Geochemistry

Geophysics
Geosystems

Article
Volume 10, Number 2
6 February 2009
Q02005, doi:10.1029/2008GC002191

AN ELECTRONIC JOURNAL OF THE EARTH SCIENCES

Published by AGU and the Geochemical Society

ISSN: 1525-2027

Water and gas chemistry at Lake Kivu (DRC): Geochemical

evidence of vertical and horizontal heterogeneities in a
multibasin structure
F. Tassi
Department of Earth Sciences, University of Florence, Via G. La Pira 4, I-50121 Florence, Italy (francot@geo.unifi.it)

O. Vaselli
Department of Earth Sciences, University of Florence, Via G. La Pira 4, I-50121 Florence, Italy
Institute of Geosciences and Earth Resources, CNR, Via G. La Pira 4, I-50121 Florence, Italy

D. Tedesco
Department of Environmental Sciences, Second University of Naples, Via Vivaldi 43, I-81100 Caserta, Italy
Office for the Coordination of Humanitarian Affairs, United Nations, Palais de Nations, Geneva 10, CH-1211
Switzerland

G. Montegrossi
Institute of Geosciences and Earth Resources, CNR, Via G. La Pira 4, I-50121 Florence, Italy

T. Darrah
Environmental and Earth Sciences Department, University of Rochester, 227 Hutchison Hall, Rochester, New York
14627, USA

E. Cuoco
Department of Environmental Sciences, Second University of Naples, Via Vivaldi 43, I-81100 Caserta, Italy

M. Y. Mapendano
Goma Volcano Observatory, Mount Goma, Goma, Democratic Republic of the Congo

R. Poreda
Environmental and Earth Sciences Department, University of Rochester, 227 Hutchison Hall, Rochester, New York
14627, USA

A. Delgado Huertas
Estacion Experimental de Zaidin, Prof. Albareda 1, E-18008 Granada, Spain

[1] Waters and dissolved gases collected along vertical profiles in the five basins (Main, Kabuno Bay,
Kalehe, Ishungu, and Bukavu) forming the 485 m deep Lake Kivu (Democratic Republic of the Congo)
were analyzed to provide a geochemical conceptual model of the several processes controlling lake
chemistry. The measured horizontal and vertical variations of water and gas compositions suggest that each
basin has distinct chemical features produced by (1) different contribution from long circulating fluid
system containing magmatic CO2, responsible of the huge CO2(CH4)-rich reservoir hosted within the deep
lake water; (2) spatial variations of the biomass distribution and/or speciation; and (3) solutes from water-

Copyright 2009 by the American Geophysical Union

1 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

10.1029/2008GC002191

rock interactions. The Kabuno Bay basin is characterized by the highest rate of magmatic fluid input.
Accordingly, this basin must be considered the most hazardous site for possible gas outburst that could be
triggered by the activity of the Nyiragongo and Nyamulagira volcanoes, located a few kilometers north of
the lake.
Components: 11,429 words, 8 figures, 5 tables.
Keywords: Lake Kivu; lake water geochemistry; limnic eruption; geochemical modeling.
Index Terms: 1009 Geochemistry: Geochemical modeling (3610, 8410); 1065 Geochemistry: Major and trace element
geochemistry; 1041 Geochemistry: Stable isotope geochemistry (0454, 4870).
Received 28 July 2008; Revised 1 December 2008; Accepted 29 December 2008; Published 6 February 2009.
Tassi, F., O. Vaselli, D. Tedesco, G. Montegrossi, T. Darrah, E. Cuoco, M. Y. Mapendano, R. Poreda, and A. Delgado Huertas
(2009), Water and gas chemistry at Lake Kivu (DRC): Geochemical evidence of vertical and horizontal heterogeneities in a
multibasin structure, Geochem. Geophys. Geosyst., 10, Q02005, doi:10.1029/2008GC002191.

1. Introduction
[2] Lake Kivu (1460 m above sea level (asl)), the
smallest of the African Great Rift lakes, lies on
the border between the Democratic Republic of the
Congo (DRC) and Rwanda, in the tectonically and
volcanically active Western Branch (Albertine Rift)
of the East African Rift System (EARS) [e.g.,
Ebinger, 1989; Furman, 2007]. As first reported
by Damas [1937], the lake is characterized by the
presence of a large gas reservoir at depth >5080 m
that, as indicated by subsequent investigations [e.g.,
Schmitz and Kufferath, 1955; Capart, 1960], has a
CO2(CH4)-rich composition. In 2004, the calculated
total amounts of CO2 and CH4 stored as dissolved
phase in the permanently stratified deep waters of
Lake Kivu were estimated to be about 300 and 55 km3
STP (gas volume at 0C and 1 atm), respectively
[Schmid et al., 2005], and forms an exploitable gas
reservoir [Tietze, 2000; Doevenspeck, 2007]. Two
active volcanoes, Nyamulagira and Nyiragongo,
dominate the northern side of the lake and. during
two recent eruptive episodes (1977 and 2002)
Nyiragongo has produced lava flows that have
occasionally reached and partly destroyed the lakeside city of Goma (2002) and the surrounding
villages (1977) and entered the lake (2002) [e.g.,
Tazieff and Bichet, 1979; Schmid et al., 2004;
Tedesco et al., 2007]. The 17 January 2002 event
has raised serious concerns about a possible occurrence of thermally driven catastrophic degassing of
the lake, similar to those experienced at the Monoun
[e.g., Sigurdsson et al., 1987] and Nyos lakes
(Cameroon) in 1984 and 1986, respectively [e.g.,
Kling et al., 1987; Evans et al., 1993]. Previous
studies have examined the mechanisms regulating
the dynamic equilibrium and stability of Lake Kivu

to better understand the risk of limnic eruptions

[e.g., Lorke et al., 2004; Schmid et al., 2004,
2005], using water and dissolved gas chemical data
provided by previous investigations [e.g., Deuser et
al., 1973; Tietze, 1978; Schoell et al., 1988]. Other
investigations have dealt with the recent evolution
of the biomass present in the lake in relation to the
introduction of new fish species and changes of the
nutrient input from anthropogenic sources [e.g.,
Dumont, 1986; Isumbisho et al., 2004; Sarmento
et al., 2007]. However, a detailed risk assessment
requires a comprehensive investigation of the spatial
variation of dissolved species within the lake and its
control on the major physical-chemical processes.
This work examines the distribution of chemical and
isotopic compositions of the water and dissolved gas
along vertical water columns within different subbasins of Lake Kivu. The main goals of this study
are to (1) compositionally characterize the different
morphological and geochemical sectors of Lake
Kivu; (2) assess the geochemical features of the
hydrothermal fluid emissions discharging from the
lakes bottom; (3) provide a geochemical conceptual
model of the lake by taking into account precipitation and dissolution processes, effects of biological
activity, and inputs of deep-seated fluids.

2. Geographic Location and

Limnological Features
[3] Lake Kivu (located between 1300 and 2300S
and 28500 and 29230E) was formed in the Pleistocene, as a consequence of the intense volcanic
activity of the Virunga Mountains, which dammed
the Great Rift Valley and reversed the northward
flow of the rivers in the valley [Holzforster and
2 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

10.1029/2008GC002191

[4] Water density and temperature in the Main

basin show a large increase with depth that efficiently inhibit vertical mixing. The lake is indeed
meromictic, with an epilimnion, reaching a depth
of 5080 m, and a well-developed hypolimnion
hosting a vast CO2- and CH4-rich gas reservoir
[Schmid et al., 2005, and references therein]. Tietze
[1978] reported a relatively low spatial heterogeneity of water chemistry in the Main basin, ascribing this feature to water mixing because of double
diffusive convection. This process, likely promoted
by the different rates of molecular diffusion of heat
and salt, is able to induce horizontal flows and
circulation cells at depth [Turner, 1973; Spigel and
Priscu, 1998]. Conversely, the main physicalchemical parameters, i.e., density, electrical conductivity, and temperature, measured along vertical
profiles at Kabuno Bay, Kalehe, Ishungu, and
Bukavu basins, were found to be clearly distinct
[Tietze, 2000]. This suggests that the waters of the
various subbasins of Lake Kivu are likely fed by
different fluid sources and/or biochemical processes
controlling water chemistry (i.e., water-rock
interactions, bacterial activity) that are not homogeneously distributed all over the entire lake.

3. Sampling and Analytical Methods

Figure 1. Map of Lake Kivu with the location of the
sampling sites.

Schmidt, 2007, and references therein]. Presently,

Lake Kivus surface waters are maintained at an
elevation of 1462 1463 m asl by the Mururu
hydroelectric plant near Bukavu (Figure 1). The
waters are discharged toward south into the Ruzizi
river and that enter Lake Tanganyika at a rate of
3.2 km3/a. The worlds tenth-largest inland island,
Idjwi, lies in the center of Lake Kivu and has a
population of more than 100,000 DRC citizens and
about 50,000 Rwandan refugees. The 1200 km long
lake shoreline hosts several large cities and towns,
including Bukavu, Kabare, Kalehe, Sake, and Goma
in DRC and Gisenyi, Kibuye, and Cyangugu in
Rwanda, with a total lakeside population of about
2,000,000. Lake Kivu has a total surface area of
2370 km2 and a volume of 560 km3 with a maximum
depth of 485 m. Topographically, it consists of a
large basin (Main basin) and four smaller basins
(from north to south: Kabuno Bay, Kalehe, Ishungu,
and Bukavu) (Figure 1), which are separated from
the Main basin by sills of different depths (Figure 2)
[Degens et al., 1973; Tietze, 1978; Botz et al., 1988;
Spigel and Coulter, 1996; Lahmeyer International
and OSAE, 1998].

3.1. Water and Dissolved Gas Sampling

[5] The liquid and gas phases were collected during
three field campaigns in 2004, 2005, and 2007,
along profiles from the lake bottom to the surface,
at regular intervals of 25 m, corresponding to the
deepest point for each of the five basins of Lake

Figure 2. Three-dimensional bathymetric map of Lake

Kivu.
3 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

10.1029/2008GC002191

Kivu (Figure 1). A Humminbird Legend 1005

portable Eco-sonar provided the initial estimate of
maximum depth.
[6] Sampling devices used to collect deep lake
water include (1) pressure bottle [Tietze, 1987],
(2) Niskin water sampler [Oppenheimer, 1992], and
(3) evacuated stainless cylinder [Evans et al.,
1993]. For the present work a new, simple, and
low-cost technique was adopted [Tassi et al., 2004].
The sampling equipment consists of 25 m lengths of
Rilsan1 (a plastic material impermeable to both
water and gas) tubes (6 mm in diameter) connected
by steel connectors. At the surface, the Rilsan1
tube is attached via a three way valve to a 150 mL
glass syringe, the gas sampling bottle and a small
pump powered by a car battery (Figure 3). Water
was pumped up to the surface by means of the
combined suction system (syringe and pump) and
directly transferred into the storage containers after
the displacement of a water volume double than that
of the inner volume of the tube (about 0.03 dm3/m).
The dissolved gas samples were then collected into
one-way, preevacuated 250 mL glass flasks tapped
with Teflon valves (Figure 3) [Tassi et al., 2008]. A
gas phase was exolved during transit of the water
from the deepest layers of both the Main and
Kabuno Bay basins. This gas mixture was directly
convoyed into the sampling flasks with the associated liquid without any loss. Because of the small
diameter of the Rilsan tube and the relatively high
flux of the rising water (2 L/min) it is reasonable
to assume that the gas did not preferentially migrate
relative to the water and the sampling flask accurately collected a total fluid sample.

