CO2 PRETREATMENT AND PISTIA STRATIOTES L.

AS
PHYTOREMEDIATION AGENT AS AN ALTERNATIVE
PROCESS IN ALKALINE WASTEWATER TREATMENT
FROM SOAP AND DETERGENT INDUSTRY
Chemical Engineering Research Competition 2019

Arranged by:

Leader : Renard Elyon Imawanto (11217014) 2017

Member : Adrian Rinaldo Odianda Sinaga (11217029) 2017
Jevon Robinson Joel Simatupang (13017032) 2017

BANDUNG INSTITUTE OF TECHNOLGY

BANDUNG
2019

i
 CO2 PRETREATMENT AND PISTIA STRATIOTES L. AS
PHYTOREMEDIATION AGENT AS AN ALTERNATIVE PROCESS IN
ALKALINE WASTEWATER TREATMENT FROM SOAP AND
DETERGENT INDUSTRY
Renard Elyon Imawanto1, Adrian Rinaldo Odianda Sinaga1, Jevon Robinson Joel
Simatupang2

Academic consultant : Dr. Taufikurahman1

1
Bioengineering Department, School of Life Science and Technology, Bandung
Institute of Technology, Bandung, Indonesia
2
Chemical Engineering Department, Faculty of Industrial Engineering, Bandung
Institute of Technology, Bandung, Indonesia

Abstract

Wastewater from the soap industry and detergent has alkaline properties and
need to be neutralized before treated, it’s usually neutralized by the addition of
HCl or sulfuric acid, but this process produces sulfate and chloride which harm
the environment. The addition of CO2 gas into wastewater can be used to reduce
the pH, this process will reduce the pH due to the formation of H2CO3. This
method can be used as an ecofriendly alternative as there no addition of sulfate
and chloride to environment. Wastewater from detergent industry and soap also
has a high phosphate and nitrate content which can reach 144 ppm and 38 ppm,
so further processing is needed. Pistia stratiotes has potential to be used as
phytoremediation agent due to it properties as hyperaccumulator and high uptake
rate for nutrients. One of the environmental factors that influence the absorption
of nutrients and the growth of Pistia stratiotes is pH, as pH affects the equilibrium
of nutrients found in the medium. This study aims to determine the optimum
amount of CO2 gas addition to wastewater for maximum phosphate and nitrate
absorption and plant growth by Pistia stratiotes. Based on this research, it was
found that the treatment with giving CO2 until the concentration of dissolved CO2
reached 0.03 mol/(L) was the most optimum, this was indicated by the highest
value of specific growth rate of wet weight and dry weight with 0.0411 g/day and
0.026278 g/day respectively and highest phosphate absorption for plants with
16.38 ppm/day, while the highest nitrate absorption was observed when the
dissolved CO2 concentration is 0.031 mol/(L) with an absorption rate of 19.7
ppm/day. These results indicate that the pretreatment of wastewater with the
addition of CO2 gas followed by phytoremediation by Pistia stratiotes can be an
alternative treatment for wastewater from soap and detergent industry.
Keywords: Alkaline wastewater treatment, CO2 Pretreatment, Pistia stratiotes,
phytoremediation

ii
 Preface
First we praise GOD, due to all the blessing, we can complete this full paper for
Chemical Engineering Research Competition(CeRCO) organized by Diponegoro
University. The title of this paper is “CO2 PRETREATMENT AND PISTIA
STRATIOTES L. AS PHYTOREMEDIATION AGENT AS AN ALTERNATIVE
PROCESS IN ALKALINE WASTEWATER TREATMENT FROM SOAP AND
DETERGENT INDUSTRY” is based to the themes and sub themes that have
been determined by CeRCO committee.
In this occasion we would like to thank all of CeRCO committee for this
opportunity, and also to our parents, because thank to their prayers we were able
to complete this paper. Nevertheless, we also realize that this papers is still less
than perfection, for that we highly expect suggestion and input to improve our
research and paper. Finally, we hope that this work can provide information and
be useful for the development of knowledge for writers and readers.

