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Environmental Pollution 158 (2010) 2648e2658

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Arsenic in groundwater and sediment in the Mekong River delta, Vietnam


Thi Hanh Hoang a, Sunbaek Bang b, *, Kyoung-Woong Kim a, *, My Hoa Nguyen c, Duy Minh Dang c
a

Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), Republic of Korea
International Environment Research Center (IERC), Gwangju Institute of Science and Technology (GIST), Republic of Korea
c
Soil Science & Land Management Department, College of Agriculture, Cantho University, Viet Nam
b

Detailed classication of the study area; indicators for elevated As levels in groundwater; inverse relationship between As and Mn levels,
characterization of As in groundwater and sediment.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 4 June 2009
Received in revised form
20 April 2010
Accepted 1 May 2010

A study of groundwater and sediment during 2007e2008 in the Mekong River delta in Vietnam (MDVN)
revealed that 26%, 74%, and 50% of groundwater samples were above the US EPA drinking water
guidelines for As (10 mg/L), Mn (0.05 mg/L), and Fe (0.3 mg/L). The range of As, Fe, and Mn concentrations
in the MDVN were <0.1e1351 mg/L, <0.01e38 mg/L, and <0.0114 mg/L, respectively. Elevated levels of
As were found in groundwater at sampling sites close to the Mekong River and in wells less than 60
70 m deep. An inverse relationship was found between As and Mn concentrations in groundwater.
Sediment samples from An Giang and Dong Thap had the highest As concentrations (18 mg/kg and
38 mg/kg, respectively). Arsenic sediment occurred mainly in the poorly crystalline Fe oxide phases.
Reductive dissolution of the Fe oxide phase is not necessarily the dominant mechanism of As release to
groundwater.
2010 Elsevier Ltd. All rights reserved.

Keywords:
Arsenic
Iron
Manganese
Groundwater
Core sample
Mekong river delta
Vietnam

1. Introduction
Arsenic (As) occurs in a variety of environmental media
including minerals, rocks, sedimentary deposits, soil, water, and
plants, but usually co-occurs with sulde minerals. The International Agency for Research on Cancer (IARC) evaluated As and As
compounds and classied them into Group 1, which includes
chemicals causally associated with cancer in humans.
Arsenic has caused signicant contamination of soil and
groundwater in many regions of the world including China,
Mongolia, Japan, Nepal, and the United States (Smedley and
Kinniburgh, 2002). Bangladesh and West Bengal have been identied as the countries with the most seriously As-contaminated
aquifers (Anawar et al., 2002; Chowdhury et al., 2000; Mudur,
2000; Smith et al., 2001; Tchounwou et al., 1999). Groundwater
in the Red River delta (Vietnam) has also been reported to be highly
contaminated with As (Berg et al., 2001, 2007, 2008; Buschmann
et al., 2007, 2008; Nguyen et al., 2009).
The geochemical behavior, release mechanism, and distribution
of As in aquifers have been well studied in the Ganges Plain (Harvey

* Corresponding authors.
E-mail addresses: sbang@gist.ac.kr (S. Bang), kwkim@gist.ac.kr (K.-W. Kim).
0269-7491/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2010.05.001

et al., 2002; Horneman et al., 2004; Islam et al., 2004; McArthur


et al., 2001; Nickson et al., 2000), the Red River delta (Berg et al.,
2001, 2007, 2008; Nguyen et al., 2009; Postma et al., 2007), and
the upper Mekong River basin in Cambodia (Buschmann et al.,
2007, 2008; Hery et al., 2008; Kocar et al., 2008; Lear et al., 2007;
Papacostas et al., 2008; Polya et al., 2005, 2008; Rowland et al.,
2007, 2008; Van Dongen et al., 2008), but similar data are scarce
for the Mekong River delta in Vietnam (MDVN).
In Vietnam, the Mekong River consists of two main arteries (the
Tien and Hau rivers), which branch into eight smaller rivers (Fig. 1).
The MDVN covers an area of 39,713 km2 and contains deltaic
sediments with characteristics similar to those of the Ganges Plain
(Bui et al., 2005). Water resources in this area include rainfall,
surface water, and groundwater. The groundwater in this region has
been exploited for domestic use since the beginning of the 20th
century. Since the 1980s, several organizations in Vietnam have
undertaken water and hygiene promotion campaigns, which
include the construction of groundwater wells and the installation
of hand pumps. Water demand in this area is increasing: in 2000
the demand was 881,100 m3/day, but is projected to reach
1,079,350 m3/day in 2010 (Bui et al., 2005). Contamination of
groundwater with As in the MDVN was rst reported by Stanger
et al. (2005). When used as a water source for drinking and other
life-supporting activities, groundwater can directly affect human

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

2649

Table 1
Analytical results for SRM 1640.
SRM 1640

As

Fe

Mn

Certied values (ppb)


Reported values (ppb)

26.67  0.4
26.73  1.8

34.3  1.6
35.2  1.4

121.5  1.1
122.3  3.6

2.2. Chemical analysis

Fig. 1. Arsenic in groundwater of the MDVN. (1) Kien Giang, (2) An Giang, (3) Dong
Thap, (4) Long An.