3.2. Chemical and Isotopic (d18O, dD,

and d13CDIC) Analysis of Water Samples
[7] The determination of pH and the concentration
of HCO
3 (acidimetric titration with 0.01 N HCl)
were carried out in the field. Water samples were
analyzed for major cations (Na, K, Ca, Mg, NH4,



and Li) and anions (Cl, SO2
4 , NO3 , Br , and F )
by atomic absorption spectrophotometry (AAS;
AAnalyst 100 Perkin-Elmer) and ion chromatography (Dionex DX-120 and Metrohm 761), respectively. Reduced sulfur species (hereafter reported as
SS2), i.e., those deriving from dissolved H2S,
HS, S2, polysulfide, and metal-sulfide complexes, were determined as SO2
4 , after oxidation
with H2O2, by ion chromatography (Metrohm 761)
using the Cd-IC sampling and analytical procedure
described by Montegrossi et al. [2006]. Boron and
SiO2 were determined by molecular spectrophotom-

Figure 3. Schematic drawing of the gas and water

sampling equipment.

etry. Trace elements (Al, Ba Ce, Co, Cr, Cs, Cu, Fe,
Mn, Nb, Ni, P, Rb, Sr, V, Y, Zn, and Zr) were
analyzed at the Acme Laboratories of Vancouver
(Canada) by Inductively Coupled Plasma Mass
Spectrometry (ICP-MS) with a Perkin-Elmer ELAN
6600 spectrometer. The analytical error for AAS and
IC and ICP-MS was 5 and 10%, respectively.
[8] The 18O/16O and 2H/1H isotopic ratios (expressed
as d 18O and d 2H % V-SMOW) in water samples
were determined by using a Finnigan Delta Plus
XL mass spectrometer according to standard
protocols. Oxygen isotopes were analyzed using
the CO2 H2O equilibration method proposed by
Epstein and Mayeda [1953]. Hydrogen isotopic
ratios were measured on H2 after the reaction of
10 mL of water with metallic zinc at 500C [Coleman
et al., 1982]. The experimental error was +0.1%
and +1% for d 18O and d 2H values, respectively,
using EEZ-3 and EEZ-4 as internal standards that
were previously calibrated versus V-SMOW and
SLAP reference standards.
[9] The values of d 13CDIC were analyzed with a
Finningan Delta Plus XL mass spectrometer after
the reaction of 3 mL of water with 2 mL of
anhydrous phosphoric acid in vacuo [Salata et
al., 2000]. The recovered CO2 was analyzed after
a two-step extraction and purification procedures
of the gas mixtures by using liquid N2 and a solidliquid mixture of liquid N2 and trichloroethylene.
[e.g., Evans et al., 1998; Vaselli et al., 2006]. The
analytical error for d 13CDIC was 0.05.

3.3. Chemical and Isotopic (d13CCO2strip

and 3He/4He) Analysis of Dissolved
Gas Compounds
[10] The composition of the main inorganic dissolved gas compounds (CO2, N2, O2 and Ar) stored
4 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

in the headspace of the sampling flasks was determined by a Shimadzu 15A gas chromatograph
equipped with a Thermal Conductivity Detector
(TCD). The analysis of dissolved light hydrocarbons (CH4, C2H6, C3H8, n-C4H10 and i-C4H10) was
performed with a Shimadzu 14A gas chromatograph equipped with a Flame Ionization Detector
(FID) [Tassi et al., 2004]. The complete composition of dissolved gas compounds was calculated on
the basis of the Henrys law constants, regulating
the liquid-gas equilibrium for each volatile compound [Vaselli et al., 2006; Tassi et al., 2008].
[11] The 13C/12C ratios of dissolved CO2 (d 13CCO2)
were determined on the basis of those measured in
the separated gas phase stored in the headspace of
the dissolved gas flasks (d 13CCO2strip). The isotopic
analyses were performed with a Finningan Delta S
mass spectrometer, after a two-step extraction and
purification procedures as described for the determination of the d 13Cdic values. Internal (Carrara
and San Vincenzo marbles) and international
(NBS18 and NBS19) standards were used for
estimating the external precision. The analytical
error and the reproducibility are 0.05% and
0.1%, respectively.
[12] The 3He/4He and He/Ne ratios were determined by mass spectrometry by the methods described by Poreda and Farley [1992]. The gas
samples were purified in a high vacuum line constructed of stainless steel and Corning-1724 glass to
minimize He diffusion. Water vapor and CO2 were
cryogenically trapped at 90 and 195C, respectively, whereas N2 and O2 were removed by the
reaction with a Zr-Al alloy (SAES-ST707). Argon
and Ne were adsorbed on activated charcoal at
196 and at 233C, respectively. SAES-ST-101
Getters (one in the inlet line and two in the mass
spectrometer) reduced the HD+ background to
1000 ions/s. Helium isotope ratios and concentrations were analyzed on a VG 5400 Rare Gas
Mass Spectrometer fitted with a Faraday cup (resolution of 200) and a Johnston electron multiplier
(resolution of 600) for sequential analyses of the
4
He (F-cup) and 3He (multiplier) beams. On the
axial collector (resolution of 600) 3He+ was completely separated from HD+, with a baseline separation of <2% of the HD+ peak. The contribution of
HD+ to the 3He peak was <0.1 ion/s at 1000 ions/s
of HD+. For 2.0 mcc of He with an air ratio
(sensitivity of 2  104 Amps/torr), the 3He signal
averaged 2500 ions/s with a background signal of
15 cps, due to either scattered 4He ions or the
formation of 4He ions at lower voltage potentials

10.1029/2008GC002191

within the source of the mass spectrometer. The

analytical error for the determination of 3He/4He
(hereafter expressed as R/Rair, where R is the
measured 3He/4He ratio and Rair is that of the air:
1.39  106 [Mamyrin and Tolstikhin, 1984]) was
0.3%.

4. Results
4.1. Water Chemical Composition
[13] The deepest water sample from within each
basin was collected at 478 m (Main basin), 140 m
(Kabuno Bay), 200 m (Kalehe), 170 m (Ishungu),
and 90 m (Bukavu), respectively. Chemical composition (major and minor constituents) and pH
values of the water samples collected along the
vertical profiles at Lake Kivu are reported in
Table 1. Concentrations of trace elements are
reported in Table 2. Temperature was not measured
because the uprising water was warmed due to the
friction with the Rilsan1 tube. The pH values vary
between 9.47 (Kalehe basin at surface) and 6.02
(Main basin, maximum depth). In the Main,
Kabuno Bay, Ishungu, and Kalehe basins, pH show
a clearly decreasing trend with depth. All water
samples have a Mg(Na)-HCO
3 composition. With
the exception of the Bukavu basin, all subbasins
within Kivu are chemically stratified in agreement
with previous studies [e.g., Tietze, 2000]. Over the
sampling interval for the Kahele, Ishungu, and
Bukavu subbasins, their total dissolved solids
(TDS) values generally are consistent with the
TDS from the Main Basin at each depth, suggesting some communication among subbasins to a
depth of 200 m. Only the Main Basin is deeper
than 200 m and the strong increase in TDS and
therefore density inhibits vertical mixing of the
deep water. Kabuno Bay also has a clearly distinct
chemistry below 25 m (the approximate sill
depth), characterized by a sharp increase in TDS
(5,548 mg/L) (Figure 4), reaching a maximum of
8,629 mg/L at the depth of 140 m. Although at the
lake surface the gross water chemistry and TDS
above 200 m seems to be relatively homogeneous
across the lake, significant compositional differences do exist among the various basins at increasing depth. In Table 3 the values of the Cib/Cis ratio
(where Cib and Cis are the concentrations of the i
compound at lake bottom and surface, respectively)
of the main chemical compounds, i.e., Na, K, Ca,
2

Mg, HCO
3 , SO4 , and Cl , are listed. At the
Main, Kalehe, and Ishungu basins, Ca, whose
Cib/Cis ratio is up to 16.7, represents the ion with
the highest relative increase with depth, whereas at
5 of 22

7
7
8
25
53
68
72
73
78
88
91
119
122
127
135
130
129
135
130
117
8

140 2/19/2004 6.70 460 402 925

0
25
50
75
100
125
150
175
200
225
250
275
300
325
350
375
400
425
450
478
0

84
84
87
99
134
152
161
169
171
195
200
236
334
344
374
380
394
390
392
468
82

125 2/19/2004 6.90 485 396 920

83
85
85
102
116
155
162
166
169
196
193
211
277
293
317
320
326
336
334
325
80

67

100 2/19/2004 7.12 375 359 780

108
111
117
143
188
219
226
229
247
283
280
302
428
452
470
488
478
482
490
492
103

70

2/19/2004 7.25 365 357 760

75

8.76
8.68
8.56
7.48
6.89
6.77
6.71
6.64
6.52
6.53
6.45
6.33
6.35
6.24
6.18
6.15
6.07
6.08
6.11
6.02
9.47

77

2/19/2004 7.32 385 345 710

50
78

88

781
778
805
1025
1507
1730
1827
1913
1986
2239
2258
2486
3753
3795
4082
4198
4259
4314
4326
4344
738

6669

6626

5955

5638

5272

4225

1050

21
21
21
28
44
52
53
55
56
65
65
69
88
90
97
97
98
99
102
101
28

93

91

84

83

81

70

24

16
15
16
10
11
15
16
15
6
13
13
9
15
15
15
15
9
12
10
5
15

<0.1

<0.1

<0.1

<0.1

<0.1

<0.1

25

2.75 0.20 0.35

2.60 0.15 0.20

2.60 0.20 0.30

2.70 0.25 0.35

0.03
0.03
0.04
0.05
0.07
0.08
0.09
0.09
0.10
0.13
0.13
0.14
0.20
0.20
0.21
0.22
0.21
0.21
0.20
0.21
0.03

