Journal of Hazardous Materials 262 (2013) 980–988

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Linking geochemical processes in mud volcanoes with arsenic mobilization

driven by organic matter
Chia-Chuan Liu a , Sandeep Kar a , Jiin-Shuh Jean a,∗ , Chung-Ho Wang b , Yao-Chang Lee c ,
Ondra Sracek d,e , Zhaohui Li a,f , Jochen Bundschuh a,g , Huai-Jen Yang a , Chien-Yen Chen h
a
Department of Earth Sciences, National Cheng Kung University, Tainan, Taiwan
b
Institute of Earth Sciences, Academia Sinica, Taipei, Taiwan
c
National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan
d
OPV s.r.o. (Groundwater Protection Ltd.), Bělohorská 31, 169 00 Praha 6, Czech Republic
e
Department of Geology, Faculty of Science, Palacký University, 17. listopadu 12, 771 46 Olomouc, Czech Republic
f
Department of Geosciences, University of Wisconsin – Parkside, Kenosha, WI 53144, USA
g
Faculty of Engineering and Surveying & National Centre for Engineering in Agriculture, The University of Southern Queensland, Toowoomba, Australia
h
Department of Earth and Environmental Sciences, National Chung Cheng University, Chiayi 621, Taiwan

h i g h l i g h t s

 Study represents geochemical characteristics and their spatial variability among six mud volcanoes of southern Taiwan.
 Anoxic mud volcanic fluids containing high NaCl imply connate water as the possible source.
 ␦18 O-rich fluids is associated with silicate and carbonate mineral released through water–rock interaction.
 High As content in mud and its sequential extraction showed mostly adsorbed As on organic and sulphidic phases.
 Organic matter specially humic acid showed redox dependence and it may play an important role in binding and mobility of arsenic.

a r t i c l e i n f o a b s t r a c t

Article history: The present study deals with geochemical characterization of mud fluids and sediments collected from
Received 9 December 2011 Kunshuiping (KSP), Liyushan (LYS), Wushanting (WST), Sinyangnyuhu (SYNH), Hsiaokunshui (HKS) and
Received in revised form 9 June 2012 Yenshuikeng (YSK) mud volcanoes in southwestern Taiwan. Chemical constituents (cations, anions, trace
Accepted 25 June 2012
elements, organic carbon, humic acid, and stable isotopes) in both fluids and mud were analyzed to inves-
Available online 1 July 2012
tigate the geochemical processes and spatial variability among the mud volcanoes under consideration.
Analytical results suggested that the anoxic mud volcanic fluids are highly saline, implying connate water
Keywords:
as the probable source. The isotopic signature indicated that ␦18 O-rich fluids may be associated with sil-
Mud volcanoes
Taiwan
icate and carbonate mineral released through water–rock interaction, along with dehydration of clay
Geochemical processes minerals. Considerable amounts of arsenic in mud irrespective of fluid composition suggested possible
Organic matter release through biogeochemical processes in the subsurface environment. Sequential extraction of As
Arsenic mobilization from the mud indicated that As was mostly present in organic and sulphidic phases, and adsorbed on
amorphous Mn oxyhydroxides. Volcanic mud and fluids are rich in organic matter (in terms of organic
carbon), and the presence of humic acid in mud has implications for the binding of arsenic. Functional
groups of humic acid also showed variable sources of organic matter among the mud volcanoes being
examined. Because arsenate concentration in the mud fluids was found to be independent from geo-
chemical factors, it was considered that organic matter may induce arsenic mobilization through an
adsorption/desorption mechanism with humic substances under reducing conditions. Organic matter
therefore plays a significant role in the mobility of arsenic in mud volcanoes.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction

Geothermal environments are considered to be specific geo-

logical tectonic areas throughout the world, having both low
temperature (near atmospheric temperature, such as in the case
∗ Corresponding author. Tel.: +886 6 2757575x65426; fax: +886 6 2740285. with mud volcanoes) and high temperature (higher than atmo-
E-mail addresses: jiinshuh@mail.ncku.edu.tw, jiinshuh@ncku.edu.tw (J.-S. Jean). spheric temperature, such as in the case with hot springs)

