Journal of Volcanology and Geothermal Research 419 (2021) 107353

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Journal of Volcanology and Geothermal Research

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

Chemical and isotopic constraints on hydrological processes in Unzen

volcanic geothermal system
Reika Yokochi a,⁎, Roland Purtschert b, Yoshimitsu Suda c, Neil C. Sturchio d,
Jürgen Sültenfuß e, Christof Vockenhuber f
a
Department of the Geophysical Sciences, The University of Chicago, 5734 S. Ellis Avenue, Chicago, IL 60637, USA
b
Climate and Environmental Physics and Oeschger Center for Climate Change Research, University of Bern, Sidlerstrasse 5, CH-3012 Bern, Switzerland
c
Department of Geology, Faculty of Education, Nagasaki University, 1-14 Bunkyo Machi, Nagasaki 851-2125, Japan
d
Department of Earth Sciences, University of Delaware, 255 Academy Street, Newark, DE 19716, USA
e
Department of Environmental Physics, University of Bremen, Otto Hahn Allee, D-28359 Bremen, Germany
f
Laboratory of Ion Beam Physics, Eidgenössische Technische Hochschule (ETH) Zürich, Otto-Stern-Weg 5, Zurich 8093, Switzerland

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

Article history: Geothermal systems developed in volcanic regions release magmatic volatiles that may forecast volcanic erup-
Received 2 May 2021 tions. These volatiles can be emitted directly in gaseous form to the atmosphere or can be absorbed by condensed
Received in revised form 16 July 2021 geothermal fluid and groundwater that discharges at surface thermal features. The subsurface flow dynamics of
Accepted 19 July 2021
these fluids are therefore crucial for the interpretation of their chemical and isotopic compositions. Furthermore,
Available online 24 July 2021
since geothermal fluids are globally used as energy and cultural resources, such information is also important for
Keywords:
their sustainable management. In this context, we investigated the subsurface residence times of fluids from
Unzen geothermal system three geothermal areas in Shimabara peninsula (Unzen, Shimabara and Obama) by measuring their tritium
Tritium and 36Cl activities, along with their chemical and stable isotopic compositions. At Shimabara, the trace tritium ac-
Chlorine-36 tivities of the geothermal fluids indicate that magmatic volatiles were transported by pre-nuclear (residence time
>60 years) groundwaters. Tritium and δD-δ18O data indicate that the steam feeding the Unzen geothermal field
is also derived from pre-nuclear meteoric water, and contributing about a quarter of the water budget. The 36Cl/Cl
ratio of the geothermal fluids in Obama exceeds that of seawater, indicating subsurface addition of nucleogenic
chloride during prolonged water-rock interaction.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction
Mt. Unzen is a polygenetic volcano located in the graben structure of
Shimabara peninsula, southwest Japan (Fig. 1a and b). Most recent
eruption activities of Mt. Fugen occurred during 1990–1995 with over
10,000 pyroclastic flows. Prior to the onset of these eruptions, the epi-
centers of volcanic earthquakes migrated eastward from a depth of
15 km beneath Tachibana bay to a location beneath Mt. Fugen in June
1990 (Umakoshi et al., 1994). This was interpreted as evidence that
the magma chamber feeding the recent eruptions was located beneath
Tachibana bay, whereas other geophysical data suggest a presence of
another, possibly primary, magma chamber beneath Shimabara bay
(Ohmi and Lees, 1995). Interestingly, three geothermal fields are lo-
cated close to each of these key geological features: one at Obama spa
along the coast of Tachibana bay, above the inferred magma chamber
source of the recent eruptions; another at the Unzen geothermal field,
⁎ Corresponding author.
E-mail address: yokochi@uchicago.edu (R. Yokochi).
overlying the route of the seismic migration path, 4 km west of the
newly formed summit of Mt. Fugen; and a third at Shimabara city
near Shimabara bay above the postulated second magma chamber,
where there are wells bearing low-temperature geothermal fluids.
Helium isotopic compositions of the fluids from these areas were
first reported by Marty et al. (1989), showing clear evidence of mag-
matic He contributions to all three geothermal areas. However, the
3
He/4He ratios did not show a systematic decrease with distance from
the volcanic cone by a gradual addition of crustal 4He as reported at
other volcanos (Sano et al., 1984; Williams et al., 1987; Marty et al.,
1989). For example, a low temperature fluid from Shimabara, farthest
from the Mt. Fugen volcanic cone (11 km), had a higher 3He/4He ratio
compared to those of fumaroles of the Mt. Fugen lava domes. The data
of the samples collected in 1983 (Marty et al., 1989) served as a pre-
eruption reference for studies that followed as the volcano became ac-
tive and erupted on Nov 17, 1990. Three months before the eruption
of Mt. Fugen, an increase in 3He/4He ratios compared to 1983 was de-
tected in Shimabara (Kita et al., 1993), suggesting that the low-
temperature geothermal fluid carried the signal of the ongoing volcanic

https://doi.org/10.1016/j.jvolgeores.2021.107353
0377-0273/© 2021 Elsevier B.V. All rights reserved.
R. Yokochi, R. Purtschert, Y. Suda et al. Journal of Volcanology and Geothermal Research 419 (2021) 107353