health. Therefore, it is vital to assess the quality of groundwater in


the MDVN.
The objectives of this study were (i) to investigate the
geochemical characteristics of groundwater As in the MDVN
aquifer, (ii) to assess and classify the MDVN with respect to As, Fe,
and Mn contamination, and (iii), to elucidate the conditions
favoring As release to groundwater.
2. Materials and methods
2.1. Study area and sample collection
The study commenced in the middle of 2007 and included two main aspects:
a geochemical survey and the development of remediation technology for application in the eld. A good knowledge of groundwater geochemistry is essential in
developing an effective remediation strategy for contaminated groundwater. To
collect data for groundwater characterization we carried out a broad survey in four
provinces (An Giang, Dong Thap, Kien Giang and Long An) in the MDVN (Fig. 1), from
May to November 2007.
To ensure the oxygen concentration in the water was stable, samples of
groundwater were only taken after 10 min of continuous pumping. Each sample was
transferred to a 60 mL high-density polyethylene (HDPE) bottle, frozen, and shipped
to Korea for chemical analysis. No parameters were measured in the eld. For each
well, information on the well depth, the year of installation, and its geographic
coordinates were recorded.
Two sets of core samples were collected in May and November 2008, from Cho
Vam village in the Phu Tan district (An Giang province; CV), and Thanh Binh village
in the Thanh Binh district (Dong Thap province; TB). Groundwater was also
collected from around the drilling sites. Each sample set included a 125 mL volume
of raw groundwater collected in a HDPE bottle for anion measurements, 60 mL
volumes of each of raw and ltered groundwater collected in HDPE bottles for
cation measurements, and a 15 mL volume collected in a plastic tube for As
speciation. Arsenic speciation in groundwater was conducted in the eld using
disposable As speciation cartridges (Meng and Wang, 1998). Oxidationreduction
potentials (ORPs) and pH were measured on site using a portable pH meter
(HORIBA, D55).

Groundwater pH values were measured prior to acidication with concentrated


nitric acid (65% HNO3; Fluka, Switzerland). Twelve elements (As, Al, Ba, Cu, Pb, Zn, Co,
Ni, Cr, Cd, Mn and Fe) were analyzed using inductively-coupled plasma mass spectrometry (ICP-MS; Agilent 7500, USA). High concentrations of Mn and Fe were
reanalyzed using ame atomic absorption spectrometry (FAAS; FIAS 400, Perkin
Elmer, USA). Five elements (Ca, Mg, Na, K and Si) were analyzed using inductivelycoupled plasma optical emission spectrometry (ICP-OES; Optima 5300 DV, Perkin
Elmer, USA). Calibration standards were prepared by dilution of Perkin Elmer quality
control standards (QC Stds); QC Std 2A was used for ICP-MS calibration, and QC Stds 7A
and 21 were used for ICP-OES calibration. The correlation coefcients of the calibration curves were not less than 0.999. A natural water standard (SRM 1640; NIST, USA)
was included as a reference after every twenty samples, and the reported and certied
values for all elements in the reference material agreed within 5% (Table 1). Samples
were reanalyzed if relative standard deviations exceeded 5%. Total carbon (TC),
inorganic carbon (IC), and total organic carbon (TOC) were analyzed using a total
organic carbon analyzer (TOC-VCPH, Shimadzu, Japan). Total nitrogen was measured
using a total nitrogen measuring unit (TNM-1, Shimadzu, Japan). Anion concentrations were measured using a portable spectrophotometer (Hach DR/2400, USA).
Following transfer to Korea each core sample was dried under ambient conditions for 2 weeks, disintegrated, passed through a No. 80 (e200 mm) sieve (testing
sieve, Chung Gye Sang Gong Sa, Seoul, Korea), weighed (XB 220A balance; Precisa
Gravimetrics AG, Switzerland) into a 15 mL polypropylene digestion tube, and used
for total digestion and sequential extraction. Approximately 250 mg soil was
digested for 3 h at 70  C in 4 mL aqua regia solution (HCl:HNO3 3:1 v/v; 65% HNO3,
Fluka, Switzerland; 36% HCl, electronic grade, Duksan Pharmaceutical Co. Ltd.,
Korea) and ltered through a Whatman No. 41 lter paper. The ltrate was adjusted
to 50 mL in a volumetric ask, and diluted and analyzed for As using ICP-MS, and for
Fe and Mn using FAAS. Standard samples of Montana I soil (SRM 2710 and 2710a;
NIST, USA) were digested concurrently with the core samples. The recoveries of As,
Fe and Mn are shown in Tables S1 and S2 (Supporting information). Sequential
extraction of 500 mg soil was performed following the procedure of Silveira et al.
(2006), as indicated in Table 2. Particle size distributions were also determined for
all core samples.

2.3. Statistical analysis


The relationships among target parameters were analyzed and correlation
matrices (both Pearson and Spearmans rho correlations) were constructed for the
groundwater data using SPSS 15.0 for Windows. For statistical analysis the data were
checked to ensure they conformed to a standard distribution. The chi-square test
was applied to the data from various districts to determine which data sets showed
higher or lower As levels than expected. Districts showing a similar trend were
grouped into one sampling area of larger sample size. Analysis of variance (ANOVA)
was performed for all sampling areas. The equality of variance was assessed using
Levenes test. If this test was not signicant (p > 0.05) the tested sampling areas
were considered to not differ in As concentration. If the test was signicant the
Games-Howell test was performed to identify the origin of the differences. The same
procedures were conducted for Fe and Mn concentrations. From these output data
the MDVN was classied into various groups (Table 3).
Independent sample t-tests were performed to clarify the inuences of various
parameters on groundwater As concentration. Groundwater samples from each
province were divided into two groups based on several factors: distance from the
sampling site to the Mekong River (measured indirectly from a digital map using

Table 2
Sequential extraction procedure modied from Silveira et al. (2006) (0.5 g soil).
Phase

Extraction Chemical

Detail

Soluble-Exchangeable
Surface adsorbed
Organic matter
Mn oxides
Poor crystalline
Fe oxides
Crystalline Fe oxides
Residual

