DSpace at VNU: Contamination by arsenic and other trace elements in tube-well water and its risk assessment to humans in Hanoi, Vietnam

Environmental Pollution 139 (2006) 95e106
www.elsevier.com/locate/envpol

Contamination by arsenic and other trace elements in
tube-well water and its risk assessment to
humans in Hanoi, Vietnam
Tetsuro Agusa a, Takashi Kunito b, Junko Fujihara a,1, Reiji Kubota a,
Tu Binh Minh a, Pham Thi Kim Trang c, Hisato Iwata a,
Annamalai Subramanian a, Pham Hung Viet c, Shinsuke Tanabe a,*
a

Center for Marine Environmental Studies (CMES), Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577, Japan
b
Department of Environmental Sciences, Faculty of Science, Shinshu University, 3-1-1 Asahi,
Matsumoto, Nagano 390-8621, Japan
c
Research Center for Environmental Technology and Sustainable Development, Hanoi University of Science,
VNU Hanoi, 334 Nguyen Trai, Thanh Xuan, Hanoi, Vietnam
Received 4 November 2004; accepted 23 April 2005

High concentrations of arsenic, manganese and barium were found in tube-well water and human
hair in suburban areas of Hanoi, Vietnam.
Abstract
Concentrations of As and other trace elements and their association were examined in groundwater (nZ25) and human hair
(nZ59) collected at Gia Lam District and Thanh Tri District, suburban areas of Hanoi, Vietnam, in September 2001.
Concentrations of As in the groundwater ranged from !0.10 to 330 mg/l, with about 40% of these exceeding WHO drinking water
guideline of 10 mg/l. Also, 76% and 12% of groundwater samples had higher concentrations of Mn and Ba than WHO drinking
water guidelines, respectively. Arsenic concentrations in hair of residents in Gia Lam and Thanh Tri Districts (range 0.088e2.77 mg/g
dry wt.) were lower than those in other As-contaminated areas of the world, but were higher than those of people in noncontaminated areas. Concentrations of As and Mn in hair of some individuals from the Gia Lam and Thanh Tri Districts
exceeded the level associated with their toxicity and, therefore, a potential health risk of As and Mn is a concern for the people
consuming the contaminated water in this area. Cumulative As exposure was estimated to be lower than the threshold levels at

the present, which might explain the absence of manifestations of chronic As poisoning and arsenicosis in the residents of Gia
Lam and Thanh Tri Districts. To our knowledge, this study revealed for the first time that the residents are exposed not only to
As but also Mn and Ba from groundwater in the Red River Delta, Vietnam.
Ó 2005 Elsevier Ltd. All rights reserved.
Keywords: Arsenic; Manganese; Barium; Groundwater; Human hair; Hanoi; Vietnam

1. Introduction
* Corresponding author. Tel./fax: C81 89 927 8171.
E-mail address: (S. Tanabe).
1
Present address: Department of Legal Medicine, Shimane University School of Medicine, 89-1 Enya, Izumo, Shimane 693-8501, Japan.
0269-7491/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2005.04.033

Arsenic is not contained so much in the Earth’s crust
but greatly concentrated in pyrite, hydrous Fe oxides
and sulfur compounds (Smedley and Kinniburgh,


96

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

2002). It is known that As would be easily solubilized
in water from these minerals depending on pH, redox
conditions and temperature (Smedley and Kinniburgh,
2002). Nickson et al. (1998) suggested that As may be
released from As-rich Fe oxyhydroxides into groundwater under reductive conditions in alluvial sediments
in Bangladesh and West Bengal. Increased usage of
groundwater for drinking in these areas has caused

serious health problems (Bagla and Kaiser, 1996;
Nickson et al., 1998), because inorganic As is carcinogenic and causes skin and various internal cancers
(IARC, 1980; WHO, 2001). It is reported that about 36
million of the population in the Bengal Delta is at risk
from drinking As-contaminated groundwater (Smith
et al., 2000). Tondel et al. (1999) reported a relationship
between As concentration in drinking water and
prevalence of skin lesions in Bangladesh. A significant
doseeresponse relationship was also observed between
As level in well water and mortality from cancers of
bladder, kidney, skin, and lung in residents of the
southwestern coast of Taiwan (Wu et al., 1989).
Furthermore, recent studies suggest that As acts as an
endocrine disruptor at very low concentrations. Stoica
et al. (2000) reported that As activates estrogen
receptor-a through an interaction with the hormonebinding domain at concentrations as low as 1 nM
(0.075 mg/l). Kaltreider et al. (2001) demonstrated that
As blocked glucocorticoid receptor-dependent induction of gene expression when administered at 0.3 mM
(22.5 mg/L).
Around the Red River Delta in Vietnam, Berg
et al. (2001) found elevated As concentrations (up to
3050 mg/l) in the groundwater, which is over the WHO
drinking water guideline (10 mg/l) and the levels are
comparable to those in Bangladesh and West Bengal,
India. The area of the Red River Delta is much
smaller than that of the Bengal Delta, but there are 11
million people. Although the health risk to the
population consuming As-contaminated groundwater
is of great concern, there is no information on As
contamination in residents around the Red River Delta,

