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World Environmental and Water Resources Congress 2016 357

Preliminary Laboratory-Scaled Characterization of 2-Nitrophenol Transport Parameters


for Groundwater Contamination Risk Assessment
Thawat Ngamsritrakul1; Piyatida Ruangrassamee2; and Aksara Putthividhya3
1
Graduate Student, Dept. of Water Resources Engineering, Faculty of Engineering, Chulalongkorn Univ.
Bangkok, Thailand. E-mail: kim.ngamsritrakul@gmail.com
2
Lecturer, Dept. of Water Resources Engineering, Faculty of Engineering, Chulalongkorn Univ., Bangkok,
Thailand (corresponding author). E-mail: piyatida.h@chula.ac.th
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3
Assistant Professor, Dept. of Water Resources Engineering, Faculty of Engineering, Chulalongkorn
Univ., Bangkok, Thailand. E-mail: dr.aksara.putthividhya@gmail.com

Abstract
Groundwater is one of the important sources of water supply in Thailand especially in
non-irrigated areas during dry season. Numerous groundwater contaminated sites have been
reported from both natural and anthropogenic (i.e., man-made) activities with extent of plume
migration, leading to a degrading quality of groundwater which is unacceptable for human
consumption. Determination of contaminant transport parameters in the saturated zone is of great
importance for groundwater risk assessment. For our study, a series of column experiments were
conducted to obtain the transport parameters of 2-nitrophenol in natural soil which are collected
from a contaminated site in Thailand. 26 porous media samples were randomly collected from
the site from 1.5 m depth below ground surface and further analyzed for their grain size
distribution using ASTM D422-63 standard method (Standard Test Method for Particle-Size
Analysis of Soils) to cluster the sample. Upward flow direction column setup was employed with
23.7 mM phosphate buffer containing 10 mg/L NaCl solution (as a conservative tracer) influent
for at least five pore volumes (PV) at 30 mL/h constant rate injection, then switched to 10 mg/L
of 2-nitrophenol in 23.7 mM phosphate buffer solution and the column was consecutively
flushed for another 5 PVs. Effluents were systematically collected in every 0.25 PV and further
analyzed for their Cl- and 2-nitrophenol contents by using a well-calibrated conductivity meter
and gas chromatograph (GC), respectively. Natural soil from the study area could be clustered
into three groups based on their D50 values of 0.16 mm, 0.27 mm, and 1.08 mm, respectively. Cl-
and 2-nitrophenol breakthrough curves were plotted and compared to assess the contaminant
transport parameters, including its dispersivity and retardation factor in comparison to the
conservative tracer. The dispersivity of 2-nitrophenol for three groups of sample is 0.41 cm, 0.34
cm, and 0.35 cm, respectively. For retardation factor, they were equal to 1.127, 1.086, and 1.086,
respectively.
Keywords: 2-nitrophenol; Groundwater contamination; Column experiment.
INTRODUCTION
Groundwater is an important source of water supply in Thailand especially in non-
irrigated area or dry season. Unfortunately, Thailand confronts with contamination problems in
subsurface water due to natural or anthropogenic contaminants. Several contaminated sites have
been reported with extent of contaminant plume migration. In our study, we selected the

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contaminated site where has been reported with phenol contamination and 2-Nitrophenol is a
prominent contaminant in shallow groundwater due to the leachate of the mismanagement
landfill, the wastewater in the night-dumping site, and etc. To model the transport of contaminant
and determine the location of potential source by using inverse modeling in the study site, we
must have the related data such as the contaminant transport parameter. In general, there are 2
methods to getting the data of contaminant transport parameter: field test and column
experiment. In our study, we selected the column experiment because experiment uses less time
and budget when compare with field test and the result of the experiment is reliable.
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The transport of organic carbon is governed by the process of advection, dispersion,