Bandung, 20th August 2019

Writer

iii
 TABLE OF CONTENT

Abstract ............................................................................................................................... ii
Preface ................................................................................................................................iii
TABLE OF CONTENT ......................................................................................................iv
LIST OF TABLES ..............................................................................................................vi
FIGURE LIST.................................................................................................................... vii
CHAPTER I PRELIMINARY ............................................................................................ 1
- Background ............................................................................................................. 1
- Problems ................................................................................................................. 2
- Writing’s goals ........................................................................................................ 2
- Writing’s benefit ..................................................................................................... 2
- Systematical writing................................................................................................ 2
CHAPTER II LITERATURE REVIEW ............................................................................ 3
- Soap and Detergent Industry Wastewater ............................................................... 3
- Solution that has been applied ................................................................................ 4
- Pretreatment with CO2 gas ...................................................................................... 5
- Bubble Column Reactor .......................................................................................... 6
- Phytoremediation .................................................................................................... 6
- Pistia stratiotes ....................................................................................................... 7
CHAPTER III RESEARCH METHOD ............................................................................. 7
- Pistia stratoites ....................................................................................................... 7
- Formulation of growth medium .............................................................................. 7
- Formulation of Test Reagent................................................................................... 8
o Formulation HCl and NaOH 1M ........................................................................ 8
o Formulation Ammonium Molybdate Reagent ..................................................... 8
o Formulation of Tin Chloride Reagent ................................................................. 8
- Standard Curve........................................................................................................ 8
- Plant Growth Rate ................................................................................................... 8
- Measurement of medium phosphate and nitrate concentration ............................... 9
- Dissolve CO2 concentration and CO2 partial pressure estimation ........................ 10
CHAPTER IV RESULTS AND DISCUSSION ............................................................... 11
- CO2 and Growth Medium pH ............................................................................... 11

iv
 - Pistia stratiotes growth and nutrient absorption ................................................... 12
- Bioreactor design .................................................................................................. 14
BIBLIOGRAPHY ............................................................................................................. 17
ATTACHMENTS ............................................................................................................. 22

v
 LIST OF TABLES

Table 1. Characteristics of Soap and Detergent Industry Wastewater…………..4

Table 2. Series of reaction that occur when adding CO2 gas into water………..6

vi
 FIGURE LIST

Figure 1 Effect of Carbon Dioxide addition to Ground Water pH...…………...…5

Figure 2 Change in medium pH during the CO2 addition……………………......11
Figure 3 Pistia stratiotes growth in different CO2 addition……………………...12
Figure 4 Change in phosphate concentration…………………………………….13
Figure 5 Change in nitrate concentration……………………………………...…14
Figure 6. Isometric View…………………………………………………………15
Figure 7. Right and Left View…………………………………………………...15
Figure 8. Front View……………………………………………………………..15
Figure 9. Top View………………………………………………………………16

vii
CHAPTER I PRELIMINARY

- Background

Indonesia is a developing country. Indonesia as a developing country

continues to spur its growth in all section, one of them is economic section.
Economic growth causes an increase in industrial segments that makes the
amount of B3 wastes as well as liquid wastes from industrial processes
increased. All wastes especially liquid wastes that disposed from industrial
processes usually contain hazardous chemical substances that can harm
human and other living being (Sugiharto, 2008). A less proper wastewater
treatment attempt can cause environmental and health degradation such as
waste water that contains detergent polluted the river water in Jawa and
Kalimantan (Kementrian Lingkungan Hidup dan Kehutanan, 2015).

Attempt to treat liquid wastes has been done in Indonesia using activated
sludge and aerated lagoon that utilize bacterial degradator and air bubbles to
clean the waste from organic residue and other impurities (Environmental
Services Program, 2006). However, residual detergent water has additional
problem that is the water is alkaline with pH around 10.5 (Allah et.al., 2016),
so that additional methods are needed to treat the waste with the intend to
neutralize the wastewater. One method usually used is addition of acid such as
sulfuric acid (H2SO4) and hydrochloric acid (HCl) into wastewater
(Prisciandaro et.al., 2005), besides that the addition of coagulating agent such
as alum (El-Gohary et.al., 1987), Fe2+ and Fe3+ ions (Senn et.al., 2014) is used
too. Although this methods have high effectivities in neutralizing wastewater,
it can cause further problem that is the formation of chloride as well as sulfate
salts that can endanger the enviroment.

