Journal of Hydrology 498 (2013) 59–75

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Journal of Hydrology
journal homepage: www.elsevier.com/locate/jhydrol

Hydrogeochemical and mineralogical investigations

of arsenic- and humic substance-enriched aquifers
Chen-Wuing Liu ⇑, Chih-Chieh Lai, Yen-Yu Chen, Kuang-Liang Lu
Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC

a r t i c l e i n f o s u m m a r y

Article history: This study investigated the hydrogeochemical and mineralogical characteristics of arsenic-contaminated
Received 7 August 2012 and humic-substance-enriched aquifers in the Chianan Plain, Taiwan, which is an endemic area for black-
Received in revised form 12 May 2013 foot disease (BFD). Factorial analysis (FA) was used to evaluate the hydrochemical characteristics of 83
Accepted 10 June 2013
groundwater samples in the Chianan Plain, and 462 geological core samples obtained from 9 drilling
Available online 19 June 2013
This manuscript was handled by Laurent
wells were collected to analyze their arsenic and iron contents. The major mineral phases and chemical
Charlet, Editor-in-Chief, with the assistance components were determined using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and
of Prosun Bhattacharya, Associate Editor scanning electron microscopy and energy dispersive spectrometry (SEM–EDS). Partition of arsenic among
various hosting solids in sediments was determined by sequential extraction. The results of FA showed
Keywords: that the hydrochemical characteristics of the groundwater samples could be grouped by 4 factors: sali-
Arsenic nization, arsenic, sulfide, and iron. Arsenic was positively correlated with alkalinity, dissolved organic/
Groundwater inorganic carbon, and fluorescence intensity [humic acids, (HAs)]. As(V) has a higher chelating affinity
Humic substance with HAs than does As(III), resulting in higher As(V) concentrations distributed throughout the reducing
Sediment environment. High levels and correlations of As and HAs may cause BFD in the Chianan Plain. No corre-
Sources lation was found between the measured and calculated redox potentials of the various redox couples. The
Chianan Plain
As(III)/As(V) was under a chemical non-equilibrium condition. The vertical distribution of the sedimen-
tary As (solid phase) typically increased with depth, but the aqueous As concentrations were higher in the
second aquifer (depth of 80–120 m). Arsenic content (solid phase) was higher in the clay/silt sediments
and marine formations. The major minerals identified by XPS and SEM–EDS were goethite, hematite,
magnetite, pyrite, and siderite, agreeing with the SI values calculated by PHREEQC. Arsenic content
was strongly correlated with sulfur (weight%; R2 = 0.76, p < 0.05), but was weakly correlated with iron
(weight%). However, a moderate correlation (R2 = 0.44–0.75; p < 0.001) between As(s) and Fe(s) in the sed-
iments was found in the transitions in the marine and non-marine formations, especially in the fine
grains. The chelation of humic complex, competition for sorption sites of organic carbon, reduction dis-
solution of Fe oxides are mainly responsible for the groundwater As mobility in the Chianan Plain, espe-
cially for the marine sequence.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction
Naturally occurring As in the groundwater of sedimentary aqui-
fers is a worldwide problem (Bhattacharya et al., 2002; Smedley
and Kinniburgh, 2002). In the sedimentary aquifers in the Chianan
Plain in Southwest Taiwan, the high arsenic concentrations in
groundwater are a paramount environmental health concern that
causes blackfoot disease (BFD). Blackfoot disease is a peripheral
vascular disease that was first reported between 1910 and 1920
(Kao and Kao, 1954). Outbreaks of BFD increased dramatically in
the 1950s when local villagers drilled deep artesian wells for drink-
ing water. Blackfoot disease is associated with the ingestion of
⇑ Corresponding author. Tel.: +886 2 2362 6480; fax: +886 2 2363 9557.
E-mail address: cwliu@ntu.edu.tw (C.-W. Liu).
deep well water that contains high amounts of arsenic (Tseng
et al., 1961). Previous studies have proposed that fluorescent com-
pounds known as humic acids (HAs) cause BFD (Lu et al., 1975; Lu,
1990). The carbon–metal bonds between HAs and As are thought
to be responsible for causing BFD. The monomers of HAs and As
may not cause BFD (Reza et al., 2011). However, the geochemical
and mineralogical characteristics of the groundwater and sediment
in the Chianan Plain have not been comprehensively studied.
Several studies have recently investigated the hydrogeochemi-
cal characteristics of As in the Chianan Plain (Wang et al., 2007;
Chen and Liu, 2007; Nath et al., 2008, 2011; Lu et al., 2011; Reza
et al., 2011). Wang et al. (2007) determined that salinization and
As enrichment are the 2 chief hydrogeochemical characteristics
of the Chianan Plain. Chen and Liu (2007) found that the As-rich
groundwater in the Chianan Plain is under strongly reducing

0022-1694/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhydrol.2013.06.017
60 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75

conditions with low Eh (<110 mV; Ag/AgCl reference electrode) 2620000

and low SO24 (<2 ppm). The reductive dissolution of As-rich Fe (hy-
dr)oxides has been proposed as being the chief source of As in
2610000
groundwater, and the content of SO2 4 , humic substances, and res-
B'
idence times of the water cause variations in the dissolved As in
the Chianan coastal area. Nath et al. (2008) indicated that As con- 2600000
centrations and mobility in Chianan Plain aquifers are influenced
by several biogeochemical processes, including (1) chemical and 2590000
redox changes associated with sea water intrusion; (2) bacterial
Fe(III)- and Mn(IV)- reduction; (3) biomineralization of Fe carbon-
2580000
ate and sulfide minerals; and (4) hydrolysis and weathering of the
silicate minerals in metamorphic rock. Furthermore, there may be
a link between the mud from volcanic activity (the exhumation of 2570000
fluids from the deep crust) and As enrichment in the Chianan Plain
(Lewis et al., 2007; Nath et al., 2008). Lu et al. (2011) assessed the
2560000
spatial variations in groundwater quality in BFD-endemic areas
and found that 76% of the groundwater samples had As amounts
exceeding 10 lg/L. The primary geochemical process in this area 2550000
pertains to the reducing dissolution of As-bearing Fe/Mn oxyhy- B
droxides. Reza et al. (2011) indicated that these high levels of As 2540000
and humic substances may play a critical role in causing the prev-
alence of BFD in the Chianan Plain.
2530000
Over the past decade, the Water Resources Agency of the Min-
150000 160000 170000 180000 190000 200000
istry of Economic Affairs has established a Groundwater Monitor-
ing Network (GMN) program, and 33 hydrological stations and Fig. 1a. Study areas of the Chianan Plain. The solid squares (j) and solid diamonds
100 monitoring wells with depths ranging from 4 to 289 m have () represent the hydrological stations and sampling sediment core drilling wells in
been established in the Chianan Plain (Taiwan Sugar Company, the Chianan Plain, respectively. Wells 29–33 in the upper part of the Chinan Plain
belong to the Choushui River alluvial fan.
2003). The hydrogeochemical measurements were funded by the
Water Resources Agency of the Ministry of Economic Affairs,
Groundwater Monitoring Network program, and conduct by Na-
tional Taiwan University and Agricultural Engineering Research
Center jointly. This study investigates the hydrogeochemical and
mineralogical characteristics of arsenic-enriched and humic-sub-
stance-enriched aquifers in the Chianan Plain, Taiwan. This study
analyzed groundwater samples from GMN monitoring wells. Ar-
senic and iron contents and the mineralogical characteristics of
core samples from 9 drilling wells were evaluated. Aqueous chem-
ical speciation and mineral saturation calculations were performed
using PHREEQC. The sources, distribution, and geochemical and
mineralogical characteristics of As in humic substance-enriched
groundwater and sediments in the Chianan Plain were assessed.
In addition, the relationship between the arsenic species and hu-
mic substances were elucidated.