7.5 ml 0.1 M CaCl2


10 ml 1 M NaOAc (pH 5)
5 ml NaOCl (pH 8.5)
10 ml 0.05 M NH2OH/HCl
10 ml oxalic acid 0.2 M;
NH4 oxalate 0.2 M
10 ml HCl 6 M
8 ml aqua regia

2 h, room temperature
5 h, room temperature
30 min, 95  C
30 min
2 h, dark
24 h, room temperature
3 h, 85  C

2650

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

Table 3
Classication of sampling areas (AG1: Cho Moi; AG2: Phu Tan; AG3: Chau Thanh; AG4: Tan Chau; AG5: An Phu; DT1: Cao Lanh; DT2: Thanh Binh and Hong Ngu; DT3: Tan Hong
and Lai Vung; DT4: Tam Nong, Lap Vo and Thap Muoi; LA1: Can Giuoc, Ben Luc, Can Duoc and Tan Tru; LA2: Chau Thanh and Thu Thua; KG1: Hon Dat and Go Quao; KG2: Rach
Gia, Kien Luong, Tan Hiep and Chau Thanh; KG3: Ha Tien).
Sampling Area

As

Mn

Safe-Slightly
contaminated
(50 ppb)

Moderately
contaminated
(50-100 ppb)

Seriously
contaminated
(> 100 ppb)

Fe

Safe-Slightly
contaminated
(0.5 ppm)

Moderately
contaminated
(0.5e3 ppm)

AG 1
AG 2
AG 3
AG 4
AG 5
DT 1
DT 2
DT 3
DT 4
LA 1
LA 2
KG 1
KG 2
KG 3

Seriously
contaminated
(>3 ppm)

Safe
(0.3 ppm)

C
C

C
C
C

C
C

C
C
C
C
C

C
C
C
C
C
C
C
C

C
C
C
C

C
C

C
C

C
C

MapInfo Professional 7.5 SCP), well depth, groundwater pH, Mn concentration, Fe


concentration, and TOC content. Cutoff points were selected based on the specic
grouping factor for each province. If the assumptions of equal variance for the independent sample t-tests were markedly violated, the nonparametric ManneWhitney
U-test was performed to assess whether the t-tests with modied degrees of freedom
were reliable. The outputs for some target parameters were interpreted in detail.

3. Results
3.1. Groundwater quality
For all analyzed elements except As, Fe, and Mn, groundwater
concentrations in samples collected during the rainy season in
2007 from four provinces in the MDVN were well below drinking
water guidelines (Table 4 and Table S3). Excessive concentrations of
As were found principally in groundwater of An Giang and Dong
Thap provinces, whereas very high concentrations of Fe were found
in the groundwater of Dong Thap, Kien Giang, and Long An (Fig. 2).
Unlike the other provinces, approximately half of groundwater
samples collected from An Giang and Dong Thap had As

Seriously
contaminated
(>3 ppm)

C
C
C
C
C

C
C

Slightly
contaminated
(0.3e3 ppm)

concentrations exceeding WHO guideline levels (10 mg/L) (Table 5).


More than 50% of samples from each of An Giang and Dong Thap
contained Mn concentrations above the US EPA guideline level
(0.05 mg/L) (Table 6). In particular, elevated As concentrations were
found in the AG2, AG5, and DT2 areas. In the AG5 area, approximately 72% and 64% of groundwater samples exceeded WHO
guidelines for As and Mn, respectively. In contrast, all groundwater
samples from area AG3 were below the guideline level for As, but
exceeded the guideline level for Mn. A similar situation was
observed in area LA1. Some regions were more contaminated by As
and Mn than expected. Groundwater samples from Kien Giang and
Long An were below guidelines level for As, but both Fe and Mn
concentrations were of signicant concern. A large proportion of
groundwater samples from these two provinces contained levels of
Fe and Mn in excess of guidelines, whereas no sample was found to
exceed the guideline for As (Table 6).
From Fig. 2 it is evident that an inverse relationship occurred, at
the local scale, in the ranges of As and Fe concentrations in
groundwater. Thus, the groundwater of An Giang had a wide range

Table 4
Average and median values, and ranges for groundwater parameters.
Parameter

Well depth
pH
As
Al
Ba
Cu
Pb
Zn
Co
Ni
Cr
Cd
Mn
Fe
Ca
Mg
Na
K
Si
TOC

Unit

mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L

An Giang

Dong Thap

Kien Giang

(n 107)

(n 86)

(n 123)

Long An
(n 89)

Mean

Median

Range

Mean

Median

Range

Mean

Median

Range

Mean

Median

Range

70
7.75
110
26
361
57
0.5
32
1.8
1.6
0.6
0.4
1595
225
67
42
252
12.5
13.7
3

45
7.84
4
15
257
34
0.4
19
0.9
1
0.5
0.3
634
37
58
29
163
10.8
14.2
1.2

12e128
5.76e8.4
NDe1351
4e343
22e1272
8e722
<0.1e3
8e647
<0.1e12
0.2e15
<0.1e3
<0.1e2
<1e13,988
<1e4755
<0.1e200
2e149
21e1030
2.5e35
2e40
NDe5.8

230
7.4
57
20
366
27
0.7
32
2
3
0.6
0.6
1069
1983
70
51
187
11
21
4

50
7.43
9
13
156
9.5
0.6
132
0.8
1.2
<0.1
0.4
139
339
51
28
109
6
19
1

12e450
5.63e8.12
NDe666
2e253
4e4447
1e519
<0.1e3
3e508
<0.1e29
<0.1e26
<0.1e2
<0.1e6
4e11,038
5e36,277
2e467
2e357
13e1680
2e211
2e47
0.33e8.2

