anoxic condition, the phosphorus release from sediment In this way, the PO43-P in the sediment of the FOSP
is highly increase is well documented. In this experi- applied column was adsorbed effectively onto the CaO2
ment, sediment water column was not anoxic condition, with the precipitation of calcium phosphates. Because, P
because the overlying water indicates the dissolved oxy- forms in water body mainly include HPO42− and H2PO4 −,
gen was 6.7 to 5.2 mg/L in the control column. which are in dynamic adsorption equilibrium to the sed-
At day 0, the oxidation reduction potential in the sedi- iment25). So, the PO43-P concentration in the overlying
ment was significantly negative (-211.9 mV), which indi- water highly increased in the NOSP applied column with
cates the sediment was highly reduced condition. Under control column. But, the concentration of phosphates the
reduced condition, phosphates release from sediments into overlying water in the FOSP applied column decreased
overlying water. As shown fig.6, the PO43-P concentra- compared to others column due to the suppression of
tion of the sediment pore water was decreased all experi- PO43-P releasing flux.
mental column. At day 0, the concentration of PO43-P of
the FOSP applied sediment pore water was significantly IV. Conclusions
decreased due to the formation of calcium phosphates.
FOSP contains calcium peroxide and its surface is alka- The natural oyster shell powder (NOSP) and func-
line, which is formation of phosphates salts with calcium. tional oyster shell powder (FOSP) are mainly composed
of calcium carbonate and calcium peroxide. The func-
3CaO2 + 2H2PO4 Ca3(PO4)2 + 2H2O + 2O2 tional oyster shell powder is increasing the dissolved
(5) oxygen level in the overlying water as a slow oxygen
 Evaluation of the Remediation Efficiency of Functional Oyster Shell Powder Application to Organically Enriched Sediment 333

releasing compound which could effectively improve the 11169 (2015)

anoxic condition in the sediment and overlying water. In 4. Boyjoo, Y., Pareek, V. K. and Liu, J. : Synthesis of
addition, obtained result suggested that, DO and pH at micro and nano-sized calcium carbonate particles and
sediment-water interface are closely associate with nutri- their applications, Journal of Material Chemistry A,
Vol. 2, No. 35, pp. 14270-14288 (2014)
ent release and their effect on nutrient migration is also
5. Lee, J. Y., Hong, C. O., Lee, C. H., Lee, D. K. and
summarized in this study. The results of column experi-
Kim, P. J. : Dynamics of heavy metals in soil amended
ments proved that, FOSP can reduce NH4+-N and PO43- with oyster shell meal, Korean Journal of Environ-
P concentration and slightly increased NO3−-N concen- mental Agriculture, Vol. 24, No. 4, pp. 358-363 (2005)
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effectively compared to control. According to obtained as substitute for aggregate in mortar, Waste Manage-
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(2005)
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8. Lee, C. H., Lee, D. K., Ali, M. A. and Kim, P. J. :
tal solution, namely the remediation of organic matter Effects of oyster shell on soil chemical and biological
enriched coastal sediment and the eliminating disposal properties and cabbage productivity as a liming
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Acknowledgments
of cement clinker from the mixture of oyster shell,
casting dust and BOF slag, Journal of Korean Ceramic
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