0.32
0.19
0.13
2.32
7.25
9.83
10.62
11.59
12.72
18.03
18.03
21.57
47.65
48.29
54.09
55.38
56.66
56.66
57.31
58.92
0.01

1.57
1.57
1.60
1.82
2.26
2.75
2.60
2.58
2.60
2.72
2.70
2.78
3.35
3.36
3.33
3.34
3.20
3.15
3.18
3.15
1.64

0.08
0.09
0.09
0.10
0.10
0.15
0.10
0.10
0.15
0.20
0.20
0.25
0.20
0.25
0.40
0.35
0.37
0.35
0.30
0.35
0.07

<0.01
<0.01
<0.01
0.18
0.28
0.30
0.18
<0.01
0.13
0.15
1.78
0.13
0.18
0.32
0.20
<0.01
<0.01
0.25
0.00
0.25
0.06

0.14 10.15 2.65 0.30 0.20

0.14 9.66

0.12 9.83

0.11 10.30 1.88 0.20 0.30

0.11 9.50

0.10 6.93

dD

1.00

2.46 2.91

1.24

2.07
2.36
2.69
2.75
3.38
3.52
3.49
3.65
4.01
4.11
4.44
4.44
5.97
6.55
6.95
7.20
7.25
7.70
7.75
7.81

0.05
0.05
0.05
0.08
0.15
0.19
0.20
0.21
0.24
0.27
0.24
0.29
0.47
0.43
0.45
0.44
0.42
0.46
0.42
0.44
0.06

11
10
11
20
33
41
47
51
54
54
55
66
93
95
103
105
100
103
102
103
14

1102
1102
1141
1436
2063
2405
2530
2634
2729
3099
3122
3456
5068
5168
5548
5687
5753
5828
5845
5915
1057

29.69
26.81
26.83
27.20
24.95
25.13
25.87
24.95
26.58
21.94
23.57
25.05
13.85
15.25
13.43
12.79
11.59
12.15
12.27
11.44
20.80

4.54 0.35 166 8629 7.24

4.42 0.34 161 8601 4.58

4.58 0.32 154 7643 3.59

4.42 0.33 154 7295 2.53

1.17
1.85
2.20
2.02
2.11
1.04
1.25
1.11
1.65
2.02
2.12
1.65
1.22
1.31
1.70
1.25
0.31
0.55
0.50
0.72
2.41

3.35
3.45
1.65
1.21
1.12
1.25
1.00
0.52
1.12
0.56
0.88
0.88
3.31
3.23
4.62
3.69
3.92
3.74
3.66
3.71

2.66 3.29

2.45 3.16

2.58 2.70

2.40 2.25

3.21
2.56
2.65
3.32
3.95
4.11

2.32

1.71

2.63

2.00

0.17

6.04

6.23

7.48

5.38

4.86

d 18O d 13CDIC d 13CDICcalc

4.17 0.30 145 6884 10.00 2.44 2.06

3.62 0.11 136 5548 5.08

1493 20.16

SiO2 TDS

0.32 0.03 28

Br NO3 S2

0.04 <0.01 2.05 0.05 0.23

F

tassi et al.: water and gas chemistry at lake kivu (drc)

109

23
19
15

81

40

NH4+

2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
2/21/2004
6/15/2005

80

2/19/2004 8.58 328 297 530

25

27

2/19/2004 8.88 148 107 111

Kabuno
Bay
Kabuno
Bay
Kabuno
Bay
Kabuno
Bay
Kabuno
Bay
Kabuno
Bay
Kabuno
Bay
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Kalehe

pH Na+ K+ Mg2+ Ca2+ HCO3 CO32 Cl SO42 Li+

Depth

Basin

Sampling
Date

Table 1. Chemical Composition and pH, Total Dissolved Solids, dD, d18O, d13CDIC, and d13CDICcalc Values of the Main, Kabuno Bay, Kalehe, Ishungu, and Bukavu
Basins, Lake Kivu, Democratic Republic of the Congoa

Geochemistry
Geophysics
Geosystems

10.1029/2008GC002191

6 of 22

9.31
9.14
8.19
7.24
6.96
7.11
7.05
6.78
9.09
8.95
8.61
8.55
8.36
8.90
9.02
9.00
8.60
7.39
6.98
6.57
6.55

103
107
116
157
191
212
220
231
95
96
96
97
91
96
96
95
96
123
200
204
226

80
82
90
116
139
155
163
173
79
81
80
82
87
81
82
87
84
105
156
154
168

80
84
96
119
141
156
165
154
67
69
71
71
71
72
73
71
76
90
121
138
145

8
9
16
40
61
77
79
86
9
11
12
11
13
10
12
13
15
30
67
69
82

738
753
847
1156
1477
1662
1742
1861
732
732
763
750
769
750
756
781
799
1025
1635
1641
1806
45
33
16
13
9
30
40
39
16

76
52

27
26
23
44
54
60
64
55
24
24
24
25
24
24
24
24
26
32
47
48
54

16
15
14
13
12
13
14
12
15
15
14
14
13
15
15
15
14
11
11
13
13

0.03
0.03
0.04
0.05
0.06
0.07
0.07
0.07
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.04
0.07
0.07
0.07

0.41
0.43
1.07
15.47
10.31
16.86
19.51
25.15
0.01
0.10
0.14
0.07
0.33
<0.01
<0.01
<0.01
0.20
6.79
16.01
18.67
21.93

NH4+
1.52
1.52
1.62
2.24
2.69
2.92
3.04
3.01
1.56
1.66
1.67
1.53
1.55
1.60
1.69
1.54
1.55
2.13
2.82
2.78
2.98

F
0.12
0.05
0.05
0.05
0.06
0.10
0.09
0.11
0.07
0.04
0.05
0.04
0.05
0.04
0.07
0.03
0.04
0.05
0.07
0.06
0.07

<0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
0.36
0.10
0.05
0.02
0.02
0.02
<0.01
0.07
<0.01
<0.01
0.05
<0.01
0.20

Br NO3 S2

0.06
0.06
0.09
0.17
0.20
0.24
0.25
0.21
0.04
0.04
0.05
0.05
0.06
0.06
0.05
0.06
0.07
0.12
0.22
0.23
0.25

B
13
14
21
42
54
68
71
55
9
9
10
11
13
14
14
13
15
30
59
63
70

1054
1078
1206
1662
2089
2355
2471
2600
1023
1030
1062
1051
1071
1050
1060
1088
1112
1426
2255
2288
2518

SiO2 TDS

Ion concentrations and total dissolved solids (TDS) are in mg/L; dD and d 18O values are in % V-SMOW; d13CDIC and d 13CDICcalc values are in % V-PDB.

6/15/2005
6/15/2005
6/15/2005
6/15/2005
6/15/2005
6/15/2005
6/15/2005
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007
6/12/2007

25
50
75
100
125
150
175
200
0
25
50
75
90
0
25
50
75
100
125
150
170

Kalehe
Kalehe
Kalehe
Kalehe
Kalehe
Kalehe
Kalehe
Kalehe
Bukavu
Bukavu
Bukavu
Bukavu
Bukavu
Ishungu
Ishungu
Ishungu
Ishungu
Ishungu
Ishungu
Ishungu
Ishungu

pH Na+ K+ Mg2+ Ca2+ HCO3 CO32 Cl SO42 Li+

22.85
24.51
20.51
18.22
21.02
23.12
24.99
24.53
31.31
31.19
32.21
30.42
32.36
32.41
29.68
27.27
31.53
28.48
27.88
25.01
24.20

dD

2.55
2.67
2.33
2.17
1.97
2.30
2.66
2.06
3.27
3.14
3.21
3.50
3.19
3.42
3.40
3.23
3.25
2.91
2.50
2.39
2.26

2.14
2.21
2.41
0.22

2.81
2.97
2.92
3.18
4.19

d 18O d 13CDIC d 13CDICcalc

tassi et al.: water and gas chemistry at lake kivu (drc)

Sampling
Date

Depth

Basin

Table 1. (continued)

Geochemistry
Geophysics
Geosystems

10.1029/2008GC002191

7 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

10.1029/2008GC002191

Table 2. Concentrations of Trace Elements in the Main and Kabuno Bay Basins, Lake Kivu, Democratic Republic
of the Congoa
Basin
Kabuno
Kabuno
Kabuno
Kabuno
Kabuno
Kabuno
Kabuno
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
a

Bay
Bay
Bay
Bay
Bay
Bay
Bay

Depth

Al

Ba

Ce

Co

0
25
50
75
100
125
140
0
25
50
75
100
125
150
175
200
225
250
275
300
325
350
375
400
425
450
478

18
21
6
5
10
16
7
59
24
19
9
55
108
25
14
19
39
38
14
22
17
13
18
16
6
13
10

45
580
132
163
164
292
230
25
22
29
103
252
313
331
327
368
465
465
488
578
450
497
652
653
516
618
514

0.05
0.07
0.02
0.01
0.02
0.01
0.01
0.08
0.06
0.02
0.01
0.07
0.07

0.10
0.14
0.70
0.44
0.41
0.63
0.63
0.18
0.17
0.15
0.18
0.12
0.22
0.14
0.12
0.21
0.39
0.31
0.30
0.53
0.54
0.64
0.70
0.70
0.46
0.66
0.52

0.01
0.05
0.05

0.01
0.01

Cr

Cs

Cu

Fetot Mntot

Nb

Ni

Rb

Sr

Zn

Zr

368
393
447
278
489
72
20
12
40
9
8
177
173
167
12
7
182
245
281
295
294
197
280
239
281

0.8
0.6
0.9
0.6
0.6
0.6
0.5
1.2
1.3
1.2
1.8
2.6
3.5
3.8
3.7
4.4
5.9
5.7
6.3
8.5
8.4
9.1
9.8
9.4
9.2
9.0
8.5

3
55
23
26
20
22
24
7
79
153
29
114
107
22
16
17
75
108
33
29
50
53
47
27
16
20
15

104
359
687
498
394
530
539
403
430
423
292
1022
413
313
367
328
449
274
298
392
246
340
564
388
243
464
222

0.1
9.4
13.0
12.5
12.0
12.4
14.8
0.1
0.1
0.1
0.5
1.3
1.7
2.1
1.9
2.3
1.6
2.1
3.1
4.9
4.9
5.3
5.5
5.1
5.1
5.3
4.9

2
24
5
23
5
8
6
3
2
6
3
2
1
1
2

359
722
311
243
540
302
983
142
69
80
143
1540
1692
1336
980
1512
2628
2718
3225
4629
5286
5899
6669
7065
5304
5012
4829

46
109
174
179
187
209
213
58
57
57
67
93
103
110
112
117
129
126
138
191
195
206
211
207
203
207
209

556
3568
4243
4748
4716
6477
5809
185
182
222
800
1739
2305
2580
2665
2892
3527
3514
3836
5131
4584
4789
5346
5215
4887
5135
4712

1.3
5.7
24.2
26
33.6
27.1
32.4
1.7
1.4
0.4
1.2
1.7
1
0.6

0.03
0.10
0.02
0.02
0.04
0.02
0.07
0.06
0.04
0.04
0.01
0.10
0.11
0.03
0.03
0.04
0.09
0.14
0.05
0.05
0.04
0.02
0.09
0.09
0.03
0.05
0.02

7
83
9
7
8
10
10
23
74
136
99
91
74
17
10
13
56
75
22
12
12
4
20
14
2
10
4

0.5
13.7
42.6
40.6
47.1
15.6
60.5
0.4
0.5
0.6
0.2
1.5
1.9
2.6
2.2
2.3
1.3
2.2
4.5
7.9
7.5
8.7
9.2
6.9
9.5
7.9
8.3

7
784
376
348
5
256
171
3
2
54
643
606
481
418
385
414
374
365
362
398
286
300
411
399
272
371
271

2
1

1
1
1

0.3
0.2
2.4
3.6
3
3.1
2.1
2.6
1.6
2.4

Trace elements are measured in mg/L.