Fig. 1. (a)Shimabara peninsula with locations of three geothermal field sites. The blue dashed line is the transect of the cross section in (c). Red lines are locations of faults that delineate the
Unzen graben. (b) Location of Shimabara peninsula. (c) Cross section of the transect shown in (a). Three boreholes between Unzen and Obama show temperature anomalies, indicating
lateral and slightly upward flow of high temperature fluid westward toward Obama. Stars in the east side of Mt. Fugen are locations of springs, compositions of which were reported in
previous study. (d) Geothermal area of Unzen is located within a small basin surrounded by Yadake and Mt. Kinugasa. Pricipitation on the west flank of Yadake feeds the Unzen geothermal
field.

activity. This is one of few volcanoes where a clear change of He isotope
signal was observed before disastrous volcanic activity started. Two
other geothermal fields close to the Mt. Fugen volcanic cone did not
show clear changes, partly due to the varying sampling locations (Kita
et al., 1993).
The change in He isotopic compositions may reflect enhanced flux of
volcanic volatiles to the surface via a complex geothermal fluid circula-
tion system, and He isotope ratios are considered to be a useful tool for
forecasting volcanic activity (e.g. Sano et al., 1988; Sano et al., 2015). As
carriers of the volcanic He signal, understanding the origin and flow dy-
namics of water constituting these hydrothermal systems is crucial for
estimating the response time of the volcanic signal in the accessible
fluid sampling locations, as well as for understanding the evolution of
the geothermal system. Here we report tritium and 36Cl values mea-
sured in geothermal fluids along with their chemical and δD-δ18O com-
positions in two geothermal source wells in Shimabara region, a mineral
spring and a shallow well bearing high temperature fluid in Obama re-
gion, as well as frying-pan type geothermal features and surface streams
in the Unzen geothermal field. We use these data to infer a conceptual
hydrologic model for the geothermal fluid circulation system in the
Unzen region.
2. Study area and methods
2.1. Hydrogeology
Unzen graben is bound by EW-striking Chijiwa fault in the north and
Kanahama-Futsu faults in the south (Fig. 1a). Most volcanic and hydro-
thermal activity on the Shimabara peninsula occur within the graben.
According to geological and hydrological studies of the region (Otsuka,
1984; Furukawa, 1962; Watanebe and Hoshizumi, 1995; Sugimoto,
2006), basement rocks within the Unzen graben consist of Lower Pleis-
tocene marine sediments known as the Kuchinotsu formation, thick silts
and clays which form an aquitard in the eastern foothill region. The
overlying Tatsuishi aquifer consists of basal pyroclastic rocks from
early Unzen volcanism, intercalated by tuffs, volcanic mudflows and
andesite lavas (Furukawa, 1962). Silts of this formation occasionally
form perched aquifers which seep springs on the volcanic flank

