Water-Rock interaction (WRI-11) 2004. Wanty & Seal II eds. A.A Balkema Publishers.

Geochemical evolution of the young crater lake of Kelud volcano in

Indonesia
A. Bernard & A.Mazot
BRUEGEL (Brussels unit for Environmental, Geochemical and Life Sciences Studies), Universit Libre de
Bruxelles, Brussels, Belgium

ABSTRACT: After the February 1990 plinian eruption of the Kelud volcano, a new lake rapidly filled its cra-
ter. This young lake offers the opportunity to study the evolution and re-equilibration of a volcanic-
hydrothermal system after a magmatic eruption. Geochemical and thermal changes of the crater lake have
been recorded during the period 1993-2003 in which a decrease in temperature and ionic concentrations of the
lake was observed. The initial lake chemistry (1993-1997) was dominated by Na-K chloride waters. Today,
Ca-Mg sulfate waters are the main component in the lake. The temporal evolution in the chemistry of the lake
waters suggests the presence of two distinct hydrothermal systems feeding the lake: a deep system at high
temperature (250C) with neutral alkali-chloride fluids and a shallow aquifer at lower temperature dominated
by Ca/Mg-sulfate waters.

1 INTRODUCTION (~6) relatively diluted water with a TDS of a few

g.kg-1 (Table1).
Kelud is one of the most active volcanoes of Java This neutral composition contrasts with the
with a record of 29 eruptions since 1311 and with highly acidic waters (pH = 0-1) most frequently ob-
repose intervals between eruptions ranging from 1 to served in active crater lakes where the discharge of
75 years. After the last eruption that occurred in magmatic volatiles (SO2, HCl, HF) directly into the
February 1990, a new lake rapidly filled the crater of lake or into the sub-surface hydrothermal system
this volcano. Persistent degassing from subaqueous produces acid sulfate-chloride waters with elevated
fumaroles and hot springs discharging into the lake Al and Fe contents.
maintain water temperatures between 31-50C,
higher than the ambient temperature of 19C. The
lake is shallow with a maximum depth of 34 m and a
volume estimated at 2.1 million m3. Table 1. Selected compositions of Kelud crater lake. Data are
A tunnel was drilled through the crater wall in 1926 in mg.kg-1.
__________________________________________________
to drain the lake and keep its volume constant. High KCL3 KCL9 KCL37 KCL56
overflows through the drainage tunnel (between 300 Date 18 Dec 93 1 Aug 94 24 Sept 02
__________________________________________________ 4 Sept 03
and 500 kg s-1) are typically observed even during Temperature 42.8 42.1 33.2 30.7
the dry season. This high overflow combined with (C)
Depth 15 32 0 0
the small volume of the lake make the residence (m)
times of the elements in the lake particularly short, pH 5.9 6.3 6.5 6.5
around 80-100 days. The temperature and geochem- TDS 3.2 3.7 2.2 2
istry of the lake has been regularly monitored since (g/kg)
1993 in order to understand the processes leading to Na 700 1020 342 271
the re-equilibration of the lake-hydrothermal system K 92 102 39 30
Ca 105 130 135 147
after the February 1990 magmatic eruption. Mg 55 67 80 78
Si 109 133 129 111
B 11 14 4 3
2 GEOCHEMISTRY OF THE LAKE WATERS F 6 7 <1 <1
Cl 1300 1300 290 200
SO4 631 692 670 679
The composition of the lake is rather unusual for an HCO -
238 207 435 472
active volcano and corresponds to a near-neutral pH __________________________________________________
3
 Water-Rock interaction (WRI-11) 2004. Wanty & Seal II eds. A.A Balkema Publishers.

The evolution of temperature and geochemistry
during the period 1993-2003 is shown on Figure 1.
The general trend is toward a decrease in tempera-
ture and TDS, the lake becoming more diluted with
time. The main geochemical change observed is a
decrease in Na+K chlorides, sulfates and Ca/Mg re-
maining almost constant during this period (Table
1).
1994 1995 1996 1997 1998 1999 2000 2001 2002 2003
55
Temperature C
served 3 months before the 1990 eruption (Vande-
meulebrouck et al. 2000).
The temperature increases observed in 1996 and
2001 were accompanied by rapid changes in lake-
water composition with a net increase in Na+K chlo-
rides, B and Li. These heating episodes could be the
consequence of the (re)opening of fractures at depth
leading to an increase in the contribution from a
deep hydrothermal aquifer. This evolution suggests
that two distinct hydrothermal systems are feeding
the crater lake. The first aquifer has neutral alkali
chloride waters enriched in B and Li typical of the
deepest part of hydrothermal systems and the second