0304-3894/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2012.06.050
 C.-C. Liu et al. / Journal of Hazardous Materials 262 (2013) 980–988
conditions. Taiwan mud volcanoes, located mainly in southern
Taiwan, are well known tectonic features linked to subduction
zones [1,2]. In mud volcanoes, mud and fluids, consisting of fine-
grained sediments and consolidated mudstones, are brought up
to the surface from deep sources during eruption periods [3–6].
Formation of a mud volcano is often connected with clay mineral
dehydration, conformation compression, and quick deposition of
sediments such as turbidities and slumps [7–9]. Most studies on
mud volcanoes have described mainly the geochemical character-
istics of mud and fluids [2,10–12] with a notable lack of information
on the geochemical processes conductive to the release and trans-
port of chemical constituents such as arsenic.
Arsenic enrichment and its mobilization in subsurface environ-
ments is a well known phenomenon which causes health concerns
in many parts of the world along with Taiwan [13,14]. The Chianan
plain of southwestern Taiwan, reported to be an arsenic-enriched
region, has also been well associated with mud volcanoes and
geothermal fields [15,16]. Some investigations have suggested that
pyrite oxidation and siderite dissolution were among the possi-
ble As sources in the groundwater of the Chianan plain and the
Choushui River alluvial fan in Southern Taiwan [17,18]. Arsenic is
well known to be adsorbed on Fe or Mn oxide/hydroxide miner-
als in subsurface sediments [13]. As-rich minerals may therefore
release arsenic as a result of weathering of alluvial sediments [19],
and arsenic may subsequently be released into the groundwater
through reductive dissolution of Fe(III) oxyhydroxides under reduc-
ing conditions [15,20,21].
Microbial activity is one of the important factors in the release
of As to groundwater through the Fe-reduction process [22]. Ear-
lier reports have suggested that As(V) can be reduced in an
anoxic environment through an organic matter-driven microbial
reduction mechanism [22]. Humic substances (HS), an important
part of sedimentary organic matter, are abundant in mud sedi-
ments. Humic acid (HA) is the major component of HS produced
by biodegradation of decomposed organic matter during subsur-
face humidification. HS may exist in environments in soluble and
adsorbed forms in both liquid and soil. It is basically a large poly-
mer molecule composed mainly of C, H, O, and N and can form
complexes with many different acids containing carboxyl, phenolic,
and aldehyde groups. There are many kinds of activated functional
groups, bridging bonds, and sponge network textures in HA, serv-
ing to adsorb and complex a variety of metals, metallic oxides, salts,
clay minerals, and some other non-metallic elements [23]. They are
also hydrophilic substances capable of forming a hydrogen bond
and can dissolve more readily in water than in hydrophobic sol-
vents. HA interacts with many pollutants, including heavy metals,
pesticides, and hydrophobic organic compounds. For example, ele-
ments like Ca2+ , Mg2+ , and especially Al, Fe, and Mn are known to
play an important role in bridging the As(V) complexes with HS
[24,25]. Formation of the HA-As complex in groundwater is one
of the principal etiological agents for the occurrence of blackfoot
disease in SW Taiwan [26]. HS is reported to play an active role in
binding with arsenic and in its mobilization [27]. For example, 40%
and 15% of total arsenite and arsenate, respectively, can bind with
soluble HA in the presence of bridging metals [28]. With an initial
concentration of 1000 ␮g L−1 , As in arsenate and arsenite may bind
with HS in 48 h under dark incubation conditions at 25 ◦ C and at a
pH = 6.8 [28]. Negatively charged As species can also compete with
HS for adsorption sites on iron oxide surfaces [29].
Although the geochemical characteristics of mud volcanoes in
Taiwan have been previously well documented, as stated earlier,