2. Materials and methods

2.1. Hydrogeological setting of the study area

Taiwan is a relatively young and active mountainous island that

was formed by the collision of the Philippine Sea plate and the con-
tinental margin of the Eurasian plate (Teng, 1987). The backbone of
Taiwan (Central Range of Taiwan) is chiefly composed of Tertiary
sedimentary rocks consisting of metamorphosed rocks. The Chia-
nan Plain in Southwest Taiwan is primarily a coastal alluvial-del-
taic plain formed during the Quaternary. The plain extends Fig. 1b. Hydrogeological profile along A–A0 denoted in (a) in the Chianan Plain.
40 km from east to west and 60 km from north to south and is en-
closed by the Taiwan Strait to the west and the Central Mountains
to the east. Furthermore, it is located between Pachang River to the extensively covered the coastal plain (Wu, 1999). The hydrogeo-
north and Ernjen River to the south, and the plain covers an area of logical profiles of the Chianan Plain exhibit no obvious layer struc-
2100 km2 (Fig. 1a). Fast erosion of surface water upstream and a ture (Wang et al., 2007; Nath et al., 2008). Four aquifers are in the
sharp change of river gradient have caused thick clay-rich muddy plain. Aquifer 1 has a depth of 0–80 m, Aquifer 2 is 80–120 m,
sediments to be deposited in the upper plain and have led to poor Aquifer 3 is 120–210 m, and Aquifer 4 is located at depths beyond
hydraulic properties in the aquifers. Regional geological studies re- 210 m (Fig. 1b; Wang et al., 2007). The uppermost 100-m layer was
vealed that the sedimentation rate since the Pliocene has been very deposited in the last 10,000 years. These sediments were deposited
high. Alluvial deposits of clay, silt and fine-grained sand have in mixed alluvial and delta environments, such as fluvial flood
 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75
Aquifer 1
Aquifer 2
Aquifer 3
Aquifer 4
N S
0
Fig. 1c. Hydrogeological profile along B–B denoted in (a) in the Chianan Plain.
plains, lagoons, and shallow marines, in the Late Pleistocene (Wu,
1999). Alluvial deposits of clay, silt and fine-grained sand have
extensively covered the coastal plain. The regional groundwater
flows, in general, from the mountain area in the east towards the
Chianan Plain in the west. The groundwater recharge is from the
mountainous coarser-grained material in the east hill (Nath et al.,
2008).
2.2. Groundwater sampling and analysis
The field sampling procedure followed NIEA code W103.50B
[Taiwan Environmental Protection Administration (TEPA)]. At least
three wellbore volumes of groundwater were pumped before sam-
pling. Dissolved oxygen (DO), temperature, pH, electrical conduc-
tivity (EC), and redox potential (Eh; Ag/AgCl reference electrode
in 3 M KCl solution) were measured in a flow-through cell every
5 min during the well-purging process. This study also used the 5
equations proposed by Cherry et al. (1979) to calculate the oxida-
tion–reduction potentials of three redox couples Fe2+/Fe3+, As3+/
As5+, and SO2 
4 /HS . The purpose of Eh calculation with different
Fe, As, S species is to determine the major redox couples that are
close to the measured redox potential of high As groundwater sam-
ples. Water samples for metal and other ion concentrations mea-
surement were filtered with 0.45 lm glass filtering papers and
acidified with HNO3 to pH 2. Samples obtained for the HS analy-
ses were collected in narrow-mouthed biochemical oxygen de-
mand (BOD) bottles with tapered ground-glass stoppers and
flared mouths. To avoid trapping or dissolving any atmospheric
O2, a rubber tube was extended to the bottom of the bottle. Sam-
ples were then kept in the ice boxes and delivered to the laboratory
within 24 h. The preservation procedure of As species followed
Gallagher et al. (2001). The total alkalinity (Alk) was determined
by acid titration using methyl-orange. The total organic carbon
(TOC) was measured using the high-temperature combustion
method by SHIMADZU TOC-5000A (APHA, 1998). The ions such
as SO2  þ 
4 , Cl , NH4 and HS , were determined using an ion chro-
matograph (IC) (DIONEX ICS-900). The dissolved metal ionic com-
ponents such as Na+, Mg2+, Ca2+, K+, Fe, and Mn could be measured
by an inductively coupled plasma-optical emission spectrometer
(ICP-OES) (Perkin Elmer Optima 7300DV ICP-OES).
The ferrous (Fe2+) concentrations were measured colorimetri-
cally using the ferrozine method (Lovely and Phillips, 1987). The
61
difference between the total Fe and Fe2+ concentrations was equal
to the Fe3+ concentration. The 4 major As species (As(III), As(V),
MMA, and DMA) were separated using an anion column (Phenom-
enex Nucleosil, 10 lm, 250 mm  4.6 mm) connected to a high-
performance liquid chromatography (HPLC) (Perkin Elmer Series
200 HPLC Pump) that was interfaced to an electro-thermal atomic
absorption spectrometer (AAS) (Perkin Elmer AAnalyst 200 AAS)
and a hydride generation (HG) system (Perkin Elmer FIAS 100).
The mobile phase was a 25 mM phosphate buffer solution
(pH = 5) and the flow rate of pump was 1.5 mL/min (Huang et al.,
2003). The variances of the duplicate measurements were less than
10%, and the recoveries of the check and spike samples were be-
tween 85% and 115%, respectively.
There is a positive correlation between fluorescence intensity
and humic substances (Nagao et al., 2003; Wang, 2003). Therefore,
this study followed NIEA code W940.50T to obtain the fluorescence
intensity. The water samples were filtered with 0.45 lm glass-fiber
papers and added a few drops of H2SO4 or NaOH to maintain at a
pH to 7. Thereafter, the fluorescence intensity of the humic sub-
stances was measured using a fluorescence spectrophotometer.
Fluorescence spectral analysis of the groundwater was conducted
at an excitation wavelength of 340 nm and an emission wave-
length of 415 nm by using a Hitachi F-2000 fluorescence spectro-
photometer with sulfuric acid-quinine (10 lg/L quinine in 0.05 M
H2SO4) as the reference standard (Nagao et al., 2003). The equiva-
lent concentration of each peak was determined by subtracting the
blank peak height from the sample average peak height, and divid-
ing by the slope of the standard curve. The precision were was ±0.1
QSU. The relative fluorescence intensity (RFI) was expressed in qui-
nine standard units (QSUs). Ten QSUs corresponded to the fluores-
cence intensity of the quinine sulfate (10 mg/L in 0.05 M sulfuric
acid) at an excitation wavelength of 340 nm and an emission
wavelength of 415 nm.
2.3. Factorial analysis
Factorial analysis (FA) is a multivariate statistical method, and
yields the general relationship between measured chemical vari-
ables by elucidating the multivariate patterns that may help to
classify the original data. It can be used to determine the geograph-
ical distribution of the resulting factors. The geochemical interpre-
tation of factors yields insight into the main processes that may
govern the distribution of hydrochemical variables. Sixteen hydro-
chemical parameters of the Chianan Plain (Table 1), including Eh,
pH, EC, Alk, Cl, SO2 þ 2+ 2+ +
4 , NH4 , TOC, Fe, As, Ca , Mg , Na , K , and
+

HS concentrations and fluorescence intensity (FI) were examined
to evaluate the characteristics of the groundwater using FA with
SPSS software (SPSS Inc., 1998). Metals found in low concentra-
tions (Zn, Cu, Cd, Cr, Pb, Ag, and Hg) were excluded. The accuracy
of complete chemical analysis of a groundwater sample was
checked by computing the cation–anion balance ([(TCC–TCA)/
(TCC + TCA)]  100(%)) in Table 1, where the total concentrations
of cations, Ca2+ + Mg2+ + Na+ + K+ (TCC) in milliequivalents per liter
should equal to the total concentrations of anions, HCO 
3 + Cl + -
SO2
4 + NO 
3 + F
(TCA) expressed in the same units. The method
2 2+ 2+ +
limit of detections in Alk, TOC, NHþ 
4 , SO4 , Cl , Ca , Mg , Na ,
K+, As, Fe, FI, HS, As(III) and As(V) are 3.4 mg/L, 0.17 mg/L,
0.02 mg/L, 2.3 mg/L, 1.3 mg/L, 2.09 mg/L, 0.5 mg/L, 1.24 mg/L,
0.22 mg/L, 0.005 mg/L, 0.04 mg/L, 10 lg/L (Q.E.), 0.01 mg/L, 5 lg/L
and 5 lg/L, respectively.
2.4. Geological core sample analysis
A total of 462 geological core samples were collected in 5 m
intervals from the top to the bottom of 9 GMN program drilling
wells, including Wells 4, 8, 9, 12, 13, 23, 24, 25, and 27 (Fig. 1a).
 62
Table 1
Sixteen hydrochemical parameters and the concentrations of As3+ and As5+ of groundwater samples in the Chianan Plain.

Well Layer Elevation Longitudea Latitudea EC (lS/ Eh pH Alk TOC NHþ

4 SO2 Cl Ca2+ Mg2+ Na+ K+ As Fe FIb (lg/ HS As(III) As(V) Charge
4
(m) cm) (mV) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/ L) (Q.E.) (mg/L) (lg/L) (lg/L) balance (%)
L)
2 1 10 163,950 2,544,815 3563.3 98.0 8.1 414.5 2.3 9.2 124.7 890.8 24.3 47.6 692.6 57.8 0.04 <0.04 34.0 <0.01 <5 81.6 0.49
2 2 50 163,950 2,544,815 61433.3 125.3 7.1 251.1 1.6 11.4 4399.0 33795.7 760.1 2678.9 19245.3 827.5 0.03 11.76 14.7 <0.01 <5 26.6 3.01
3 1 34 160,526 2,548,099 104150.0 154.5 7.0 260.5 2.7 11.9 6392.0 41535.5 1127.0 4052.4 21300.5 1542.8 0.23 7.55 33.6 <0.01 – – 6.41
3 2 114 160,526 2,548,099 9430.0 229.5 8.1 633.6 21.7 26.2 5.3 3172.6 19.0 73.4 2219.2 81.7 0.61 1.24 575.4 0.02 <5 1162.7 0.24
3 3 192 160,526 2,548,099 1921.3 148.7 7.2 704.4 12.6 14.1 <2.3 230.5 38.3 27.5 342.0 11.4 0.50 2.01 327.6 0.02 <5 2033.7 5.39
3 4 257 160,526 2,548,099 3270.0 277.3 6.9 731.4 13.3 14.0 34.3 827.6 91.0 88.8 561.7 21.5 0.52 0.09 321.9 3.33 <5 43.8 11.92
4 1 35 166,368 2,549,095 75150.0 281.5 7.2 329.6 3.0 29.0 2877.4 28992.6 673.8 2031.0 16048.5 1066.0 0.02 0.65 44.7 <0.01 – – 3.88
4 2 74 166,368 2,549,095 66766.7 213.3 8.0 108.2 2.3 10.5 4894.3 38828.9 673.9 2701.4 19999.3 1116.1 0.07 0.85 17.8 0.44 6.7 66.7 7.67
4 3 188 166,368 2,549,095 9703.3 413.3 7.4 868.8 9.3 16.6 77.0 3828.8 85.9 199.1 1693.9 94.0 0.23 0.29 242.8 27.00 109.0 202.9 20.30
4 4 248 166,368 2,549,095 11996.7 374.3 7.3 953.4 11.5 22.5 64.9 4121.8 134.0 255.4 1985.2 96.7 0.24 1.12 203.9 44.90 186.4 939.3 16.00
5 1 18 172,843 2,547,566 1414.7 85.7 7.0 447.5 1.5 5.4 150.2 115.5 135.2 33.9 133.9 9.2 0.02 6.37 10.0 <0.01 52.4 <5 14.78
5 2 90 172,843 2,547,566 3990.0 117.3 7.5 381.3 1.1 2.9 104.9 1061.0 55.5 56.7 725.2 32.9 0.01 1.41 19.6 0.04 <5 <5 3.49
6 1 89 178,148 2,549,104 1966.3 130.5 7.3 432.1 3.4 3.4 3.4 381.5 103.5 48.4 216.9 15.0 0.03 2.24 58.1 0.02 7.2 12.4 19.21