Kabuno Bay the strongest variation among the

dissolved species along the vertical water column
is that of Mg (Cib/Cis = 8.4). All the stratified
basins are also characterized by remarkable
increases of HCO
3 concentrations (Cib/Cis ratio
up to 6.4). Sulfate concentrations tend to decrease
with depth (Cib/Cis < 1), particularly at Kabuno
Bay, where at depth >25 m, this compound is
below the instrumental detection limit (<0.1 mg/L;
Table 1). In contrast, the SS2 concentrations
increase with depth with a Cib/Cis ratio is 3.8 and
14.2 at the Main and Kabuno Bay basins,
respectively. The Cib/Cis ratios of the main
chemical compounds of the Bukavu basin are
1, indicating a substantial compositional homogeneity of the vertical water column.
[14] With respect to the minor chemical compounds, the ratio of Br to Cl is constant among
the profiles at about 1 to 300, consistent with
waters from natural sources. Boron and Li concentrations are relatively low, not exceeding 0.44 and
0.21 mg/L, respectively. In contrast, F concentrations are remarkably high, up to 3.36 mg/L, from
to the leaching of the F-rich volcanic rocks of the

Figure 4. Vertical profiles of the TDS values (in mg/L)

of the Main, Kalehe, Ishungu, Kabuno Bay, and Bukavu
basins, Lake Kivu, Democratic Republic of the Congo
(DRC).
8 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

10.1029/2008GC002191

Table 3. Values of the Cib/Cis Ratio of the Main Chemical Compounds in the Main, Kabuno Bay, Kalehe, Ishungu,
and Bukavu Basins, Lake Kivu, Democratic Republic of the Congoa

Kabuno Bay
Main
Kalehe
Bukavu
Ishungu

Na

K Mg

3.1
4.6
2.2
1.0
2.4

3.8
3.9
2.2
1.1
2.1

8.4
5.6
1.9
1.1
2.0

Ca
2.5
16.7
10.5
1.4
7.8

HCO3 Cl SO42 Li

6.4
5.6
2.5
1.1
2.4

3.9
4.8
2.0
1.0
2.2

0.3
0.8
0.9
0.9

NH4 F Br NO3 S2

3.5
7.0 183
2.8 3609
1.0 65
2.3

1.3
2.0
1.8
1.0
1.9

6.0
4.7
1.7
0.7
2.0

0.9

Si Mntot Fetot Sr Ba Rb

14.2 12 6.0
3.8 8.1 9.4
3.6 3.9
0.1
1.5 1.5
11.1
4.4 5.0

25
54
95
19
77

5.2
0.6
3.9
0.7
1.6

10
25
10
1.3
17

5.1
20
12
2.0
21

4.7
3.6
1.6
1.0
1.9

Cib and Cis are the concentrations of the i compound at lake bottom and surface, respectively. Main chemical compounds are Na, K, Ca, Mg,

2
HCO
3 , SO4 and Cl .

area [Gerasimoskiy and Savinova, 1969] and/or the

input of F rich geothermal fluids from the Nyiragongo volcano [Vaselli et al., 2007]. Ammonia
concentrations increase sharply with depth in all
basins (Cib/Cis ratio between 65 and 3609) while
NO
3 has low and variable concentrations in the
lake. The contents of Fetot, Mntot, and Cu at Main
and Kabuno Bay basins vary significantly with
depths but have no specific trends (Table 2). The
concentrations of Cr, Ba, Co, Nb, P, Rb, V, and Zr
significantly increase with depth at both the
Kabuno Bay and Main basins (no trace element
analysis were performed for the other profiles)
(Table 2). In the Main basin, Sr, whose geochemical
behavior is intimately associated with Ca-bearing
minerals, shows a strong positive correlation with
Ca. In contrast, at Kabuno Bay these two cations
are decoupled, likely because of CaCO3 precipitation that limits Ca enrichment with depth without
significantly affecting Sr concentrations. Aluminum, Ce, Fe, Mn, Ni, Y, and Zn concentrations do
not show significant variations along the vertical
profiles. Finally, Cs concentrations are relatively
constant (clustering around 0.6 mg/L) at Kabuno
Bay, while increasing with depth at the Main basin
(from 1.2 to 8.5 mg/L) (Table 2).

4.2. Water Isotopic (dO18 and d2H)

Composition
[15] The d 18O and d 2H values cover a wide range,
varying from 2.66 to 3.50 and from 10.00 to
32.41% V-SMOW, respectively, as function of
depth, especially at the Main, Kabuno Bay, and,
to lesser extent, Ishungu basins (Table 1). All
waters plot near the Global Meteoric Water Lines
(GMWL) and show little evidence of evaporative
enrichment or O-18 shift to higher ratios. It is
worth noting that the southernmost basins (i.e.,
Ishungu and Bukavu) are characterized by a positive shift of both the oxygen and hydrogen isotopic values with respect to those of the other basins
at similar depth, whereas Kabuno Bay has a
distinctly negative isotopic signature (Table 1).

4.3. Dissolved Gas Composition

[16] The presence of a huge gas reservoir characterizes the permanently stratified deep portions of
Lake Kivu. The maximum value of dissolved gas
concentration (171 mmol/L) was measured at the
depth of 478 m in the Main basin (Table 4). In all
the basins the gas concentrations increase with
depth and the bottom waters of the Ishungu,
Kalehe, and Kabuno Bay basins (up to 20.6,
46.2, and 54 mmol/L, respectively) have similar
dissolved gas concentrations as the Main basin at a
similar depth. In the Bukavu basin the concentration of dissolved gas is relatively low even at the
maximum depth (<4.5 mmol/L), in agreement with
the lack of any water chemical stratification. The
dissolved gas composition is different in the various basins and shows strong changes with depth.
At the Main and Kalehe basins, the CO2 percentage
of the total at depth 100 m ranges up to 81 and
92% by volume, showing a large relative increase
when compared to N2, which is the most abundant
dissolved gas compound at depth 75 m. The
dissolved gas composition of the Ishungu basin at
depths 100 m is characterized by (1) dominant
CO2 (5060%), (2) relatively high N2 and O2
concentrations (up to 38.9 and 8.5%, respectively),
and (3) a strong increase in CH4 at the deepest
sampling point (170 m), where it reaches up to
24% of the total dissolved gas. Kabuno Bay, the
basin located most northerly and closest to the
Nyamulagira volcano, exhibits a dissolved gas
composition that is marked by particularly high
CO2 concentration of 32 mmol/L at relatively
shallow depth (50 m), representing 96% of the
dissolved gas composition. Conversely, at the
Bukavu basin, the southernmost and most shallow
basin, the dissolved gas phase consists almost
exclusively of atmospheric-related gases, with a
modest CO2 increase (up to 19.6%) at the bottom
of the basin at a depth of 90 m.
[17] The N2 and Ar concentrations in the deep lake
strata of all the basins, with the only exception of
that of the Kabuno Bay (Table 4), are higher than
9 of 22

Depth

0
50
75
100
125
140
0
50
100
150
200
250
300
350
375
400
425
450
470
50
100
125
150
175
200
50
75
90
100
125
150
170

Lake

Kabuno Bay
Kabuno Bay
Kabuno Bay
Kabuno Bay
Kabuno Bay
Kabuno Bay
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Kalehe
Kalehe
Kalehe
Kalehe
Kalehe
Kalehe
Bukavu
Bukavu
Bukavu
Ishungu
Ishungu
Ishungu
Ishungu

0.01
32.18
36.68
41.43
47.18
52.12
0.01
0.04
8.27
14.64
21.33
31.79
55.03
58.89
61.98
69.07
86.07
102.87
136.89
0.02
22.97
29.55
31.21
34.76
42.47
0.01
0.05
0.88
6.70
7.44
8.70
10.62

CO2

0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.04
0.04
0.06
0.08
0.12
0.15
0.20
0.24
0.24
0.25
0.27
0.41
0.07
0.07
0.04
0.03
0.02
0.02
0.04
0.05
0.07
0.15
0.16
0.20
0.02

Ar
0.28
0.05
0.08
0.16
0.17
0.07
0.27
0.10
0.39
0.65
0.38
0.28
0.05
0.88
0.14
0.10
0.04
0.12
0.20
0.85
0.13
0.05
0.04
0.03
0.05
0.36
0.45
0.63
1.07
1.33
0.58
0.01

O2
0.58
0.34
0.39
0.53
0.73
0.33
0.57
1.56
1.52
2.13
3.25
4.96
6.17
8.03
9.82
10.04
9.74
11.62
16.26
2.96
2.50
1.81
1.37
0.99
0.94
1.55
1.97
2.89
4.58
4.71
7.01
5.10

N2
38.49
42.25
41.31
39.25
38.93
40.78
38.84
40.53
41.14
38.60
39.28
40.29
41.60
40.86
41.26
42.11
38.79
42.78
39.57
41.30
38.42
42.44
41.78
41.40
42.47
38.75
39.40
41.29
30.53
29.44
35.05
255.00

N2/Ar
0.99
4049
3849
3049
2499
6511
1.0
1.0
224
266
258
258
371
300
260
290
343
379
333
0.26
353
691
953
1459
1922
0.2
1.0
13
45
47
44
531

CO2/Ar
<0.001
0.387
0.500
0.732
0.960
1.518
<0.001
<0.001
1.886
3.060
3.769
4.915
7.980
10.604
11.335
11.507
11.825
12.256
16.977
0.001
4.250
4.495
3.845
2.722
2.749
0.002
0.003
0.018
0.083
1.757
1.518
4.908