these studies were mainly focused on their geological, geochemi-
cal, and mineralogical characteristics [1,2,30,31]. However, organic
matter-rich mud sediment may play a significant role in the
geochemical processes occurring in the subsurface environment
of mud volcanoes. The present study is therefore aimed at an
981
investigation of geochemical variations and processes and their
relationship with organic matter, particularly HS in the mud volca-
noes of southern Taiwan. Possible linkage of As mobilization with
geochemical processes driven by organic matter in these mud vol-
canoes is also investigated.
2. Geological setting of the study area
The mud volcanoes under investigation are located in southern
Taiwan (Fig. 1) at the boundary between the Eurasian continental
plate and the Philippine Sea plate in East Asia. Five major morpho-
tectonic units including the coastal plain, the western foothills, the
Hsueshan Range, the Central Range, and the Coastal Range are sepa-
rated by N-S oriented major thrust faults [32,33]. Six mud volcanoes
from three different geologic formations in southern Taiwan were
included in the present study. The Kunshuiping (KSP) and Liyushan
(LYS) mud volcanoes belong to the coastal plain, and the Wushant-
ing (WST) and Sinyangnyuhu (SYNH) mud volcanoes fall into the
Chishan (CS) fault region. The region between the CS fault and
the coastal plain is called the Kutingkeng anticline, which contains
two mud volcanoes, Hsiaokunshui (HKS) and Yenshuikeng (YSK)
(Fig. 1). All the mud volcanoes have been continuously erupting
gases (mainly CH4 ) and muddy fluids for several years [1].
3. Materials and methods
3.1. Sample collection and analysis
Both mud and fluid samples were collected from six mud vol-
canoes for geochemical analysis. The pH, electrical conductivity,
total dissolved solid (TDS), temperature, salinity, and alkalinity of
fluids were determined in the field. A pH/Eh/Temperature meter
(SP701, Suntex, Kaohsiung, Taiwan) was used to measure the pH, Eh
(redox potential), and temperature. EhS.H.E. values were expressed
with respect to the standard hydrogen electrode. A conductivity
meter (Suntex; WTW, LF320, Germany) was used to measure elec-
trical conductivity, salinity, and TDS. A microprocessor-controlled
Photometer-PC MultiDirect (Lovibond, Germany) was used to mea-
sure alkalinity.
Mud fluids were collected in opaque bottles (500 mL) and sep-
arated into aliquots of acidified (using HNO3 to pH 2) for cations
(Na+ , K+ , Ca2+ , Mg2+ ) and trace element (As, Fe) analyses and non
acidified for anion (Cl− , SO4 2− ) analyses. Anion (Cl− , SO4 2− ) and
cation (Na+ , K+ , Ca2+ , Mg2+ ) concentrations were measured with
Ion Chromatography (IC, Dionex, CA, USA) with an accuracy of
±6% and precision of ±5% using external calibration. For Fe and As
analysis, the supernatants were collected after the acidified mud
fluids were centrifuged for 10 min at 9391 × g and passed through
0.45 ␮m filter paper (Advantec MFS Inc., CA, USA) and analyzed
using Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
(Hewlett-Packard 4500, Yamanashi-Ken, Japan). The ICP-MS data
were evaluated by measuring the standard deviations of three indi-
vidual runs, which was typically better than 2%. Mud samples were
oven-dried under 50 ◦ C and ground to a powder (< sieve #200
mesh) before being microwave-digested for total arsenic determi-
nation. Powdered mud samples were also used to determine the
solid phase arsenic content using ICP-MS after sequential extrac-
tion (Table 1). The total organic carbon (TOC) contents in the mud
and dissolved organic matter (DOC) in fluids were measured using
a high-temperature combustion (HTC) TOC analyzer (Analytic Jena,
Micro N/C model HT 1300, Germany).
The hydrogen and oxygen isotope compositions of mud fluids
were analyzed in the Institute of Earth Sciences, Academia Sinica,
Taipei, Taiwan. Isotope compositions were analyzed by a MM602D
mass spectrometer for ␦D and a SIRA 10 mass spectrometer for
982 C.-C. Liu et al. / Journal of Hazardous Materials 262 (2013) 980–988