Vietnam.
In the present study, the contamination status of As
was evaluated in groundwater pumped from the tube
wells in the households at the suburban areas of Hanoi.
Also, As level in human hair from the corresponding
household with the tube well was determined. Recently,
Frisbie et al. (2002) revealed that concentrations of
Mn, Pb, Ni, and Cr as well as As were above the
WHO drinking water guidelines in some groundwater
of Bangladesh, suggesting the need for research on
contamination of multiple elements in groundwater and
their mixture toxicity. Hence, concentrations of other
trace elements in groundwater and human hair were also
determined to assess the health effect of multielements in
the present study.

2. Materials and methods
2.1. Samples
Groundwater samples were randomly collected from
25 tube wells in Gia Lam District and Thanh Tri District
in the suburban area of Hanoi, Vietnam (Fig. 1), during
September (dry season) 2001. These sampling locations
correspond to the As-contaminated area reported by
Berg et al. (2001). Pond water (nZ1) and rainwater
stored for drinking (nZ2) in Thanh Tri District were
also sampled. Polypropylene bottles (100 ml), which
were soaked in a nitric acid bath and then washed with
Milli-Q water, were used for water sampling. Collected
groundwater, pond water, and rainwater samples were
stored at ÿ20  C as immediately as possible.

Human hair samples (nZ59; 24 families) were also
collected from each house equipped with a tube well at
Gia Lam District (nZ20; 8 families) and Thanh Tri
District (nZ39; 13 families). We obtained the informed
consent from all the donors in an ethical manner. Hair
samples were taken into the polyethylene bags and were
kept at ÿ20  C until chemical analysis. The details of
the hair samples are shown in Table 1.
2.2. Water analysis
After transporting to the laboratory, the water
samples were acidified with H2SO4 for As and HNO3
for other elements. Milli-Q water acidified with H2SO4
or HNO3 was used as control. Arsenic concentration of
water was measured by hydride generation atomic
absorption spectrometry (AAS) using a Shimadzu
HVG-1 hydride system coupled to a Shimadzu-AA680
AAS (Kubota et al., 2001; Agusa et al., 2002).
Concentrations of V, Cr, Mn, Co, Cu, Zn, Ga, Rb, Sr,
Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Tl, Pb and Bi were
determined by inductively coupled plasma mass spectrometry (ICP-MS; Hewlett-Packard, HP-4500) (Anan
et al., 2001; Agusa et al., 2003). Yttrium was used as an
internal standard for ICP-MS measurements. Concentration of Hg was determined with a cold vapor AAS
(CV-AAS) (Sanso, Model HG-3000). Iron was measured by AAS. Water pH was measured by a glass
electrode pH meter (Asahi Techno Glass).
2.3. Hair analysis
Human hair samples were washed by sonication with
0.3% polyoxyethylene lauryl ether (Okamoto et al.,
1985), and subsequently dried for 12 h at 80  C. For As
analysis, dried hair sample was accurately weighted
directly into a Kjeldahl flask and 8 ml of purified HNO3

was added. After pre-digestion at room temperature
overnight, the sample was treated with 16 ml of acid
mixture (HNO3:HClO4:H2SO4Z1:2:1) and digested by


97

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

China

Laos

Thailand
Gia Lam
Cambodia
Vietnam

Thanh Tri

Fig. 1. Map showing sampling location. Groundwater, rainwater, pond water, and human hair were collected from Gia Lam District and Thanh Tri
District in the suburban areas of Hanoi during September 2001.

heating to over 300  C until the perchloric acid was
removed (Kubota et al., 2001). Arsenic concentration was
measured by HG-AAS. For analysis of other trace
elements, about 0.1 g of hair sample was digested in
1.5 ml of concentrated HNO3 in a Teflon PTFE tube in
a microwave oven (Agusa et al., 2003; Ikemoto et al.,
2004). Concentrations of 20 elements (V, Cr, Mn, Co, Cu,

Zn, Ga, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Tl, Pb and
Bi) and Hg were determined by ICP-MS and CV-AAS,
respectively. The accuracy of the method was assessed
using a certified reference material NIES No.5 Human
Hair (Okamoto et al., 1985) provided by the National
Institute for Environmental Studies (NIES), Japan.
Recoveries of the elements ranged from 79.2 to 108%.

distribution with KolmogoroveSmirnov’s one sample
test. Because some variables were not normally distributed, nonparametric tests were used to compare
different groups and correlation for analysis. The
ManneWhitney U-test was employed to detect gender
and regional (Gia Lam and Thanh Tri) differences in
trace element concentrations. KruskaleWallis test was
also used for comparison of more than two groups.
Spearman’s rank correlation coefficient was used to
measure the strength of the associations between As
concentration and other variables. A p value of less than
0.05 was considered to indicate statistical significance.
All statistical analyses were performed with StatView
(version 5.0, SASÒ Institute, Cary, NC, USA) and
SYSTAT (version 9, SPSS, Chicago, IL, USA).