C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75

6 2 114 178,148 2,549,104 1824.7 105.7 7.3 442.7 3.1 3.5 3.9 314.1 81.2 29.9 226.8 13.5 0.03 4.23 45.5 0.14 <5 24.9 15.35
7 1 42 182,416 2,552,332 1231.5 69.1 7.5 456.9 1.5 0.3 123.3 87.3 177.2 36.1 68.6 3.8 0.00 0.10 <10 <0.01 – – 27.42
7 2 98 182,416 2,552,332 562.3 108.0 7.5 313.8 0.9 0.3 3.0 16.9 57.9 10.0 60.2 3.3 0.01 0.70 10.8 0.02 <5 6.0 21.63
7 3 147 182,416 2,552,332 610.0 127.0 7.5 339.0 0.8 0.8 8.8 9.8 37.8 13.2 59.2 3.6 0.00 0.47 <10 0.02 <5 <5 26.57
8 1 54 177,117 2,553,431 1020.0 136.0 8.0 536.8 4.9 3.6 <2.3 13.5 10.9 5.9 219.6 13.9 0.31 1.09 135.6 <0.01 – – 5.02
8 2 120 177,117 2,553,431 1759.7 171.7 7.5 693.1 11.5 9.3 3.4 237.4 31.4 17.4 346.6 10.1 0.35 0.85 304.1 0.01 <5 1081.5 5.81
8 3 204 177,117 2,553,431 902.0 63.6 7.2 391.8 1.1 0.8 2.6 48.6 55.2 13.7 122.9 3.0 0.00 0.06 <10 0.01 <5 <5 9.94
9 1 33 175,430 2,556,230 828.0 123.9 7.9 458.4 3.4 3.2 <2.3 8.2 17.4 14.0 159.9 9.9 0.11 0.82 121.7 <0.01 – – 0.27
9 2 93 175,430 2,556,230 1694.3 169.7 8.4 915.4 12.8 5.2 <2.3 48.3 3.8 3.4 394.8 10.0 0.67 0.73 459.3 0.02 <5 2772.4 3.45
9 3 177 175,430 2,556,230 901.7 120.2 7.1 496.4 10.6 9.9 3.1 38.1 59.3 20.2 123.6 4.4 0.26 2.98 100.6 0.01 <5 1243.1 16.27
9 4 203 175,430 2,556,230 711.7 139.1 7.7 400.0 2.1 3.1 4.3 5.0 31.1 20.2 100.6 10.0 0.10 1.02 166.0 <0.01 <5 183.6 10.54
10 1 30 169,053 2,553,702 48300.0 217.0 7.1 669.0 4.8 64.1 576.5 17955.5 314.2 871.9 9562.8 430.8 0.02 2.21 88.7 <0.01 – – 7.38
10 2 68 169,053 2,553,702 42533.3 210.5 7.6 294.7 3.7 63.9 946.4 24085.5 344.4 857.1 10033.3 501.5 0.04 1.73 68.1 0.03 <5 9.8 18.78
10 3 167 169,053 2,553,702 2476.7 165.3 7.1 679.2 10.3 14.3 4.2 618.5 41.4 42.2 424.0 8.1 0.75 2.48 270.9 0.01 <5 39.6 17.61
10 4 227 169,053 2,553,702 18804.7 287.0 7.3 527.1 4.9 39.3 394.2 1856.7 156.5 23.3 3613.7 68.4 0.29 1.61 107.4 0.03 <5 526.0 43.81
11 1 36 178,501 2,558,459 791.7 84.7 7.2 318.8 1.0 1.6 65.3 961.9 95.9 27.0 31.6 3.5 0.04 2.86 10.1 0.03 <5 46.0 82.09
11 2 102 178,501 2,558,459 929.7 125.8 7.1 497.8 4.1 11.8 71.9 15.7 67.9 21.8 91.3 4.0 0.45 2.73 122.2 <0.01 <5 823.8 25.13
12 1 45 176,201 2,559,721 723.5 78.2 8.0 425.3 1.5 6.7 5.0 10.1 28.2 25.5 95.3 21.9 0.32 0.48 32.0 <0.01 – – 13.22
12 2 113 176,201 2,559,721 1145.0 82.4 7.5 569.1 5.1 7.0 4.0 56.9 26.4 22.1 192.8 8.9 0.51 4.91 136.8 0.05 <5 512.6 7.63
12 3 167 176,201 2,559,721 647.0 98.3 7.6 388.4 1.7 1.5 2.7 3.8 50.2 11.2 89.1 3.7 0.00 0.90 34.2 0.04 <5 <5 14.66
12 4 213 176,201 2,559,721 661.3 57.2 7.7 387.1 1.6 1.0 2.9 3.3 45.0 10.8 97.0 4.3 0.00 0.91 32.6 0.04 <5 <5 11.62
13 1 26 167,156 2,558,381 2730.0 204.5 7.6 635.9 2.4 3.9 18.5 535.0 98.3 43.8 404.3 36.9 0.05 1.35 39.8 <0.01 – – 10.70
13 2 61 167,156 2,558,381 60743.3 139.0 7.2 216.8 2.9 21.6 3304.3 35232.4 716.6 2140.1 17888.3 861.9 0.01 2.81 37.9 0.02 <5 <5 8.64
13 3 239 167,156 2,558,381 919.7 193.0 7.7 583.1 4.5 3.5 4.4 14.2 26.9 13.9 178.0 5.8 0.18 1.39 136.7 0.02 <5 <5 7.92
13 4 283 167,156 2,558,381 1133.0 191.3 7.6 601.6 4.5 5.1 4.3 86.4 34.4 25.2 207.9 8.9 0.11 4.41 102.6 0.01 <5 346.5 9.32
14 1 64 158,802 2,556,075 59900.0 410.3 7.5 603.2 3.4 102.7 2069.2 37609.4 518.4 2445.4 19229.3 922.3 0.21 1.34 44.5 188.00 <5 8.7 8.24
14 2 224 158,802 2,556,075 29700.0 243.7 7.1 542.0 8.8 58.8 18.4 12499.1 271.7 561.4 6618.2 304.3 0.11 24.41 204.6 0.01 <5 83.4 7.58
15 1 32 154,146 2,556,442 80350.0 130.0 7.6 330.9 2.5 39.5 3744.1 34356.2 743.2 2376.6 17496.5 1141.1 0.07 4.06 44.3 <0.01 – – 7.90
15 2 209 154,146 2,556,442 14770.0 389.7 7.7 1135.0 28.1 21.6 423.9 3888.1 92.7 296.2 2782.1 163.5 0.60 0.97 650.4 3.26 <5 2433.0 0.75
15 3 278 154,146 2,556,442 2780.0 236.3 8.4 1110.0 25.3 6.1 <2.3 418.0 5.1 3.5 626.3 26.0 0.15 5.27 392.0 0.04 <5 205.9 3.36
16 1 33 158,102 2,565,025 77133.3 296.7 8.4 69.2 3.7 9.6 8062.3 48163.7 652.0 2569.6 23880.3 1313.6 0.18 1.22 123.3 0.07 <5 <5 10.58
16 2 231 158,102 2,565,025 1589.3 276.3 7.4 920.6 14.6 8.8 <2.3 70.7 21.5 17.3 362.9 6.3 0.78 1.55 376.3 0.03 <5 42.0 1.54
17 1 33 162,586 2,561,292 49000.0 161.5 7.4 338.6 4.3 53.6 1051.7 18465.2 430.6 975.8 9600.9 440.2 0.03 5.34 56.1 <0.01 – – 7.86
17 2 106 162,586 2,561,292 39783.3 249.7 7.3 229.7 6.3 73.1 25.8 21240.8 402.8 854.6 11291.7 448.3 0.24 32.34 186.0 14.10 18.5 <5 6.89
17 3 133 162,586 2,561,292 23583.3 217.3 7.1 425.8 12.7 62.1 24.4 10768.4 237.4 474.1 5339.1 207.6 0.19 6.91 362.0 0.14 <5 17.6 10.80
17 4 232 162,586 2,561,292 1203.3 215.7 7.8 690.5 9.5 9.5 4.5 54.2 10.7 6.5 266.8 5.1 0.52 1.02 362.0 0.02 <5 620.2 3.48
18 1 42 171,010 2,561,511 683.0 112.0 7.5 328.0 1.0 1.6 126.8 37.3 46.1 47.9 40.1 5.3 0.02 2.02 <10 0.08 530.5 278.1 34.69
18 2 209 171,010 2,561,511 5755.0 142.5 7.1 397.5 9.4 15.3 8.1 2006.0 164.5 117.7 941.0 24.2 0.12 10.43 86.1 0.59 79.5 <5 15.68
19 1 30 167,942 2,567,431 41500.0 293.0 7.7 467.3 2.5 60.3 335.7 15573.5 308.3 666.0 8268.7 348.7 0.09 0.88 38.0 <0.01 – – 7.49
19 2 126 167,942 2,567,431 9120.0 132.5 7.3 481.8 13.8 48.8 6.8 3716.4 180.7 201.9 1798.9 87.4 0.07 7.41 278.7 0.01 <5 185.8 12.95
 19 3 190 167,942 2,567,431 6166.7 167.0 7.0 480.5 12.5 27.3 6.5 2381.5 571.1 131.4 1138.4 52.1 0.23 7.31 284.7 0.02 10.3 462.8 10.61
19 4 250 167,942 2,567,431 1466.0 206.0 7.8 604.2 5.9 10.4 4.7 160.6 23.0 14.1 301.9 8.7 0.19 4.81 122.1 0.01 63.6 <5 1.85
20 1 40 174,375 2,565,395 749.0 95.3 7.6 385.0 2.3 0.5 2.8 17.2 95.0 36.4 32.9 6.1 0.00 1.23 10.8 <0.01 – – 31.83
20 2 110 174,375 2,565,395 5730.0 152.0 7.3 410.0 15.9 39.1 3.2 5177.0 78.8 205.5 2816.0 104.7 0.09 3.01 492.0 0.01 <5 98.0 7.90
20 3 194 174,375 2,565,395 4200.0 113.5 6.9 365.0 5.5 13.0 3.4 2445.0 90.9 94.9 1217.5 49.8 0.12 4.70 84.5 0.01 <5 28.1 13.34
21 1 65 181,773 2,565,588 825.5 156.0 7.6 451.5 1.7 2.1 2.5 9.6 37.9 17.4 132.1 5.2 0.02 0.67 29.0 <0.01 – – 6.78
21 2 102 181,773 2,565,588 948.7 97.5 7.3 578.3 2.4 3.4 3.7 11.2 14.1 7.3 198.1 6.8 0.01 1.02 33.7 0.02 <5 <5 3.67
21 3 185 181,773 2,565,588 902.7 144.0 7.7 490.2 2.0 2.4 26.3 24.9 24.4 7.6 184.5 6.1 0.01 0.50 44.4 0.04 <5 8.4 1.32
22 1 63 182,708 2,569,605 1890.0 209.0 7.5 608.0 5.2 11.5 3.9 288.0 40.0 29.0 314.0 23.1 0.02 1.71 128.2 <0.01 – – 8.26
22 2 174 182,708 2,569,605 855.0 159.0 7.6 431.5 1.5 3.4 4.3 58.9 44.6 30.4 109.5 7.4 0.01 1.18 30.1 0.03 <5 14.8 17.59
22 3 222 182,708 2,569,605 838.0 174.0 7.7 491.0 1.1 2.0 48.5 32.5 16.6 8.9 167.0 3.9 0.04 0.84 14.6 0.02 <5 40.3 8.61
23 1 30 173,545 2,570,238 4035.0 141.0 7.4 696.5 2.5 6.5 54.8 930.1 66.8 31.2 753.2 24.4 0.11 1.41 63.6 <0.01 – – 4.22
23 2 114 173,545 2,570,238 3756.0 147.7 7.2 706.9 11.3 22.1 4.7 1262.4 48.1 59.7 801.1 24.8 0.11 2.10 387.5 0.04 <5 24.4 11.72
23 3 182 173,545 2,570,238 3810.0 141.0 7.2 722.0 12.0 20.3 4.6 1160.6 45.9 53.4 790.6 29.5 0.11 1.75 323.8 0.01 <5 212.7 9.55
23 4 228 173,545 2,570,238 3300.8 134.0 7.4 717.1 9.6 22.3 5.0 1278.1 50.3 60.2 901.4 34.1 0.18 1.60 363.8 0.01 <5 226.5 6.55
24 1 18 178,884 2,575,010 1006.7 67.3 6.8 417.7 2.5 8.3 80.0 63.3 92.5 27.5 84.0 13.3 0.01 2.61 14.4 0.02 <5 <5 22.59
25 1 48 184,263 2,576,361 944.0 186.0 7.8 493.9 4.8 8.1 1.9 14.2 9.9 10.8 194.2 11.7 0.30 1.05 119.5 <0.01 – – 12.66
25 2 116 184,263 2,576,361 389.0 148.0 7.1 333.0 1.1 5.2 2.4 10.0 40.0 12.2 47.6 3.5 0.02 1.23 41.9 <0.01 <5 19.4 3.32
25 3 172 184,263 2,576,361 671.3 208.7 7.8 403.1 1.8 3.6 <2.3 4.3 22.6 16.2 105.8 9.4 0.14 1.30 39.5 <0.01 <5 222.1 32.80
25 4 240 184,263 2,576,361 566.0 82.0 7.6 391.0 1.1 3.6 2.4 12.9 28.8 12.8 73.0 7.1 0.04 0.64 14.0 <0.01 <5 49.8 10.52
26 1 32 158,374 2,576,594 31280.0 151.3 7.4 303.2 4.1 43.0 1024.3 16737.3 257.6 797.8 8472.6 399.8 0.08 3.08 39.8 <0.01 <5 <5 26.06