Fig. 1. Study area showing the six mud volcanoes in southern Taiwan.

␦18 O, respectively. All ␦D and ␦18 O isotope values of samples were and a 32× objective (0.65 numerical aperture). The synchrotron
determined using well-established methods [34–36]. Repeated was operated in a top-up mode at a beam current of 360 mA. The
analyses of samples and laboratory standards showed that the 1␴ peak position, baseline corrections, and smoothing were automat-
uncertainties were 1.5‰ for ␦D and 0.11‰ for ␦18 O, respectively. ically performed with peak resolution. The optical system of the
Isotope data are reported as per mil (‰) relative to the V-SMOW end-station of infrared microspectroscopy were purged with dry
(Vienna Standard Mean Ocean Water) standard [34,37,38]. N2 , and the automatic atmospheric suppression function in the
OMNICTM software was used to minimize infrared absorption by
3.2. Extraction of HA and FTIR analyses CO2 and water vapor in the ambient air. A single-beam background
spectrum was collected from an area free of the sample. Stage
HA was extracted from mud samples using the International control and data collection were performed using OMNICTM soft-
Humic Substance Society (IHSS) method [39]. A 20 g mud sample ware. The Spectrum software (PerkinElmer V5.0; Perkin Elmer Co.,
was mixed with 200 mL of 0.1 M HCl in a 500 mL serum bottle. Beaconsfield, Bucks, UK) and KnowItAll software (Bio-Rad IR/NIR
The mixture was shaken at 1.46 × g for 1 h and then centrifuged Edition; BioRad laboratories Inc., version 7.7.5.61, Taiwan) provided
at 9391 × g for 10 min. After the supernatant was removed, 200 mL functional groups and possible bond assignments, respectively. The
0.1 M NaOH was added to the residue and the mixture was shaken physico-chemical and structural characteristics of the HA were
again at 1.46 × g for 1 h. After being centrifuged at 9391 × g for compared with those of the Standard HA obtained from Aldrich
10 min, the supernatant was removed and acidified to a pH of 1.0 (USA).
using HCl. The HA was precipitated at an interval of 16–24 h of
settlement at room temperature, and the precipitate was sepa- 3.3. Sequential extraction of arsenic from mud samples
rated by centrifuging at 9391 × g for 10 min. The HA precipitate
was then freeze-dried and prepared for Fourier Transform Infrared Dried and powdered mud samples were treated with sev-
Spectroscopy (FTIR) analysis. eral agents to extract different solid phase As fractions using a
The FTIR spectra of the extracted HA fraction of the mud were suitable sequential extraction method with some modifications
recorded using an end-station of infrared microspectroscopy at [40,41]. Arsenic from the sequential extraction was determined
BL14A1 of the National Synchrotron Radiation Research Center in by ICP-MS (Hewlett Packard 4500, Yamanashi-Ken, Japan). Five
Hsinchu, Taiwan. The spectra were recorded in transmission mode different extraction steps were followed (Table 1). In step one,
in the mid-IR range of 4000–600 cm−1 with spectral resolution of water soluble As was extracted from powdered mud samples
4 cm−1 and Happ-Genzel apodization, using an FTIR spectrometer using deionized water. In the next step, the exchangeable As
(Thermo-Nicolet, Magna-IR 860, USA) coupled with an Contin- co-precipitated with carbonate was extracted from the remnant
uum IR microscope (Spectra Tech) with a liquid-nitrogen-cooled using 1 M ammonium-acetate. In the third step, the residue was
mercury-cadmium-telluride (MCT) detector, a KBr beamsplitter mixed with 0.1 M Na-pyrophosphate to extract As adsorbed by
organic matter or in As-sulphide. The remnant was then mixed
Table 1 with a 0.1 M hydroxylamine solution in the fourth step to extract
Sequential extraction procedure for As-bearing solid phases. As strongly sorbed on amorphous Mn oxyhydroxides. Finally, the
Step Extractant Target phase remnant was mixed with a 0.25 M hydroxylamine solution to
extract As strongly sorbed on amorphous Fe and crystalline Mn
1 Deionized water at 1:1 weight Water-soluble As phase
ratio, shaken for 2 h at 1.46 × g
oxyhydroxides.
2 1 M ammonium-acetate for 1:1 Exchangeable As adsorbed by
weight ratio, shaken for 2 h at clay and co-precipitated with 3.4. Statistical analysis
1.46 × g carbonates
3 0.1 M Na-pyrophosphate at 1:1 As adsorbed by organic matter or
weight ratio, shaken for 2 h at arsenic sulphides Factor analysis and correlation matrices of geochemical con-
1.46 × g stituents were calculated using STATISTICA software (Version 5.1,
4 0.1 M hydroxylamine solutions Strongly sorbed As with USA). The former was aimed at identifying the principal factors
for 1:1 weight ratio, shaken for amorphous Mn oxyhydroxides
responsible for geochemical variations among the six mud volcano
2 h at 1.46 × g
5 0.25 M hydroxylamine solutions Strongly sorbed As with samples, while the latter was intended to determine correlations
for 1:1 weight ratio, shaken for amorphous Fe oxyhydroxides between As and chemical parameters.
2 h at 1.46 × g and crystalline Mn
 C.-C. Liu et al. / Journal of Hazardous Materials 262 (2013) 980–988 983

microwave digestion)
Total As in muds (by

(␮g kg−1 )

6920
12,320
9760
5090
8950
5400
non-leachable

6538 (94.5%)
11,656 (94.6%)
9182 (94.1%)
3375 (66.3%)
8576 (95.8%)
4492 (83.2%)
As (␮g kg−1 )
Total
Total leachable

382 (5.52%)
664 (5.39%)
578 (5.92%)
1715 (33.7%)
374 (4.18%)
908 (16.8%)
As (␮g kg−1 )

Fig. 2. Plot of ␦18 O vs. ␦D of the volcanic liquids from the six mud volcanoes in
Taiwan.

4. Results and discussion

amorphous Fe oxyhydroxides
and crystalline Mn (␮g kg−1 )
Strongly adsorbed As from

4.1. Geochemical characteristics of the mud and fluids

The geochemical characteristics of the mud and fluids from six

mud volcanoes indicated a reducing environment in most of the
64.7 (16.9%)
75.4 (11.4%)
25.7 (4.44%)