2.4. Statistical analysis
One half of the value of the respective limit of
detection was substituted for those values below the
limit of detection and used in statistical analysis. All
data were tested for goodness of fit to a normal
Table 1
Details of human hair samples from suburban areas of Hanoi

Area

N

Agea

Gia Lam
Total
Female
Male

20
8
12

29 (2e71)
26 (4e38)
31 (2e71)

Thanh Tri
Total
Female
Male

39
20
19

25 (4e50)
27 (4e50)

22 (5e41)

a

Mean and range.

3. Results and discussion
3.1. Contamination status of As in groundwater
Concentrations of As in the groundwater ranged
from !0.1 to 330 mg/l (Table 2). Median As concentration in groundwater in Gia Lam (5.0 mg/l) was
comparable to that in Thanh Tri (1.5 mg/l) ( pO0.05;
Table 2). About 40% of these samples contained As
concentrations exceeding WHO drinking water guideline of 10 mg/l (WHO, 1996) (Fig. 2), which confirmed
the findings of Berg et al. (2001) in which an elevated
level of As was observed in the groundwater of the Red
River Delta. In contrast, As concentrations were low in
pond water and rainwater (Table 2 and Fig. 2).
To understand the magnitude of As contamination,
concentrations of As in groundwater in the present study
were compared with those in other As-contaminated


98

Table 2
Concentrations of arsenic and other trace elements (mg/l) in groundwater, rainwater, and pond water in suburban areas of Hanoi
Sample

Cr

Mn

Fe

Co

Cu

Zn

Ga

As

Rb

Sr

Mo

Mean
SD
Min
Max
Median
Na

0.14
0.13
0.04

0.48
0.07
11/11

2.1
0.37
1.6
3.0
2.1
11/11

1520
1530
2.67
5530
1040
11/11

5100
5100
290
13000
1700
11/11

1.1
1.2
0.09
3.9
0.82

11/11

3.85
1.82
0.894
6.81
3.74
11/11

6.42
5.54
0.24
17.6
4.59
11/11

22.0
12.7
7.77
44.0
17.6
11/11

10.8
14.2
!0.1
38.2
5.04
7/11

3.32
3.41
0.24
10.9
1.76
11/11

370
92.7
249
552
348
11/11

1.18
1.86
0.16
6.69
0.73
11/11

Mean
SD
Min
Max
Median
N

0.90
0.91

0.05
2.7
0.67
14/14

2.2
0.45
1.3
3.0
2.2
14/14

1260
1130
25.2
4190
1100
14/14

4400
6000
220
16000
1000
14/14

1.6
1.5
0.26
5.8

1.2
14/14

2.63
2.28
0.88
8.22
1.65
14/14

18.3
28.2
2.03
95.1
4.89
14/14

15.5
10.8
6.43
49.9
12.0
14/14

44.0
88.2
!0.1
330
1.5
10/14

2.01
2.40
0.06
7.38
1.00
14/14

582
151
358
909
585
14/14

1.58
1.50
0.23
5.25
1.26
14/14

Rainwater

Mean (median)
Min
Max
N

1.9

1.3
2.5
2/2

0.30
0.19
0.41
2/2

1.61
1.34
1.88
2/2

48
38
58
2/2

0.03
0.03
0.04
2/2

0.76
0.32
1.2
2/2

1.06

0.35
1.77
2/2

0.91
0.57
1.26
2/2

0.58
0.56
0.59
2/2

6.01
4.26
7.75
2/2

46.2
14.6
77.7
2/2

0.10
0.07
0.14
2/2

Pond water

Concentration
N

1.7
1/1

0.34
1/1

105
1/1

220
1/1

0.27
1/1

1.52
1/1

1.99
1/1

1.57
1/1

4.45
1/1

4.36
1/1

54.6
1/1

0.85
1/1

50

500

Ag

Cd

In

Sn

Sb

Cs

Ba

Hg

Tl

Pb

Bi

!0.01

0.03
0.04
!0.01
0.13
!0.01
3/11

0.01
0.00
!0.01
0.01
!0.01
1/11

!0.1

!0.1

!0.5

!0.1
0.2

!0.1
1/11

0.01
0.02
!0.01
0.06
!0.01
2/11

0.08
0.09
!0.01
0.22
0.02
7/11

!0.01

!0.1
!0.1
!0.1
0/11

410
240
160
820
360
11/11

!0.01
0.01
!0.01
1/11

0.27
0.29
!0.01
0.93
0.13
13/14

0.01
0.02
!0.01
0.06
!0.01
2/14

Gia Lam
Groundwater

Thanh Tri
Groundwater

Drinking water guideline (WHO, 1996)