C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75

26 2 198 158,374 2,576,580 1522.3 223.0 7.9 824.9 13.7 6.3 4.2 172.4 12.8 10.1 363.2 12.7 0.15 1.17 253.5 0.16 <5 230.2 9.54
27 1 50 164,163 2,577,533 71500.0 402.0 7.6 558.6 11.0 39.2 2627.4 29626.5 637.5 2071.5 16071.0 947.3 0.12 0.20 139.5 <0.01 – – 5.48
27 2 119 164,163 2,577,533 1569.0 188.7 7.6 646.7 7.9 19.5 5.2 170.3 24.9 21.9 287.4 18.0 0.53 1.03 227.5 0.04 <5 972.4 5.18
27 3 168 164,163 2,577,533 1383.7 150.3 7.3 687.7 6.5 7.5 2.9 98.3 29.8 16.1 265.7 7.2 0.34 1.61 182.8 0.02 <5 540.3 5.84
28 1 26 179,177 2,582,776 774.0 102.6 7.5 348.7 1.5 2.5 86.7 17.4 67.5 39.2 42.4 8.9 0.05 2.55 18.7 <0.01 – – 6.08
28 2 86 179,177 2,582,776 1554.7 141.0 7.5 552.4 5.1 7.3 3.3 211.8 33.6 20.1 272.2 14.2 0.03 1.51 131.2 <0.01 <5 47.6 28.34
28 3 128 179,177 2,582,776 1053.0 135.5 7.8 426.2 3.4 4.2 4.4 110.0 52.2 15.7 155.8 9.9 0.04 0.41 130.8 <0.01 <5 94.2 7.16
28 4 239 179,177 2,582,776 1299.3 104.8 7.5 509.4 3.8 6.8 3.1 168.4 29.2 17.7 160.4 11.4 0.04 0.86 94.9 <0.01 <5 22.9 11.64
*
-: Not detected.
2
*
The method limit of detections in Alk, TOC, NHþ  2+ 2+ + + 
4 , SO4 , Cl , Ca , Mg , Na , K , As, Fe, FI, HS , As(III) and As(V) are 3.4 mg/L, 0.17 mg/L, 0.02 mg/L, 2.3 mg/L, 1.3 mg/L, 2.09 mg/L, 0.5 mg/L, 1.24 mg/L, 0.22 mg/L, 0.005 mg/L, 0.04 mg/
L, 10 lg/L (Q.E.), 0.01 mg/L, 5 lg/L and 5 lg/L, respectively.
a
The longitude and latitude are 2-degree transverse Mercator in Taiwan national grid.
b
FI: Fluorescence intensity.

63
64 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75

The As and Fe contents of these samples were analyzed following
EPA 3050B using 30% H2O2 to remove organic matter, and 9.6 M
HCl was used for all core samples digestion to determine As con-
tents. Following the filtering process, all of the samples’ As concen-
trations were analyzed using an electro-thermal atomic absorption
spectrometer (AAS) and a flow injection analysis system (FIAS). A
mixture of 0.5% NaBH4 in 0.25% NaOH and 1 M HCl was added to
reduce the arsenic to arsine (AsH3). In addition, 30% H2O2 was used
to remove organic matter, and HNO3 digested the core samples to
acquire the Fe content. Following filtering, the Fe concentrations in
the samples were analyzed using a flame atomic absorption spec-
trometer (Flame-AAS).
A high-resolution X-ray photoelectron spectroscopy (HR-XPS)
(PHI Quantera SXM) equipped with a Ka X-ray beam at 3.8 kW
generated from an Al rotating anode was used to characterize solid
surfaces. Each spectrum was obtained by plotting the measured
photoelectron intensity as a function of the binding energy (BE).
The BEs of the photoelectrons were calibrated by referencing the
aliphatic adventitious hydrocarbon C (1s) peak at 284.6 eV. The
elemental compositions of the mineral grains were determined
using scanning electron microscopy (SEM) and energy-dispersive
spectroscopy (EDS) with an S-3000 N instrument. The amounts of
the various elements (e.g., Si, Al, Fe, Ca, K, and Mg) in the core sam-
ples were determined by X-ray fluorescence (XRF) (Spectro XE-
POS). The constituent minerals of the sediments were identified
using X-ray diffraction (XRD) (Bruker D8).
Sequential extraction using freeze-dried sediments was con-
ducted to determine the As and Fe contents in the operationally
defined mineral phases (Keon et al., 2001). Forty millimeters of
each extractant was added to 1.0 g dried sediment in a 50 mL

(a) Aquifer 1 (depth: 0-80 m) (b) Aquifer 2 (depth: 80-120 m)

(c) Aquifer 3 (depth: 120-210 m) (d) Aquifer 4 (depth: >210 m)