57
7.32
1.74
89
195
25
1.44
83.96
2.75
3.98
2.26
0.57
580
2527
63
68
236
11
29
5.3

50
7.4
0.7
16
122
7
0.5
16
0.5
1.4
<0.1
0.3
119
363
48
50
209
9
30
3.6

3e123
4.09e8.03
NDe16
3e7880
7e1393
<1e479
<0.1e29
5e5101
NDe95
0.2e197
<0.1e13
<0.1e8
1e9569
3e37,861
3e312
1e379
12e1200
2e124
3e66
0.5e18

223
6.67
4.4
273
19
10
0.4
17
1.4
2
0.4
0.13
670
2898
50
32
92
24
21
4.7

215
6.67
2
230
7
2
0.3
11
0.5
1
0.3
<0.1
491
826
41
24
61
22
19
4.1

100e350
3.52e7.86
NDe25
67e1034
<1e435
<1e513
<0.1e6.4
2e231
<0.1e9
<0.1e12
<0.1e2
<0.1e0.3
<1e9088
28e30,669
7e307
5e131
15e323
7e50
12e34
0.2e23

ND: not detected (<0.1 mg/L).

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

2651

Fig. 2. Ranges of a) pH, b) arsenic, c) iron, and d) manganese in groundwater of the MDVN (AG: An Giang; DT: Dong Thap; KG: Kien Giang; LA: Long An).

of high As concentration but a narrow range of low Fe concentration.


The reverse was seen in the groundwater of Long An and Kien Giang.
3.2. Characteristics of groundwater arsenic
3.2.1. Spatial relationships
Covariation of the As concentration in groundwater with well
depth and distance of the well from the Mekong River are shown
for An Giang and Dong Thap in Fig. 3a and b, respectively. When
contaminant levels in the two groups of groundwater samples were
divided by the distance from the sampling site to the Mekong River,
we observed differences in mean As concentrations. In An Giang,
sampling sites less than 2 km from the Mekong River had mean As
concentrations nearly 10-fold higher than those from sampling
sites at distances beyond 2 km (Table 7). This observation was
signicant at the p < 0.01 level. However, the difference between
the two mean values was not statistically signicant for Dong Thap.
Well depths ranged from 12 to 128 m and from 12 to 450 m for
wells in An Giang and Dong Thap, respectively. However, wells were
commonly less than 100 m deep. There was a marked difference
between mean As concentrations in wells of the two provinces
divided by well depth (Table 7). Shallow wells in An Giang (less than
60 m deep) and Dong Thap (less than 70 m deep) had mean As
concentrations of 115 and 63 mg/L, respectively, whereas values for
deeper wells were only 19 and 3 mg/L, respectively. Thus, shallow
wells usually had higher concentrations of As, whereas deep wells
appeared to be unaffected. No spatial inuence on As concentration
was found for groundwater of Kien Giang and Long An.

3.2.2. Hydrogeochemical inuences


Independent sample t-tests showed strong inuences of pH,
TOC, and Mn on As concentrations in groundwater. The differences
between mean As concentrations of two groups of wells with
respect to each factor were marked (Table 7). Wells of pH < 8,
TOC > 1 mg/L, or Mn < 3 mg/L were heavily contaminated with As,
whereas the remainder were below As guideline levels. All differences were signicant at the p < 0.01 level. No evidence was found
for an inuence of Fe on As concentrations in An Giang groundwater. The relationships between As and the studied parameters in
groundwater of An Giang and Dong Thap are shown in Fig. 3.
Correlations between As and some other groundwater parameters are summarized in Table 8. Arsenic concentrations in An
Giang groundwater were positively correlated to TOC and Ba
concentrations, and negatively correlated with well depth, pH;
and Mn, Ca, Mg, Na, Co, Ni, and Si concentrations. Correlations
were weak for Dong Thap province. Positive correlations were also

Table 5
Percentage of samples from four provinces exceeding the guidelines for drinking
water.
Parameter
(guidelines)

Percentage above the guidelines (%)


An Giang
(N 107)

Dong Thap
(N 86)

Kien Giang
(N 122)

Long An
(N 89)

As (10 ppb)
Mn (0.05 ppm)
Fe (0.3 ppm)

43
87
13

38
69
54

2.4
66
55

12
81
71

2652

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

Table 6
Sampling areas contaminated by arsenic, iron and manganese.
Parameter
(guidelines)

Percentage above the guidelines (%)


AG 1
(n 12)

As (10 ppb)
25
Mn (0.05 ppm) 100
Fe (0.3 ppm)
17

AG 2
(n 12)

AG 3
(n 17)

AG 4
(n 41)

AG 5
(n 25)

DT 1
(n 17)

DT 2
(n 23)

DT 3
(n 27)

DT 4
(n 19)

LA 1
LA 2
(n 64) (n 25)

KG 1
(n 60)

KG 2
(n 53)

KG 3
(n 10)

50
92
17

0
100
0

44
90
2.4

72
64
36

41
82
41

83
83
83

15
59
63

16
53
16

0
96
88

1.7
73
54

1.9
64
59

10
40
40

found between As concentration and TOC and Ba concentrations,


whereas negative correlations were found only between As level
and distance from the well to the Mekong River, pH, and Si
concentration.