2
R. Yokochi, R. Purtschert, Y. Suda et al.
(Takamura et al., 1999), or divide the aquifer horizontally to confine
deeper strata. Two generations of andesite lavas and pyroclastic rocks
overlie the aquifer and constitute the primary lithology above 300 m alti-
tude; the older Unzen volcanism during Middle Pleistocene covered a
large fraction of the graben whereas younger Unzen volcanism during
Late Pleistocene to Holocene is limited to the eastern part of the graben.
Drilled cores from groundwater and geothermal wells within the
Unzen graben consist mostly of pyroclastic rocks, but the Unzen geother-
mal area is underlain by a ~20m thick clay layer, underlain by 130 m of
andesite lava flow. A 50–150 m thick alluvial fan deposit, with an Upper
Pleistocene loam at its base, unconformably overlies the Tatsuishi forma-
tion in the eastern coastal Shimabara region. The stratigraphic profile of a
geothermal well in this area shows multiple impermeable layers (clays
and tuffs) above 200 m depth (Murakami, 1975). The geothermal reser-
voir located beneath is therefore likely confined and isolated from the al-
luvial aquifer. The shallow alluvial aquifer (Fukae formation) discharges
numerous springs of bicarbonate-type water in the Shimabara city area,
which historically served the local communities (Takamura et al.,
1999). However, this shallow unconfined aquifer is subject to nitrate pol-
lution (Amano et al., 2018), highlighting the importance of deeper
groundwater as a water resource. In the west coastal region of the
Unzen graben, the Kuchinotsu formation (basement rocks) typically ap-
pears at depths below 500 m. The Tatsuishi formation has low permeabil-
ity in the Obama geothermal area; the intercalating andesite lavas serve
as reservoir rocks for the geothermal fluids (Saibi and Ehara, 2010).
The geothermal fluids show clearly distinct chemical features, pre-
sumably reflecting different stages of the evolution of geothermal fluids
(Ohta, 1973; Ohsawa et al., 2002a). The high salinity of Obama thermal
water has been attributed to seawater contribution. In the Unzen geo-
thermal field (Jigoku) and Shimabara area, acid-sulfate- and
bicarbonate-type fluids occur, respectively, resulting from the interac-
tion between meteoric water and gas/vapor released from the magma
with varying extents of rock-fluid interaction.
2.2. Sampling sites
In the eastern coastal region of the Unzen graben, two geothermal
wells are present and the blended fluid is supplied for public and private
Fig. 2. Geothermal areas of Unzen delineated with yellow lines on a satellite image, identifiable due to the lack of vegetation. H: Hachiman jigoku, S: Seishichi jigoku, D: Daikankyo jigoku, J:
main jigoku area. Samples were collected at locations with white circled letters, shown with its watersheds (blue polygons).
3
Journal of Volcanology and Geothermal Research 419 (2021) 107353
use. Samples were collected from wells at Motoike spa (350 m well
depth) and Kan'nonjima spa (190 m well depth). Both wells bear
bicarbonate-type fluids at moderate temperatures (~30°C). According
to the resistivity contrast, Kawabe (1997) identified the unconformity
between Tatsuishi and Fukae formations around 100 m depth. The geo-
thermal wells are therefore tapping the Tatsuishi aquifer. Numerous
wells are present in the Obama geothermal field, and we collected fluids
from one artesian well bearing hot saline fluid typical of this region and
a cold mineral spring (’Karimizu’). The Unzen geothermal field has sev-
eral gas emanations and frying-pan features. Two of the frying-pan fea-
tures isolated from visible surface water flow were selected (Fig. 2; S:
Suzume-Jigoku and J: Jigoku Jizo). Additionally, we sampled leakage
from a pipe distributing the hot geothermal fluid to local geothermal
baths. The inlet of the pipe appeared to have been inserted into a geo-
thermal spring covered with cement and soil for pressurization [P].
One sample was collected at a creek flowing between two geothermal
areas [C]. Two additional samples were collected from surface flows
near the outlet of the geothermal basin [E, W].
2.3. Methods
All fluid samples were collected in polypropylene bottles. Fluid sam-
ples used for cation concentration measurements were filtered by using
0.45-μm polypropylene syringe filters. Cation concentrations were mea-
sured by inductively-coupled plasma mass spectrometry (Agilent
7500). Anion concentrations were measured by ion chromatography
(Dionex ICS-2100). Sample pH was measured in the laboratory, with in-
strument calibrated to certified pH buffers. Alkalinity (reported as
HCO− 3 ) was measured by acidimetric titration using certified 0.1 M
HCl (Fisher Scientific). Stable isotope compositions of H2O in unfiltered,
unacidified water samples were measured by infrared absorption spec-
trometry (Los Gatos Research, Inc. model IWA-45EP), with data normal-
ized to standard isotope reference materials.
Analyses of tritium were conducted by the ingrowth method at the
noble gas laboratory of the Institute of Environmental Physics, Univer-
sity of Bremen, Germany (Sültenfuß et al., 2009). The 36Cl/Cl ratios
were measured at the Laboratory of Ion Beam Physics (ETH, Zurich)
using AMS. The extraction and purification of Cl from samples followed
R. Yokochi, R. Purtschert, Y. Suda et al.
the chemical procedures described in Ivy-Ochs et al. (2004); Cl was pre-
cipitated as AgCl from the water samples by addition of AgNO3. After
rinsed and centrifuged, the AgCl was purified by re-dissolving in
NH4OH, from which hydroxides were removed by centrifugation. Sulfur
