Proceedings of the 19th IAHR-APD Congress 2014, Hanoi, Vietnam

ISBN xxx-xxxx-xx-x

ARSENIC CONTAMINATION IN SHALLOW AQUIFERS OF DONG THAP PROVINCE, VIETNAM:

SOURCE, DISTRIBUTION, SPECIATION AND RELEASE MECHANISM

QUYEN. DO THI THUY (1), AVNER. VENGOSH (2), BRITTANY MEROLA (3), HIEN. TO THI (4)

(1) University of Science Vietnam National University, Ho Chi Minh city, Vietnam, email: dttquyen@hcmus.edu.vn
(2) Nicholas School of the Environment, Duke University, North Carolina, USA, email: vengosh@duke.edu
(3) Nicholas School of the Environment, Duke University, North Carolina, USA, email: rose.merola@duke.edu
(4) University of Science Vietnam National University, Ho Chi Minh city, Vietnam, email: tohien@hcmus.edu.vn

ABSTRACT:

This study investigated the source, release mechanism and speciation of geogenic Arsenic in shallow aquifers in Dong Thap
Province, Mekong delta, Vietnam. The rural areas in Thanh Binh isle and Tan Hong border district were chosen since drilled
wells remain the major fresh water source for drinking and irrigating at these areas. A total of 60 groundwater samples were
collected in February and March, 2012. Field parameters (pH, temperature, DO, EC, Eh) were measured on sites using
portable devices. Water samples were analyzed in laboratory for major ions, total As, As speciation, Fe, Mn and stable
isotopes. The analysis result showed the entirely difference between groundwater chemistry of Thanh Binh and Tan Hong.
Water type in Thanh Binh was Ca(Mg)-HCO3 while the composition in Tan Hong water samples showed variety of types
but mostly Na-Cl. Groundwater in Thanh Binh was predominantly reducing, contrary to the oxidizing condition of Tan
Hong aquifer. Arsenic concentrations also showed spatially heterogeneous distribution over the whole study area.
Groundwater from the shallow aquifers in Thanh Binh was far exceeding the permissible WHO Standard limits as well as
the Vietnam Standard limit of 10 g/L for As. As(III) species was dominant and made up 70% of total As concentration. In
contrast, 100% water samples in Tan Hong contained less than 10 g/L As. Stable isotope 2H and 18O analysis technique
firstly introduced in this area also provide valuable evidence for the difference recharges for groundwater in two research
sites. The reducing condition, high concentration of Fe and HCO3- and the depletion of SO42- indicated reductive dissolution
of the Fe oxyhydroxide as the significant mechanism that released As to Thanh Binh groundwater.
Keywords: arsenic, Dong Thap, groundwater, release mechanism, source.

1. INTRODUCTION groundwater exploited from shallow aquifers as the major

source for drinking and irrigating.
Arsenic poisoning due to drinking groundwater with high
As concentration was considered the most serious disaster
in the history, in term of the number of people exposed. A
2007 study found that over 137 million people in more than
CAMBODIA
70 countries are probably affected by arsenic poisoning of
drinking water. High concentrations of arsenic in
Tan Hong
groundwater are found in various parts of the world,
especially in Ganges delta (India) and Brahmaputra delta
(Bangladesh) where scientist detected the first case of Hong Ngu
chronic As poisoning.
Similarities in geological feature of the fluvial delta in
Vietnam and the delta in India and Bangladesh has initiated Tien River
various research on arsenic in Vietnam since 2000. The Tam Nong
arsenic problem in Red River Delta had been studied in
detail level (Micheal Berg et al. (2001); Flemming et al.
(2008); Pham Quy Nhan (2008)). However, arsenic
Hau River
investigations in Mekong Delta had just initiated recently.
The lack of research and knowledge about the release Thanh Binh
mechanism and source of arsenic in groundwater of this
area has led us to conduct this study.
Cao Lanh
2. MATERIALS AND METHODS

2.1. Research sites 15 km

This study was conducted in March, 2012 in Dong Thap

province, where several previous research in Mekong delta
has reported the high level of As in groundwater. Two Figure 1. Spatial distribution of Arsenic in
selected research sites were Thanh Binh isle and Sa Rai groundwater at research sites
commune, Tan Hong districts. Local people here use

