Biocementation for Sand Using an Eggshell as Calcium

Source
 ABSTRACT

A method to generate biocementation in sand using the microbially induced carbonate

precipitation (MICP) process and calcium source produced from eggshell is presented in
this paper. Instead of using calcium chloride or other calcium salts, soluble calcium was
produced by mixing eggshell with vinegar and used for the MICP process. The
compressive strength and permeability of sand treated using this method were measured
using unconfined compression and permeability tests. A comparative study between sand
samples treated using calcium produced from eggshell and those using calcium chloride
with the same concentration of calcium was carried out. The study shows that the effect of
the MICP process using calcium produced from eggshell is just as good as that using
calcium chloride. The optimum ratio of eggshell and vinegar for the MICP process was
established.
Chapter 1
Introduction

Recently, there are many studies on the use of the microbially in-duced carbonate
precipitation (MICP) process for soil improvement (Mitchell and Santamarina 2005;
Dejong et al. 2006, Dejong 2013; Van Paassen et al. 2010; Burbank et al. 2011; Chu et al.
2012, 2013; Al Qabany et al. 2012; Feng and Montoya 2015; Li et al. 2015; Ivanov et al.
2015; ODonnell and Kavazanjian 2015). In almost all the studies previously mentioned,
calcium salt such as CaCl2 was used. However, excessive presence of CaCl 2 in concrete or
soil can be harmful (Chung et al. 2014). It is also expensive to use CaCl 2 in large amounts.
On the other hand, calcium may be ex-tracted from waste materials such as eggshell,
seashell, or oyster shell. Chang et al. (2014) studied the production of water-soluble
calcium using eggshell and vinegar. Choi (2014) produced precipi-tated calcite from
discarded eggshell and oyster shell as a calcium resource with plant extracts.

In this study, an attempt was made to produce soluble calcium from eggshell and use it
for the MICP process to treat sand. To assess the effectiveness of this method, a
comparative study of the shear strength and permeability of sand treated using the MICP
process with calcium from eggshell and those of sand with calcium from CaCl 2 was
carried out. The results are presented in this paper.

Method to Produce Soluble Calcium from Eggshells

Eggshell contains more than 94% of calcium carbonate (Lechtanski 2000), and it can be
dissolved using an acid liquid. In this study,

1
Ph.D. Researcher, Dept. of Civil, Construction, and Environmental Engineering, Iowa
State Univ., Ames, IA 50011.

2
Research Fellow, School of Civil and Environmental Engineering, Nanyang
Technological Univ., Singapore 639798.
3
Professor, School of Civil and Environmental Engineering, Nanyang Technological
Univ., Blk N1, 50 Nanyang Ave., Singapore 639798 (cor-responding author). E-mail:
cjchu@ntu.edu.sg
 Note. This manuscript was submitted on October 24, 2015; approved on March 4, 2016;
published online on May 23, 2016. Discussion period open until October 23, 2016;
separate discussions must be submitted for indivi-dual papers. This technical note is part
of the Journal of Geotechnical and Geoenvironmental Engineering, ASCE, ISSN 1090-
0241.
distilled white vinegar brought from Walmart and diluted with water to 5% acidity was
used. The steps for making soluble calcium using eggshell and vinegar are as follows.
Eggshells were washed with distilled water, put in the oven at a temperature of 105C for
one day, and then crushed into powder. The crushed eggshell was mixed with vinegar in a
bottle and placed in a shaker for several days. Eggshells have an inner membrane. The
ratio of eggshell and inner membrane in eggshell was 96.8/3.2 by weight (w/w). Chang et
al. (2014) suggested removing the membrane when using egg-shells to produce a calcium
source. In this study, a comparison between the use of eggshell with and without inner
membrane was made to study the influence of inner membrane. The calcium con-
centrations of the soluble calcium solution made from eggshell with and without
membrane were measured using the ASTM D511-14 (ASTM 2014b) method and the
results are shown in Fig. 1. The calcium production versus time curves are shown in Fig.
1(a) in which 10 g eggshell without membrane and 10.32 g eggshell with membrane were
used. It can be seen that there is little difference in terms of production of soluble calcium
between the use of whole eggshell (eggshell and membrane) and eggshell without
membrane. It also implies that the inclusion of inner membrane in the eggshell has little
effect on the production of soluble calcium.