was precipitated as BaSO4 by addition of Ba(NO3)2 and were removed
by centrifugation, with residual S concentrations typically below the
ppm level. The measurements were performed in the 6 MV EN Tandem
Accelerator, extracting negative Cl ions from the silver chloride samples,
applying mass analysis and molecule destruction, and final separation of
the isobar 36S in the gas-filled magnet (Vockenhuber et al., 2019). The
measured 36Cl/35Cl ratios were blank corrected and normalized to the
internal standard K382/4 N (Christl et al., 2013).
3. Results
Chemical compositions of the collected fluid samples are mostly in
agreement with findings in previous studies, as shown in ternary dia-
grams together with relevant data from the literature (Fig. 3 and
Table 1: NEDO1988, Ohsawa et al., 2002a; Saibi and Ehara, 2010). As
stated in these literature, the geothermal fluid samples from this region
are not in chemical equilibrium and plot in the range of ‘immature
water’ on the K-Na-Mg ternary plot (Fig. 3a) defined by Giggenbach
(1986). Compared to Ca-bicarbonate type river waters and shallow
groundwaters in this peninsula (Saibi and Ehara, 2010; Nakagawa
et al., 2017; Amano et al., 2018), bicarbonate-type fluids from two geo-
thermal wells in Shimabara area were enriched in most solutes except
sulfate and Ca. Fluids from Unzen geothermal field (called ‘jigoku’) are
acidic and highly enriched in sulfate while other solute contents are
generally low and are comparable to surface water and shallow ground-
water. The fluid from Karimizu mineral spring in Obama area also had
an acid-sulfate-dominated composition with a pH value of 2.1 mea-
sured in this study in July 2019. This contrasts with the bicarbonate-
type fluid composition reported by Ohsawa et al. (2002a) who mea-
sured pH value of 5.7 in Dec 2000 and by Morikawa et al. (2008) who
measured a pH value of 6.9 in Nov 2002. Shallow wells in the coastal
Obama area bear artesian flow of boiling NaCl-type fluids. A single sam-
ple collected for this study plots within the previously reported range of
chemical compositions. The chloride concentration of 4388 mg/L, ap-
proximately 25% that of seawater, is within the typical range of fluids
from this area.
Fig. 3. Ternary diagrams of (a) cation and (b) anions with a curve representing equilibrium compositions following Giggenbach (1986). Solid symbols are data from this study, open
symbols are from previous studies (NEDO, 1988; Ohsawa et al., 2002a; Saibi and Ehara, 2010).’SW’ represents seawater, and N61-UZ-7 is the borehole near Unzen-jigoku bearing
NaCl-type high temperature fluid (NEDO, 1988). Reference numbers in the legend are: [1] Ohsawa et al., 2002a; [2] Saibi and Ehara, 2010; [3] Nakagawa et al., 2017; [4] Amano et al.,
2018. Studied water samples have not reached chemical equilibrium unlike N61-UZ-7.
4
Journal of Volcanology and Geothermal Research 419 (2021) 107353
The δ18O and δ18D values, tritium activities and 36Cl/Cl ratios of
water samples are listed in Table 2. Previous studies on the Shimabara
peninsula (Kawabe, 1997; Ohsawa et al., 2002a) concluded that most
geothermal fluids are of meteoric origin as they plot close to the global
Meteoric Water Line (Craig, 1961). Mizota and Kusakabe (1994) de-
fined three zones each characterized by distinct local meteoric water
lines within Japan. Shimabara peninsula belongs to zone 3 with the
zonal meteoric water line (JZ3-MWL) expressed as:
δD ¼ 7:73  δ18 O þ 12:7 ð1Þ
Our samples from Shimabara city plot on this line, as does the water
from the creek flowing down the side of Unzen-jigoku (Fig. 4). Five
other geothermal fluid samples from Unzen-jigoku align to the right
of JZ3-MWL passing through the data point of the creek, which encom-
passes either a systematic fractionation trend and/or mixing of two
components. The cold mineral spring near the Obama region plots
close to the river composition of this area (Saibi and Ehara, 2010), con-
sistent with local meteoric origin of the mineralized water in the area
(Ohsawa et al., 2002a). The fluid from the geothermal well in Obama
shows heavy stable isotope signals and deviates below JZ3-MWL. The
data fall within the range of Obama geothermal water reported in the
literature (Ohsawa et al., 2002a; Saibi and Ehara, 2010).
Tritium activities of the fluid samples varied between 0 and 2.5 TU.
Monitoring programs of tritium in local precipitation started in 1961
in the Tokyo area (by International Atomic Energy Agency, 2021; Na-
tional Institute of Radiological Science, 2017 [database discontinued,
data kindly provided by Dr. M. Gusyev]; Nuclear Regulation Authority,
2021). The peak shape evolution was fitted by a piecewise function f1
(t) for t≤1963 and f2(t) for t≥1964, expressed as: Ln[f1(t)] = 1.15(t-
1963) + 5.90 and Ln[f2(t)] = 5.53 e−0.071(t−1963)+0.80. The 1-σ
range of the deviation of the fitted curve from the measured values is
shown in gray (Fig. 5). Other detailed studies on tritium levels of rainfall
in Japan revealed a latitudinal variation (Momoshima et al., 1991;
Nakasone et al., 2019), as well as tritium spikes transported by air
masses from Asia (Matsuoka et al., 1994; Yokoyama et al., 2011;
Gusyev et al., 2019). However, the limited number of monitoring data
from Fukuoka and Kumamoto, the closest monitoring stations to the
study sites, showed compatible results to Tokyo (Fig. 5: Momoshima
et al., 1991; Matsuoka et al., 1994; Hayashi et al., 1999; Momoshima
et al., 2005, 2008; Yokoyama et al., 2011), which we use as a reference
R. Yokochi, R. Purtschert, Y. Suda et al. Journal of Volcanology and Geothermal Research 419 (2021) 107353