CH4

0.00057
0.00070
0.00086
0.00095
0.00105
0.00076
0.00099

C3H8

0.00004
0.00006
0.00006
0.00007
0.00006

n-C4H10

0.00011
0.00017
0.00020
0.00023
0.00025
0.00016
0.00021

0.88

i-C4H10
32.96
37.67
42.87
49.05
54.05
0.87
1.73
12.11
20.56
28.85
42.09
69.37
78.61
83.52
90.96
107.93
127.14
170.75
3.91
29.91
35.96
36.49
38.51
46.23
1.96
2.53
4.48
12.59
15.39
18.01
20.65

Gas Total
10.79
11.21
13.19
11.91
11.48
5.93
7.39
7.48
6.03
6.50
7.42
6.67
6.58
6.85
7.14
6.79
6.49
6.64
6.66
6.80
7.55

7.96
8.58
8.48
6.13

4.74
6.20
6.29
4.84
5.31
6.23
5.48
5.39
5.66
5.95
5.60
5.30
5.45
5.47
5.61
6.36

6.77
7.39
7.29
4.94

d 13CCO2

9.60
10.02
12.00
10.72
10.29

d 13CCO2strip

35.2
2.05
28.6
92.8
7.83
78.9
82.2
0.51

3.17
2.35
2.21
2.24
2.49
2.28
2.59
1.21

3.90

2.13
2.55
2.48
2.15

2.32
2.40
2.58
2.49

tassi et al.: water and gas chemistry at lake kivu (drc)

2.19

1.55

2.78

5.54
2.10

2.15

He/Ne

5.33

R/Ra

0.00243
0.00369
0.00309
0.00337
0.00370

0.00140
0.00186
0.00286
0.00316
0.00435
0.00476
0.00491
0.00584
0.00728
0.00808
0.01105

C2H6

Table 4. Chemical Composition of Dissolved Gas and d13CCO2strip, d13CCO2, and R/Rair Values in the Main, Kabuno Bay, Kalehe, Ishungu, and Bukavu Basins, Lake
Kivu, Democratic Republic of the Congo

Geochemistry
Geophysics
Geosystems

10.1029/2008GC002191

10 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

the one atmosphere solubility levels at the temperature and elevation of the lake surface (0.5 and
0.01 mmol/L, respectively). This peculiar feature
may occur by the following mechanisms:
[18] 1. The first mechanism is the presence of
extra-atmospheric N2 from processes related to
organic activity, i.e., denitrification in the anoxic
environment.
[19] 2. The second is the presence of radiogenic Ar,
as supported by the 40Ar/36Ar values (up to 320)
measured at Cap Rubona (Rwanda), which is a
factory for CH4 extraction from the depth of 320 m
in the Main basin (D. Tedesco et al., manuscript in
preparation, 2008).
[20] 3. The third is the input of meteoric N2 and Ar
from the CO2-rich vents of the lake bottom invoked by several author [e.g., Tietze et al., 1980;
Schoell et al., 1988] for the origin of the CO2
stored in the Lake Kivu reservoir. Both the northern and southern lake borders are indeed characterized by presence of several fluid discharges (i.e.,
Rambo, Kankule, Muganzo), likely having a composition similar to that of the sublacustrine vents,
showing N2 and Ar concentrations up to 6 and
0.1% by volume, respectively (O. Vaselli et al.,
manuscript in preparation, 2008).
[21] Oxygen, dissolved in the lake surface from the
atmosphere as predicted by the Henrys law, shows
a dramatic decrease with depth likely resulting
from aerobic bacterial consumption, while the
Main, Kalehe, and Ishungu basins show strong
increases of CH4 at depth >50 m. As already
observed by Tietze [1978], in the Main and Kelehe
basins, at depths 100 m, the presence of light
hydrocarbons (ethane, propane, normal, and isobutane), although at relatively low amounts (Table 4),
represents a peculiar compositional feature. Both
the O2 and CH4 concentrations profiles provide
insights into redox potential and bacterial activity
along the vertical columns within each basin.

4.4. Carbon Isotope Composition of

Dissolved CO2 (d13CCO2) and DIC
(d13CDIC)
[22] To obtain the d 13C values of dissolved CO2
(d 13CCO2) from the measured d 13CCO2strip values,
the carbon isotopic fractionation can be quantified
by using the e1 factor for the gas-water equilibrium
[Zhang et al., 1995], as follows:
e1 d13 CCO2  d13 CCO2strip 0:0049 * T  1:31

10.1029/2008GC002191

Both the measured d 13CCO2strip and the calculated

d 13CCO2 values are listed in Table 4. The isotopic
analysis of those samples with dissolved CO2
concentration <1 mmol/L (i.e., Bukavu basin and
the surface of the Main and Kabuno Bay basins)
are not available because the analytical procedure
was not suitable (Table 4). The calculated d 13CCO2
values (Table 4) of the Main, Kalehe, and Ishungu
basins, range from 8.58 to 5.93% V-PBD, and
are almost consistent with those typical of mantlederived CO2 [e.g., Hoefs, 1973; Rollinson, 1993],
although distinct from the d 13CCO2 values of the
summit fumaroles of Nyiragongo (3 to 4% VPBD) (D. Tedesco et al., manuscript in preparation,
2008). At Kabuno Bay the d 13CCO2 values range
between 13.19 to 10.79% V-PBD, indicating
either a different CO2 source or the occurrence of
isotopic fractionation processes as CO2 interacts
with water. No significant trends of carbon isotope
composition are shown along the vertical profiles.
[23] Water samples from the Main and Kabuno
Bay basins were also analyzed for the determination of the d 13CDIC values that vary from 4.62 to
3.45 and from 3.29 to 1.00% V-PBD, respectively (Table 1). The d13Cdic values of these
two basins abruptly decrease with depth as the
dissolved CO2 increases.

4.5. Helium Isotopic Composition

[24] The R/Rair values in the Main, Kalehe, and
Ishungu basins lie in a narrow range, from 2.10 to
2.59, with the exception of the dissolved gas sample
collected at the maximum depth (478 m) of the Main
basin that is significantly higher (3.17). Kabuno Bay
has a different He isotopic signature, with R/Rair
values up to 5.54. In comparison, the Bukavu basin
displays the lowest R/Rair value (1.21) measured in
Lake Kivu. The relatively low He/Ne ratio (0.51)
does not likely reflect air contamination during
sampling, but instead reflects the atmosphericderived gases dissolved in lake water directly or
dissolved into groundwater during precipitations
recharging the aquifer that are subsequently discharged into the lake. The correction that subtracts
the solubility He indicates that the added component
is consistent with the He in the other basins.

5. Discussion
5.1. Processes Governing Lake Water
Chemistry
[25] The compositional and isotopic features of the
Lake Kivu water, as well as its permanent stratifi11 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

Figure 5. SiO2 (in mg/L) versus CO2 (in mmol/L)

binary diagram for the Main (square), Kalehe (upward
facing triangle), Ishungu (diamond), Kabuno Bay
(circle) and Bukavu basins (downward facing triangle),
Lake Kivu, DRC.

cation, are mainly produced by the complex combination of (1) mineral dissolution-deposition processes, (2) bacterial activity, and (3) fluid inputs
from the lake bottom [e.g., Degens et al., 1973;
Tietze et al., 1980; Haberyan and Hecky, 1987;
Schoell et al., 1988; Spigel and Coulter, 1996].

10.1029/2008GC002191

(Figure 1). To evaluate the effects of the water-rock

interaction process on lake chemistry, concentrations
of selected major and trace solutes from the bottom
waters of the Main and Kabuno Bay basins are
normalized to those of primitive mantle [Jagoutz et
al., 1979; McDonough and Frey, 1989], and
compared with the volcanic rocks of the Lake Kivu
area, including (1) tholeiitic basalts [Auchapt et al.,
1987], (2) basanites [Auchapt et al., 1987], (3) alkaliolivine basalts [Platz et al., 2004], (4) tephrites
from the Nyamuragira volcano [Aoki et al., 1985],
and (5) foiditic lavas from the 2002 Nyiragongo
eruption [Santo et al., 2002, 2003]. For comparison
we also added the thermal spring of Rambo,
discharging in Rwanda close to the CH4 factory of
Cap Rubona, and the mineral spring of Sake, located
to the westernmost border of the Lake Kava. The
spider diagrams for the two basins, consistent with
those of the selected springs, show a depletion in
compatible elements, i.e., Fetot, Mntot, Si, and Ni and,
to a lesser extent, Mg, Ca, Ba, Sr, V, Y, Zn, and Zr,
with respect to the volcanic rocks (Figures 6a and 6b).
Thus, the geochemical behavior of these elements
appears to be related to their respective ionic
potential, which predicts a preferential removal of
these species from aqueous solutions because of the
formation of carbonate and/or oxyhydroxide mineral
phases. Conversely, incompatible elements (Na, K,

5.1.1. Mineral Dissolution and Deposition

[26] Water-rock interaction involving both groundwater and hydrothermal fluids plays a significant
role in major and minor solute chemistry of the
lake. Mineral dissolution of the strongly undersaturated basanitic bedrock surrounding the lake can
be enhanced by the presence of CO2, as described
by the following general basalt weathering reaction
[Navarre-Sitchler and Brantley, 2007, and references therein]:
Ca0:3 Mg0:1 Fe0:4 Al0:3 SiO3:25 2:5CO2
3:25H2 O ! 0:3Ca
2

0:4Fe

0:3Al

0:1Mg

H2 SiO4 2:5HCO
3

Accordingly, SiO2 concentrations in lake water show

a strong correlation with dissolved CO2, as both
increase strongly with depth in the stratified basins,
particularly the Kabuno Bay basin (Figure 5), whose
northern shoreline mostly consists of relatively fresh
rocks recently erupted by the Nyamuragira volcano

Figure 6. Concentrations, normalized to primitive

mantle [Jagoutz et al., 1979; McDonough and Frey,
1989] of (a) Na, K, Mg, Ca, Fe, Mn, Si, Ba, and Sr and
(b) Ce, Co, Nb, Ni, Rb, V, Y, Zn, and Zr in the Main
(closed circle) and Kabuno Bay (closed square) water,
Lake Kivu, DRC. Relative concentrations of the volcanic
rocks of the area (gray shaded area), i.e., tholeiitic
basalts, basanites, alkali-olivine basalts, tephrites from
Nyamuragira volcano and foidite lavas from the 2002
Nyiragongo eruption, and thermal (Rambo) and mineral
(Sake) springs (open circle) (O. Vaselli, unpublished
data, 2005) were also reported.
12 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