One alternative that can be used is by using carbon dioxide gas as a

neutralization agent. Besides offering eco-friendly solution, this method also
offers solution that are safe, inexpensive, flexible, and easy to control (Al-
Mutaz & Al-Ghuinaimi, 2001). Other than that, phytoremediation is also used
in further processing of the soap water waste. This process is done in order to
reduce excessive compound such as phosphate and nitrate that can cause
eutrophication, this happen because besides having high pH, soap water waste
also contains high composition of phosphate and nitrate which is 144 ppm and
38 ppm (Allah et.al., 2016).
Other than offering a solution for waste processing, phytoremediation also
offered effective and sustainable solution, by using plant as remediator agent
further utilization can be done against this remediator agent (Greipsson, 2011).
One of the remediator agent that is used in this research is water lettuce or
Pistia stratiotes. This plant is choosed due to its capability in absorbing
nutrients and its high growth rate (Sundaralingam & Gnanavelrajah, 2014).
Absorbed nutrients will be assimilated into plant biomass. The greater the rate
 2

of nutrients absorption, the greater the rate of accumulation of biomass

produced.
pH is one of the environmental factors that influence absorption rate and
chemical compounds distribution. pH of the growth medium determined the
ratio between NH4+ and NH3 (Ahammad et.al., 2003) and also determine the
ratio between H2PO4- and HPO42- because the dissociated form affect the
absorption rate (Cerozi & Fitzsimmons, 2016). So it is necessary to measure
the addition of CO2 to the medium to obtain the most efficient rate of nutrient
absorption and biomass growth.

- Problems

The problems that this paper wants to solve are:

1. How the addition of CO2 into the wastewater effect the absorbtion of
nitrate and phosphate by Pistia stratiotes.
2. How the difference in CO2 amount added into the wastewater effect
the growth rate of Pistia stratiotes.
3. How the application of CO2 addition pretreatment and
phytoremediation with Pistia stratiotes in industrial scale.

- Writing’s goals

The objectives of this scientific paper are:

1. Determine the amount of addition of CO2 gas which produces the
highest absorption rate of nitrate and phosphate in the Pistia stratoites
plant.
2. Determine the amount of addition of CO2 gas which produces the
highest growth rate of the Pistia stratiotes plant.
3. Determine the sustainable soap and detergent industry wastewater
treatment systems that utilize pretreatment method using CO2 gas and
phytoremediation.

- Writing’s benefit

The benefits of making this scientific paper are as follows.

1. As an effort to provide environmentally friendly and sustainable
solutions to handle soap and detergent industry wastewater.
2. As an effort to introduce phytoremediation methods in waste treatment
as an alternative to achieve sustainable waste management.
3. As an effort to support the Sustainable Development Goals.

- Systematical writing

This paper have the following systematic which are CHAPTER I which
contains the background, problem formulation, research objectives, and
systematic writing. CHAPTER II literature review containing soap and
detergent industry wastewater, solution that has been applied, pretreatment
 3

with CO2 gas, bubble column reactor, phytoremediation, Pistia stratiotes.

Chapter 3 research methods that contain Pistia stratiotes, formulation of
growth medium, formulation of test reagent which consists of 1M HCl and
NaOH formulation, ammonium molybdate reagent formulation, and
formulation of tin chloride reagent, then there is standard curve, plant growth
rate, measurement of medium phosphate and nitrate concentration, dissolve
CO2 concentration and CO2 partial pressure estimation, Bioreactor modeling.
Then there is chapter 4 results and discussion that contains CO2 and Growth
Medium pH, Pistia stratiotes growth and nutrient absorption, Bioreactor
design, then there is a bibliography and finally the attachments.

CHAPTER II LITERATURE REVIEW

- Soap and Detergent Industry Wastewater

Detergent and soap are chemical compounds whose existence is close to

our daily lives. The use of detergent and soap can be found in the process of
cleaning clothes, household appliances, and industry. In general, the
components of detergent and soap can be grouped into three types, namely
surfactant substances that function as cleaners, builder substances that
function in optimizing the work of detergents and soaps as cleaners, and
additives such as fragrances, foam scavengers, or bleach (Solomons & Fryhle ,
2011). Surfactant substances can be used as a cleaner, because these
substances have sides that are hydrophobic, and sides that are hydrophilic, so
surfactants are able to interact with impurities that are generally hydrophobic
and also with water, this is what causes dirt to be carried along with water
(Solomons & Fryhle, 2011).
The use of detergent that is closely related to daily life causes its use along
with the rate of population growth each year, so that detergent and soap
produced will be even greater (Astuti & Sinaga, 2015). Besides that based on
statistics in 1998, detergent consumption per capita was 1.97 kg which
increased throughout the year to 2.32 kg in 2002, while based on the hail data
estimated by the Notepad Team of the DKI Jakarta Regional Environment
Office (NKLD) 2000, the production of boating detergent was 116.7 thousand
tons with an estimated waste volume of 327.04 thousand m3 / year (Sopiah,
2004). Chemicals that commonly found in detergent and soap are ammonium
chloride, sodium dodecyl benzene, sodium sulfate, and sodium carbonate.
Compounds previously mentioned are non-biodegradeable. This means if the
compounds have not been processed it can accumulate in nature (Kurniati,
2008). The problem of surfactant buildup this can have a negative impact on
water bodies such as silting, inhibiting oxygen transfer and changing the
normal pH of water (Nasution, 2013).
In addition to those problems, soap and detergent wastes also contains high
phosphate content derived from sodium tripolyphospate (STPP) which
function are deactivating hardness in water to optimize the work of detergent
and soap (Hermansyah, 2010). High phosphate content in wastewater can
 4