1
The total 55 samples was collected at household wells, all
are at the depth smaller than 80m. 34 samples in Thanh
Bnh isle with the depth from 12-60 m (Holocene and
Pleistocene aquifers) gather in the research area of 10 km x
20 km, all wells are located near Tien River (Figure 1)
within the average distance of 1 km. The other 21 samples
in Sa Rai commune, Tan Hong district was taken from 15-
73 m deep wells (Pleistocene aquifer) in the area of 10 km x
15 km. The average distance from those wells and Tien
River is 15 km.
2.2 Sampling and analytical methods
Information on the well depth, the installation year, and its
geographic coordinates were recorded. To ensure the
oxygen concentration in the water was stable, samples of
groundwater were only taken after 15 min of continuous
pumping. Groundwater were collected following the USGS
Protocols. Parameters measured in the field include pH,
temperature, conductivity (EC), dissolved oxygen (DO),
and oxidation-reduction potential (ORP).
Samples to be analyzed for trace metals were filtered at the
site using 0.45 m syringe filters and preserved using nitric
acid. Samples were analyzed for major elements using
direct current plasma optical emission spectrometry (DCP-
OES), anions by ion chromatography (IC), and trace metals
by inductively coupled plasma mass spectrometry (ICP-
MS). Speciation of As was separated in the field and
preserved according to methods in Bednar et al. (2002).
Water was transferred to 60 mL high-density polyethylene
(HDPE) bottles and shipped to Earth and Ocean Sciences
Laboratory, Duke University, USA for chemical analysis.
3. RESULTS AND DISCUSSION
3.1. Field parameters
Table 1. Field parameters data
Thanh Binh (n=34) Tan Hong (n=21)
Parameter
Mean Range Mean Range
pH 7.0 6.7 7.7 6.1 5.8 6.6
Temp oC 29.5 28.7 30.6 29.8 29.3 30.2
EC S/cm 1312 382.6 6330 1540 304.2 3035
DO mg/L 2.1 0.7 4.0 1.32 0.2 3.7
Eh mV -93 -139 149 182.2 60 261
pH value of all samples range in the normal from 6 - 8.5.
Samples taken from Tan Hong are relatively more acidic in
comparison to Thanh Binhs.
There is a remarkable difference in oxidation-reduction
potential value between 2 sampling sites. The shallow
aquifer in Thanh Binh District is in reduced condition,
ranging from -139 mV to -28 mV. In contrast, the oxidation
condition is predominant in Tan Hong groundwater, with
the ORP values range from 60 to 261 mV. The disparity in
geological features of two research sites is supposed to be
one of the reasons for this interesting contrast. Thanh Binh
is an isle and belong to the floodplain of Tien River. It
receive fluvial sediment annually from Mekong flood
during rainy season. The large amount of organic sediment
in alluvial deposit is an appropriate environment for
reduced microorganisms to develop and caused the
reduced condition underground. Tan Hong district is part
of an absolutely different geological sub-unit. It is located
in the outermost of the backswamp and belongs to the high
steep natural bank. This feature is also an evidence for
arsenic release mechanism in groundwater at Thanh Binh
district, which will be discussed in the following part.
3.2. Distribution and speciation of arsenic
The spatial distribution of the sampling locations as well as
the As concentrations are shown in Figure 1 Arsenic
concentrations showed spatially heterogeneous
distribution over the whole study area. Groundwater from
the shallow aquifers in Thanh Binh was far exceeding the
permissible WHO Standard limit of 10 g/L for As (n=34;
ranging from 3.22 981.43 ppb; mean value 408.16 ppb). In
contrast, 100% of water samples in Tan Hong contained less
than 10 g/L As (n=21; ranging from below limit of
detection-8.91 ppb; mean value 2.63 ppb).
Arsenic in all groundwater samples at Thanh Binh was
composed of a mixture of As(III) and As(V) species. On
average, As (III) constituted 79% of the total As, while As
(V) consists of only 21% of the total As. This is consistent
with the dominant reduced condition of Thanh Binh
groundwater when considering the oxidation state of
Arsenic from the Eh-pH diagram.
Figure 2. As-O-H Eh-pH diagram
3.3. Arsenic release mechanism
As concentration and Eh value correlation
There is a significant negative Pearson correlation between
total As concentration and Eh value (r= -0.713). Due to the
fact that As is sensitive with the groundwater oxidation-
reduction potential, it is highly likely that the reduced
environment is the key factor control the arsenic release in
Thanh Binh shallow aquifer.
300
250
200
150
100
Eh (mV)
50
As (g/L)
0
-50 0 200 400 600 800 1000 1200
-100
-150
-200
Tn Hng Thanh Bnh
Figure 3. As and Eh value correlation
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Fe concentration in groundwater
High Fe concentration were found in most of the
groundwater samples of Thanh Binh district, ranging from
0.36 12.68 ppm, average value is 4.45 ppm. All is above
the QCVN 01:2009/BYT standard for drinking water.
Meanwhile, the Fe concentration in Tan Hong groundwater
is much lower, ranging from under detection limit to 2.66
ppb. The average value is 0.4 ppm, which is ten times lower
in comparison to Thanh Binh.
It is obvious to identify the relationship between total As
and Fe at two research sites. Pearson statistic showed the
significant positive correlation between Fe and As
concentration (r = 0.708). To be more specific, the