50
45 shallow system is dominated by Ca-Mg sulfate wa-
40 ters.
35
Cl (mg/kg)
30
25 200 400 600 800 1000 1200 1400
1400

3 1200
Na + K (mg/kg)
1000
-1
TDS (g.kg )
2 Cl/SO4 800
1993
600

1 400

Na/SO4 200
14

12

K/SO4 10
B (mg/kg)

1993
8
0
1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 6

4
Date
2
Figure 1. Temporal evolution of the temperature and chemistry
of the lake during 1993-2003. Arrows represent the start of a 0
heating episode. TDS is the Total Dissolved Solids. 200 400 600 800 1000 1200 1400

With the exception of the 1993 data, there are
positive correlations between chloride and the alkali
metals or with B and Li but no correlation exists
with Ca or Mg (Figs. 2 and 3).
During the 10-year monitoring period, two nota-
ble events were observed in 1996 and 2001 when a
sudden increase in lake temperatures and bubbling
occurred. In both events, the lake temperature
peaked at 50C. Heating episodes, sometimes cyclic,
are relatively frequent in some crater lakes and re-
flect changes in the flow rate or in the enthalpy of
hot fluids entering the lake. These heating episodes
always represent an alarming situation because an
increasing lake temperature can be a precursory sig-
nal for the renewal of magmatic activity as was ob-
Cl (mg/kg)
Figure 2. Evolution of chloride versus Na+K and boron during
1993-2003.
3 TEMPERATURE ESTIMATION OF THE
DEEP HYDROTHERMAL SYSTEM
The presence of a deep alkali chloride system sug-
gests the use of Na-K and K-Mg as geoindicators.
Equilibrium temperatures for Na/K and K/Mg and
based on Giggenbach (1988) are presented in Figure
4.
The lake water compositions are far from the
equilibrium with a mineral assemblage as expected
for waters resulting from the mixing between two
 Water-Rock interaction (WRI-11) 2004. Wanty & Seal II eds. A.A Balkema Publishers.

600 plinian eruption. The average log Na/K value around

0.9 could reflect equilibrium temperatures close to
250C in the deep hydrothermal system. On Figure
500
5, these Na/K equilibrium temperatures are com-
Na (mg/kg)

pared to the Na-Li geothermometer of Verma &

400 Santoyo (1997) assuming a saline brine.

300 4 STABLE ISOTOPE COMPOSITIONS

The hydrogen (D/H) and oxygen (18O/16O) isotope

200 ratios also show changes clearly correlated with
200 300 400 500 600 700 changes in temperature or chloride contents. Figure
Li (g/kg) 6 shows the strong positive correlation between
Figure 3. Evolution of Li versus Na during 1993-2003. chloride and oxygen isotopic composition, except
for the 1993 data. The same positive trend exists be-
tween chloride and (D/H). This trend can be inter-
preted as a mixing line between two end members.
150

TNa-K C The first is represented by the deep neutral-chloride

200

100
250
300
350

7 350 fluids with a heavier isotopic composition and the

Fu
ll 300 second by the shallow sulfate fluids with an isotopic
Log K2 / Mg (mg/kg)

6 Eq
ui l 250 composition identical to meteoric fluids (spring).
5 ibr
Im ium 200
ma
4 tur
e wa 150 -1
3 ter 8/1996
s -2
2 100
-3
TK-Mg C
1993
1
18O ()

-4 1/2001
0.0 0.5 1.0 1.5 2.0

Log Na / K (mg/kg) -5
5/2000
Figure 4. .K-Mg and Na-K equilibrium temperatures. -6