disrupt the environment around water bodies, such as causing eutrophication

(Kurniati, 2008). Besides having a high concentration of phosphate, soap and
detergent industry wastewater also have other characteristics such as high pH,
high BOD (Biological Oxygen Demand), high COD (Chemical Oxygen
Demand) and high nitrates, which are shown in table 2.1.

Table 1. Characteristics of Soap and Detergent Industry Wastewater

(Allah, et.al., 2016)
Parameter Unit Average
pH 10.5
Chemical Oxygen Demand mgO2/l 11976
Biological Oxygen Demand mgO2/l 3420
Total Suspended Solids mgSS/l 277
Total Phosphate mgP/l 144
Total Nitrate mgN/l 38

Based on the PPRI No. 82 of 2001 concerning the quality standards of

domestic wastewater, domestic wastewater is waste water originating from
business and / or surface activities (real state), restaurants, offices, businesses,
apartments and dormitories Based on the regulation the industrial wastewater
soap and detergent is not in range with water quality standard, especially
phosphate and nitrate levels that exceed the quality standard of 0.2-5 mg / L
and 10-20 mg / L.

- Solution that has been applied

Solutions to deal with soap and detergent industry wastewater have been
widely carried out. The solutions offered vary from replacing compounds in
detergents with safer counterpart through filtration methods or neutralization
of these wastes using acidic substances or coagulating agent. Detergent waste
treatment especially surfactant compounds such as LAS (linear alkyl
benzenesulfonate) comprises of three main stages namely alkyl chain
oxidation, desulfonation, and benzene ring degradation (Sopiah, 2004) which
is commonly carried out by microorganisms such as Genera vibrio,
Pseudomonas enterobacter, Bacillus, Escherichia, and Citobacter (Said,
1999). In addition, there are also other solutions such as the utilization of
Biosand Filter (BSF) which is a further development of slow sand filters,
where in this method wastewater will be flowed through the sand as a filter
which is then continued with the process of remediation by microorganisms
contained in biofilms (Astuti & Sinaga, 2015), but this system is very
dependent on the flow of wastewater and the system is easily damaged or
disturbed (Sukawati, 2008).
 5

There is also another treatment method that is through pretreatment of this

wastes because generally industrial soap and detergent production wastewater
is alkaline therefore wastewater must first be neutralized in order to facilitate
subsequent processes which is remediation process using microorganisms or
plants (Prisciandaro et.al., 2005). One method commonly used is the
acidification method using sulfuric acid (H2SO4) or hydrochloric acid (HCl)
(Prisciandaro et.al., 2005), or using iron ions as a coagulating agent to
precipitate insoluble compounds (Senn et al., 2014).
Although the remediation method with the acid pretreatment method has a
good effectiveness that is able to reduce waste by up to 20% (Prisciandaro
et.al., 2005), but the disadvantage of this method is its waste, namely sulfate
and chloride salts. Other processing methods also have few disadvantages
such as a system that is easy to be damaged and disrupted, or the high cost of
filtration and pretreatment process (Hermansyah, 2010).

- Pretreatment with CO2 gas

Since the Kyoto Protocol in 1997, countries of the world have been
actively working to reduce carbon dioxide (CO2) emissions, which are emitted
from power plants and industry (Lim et.al., 2010 & Lee et.al., 2016). Among
possible strategies for reducing atmospheric CO2 concentrations, carbon
capture utilization and sequestration (CCUS) technologies are the most
available and widely applied strategies (Pan et.al., 2012). In this method, CO2
gas produced from industry is taken back from the atmosphere for further use
(Franca et.al., 2015). One example is the consumption of CO2 flue gas
(Ghacham et.al., 2015) which is used to neutralize alkaline solutions (Pan et
al., 2012; Chen, et al., 2009).
When carbon dioxide was added into the air flowing into the diffuser the
ground water pH decreased (see Fig. 2.1). Two tests were conducted to
measure how the pH of the water varied with the concentration of CO2 in the
stripper air (Krauter et.al., 1998).