Fig. 2. Piper diagram of different aquifers in the Chianan Plain.
 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75 65

centrifuge tube. The suspensions were shaken for a specified time As concentration in the groundwater samples (ppb)
and the supernatant was decanted. These procedures targeted 0 100 200 300 400
0
weakly adsorbed As (1 mol/L MgCl2, pH 8; MG step), strongly ad-
sorbed As (1 mol/L NaH2PO4, pH 4–5; PHOS step), As coprecipitat- Sediment core sample
ed with carbonates, acid volatile sulfides, amorphous metal oxides Groundwater samples
and magnetite (1 mol/L HCl followed by 0.2 mol/L oxalic acid, pH
3; HCl and OX steps), As coprecipitated with crystalline Fe oxides
and amorphous sulfides (0.5 mol/L titanium chloride–sodium cit-
rate–tetrasodium EDTA-bicarbonate, pH 7; TiCEB step), As copre- -100
cipitated with silicate minerals or As2O3 (10 mol/L HF; HF step),

Depth (m)
and As incorporated in pyritic phases (concentrated HNO3; NIT
step). A final hot concentration of HNO3 and H2O2 digest (EPA
3050B) of the residue targets As incorporated in crystalline sulfides
such as orpiment and other recalcitrant phases (HOT NIT step;
USEPA, 1997). These extraction steps are hereafter referred to as -200
MG, PHOS, HCl, OX, TiCEB, HF, NIT, and HOT NIT, respectively, as
classified by Swartz et al. (2004).

2.5. PHREEQC model

The geochemical program (PHREEQC Interactive version 2.17) -300

was based on the WATEQF4f database and was used to calculate 0 20 40 60 80 100
the distribution of the aqueous species (Parkhurst, 1995). In addi- As concentration in the sediment core samples (ppm)
tion, the program was based on an ion-associated aqueous pro-
gram and was designed to perform a wide variety of aqueous Fig. 3. Vertical distribution of As concentrations in the groundwater and sediment
core samples.
geochemical calculations. PHREEQC can handle problems of envi-
ronmental pollutants speciation, and it can also determine which
solids might precipitate, based on saturation index (SI). The SI is
Table 2
defined as the logarithm of the ratio of ion activity product (IAP)
The arithmetic mean values of TOC, As, Eh, Alk, and FI in various aquifers in the
of component ions for a solid in solution, to the solubility product Chianan Plain.
(Ksp) of the solid, SI = log (IAP/Ksp). Negative and positive SI values
Aquifer TOC (mg/L) As (mg/L) Eh (mV) Alk (mg/L) FI (lg/L)(Q.E.)
represent the potential for dissolution and precipitation, respec-
tively (Nordstrom and Alpers, 1999). In this study, the data from 1 3.1 0.087 166.6 407.5 52.1
2 7.1 0.230 147.8 521.0 202.0
8 groundwater samples were selected based the groundwater flow
3 7.9 0.192 171.9 543.9 179.7
path to illustrate the variation of arsenic speciation and mineral 4 8.0 0.226 203.5 650.6 189.9
saturation of the groundwater in the Chianan Plain. Notably, the
location of Well 27 was in blackfoot disease area. Well 9 has the
highest As concentration. The SEM result showed that iron carbon-
salinization on promoting the release of sedimentary As. Respect-
ate minerals only in Well 12. Fifteen analytes from the 8 ground-
able cation and anion contents increased the ion strength in
water samples were used in the calculation, including pH, Eh,
groundwater and induced As desorption (Keon et al., 2001; Appelo
temperature, Alk, SO2  2+ 2+ + +
4 , Cl , Ca , Mg , Na , K , As, Fe, Mn, NH4 ,
þ
et al., 2002). The dominance of alkali carbonate type water re-
and HS. The thermodynamic database used for the calculations
flected the slow deposition of fine particles, leading to the en-
was from the WATEQF4f which was the same as that used by Wang
hanced sediment–water interaction (Halim et al., 2009). The high
et al. (2007).
prevalence of alkali carbonate water in the Chianan Plain is attrib-
uted to the poor hydraulic property of the subsurface.
3. Results and discussions

3.1. Piper diagram analysis 3.2. Factorial analysis

The hydrochemical data of the 83 analyzed groundwater sam-
ples are listed in Table 1. Fig. 2 shows the plot of a Piper diagram
for the various aquifers in the Chianan Plain. According to the clas-
sifications of the Piper diagram, Type I represented the carbonate/
temporary hardness, Type II represented the alkali carbonate, Type
III represented the non-carbonate/permanent hardness, and Type
IV represented saline (Piper, 1953). Seawater intrusion caused
the salinity water (Type IV) to enter the shallow aquifer. However,
the source of saline in the deep aquifer may have been the mixing
of marine strata and ancient seawater. The Piper diagram indicated
that the principal water type in the Chianan Plain is Type IV
(n = 39), followed by Types II (n = 32), I (n = 11), and III (n = 1).
Widespread saline water in the Chianan Plain indicated severe sali-
nization in the subsurface, especially in the upper 3 aquifers (Fig. 2;
Nath et al., 2008). Furthermore, the saline water samples contained
high As concentrations, potentially indicating the effect of
The eigenvalues of the 4 main factors were identified when the
eigenvalues exceeded 1, and they explained 85.17% of the total var-
iance. The loadings for the varimax-rotated factor matrix for the 4
main factor models and the terms ‘‘strong’’ and ‘‘moderate,’’ when
applied to the factor loadings, refer to the absolute loading values
of >0.75 and 0.75–0.5, respectively. This study selected factor load-
ings that exceeded 0.5 as parameters to elucidate the relationships
among the hydrochemical data. Factor 1 was the salinization factor
with Na+, Mg2+, Cl, K+, SO2 2+
4 , Ca , and EC that had strong positive
loadings and explained 46.44% of the total variance. The strong po-
sitive items were the dominant components of the seawater. Be-
cause the Chianan Plain is located near the Taiwan Strait,
excessive pumping of groundwater in the Chianan Plain has led
to seawater intrusion and land subsidence over the past several
years. Furthermore, the Chianan Plain has the largest salt produc-
tion fields in the coastal region of Southwest Taiwan. Infiltration
66 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75

2620000 2620000

2610000 2610000

500 18
2600000 2600000 17
460 16
420 15
2590000 380 2590000 14
13
340 28 12
2580000 300 2580000 11
26 27
260
25 10
24
9
220 23 8
2570000 180 2570000 7
16 20 21
140 6
18 17 5
100 12
2560000 13 11 2560000 11 4
14 9
60 3
10 8
20
7 2
2550000 4 2550000 3 6 1
5 -20 5
0
2
-60 -1

2540000 2540000

2530000 2530000
150000 160000 170000 180000 190000 200000 150000 160000 170000 180000 190000 200000
Aquifer 1 (depth: 0-80 m) Aquifer 2 (depth: 80-120 m)

2620000 2620000

2610000 2610000

110 190
2600000 105 2600000 180
100
95 170
90 160
2590000 85 2590000 150
80 140
75 130
28 28
70
120
2580000 65 2580000
26 27
25 60 25 110
24 55 100
50 90
23 22 45 23 22
2570000 2570000 80
19 40 19
20 21 70
35 16
30 60
17 18 17
12 25 12 50
2560000 20 2560000 13 40
15 9 15 14
15 30
10 8 10 10
7 20
5
2550000 3 4
0 2550000 3 4 10
-5 0
-10 -10
1 1
2540000 2540000

2530000 2530000
150000 160000 170000 180000 190000 200000 150000 160000 170000 180000 190000 200000
Aquifer 3 (depth:120-210 m) Aquifer 4 (depth: >210 m)

Fig. 4a. Spatial distributions of As(III) concentrations (ppb) in the different aquifers.

from salt fields has caused the groundwater to having a high
salinization.
Factor 2 was arsenic, which had strong positive loadings on As
(0.78), Alk (0.75), TOC (0.94), and FI (0.94), and explained 21.47% of
the total variance. Alkalinity and TOC are closely associated with
inorganic or organic carbon in reducing condition groundwater.
The mobilization of the adsorbed As with dissolved carbonate
has been proposed as one of the chief causes of the high levels of
As in the groundwater (Appelo et al., 2002; Anawar et al., 2003,
2004). The As-enriched groundwater was strongly correlated with
 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75 67

2620000 2620000

2610000 2610000

2600
280
2600000 2600000 2400
260
240 2200

220 2000
2590000 2590000
200 1800
180 28 1600
2580000 160 2580000 27 1400
26 25
24 140 1200
120
23 1000
2570000 100 2570000
20 21 800
16 80
18 600
60 17
12
2560000 13 11 2560000 11 400
40 9
14
10 20 200
8
7
0 0
2550000 4 2550000 3 6
5 -20 5 -200
2
-40 -400

2540000 2540000

2530000 2530000
150000 160000 170000 180000 190000 200000 150000 160000 170000 180000 190000 200000
Aquifer 1 (depth: 0-80 m) Aquifer 2 (depth: 80-120 m)

2620000 2620000

2610000 2610000

2600 950
2600000 2500 2600000
2400 900
2300 850
2200 800
2100
2590000 2000 2590000 750
1900 700
28 1800 28 650
1700
1600 600
2580000 27 1500 2580000 550
26 25 25
24 1400 500
1300
1200 450
23 22 23 22
2570000 1100 2570000 400
19 1000 19
20 21 16 350
900
800 300
17 18 17
12 700 12 250
2560000 600 2560000 13 200
15 9 500 15 14
10 400 10 150
8
7 300 100
4 200 4 50
2550000 3 100 2550000 3
0 0
-100 -50
1 1
2540000 2540000