Intuitively, one would think the size of the powder made from eggshell will affect the
production of soluble calcium. Two sizes of eggshell powder were tested. One was above
0.85 mm and another was between 0.85 and 0.075 mm. As shown in Fig. 1(b), the test
using finer powder gives about 10% higher calcium concentration. This difference is only
marginal.

The results shown in Figs. 1(a and b) were carried out using an eggshell to vinegar ratio
of 14 by weight. To check the effect of the eggshell-to-vinegar ratio, tests with other
eggshell to vinegar ratios of 18 and 112 were also conducted and results are shown in
Fig. 1(c). In general, a sufficient amount of vinegar should be used, but too much may not
help in producing more soluble cal-cium. The data shown in Fig. 1(c) indicate that an
eggshell-to-vinegar ratio of 18 appears to produce the highest calcium concentration. The
data in all the tests in Fig. 1 also show that the production of calcium reaches a peak in
three days. Thus, three days were taken as the duration for the production of calcium us-
ing eggshell.
rights reserved. use only; all
Fig. 1. Optimum ratio of eggshell and vinegar: (a) influence of membrane in eggshell; (b)
influence of size of eggshell; (c) influence of ratio of eggshell to vinegar
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 Fig. 2. Arrangement for biotreatment of a sand sample

Sample Preparation and Testing Methods

The soluble calcium was used for biocementation for soil samples prepared in PVC pipes
with an inner diameter of 50 mm. The sand used was Ottawa sand with a mean grain size
of 0.42 mm. The urease-producing bacteria (UPB) used was Bacillus sp. All samples were
prepared using the following procedure: A drainage layer of 10-mm-thick gravel and
synthetic filter was put at the bottom of the
tube. Above the drainage layer, a 100-mm-high dry sand column was formed through a
funnel, and then a filter was placed on top of the sample as shown in Fig. 2. The sand was
compacted by taping to achieve a relative density of 40%. The UPB solution was poured
into the sample with a rate of 2.5 mM=min and kept there for 2 h before it was drained
out. For tests treated using CaCl2, the CaCl2 solution with a concentration of 0.45 M was
added to the top of the sample. For samples treated using the soluble calcium, the calcium
solution with a concentration of 0.45 M was used. This process was repeated 15 times.

The UPB in a freeze-drying state was added to distilled water to make a 50-mL solution
using a ratio of 1100 by weight (solution A). The 50-mL solution A was applied by adding
it to the top of the samples and letting it drain out from the bottom using a setup as shown
in Fig. 2. The solution that drained out was collected, and added to the samples for the
second time. This time, the solution was allowed to remain in the samples for 3 h before
being drained out. After the samples were treated with UPB, 300 mL of solution A with a
mixture of calcium and urea solution was applied. For the control tests, the solution used
contained 0.45 M of calcium chlo-ride and 1 M of urea in a 21 proportion (referred to as
solution B). For the rest of the tests, a solution with 0.45 M eggshell aqueous solution and
1 M urea in the proportion of 21 (referred to as solution C) was used. Either solution B or
C was applied in the same way by pouring the solution on top of a sample and draining it
out from the bottom. The drainage rate was controlled in a way that a complete drainage
would take about two days. The solution that drained out was collected and reapplied to
the samples. This process was repeated 15 times. A summary of the three solutions used is
given in Table 1. The pH of the solution was measured every time after it was drained out.
The pH increased to 8.28.5 after solution B was applied and to 8.38.7 after solution C
was used. To promote uniformity of the treatment, the sample column was turned upside
down after eight times of treatment. After 15 times of treatment, the sample was taken out
of the mold and dried in an oven under 50C

Table 1. Mixing Ratio of Cementation Material Using Different Calcium Source

Solution
Solution B C
 Solution A (UPB CaCl2 Urea Calcium from eggshell Urea
Method solution) (Mol) (Mol) (Mol) (Mol)
UPB-CaCl2 (samples CC-
1 to 4) 1/100 0.45 1.0
UPB-eggshell (samples
ES 1 to 4) 1/100 0.45 1.0
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Table 2. Summary of Testing Results