Figure 1 Effect of Carbon Dioxide addition to Ground Water pH (Krauter

et.al., 1998)
 6

Air stripping shifts the pH to the range of 8-9, which releases small
amounts of free CO32- ions. The use of this method can replace the alkaline
wastewater neutralization method commonly used, namely by the addition of
sulfuric acid and hydrochloric acid. This is due to the sulfate and chloride salts
released to the environment afterwards that can be harmful to the ecosystem.
The ideal method of pH control would be one that results in little or no
chemical change in the water (Krauter, et al, 1996).
Neutralization phenomena can happen because when CO2 gas added in
water, CO2 can react with water through equilibrium reaction that will produce
carbonic acid. Carbonic acid directly related to the process of neutralization of
alkaline water by the addition of CO2 gas. Yoo et al. (2017) also shows that
increasing the amount of CO2 added to water will also accelerate the reaction
so that a faster pH decrease will be observed. Table 2.2 shows the series of
reactions that occur when adding CO2 gas into water.
Table 2. Series of reaction that occur when adding CO2 gas into water
(Stumm and Morgan, 1996)

- Bubble Column Reactor

Bubble column reactor is a cylindrical vessel with a gas distributor at the

bottom. The gas sparged using a sparger in the form of air bubbles into liquid-
liquid or liquid-solid system. Bubble column reactors belong to the general
class of multiphase reactors which consist of three main categories namely,
the trickle bed reactor (fixed or packed bed), fluidized bed reactor, and the
bubble column reactor (Kantarci, Borak, & Ulgen, 2005). Bubble columns
serve as multiphase contactors and reactors in the chemical, petrochemical,
biochemical, and metallurgical industries (Degaleesan, Dudukovic, & Pan,
2001). Bubble columns also have found wide application as fermentors, in
wastewater treatment, and in a variety of metallurgical operations. Bubble
columns can be applied in many fields due to several advantages they provide
both in design and operation as compared to other reactors. The advantages
are it has excellent heat and mass transfer properties which means high heat
and mass coefficients, low maintenance and operating costs (Kantarci, Borak,
& Ulgen, 2005).

- Phytoremediation

Phytoremediation is an emerging technology that uses plants to clean up

contaminants or remediate sites by removing pollutants (Chandra et.al., 2003),
plants remove the pollutants by various methods such as degrade, contain, or
immobilize the contaminants ( Environmental Protection Agency, 2000). This
 7

technology offers cost-effective and eco-friendly alternative to the treatment

methods used in removing pollutants in waste site (Ahalya & Ramachandra,
2006), but phytoremediation process is limited to the root-zone of plants and
limited application, because in high contaminated sites high concentration of
contaminants can be toxic plants (Grepsson, 2015). However
phytoremediation can offer utilization, as plants that used as phytoremediation
agent can act as host to soils microorganism (Ahalya & Ramachandra, 2006),
and the plants biomass like the leaves or roots can be further processed such
can be used to produce extraction products or bioethanol.

- Pistia stratiotes

Pistia stratiotes commonly known as water lettuce has potentials to be used

as phytoremediation agent. The plant has an extensive root system that
aggressively accumulates contaminants and nutrients in its surrounding waters
(Pavithra & Kousar, 2016). This plant is currently employed in many parts of
the world for heavy metal removal from wastewater and has shown promising
results for the degradation of organic and inorganic wastes from contaminated
water sources (Odjegba & Fasidi, 2004; Gupta et.al., 2012).
The plant also can be used to to improving water qualities and found to be
effective in improving water qualities by removing nutrients pollutants such
as nitrate and phosphate . Previous research suggest that Pistia stratiotes can
removed 11.3 mg/L in the first week interval and reduce up to 91.8% of total
nitrate (Sundaralingam & Gnanavelrajah, 2014), Pistia stratiotes can also
reduce up to 99.6% of total phosphate and removal of 17.3 mg/l phosphate in
the first week (Sundaralingam & Gnanavelrajah, 2014). Pistia stratiotes also
has high growth rate and big biomass production (Reddy and Sutton 1984),
and can double it number and biomass in 6 to 15 days (Lindsey and Hirt
1999), with this invasive capability, pistia can be further used as bioresources
to produce biofuel or used as a feed. (Lu et al. 2010)

CHAPTER III RESEARCH METHOD

- Pistia stratoites

The plants used were obtained from an area in Lembang, Bandung. Plants
are grown with a floating raft hydroponic system using AB mix solution as a
medium. Each tray contains 1L medium and 4 Pistia stratiotes plants.