2530000 2530000
150000 160000 170000 180000 190000 200000 150000 160000 170000 180000 190000 200000
Aquifer 3 (depth: 120-210 m) Aquifer 4 (depth: >210 m)

Fig. 4b. Spatial distributions of As(V) concentrations (ppb) in the different aquifers.

the fluorescent intensity of the humic substances in the Chianan
Plain (Lu et al., 1975, 1990). Dissolving carbon may influence
adsorption or precipitation by competing for sites on sediment sur-
faces or metals. Harvey et al. (2002) indicated that dissolved car-
bon in groundwater in Bangladesh was positively correlated with
arsenic content, concluding that the mobility of As was closely
related to the inflow liable of carbon, either through competition
of sorption by carbonate or by the organic carbon-driven reduction
of Fe oxide. The reductive dissolution of As-containing Fe oxide
was catalyzed by the microbially mediated oxidation of NOM
(e.g., nature organic carbon) (McArthur et al., 2001, 2004; Mukher-
jee and Fryar, 2008). The competitive exchange of adsorbed As has
68 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75

been proposed as one of the leading causes of high levels of As in 2

Logarithm arsenic concentration (log mg/kg)

groundwater, especially in carbonate complexes and dissolving
carbon (Anawar et al., 2003, 2004; Kim et al., 2000). Generally,
the areal distributions of the arsenic increase from the recharge 1
area (east of the plain) to the downstream coastal area, with the
exception of the uppermost aquifer. The vertical distributions of
the arsenic demonstrate that the aqueous arsenic concentrations 0
in the second aquifer are high (depth 80–120 m). However, the so-
lid-phase As concentrations increase with depth (Fig. 3). When the
As, Alk, redox potential, TOC, and FI in the 4 aquifers in the Chianan -1
plain were averaged, the As, Alk, TOC, and FI in the first aquifer
were all smaller than those in the second, third, and fourth aquifers
(Table 2). Mixing with infiltrated surface water may cause the low -2
values contained in the first aquifer. Furthermore, Factors 1 and 2
of the Chianan Plain were similar to those found in the Southern
Choushui River alluvial fan (Taiwan), and were denoted, regardless -3
of differences between the factorial compositions (Liu et al., 2003). Clay and Silt Sand and Gravel
Factor 3 was sulfide, which had a strong positive loading on Fig. 6. The box-plot of the logarithm arsenic concentration in the clay/silt and sand/
HS, a moderate positive loading on NHþ 4 , and a moderate negative gravel.
loading on Eh, explaining 9.52% of the total variance. The negative
correlation of the sulfide and Eh indicated that the redox potential
is closely associated with the redox couple of SO2 
4 /HS . Factor 4

Logarithm arsenic concentration (log mg/kg)

2
was iron, which had a strong positive loading on Fe and a moderate
negative loading on pH, explaining 7.74% of the total variance. The
results may be confirmed that pH decreases with increasing Fe(II) 1
(Stumm and Morgan, 1981). However, the significant correlation
between pH and Fe may be caused by complicated geochemical
reactions. 0

3.3. Distribution of arsenic species and redox potential -1

Natural groundwater is typically found in reducing conditions.

2
Total inorganic As(III) such as H3AsO3, H2 AsO 3 , HAsO3 , and -2
AsO23 are normally the dominant arsenic species (Smedley and
Kinniburgh, 2002). Figs. 4a and 4b shows that high As(III) concen-
trations were only found in Aquifer 1, and that the other aquifers -3
were dominated by As(V). There are two possible explanations Marine Non-marine
for these results. First, the need to pump groundwater for agricul-
Fig. 7. The box-plot of the logarithm arsenic concentration in the clay/silt and sand/
tural and aquacultural purposes is substantial in the Chianan Plain,
gravel.
and this activity may have introduced excess oxygen into the
groundwater, altering the redox condition. The oxidation of As(III)
by dissolved oxygen is particularly slow ranging from several effect on redox potential. The Ehs were thus all negative and exhib-
months to a year (Johnson and Pilson, 1975). In addition, As3+ ited in a reducing condition. Second, the Chianan Plain has a higher
and As5+ are not the primary redox couple and only have a mild FI than other As-contaminated areas (Lu, 1990). The results of FA
showed that FI and As were highly correlated (R2 = 0.45). As(III)
0 is normally the dominant arsenic species in groundwater, under
-50 reducing condition. However, As(V) dominated in the almost all
the deep aquifers, which were located in the down-gradient side
-100
and long residence time of groundwater. Hence, this study pro-
measured Eh (mV)

-150 posed that the chelation of As by fluorescent humus substances

-200
is a major factor of high As in groundwater, especially for As(V),
causing BFD in the coastal area of the Chianan Plain. According
-250 to Peng et al. (2010) reported that high HA concentration have high
-300 chelating affinity with As(V), result in enrichment of As(V) and HA
concentrations. Jiang et al. (2009) showed that semiquinone radi-
-350
cals are produced during the microbial or chemical reduction of
-400 humic substances. Model quinones are strongly oxidant and can
oxidize As(III) to As(V), thereby decreasing As mobility. This ex-
-450
-600 -400 -200 0 200 plains the occurrence of oxidized As(V) in the anoxic environment.
calculated Eh (mV) Therefore, most of the aquifers in the Chianan Plain are dominated
by As(V).
HS-/SO42- Fe2+/Fe3+ As3+/As5+ Fig. 5 shows a comparison of the measured Eh values and calcu-
lated Eh values of three redox couples (Fe2+/Fe3+, As3+/As5+, and
Fig. 5. Comparison of measured Eh values (blue dotted line) and calculated Eh SO2 
4 /HS ). The redox potential calculated by the iron and arsenic
values of sulfur, arsenic, and iron species. couples departed from the results of the Eh measurement,
 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75 69

(a) (b)

(c) (d)

Fig. 8. Correlations between the arsenic and iron in wells 4(a), 13(b), and 23(c) where the sediment were all in fine grains of non-marine formations; 27(d) was in fine grains
and marine formation.

Table 3
Major elements (g/kg), As, and Mn (mg/kg) contents of core samples (n = 20).

Sample 9 9 9 9 9 13 13 13 13 13
Depth (m) 80 90 130 160 200 20 55 235 270 280
Si 654.9 693.1 623.1 717.8 575.3 690.1 730.4 683.7 694.9 711.1
Al 172.8 119.8 123.4 100.9 125.6 168.5 141.1 152.0 165.0 133.8
Fe 61.4 48.0 53.4 42.7 56.8 48.6 37.3 54.7 44.4 52.8
K 53.6 38.6 36.3 35.6 35.7 54.5 48.4 47.0 50.2 45.5
Ca 33.5 85.6 150.2 92.1 189.2 26.5 29.4 45.1 26.9 43.4
Mg 11.7 4.2 4.1 4.0 4.0 3.7 4.1 7.6 9.0 3.9
Ti 11.5 8.1 8.0 6.3 8.3 7.8 8.6 8.4 7.8 7.7
S 0.6 2.7 1.5 0.6 5.0 0.4 0.7 1.4 1.9 1.6
As 12.5 13.6 13 6.3 39.2 13.8 8.8 8.9 10.0 8.2
Mn 332.4 692.0 1330.0 0.0 0.1 248.6 74.0 940.0 243.4 451.7
Sample 27 27 27 8 8 8 8 8 8 9
Depth (m) 40 110 160 50 90 105 115 185 195 25
Si 635.1 719.5 685.1 663.4 665.9 681.4 664.7 707.3 701.3 646.1
Al 183.0 162.8 164.1 159.6 162.1 144.7 140.9 119.8 146.2 156.4
Fe 61.5 45.5 55.9 53.0 60.7 52.8 59.6 50.7 45.8 61.6
K 58.1 51.9 51.4 49.1 48.7 43.1 42.8 40.6 47.4 46.9
Ca 30.3 6.5 20.2 51.1 46.9 65.6 78.6 70.6 34.5 60.8
Mg 18.3 4.0 4.0 12.6 4.8 4.4 3.8 4.0 14.8 16.9
Ti 10.3 9.3 9.4 9.7 9.4 6.9 8.3 6.7 8.8 9.4
S 3.3 0.4 9.8 1.6 1.4 1.0 1.4 0.3 1.2 1.9
As 28.6 10.3 47.9 13.3 11.6 9.0 17.2 19.0 6.3 8.3
Mn 195.4 9.5 269.3 237.7 983.0 212.1 732.0 219.9 132.0 246.4