sorption/desorption, and biodegradation. There are many study about contaminant fate and
transport that use the column experiment to determine the contaminant transport parameter (eg.
dispersivity (α), retardation factor (R), biodegradation factor, and etc.). Saquing et al. (2012)
have studied the fate and transport of phenol in a packed bed reactor containing simulated solid
waste. Pipitsombat (2010) has used the column experiment to study the leaching and transport of
nitrate in saturated aquifer system. Guo et al. (2003) have used soil column experiment to study
the transport of dissolved organic matter. Perfect et al. (2002) have use column experiment and
method of moment to predicted the dispersivity of six soil types ranging in texture from loamy
sand to silty clay. Li et al. (1997) have estimated the retardation factor of dissolved organic
carbon in sandy soil column. The objective of this study were to (1) conduct the column
experiment to measure the transport of 2-Nitrophenol in a soil samples, (2) grouping the soil
sample in our study site for using as porous media in column experiment.
METHODOLOGY
In this paper, we have divided our study to 2 main parts: the first is the sieve analysis for
grouping 26 soil samples which we got from the study site base on its d50 and the second part is
the column experiment to determine the hydrogeological parameter of contaminant.
Sieve Analysis
In this study, we have gotten 26 soil samples from our study site and clustering by
following the ASTM standard method D422-63 (Standard Test Method for Particle-Size
Analysis of Soils). We selected the sieve No. 4, 20, 40, 50, 100, and 200 (4.75, 0.85, 0.425, 0.3,
0.15, 0.075 mm. respectively) to grading the soil particle size for particle size distribution and
grouping the soil sample base on size distribution and d50.
Column Experiment
We have designed to use the column experiment for studying the transport of the
contaminant in porous media. The apparatus is a glass column (2.5 cm. diameter, 20 cm. length.),
syringe pump (HARVARD Apparatus), conductivity meter (WTW LF 325), Vials, Gas
Chromatograph (Agilent 7890A). The soil samples in each group which we use in this step have
been mixed together in their group, and are packed in the glass column with saturated soil
environment by using phosphate buffer solution (pH 7.0) 23.7 mM. The height of soil column is
10 cm.

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The
T 2-Nitrop phenol that we
w use in th
his study is tthe chemicaal which has been detectted in
many co ontaminated sites. This substance formula
f is C6H5NO3, m molecular weeight is equual to
139.11 g/mol,
g light-y
yellow colorr powder, melting
m pointt is 45°C, booiling point 214°C, sensitive
with ligh
ht.
The
T experimeent apparatuss is installed
d as shown inn Figure 1 .
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Figure 1 Schematic
S diagram of expperiment appparatus
The procedure of
o column experiment
e for
f Sodium C
Chloride annd 2-Nitrophhenol is show
wn in
Figure 2..

Figure 2 The proced


dure of transsport experim
ment
The
T flow thro ough column
n is upward with
w 30 ml/hhr and phospphate buffer solution (pH H 7.0)
23.7 mM
M containing 10 mg/L of NaCl is con
ntinuously feed into the sooil column ffor 3 pore voolume

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and switch to feed the phosphate buffer solution for the next 3 pore volumes. Then, we redo this
experiment by feeding phosphate buffer solution (pH 7.0) 23.7 mM mixing with 10 mg/L of 2-
Nitrophenol. The samples for analysis of 2-Nitrophenol and NaCl were collected at strategic
times during the column experiments from the outlet point of column. We use the conductivity
meter to analyze the concentration of NaCl and Gas Chromatograph for analyzing the
concentration of 2-Nitrophenol. To determine the concentration of NaCl, we measure the
electrical conductivity (EC) of water sample and convert to the concentration of NaCl
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Gas Chromatography
In this study, we used Gas Chromatograph (Agilent 7890A) to analyze the concentration
of 2-Nitrophenol in the effluent from column experiment with following the gas chromatography
condition which shown in Table 1 Before analysis by gas chromatograph, we have to extract the
2-Nitrophenol from water sample to Dichloromethane, and then inject the extracted sample into
the gas chromatograph.
Table 1 Gas chromatograph condition

Column: HP-5
19091S-433
30 m × 0.25 mm, 0.25 µm
Carrier gas: Helium
Flow velocity: 33 cm/sec,
constant flow
Temperature program: 5 min hold
35°C to 220°C
(8°C/min)
Injector temperature: 250°C
Detector temperature: 300°C
Detector type: FID