Gia Lam
Groundwater

2000

10

70

Mean
SD
Min
Max
Median
N

!0.01
0.02
!0.01
1/11

0.04
0.05
!0.01
0.16
0.02
7/11

Mean
SD
Min
Max

Median
N

0.06
0.20
!0.01
0.75
!0.01
3/14

0.12
0.21
0.01
0.81
0.06
14/14

0.07
0.05
!0.01
0.23
0.06
13/14

0.01
0.02
!0.01
0.07
!0.01
2/14

0.1
0.1
!0.1
0.3
!0.1
6/14

0.1
0.0
!0.1
0.2
!0.1
2/14

250
170
95
770
210
14/14

!0.5
!0.5
!0.5
0/14

0.01
0.02
!0.01

0.07
!0.01
3/14

Rainwater

Mean (median)
Min
Max
N

!0.01
!0.01
!0.01
0/2

!0.01
!0.01
!0.01
0/2

!0.01
!0.01
!0.01
0/2

!0.01
!0.01
!0.01
0/2

0.4
0.3
0.4
2/2

!0.1
!0.1
0.1
1/2

13
8.0
18
2/2

!0.5
!0.5
!0.5
0/2

0.01
!0.01
0.02
1/2

0.05
0.03
0.08
2/2

!0.01
!0.01
!0.01
0/2

Pond water

Concentration
N

!0.01
0/1

0.02
1/1

!0.01
0/1

!0.01
0/1

0.5
1/1

!0.1
0/1

26

1/1

!0.5
0/1

!0.01
0/1

0.51
1/1

0.02
1/1

700

1

Thanh Tri
Groundwater

Drinking water guideline (WHO, 1996)
a

N, number of samples with detectable concentration.

3

5

!0.5
!0.5
!0.5
0/11
!0.5

10

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

V


99

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

Gia Lam district
Groundwater

Thanh Tri district
Groundwater

F21
F22
F23
F24
F25
F26
F27

F28
F29
F30
F31
F01
F02
F03
F04
F05
F06
F07
F08
F09
F10
F11
F12
F13
F14

Rainwater

F07
F09

Pond water

F12

ND
ND

ND
ND

ND
ND

ND
ND
ND
ND

0

WHO guideline (10 µg/l)

50

100

150

200

250

300

350

As concentration (µg/l)

Fig. 2. Arsenic concentrations in groundwater, rainwater and pond water in the suburban areas of Hanoi. Sample number of groundwater (F01-14,
F21-31) indicates well in each home.

areas (Fig. 3a). Median values in groundwater in Gia
Lam and Thanh Tri were lower than those in other Ascontaminated areas. However, the maximum value
(330 mg/l) was comparable to the levels in other Ascontaminated areas. In a previous report, high
concentrations of As were observed in groundwater
of Gia Lam (2e3050 mg/l) and Thanh Tri (9e3010 mg/l)
(Berg et al., 2001). In the present study, however,
a lower concentration (!0.1e330 mg/l) of As was
observed in groundwater though these samples were
collected from the same area (Fig. 3a). Because the As
level in groundwater varied considerably between tube
wells (2e3050 mg/l) (Berg et al., 2001), the difference in
As concentration between the present and previous
studies might be related to the sampling points even
within the same area. Also, annual and seasonal
variation of the As level might be partly responsible
for the inconsistency between the studies.

3.2. Contamination status of other trace elements
in groundwater
Various trace elements in the groundwater, pond
water and rainwater were also measured in the present
study (Table 2). Concentrations of Fe and Mn in
groundwater were higher than those of other elements,
followed by alkaline earth metals such as Sr and Ba. On
the other hand, concentrations of Ag, In, Sn, Sb, Cs,
Hg, Tl and Bi were very low. Concentrations in pond
water and rainwater were lower than those in groundwater for most of the elements.