correlation between Fe concentration and As speciation,
e.g. As (V) and As (III), have been examined. Apparently,
the correlation between Fe and As (V) is more substantial
than Fe-As(III) correlation.
As - Fe
1200
1000
800
As (g/L)
600
As total
As tng
400
As (III)
200
As (V)
0 Figure 5. D and 18O relationship
0 2 4 6 8 10 12 14
Fe (mg/L)
Figure 4. As and Fe correlation
This could be explained by the reactions in shallow aquifer
where the reduced condition is predominant:
- The dissolution of As (V) from oxyhydroxide Fe (III)
- Solid Fe (III) was reduced to soluble Fe(II)
- Arsenate As (V) was reduced to Arsenite As (III) which
is in non-charged state and therefore, more mobile in
aqueous phase.
The reduction process is summarized in the following
reaction:
4FeOOH(As)+CH2O+7H+ Fe2++HCO3-+6H2O+As(III)+As(V)
As a result of this process, As (V) and Fe (II) were released
concurrently into groundwater. For that reason, the Fe As
(V) correlation is stronger than Fe As (III).
Previous studies have suggested that As release from the
delta sediments is due to the reductive dissolution of the
iron bearing minerals. The As contents of groundwater in
this study were consistently associated with low ORP
values, which infer reducing conditions. It has been
demonstrated that during sediment transport under oxic
conditions oxyanion, As species are bound to Fe-oxides,
peat, clay, and other humic substances. Under the delta
reducing conditions As is mobilized to the ambient
groundwater (Micheal Berg et al. 2001; Nguyen Kim
Phuong 2008; Nickson et al. 2000; Smedley et al. 2002).
3.4. Stable isotope result
Stable isotope is a state-of-the-art technique to identify the
groundwater recharge source. The isotope used to discuss
in this study is Deuterium and Oxygen -18. Because those
isotopes are stable, their concentrations do not change over
the time or through transport processes. As the result, the
stable isotope level in specific aquifer is similar to the
recharge water which is, in most of the cases, precipitation
(e.g. rainwater or snow). Stable isotope research require a
large hydrometeorology base data to provide exactly
conclusion. However, the only isotope monitoring station
of Vietnam is located in Ha Noi and owned by the Global
Network of Isotope in Precipitation IAEA (working from
2004-2007). Thus, research in this field has been limited due
to the shortage of base data. This study is one of the initial
research on isotope and aimed to provide several useful
evidence for the arsenic source in Mekong delta.
-30 Variable
Thanh Binh
Tan Hong
-40
2H (per mil)
-50
-60
-70
-10 -9 -8 -7 -6 -5
18O (per mil)
Isotope composition of precipitation from all over the
world, plotted in 2H versus 18O graphs, are strongly
correlated according to the equation:
D (per mil) = 8. 18O + 10 (Global Meteoric Water Line)
D and 18O of Tan Hong and Thanh Binh groundwater are
well correlated and obtained data fit to the GMWL, shown
in figure 5. This indicates the source of both sites from
modern rain water. Nevertheless, there is a notable
disparity in the distribution of D and 18O on the GMWL.
The stable isotope concentration in Tan Hong groundwater
is relatively richer than Thanh Binhs. The average value of
D and 18O is -39 and -5.68 at Tan Hong and
55.63 and -7.99 at Thanh Binh.
Stable isotope concentration in groundwater samples are
similar to local rain water and the evidence of oxidized
groundwater in Tan Hong indicated that water is recently
recharged, probably from annual flood from July to
November. In contrast, low concentration of stable isotope
and reduced condition of groundwater illustrated the long-
term process groundwater exposed to geological
components. The isotope value in Thanh Binh is similar to
that of Hymalayan rainwater. It is highly likely that
groundwater in Thanh Binh is the mixture of surface water
and groundwater from high altitude area.
This result is consistent with the research on arsenic source
in Red River Delta (Pham Quy Nhan, 2008), which
suggested that As in Himalayan rock and minerals was
dissolved and released to the groundwater through
weathering processes. It is transported to lower terrain
through downstream and underground flows. This is
supported by the distribution of arsenic in groundwater at
the fluvial delta in the southern of Hymalaya Mount.
3
4. CONCLUSION
Tan Hong and Thanh Binh are much different in geological
features and it affects the distribution and speciation of
Arsenic in Dong Thap groundwater.
Arsenic in Thanh Binh is released from reduction-
dissolution iron oxyhydroxide mechanism. This is
supported by evidences such as groundwater reduced
environment, dominant As (III) speciation, high Fe
concentration.
The stable isotope result indicated that groundwater in Tan
Hong and Thanh Binh probably have different recharge
sources. Tan Hong shallow aquifer is recharged by local
rain water. Meanwhile, Thanh Binh groundwater is
recharged from different source. It is probably derived
from the rain water from Hymalaya mountain.
ACKNOWLEDGMENTS
This research was conducted thanks to the cooperation
project between HCMVNU University of Science and
Duke University. We are grateful for the valuable guidance
and support form Prof. Avner Vengosh and all the effort in
lab work of Dr. Brittany Merola.
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