1-DIMENSIONAL ADVECTION DISPERSION EQUATION


To calculate the dispersivity (α) of Cl- and 2-Nitrophenol, we used 1-dimensional
advection dispersion equation as shown in (1) by
C0 x-vt vx x+vt
C= erfc +exp erfc (1)
2 2√Dh t Dh 2√ D h t

When C is the concentration of effluent (mg/L), C0 is the concentration of influent


(mg/L), x is length of column (m), v is average pore velocity (m/hr), t is time (hr), Dh is
longitudinal dispersion coefficient (m2/s), and erfc is the complementary error function. The pore
velocity can be calculated from the Darcy velocity (q) and porosity (θ) as shown in Eq (2).
q
v= (2)
θ

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The longitudinal dispersion coefficient The dispersivity (α) is the hydrogeological


parameter which use to describe the hydrodynamic characteristic of solute that relate with
longitudinal dispersion coefficient as shown in Eq. (3)
Dh =αv (3)

MEAN RESIDENT TIME


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Mean Residence Time (MRT) is the formula which is used to calculate the time of solute
flow from inlet to outlet Mean residence time can be calculated by Eq.(4)

0 C t tdt
MRT= ∞ (4)
0 C t dt

When C(t) is concentration of effluent at t (mg/L), t is the time after flow in (min)
The retardation factor can be calculated by proportion of MRT of solute and MRT of
conservative tracer as shown in Eq. (5)
MRTSolute
R= (5)
MRTTracer

RESULTS AND DISCUSSION


After sieve analysis, we can make the particle size distribution for all of the 26 soil
samples. Then, we classify the soil sample to 3 groups by considering the 50% finer of each soil
sample as shown in Table 2.
Table 2 Average D50 of 3 groups of soil sample
Number Average
Name of D50
Sample (mm.)
Group 1 15 0.1552
Group 2 8 0.2683
Group 3 3 1.0803
The particle size distribution of each group of soil sample is shown as Figure 3 (a), 3 (b),
and 3 (c) respectively.

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Figure 3 Particle sizze distributio


ons of soil saample groupp 1, group 2, and group 3
According
A to Figure 3 (a)), 3 (b), and 3 (c), the sizze distributioon of soil saample in the same
soil grou
up are similarr to the otheer sample and D50 is harm monized witth average D50 of soil saample
group.

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The
T dispersiv vity and rettardation faactor are reqquired inpuut parameterr in contam minant
transportt models bassed on the 1-dimension
1 al advectionn – dispersioon equation (Eq. (1)). T These
parameteer describee the hydro odynamic characteristic
c cs of soil column. Too determinee the
contamin nant transporrt parameterrs such as diispersivity ((α) or retarddation factorr (R), we haave to
design th
he column ex xperiment foor gathering the concentrration data oof the conserrvative traceer and
the contaaminant to deetermine botth of parameeters.
For the conseervative tracer experimen nt, we use thhe conductivvity meter (W
WTW LF 3225) to
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measure the conducttivity of sam mple and con nvert to conncentration oof NaCl (mgg/L). Then, m make
the break
kthrough currve by plot thhe relative co
oncentrationn at pore voluume as showwn in Figuree 4.

Figure 4 Breakthrou
ugh curve off NaCl vs poore volume fo
for soil groupp 1-3
In
n Figure 4, the
t breakthrrough curve NaCl are quuite similar w with other ssoil groups iin the
first 3 po
ore volume which
w conforrm to the disspersivity off NaCl as meention in Tabble 2.
For the con ntaminant trransport, wee used the same expeerimental pprocess withh the
conservaative tracer and analyzed the concentratioon of 2-N Nitrophenol by using Gas
Chromatograph (Agiilent 7890A)). The resultt of contaminnant transpoort experimennt is displayyed in
the relative concentraation of 2-Nitrophenol vs
v Time as shhown in Figuure 5.