Concentrations over the WHO drinking water
guideline were also found for Mn (500 mg/l) and Ba
(700 mg/l) (WHO, 1996) in some groundwater samples
from Gia Lam and Thanh Tri (Fig. 4a,b). Particularly,
the median value of Mn concentration in groundwater
in both Gia Lam and Thanh Tri was higher than
1000 mg/l and about 76% of the samples exceeded the
WHO guideline of 500 mg/l (Fig. 4a). Our study also
indicates that Ba concentrations in three samples of
groundwater were higher than WHO drinking water
guidelines (700 mg/l) (Fig. 4b). These findings indicate
that people in the Red River Delta may be exposed not
only to As but also to Mn and Ba from groundwater,
and the possible adverse effects are of concern as
described later.
3.3. Influence of various factors on As concentration
in groundwater
A significant positive correlation was found between
As and Fe concentrations in the groundwater
( p!0.001; Fig. 5). Hence, the As level in groundwater
may be the result of reductive dissolution of Fe
oxyhydroxides adsorbed with As in the Red River
alluvial tract as suggested by Berg et al. (2001).
Significant positive correlations were also found between
As, and Mo, Ga and Ba in groundwater ( p!0.01),
while the As concentration was negatively correlated
with Pb and V ( p!0.01). The reasons for these
relationships are not known, but these might be related
to geological and geochemical properties in the subsurface of Red River alluvial tract. Concentrations of

100

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

(a)

Gia Lam, Vietnam (This study)
Thanh Tri, Vietnam (This study)

Bangladesh-1 (Karim, 2000)
West-Bengal, India-1 (Das et al., 1995)
Vietnam (Berg et al., 2001)
Thailand (Foy et al., 1992)
Inner Mongol, China (Yoshida and Yamauchi, 2000)
Taiwan (Wu et al., 1989)
Bangladesh-2 (Chowdhury et al., 2000)
West-Bengal, India-2 (Chowdhury et al., 2000)
Finland-1 (Kurttio et al., 1998)
Kratie, Cambodia (Agusa et al., 2002)
Kandal, Cambodia (Agusa et al., 2002)
Mexico (Cebrian et al., 1983)
Utah, USA-1 (Lewis et al., 1999)
Finland-2 (Kurttio et al., 1999)
10-1

100

101

102

103

104

105

As concentration (µg/l)

(b)

Gia Lam, Vietnam (This study)
Thanh Tri, Vietnam (This study)
Chile (Das et al., 1995)
West-Bengal-1 (Das et al., 1995)
Bangladesh-2 (Chowdhury et al., 2000)
West-Bengal-2 (Chowdhury et al., 2000)
Bangladesh-1 (Karim et al., 2000)
Finland-1 (Kurttio et al., 1998)
Kratie, Cambodia (Agusa et al., 2002)
Utah, USA-2 (Das et al., 1995)
Kandal, Cambodia (Agusa et al., 2002)
Alaska, USA (Das et al., 1995)
Normal people (Arnold et al., 1990)
10-2

10-1

100

101

102

As concentration (µg/g dry wt.)
Fig. 3. Arsenic concentrations in groundwater (a) and hair (b) in arsenic-contaminated areas. Bar and circle indicate range and median (or arithmetic
mean), respectively.

As and Mn were not significantly correlated in
groundwater ( p>0.05), suggesting that the contamination source of As and Mn was different in the wells.
Depth of well (12e45 m) and pH in groundwater
(7.6e9.0) were not related to the As concentration in
the groundwater (data not shown).

3.4. Contamination status of As in human hair
Arsenic concentrations in hair of residents from Gia
Lam and Thanh Tri ranged from 0.088 to 2.77 mg/g dry
wt. (Table 3). Arsenic levels in hair of residents at both
sites were comparable, which was consistent with the
results of groundwater (Table 2). Variation in As levels
in hair resembled the geographical pattern of As level in
groundwater, showing higher concentrations of As both
in hair and water of households F05, F07, F08 and F11

(Figs. 2 and 6a). Also, a significant positive correlation
between As concentrations in groundwater and human
hair was observed (rZ0.57, p!0.001; Fig. 7a). A similar
doseeresponse relationship between As concentrations

in groundwater and human hair was reported in
southwest Finland (Kurttio et al., 1998). This result
suggests that groundwater is probably the main source
of As exposure for these people.
Arsenic levels in human hair in the present study were
lower than those from other contaminated areas such as
Bangladesh and West Bengal, India (Das et al., 1995;
Chowdhury et al., 2000; Karim, 2000), but higher than
those of people in non-contaminated areas (Arnold
et al., 1990) (Fig. 3b). Also, As levels in hair of some
individuals exceeded the level that may be related to skin
pathology (Arnold et al., 1990) (Fig. 6a), suggesting the
potential health effects for populations in the area
investigated.


101

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

(a)
Gia Lam district
Groundwater

Thanh Tri district
Groundwater

F21
F22
F23

F24
F25
F26
F27
F28
F29
F30
F31
F01
F02
F03
F04
F05
F06
F07
F08
F09
F10
F11
F12
F13
F14

Rainwater

F07
F09

Pond water

F12

WHO guideline (500 µg/l)

0

1000

2000

3000

4000

5000

6000

Mn concentration (µg/l)

(b)
Gia Lam district
Groundwater

F21
F22
F23
F24
F25
F26

F27
F28
F29
F30
F31

Thanh Tri district
Groundwater

F01
F02
F03
F04
F05
F06
F07
F08
F09
F10
F11
F12
F13
F14

Rainwater

F07
F09

Pond water

F12

WHO guideline (700 µg/l)

0

200

400

600

800

1000

Ba concentration (µg/l)
Fig. 4. Concentrations of manganese (a) and barium (b) in groundwater, rainwater and pond water in the suburban areas of Hanoi. Sample number
of groundwater (F01-14, F21-31) indicates well in each home.