44
40
28

Table 9 summarizes all the effects correlations found between


various parameters and As concentrations in groundwater. It is
expected that factors correlated with As will inuence As concentration. Thus, wells differing with respect to other factors may vary

Fig. 3. Interactions of arsenic and target parameters measured in groundwater of An Giang and Dong Thap.

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

2653

Table 7
Mean arsenic levels (mg/L) among sample groups from An Giang and Dong Thap.
Grouping factors

Distance

Well depth

pH
TOC
Mn
Fe

An Giang (N 107)

Dong Thap (N 86)

Groups

Mean (ppb)

Median (ppb)

Range

Groups

Mean (ppb)

Median (ppb)

Range

 2 km
>2 km
N.A
 60 m
>60 m

99
7
1
100
7

118
12
0.7
115
19

6
0.9

ND-1351
0.4e66

10
2

NDe666
0.2e16

8
>8
1 ppm
>1 ppm
3 ppm
>3 ppm
0.3 ppm
>0.3 ppm

83
24
43
64
89
18
95
12

132
32
5
180
127
4
105
194

6
1.5
0.8
55
15
3.7
2
111

0.2e1351
ND-275
NDe110
0.4e1351
NDe1351
0.2e32
NDe1351
0.8e543

57
14
21
63
3
4
56
4
6
104
56
2
7
90

NDe666
NDe42

0.2e1351
ND-110

74
9
3
69
15
2
79
7
46
40
78
8
40
46

3
7

6
0.9

15 km
>15 km
N.A
 70 m
>70 m
N.A
8
>8
1 ppm
>1 ppm
3 ppm
>3 ppm
0.3 ppm
>0.3 ppm

6
4
1.5
40
6
0.4
1
21

ND-666
ND e8
NDe55
NDe666
NDe666
NDe10
NDe103
NDe666

N.A: information is not available.


ND: not detected (<0.1 mg/L).

in average As concentration. Positive correlations were found


between TOC and As concentration in both An Giang and Dong
Thap province, indicating that wells with a high TOC content had
much higher mean As concentrations than did wells of low TOC.
However, despite the negative correlation between distance and As
concentration in groundwater of Dong Thap, there was no statistically signicant difference in mean As concentration between
wells close to or distant from the river. A similar result was found
for pH and As concentration in the groundwater of An Giang. It is
likely that the correlations were not sufciently strong to result in
observable trends in groundwater As concentration; alternatively,
the cutoff points used in the independent sample t-test were
inappropriate. Shallow and deep wells in Dong Thap showed
remarkable differences in mean As concentration, but the correlation between well depth and As concentration was not signicant.
3.3. Characterization of sediment arsenic
Digestion and analysis of two sets of core samples yielded As
recoveries of 85% and 92%, with concentration ranges of 2e18 mg/
kg and 0.9e38 mg/kg for the CV and TB cores, respectively. The
highest concentrations of As in CV and TB cores were found at
depths of 46 m and 34.5e34.9 m, respectively. Relatively high As
concentrations were detected in the brown and blackbrown clay
layers, where pH values were approximately pH 7.5. Arsenic
concentrations did not exceeded 5 mg/kg in layers of yellow-tobrown clammy clay, and brown-to-gray and ne-to-medium grain
sands. Concentrations of As and Fe in core samples varied considerably with depth. In general, levels were relatively high in
subsurface zones and gradually decreased with depth (Fig. 4). A
strong correlation was found between total As and Fe concentrations in core samples (Pearsons r 0.4; p < 0.05).
Fig. 5 shows the results of sequential extraction of core samples.
Only in very few core samples was As associated with the surface
adsorbed phase or the Mn oxide phase. The organic matter phase
and the exchangeable phase contained small amounts of As.
Arsenic in sediment was mainly (3785%) in the poorly crystalline
Fe oxide phases, which may explain the similarity between the
distribution patterns of total As and Fe, and the strong correlation
observed between total As and Fe concentrations, as noted above.
The total As concentration in core samples was strongly correlated
with the As level in the poorly crystalline Fe oxide phase (Pearsons
r 0.95; p < 0.01). Only a small proportion of As remained in the
residue. The toxicity characteristic leaching procedure (TCLP) and
the synthetic precipitation leaching procedure (SPLP) did not result
in extraction of any leachable As.

3.4. Characterization of arsenic in groundwater surrounding


drilling sites
Arsenic in groundwater was mainly in the form of arsenite [As
(III)], and the ratios of As (III) to total As varied between 0.29 and
1.00. Positive correlations were found between total As level versus
As (III) and NH
4 . No correlation was found between As concentrations and PO3
4 , total Fe, or Mn. Negative ORPs were recorded for
wells with either high or low As concentrations. However, positive
ORPs were noted in wells containing very low As concentrations
(Fig. 6). It is likely that positive ORPs may be a good indicator of
groundwater that contains safe levels of As. A negative correlation
(0.68; p < 0.05) was found between total As concentration and the
ORP in groundwater surrounding drilling sites. It is noteworthy that
the three positive values of ORP coincided with the three deepest
wells (7075 m depth) for which pH values were below pH 7. It may
be that deep sedimentary layers are often strongly reducing and
shallow subsurface layers are zones of oxidation. However, that is
not true in our study area, and our results may indicate the presence
of complex hydrobiogeochemical conditions in the local aquifer.
4. Discussion
4.1. Distribution of arsenic in the MDVN aquifer
Arsenic concentrations in well water varied markedly with the
distance of the well from the Mekong River. It has been reported
Table 8
Inuence of various factors on the arsenic concentration in groundwater of An Giang
and Dong Thap and their correlations with arsenic.
Parameter

Distance
Well depth
pH
TOC
Mn
Fe
Ba
Ca
Mg
Na
Si
Co
Ni

Correlation with As
An Giang

Dong Thap

n.s
(0.244; 0.011)
(0.339; 0.000)
(0.390; 0.000)
(0.269; 0.005)
n.s
(0.209; 0.031)
(0.210; 0.030)
(0.294; 0.002)
(0.270; 0.005)
(0.293; 0.002)
(0.245; 0.011)
(0.226; 0.019)

(0.252; 0.025)
n.s
(0.394; 0.000)
(0.367; 0.001)
n.s
(0.243; 0.026)
(0.464; 0.000)
n.s
n.s
n.s
(0.234; 0.030)
n.s
n.s

Values in the parameter are the correlation and signicance, respectively. n.s:
correlation is not signicant.