36.9 (9.86%)

mud volcanoes with EhS.H.E . values between −116 and 172 mV. Sim-
101 (11.1%)

ilar observations of mildly to strongly reducing conditions were

223(13%)

reported previously in other mud volcanoes in Taiwan [42]. High

concentrations of Na+ and Cl− (Na+ : 1045–10,583 mg L−1 ; Cl− :
327–25,607 mg L−1 ) in mud fluids are consistent with high salin-
ity (1.1–18.3 ‰), suggesting a marine source of fluids except in
Strongly adsorbed As from

oxyhydroxides (␮g kg−1 )

the case of LYS mud volcano. Early stages of highly saline mud flu-
HKS: Hsiaokunshui; WST: Wushanting; YSK: Yenshuikeng; KSP: Kunshuiping; LYS: Liyushan; SYNH: Sinyangnyuhu.

ids may have come from connate water, which was mixed with
volcanic mud in the Philippine Sea plate and the Eurasian active
amorphous Mn

23.1 (4.00%)

collision zone. Other cations like K+ , Ca2+ , and Mg2+ were observed
131 (34.3%)
370 (55.8%)

768 (44.8%)
122 (32.7%)
226 (24.9%)

at significantly lower concentrations. The pH values of mud volca-

noes were slightly alkaline in nature (7.2–8.04). The temperature
of the erupted fluids (ranging from 20.6 to 38.1 ◦ C) showed no sig-
nificant difference from the shallow groundwater temperature in
the study area. High TDS (1950–50,000 mg L−1 ) and high electric
As adsorbed by organic

conductivity (3.02–28.2 mS cm−1 ) are also well known phenomena

matter or arsenic
oxides (␮g kg−1 )

in mud volcanoes. To characterize the organic matter, DOC in flu-

ids and TOC in mud were analyzed. A higher abundance of organic
178 (46.5%)
178 (26.8%)

595 (34.7%)
207 (55.4%)
470 (51.8%)

matter in terms of TOC in mud samples (11,450–22,060 mg kg−1 ;

451(78%)

mean = 15,893 ± 3930 mg kg−1 ) was observed in comparison to

Note: Percentage of different solid phase arsenic is given in parentheses.

DOC in mud fluids (141–530 mg L−1 ; mean = 270 ± 135 mg L−1 ),

suggesting that some of organic matter were released to these fluids
Arsenate concentration in different solid phases

through subsurface geochemical interactions.

As adsorbed by clay and

carbonates (␮g kg−1 )

co-precipitated with
Arsenic content in different solid phases of mud samples.

4.2. Isotopic signature of mud fluids

Fig. 2 represents the isotopic signature of the studied mud vol-

4.72 (1.26%)
1.12 (0.29%)
5.85 (0.88%)
9.01 (1.56%)
5.66 (0.33%)

0.83 (0.09%)

canoes in southern Taiwan. The ␦18 O and ␦D values are in the

range of 0.2–6.1 ‰ and −11 to −24‰, respectively, whereas in
the case of Canten groundwater, whose sampling site was 500 m
away from the HKS mud volcano, the values are −8.6 and −60
‰, respectively. The ␦D/␦18 O ratio was negative in mud volcano
7.56 (1.98%)

3.07 (0.82%)
Water-soluble

34.5 (5.19%)
69.3 (11.8%)
As (␮g kg−1 )

124 (7.24%)

110 (12.1%)

fluids, but positive for Canten groundwater, suggesting a distinct

hydrological environment for mud volcanoes. Isotope results from
different mud volcanoes worldwide have been compiled and are
presented in Fig. 3 together with the global meteoric water line
(GMWL) [43] and local meteoric water line (LMWL) [44]. The ␦18 O-
Mud volcano