3.5. Contamination status of other trace elements
in human hair
Concentrations of trace elements other than As were
also determined in human hair from Gia Lam and Thanh
Tri (Table 3). To understand the accumulation status of
trace elements in this population, trace element levels of
hair were compared with those in other studies (Chittleborough, 1980; Takeuchi et al., 1982). Concentrations of
‘‘Rb, Cd and Hg’’ in hair of the residents from Gia Lam
and Thanh Tri (Rb: !0.001e0.124 mg/g dry wt., Cd:

!0.001e0.965 mg/g dry wt., Hg: 0.09e0.98 mg/g dry wt.;
Table 3) were lower than those reported by Chittleborough (1980) (Rb: 0.2e0.23 mg/g dry wt.; Cd: 0.34e
1.6 mg/g dry wt.; Hg: 1.08e1.55 mg/g dry wt.) and
Takeuchi et al. (1982) (Cd: 1.18 mg/g dry wt.; Hg:

3.9 mg/g dry wt.). In contrast, concentrations of V
(median, 0.119 mg/g dry wt.) and Mn (median, 16.7 mg/
g dry wt.) in residents of Gia Lam and Thanh Tri (Table
3) were high, compared to the median values of V
(0.029 mg/g dry wt.) and Mn (0.42 mg/g dry wt.)
for Japanese (Takeuchi et al., 1982). Also, the hair
concentrations of Ga and Ba in residents of Gia Lam and
Thanh Tri (Ga: 0.019e3.02 mg/g dry wt., Ba: 0.3e34 mg/
g dry wt.; Table 3) were higher than the levels in the
population in non-contaminated areas (Ga: 0.02e
0.14 mg/g dry wt., Ba: 0.6e5.6 mg/g dry wt.; Chittleborough, 1980). The high hair concentrations of Mn and
Ba in the residents were consistent with the results
obtained for the drinking water (Fig. 4). Also, concentrations of Mn ( p!0.001), Co ( p!0.001), Ga ( p!0.01),
Ba ( p!0.05), Mo ( p!0.05) and Sr ( p!0.05) in human


102

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106
103

p <0.001

As concentration (µg/l)

102

101

100
Gia Lam
Thanh Tri

10-1
102

103

104

105

Fe concentration (µg/l)
Fig. 5. Relationship between arsenic and iron concentrations in
groundwater in the suburban areas of Hanoi. Samples with arsenic
concentrations below the detection limit are plotted as the value of
detection limit.

hair were positively correlated with those in groundwater. Thus, consumption of the groundwater may be the
main source to the residents for these elements.
Although Mn is known as an essential element,
teratogenicity and neurotoxic effects are caused at high
doses (Barceloux, 1999). Abnormal neurological scores
were observed in older persons (nZ77) who had
consumed Mn-contaminated drinking water (range

1800e2300 mg/l) in northwest Peloponnesos, Greece;
their mean hair Mn concentration was 10.99 mg/g dry
wt. (Kondakis et al., 1989). Recently, Woolf et al. (2002)
also reported striking difficulties in both visual and
verbal memory, which are known toxic effects of Mn,
in a child who received Mn loading for 5 years from
drinking water. The Mn concentrations of water and
hair of the child in the study of Woolf et al. (2002) were
1210 mg/l and 3.09 mg/g dry wt., respectively. The mean
Mn values of both Gia Lam (1520 mg/l for groundwater
and 15.5 mg/g dry wt. for hair) and Thanh Tri (1260 mg/l
for groundwater and 38.9 mg/g dry wt. for hair) in the
present study were comparable to or higher than these
Mn levels in drinking water and hair associated with
chronic Mn poisoning (Tables 2 and 3). Although
neurological tests were not conducted in the present
study, possible adverse effects of Mn through consumption of Mn-contaminated groundwater is of great

Table 3
Concentrations of arsenic and other trace elements (mg/g dry wt.) in hair of residents in suburban areas of Hanoi
Sample