2654

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

Table 9
Correlations between As and parameters in groundwater of An Giang and Dong Thap.
Province

An Giang
Dong Thap

Distance

Well depth

pH

TOC

Mn

Fe

Cor.

Inf.

Cor.

Inf.

Cor.

Inf.

Cor.

Inf.

Cor.

Inf.

Cor.

Inf.


O ()




O ()


O
O

O ()
O ()


O

O ()
O ()

O
O

O ()


O



O ()


O

Cor. e correlation between the parameter and As. Inf. inuence of the parameter on As concentration examined by independent sample t-test.  correlation or
inuence is not signicant. O - correlation or inuence is signicant.

that hazardous concentrations of As in Cambodian groundwater


were associated with proximity, usually within 10 km, to modern
major channels of the Mekong River and its distributary, the Bassac
River (Berg et al., 2007; Buschmann et al., 2007; Polya et al., 2005).
Among ve sampling areas in An Giang, samples from the AG3 area,
located southwest of the Hau River, were not contaminated with As,
whereas groundwater in other areas between the Tien and Hau
rivers was clearly contaminated. In Dong Thap, higher levels of As
were apparent 1213 km from the river bank and in the vicinity of
Cao Lanh district.
The variation of As in groundwater with distance from the local
river may suggest that the Mekong River plays an important role in
contamination of the local aquifer. Based on data from the Center
for Information and Archives of Geology, Department of Geology
and Minerals of Vietnam (http://www.idm.gov.vn), the Mekong
River has a maximum depth of 45 m and intersects with the entire
Holocene aquifer and part of the Pleistocene aquifer. The River
naturally recharges the adjacent aquifer (at a transmissivity of
0.45 L1 m1) because river water level is higher than the
groundwater table. It is notable that the As concentration in waters
of the Mekong River is usually much lower than that in groundwater (Lee et al., 2006). Thus, it is unlikely that the water of the
Mekong River is a source of As into the local aquifer. Conversely,
lateral inltration of river water into the adjacent aquifer could
have a dilution effect, acting to reduce As concentration in the
aquifer. However, river water may contain a considerable amount of
organic carbon originating from various waste water sources. This
allochthonous organic carbon, together with autochthonous
organic matter in channel, bank and swamp deposits along the
Mekong River system, may enhance reduction of Fe (hydr)oxides,
resulting in As mobilization (Harvey et al., 2002). Nguyen et al.

(2000; Fig. 3) showed the distribution of organic matter along the


Mekong River in an environmental sedimentary map. In addition,
the intrusion of river water containing higher dissolved oxygen
levels than are present in groundwater may change the ORP in the
local aquifer from strongly reducing to moderately reducing. If that
is the case, As release from aquifer sediments into groundwater
would be enhanced, resulting in high As concentrations in riparian
groundwater. Depending on the intensity of river wateregroundwater interactions, more or less contamination could be expected
as a result.
Groundwater containing more than 10 mg/L As can occur at any
depth in the Mekong River basin (Stanger et al., 2005). However,
well depths greater than 16 m are considered to be an indicator of
hazardous concentrations of As in Cambodian groundwater (Polya
et al., 2005). The greatest As concentrations in groundwater in
Kandal province usually occur below 48 m in the area adjacent to
the Mekong River, whereas As content of groundwater adjacent to
the Bassac River appears to be independent of depth (Rowland
et al., 2008). Nguyen and Ryuichi (2009) also established that, in
the Mekong Delta in Vietnam, wells shallower than 100 m usually
have As concentrations higher than 100 mg/L, whereas wells deeper
than 150 m usually have low As levels. In our study, well depths
varied between 12 and 450 m, but were typically under 100 m.
Groundwater containing elevated As concentrations usually
occurred at depths not exceeding 6070 m, and the near-surface
zone was rarely contaminated. It is clear that As concentration in
groundwater was strongly dependent on the depth from which the
groundwater was extracted, allowing the inuence of the sedimentary layer to be conrmed. These ndings indicate that wells
should be drilled to depths exceeding 100 m to help ensure access
to safe groundwater.

Fig. 4. Depth prole of arsenic, iron and manganese in core samples from a) Cho Vam-An Giang and b) Thanh Binh-Dong Thap.

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

2655

Fig. 5. Operationally-dened phases of As in core samples from a) Cho Vam-An Giang and b) Thanh Binh-Dong Thap.