Ce, Nb, and Rb) seem to behave concordantly with

the outcropping lava flows indicating a clear input of
cations deriving from water-rock interactions. Niobium, which is considered as a relatively immobile
element in aqueous solutions, occurs at high
concentrations (up to 15 mg/L) in the deepest parts
of the basins. In silicate melts, Nb behaves in a highly
incompatible manner (up to 1000 times when
normalized to the primitive mantle) during the
formation of alkaline magmas as those of Nyiragongo [e.g., Chakrabarti et al., 2009], whereas depletion
of Nb (and Ta) is likely the most typical geochemical
feature of magmas produced in subduction zones
[e.g., Pearce, 1982]. As most of the Nyiragongo
volcanic rocks are aphiric, Nb can likely occur in the
glass-rich groundmass from which it can easily be
released during weathering processes. Therefore, the
relatively high concentrations of compatible normally immobile elements at Kabuno Bay basin
reflects the weathering habits of young basic lavas
of the northern shoreline. The water chemistry is
subsequently altered by the formation of dissolved
minerals (oxyhydroxides) and mineral precipitates
(carbonates and clays). The saturation index values
(SI = logIAP/KS, where SI is the saturation index,
IAP is the ion activity product and KS is the solubility
product constant) were calculated by using the
equilibrium geochemical speciation/mass transfer
model PHREEQC v. 2.15.02 [Parkhurst and Appelo,
1999; Charlton and Parkhurst, 2002] with the
database of the speciation model LLNL [Johnson et
al., 2000]. Because the ionic strength of all solutions
<0.1, calculation of the activity coefficient of each
ionic species was performed using the B-dot approach.
Owing to the strong influence of CO2 concentrations
on rock-water interactions (see equation (2)), SI
calculations were carried out only in those samples
for which the dissolved gas composition was
available (Table 4).
[27] The SI values, whose representative data are
reported in Table 5, indicate that among the carbonate species, only witherite and dolomite are
systematically oversaturated in all the five basins
independently by the depth. In contrast, calcite and
magnesite are slightly oversaturated in the surficial
water strata (200 m) but tend to be undersaturated
at deeper levels. Thus, Ca, Mg, and HCO
3 concentrations, which strongly increase along the
vertical profiles of the stratified basins (Table 1),
are governed by the solubility and stability of
calcite and magnesite. Their SI values are strongly
related to dissolved CO2 that produces HCO
3,
significantly lowers the pH of lake water and

10.1029/2008GC002191

moves the lake system out of the stability field

for calcite and magnesite.
[28] The SI values indicate that hematite is oversaturated, whereas boehmite is undersaturated.
Most secondary minerals (e.g., beidellite-Mg, celadonite, clinoptilolite, clinochlore, illite, kaolinite,
montmorillonite-Mg, nontronite, saponite-Mg,
typically related to chemical weathering of basic
to ultrabasic volcanic rocks) are oversaturated.
Nevertheless, their SI values decrease at increasing
depths, further illustrating the key role played by
changing pH due to the presence of CO2. Muscovite and phyrophyllite are mostly oversaturated to
slightly above saturation. Among the main and
accessory minerals, only K-feldspar is characterized by SI values >1, whereas albite, anorthite,
diospide, enstatite, nepheline, forsterite, and monticellite are generally undersaturated. Finally,
quartz and amorphous quartz range from near
saturated to undersaturated.
[29] In conclusion, our data suggests that most of
the solutes of the Lake Kivu waters are mainly
controlled by water-rock interactions and chemical
alteration of the glass-rich volcanic rocks forming
most of the northern and southern shorelines of the
lake. The chemistry of the deep water layers
changes according to the chemical stability of
mineral species controlled by pH, which at its turn
depends on CO2 concentration. The addition of
dissolved solids from the Archaean metamorphic
complex appears to be masked by that from the
more easily altered basaltic rocks.

5.1.2. Effect of Bacterial Activity

[30] The planktonic assemblage of Lake Kivu
closely resembles that of the other East African
Lakes, i.e., dominated by chlorophytes and cyanobacteria, with lower abundances of diatoms [Hecky
and Kling, 1987]. The effect and degree of bacterial activity on the water chemistry of Lake Kivu
strongly affects the distribution of S and N compounds. For example, SO2
4 is a common source of
energy for anaerobic sulfobacteria under reducing
conditions, such as those dominating in the deep
lake water strata. These biological processes produce reduced S species (SS2) as well as elemental
sulfur [e.g., Kallistova et al., 2006, and references
therein]. Accordingly, SS2 concentrations at both
the Kabuno Bay and Main basins show marked
increases with depth (Table 1). Similarly, the vertical patterns of NH+4 , a product of reducing microbial and bacteria activity, show increases by up
to three orders of magnitude in all the stratified
13 of 22

Kabuno Bay
Kabuno Bay
Kabuno Bay
Kabuno Bay
Kabuno Bay
Kabuno Bay
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Main
Kalehe
Kalehe
Kalehe
Kalehe
Kalehe
Kalehe
Bukavu
Bukavu
Bukavu
Ishungu
Ishungu
Ishungu
Ishungu

0
50
75
100
125
140
0
50
100
150
200
250
300
350
375
400
425
450
478
50
100
125
150
175
200
50
75
90
100
125
150
170

0.57
2.66
2.63
2.88
3.01
2.15
0.20
0.65
1.08
0.64
0.02
0.13
0.16
0.55
0.48
0.88
1.21
0.76
1.18
1.05
0.86
1.06
1.76
1.16
0.16
0.24
0.20
0.16
0.78
1.72
0.04
0.24

4.25
3.47
3.59
3.13
3.20
4.97
4.48
5.37
3.50
5.03
6.54
6.43
7.54
9.17
9.12
9.80
10.51
9.63
10.53
6.39
4.32
4.35
3.36
4.65
6.20
4.14
4.28
4.32
3.80
3.19
6.65
6.47
1.53
6.25
6.29
7.10
7.55
5.93
1.55
0.81
6.07
4.73
3.38
3.63
2.79
1.24
1.40
0.73
0.12
0.86
0.07
1.37
4.67
5.16
6.06
4.70
3.23
1.91
1.95
2.27
4.89
6.48
3.28
3.52

1.53
0.99
0.95
0.81
0.55
0.31
0.81
0.72
0.08
0.05
0.12
0.12
0.01
0.16
0.21
0.33
0.29
0.26
0.45
1.14
0.26
0.21
0.51
0.47
0.22
0.93
0.84
0.77
0.28
0.31
0.17
0.09

6.90
7.42
7.33
7.32
7.02
5.81
5.46
4.61
3.63
3.11
2.17
2.21
2.41
1.47
1.49
0.95
0.65
1.14
0.62
5.36
4.25
4.06
5.18
4.51
2.83
5.09
5.07
4.86
4.29
4.75
2.33
2.54

0.86
2.77
2.97
3.50
4.33
5.09
0.95
1.63
6.25
6.48
7.07
7.21
6.93
7.43
7.54
7.88
7.81
7.71
8.03
0.62
4.79
5.46
4.56
4.74
6.03
1.36
1.52
2.04
4.69
5.35
6.84
6.75

0.05
1.62
1.71
1.96
2.32
2.69
0.64
1.00
3.65
3.79
4.09
4.16
3.97
4.21
4.26
4.42
4.39
4.34
4.43
0.12
2.88
3.28
2.85
2.94
3.61
1.00
1.07
1.37
2.83
3.27
4.00
3.98
12.03
11.97
10.25
10.73
10.93
10.34
10.37
11.74
12.14
10.94
10.92

12.26
14.00
13.71
13.45
13.63
13.52
13.50
13.59
12.19
13.07
12.97
12.73
12.94
12.62
13.01
12.59
12.18
12.78
12.01

3.49
7.18
7.17
7.87
8.18
6.42
3.40
2.52
6.44
5.05
3.58
3.80
2.97
1.34
1.48
0.77
0.06
0.93
0.07
0.79
5.32
5.62
6.64
5.27
3.63
3.62
3.62
3.80
5.64
6.96
3.49
3.72

3.25
5.44
5.45
5.68
5.75
4.91
2.50
2.02
3.68
3.31
2.66
2.78
2.79
2.09
2.15
1.77
1.44
1.88
1.45
1.64
3.54
3.74
4.43
3.84
2.85
2.49
2.54
2.63
3.52
4.43
2.73
2.92

1.38
4.89
4.91
5.64
6.06
4.71
1.89
1.30
5.67
4.38
3.21
3.42
2.45
1.11
1.24
0.71
0.03
0.80
0.13
0.78
4.25
4.62
5.23
4.06
3.00
2.26
2.26
2.51
4.59
5.71
3.05
3.20

2.01
1.76
1.74
1.63
1.48
1.26
1.73
1.58
0.27
0.19
0.01
0.02
0.25
0.08
0.06
0.04
0.03
0.02
0.04
2.00
0.52
0.36
0.60
0.58
0.26
1.53
1.47
1.31
0.54
0.36
0.08
0.06

3.32
6.84
6.86
7.34
7.55
6.27
2.69
2.02
5.31
4.44
3.42
3.58
3.28
2.12
2.23
1.67
1.08
1.80
1.20
0.93
4.69
5.01
5.91
4.92
3.50
2.79
2.85
3.03
4.73
5.99
3.46
3.68

9.99
12.79
10.79
6.85
2.28
2.60
3.18
8.08
12.43
6.73
7.55

6.63
16.85
16.92
17.72
18.02
15.12
2.21
0.63
9.09
8.22
6.23
6.62
7.42
5.10
5.37
3.91
2.81
4.32
2.87

Depth (m) Albite Anorthite Beidellite-Mg Calcite Celad-onite Clino-ptilolite Diopside Enstatite Hematite Illite K-Feldspar Kao-linite Magn-esite Montmor-Mg

Table 5 (Sample). Selected Saturation Index Values Calculated on the Basis of the Physical-Chemical Features of Water in the Main, Kabuno Bay, Kalehe, Ishungu,
and Bukavu Basins, Lake Kivu, Democratic Republic of the Congo [The full Table 5 is available in the HTML version of this article at http://www.g-cubed.org]

Geochemistry
Geophysics
Geosystems
tassi et al.: water and gas chemistry at lake kivu (drc)

10.1029/2008GC002191

14 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

10.1029/2008GC002191

Figure 7. The d 2H versus d18O binary diagram of water samples from (a) the Main and Kabuno Bay basins and (b)
the Kalehe, Ishungu and Bukavu basins. GMWL: Global Meteoric Water Line; d2H = 8d18O + 10. Symbols as in
Figure 5.

basins, whereas NO

3 in the various water strata
is present only in minor amounts (Table 1). The
relatively high concentrations of dissolved Si
measured at Kabuno Bay (up to 166 mg/L) most
likely explain the abundance of Si diatoms that
characterizes this basin [Sarmento et al., 2006] and
that easily weather volcanic rock. An unusual
geochemical feature characterizing Lake Kivu,
especially the Main basin at depth >100 m, is
represented by the high P concentrations, pointing
to massive decomposition of organic matter, as
supported by the strong correlation between P
and NH4 (Table 2). This may also support the
already mentioned hypothesis suggesting that the
relatively high N2 concentrations of the deep lake
water strata are, at least partially, due to bacterial
activity.