-7
spring
-8
350

250

100
300

200

150

TNa-K C 0 200 400 600 800 1000 1200 1400

100
Cl (mg/kg)
Log Na / Li (moles/kg)

3.0
equ
ll
Fu
2.5
2.0
0.5 1.0
Log Na / K (mg/kg)
Figure 5. Na-Li and Na-K equilibrium temperatures.
types of fluids. However, the Na/K remained almost
constant during the entire period despite a large de-
crease in their concentrations. This suggests that the
composition of the deep neutral-chloride hydrother-
mal system remained stable during this period. The
deep hydrothermal system most probably existed be-
fore the 1990 eruption and its composition was not
significantly affected by the relatively brief (1 hour)
m
ibriu
il
150 Figure 6. Evolution of the 18O () isotopic composition ver-
sus chloride for the lake.
200
250
5 THERMAL REGIME
300
350 Like many other active crater lakes, Kelud acts as a
1.5 2.0
TNa-Li C calorimeter trapping the heat supplied into the lake
by subaqueous fumaroles and hot springs. A heat
and mass balance model was used to evaluate the
changes in the heat supplied to the lake by the
hydrothermal fluids. The model is derived from Ste-
venson (1992) and assumes that the lake is in steady-
state equilibrium, i. e. that the lake temperature is
constrained by the balance between heat input and
output. Heat is derived from the enthalpy of hydro-
thermal fluids (brine + steam) entering and mixing
within the lake and from solar and atmospheric ra-
diation (rad). Heat is lost by evaporation (evap),
conduction (cond), radiation (rad) and by the over-
 Water-Rock interaction (WRI-11) 2004. Wanty & Seal II eds. A.A Balkema Publishers.

flow (over) of the hot waters through the drainage
tunnel. The lake surface radiated a thermal power es-
timated at 130 MW for the period 1993-1995 (Fig.
7), peaked to 250 MW in 1996 and 2001 when the
lake surface reached 50C and is today close to 80
MW.
canic edifice or are only accessible by well-drilling.
For Kelud, the 1990 eruption cleared the vent and
permitted the ascent of fluids from the deep neutral-
chloride hydrothermal system. Today, this channel
opens towards the surface, is progressively clogged
and the contribution from the deep Na/K chloride
fluids to the lake is decreasing.

T air : 19C REFERENCES

T water : 42C

Chiodini, G., Frondini, F. & Raco, B. 1996. Diffuse emission

of CO2 from the Fossa crater,Vulcano Island (Italy): Bull.
Eevap : 80 MW Volcanol. 58: 41-50.
Mevap : 32 kg.s
-1 Eover : 29 MW
Econd :15 MW Giggenbach, W.F. 1988. Geothermal solute equilibria. Deriva-
Erad : 7 MW Mover : 300 kg.s-1
Cl : 33 T.day
-1 tion of Na-K-Mg-Ca geoindicators. Geochim. Cosmochim.
S : 6 T.day
-1 Acta 52: 2749-2765.
Stevenson, D.S. 1992. Heat transfer in active volcanoes: mod-
els of crater lake systems. PhD thesis, The Open University,
235p.
E brine + steam : 130 MW Vandemeulebrouck, J., Sabroux, J.C., Halbwachs, M., Surono,
Poussielgue, N., Grangeon, J. & Tabbagh, J. 2000. Hy-
droacoustic noise precursors of the 1990 eruption of Kelut
Figure 7. Heat and mass balance model calculated for a lake volcano, Indonesia. J. Volcanol. Geotherm. Res. 97: 443-
temperature of 42C. 456.
Verma, S.P. & Santoyo, E. 1997. New improved equations for
Na/K, Na/Li and SiO2 geothermometers by outlier detection
6 CO2 DEGASSING and rejection. J. Volcanol. Geotherm. Res. 79: 9-23.

The CO2 flux emitted by the surface of the lake was

measured during 2001-2003 by IR spectrophotome-
try using a Drger Polytron. We modified the tech-
nique initially developed for soil gas flux monitoring
by Chiodini et al. (1996) in order to work on a crater
lake by using a floating accumulation chamber. Dur-
ing each field campaign, about 260 measurements
were obtained to cover the entire lake surface
(105,000 m2). Results show a decrease in the CO2
flux from 30,000 T/year in 2001 to 13,000 T/year in
2003 following the temperature decrease. These re-
sults compared to the CO2 lost as HCO3- by the
overflow of the lake waters through the drainage
tunnel show that most of the CO2 degasses from the
lake surface and escapes to the atmosphere. Only a
small fraction (<15%) is trapped and converted as
HCO3- in the lake waters.

7 CONCLUSION

In the case of Kelud, the lack of acidity and low

fluoride content suggest that the input of magmatic
volatiles to the hydrothermal system is low or lim-
ited. Only the samples collected in 1993 are slightly
different in Cl and stable isotopic compositions. This
could suggest that a small input of magmatic vola-
tiles was still present 3 years after the eruption.
The emission of neutral-chloride fluids at the top
of a volcanic edifice is a relatively rare situation.
These neutral-chloride fluids are generally dis-
charged at low elevation on the flanks of the vol-