4.2. Conditions favoring release of arsenic to groundwater


The behavior, distribution, and processes controlling As levels in
groundwater have been intensively investigated in the Ganges
Plain, the Red River delta, and the upper Mekong River basin of
Cambodia (Anawar et al., 2002; Berg et al., 2001, 2007, 2008;
Buschmann et al., 2007, 2008; Chowdhury et al., 2000; McArthur
et al., 2001; Nickson et al., 2000; Polya et al., 2003, 2005, 2007,
2008; Postma et al., 2007). However, few comparable studies have
been undertaken in the lower Mekong River delta in Vietnam
(Nguyen and Ryuichi, 2009).
It is widely agreed that the occurrence of As in groundwater is
regulated by the ORP and pH of groundwater, the oxidation state of
As, and the content and solubility of other components in
groundwater. Among these factors, ORP is of major signicance
because of an ability to directly control or indirectly affect As
behavior through effects on other components of groundwater.
According to Sracek et al. (2004), under low ORP and pH conditions,
Fe(III) oxide and hydroxides can dissolve and thereby release
adsorbed As. In very reducing environments, where SO2
4 reduction
takes place, secondary sulde minerals including As-bearing pyrite
and orpiment can incorporate As. However, if the concentration of
dissolved SO2
4 is low, no precipitation of secondary suldes occurs,
and As remains mobile. High concentrations of As have been
reported in reducing shallow alluvial aquifers in Cambodia, at circumneutral pH and with high alkalinity (Berg et al., 2007; Polya
et al., 2003; and Rowland et al., 2007, 2008). Our results also
indicate an association between neutral pH and elevated As levels

in groundwater. Differing mean concentrations of As were found in


groundwater at pH values below and above 8 (Table 7).
Arsenic may be released to groundwater through a number of
processes including (i) oxidation of arsenical pyrite and other Asbearing sulde minerals; (ii) exchange of adsorbed As with other
competitive anions (phosphate, bicarbonate, and silicate); and, (iii)
reductive dissolution of As-rich Fe (III) (hydr)oxides and Al-(hydr)
oxides (McArthur et al., 2001; Nickson et al., 2000). The rst
process is unlikely in our region because, following oxidation of
such minerals, As would be sorbed to newly formed Fe(III) (hydr)
oxides rather than released to groundwater. Any contribution of the
second process is probably minor in our study area. The third
process is widely accepted as the main mechanism of As mobilization, although reductive dissolution of Fe phases alone may not
sufce for As mobilization, and microbial metabolism of sedimentary organic matter or buried peat deposits may play an indispensable role in this process (McArthur et al., 2001; Nickson et al.,
2000). Arsenic mobilization in a southern Bangladeshi aquifer has
been reported to be under the control of organic carbon, and the
availability of other electron donors in the sediment, because these
components can drive the reduction of Fe(III) (hydr)oxides, and
carbonate can displace adsorbed As (Harvey et al., 2002). Moreover,
microbial transformations of As in the Bangladesh aquifers may
result in As release (Oremland and Stolz, 2003). Islam et al. (2004)
provided direct evidence that release of As from the sediment of
a West Bengal aquifer did not occur simultaneously with Fe(III)
reduction, but rather through subsequent As(V) reduction in the
presence of metal-reducing bacteria.

Fig. 6. Relationship between total As and a) ORP, b) As(III), and c) NH


4 in groundwater around the drilling site CV.

2656

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

A series of sediment experiments have demonstrated the roles


of organic matter and microorganisms in releasing As into
groundwater of the Upper Mekong River basin (Hery et al., 2008;
Lear et al., 2007; Quicksall et al., 2008; Rowland et al., 2007; Van
Dongen et al., 2008). Certain organic matter components can act
as electron donors in Fe reduction mediated by microbes, or as
electron shuttles accelerating As release (Rowland et al., 2007).
Microbes can directly use Fe(III) and/or As(V) as electron acceptors,
and directly convert As(V) to the potentially more mobile As(III)
(Islam et al., 2005; Lear et al., 2007). In fact, As contamination
results from a combination of microbial decomposition of organic
matter and reductive dissolution of As-bearing Fe compounds.
Therefore, As contamination is spatially heterogeneous and may
occur under certain biogeochemical conditions or within certain
geomorphic features in which reactive organic matter was rapidly
buried (Kocar et al., 2008; Papacostas et al., 2008). Thus, the
occurrence of As abnormalities in the MDVN aquifer, such as the
Cao Lanh hot spot, is understandable.
Correlations between As and the levels of other components in
groundwater have been widely invoked as inferring the presence of
an As release mechanism and explaining As contamination of
groundwater (Berg et al., 2007, 2008; Buschmann et al., 2008;
Nguyen and Ryuichi, 2009; Polya et al., 2003; and Rowland et al.,
2008). However, such interpretations may be mistaken because
these components may not behave conservatively in the aquifer
(McArthur et al., 2001). In our study of the characteristics of
groundwater next to drilling sites, we observed positive correlations only between total As and As (III), NH
4 , TN, and TC. Although
As, Fe, and Mn concentrations in core samples were strongly
correlated, no similar correlation was found in groundwater
samples. The high proportion of As found in Fe oxide-related
phases in core samples provided convincing evidence that such
phases were the principal source of As released to groundwater. It
would be unwise to reject the possible involvement of a reductive
dissolution mechanism based on the absence of any correlation
among the parameters studied. This is because total concentrations
of materials in the aqueous phase may be affected by other
processes, so that following dissolution and release to groundwater,
material concentrations may not be strongly correlated, as is the
case in sediment. In this regard, we note that reductive dissolution
of the Fe and Mn phases was not necessarily the dominant source of
release of As to groundwater. Following release by these processes,
As may not have been readily introduced into the aqueous phase, or
may have been transferred to a different phase (e.g., adsorbed onto
suitable substrates or precipitated in the form of sulde
compounds). This is suggested by several reports showing that As
(V) reduction by metal-reducing bacteria was necessary for release
of As from a West Bengal aquifer sediment (Islam et al., 2004), and
that secondary Fe phases may sequester mobilized As, resulting in
no increase in dissolved As (Coker et al., 2006; Horneman et al.,
2004), In fact, the partitioning behavior of As, Fe, and Mn in the
local aquifer may explain their remarkably different relationships.
We expected to observe high As concentrations in core samples
in our study region because of the high levels of As detected in
groundwater. However, the concentration ranges of As in sediment
in our study area and in other studies (Berg et al., 2007; Rowland
et al., 2008) are not particularly high relative to the ranges reported for various unconsolidated sediments (0.6e50 mg/kg; average
3 mg/kg; Azcue and Nriagu, 1995) and soils (0.1e55 mg/kg; average
7.2 mg/kg; Boyle and Jonasson, 1973). It is likely that As content in
aquifer sediments need not be high to cause elevated As concentrations in groundwater. Local hydrobiogeochemical conditions in
the aquifer (including the presence of sedimentary organic matter
or other electron donors, indigenous microorganisms, groundwater
ORP, pH, and the combined effects of coexisting ions in