␦D trends of the Taiwan mud fluids showed deviation from the

LMWL and enrichment of ␦18 O. Enrichment of ␦18 O was appar-
SYNH
Table 2

WST
HKS

YSK
KSP
LYS

ently due to water–rock interaction caused by an exchange of mud

fluids between ␦18 O-rich silicate and carbonate rocks in the crust
984 C.-C. Liu et al. / Journal of Hazardous Materials 262 (2013) 980–988
Fig. 3. Plot of ␦18 O vs. ␦D of volcanic liquids compared with the global meteoric water line (GMWL) [43] and the local meteoric water line (LMWL) [44].
or dehydration of clay mineral at a deep source [45–47]. Connate
water that plays an important role in the fluids of mud volcanoes
may be attributed to the mixing of meteoric water [48] and then
affected by fluid–mineral exchange during clay dehydration at ele-
vated temperatures [27].
4.3. Arsenic in mud and fluids
The arsenic concentration in the fluids was significantly
low (0.02–0.06 mg L−1 ) in all of the mud volcanoes except LYS
(29.8 mg L−1 ). Irrespective of fluids, total arsenic content in
the mud sediments was significantly high (5.09–12.3 mg kg−1 ;
mean = 8.03 ± 2.79 mg kg−1 ) (Table 2). This observation indicates
possible release of arsenic from mud sediments. To understand
the arsenic mobilization process in mud volcanic fluids, adsorbed
arsenic content in the solid phase of mud sediments was deter-
mined using a sequential extraction method (Table 1). Fig. 4 shows
the graphical view of the percentage of leachable and non-leachable
arsenic with different solid phase arsenic. Leachable As in mud
was observed in the range of 374–1715 ␮g kg−1 , whereas total As
content in the mud was from 5090 to 12,320 ␮g kg−1 (Table 2).
Total leachable As varied from 4.2 to 33.7% among all of the mud
volcanoes, and this indicates that most of the As was strongly
bound in the mud sediments. A major portion of the As (46–78%)
was found to be adsorbed on organic matter or in the arsenic
sulphide phase in most of the mud volcanoes. However, in HKS
and LYS, a higher amount (44.8–55.8%) of adsorbed As was in
the amorphous Mn oxyhydroxides phase. The adsorbed As in the
solid phase of clay and co-precipitated with carbonate was found
to be relatively low (0.09–1.56%). Maximum leachable As (33.7%)
was observed in LYS with respect to the total arsenic, whereas
in the other mud volcanoes, the leachable arsenic varied from
4.2 to 16.8%. The current study indicates binding of arsenic with
different solid phases of mud sediments especially with organic
matter, As-sulphides, and amorphous Mn oxyhydroxides. High
solid phase As, therefore, suggests possible release of As to the mud
fluid and subsequently to the environment during a mud volcanic
eruption.
4.4. Factor analyses and geochemical characterizations
Factor analysis was performed using statistical software to char-
acterize the geochemical constituents of the fluids among the
studied mud volcanoes. The database of mud fluids included cations
(Na+ , K+ , Ca2+ , Mg2+ ), anions (Cl− , SO4 2− ), metalloids and metals
(As, Fe) and field parameters (pH, alkalinity, salinity, temperature,
EhS.H.E. , electric conductivity, and TDS). Three factors which may
affect the composition of volcanic fluids were identified. The first
factor includes Ca2+ (0.95), Na+ (0.85), K+ (0.89), Cl− (0.92), TDS
(0.94), pH (0.78) having Eigenvalues and a percentage of variance
of 6.87 and 45.8%, respectively. The impact of connate water and
also the exchange between Ca2+ and Na+ in Na-enriched clay min-
eral may therefore cause high Na+ and Cl− in mud fluids. The second
factor includes alkalinity (0.95), SO4 2− (0.83), and EhS.H.E. (−0.82),
which had Eigenvalues and a percentage of variance of 3.49 and
23.2%, respectively. This factor is mainly responsible for the reduc-
ing environment causing variations in carbonate/bicarbonate and
sulphate concentrations. The third factor includes Mg2+ (0.97), elec-
tric conductivity (0.88), and salinity (0.95), which had Eigenvalues
and a total variance percentage of 2.72 and 18.1%, respectively.
This factor may reflect the original depositional environment by
controlling the factors like salinity and electric conductivity. Other
parameters like As, iron, and temperature have no such impact on
the chemical composition of mud fluids. No significant correlation
was observed between As and any other geochemical parameters.
High p values of each chemical index (>0.05) also imply similar indi-
cations that the As concentration in mud fluids is not affected by
other geochemical constituents.
4.5. Organic matter and its relationship with geochemical
processes
Availability of organic matter in mud fluids and its interaction
with geochemical processes is an important phenomenon in mud
volcanoes. Among the organic matter in fluids, HS and especially HA
may play a major role in subsurface biogeochemical processes. The
TOC content of mud samples varied from 11,450 to 22,060 mg kg−1
(mean = 15,893 ± 3930 mg kg−1 ). Significant levels of TOC, there-
fore, imply enrichment in organic matter in mud volcanoes. The
concentrations of As, Fe, Mn, organic matter, and HA in mud and
fluids in the six mud volcanoes are presented in Table 3. The corre-
lation analyses revealed significant correlations between As and
organic matter (r = 0.94, p = 0.005, n = 6), Fe and organic matter
(r = 0.94, p = 0.005, n = 6), and As and Fe (r = 1, p = 0.000, n = 6) in
mud fluids. However, Mn in mud fluids is not significantly corre-
lated with organic matter (r = 0.34, p = 0.51, n = 6). This indicates that
 C.-C. Liu et al. / Journal of Hazardous Materials 262 (2013) 980–988 985

Fig. 4. Percentage of arsenic adsorbed onto soil phases of mud sediments in studied mud volcanoes estimated by sequential extraction methods.

Table 3
The concentrations of As, Fe, Mn, and organic matter in the mud fluids of six mud volcanoes.