5.1.3. Sublacustrine Fluid Discharges

[31] Seismic reflection profiles performed across
the northern sector of the Main basin show high
sharp echoes and represent the first direct evidence
for the presence of sublacustrine fluid vents
[Degens et al., 1973]. This was also inferred on
the basis of the strata-bound metal deposits
recorded within the Lake Kivu sediments [Degens
and Kulbicki, 1973]. The discharge into the lake of
fluids from a diffuse deep system is considered to
be the main source of the CO2-dominated gas
reservoir of the deep lake strata [e.g., Tietze et
al., 1980; Schoell et al., 1988]. According to this
hypothesis, the d 2H and d 18O values of the water
samples collected along the vertical profile at the

Main basin (Figure 7a) from depths 225 m show

a sharp shift along the global meteoric water line
(GMWL) [Craig, 1961] with respect to those of the
shallower water strata. At Kabuno Bay, the difference between the isotopic composition of water at
depth 25 m and that of the lake surface is even
more pronounced. An isotopic stratification is less
evident for the Kalehe and Ishungu basins and
completely absent at Bukavu (Figure 7b). A slight
difference in surface waters across the lake is most
likely caused by variable isotopic composition of
the river and groundwater inputs. The stratified
basins are likely fed by significant contribution of
meteoric water from a hydrological system
recharged at altitudes significantly higher than lake
surface. The circulation of the recharging aquifer
system is driven by the NNESSW trending faults
that are associated to the rift-related tectonic activity and is also responsible of the complex morphology of the lake.
[32] As also suggested by Degens and Kulbicki
[1973], the fluids discharged into Lake Kivu from
the sublacustrine vents are likely Na-HCO
3 -rich.
Similar chemical features characterize the sublacustrine emissions discharging at Pemba, in the
northern basin of Lake Tanganyika [Tiercelin et al.,
1989; Pflumio et al., 1994] and those of Lake
Bogoria, Kenya [Cioni et al., 1992]. The relative
increases with depth of Cl, B, Cs, and Li (Tables 1
and 2), commonly considered as tracers of thermal
fluids [e.g., Giggenbach, 1991], suggest that the
sublacustrine discharges could be related to a
hydrothermal system. Hydrothermal fluid contri15 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

bution may also be responsible, at least partially, of

the SiO2 increases characterizing the vertical profiles of Main, Kabuno Bay, Kalehe, and Ishungu
basins.
[33] The contribution of Na-HCO
3 -rich fluids
seems to be mainly focused beneath Kabuno Bay
basin and in general seems to be added to Lake
Kivu from the N, as suggested by the continuously
decreasing CO2/Ar ratios measured along a transect from Kabuno Bay to Bukavu passing through
Kalehe and the Main basins (Table 4).

5.2. Origin of Dissolved Gas Compounds

[34] The origin of the main extra-atmospheric dissolved gas compounds in Lake Kivu (i.e., CO2 and
CH4) has been extensively debated since the discovery of the huge gas reservoir stored in the deep
water strata in 1935 [Damas, 1937]. Contrasting
hypotheses were initially advanced to explain the
origin of CH4. Schmitz and Kufferath [1955] suggested that CH4 was produced by methanogenic
processes related to anaerobic bacterial activity,
whereas Gold and Soter [1980] proposed that this
hydrocarbon was emanated from a magmatic
source. On the basis of the d13CCH4 and dDCH4
values (58% V-PDB and 218% SMOW, respectively) and the 14C activity, the latter being
considerably lower in CH4 (9% modern) compared to the sediment (27% modern), Schoell et
al. [1988] assessed that CH4 is predominantly (60
70%) produced by reduction of CO2 and, to a
lesser extent (3040%), by acetate fermentation.
Schoells hypothesis for CH4 origin is also supported by the CH4/(C2H6 + C3H8) ratios, which are
>1000 at both the Main and Kalehe basins, the
only two basins where significant concentrations of
light hydrocarbons were detected (Table 4). Such
values of >1000 are indeed consistent with bacteria-driven genetic processes occurring at low temperatures within the lake and the lake bottom
sediments [Bernard et al., 1978; Whiticar and
Suess, 1990]. This finding indicates that CH4
results from reduction of CO2, but no insights
on the ultimate source of the carbon dioxide are
provided.
[35] The d 13CCO2 values measured in the Main,
Kalehe, and Ishungu basins (Table 4) confirm the
commonly accepted hypothesis [e.g., Schoell et al.,
1988; Schmid et al., 2005] suggesting that the
dissolved CO2 is mainly deriving from a magmatic
source. Considering that the carbon isotopic fractionation factor between solid calcium carbonate
and gaseous CO2 is 10.2% at 20C [Emrich et al.,

10.1029/2008GC002191

1970], the d 13CCO2 values of the Main basin (d 13C

values of carbonate sediments are not available for
the Ishungu and Kalehe basins) show isotopic
equilibrium with aragonite, calcite, and monohydrocalcite of primary deposition from lake water,
whose d 13C values are +4% V-PDB [Botz et al.,
1988]. Conversely, dissolved CO 2 from the
Kabuno Bay basin has an isotopic signature showing a significant depletion in 13C (Table 4). Moreover, at Kabuno Bay dissolved CO2 is not in
equilibrium with calcite, the latter having a d 13C
value of 2.3% V-PDB, i.e., lower than that
expected for calcite of primary deposition (0.8%
V-PDB). The negative carbon isotopic signature of
Kabuno Bay basin has been ascribed to the presence of diagenetic calcite in the bicarbonate-rich
pore waters [Botz et al., 1988]. However, our data
from the Kabuno Bay basin belongs to a peculiar
geochemical domain, which is characterized by
strong contribution of mantle-related He and CO2
altered by (1) removal or scrubbing processes as
CO2 interacts with groundwater, and (2) a possible
addition of isotopically light biogenic carbon. The
Kabuno Bay basin waters have CO2/Ar ratios up to
6.5  103, up to 10 to 20 times greater than those
of the other basins, with the exception of the
deepest Kalehe water whose CO2/Ar ratio is only
3 times lower. Assuming that the CO2/Ar ratio of
the mantle-related fluids is represented by the
fumarolic discharges from the Nyiragongo crater,
i.e., up to 1  104 (D. Tedesco et al., manuscript in
preparation, 2008), the dissolved gas at Kabuno
Bay is a 50% mixture of mantle derived and air
soluble gases. This should be considered the minimum estimate since CO2/Ar may be lowered by
CO2 scrubbing (removal) and therefore becoming
less abundant in the gases directly discharged into
the lake.
[36] In the Main, Ishungu, and Kalehe basins CO2
does not exhibit the same degree of carbon fractionation as Kabuno Bay, and a more significant
addition of crustal He is shown. The R/Rair values
and the CO2/Ar ratios of these three basins (Table 4)
seem to indicate that the mantle contribution
significantly decreases toward S. Accordingly, the
Bukavu basin, furthest S and most isolated from
the main portions of Lake Kivu, is characterized
by (1) the lowest He contribution from the mantle
(R/Rair = 1.21) and CO2 concentrations (4 to 5 times
lower than that observed at similar depths in other
basins; Table 4), (2) relatively high concentrations
of atmospheric gas components, (3) near atmospheric He/Ne ratios, and (4) the lowest CO2/Ar
ratio (44) (Table 4). This finding implies that
16 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

input of deep fluids in this area can likely be

regarded as negligible. In addition, the d 13C values
in carbonate from the Bukavu bottom sediments
indicate that this basin has experienced periods of
low water level leading to a complete separation
from the rest of the lake [Botz et al., 1988].
13

[37] The apparent decoupling of CO2 (d CCO2 

10% V-PDB) and He (R/Rair  5) at Kabuno Bay
is confirmed by the geochemical features of the
inland thermal springs (Sake springs) and the
mazukus (mazukus is a Swahili word literally
meaning evil winds and locally used to describe
the dry CO2-rich gas emissions) located near to the
northern shoreline of this basin [Vaselli et al., 2002,
2003; D. Tedesco et al., manuscript in preparation,
2008]. A possible explanation for this peculiar
feature could be related to a restricted presence of
organic-rich sedimentary material buried by the
volcanic products emitted from the Nyamulagira
volcano [Thonnard et al., 1965] that interacts with
long-circulating fluids discharging from the bottom
of the Kabuno Bay basin, as well as those feeding
the subaereal emissions of the Sake area (Figure 1).
This process could be the main cause of the
particularly negative d13CCO2 values of the fluids
of these areas in that the addition of thermally
generated CO2 would not affect the magmatic He
isotopes because of the lack of radiogenic hHe in
modern organic sediments. In contrast, in the Main
basin the d 13CCO2 values show only a little difference from that of CO2 from the Nyiragongo magmatic system that feeds Lake Kivu, suggesting a
scarcity of organic material in the pre-Nyiragongo
sedimentary formations between the volcano and
the lake. The relatively slight difference between
the d 13CCO2 values of the Main basin and those
of the Nyiragongo crater fumaroles (3.5%
V-PDB) (D. Tedesco et al., manuscript in preparation, 2008) is likely due to (1) CO2 scrubbing in the
lake neutral-alkaline water [e.g., Vogel et al., 1970;
Mook et al., 1974], (2) bacterial conversion of CO2
to CH4, and (3) isotopic exchange.
[38] The negative d 13CDIC values of Kabuno Bay
water also supports the d 13CCO2 signature of this
basin that is significantly more negative than that
of the Main basin (Table 1). It has to be considered
that the measured d 13CDIC values are produced by
combining the d 13C values of the main carbon
species, as follows:


d 13 CDIC d13 CCO2 * CO2  d13 CHCO3 * HCO
3



d13 CCO3 * CO2
3

 



HCO
= CO2
3
3 CO2 

10.1029/2008GC002191

2
where [CO2] (dissolved CO2), [HCO
3 ] and [CO3 ]
are in mmol/L. As shown in Table 1, the CO2
3
concentrations ([CO2
3 ]) are negligible with respect

to those of HCO
3 ([HCO3 ]). Thus, equation (3)
can be expressed as follows:




d 13 CDIC d 13 CCO2 * CO2  d13 CHCO3 * HCO
3




= HCO
3 CO2 

Isotopic fractionation due to the reaction between

dissolved CO2 and HCO
3 can be quantified by the
e2 enrichment factor [Mook et al., 1974], as
follows:
e2 d13 CHCO3  d13 CCO2 9483=T  23:9

where T is the water temperature in K.