groundwater) may control As leaching from sediment to groundwater. Prerequisites for As release to groundwater may differ
among locations.
4.3. Relationship between arsenic and manganese levels in
groundwater
The relationship between As and Fe in groundwater has been
considered in many studies, including those cited above. However,
it is only recently that concerns about Mn in groundwater have
been raised because of increasing evidence of Mn-caused oral
neurotoxicity, especially in infants (Wasserman et al., 2006).
We observed an inverse relationship between As and Mn
concentrations during our study of more than 400 wells (Fig. 7),
and a high proportion of samples did not meet drinking water
guidelines for these two elements. Table 2 shows that 49% and 88%
of groundwater samples from An Giang exceeded guidelines for As
and Mn, respectively. Up to 93% of groundwater samples from An
Giang were found to have unsafe levels of As and/or Mn. In Dong
Thap, 76% of groundwater samples were contaminated with As
and/or Mn, and only 48% and 37% of groundwater samples had
elevated levels of either of As or Mn (thus not both), respectively.
Only 35% of groundwater samples in the study area had safe levels
of both As and Mn. A similar trend has been reported for groundwater in the Mekong River delta oodplain of Cambodia
(Buschmann et al., 2007).
Manganese is an essential trace element for plants, animals, and
many microorganisms. Mn has been regarded as one of the least
toxic metals when taken orally because homeostasis limits
gastrointestinal absorption. The presence of Mn and Fe in a water
source has been considered problematic because of undesirable
odor and taste. Elevated Mn concentrations may have effects on
plants and humans, especially infants. In 1995, the British Columbia
Ministry of Environment, Lands and Parks established a recommended maximum level of Mn for fresh water aquatic life of
0.1e1 mg/L. In 1987, the Canadian Council of Ministers of the
Environment set an irrigation water guideline of 0.2 mg/L for
continuous watering of any soil types, specically to protect against

Fig. 7. Inverse relationship between arsenic and manganese in groundwater of the


study area.

T.H. Hoang et al. / Environmental Pollution 158 (2010) 2648e2658

the possible toxic effects on plants growing in acidic soils. An irrigation water guideline of 10 mg/L was recommended for continuous watering of up to 20 years on neutral and alkaline soils. A
guideline of 0.05 mg/L for Mn in drinking water recommended by
the US EPA was not toxicologically based, but was rather established to address aesthetic considerations including staining of
plumbing and laundry, and an undesirable taste. From 1958 to
2006, the World Health Organization modied the drinking water
guideline for Mn several times: 500 mg/L (1958), 100 mg/L (1983),
500 mg/L (1993), and 400 mg/L (2006). The Vietnamese guideline for
Mn in drinking water is 0.5 mg/L (TCVN 6002-1995). However,
a level of 0.01 mg/L was recommended for Mn based on a study of
Mn deposition in a drinking water distribution system (Sly et al.,
1990). In our study region, the occurrence of Mn in the water
supply is a serious issue that should be addressed, particularly in
view of the inverse relationship between Mn and As.
5. Conclusion
In a study of 460 wells in the MDVN, we found that 26% and 50%
of groundwater samples exceeded WHO guidelines for As and Fe,
respectively, and 74% of groundwater samples exceeded the US EPA
guideline for Mn. Groundwater in the AG2, AG5, and DT2 areas was
seriously contaminated by As. Convincing evidence was found for
the dependence of groundwater As concentrations on spatial
parameters (distance to the Mekong River and well depth) and
hydrogeochemical variables (pH, TOC, and Mn and Fe concentrations). Indicators of elevated As concentration in groundwater
included well location within 2 km of the Mekong River bank, and
well depths less than 6070 m. An inverse relationship found
between As and Mn, that negatively affected groundwater quality.
The maximum concentrations of As in the CV and TB cores were
found at depths of 46 m and 34.5e34.9 m, respectively. The largest
proportion of sedimentary As was associated with poorly crystalline Fe oxides, whereas As was almost absent in carbonate and Mn
oxide phases. Local hydrobiogeochemical conditions in the aquifer,
including presence of sedimentary organic matter (or other electron donors), indigenous microorganisms, groundwater ORP, pH,
and the combined effects of ions in groundwater, may control As
leaching from sediment to groundwater.
Acknowledgement
This study was supported by the UNU & GIST Joint Programme
on Science and Technology for Sustainability, and also by the
Vietnamese Ministry of Education and Training (MOET) through
the HUS-GIST Joint PhD Programme.
Appendix. Supporting information
Supplementary information associated with this paper can be
found, in the online version, at doi:10.1016/j.envpol.2010.05.001
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