indicating that the iron and arsenic species were not the major re-
dox couples or that they were under non-equilibrium chemical con-
ditions. There was a lack of correlation between the measured and
calculated redox potentials. These discrepancies suggest that the
major redox couples considered in this study did not establish the
redox equilibrium in the groundwater of the Chianan Plain. The cal-
culated redox potentials (except by As3+/As5+) and measured redox
potentials all had negative values, indicating that the groundwater
of the Chianan Plain is under an anoxic reducing environment.
3.4. Sediment characteristics and distribution of elements
The arsenic content of the 462 samples had a log-normal distri-
bution and with a geometric mean, geometric standard deviation,
and a minimum and maximum of 5.98, 2.69, 0.001, and
99.72 mg/kg, respectively. The geometric mean (5.98 mg/kg) ex-
ceeded the average concentration found in the crust (1.8 mg/kg)
and was higher than the geometric mean arsenic concentration
of 2.27 mg/kg found in the Southern Choushui River alluvial fan
(Liu et al., 2006). The vertical distribution of the As concentrations
of the 462 sediment core samples typically increased with depth
with 2 peaks in the depths of 170–180 and 240–250 m (Fig. 3).
Based on the grain size of the core samples, the sediments can be
classified into 2 groups: clay/silt and sand/gravel. The logarithms
of the As concentrations for the clay/silt and sand/gravel were
0.81 ± 0.43 mg/kg and 0.74 ± 0.43 mg/kg, respectively (Fig. 6). The
small grain size of sediment materials provides a large surface area,
enabling the high adsorption capacity of arsenic (Smith et al.,
70 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75
Fig. 9a. Correlation of arsenic content and sulfur percentage weight.
Fig. 9b. Correlation of arsenic content and iron percentage weight.
1998) and resulting increased As enrichment of the clay and silt.
Furthermore, the sediment cores represent both non-marine and
marine sequences indicating aggradational sedimentation pattern.
The As concentrations of the non-marine and marine sequences
agree with a log-normal distribution. The logarithms of the As con-
centrations in the non-marine and marine sequences were
0.78 ± 0.44 [log (mg/kg)] and 0.88 ± 0.31 [log (mg/kg)], respectively
(Fig. 7). The sediment structure of the Chianan Plain was formed by
alternating invasions and withdrawals of seawater with interlaid
formations of marine and non-marine sequences over the last
10,000 years. The marine formation contains fine clay with sea
organisms that may have high arsenic content resulting from bio-
accumulation and bioconcentration (Francesconi et al., 1998; Fran-
cesconi and Edmonds, 1997). Sandstone and shale are the primary
sedimentary rocks in the mountain area of eastern Chianan Plain.
High As concentrations were found in the groundwater from the
deep artesian wells (typically 100–280 m) abstracted from the sed-
iments that consisted of fine sand, mud, and black shale (Tseng
et al., 1968). Black shale has a high As concentration because of
its enriched pyrite content (Smedley and Kinniburgh, 2002).
Arsenic in the Chianan Plain might be derived from the Chukou
black shale (Nordstrom, 2002; Hsu et al., 1997) that may contain
As-bearing pyrite. Hence we proposed that the primary As sources
in the Chianan Plain are the terrestrial weathering of As-rich black
shale. Black shale accounts for the majority of high arsenic concen-
trations found in non-marine formations (Nath et al., 2008). The
black shale was widely found in the sedimentary rocks of the Chi-
anan Plain. The sulfide mineral such as pyrite is stable in subsur-
face environment. According to previous studies, the sulfide
minerals facilitate for As sorption or co-precipitation. The main
governing factor on As mobility and transformation in this study
is the chelation of humic complex of groundwater (Peng et al.,
2008).
The results for the As and Fe concentrations of the 462 core
samples showed a nil correlation (R2 = 0.03) in the Chianan Plain.
However, a positive correlation was observed between the As
and Fe concentrations in the marine and non-marine formations
in certain core samples. A highly positive correlation (R2 = 0.75;
p = 0.025) between As and Fe in the fine grains and marine sedi-
ment was found in Well 27. A moderate correlation (R2 = 0.44–
0.57; p < 0.001) for the logarithmic As and Fe concentrations in
the fine grains and non-marine sediment was found in Wells 4,
13, and 23 (Fig. 8). The positive correlations between As and Fe
of coastal marine and inland non-marine sediments are both sig-
nificant. The well correlation between As and Fe concentrations
of core samples, especially in marine sedimentary supports that
the As-contained Fe oxyhydroxides is the sink of aqueous As in
subsurface environment.
Twenty core samples from the intervals in the well screens of 5
wells were selected for the bulk analysis of the elemental distribu-
tion by XRF (Table 3). The main chemical constituents of the sedi-
ments included SiO2, Al2O3, Fe2O3, K2O, CaO, TiO2, and MgO,
accounting for the majority of the samples’ weight. According to
the semi-quantitative results, the correlations between different
elements can be established to understand the characteristics of
As mobility. Sulfur and manganese were the minor compositional
elements, ranging from 187 to 6068 mg/kg, and from 9.5 to
1495 mg/kg, respectively. Among these samples, As content was
significantly correlated with S (R2 = 0.76, p < 0.05; Fig. 9a) and
weakly correlated with Fe (R2 = 0.14, p < 0.05; Fig. 9b), indicating
that the sulfides were the predominant As-host minerals in the
sediments, particularly at the depth of the well screens. A poor cor-
relation between As and Fe was caused by that the occurrence of
many non-As-bearing Fe phases (e.g. phyllosilicates, siderite).
The types of Fe minerals in the collected sediments were char-
acterized using HR-XPS, and the results were presented using 2
curves: (1) the experimental curve following the smoothing pro-
cess, and (2) the curve of the fitted components. The Fe signal
was a doublet because of the spin coupling, and correspaonded
to Fe2p3/2 (B.E. = 706–718 eV) and Fe2p1/2 (B.E. = 723–732 eV).
The results of the Fe2p3/2 lines can be fitted by multiple compo-
nents (Fig. 10). Seven types of Fe minerals were observed, includ-
ing a mixing-valence type (Fe3O4), 4 reducing forms types (FeO,
FeSO4, FeS, and FeCl2), and 2 oxidizing form types (Fe2O3 and FeO-
OH). The reducing form of the Fe mineral phase was dominated by
FeO, FeSO4, and FeS2, in contrast to the oxidizing form in FeOOH.
Furthermore, all of the analyzed samples contained both reduced
and oxidized Fe oxyhydroxides, confirming the redox cycling of
Fe in the shallow aquifers.
Four samples were chosen for further investigation by SEM-
EDS. Pyrite was found in Samples 27 (depth = 160 m) (Fig. 11a),
and Samples 27 (depth = 110 m) were similar to the framboidal-
early-diagenetic samples that were found in Bangladesh (Nickson
et al., 2000). Siderite was found in Samples 12 (depth = 160 m)
(Fig. 11b). The discovery of pyrite and siderites in these core sam-
ples supported the SIs results for these 2 minerals as calculated by
PHREEQC (detailed in Section 3.6).
3.5. Partitioning of As
Sequential extractions were conducted on 42 core samples from
9 wells, revealing that the content of the operationally defined
fractions of the solid phase As was covaried to location and lithol-
ogy, and that the content range for either pool typically spanned
more than one order of magnitude. Table 4 lists the extraction re-
sults of the averages of the As content and the corresponding per-
centages of the total As content. The factors controlling As
partitioning in aqueous/solid phases varied with the hydrogeo-
chemical condition of different areas. Based on previous studies,
 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75 71

Fig. 10. Curve fitting data of the Fe2p3/2 core level. The solid line represents the experimental curve following smoothing and the dotted lines represent the fitted curve.

the Fe(II)/Fe(III), sulfate/sulfide, organic/inorganic carbon cycling as the residue phase and discussed with the last two steps. The
were considered as the main processes of As-riched groundwater extract processes of HF should result in the samples acidity, hence
in the Chianan Plain. The extraction step of HF targets the co-pre- we cannot measure As content in HF extractant. The arsenic
cipitation of As with silicate minerals or As2O3, which is regarded amounts in the MG and HOT NIT extractants were generally small.
72 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75

(b)
(a)

(c) (d)

Element Weight% Atomic%

Element Weight% Atomic%
O 40.81 62.80
C 32.46 50.27
Al 3.41 3.11
O 29.74 34.58
Si 6.62 5.80
Al 0.31 0.21
S 20.32 15.60
Si 0.84 0.56
Fe 28.68 12.64
S 8.88 5.15
As 0.17 0.05
Mn 0.31 0.1
Totals 100.00
Fe 27.18 9.05
As 0.29 0.07
Totals 100

Fig. 11. Scanning electron microscope analysis of Samples 27 (depth = 160 m) and 12 (depth = 160 m) (a) Framboidal-early-diagenetic pyrite in samples 27 (depth = 160 m);
(b) Siderite in samples 12 (depth = 160 m); (c) EDS data of samples 27 (depth = 160 m); (d) EDS data of samples 12 (depth = 160 m).

The NIT extractant contained the highest As content (2.8 mg/kg),
elucidating the As-hosting capacity of sulfide minerals such as pyr-
ite and amorphous As2S3. In addition, the HCl, OX, and TiCEB
extractants accounted for the largest portion of As (59.4%) in the
sediments, revealing that Fe oxyhydroxides contain more As than
do As-bearing sulfides. In addition, the PHOS extractant found a
significant amount of As (14%), suggesting that the competitive ex-
change of reaction ions, such as PO3 2
4 , CO3 and organic C, occurred.
3.6. Aqueous speciation and saturation indices
Tables 5 and 6 present the ratios of the contents of particular
chemical species to the total contents and the resulting saturation
indices for various minerals. The major species of As, C, and S were
2
H3AsO3, HCO 3 , and SO4 , respectively. However, the major Fe spe-
cies were Fe2+, FeHCOþ 3 , and FeCO3 because of the high Alk
(>500 mg/L) in the deeper aquifers.
The SIs values for most of the iron minerals, including goethite,
hematite, magnetite, pyrite, and siderite, were greater than zero,
indicating that these minerals may be precipitated. The XPS
(Fig. 10) and SEM–EDS (Fig. 11) results confirmed these findings.
Although the XRF data showed that As and S were significantly cor-
related, the SI values of the orpiment were all negative, suggesting
that arsenic–sulfide minerals did not form. Arsenic and sulfur iron
can be adsorbed to other minerals’ surfaces to participate in sec-
ondary mineralization processes (Bostick et al., 2003; Wilkin
et al., 2003). The positive SIs of pyrite indicated the potential for
precipitation, that Fe2+ may be co-precipitates with HS, resulted
in low concentration of HS (<0.01–0.04 mg/kg) and low Eh value
(108 to 402 mV) in samples 7, 9 and 27. The results of SEM also
showed that framboidal-early-diagenetic such as Pyrite in Samples
27 (depth = 160 m) and Samples 27 (depth = 110 m).
3.7. Discussion
The high arsenic concentration in the groundwater may be
caused by a geogenic release and anthropogenic activities, such
as the infiltration of arsenic containing industrial agrichemicals
and mining waste (Williams et al., 1996; Bhattacharya et al.,
1997). Liao (1995) indicated that arsenic concentrations in
 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75 73

Table 4
The minimum, maximum, average and standard deviation As contents (n = 42) from sequential extraction.