Mud volcano As Fe Mn Organic matter

−1
Mud Fluid Mud Fluid Mud Fluid (mg L ) TOC in mud DOC in fluid
(mg kg−1 ) (mg L−1 ) (mg kg−1 ) (mg L−1 ) (mg kg−1 ) (mg kg−1 ) (mg L−1 )

HKS 3.2 0.06 4.6 0.02 1.4 n.d. 14.65 196.6

WST 2.1 0.02 4.6 0.01 1.4 n.d. 15.73 254.9
YSK 0.59 0.02 951 0.14 29.2 0.02 11.45 140.6
KSP 0.55 0.06 1130 0.09 26 0.01 15.16 233.7
LYS 0.65 29.8 1190 68.9 28.6. 0.02 22.06 530.0
SYNH 2.2 0.02 5.2 0.05 1.4 n.d. 16.31 263.7

Samplings in February 2008 and Februray–April 2009. n.a.: not available; n.d.: not detectable.
HKS: Hsiaokunshui; WST: Wushanting; YSK: Yenshuikeng; KSP: Kunshuiping; LYS: Liyushan; SYNH: Sinyangnyuhu.

mobilizations of As and Fe were driven by organic matter, but not spectrometry (Fig. 5). Functional groups of HA were identified and
for Mn. are shown in Table 4. The potential role of HA in reduction of arse-
HA, an important part of subsurface organic matter, was nate to arsenite in mud liquids has been previously reported [30].
extracted from the mud sediments and characterized by FTIR The present study showed the relationship between HA and redox

Fig. 5. FTIR spectra of HA extracted from different mud sediments under study.
986 C.-C. Liu et al. / Journal of Hazardous Materials 262 (2013) 980–988

Table 4
Abundance of functional groups in humic acid extracted from volcano muds.

Function groups Band position (cm−1 ) Name of mud volcanoes and location areas

Chishan fault Coastal plain Kutingkeng anticline

Wushanting Sinyangnyuhu Hsiaokunshui Yenshuikeng Kunshuiping Liyushan

Free Hydroxyl group O H 3640–3610 䊉  䊉   

Amine N H 3500–3300 䊉 䊉 䊉  䊉 
Strong hydrogen bonded O H 3500–3200  䊉 䊉 䊉 䊉 䊉
Carboxylic acid O H 3500–2500 䊉 䊉 䊉 䊉 䊉 䊉
Aromatic C H 3100–3000 䊉 䊉  䊉  䊉
Methylene; methyl group 2960–2850 䊉 䊉 䊉 䊉 䊉 䊉
Alkyne C C 2260–2100  䊉   䊉 䊉
Carboxylic acid C O 1760–1660 䊉 䊉 䊉 䊉 䊉 䊉
Ester C O 1750–1715 䊉 䊉  䊉 䊉 䊉
Ketone C O 1720–1700  䊉  䊉  
Amide 1690–1630 䊉 䊉 䊉 䊉  䊉
Alkene C C 1680–1640  䊉  䊉  䊉
Aromatic C C 1600–1450 䊉 䊉 䊉 䊉 䊉 䊉
Amine C N 1230–1030 䊉 䊉  䊉  䊉
Alcohol C O 1150–1050 䊉 䊉    䊉

Note: 䊉 present;  absent.