- Formulation of growth medium

The hydroponic medium uses AB mix solution. 5 mL of solution A and 5

mL of solution B was added to 1 liter of detergent and soap wastewater.
Medium pH was measured using a pH meter and 3 treatment variations were
made in the form of pH 6, pH 7, and pH 8.
 8

- Formulation of Test Reagent

o Formulation HCl and NaOH 1M

The 12 M HCl solution was taken as much as 16.7 mL, then
dissolved with 200 mL of distilled water. NaOH solid weighed as
much as 8 grams, then dissolved with 200 mL of distilled water

o Formulation Ammonium Molybdate Reagent

Ammonium molybdate tetrahydrate weighed around 2.5 grams and
then dissolved with 17.5 mL of water. The mixture is then added
with 28 mL of concentrated H2SO4 and 40 mL of distilled water is
added, then the distilled water is added until the volume reaches
100 mL.

o Formulation of Tin Chloride Reagent

Powdered SnCl2 weighed as much as 2.5 grams, then dissolved
with 100 mL of glycerol solution.

- Standard Curve

A standard phosphate solution is made from a 1000 ppm KH2PO4 stock

solution. Dilution is carried out using serial dilution with concentrations of 5,
2.5, 1.25, 0.625 and 0 ppm. 0.5 mL of ammonium molybdate reagent is added
to 12.5 mL of distilled water. Then 1 drop of SnCl2 reagent is added and
homogenized with vortex. The sample was then incubated for exactly 10
minutes after the SnCl2 reagent was added. The absorbance of the sample is
measured at wavelength of 660 nm. Nitrate concentration was determined
with the same method, the standard curve was made with 0, 200, 300, 400,
600, 800, 1200, 1600, and 2400 ppm. First 0.125 ml of sample was added
with 0.4 mL salicylate acid 5% and wait for 20 minutes. Then 8ml NaOH 2M
was added, and wait until the solution get cool. The absorbance was of the
sample is measured at wavelength of 410 nm. The data obtained is processed
using linear regression with the following equation:

y = A + Bx (1)
y = absorbance
x = concentration (ppm)
- Plant Growth Rate

The growth rate of plants was observed through the number of leaves, wet
weight, and dry weight of the sample. Observation of the number of leaves
and wet weight is done every 4 days, while the observation of dry weight is
done every 8 days until the 16th day. Observation data obtained are then
transmitted over time. Specific growth rates are calculated using the equation:
 9

μ= (lnxt-lnxo)/t (2)

μ = specific growth rate (day-1)

xt = measured weight (g)
xo = initial weight(g)
t = time (day)

- Measurement of medium phosphate and nitrate concentration

Samples come from plant medium. Each sample was diluted 200 times,
then 12.5 mL samples were taken and added with 0.5 mL of ammonium
molybdate reagent. Samples is added with 1 drop of the SnCl2 reagent and
homogenized with vortex. The sample was incubated for exactly 10 minutes
after the SnCl2 reagent was added. The absorbance of the sample is measured
at a wavelength of 660 nm. From the absorbance of the sample, phosphate
concentration can be calculated using the same equation as standard curve
estimation. From the estimation of standard curve, obtained A = 0.0279 and B
= 0.1356. So the equation becomes:
y=0,0279+0,1356x (3)

x = phosphate concentration (ppm)

y = measured absorbance
The phosphate absorption rate is calculated using the following equation:

v= (4)

v = phosphate absorption rate (ppm/day)

x = phosphate concentration(ppm)
t = time (day)
Medium nitrate concentration was determined by first 0.125 ml of sample
was added with 0.4 mL salicylate acid 5% and wait for 20 minutes. Then 8ml
NaOH 2M was added, and wait until the solution get cool. The absorbance
was of the sample is measured at wavelength of 410 nm. From the absorbance
of the sample, phosphate concentration can be calculated using the same
equation as standard curve estimation. From the estimation of standard curve,
obtained A = -0.0715 and B = 0.0005. So the equation becomes
y= -0.0715+0,0005x (5)
The nitrate absorption rate is calculated using equations (4).
 10