V

Cr

Mn

Co

Cu

Zn

Ga

As

Rb

Sr

Mo

Gia Lam

Mean
SD
Min
Max
Median
Na

0.086
0.044
0.020
0.18
0.075
20/20

0.33
0.16
0.16
0.86
0.27
20/20

15.5
16.5
1.18
61.9
8.36
20/20

0.048
0.044
0.008
0.17
0.036
20/20

9.85
2.19
7.03
14.8
9.37
20/20

169
44.4

87.4
283
160
20/20

0.566
0.633
0.066
3.02
0.423
20/20

0.399
0.153
0.122
0.752
0.383
20/20

0.028
0.019
!0.001
0.085
0.029
18/20

2.82
1.51
0.813
6.07

2.96
20/20

0.054
0.019
0.019
0.099
0.052
20/20

Thanh Tri

Mean
SD
Min
Max
Median
N

0.19
0.13
0.026
0.52
0.13
39/39

0.36
0.11
0.16
0.72

0.36
39/39

38.9
55.7
0.841
263
18.3
39/39

0.14
0.25
0.002
1.3
0.051
39/39

11.6
4.61
5.48
29.6
10.0
39/39

178
59.5
68.5
388
171
39/39

0.403
0.305
0.019
1.30
0.363
39/39

0.617
0.585
0.088
2.77
0.424
39/39

0.039
0.029
!0.001
0.124
0.035
39/39

4.84
3.18
0.297
15.1
4.08
39/39

0.085

0.039
0.035
0.199
0.072
39/39

Ag

Cd

In

Sn

Sb

Cs

Ba

Hg

Tl

Pb

Bi

Mean
SD

Min
Max
Median
N

0.79
2.1
!0.001
8.0
0.027
19/20

0.101
0.094
!0.001
0.285
0.057
17/20

0.003
0.004
!0.001
0.014
0.001
11/20

0.833
1.06
0.117
3.98

0.381
20/20

0.06
0.03
0.01
0.13
0.05
20/20

!0.01

7.5
7.2
1.0
34
5.8
20/20

0.37
0.19
0.13
0.98
0.34
20/20

0.002
0.002
!0.001
0.006

!0.001
8/20

4.99
4.33
0.963
18.7
3.15
20/20

0.009
0.010
!0.001
0.037
0.005
17/20

Mean
SD
Min
Max
Median
N

0.14
0.46
!0.001
2.9
0.030
39/39

0.171
0.250
!0.001
0.965
0.108
32/39

0.004
0.005
!0.001
0.023
0.002
24/39

0.759
1.00
0.057
5.52
0.417
39/39

0.06
0.04
!0.01
0.20
0.06
38/39

5.5

4.0
0.32
20
4.4
39/39

0.30
0.11
0.09
0.64
0.28
39/39

0.003
0.004
!0.001
0.021
!0.001
17/39

9.83
19.9
0.570
121
3.88
39/39

0.015
0.021
!0.001

0.121
0.008
37/39

Gia Lam

Thanh Tri

a

N, number of samples with detectable concentration.

!0.01
!0.01
!0.01
0/20
!0.01
!0.01
0.04
!0.01
4/39


103

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

(a)
Gia Lam district

Thanh Tri district

F21
F24
F25
F27
F28
F29
F30
F31

Father
Mother
Son
Daughter
Unknown

F01
F02
F03
F04
F05
F06
F07
F08
F09
F10
F11
F12
F13

Skin pathology (1 µg/g dry wt.)

0

0.5

1

1.5

2

2.5

3

As concentration (µg/g dry wt.)

(b)
Gia Lam district

Thanh Tri district

F21
F24
F25
F27
F28
F29

F30
F31
F01
F02
F03
F04
F05
F06
F07
F08
F09
F10
F11
F12
F13

Father
Mother
Son
Daughter
Unknown

0

5

10

15

20

25

30

35

40

Ba concentration (µg/g dry wt.)
Fig. 6. Arsenic (a) and barium (b) concentrations in hair of residents in the suburban areas of Hanoi. Sample number of family (F01-13, F21, F24,
F25, F27-31) indicates the well used in the household, as shown in the legend of Fig 4. Unknown indicates that information on family members was
not available.

concern for the residents in Gia Lam and Thanh Tri.
Barium exerts toxic effects associated with hypokalemia
and electrocardiographic changes (Anonymous, 1988),
but there is very little information on the relationship
between Ba concentration in hair and its health effects.
3.6. Factors influencing As, Mn and
Ba concentrations in human hair
A significant influence of age on As accumulation was
not observed in hair of residents of Gia Lam and Thanh
Tri, which agreed with the results of Paschal et al.
(1989). Also, sexual difference in As level was
not significant in the present study. In addition,
a conspicuous trend in hair As level within the family
(father, mother, son, and daughter) was not found
(Fig. 6). Chung et al. (2002) also reported that total As

levels in urine samples did not differ between father,
mother, sons, and daughters. Similar to the results of As
in hair, Mn concentration in hair was not related to age
and sex in this population. In marked contrast, a weak
but significant positive correlation was found between
hair Ba concentration and age of the residents ( p!0.05)
and Ba concentration in hair of female was significantly
higher than those of male ( p!0.01), leading to the
highest level of Ba in the mother among family members
( p!0.01) (Fig. 6b).
3.7. Risk assessment of cumulative exposure to As
Although unsafe levels of As, Mn and Ba were
observed in groundwater as described above, available
data are insufficient to discuss the relationship between
the chronic exposure and toxicity of Mn and Ba. Thus,


104

T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

(a)

101

As concentration in hair (µg/g dry wt.)

p <0.001

Skin pathology (1 µg/g dry wt.)
100

10-1

Gia Lam
Thanh Tri

10-2 -1
10

100

101

102

103

As concentration in ground water (µg/l)

(b)

101

As concentration in hair (µg/g dry wt.)

p <0.001

Skin pathology (1 µg/g dry wt.)