potential through a laboratory experiment under anaerobic condi-
tions (Fig. 6). Standard HA (Aldrich, USA) was used to prepare the
HA solutions (0–1000 mg L−1 ) to carry out the experiment. Stan-
dard HA solutions were kept inside a glove box (under 90% N2
and 10% H2 mixed gas) for 14 days to observe the variation of
redox potential in terms of measuring oxidation-reduction poten-
tial (ORP). The ORP values were converted to EhS.H.E. by adding
210 mV. After 7 days of observation, EhS.H.E. values were found to
be stable (−199 to −227 mV) at a concentration of up to 200 mg L−1
of HA. In the case of higher HA concentrations (300–1000 mg L−1 ),
the EhS.H.E. values stabilized at −240 mV after 11 days of incu-
bation. Interestingly, the EhS.H.E. values became quickly stable at
HA concentrations over 1000 mg L−1 . The findings thus suggest
higher concentrations of HA to be related to lower EhS.H.E. values.
Part of the organic matter (especially HA) may therefore affect the
redox conditions of groundwater. Earlier reports have suggested
that microbial degradation of organic matter has a potential role
in release of As into groundwater [49]. The present study is also in
a good agreement with assumption that organic matter and par-
ticularly HA may control the redox conditions and induce arsenic
mobilization.
The FTIR spectra of HA extracted from the mud samples are
presented in Fig. 5. Significant spectral bands of characteristic
fundamental vibrational transition were observed at different
wavenumber regions from 650 to 4000 cm−1 . The bands at
Fig. 6. Variation of EhS.H.E with different concentrations of HA under anaerobic
conditions.
3400 cm−1 and 3620 cm−1 represent strong hydrogen bonded O H
and free hydroxyl group O H, whereas those at 2850–2960 cm−1
are assigned to methylene ( CH2 ) and methyl group ( CH3 ) of
H (Table 4). The presence of C C bonding of aromatic com-
pounds was confirmed with some medium intense peaks at
1450–1600 cm−1 (Fig. 5). The presence of combined aliphatic and
aromatic groups in the studied samples confirmed the presence of
HS in the mud sediments [50]. The aromatic carbon content of HA
observed in the mud samples indicated sorption of HS on the min-
eral surface, and this sorption was found to be proportional to the
aromatic HS content and inversely proportional to the O/C ratio
and hydrophilicity [51,52]. Spectral bands of mineral composition
also can be interfered with by organic residues, namely cellulose or
hemicellulose in the case of peats [53]. The absorption bands of the
carboxylic group were observed in spectral regions of 1760–1660
and 3500–2500 cm−1 , respectively. In addition, the vibration band
of C O bonding of carbonyl group was observed in the range of
1540–1870 cm−1 . Phenolic and carboxylic groups of HS have been
reported to contribute to the surface charge and the reactivity of
HS [50].
Free hydroxyl groups were observed respectively for the mud
sediments of WST and HKS mud volcanoes at 3621 cm−1 and
3629 cm−1 . After treatment of 0.1 M NaOH for mud sediments,
characteristic absorption of carboxylic group of organic acid at
1748 cm−1 disappeared and absorption of hydroxyl group at
3300 cm−1 was reduced for all mud sediments except standard
sample of HA.
The bands in the range of 975–804 cm−1 for the sediments of
WST and HKS were assigned to As O stretching vibration of a
bidentate and a monodentate complex of Fe(III) O As, respec-
tively. The result is consistent with the previous observations
[54–56]. Therefore, the absorption bands strongly suggested the
binding nature of arsenate adsorbed on the metal complexes to
form chelate complexes. The strong vibration at 974–862 cm−1
and weak vibration at 804–862 cm−1 are assigned to As O
stretching vibration of a bidentate and a monodentate complex
of Fe(III) O As, respectively. In this study, the bands were at
901 cm−1 and 825 cm−1 , respectively, indicating that both biden-
tate and monodenate complexes of Fe(III) O As formed on the
minerals surface. The bands of the FTIR spectra revealed the charac-
teristics of different functional groups of HA and chelate complexes
in the mud volcano samples. The fingerprint region of the spec-
tra also represented important features of As chelate complexes
in extracted HA from the mud volcanoes of southern Taiwan. Our
 C.-C. Liu et al. / Journal of Hazardous Materials 262 (2013) 980–988
findings strongly suggested that HA interact with metal complexes
in the basic environment to enable the formation of chelate com-
plexes so as to play a role of carrier for As.
5. Conclusions
The present investigation highlighted the geochemical charac-
teristics of mud fluids and sediments from the mud volcanoes of
southern Taiwan. The low EhS.H.E. of fluids indicated a moderate to
strongly reducing environment. High NaCl and salinity indicated
that the origin of volcanic fluids may come from connate water
in the deep geological formation. Most mud volcanoes are rich in
organic matter along with HS, and significant correlations between
As and organic matter, Fe and organic matter, and As and Fe in mud
fluids indicate an important role of organic matter in mobilization
of arsenic. However, Mn in mud fluids is not significantly corre-
lated with organic matter. This indicates that mobilizations of As
and Fe were driven by organic matter, but not for Mn. The ␦18 O-
rich mud fluids suggested interactions with silicate and carbonate
minerals. Furthermore, the dehydration of clay minerals may also
cause ␦18 O enrichment. The concentration of As in the mud fluids
was low except in the case of the LYS sample, and no correlation was
found among As and other chemical constituents. A considerable
amount of As in the mud sediments suggested its possible release to
mud fluids through geochemical processes. The functional groups
of HA identified by the FTIR study demonstrated the binding nature
of HS with arsenic. Organic matter may induce arsenic mobiliza-
tion through an adsorption/desorption mechanism with HS under
reducing conditions. Organic matter therefore plays a significant
role in the mobility of arsenic in mud volcanoes.
Acknowledgments
This work was supported by the National Science Council of
Taiwan (Grant number NSC 99-2116-M-006-010). The authors are
grateful for the support and assistance of Dr. Jyoti P. Maity and Mr.
Jiann-Hong Liu during field surveys.
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