- Dissolve CO2 concentration and CO2 partial pressure estimation

The estimation of dissolved CO2 concentration is based on several

assumptions which are ideal gas, ideal fluid, salinity can be ignored, in
equilibrium, and strong base in wastewater.
Dissolved CO2 concentration estimation in the carbonate system is done by
looking at the relationships among these different chemical species of the
carbonic acid system represented by a sequence of reaction below

Each chemical has its equilibrium constant. From its equilibrium constant
we can estimated the dissolved carbon dioxide concentration using the
equation below.

[ ] (6)

[ ] (7)

Equation (7) used to determine the amount of dissolved CO2 to change the
pH from 10 to 7 because H2CO3 is considered to reacted completely with
strong base within the wastewater. Equation (6) and (7) used to determine the
amount of dissolved CO2 to change the pH from 10 to 6 because the
remaining H2CO3 from the reaction with the base is considered deprotonated
to HCO-.
pH changes depend on the dissolved CO2 so it is necessary to know the
partial pressure of CO2 based on Henry law the partial pressure of the gas
affects the solubility of the gas in a solution. Partial pressure of CO2
estimated
[ ]
(8)

The equilibrium constants can be given by following expressions (Morse

& Mackenzie, 1990)

(9)

(10)

Hydration equilibrium constant (Ko) value is 1.7x10-3 (Housecraft &

Sharpe, 2005).
 11

- Bioreactor modeling
Bioreactor modeling is done to visualize the system that will be used to
process soap and detergent wastewater with CO2 pretreatment and
phytoremediation by Pistia stratiotes when applied on an industrial scale. The
modeling is done using Solidworks application.

CHAPTER IV RESULTS AND DISCUSSION

- CO2 and Growth Medium pH

Figure 2 track the changes in plant medium pH. It shows that with more
CO2 addition to the wastewater medium, pH of the wastewater become more
reduced, this effect caused by more protons generated by carbon reaction with
water, while consuming OH- ions (Han et.al., 2017). Previous research also
reported that an increase in CO2 gas injection (gas total pressure) enhanced the
carbonation efficiency, and results in more reduced pH (Azdarpour et.al.,
2015). pH decrease were generated by the formulation of CO32-, not because
HCO3- (Yoo et.al., 2017), it also reported that further increasing CO2 gas
pressure below a pH of 6.4 did not reduce the pH value further more, this is
caused by at pH 6.4 carbonic acid and dissolved carbon dioxide gas exist in
equilibrium at the medium water (Al-Mutaz & Al-Ghunaimi, 2001).

Figure 2. Change in medium pH during the CO2 addition

Effect of CO2 Addition to Wastewater pH

12

10

8
pH

6
0.031 mol/L CO2
4 0.03 mol/L CO2

0
0 4 8 12 16
Time (Day)
 12

- Pistia stratiotes growth and nutrient absorption

Plant growth is influenced by several environmental factors, one of which

is the pH of the plant medium. Alkaline pH is less optimal for plant growth
(Becquer et.al., 2014) Each plant has an optimum pH range that varies,
depending on the needs of the elements and the environment in which they
lived. Water lettuce plants have the optimum pH of growth in the range of
5.5-6.0 (Lu et.al., 2010), the writer experiment result provided that Pistia
stratiotes planted in wastewater medium with 0.03 mol.liter -1 dissolved CO2
have the greatest biomass growth and the highest specific growth rate with
value 0.0411 gr/day, which mean the result is consistent with the reference,
figure 4.2 shows Pistia stratiotes growth in each medium wastewater.
Figure 3. Pistia stratiotes growth in different dissolved CO2 concentration

45
40
35
30
Biomass (gr)

25
20 0.031 mol/L CO2
15 0.03 mol/L CO2
10
5
0
0 5 10 15 20
Time (day)