Mg PHOS HCl OX TiCEB HF NIT HOT NIT Total As

Minimum (mg/kg) 0 0.22 0.37 0.14 0.08 – 0.50 0 2.00
Maximum (mg/kg) 0.38 4.65 8.58 11.44 10.14 – 10.14 0.24 41.78
Average (mg/kg) 0.06 1.38 2.33 1.8 1.94 – 2.81 0.06 10.45
Standard deviation (mg/kg) – 1.18 2.05 2.03 2.29 – 2.25 0.06 7.57
Arithmetic mean percent (%) 0.5 14 23.4 17.3 17.7 – 32.2 0.7 –

Table 5
Ratio of amount of different chemical species contents to the total elemental contents of eight high As groundwater samples in the Chianan Plain modeled using PHREEQC. Input
groundwater chemical concentrations of eight samples were given in Table 1.

Element Species Well 27 27 9 9 9 12 12 12

Layer 2 3 2 3 4 2 3 4
As H3AsO3 100.0 98.3 89.0 99.0 97.0 96.7 94.9 97.2
AsS(OH)(HS) 3.3 2.7
H2 AsO
3 1.7 11.0 1.0 3.0 2.3 2.8
Fe Fe+2 50.7 48.7 42.9 57.1 56.2 52.4 58.4 57.9
FeHCOþ3
39.5 42.5 30.0 38.3 31.6 37.9 31.9 31.3
FeCO3 9.8 8.7 27.0 4.6 12.3 9.7 9.7 10.8
C HCO3 92.7 91.1 97.7 84.8 94.9 92.7 93.5 94.2
CO2 7.3 8.9 1.3 14.2 5.1 7.3 6.5 5.8
S SO2 87.8 91.4 91.0 83.7 87.2 87.67 87.3 88.1
4
MgSO4 6.0 2.8 1.1 6.2 7.0 6.74 4.2 4.4
NaSO4 3.4 2.9 4.5 1.3 2.26
CaSO4 2.7 2.9 0.3 10.1 4.5 3.32 8.5 7.5

Table 6
Saturation index for high As concentration groundwater in the Chianan Plain computed using PHREEQC.

Minerals Formula Well 27 27 9 9 9 12 12 12

Layer 2 3 2 3 4 2 3 4
Goethite FeOOH 2.36 2.39 2.85 1.98 2.48 3.53 3.02 3.81
Hematite Fe2O3 6.73 6.8 7.72 5.98 6.97 9.08 8.06 9.64
Magnetite Fe3O4 8.77 8.85 10.72 7.8 9.36 11.83 10.28 12.79
Orpiment As2S3 5.76 6.57 8.81 6.97 9.74 5.45 9.14 9.44
Pyrite FeS2 10.2 9.84 8.04 9.05 8.1 11.89 11.22 11.69
Siderite FeCO3 0.96 1.1 1.32 0.98 0.95 1.61 0.85 1.7

seawater in the coastal area near the Tsengwen and Ernjen Rivers
were 0.79 and 0.72 ppb, respectively, and 0.85 and 0.26 ppb in the
river water, respectively. These arsenic concentrations are 2–3 or-
ders of magnitude less than that in the groundwater. Chen and Liu
(2007), using the C14 dating, found that the infiltration of the sur-
face water had only reached 40 m in the first aquifer over the last
50 years. Deep groundwater recharge primarily originates from the
eastern mountainous area, and the flow rate is in the range of 1–
5 m/y. The age of the groundwater in the deep aquifer
(depth > 200 m) was 40,000 years, which is close to the age of sed-
imentary formation (Chen and Liu, 2007). Therefore, the cause of
the high arsenic concentration is primarily geogenic release.
Arsenic concentration was positively correlated to Alk, TOC, and
FI, and negatively correlated to Eh. The slow groundwater flow rate
coupled with the strong reducing conditions, resulting in the for-
mation of humic substances during the long-term interaction be-
tween the rich organic sediment and the groundwater. As the
redox potential reached the threshold of the Fe and As reduction,
As-bearing iron minerals were dissolved and might mediated by
microbes and were then reductively dissolved into the groundwa-
ter. The proposed mechanisms of As enrichment in groundwater
include oxidation of As-bearing sulfides, reductive dissolution of
Fe(III) oxyhydroxides, and dissimilatory reduction of As, microor-
ganisms could mediate all of those processes (Guo et al., 2008).
The highest As concentrations were primarily located in the coastal
and central areas (Fig. 1c).
The average arsenic content in the marine (clay/silt) and terres-
trial (sand/gravel) formations was 9 and 8.1 mg/kg, and the marine
formation was the aquitard and the terrestrial formation was the
aquifer (Liu et al., 2006). However, the aquifer and aquitard are
not clearly structured. For example, the aquifer and aquitard ar-
senic contents in Bangladesh are less than 2 mg/kg and approxi-
mately 10 mg/kg, respectively (Swartz et al., 2004). The As and
Fe contents were moderately correlated in the marine and terres-
trial formations. The sequential extraction results showed that
the As content in the Fe phase minerals equaled 58.4% of the total
As in the sediments. The As-bearing pyrite was identified by SEM,
although XRF analysis showed that As was strongly correlated with
S (R2 = 0.76, p < 0.05) and poorly correlated with Fe (R2 = 0.14,
p < 0.05), possibly because the Fe content was much higher than
the S content. The results from HR-XPS analysis and PHREEQC
modeling indicated that the Fe-oxyhydroxides were the major
minerals and that pyrite may be involved in the formation of the
secondary mineral, resulting in poor correlation between Fe and
S. Not only was high As content found in the marine formations,
but also in the terrestrial formations, especially in the border be-
tween the marine and terrestrial areas. Algae and other sea organ-
isms typically have high bioaccumulation capacities for As,
74 C.-W. Liu et al. / Journal of Hydrology 498 (2013) 59–75
resulting in high As content in marine formations (Liu et al., 2006).
In addition, the weathering products of the black shale in the Chi-
anan Plain have a high As content (avg. 44 mg/kg; Huang, 2009).
Although Nath et al. (2008) suggested a link between the mud from
volcanic activity and the As enrichment in the Chianan Plain, but
they have been unable to establish a convincing transport path
for the volcanic mud. Therefore, the As sources in the Chianan Plain
are probably the bioaccumulation of sea organisms for the marine
formations and black shale for the terrestrial formations (Huang,
2009; Selinus et al., 2005).
4. Conclusions
Factorial analysis was used to evaluate the hydrogeochemical
characteristics of the groundwater in the Chianan Plain. Four fac-
tors, including salinization, arsenic, sulfide, and iron, were identi-
fied. The arsenic factor consisted of As, TOC, Alk, FI, and Eh,
indicating that these five items are highly correlated. The high lev-
els of As and FI suggest that the chelation of As by fluorescent hu-
mus substances is a major factor of high As in groundwater,
especially for As(V), causing BFD in the coastal area of the Chianan
Plain. No correlation was found between the measured and calcu-
lated redox potentials, indicating a lack of chemical equilibrium
among the various redox couples. The arsenic species were under
non-equilibrium chemical conditions where the As(III) concentra-
tions were high (e.g., Aquifer 1), and As(V) concentrations were
dominant in Aquifers 2–4. Furthermore, Aquifer 1 had a low ar-
senic concentration compared to other aquifers. The iron oxyhy-
droxides and sulfides contained the majority of the As, as
determined by sequential extraction. The arsenic content was
higher in the clay/silt sediments and marine formations. The As
and Fe contents in the sediments were moderately correlated to
the transitions of the marine and non-marine formations, espe-
cially for the fine grains. The major minerals identified by XPS
and SEM–EDS included goethite, hematite, magnetite, pyrite, and
siderite, which agreed well with the SI values that were calculated
by PHREEQC. A moderate correlation was found between As(s) and
Fe(s) in the sediment transitions of the marine and non-marine for-
mations, especially for the fine grains. The chelation of humic com-
plex, competition for sorption sites of organic carbon, reduction
dissolution of Fe oxides are mainly responsible for the groundwa-
ter As mobility in the Chianan Plain, especially for the marine se-
quence. Previous studies of high As groundwater in the Chianan
Plain mostly focus on As and Fe chemical analyses of groundwater
quality and sediment composition of single or few wells. At pres-
ent, the reductive dissolution of Fe oxyhydroxides are accepted
as the most possible mechanism of As release. However, the
clay-riched marine sedimentary with high organic carbon and
the elevated sulfate content may also affect As mobility. Hence,
the major contribution of this study is to evaluate the influence
of hydrogeochemical characteristics of As, Fe, S, C species on inor-
ganic As(III) and As(V) cycling of the Chianan Plain.
Acknowledgment
The authors are thankful to National Science Council, Govern-
ment of Taiwan, R.O.C, for the financial support of this study under
the contracts NSC 96-2628-B-002-021-MY3, NSC 99-2628-B-002-
042-MY3 and NSC 101-2313-B-002-045-MY2. We are also thank-
ful to National Central University, Tao-Yuan, Taiwan, for assisting
with the SEM and EDX studies.
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