Table 1
Chemical compositions of geothermal fluids from Unzen graben.

Name ID Date T pH Cl− SO2−

4 HCO−
3 Na Mg Al Si K Ca

°C mg/L mg/L mg/L ppm ppm ppm ppm ppm ppm

Unzen
Unzen Jizo J 7/9/2019 79.0 1.7 0.7 2187 0 – 0.6 93.0 102.6 5.1 1.4
Unzen Suzume S 7/9/2019 64.9 1.9 2.6 1136 0 2.8 5.4 55.3 79.4 9.3 3.6
Unzen pipe P 7/9/2019 1.7 1.8 1949 0 10.0 9.8 61.2 128.1 10.3 6.3
Unzen Creek C 7/9/2019 28.1 2.6 3.1 311 0 3.1 1.9 15.3 44.4 3.3 1.6
Unzen East Stream E 7/9/2019 1.8 2.1 1689 0 3.4 7.3 52.3 110.8 5.8 3.5
Unzen West Stream W 7/9/2019 1.8 3.8 2129 0 8.8 8.4 84.5 107.4 17.2 5.4
Shimabara
Motoike Spa 7/10/2019 31.0 8.1 27.8 6.0 1427 246.8 87.7 – 33.3 29.7 8.6
Kan'nonjima Spa 7/10/2019 29.8 7.9 43.8 18.1 1595 101.0 150.0 – 32.6 24.7 14.3
Obama
Obama Spa 7/11/2019 97.8 6.2 4388.4 279 227 2706.8 126.7 – 89.8 241.0 17.4
Karimizu 7/9/2019 25.8 2.1 6.4 143 0 7.3 13.4 – 47.7 7.5 3.7
Seawatera 12/1975 17.8 18,650 2450 138 10,250 1270 358 399

‘ID’ are location symbols shown in Fig. 2. HCO−

3 values represent total alkalinity.
a
Seawater composition was reported by Saibi and Ehara (2010).