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Figure
F 5 Breakthrough curve of 2-Niitrophenol vvs pore volum
me for Soil G
Group 1-3
1-dimensionaal advection dispersion Equation
E α) by
is used to calcculate the diispersivity (α
fitting thee dispersivitty in Eq (1), (2), (3).
The
T dispersiv vity of NaCl and 2-Nitrrophenol derrived from tthe transporrt experimennt are
providedd in Table 2. In case of NaCl,
N the disspersivity off the columnn varied fromm 0.41 – 0.433 cm.
Dispersivvity for a varriety of soilss ranges from
m <0.5 cm. ffor loamy saand (Perfect et al., 2002)). The
differencce of the disppersivity of NaCl for 3 soil groups is a result oof the differeent pore sizee and
length off soil column n that effect to the travel distance inn the soil collumn even uuse the samee flow
rate of solution.
s Forr contaminan nt transport experimentt, the disperrsivity of thhe column vvaried
from 0.34 4 – 0.41 cmm. The disperrsivity of 3 soil
s columnss for 2-Nitroophenol trannsport experiiment
are lowerr than NaCl because NaaCl is conserrvative traceer which hass only 2 proccesses (adveection
and dispeersion) will occur when n the solutionn flow in thhe column. B But in case oof 2-Nitrophhenol,
when thee solution paass through the t soil colu umn, the cheemical reactiion or biodeegradation arre the
process which
w will efffect to the 2-Nitropheno
2 ol transport characteristiic will differrence from N
NaCl.
Therefore, the disperrsivity of 2--Nitrophenoll is less than an the disperrsivity of NaaCl for all 3 soil
groups.

Table 2 Dispersivity of NaCll and 2-Nitroophenol for 3 Soil groupps


Disspersivity, α (cm.)
Sample
NaCl 2-Nitroophenol
Soil Group 1 0.42 0.441
Soil Group 2 0.41 0.334
Soil Group 3 0.43 0.335

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The mean residence time (MRT) is the statistical method which used to calculate the
average time of solute flow from inlet to outlet of column (Eq. 2). The retardation factor (R) can
be calculated by proportion of MRT of solute and MRT of conservative tracer as shown in Eq.
(5). The mean residence time of NaCl and 2-Nitrophenol and retardation factor are provided in
Table 3. For all 3 Soil groups, the mean residence time of 2-Nitrophenol is more than MRT of
NaCl that indicate the 2-Nitrophenol is slower than NaCl.
Table 3 Mean residence time and retardation factor of 3 soil groups
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Mean Residence Time (min)


Sample Retardation Factor (R)
NaCl 2-Nitrophenol
Soil Group 1 146.36 164.94 1.127
Soil Group 2 158.45 172.09 1.086
Soil Group 3 155.13 168.51 1.086

CONCLUSIONS
In our study, we got 26 soil samples from our study site and grouping them to 3 groups
by using D50 of soil sample. For contaminant transport experiment, we selected to use the
column experiment for conservative tracer (NaCl) and contaminant (2-Nitrophenol). We
determined the contaminant transport parameter by fitting the 1-dimensional advection
dispersion equation and calculate the mean residence time of solution. The results of the column
experiments described in this study are the 2 contaminant transport parameters: dispersivity (α)
and retardation factor (R). The dispersivity of NaCl for 3 soil groups has different value because
different pore size and travel distance in soil column. When compare with 2-Nitrophenol, the
dispersivity of 2-Nitrophenol less than NaCl due to the chemical reaction and biodegradation
process of 2-Nitrophenol fate and transport in soil column. In case of retardation factor which
described the transport characteristic of contaminant, the retardation factor of 2-Nitrophenol for
3 soil groups are more than 1 that mean the transport of 2-Nitrophenol is slower than the
conservative tracer. Next, the contaminant transport parameter of 2-Nitrophenol will be used to
model the contaminant transport in groundwater aquifer and determine the location of potential
source of contamination in the study site for the full potential of the source identification
problem.
ACKNOWLEDGEMENT
This thesis is supported by Graduate School Thesis Grant, Chulalongkorn University.
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