100

10-1

Gia Lam
Thanh Tri

10-2 -2
10

10-1

100

101

102

103

Cumulative As intake (mg)
Fig. 7. Relationships between arsenic concentrations in hair and groundwater (a) and between arsenic concentrations in hair and cumulative arsenic
intake (b) in residents in the suburban areas of Hanoi. Samples with arsenic concentrations below the detection limit are plotted as the value of
detection limit.

we will particularly focus on the risk assessment of
chronic As exposure hereafter.
Skin pathology is an initial symptom of chronic As
exposure (Abernathy et al., 1999; Tsunetoshi, 2000), but
manifestations of chronic As poisoning and arsenicosis

have not been observed in the residents in spite of the
high level of As in groundwater in the suburb of Hanoi
as observed in the present study and Berg et al. (2001).
The absence of As poisoning and arsenicosis in the area
might be due to the fact that the private tube wells in the
area were installed only 1e10 years ago and that chronic
As poisoning usually occurs only after 5e10 years of
exposure through consumption of As-contaminated
water, as suggested by Berg et al. (2001). To assess the

risk of chronic As exposure from groundwater in this
area, cumulative As exposure was estimated from the As
level in groundwater, year of tube-well usage, annual
ingestion rate of groundwater, and daily water consumption, using the following equation:
½Cumulative As intake ðmgފZ½As level in groundwater
ðmg=lފ!½Age of well ðyearފ!½Ingestion rate of
groundwater ð182:5 days=yearފ!½Water consumption
ð2l=dayފ:
A value of annual ingestion rate of groundwater was
set at 182.5 days/year (6 months) in the present study,


T. Agusa et al. / Environmental Pollution 139 (2006) 95e106

because there are rainy and dry seasons in Hanoi and
people mainly use rainwater, not groundwater in the
rainy season. A significant positive correlation was
found between cumulative As exposure and hair As
concentration ( p!0.001; Fig. 7b), suggesting that
residents in the area are chronically exposed to As from

groundwater. Bates et al. (1992) have summarized
threshold levels for internal cancer by As exposure for
smelter workers (6750 mg), moselle vintners (17,520e
175,200 mg), Taiwanese (30,000 mg) chronically exposed to As from groundwater, and Fowler’s solution
patients (672 and 2780 mg). The cumulative As ingestion
for the residents of Gia Lam and Thanh Tri was
0.04e241 mg, much lower than the levels which can
cause internal cancer (Bates et al., 1992). Although exact
information on water consumption rate and period of
well usage for each person was not available for the
estimation, this relatively small cumulative intake may
explain the apparent absence of As-related toxic effects
in the residents in Gia Lam and Thanh Tri.

4. Conclusions
The present study revealed groundwater contamination by As, Mn and Ba in suburban areas of Hanoi,
Vietnam. About 40% of groundwater in these areas
showed As concentrations above the WHO drinking
water guidelines. Also, 76% and 12% of groundwater
exceeded WHO drinking water guidelines for Mn and
Ba, respectively. The levels of As, Mn and Ba in hair were
positively correlated with the levels of the elements in the
groundwater, suggesting that the residents have been
exposed to these elements through drinking the contaminated groundwater in the suburban areas of Hanoi.
Because recent studies showed that As acts as an
endocrine disruptor at very low concentration (Stoica
et al., 2000; Kaltreider et al., 2001), further studies are
needed to evaluate the potential health effects of As from
groundwater in these areas. Furthermore, neurological
tests should be conducted to examine the prevalence of

chronic Mn poisoning symptoms and also, mixture
toxicity of As, Mn and Ba remains to be studied for
the residents in suburban areas of Hanoi, Vietnam.

Acknowledgements
The authors wish to thank the staff of the Research
Center for Environmental Technology and Sustainable
Development, Hanoi University of Science, Hanoi. This
study was supported by the Core University Program
between Japan Society for the Promotion of Science
(JSPS) and National Center for Natural Science and
Technology, Vietnam (NCST), and grants from Re-

105

search Revolution 2002 (RR2002) Project for Sustainable Coexistence of Human, Nature and the Earth
(FY2002) and ‘‘21st Century COE Program’’ from the
Ministry of Education, Culture, Sports, Science and
Technology, Japan.

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