input function. The range of anticipated tritium activities of fluids
in 2019 (the time of sampling = ts) was estimated by: AT (t) =
f(t)×e−λ(ts−t). These curves are shown with tritium activities of samples
in Fig. 5. The highest tritium activity observed at the creek flowing by
the Unzen-jigoku is within the range of current local precipitation. Tri-
tium activities below 0.5 TU, as observed for two fluid samples from
Shimabara and a frying pan feature in Unzen-jigoku, indicate a signifi-
cant contribution of pre-nuclear meteoric water. Two other samples
from Unzen geothermal field and one from Karimizu mineral spring
had intermediate tritium activities.
Chlorine-36 abundances were measured in three samples with rela-
tively high Cl contents; the 36Cl/Cl ratios were 9±2.4 ×10−15 and 10±
3.0 ×10−15 at Kan'nonjima spa and Motoike spa in Shimabara, respec-
tively, and 3±0.6 ×10−15 at the geothermal well in Obama. 36Cl abun-
dances have been studied in a few geothermal fields (Hedenquist
et al., 1990; Rao et al., 1996; Snyder et al., 2002), and were proven useful
for identifying sources of Cl. The study region is located at 32.8 °N where
estimated natural 36Cl fallout rate is 30 (±10) atoms/m2/sec (Phillips,
2013). With a mean annual precipitation of 2100 mm and typical Cl con-
tents of surface water between 3 and 8 mg/L, observed ratios fall within
the estimated range of 36Cl/Cl ratio in recharging meteoric water of
2.1–12×10−15, assuming a marine aerosol origin for chloride in
recharging water. A recent study of young groundwater at comparable
latitude in Chiba, Japan, reported pre-nuclear 36Cl/Cl ratios of 17–29
×10−15 (Tosaki et al., 2011). Considering the lower precipitation in
Chiba, the upper range of theoretical estimate for Shimabara appear rea-
sonable. These fluid samples have higher Cl contents compared to
surface water and shallow groundwater, suggesting contribution of Cl
from different sources as discussed below.
4. Discussion
4.1. Shimabara geothermal wells
The 36Cl/Cl ratio of 9±2.4 ×10−15 and 10±3.0 ×10−15 are within the
range of the anticipated local meteoric recharge ratio. The chloride con-
tent is several times higher than in local river waters and shallow
groundwater (Nakagawa et al., 2017; Amano et al., 2018), therefore,
chloride was probably added along the subsurface flow path. Because
subsurface-derived Cl could also have comparable or only slightly
lower 36Cl/Cl ratio, the effect of this mixing is difficult to quantify. How-
ever, the measured value clearly excludes significant contribution of
thermonuclear 36Cl which could elevate the 36Cl/Cl ratios by about
two orders of magnitude (Tosaki et al., 2011).
The tritium activities of samples from Shimabara geothermal wells
were close to background level in accordance to a single data previously
reported from this region (<0.5 TU: Kawabe, 1997). Our new measure-
ments from 2019 extend the lower limit of the water residence time by

Table 2
Isotopic compositions of geothermal fluids from Unzen graben.

Name δ18O δD Tritium 36

Cl/Cl

‰ ‰ TU ×10−15

Unzen
Unzen Jizo +3.9 ± 0.2 −5.8 ± 0.3 0.09 ± 0.06
Unzen Suzume −3.2 ± 0.3 −31.9 ± 0.9 1.23 ± 0.08
Unzen pipe −5.7 ± 0.0 −35.5 ± 0.2 1.02 ± 0.15
Unzen Creek −7.3 ± 0.0 −43.0 ± 0.1 2.50 ± 0.20
Unzen East Stream −4.7 ± 0.1 −33.4 ± 0.4
Unzen West Stream −3.6 ± 0.2 −29.3 ± 0.1
Shimabara
Fig. 4. Stable isotope compositions of geothermal fluids. Symbols are identical to Fig. 3.
Motoike Spa −8.1 ± 0.3 −48.0 ± 0.5 0.00 ± 0.05 10 ± 3.0
JZ3-MWL is the local meteoric line expressed as δD = 7.73 δ18O + 12.7 (Mizota and
Kan'nonjima Spa −7.9 ± 0.4 −48.4 ± 0.6 0.05 ± 0.05 9 ± 2.4
Kusakabe, 1994). The slope of the kinetic fractionation line (blue) is 3.44. The range of
Obama
andesite magmatic water is from Taran et al. (1989) and Giggenbach (1992a, 1992b).
Obama Spa −5.1 ± 0.2 −36.9 ± 0.1 0.55 ± 0.08 3 ± 0.6
Karimizu −6.6 ± 0.2 −44.2 ± 0.7 1.51 ± 0.08

5
R. Yokochi, R. Purtschert, Y. Suda et al. Journal of Volcanology and Geothermal Research 419 (2021) 107353

Fig. 5. Tritium activities of key samples are shown as horizontal dashed lines (Uz C = site C of Unzen, Kmz = Karimizu spring, Obm = Obama), whereas anticipated tritium level at the time
of sampling for the given time of recharge is shown in yellow zone. Temporal change of tritium levels in precipitation measured in or near Tokyo are also shown as gray symbols
(International Atomic Energy Agency/World Meteorological Organization (IAEA/WMO) (2018), Nuclear Regulation Authority (2021). Although latitudinal variation of tritium activity
across Japan was reported (e.g. Momoshima et al., 1991), detailed examination recently showed that such trend is prominent in northeastern part of Japan (Gusyev et al., 2019). Black
symbols and lines are tritium levels in precipitation measured in Fukuoka and Kumamoto, near the study area (Momoshima et al., 1991; Matsuoka et al., 1994; Hayashi et al., 1999;
Momoshima et al., 2007, 2008; Yokoyama et al., 2011), within the range of data from Tokyo. Note that two data from Fukuoka are at the higher end of the spectrum, possibly impacted
by a local anthrologenic source (Gusyev et al., 2019), but the slightly higher background level will not affect our conclusion.