Quantity of calcite (%)

Test Calcium UCS Permeability
identifier source (kPa) (106 m=s) Top Center Bottom Average

Calciu
CC-1 m 316 3.82 5.3 4.1 6.4 5.3
chlori
CC-2 de 291 5.56 5.1 4.3 6.3 5.2
CC-3 360 1.27 6.4 5.1 7.2 6.2
CC-4 370 1.06 6.9 5.4 7.5 6.6
Eggsh
ES-1 ell 392 6.54 7.1 5.6 7.7 6.8
ES-2 418 1.63 8.2 7.0 8.0 7.7
ES-3 404 2.68 8.0 6.8 8.1 7.6
ES-4 335 4.41 7.4 4.4 7.7 6.5

for 24 h. The calcium carbonate content produced in the samples was measured using the
rapid calcite content determination method suggested by the ASTM D4373-14 (ASTM
2014a).

Testing Results

Unconfined compression (UC) and permeability tests were carried out to assess the
strength and permeability of the samples treated by both methods as detailed in Table 1.
The permeability was measured
using a falling head method. The calcite content in each sample was measured at the top,
center, and bottom positions. Table 2 summa-rizes the testing results obtained from these
tests.

The UC results are shown in Fig. 3 for both CC and ES series. It can be seen that the
results for both are comparable and the UC strength for samples treated with calcium
source produced from eggshell is slightly higher. The main reason for having a higher UC
strength from the samples treated with calcium source pro-duced from eggshell was
because the calcium contents in the ES samples are higher (Table 2). The UC strength
obtained from this study was smaller than that reported by Al Qabany and Soga (2013)
(3501,300 kPa) and Ivanov et al. (2012) (7001,000 kPa) for calcite contents of 67%.
The difference was caused mainly by the difference in the bacteria and the MICP
procedure used in these three studies.

The correlations between permeability and unconfined com-pressive strength (UCS),

permeability and calcium carbonate con-tent, and UCS and calcium carbonate content are
shown in Fig. 4. It can be seen that UCS increases and permeability decreases with
increasing calcite content. This is consistent with the mechanisms of biocementation and
biocloggingit is the calcium carbonate precipitated in soil that binds the sand grains
together to increase its shear strength and fills in the pores to reduce its permeability.
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Fig. 3. UCS results using different calcium source: (a) UCS results using calcium chloride;
(b) UCS results using eggshell

Fig. 4. Test results: (a) permeability versus calcite content; (b) UCS versus calcite
content; (c) permeability versus UCS

ASCE 06016010-3 J.
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 Fig. 5. Calcium carbonate precipitated between sand grains

Based on the data presented in Fig. 4, it requires 7% or more calcite to reduce the
permeability to an order of 106 to 107 m=s. At this calcium carbonate content, the UCS is
at a level of 400 kPa.

Scanning electron microscope (SEM) photos were taken for tested samples using
calcium produced from eggshells. Fig. 5 shows that calcium carbonate is formed between
sand grains as is commonly observed by other researchers (Feng and Montoya 2015; Li et
al. 2015).

Conclusions
 A method to produce soluble calcium using eggshell and vine-gar and to use it for the
MICP process for soil improvement is presented in this paper. The geotechnical
properties of sand trea-ted using this method were determined and compared with the
method using other calcium sources (e.g., calcium chloride). The following conclusions
are derived:

The use of soluble calcium from eggshell in the MICP process for soil improvement is
feasible. The optimum mixing ratio be-tween eggshell and vinegar is 18 (by weight).
The finer the egg-shell, the higher the amount of soluble calcium produced. A size of
0.85 mm or less for eggshell fragments will be adequate.

Using the proposed method, the permeability of the sand can be reduced to an order of
106 to 107 m=s from the original value of 104 m=s at a calcium carbonate content of
7%. The UCS at this calcium carbonate content was around 400 kPa.

Acknowledgments

We would like to acknowledge that part of this study is supported by Grant No. SUL2013-
1 by the Ministry of National Develop-ment, Singapore.
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