The pH of the plant medium shows the level of acidity, this factor is
important to consider because all plants need different pH levels for optimal
growth. The acidity level of the medium also influences the distribution of
nutrients in the medium, besides the unbalanced pH can inhibit the ability to
absorb nutrients in the medium. Based on observations, pH has an influence
on the growth of water lettuce plants. In the Pistia stratiotes growth diagram
(Figure 4.2) it can be seen that water lettuce plants biomass increases with
age of plants under various pH conditions, but the highest biomass growth is
observed in water lettuce plants that grow on a medium with a pH of 7 with
the highest specific growth rate ie 0.0411 gr/days, this is because the pH
range of 6-7 is the optimal pH for the availability of nutrients for plants in its
growth. Nitrogen, phosphorus, and potassium are available in quite a lot in
that pH range. The availability of nutrient for plants makes plants grow
optimally and produce a lot of leaves. Alkaline pH conditions can reduce the
availability of the elements Fe, Mn, Cu, and Zn. Whereas acidic pH can
 13

reduce the availability of elements N, P, K, and S In addition, pH also affects

the uptake of nutrients (Schachtman et.al.,1998)

Figure 4. Change in phosphate concentration

350

300

250
Phosphate (ppm)

200

150 0.03 mol/L CO2

0.031 mol/L CO2
100

50

0
0 5 10 15 20
Time(day)

From the results of the study, it was found that water lettuce (Pistia
stratiotes) plants had relatively higher phosphate absorption rates at low pH
compared with high pH. This could be due to the more phosphate form the
plant absorbs at low pH (Cerozi & Fitzsimmons, 2016). Plants are generally
only able to absorb phosphate in the form of free orthophosphate ions namely
H2PO4- and HPO42- ions (White, 2012) Besides these ions have an
equilibrium process that is influenced by the pH value. The pKa values of
H2PO4- and HPO42- ions are 2.1 and 7.2 (Hirsch et.al., 2006). Because of this
equilibrium, there are differences in the rate of phosphate absorption at
different pH mediums. As the pH of the medium increases, the rate of
phosphate absorption decreases due to a decrease in H2PO4- concentration
(Barrow, 2016). The same results were also obtained through this research,
which was observed that water lettuce plants grown at low pH had higher
phosphate absorption rates when compared to those grown at high pH, with
the highest absorption rate found in Pistia stratiotes planted when the
dissolved CO2 concentration is 0.03 mol.liter -1 CO2 with phosphate reduction
rate of 16.38 ppm/day.
 14

Figure 5. Change in nitrate concentration

800
700
600
Nitrate (ppm)

500
400
0.03 mol/L CO2
300
0.031 mol/L CO2
200
100
0
0 5 10 15 20
Time (Day)

Nitrogen (N) is one of many macronutrients that essential for plant life.
Root and leaves are the most affected plant’s organ by Nitrogen absorption,
usually nitrogen is absorbed in form of ammonium (NH4+) or nitrate (NO3-)
(Simanjuntak & Isjwara, 2000). Environment factors can affect absorption
rate of nitrate by plant, one of them is pH. From the experiment result, it
obtained that the highest absorption rate is found when the dissolved CO2
concentration is 0.031 mol.liter -1 CO2, this means Pistia stratiotes that
planted in the lowest pH absorb more nitrate with value 19.7 ppm/day. The
same results also found in other experiment (Sundaralingam &
Gnanavelrajah, 2014). Plants absorb nitrate at the highest rate at pH 4, this is
caused by the competition of nitrate and OH- ions at higher pH which will
reduce nitrate absorption by plant(Simanjuntak & Isjwara, 2000).

- Bioreactor design

In this system we design bioreactor for detergent absorption operation

using Pistia stratoites as bioconversion agent. This system mode of operation
is batch mode because from this study we found that the plants absorption
time is quite long. We design this system based on bubble column reactor
because its excellent mass transfer of CO2 gas and turbulence velocity profile
ensure the gas dispersion through the liquid. pH transducer, heat exchanger,
and substance flow control are used as pH, temperature and wastewater flow
control, respectively. Sparger is used to disperse the CO2 gas into the liquid.
When the system operates, its lid close to prevent air discharge. The lid can be
open in order to change the plant. It aims to maintain partial pressure of CO2
because the relationship between CO2 solubility in liquid and partial pressure
of CO2. From our calculation the partial pressure of CO2 needed to maintain
pH values of 6 and 7 are 0.9 atm and 0.88 atm, therefore the partial pressure
 15

must be maintained. Air flow control is used as means to control the partial
pressure of CO2 therefore the pH is controlled. pH control is performed to
maintain the optimum pH for Pistia stratoites, so the plant absorption rate is
high. Bioreactor design can be seen in figures 6, 7, 8, and 9.

Figure 6. Isometric View

Figure 7. Right and Left View

Figure 8. Front View

 16

Figure 9. Top View

 17

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