25 years (the time difference between two sampling campaigns) at two
different geothermal wells tapping the same formation. The absence of
tritium indicates isolation of the bicarbonate fluid from the overlying al-
luvial aquifer. The tritium data in this fluid had never been discussed in
the context of volcanic signals transported in the aquifer, but this is the
area where a change in 3He/4He ratios was reported prior to the erup-
tion of Mt. Fugen in 1990. He isotope ratios continued to increase and
peaked in July 1992, which was 6 months to 1 year after the peak of
magma effusion (Nakada et al., 1999) and SO2 discharge rates
(Hirabayashi et al., 1995) in mid- to late-1991 (Notsu et al., 2001). The
prolonged residence time of the geothermal fluids from this region
(>60 years based on tritium data) means that the advective flow of
the fluid is too slow to transmit the volcanic signal in the observed re-
sponse time scale of one year or less over the 8 km distance between
the Mt. Fugen volcanic cone to Shimabara.
An alternative transport mechanism of magmatic volatiles is
through faults. Shallow groundwater and cold spring waters from
Shimabara contained significant contributions of magmatic C character-
ized with elevated δ13C compared to groundwater in equilibrium with
soil CO2, especially along the stretch of the two major faults close to
Mt. Fugen (Akamatsudani fault and Chijiwa fault; Ohsawa et al.,
2002b). Soil gas measurements transecting the Akamatsudani fault
also revealed enhanced magmatic CO2 concentrations near the fault
based on the geographic distribution of radiocarbon and δ13C
(Takahashi et al., 2004). Furthermore, an extensive mapping of
3
He/4He ratios in groundwater and thermal water showed that even
shallow, low-temperature groundwaters ubiquitously contain signifi-
cant amounts of dissolved magmatic He (Morikawa et al., 2008).
These previous studies demonstrated that, in the eastern part of the
Unzen graben, faults crosscutting aquifers and soil layers serve as path-
ways for relatively rapid vertical transport of magmatic volatiles. How-
ever, a detection of magmatic volatiles in groundwater requires lateral
transport from the fault intersecting the aquifer. The creation of fluid
pathways by rock fracturing could also be induced by pre-eruption
volcanic earthquakes. On other volcanoes where comparable time
scales of the magmatic volatile signal response time was reported
(7–15 km/yr at Nevado del Ruiz volcano by Sturchio et al., 1988; Sano
et al., 1990; Sturchio and Williams, 1990, 6–18 km/yr at Mt. Mihara by
Sano et al., 1988), either a magmatically perturbed and enhanced hy-
draulic gradient or gas phase transport were suggested as possible
mechanism for rapid signal transfer. Because the baseline measurement
(Marty et al., 1989) was carried out several years prior to the eruption, it
is unclear how the 3He/4He ratio increased over time prior to the 1990
eruption (e.g. abrupt vs. gradual). For better understanding of the mag-
matic volatile transport processes, continuous monitoring is desirable
between and during eruption cycles.
4.2. Unzen geothermal field (jigoku)
The chemical compositions of fluids from Unzen-jigoku had low
chloride and other solute contents comparable to local rivers and shal-
low groundwater, but they were acidic and highly enriched in sulfate.
Such acid-sulfate type fluids are common in geothermal fields and are
typically attributed to absorption and oxidation of H2S-containing
steam into surface waters (Craig, 1963; Giggenbach, 1978), as inferred
for Unzen-jigoku by Ohsawa (2006). The stable isotope compositions
of thermal waters from Unzen-jigoku were heavier compared to the
meteoric water from nearby creek [site C] and in a plot of δD vs. δ18O
they define a line with a slope of 3.4 (Fig. 4). All but one samples from
the Unzen-jigoku had relatively high (>1 TU) tritium activity, indicating
a significant contribution of young water, probably from precipitation
within the surface watershed. The sample collected at the site C has
highest tritium activity which is within the range of modern precipita-
tion. Taken together with the δD-δ18O values which plot on JZ3-MWL,
this samples is considered to represent the isotopic compositions of
young meteoric water with minimal geothermal input. The tritium ac-
tivity is lower in sulphate-rich samples, indicating a higher proportion
of steam condensate. A high temperature (79.0 °C) frying-pan type

6
R. Yokochi, R. Purtschert, Y. Suda et al.
feature [site J] had only trace tritium activity with the heaviest δD-δ18O
composition.
The isotopically heavy water of steam-heated surface pools results
from a kinetic isotope fractionation during evaporation where local me-
teoric water and emanating steam interact (Craig, 1963; Truesdell et al.,
1977; Giggenbach, 1978). Following Giggenbach and Stewart (1982),
water evaporation from thermal discharges at the surface can be
modeled as a kinetic process with effective fractionation factors:
ε0D ðT Þ ¼ εD ðT Þ þ 8:4
ε018 O ðT Þ ¼ ε18 O ðT Þ þ 10:12
where ε are equilibrium fractionation factors. In case of the steady-state
evaporation from continuously heated and replenished pools, the isoto-
pic compositions of water (w) and steam (s) entering (i) and leaving
(o) the pool can be expressed as:
δwo −δso ¼ ε0 ðT Þ
δwo ¼ δwi þ f ðδsi −δwi þ ε0 ðT ÞÞ
where f is the fraction of steam contributing from the depth. At 79 °C,
the effective fractionation factors (i.e. equilibrium and kinetic effects
combined) between liquid water and water vapor are 16.1 and 45.6‰
for δ18O and δD, respectively (Giggenbach and Stewart, 1982; Horita
and Wesolowski, 1994). Assuming that the sample containing the low-
est tritium level (J) has a minimal contribution from surface water, the
evaporation at the measured temperature of 79 °C leads to δDsi and
δ18Osi values of −51.4 and −12.2‰. Measured δD and δ18O values at
each geothermal site represent δwo, whereas the surface water from site
C can represent δDwi and δ18Owi values of −43 and −7.3‰. Eq. (5) for
oxygen and hydrogen gives:


δDwo ¼ δDwi þ f δDsi −δDwi þ ε0D ðT Þ ð6Þ
 
δ18 Owo ¼ δ18 Owi þ f δ18 Osi −δ18 Owi þ ε018 O ðT Þ
The evaporation curve at 28 °C (temperature of surface water from
the creek) and 90 °C are shown on a δD and δ18O diagram, together
with the fraction f of steam contribution and relevant data (Fig. 6).
The low tritium activity at site J suggests the presence of a conduit
enabling older (pre-nuclear) heated water/steam to ascend without
mixing with young, shallow groundwater or surface water. Based on
the hydrograph analyses of the Unzen-jigoku, Tabata (1960) reported
correlations between the fluid flux and time-ramped sum of the local
precipitation. Furthermore, the fluid flux was negatively correlated to
temperature. The author interpreted this anti-correlation as a result of
varying groundwater flux through a geothermal area with constant
Fig. 6. Modeled water isotope evolution (δwo) via water evaporation from thermal
discharges and mixing with surface water at the surface pool. Open triangle represents
the estimated steam composition. Solid triangles are the data of samples from Unzen
geothermal field. Key samples are shown as large symbols with location ID label.
Journal of Volcanology and Geothermal Research 419 (2021) 107353
heat flux over a transfer time scale of 60 days. The depleted tritium
data suggest that an additional, older, water source (i.e. not limited to
heat and sulfate) contributes to Unzen-jigoku features, and that the
flux is sufficient to locally form undiluted pools. Higher tritium activities
observed within this area can simply be attributed to mixing with young
meteoric water precipitated within the geothermal basin. An analysis of
stream networks within the geothermal area using a digital elevation
model (Geospatial Information Authority of Japan, 2019) indicates
that surface water and the geothermal fluids passing through the
ð2Þ main jigoku area drain through the sample collection site E (Fig. 2).
Therefore, fluid sample collected at the site E provides a first-order esti-
ð3Þ
mation of water contribution from the steam to this geothermal area. As
shown in Fig. 6, the isotopic composition at the pour point of the geo-
thermal field (site E) indicates approximately a quarter contribution of
water from the steam.
The analysis of stream networks also indicates that watershed areas
are relatively small for the three samples collected within the geother-
ð4Þ mal field (Fig. 2). Two of the samples [J and P] were located near each
other; their watersheds are practically identical, and site [P] was up-
ð5Þ stream of [J]. As described above, an artificial construction with buried
pipes appears to gather the fluids from upgradient and beneath at the
site [P] and the fluid is extracted for local spas, limiting the flow of me-
teoric surface water to the site J. This explains the low tritium activity at
site J. For the studies of acid-sulphate type fluids which can rapidly react
with oxygen, chemical compositions of gas may not necessarily be a
good indicator of contribution from surface water. Stream network
analyses can provide a useful a priori insight into possible contributions
of surface water to surface geothermal features, which would be useful
for preselecting the sampling sites most suitable for forecasting volcanic
activity.
4.3. Obama geothermal area
The chemical compositions of Karimizu spring changed from
bicarbonate-type (Ohsawa et al., 2002a; Morikawa et al., 2008) to
ð7Þ acid-sulfate -type. This change could be attributed either to variations
of flux and/or composition of the source, or due to different water-
rock-interaction and degassing processes during the transport of sulfu-
ric gas in the subsurface. It is desirable to further investigate the cause of
this compositional change and whether it is chronic, temporal or cyclic.
The similarity in chemical composition suggests a common process that
generated this mineral spring water to Unzen-jigoku.
The Obama geothermal fluid sample is greatly enriched in Cl, Na, and
K compared to surface and shallow subsurface water, requiring a contri-
bution of highly saline water. It was previously attributed primarily to a
mixing of shallow meteoric water with heated seawater or deep-seated
brine (Ohsawa et al., 2002a). The relatively low tritium activity of
Obama geothermal spa water (0.55 TU) is most probably a result of
mixing between young meteoric water similar to the one contributing
to Karimizu mineral spring and older saline water. A hydraulic connec-
tion of Obama geothermal field with the modern ocean was demon-
strated by the increased salinity during the time period of salt mining,
during which the water table dropped and induced seawater intrusion
(Saibi and Ehara, 2010). However, the Obama geothermal fluid sample
has slightly higher 36Cl/Cl ratio of 3±0.6 ×10−15 than that of modern
seawater (0.5±0.3 ×10−15; Argento et al., 2010), which indicates a Cl
contribution from a source other than modern seawater. This is consis-
tent with a larger δ18O-shift of these fluids than that produced by a sim-
ple mixing of meteoric water and seawater, necessitating a contribution
of andesitic magmatic water or high-temperature oxygen exchange
with rocks (Ohsawa et al., 2002a; Saibi and Ehara, 2010; Taran et al.,
1989; Giggenbach, 1992a, 1992b).
The subsurface production of nucleogenic 36Cl by the 35Cl(n,γ)36Cl
reaction occurs by thermal neutrons originating from U and Th fission
as well as from (α,n) reactions in the rock matrix (Davis Jr. and
Schaeffer, 1951; Lehmann and Purtschert, 1997). Under closed system
7
R. Yokochi, R. Purtschert, Y. Suda et al.
Fig. 7. Schematic diagram of geothermal systems in the Unzen graben, adapted from Ohta (2005) and Ohsawa (2006). Blue lines represent flow of cold water.’YMW’ stands for ‘young
meteoric water’.
conditions (e.g. constant Cl) the 36Cl/Cl ratio converges toward a value
proportional to the U and Th contents of the local rock matrix on a
time scale of 1.5 Myr, regardless of the Cl content (Phillips, 2000;
Purtschert et al., 2021). In the steady state, the observed 36Cl/Cl ratio
of 3 ×10−15 corresponds to a few ppm U, which is within the range of
concentration for volcanic and pyroclastic rocks from Unzen volcanism
(1.5–2.7 ppm: Takashima and Watanabe, 1994; Shimao et al., 1999).
The data can therefore be explained by a subsurface addition of
nucleogenic 36Cl during prolonged residence of the chloride-rich fluid
in crust. The tritium activity in the sample does not conflict this inter-
pretation because mixing of tritium-bearing (Cl-poor) freshwater will
have minimal effect on 36Cl/Cl ratio.
A possible candidate for the source of salinity in the Obama geother-
mal fluid is the deep-seated Na-Cl fluid detected in borehole N61-UZ-7,
lateral migration of which was anticipated toward Obama geothermal
area based on subsurface thermal anomalies (NEDO, 1988; Ohsawa,
2006). This deep-seated fluid had Cl contents comparable to the
Obama geothermal fluid but was characterized by a larger δ18O-shift
from JZ3-MWL, making it apparently an implausible contributor. How-
ever, tritium was detected in the fluid from N61-UZ-7, indicating that
this deep-seated saline fluid was diluted to some degree by young and
fresh meteoric water recharged at a higher elevation. If the original
deep-seated saline fluid prior to the dilution had been highly enriched
in Cl compared to the Obama geothermal fluid, the Cl from the deep-
seated fluid could dominate the Cl budget with minimal δ18O-shift. A
minor contribution of modern seawater is also probable, thus more sys-
tematic study is desirable for quantitative determination of Cl budget in
this geothermal system.
5. Conclusion
Aiming at understanding the origin and flow dynamics of geother-
mal fluids in volcanic geothermal systems, we analyzed tritium and
36
Cl activities of geothermal fluids along with their chemical and stable
isotopic compositions from three geothermal areas in Shimabara penin-
sula. A simplified schematic of the main processes of the geothermal
system as deduced from the new data is depicted in Fig. 7. The
bicarbonate-type fluids from low temperature wells in Shimabara are
tritium free and thus have subsurface residence times greater than 60
years. The disagreement between the time scales of advective fluid
flow and volcanic signal response reported in the literature (Notsu
et al., 2001) indicates that the transport of magmatic volatiles and
movement of geothermal fluids are decoupled in this aquifer. In the
8
Journal of Volcanology and Geothermal Research 419 (2021) 107353
Unzen geothermal field, the stable isotope compositions of six samples
plot on a line representing a mixing between isotopically enriched sam-
ples with trace tritium activity and surface waters with tritium activity
comparable to current local precipitation. Based on the estimate of the
source isotope compositions, the steam feeding this geothermal field
appears to originate from pre-nuclear groundwater of meteoric origin.
Despite the relatively long (>60 years) subsurface residence time of
the fluid, the boiling and steam generation can be an ongoing process,
i.e. the addition of the magmatic volatiles can be recent. For a better un-
derstanding of the magmatic volatile transport processes, further con-
straints on the fluid flow time scale and continuous monitoring of
volcanic signals are needed while a volcano is at rest between eruption
cycles. The first measurement of 36Cl/Cl ratios in Obama geothermal
fluids revealed that chloride in the NaCl-type fluid is not simply derived
from seawater, although a hydraulic connection to ocean had been pos-
tulated. A systematic 36Cl/Cl study in Obama geothermal fluids could
potentially help to better understand the significance of the apparent
nucleogenic 36Cl contribution.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by NSF Petrology and Geochemistry pro-
gram (EAR-1906305) and the Swiss National Science Foundation
(contract no.200020/172550). NCS thanks the University of Tokyo,
Atmosphere and Ocean Research Institute, for support as a Guest Profes-
sor during summer 2019. We are grateful to two reviewers, Tobias
Fischer and Franco Tassi, for their comments which significantly im-
proved the manuscript. We thank the ministry of the environment
and the city of Obama for granting the access to the sampling sites.
We thank Mr.Hamabe of Shimabara city office for guiding our sam-
pling at the city-operated geothermal wells. Linnea Heraty and Eliza-
beth Lofredo are thanked for laboratory assistance at the University
of Delaware. We are grateful to Ayaka Kumatani for the help in the
field. RY thanks H. Kobayashi, N. Morikawa, E. Gayer and K. Horiguchi
for help, advice and discussions. Dr. M. Gusyev is acknowledged for
very kindly providing the tritium data from the discontinued NIRS da-
tabase. RY thanks J. Eason and PSD Desktop Support for their support.
R. Yokochi, R. Purtschert, Y. Suda et al.
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