[39] Therefore, by combining equations (4) and (5)
the relation between d 13CDIC and d 13CCO2 is

 




d13 CDIC d 13 CCO2 e2 * HCO
3 = HCO3 CO2 
6

The d 13CDIC values calculated with equation (6)

(d 13CDICcalc), using the temperature values reported
by Tietze [2000], for the water samples from
Kabuno Bay are significantly more negative
compared to those measured (Table 1). This
difference (up to 4.8% V-PDB) may be caused
by the lack of complete equilibrium between the
isotopically negative CO2, continuously discharged
into the lake from the sublacustrine emissions, and
the dissolved carbonate species (i.e., CO2, HCO
3,
and CO2
).
Conversely,
at
the
Main
basis
the
3
measured and calculated d 13CDIC values are
consistent. However, the degassing of the water
prior to sampling could have occurred, especially
for the water from the deepest layers. This process
may have affected the measured d 13CDIC values,
because the residual water tends to be enriched in
13
C as a consequence of kinetic fractionation
during the gas release. Nevertheless, the effects
of kinetic fractionation cannot explain the large
misfit between measured and calculated d 13CDIC
values of the Kabuno Bay sample series. Therefore, the previously invoked disequilibrium process
cannot be completely discarded.

5.3. Temporal and Spatial Behavior of

the Gas Reservoir
[40] The vertical distribution of the molar concentrations of dissolved CO2 (Figure 8a) and CH4
(Figure 8b) at the Main basin are consistent with
those measured in 1974 [Tietze, 1978] and 2004
17 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

Figure 8. Vertical profiles of (a) CO2 and (b) CH4

concentrations at the Main, Kalehe, Ishungu, Kabuno
Bay, and Bukavu basins, Lake Kivu, DRC. Data from
Degens et al. [1973], Tietze [1978], and Schmid et al.
[2005] are also reported.

[Schmid et al., 2005] at depths 250 m, whereas,

at depths between 300 and 450 m, the concentrations of both these compounds are significantly
lower, especially with respect to those reported by
Schmid et al. [2005]. Imprecision and inaccuracy
during sampling (e.g., gas loss) cannot explain all
of the differences among the results of the Lake
Kivu water and gas chemistry presented by various
authors [e.g., Schmitz and Kufferath, 1955; Degens
et al., 1973; Tietze, 1978; Tietze et al., 1980;
TECHNIP and BRGM, 1986]. Moreover, the explanation attributing all differences to sampling

10.1029/2008GC002191

artifacts conflicts with the general agreement

among the CO2 and CH4 vertical profiles of water
strata above the gas reservoir. The difference
between the CH4 concentrations measured in
1974 [Tietze, 1978] and those determined in 2004
[Schmid et al., 2005] was linked to the progressive
increase in nutrient input to the lake from the fastgrowing human population in its catchment area
that may have lead to a more efficient CO2-CH4
conversion [Schmid et al., 2005]. This intriguing
hypothesis, although reasonable, does not explain
the significant differences among the CO2 profiles
measured by the various scientific teams (Figure 8a)
and contrasts with the CH4 concentrations measured by Degens et al. [1973] which, at depths
>350 m, are even higher than those determined
more than 30 years later (Figure 8b). Therefore, in
our opinion the disagreement among the CH4
compositional data measured at the Main basin is
related to spatial variability affecting the amounts
and types of methanogenic bacterial communities.
It has to be considered that the site where we have
performed the vertical profile in the Main basin
(Figure 1) is located at greater distance from the
shoreline hosting the towns of Goma and Gisenyi,
likely representing the main source of anthropogenic-related contamination, with respect to the
collecting sites of Schmid et al. [2005]. Accordingly, significant differences in terms of phytoplankton biomass in the epilimnion from different
areas of the lake, as well as in different seasons are
reported [Sarmento et al., 2006]. Then, a different
mechanism must be invoked to account for the
differences among the CO2 vertical profiles measured in the last decades (Figure 8a). Owing to the
fact that the dissolved CO2 is mainly derived from
mantle degassing [e.g., Schoell et al., 1988; Schmid
et al., 2005], the spatial distribution should be
depending on the location of the sublacustrine
discharges, which are likely controlled by the
tectonic setting of the area. Nevertheless, a direct
relation between the distribution of dissolved CO2
anomalies and the location of the sublacustrine
discharges is not to be expected because the effects
of horizontal mixing in open lakes, such as the
Main basin, are a complex combination of physicchemical processes, not easily modeled from a
single vertical profile [e.g., Murthy, 1976; Imboden
and Wuest, 1995; Peeters et al., 1996]. However,
because of the small size and isolated character of
the Kabuno Bay basin (e.g., sill at 7 m) then very
high CO2 concentrations constitute a permanent
and dangerous feature the this basin (Figure 8a).
The sublacustrine vents discharging CO2-rich fluids into the Kabuno Bay basin, whose CO2/CH4
18 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

and CO2/Ar ratios are one order of magnitude

higher with respect to those of the other basins
(Table 4), have a particularly high flux. The CO2
vertical profile of the Kalehe basin is intermediate
between those of the Kabuno Bay and the Main
and Ishungu basins and it is almost coincident with
that measured at Main in 1973 [Degens et al.,
1973]. In contrast, Bukavu basin, where a gas
reservoir is lacking, the contribution of deeporiginated fluids seems to be negligible.

6. Conclusions
[41] The deep water strata of the five basins
constituting Lake Kivu are characterized by distinct chemical and isotopic features related to
differential influence of, at least, three processes,
i.e., water-mineral equilibrium, biological cycle,
and deep fluid inputs. Kabuno Bay, which is
almost completely separated from the rest of the
lake, has the most peculiar vertical profiles of water
and dissolved gas compositions. This likely results
from, first, large contribution of a sublacustrine
CO2-rich mantle-derived discharge entering the
lake from the northern sector, where shallow dykes
similar to those recognized in the 2002 eruption of
the Nyiragongo volcano can be hypothesized
[Tedesco et al., 2007]. This results in extremely
strong chemical stratification of the gas reservoir
even at relatively shallow depths (25 m), leading to
relatively high He isotope and CO2/Ar ratios, and
highly concentrated minor and trace element species. Second, it can result from the presence of
local organic-rich terrains interacting with the
recharging fluid system that, combined with CO2
scrubbing by interaction with groundwater, produces an extremely negative d13C-CO2 signature.
Therefore, Kabuno Bay may represent the most
hazardous source of gas outburst based on our
findings since its gas reservoir is not only dominated by mantle-derived gases, but it is also physically isolated from mixing currents that moderate
gas accumulation in the other basins of the lake.
According to these considerations, Kabuno Bay
should continuously be controlled by means of
rapid and low-cost geochemical monitoring techniques. For example, the high CO2 concentrations
at a shallow level and the presence of a CO2
gradient with depth suggest a CO2 flux that could
be detected at the lake surface. Systematic flux
measurement could provide useful information on
variations of CO2 input at depth. The Bukavu
basin, whose chemistry seems to be exclusively
regulated by water-rock interaction and carbonate

10.1029/2008GC002191

deposition and displays no signs of interaction

with the deep hydrological circulation system, is
holomictic.
[42] Spatial variations of the biomass distribution
and/or speciation, and the local tectonic assessment
that drives rising deep fluids up to lake bottom, are
likely to be the main causes of the measured
compositional differences among deep-water layers
of the three stratified basins constituting the central
portion of the lake, i.e., Main, Ishungu, and
Kalehe. Although similar, the chemistry of the
CO2-, CH4-rich gas reservoir in each basin cannot
be considered as completely homogeneous because
the deep water influx occurs mainly in the north
and the surface outflow is to the south.
[43] Large and deep-water reservoirs in close proximity to hydrothermal and magmatic fluid discharges, particularly in active tectonic settings,
are known to constitute hazards to human life.
Lake Nyos, Cameroon, serves as example of the
dangers. In the case of Lake Kivu, an extremely
large gas reservoir in a highly active tectonic
framework, requires scrutiny. Geochemical and
isotopic investigations can help to evaluate hazard
risk and potentially inform communities to plan for
and respond to gas eruptive events. The geochemical and isotopic results of this study reveal the
complexity of the spatially and temporally evolving limnological and magmatic system and the
importance of understanding the physical-chemical
processes that dominate these systems. One of the
most important achievements of this investigation
is the partial reconciliation of apparently discordant
geochemical data obtained by different authors by
considering Lake Kivu as a heterogeneous system.

Acknowledgments
[44] The authors wish to express their gratitude to the
International Red Cross for kindly assisting the authors during
the three sampling campaigns carried out in the Lake Kivu.
The UN-OCHA is thanked for supporting the first fieldtrip
with a project initiated after the 2002 eruption of Nyiragongo
volcano (Resp. OV). Andrea Nencetti is thanked for assisting
during the first sampling campaign and performing part of the
IC analysis. Save the Children and GVO are warmly acknowledged for partly supporting the first and second fieldtrips.
Many thanks are due to J. Dixon, J. Varekamp, and W. C.
Evans for the constructive comments that have greatly
improved an early version of the manuscript. While revising
this paper in the region of northern Kivu and particularly in the
city of Goma and surrounding areas, another massacre, after that
of 1994 1995, is occurring. Once again about 1,000,000
refugees are trying to find a safe place, far from the rebels and
the DRC army who are committing dreadful atrocities to the
19 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

defenseless population. Our thought is to the GVO personnel

and their families.

References
Aoki, K., T. Yoshida, K. Yusa, and Y. Nakamura (1985), Petrology and geochemistry of the Nyamuragira volcano, Zaire,
J. Volcanol. Geotherm. Res., 25, 1 28, doi:10.1016/03770273(85)90002-2.
Auchapt, A., C. Dupuy, J. Dostal, and M. Kanika (1987),
Geochemistry and petrogenesis of rift-related volcanic rocks
from South Kivu (Zaire), J. Volcanol. Geotherm. Res., 31,
33 46, doi:10.1016/0377-0273(87)90004-7.
Bernard, B. B., J. M. Brooks, and W. M. Sackett (1978), Light
hydrocarbons in recent Texas continental shelf and slope
sediments, J. Geophys. Res., 83, 4053 4061, doi:10.1029/
JC083iC08p04053.
Botz, R., P. Stoffers, E. Faber, and K. Tietze (1988), Isotope geochemistry of carbonate sediments from Lake Kivu (East-Central
Africa), Chem. Geol., 69, 299 308, doi:10.1016/00092541(88)90041-1.
Capart, A. (1960), Le Lac Kava, Nat. Belge, 41, 397 417.
Chakrabarti, R., A. R. Basu, A. P. Santo, D. Tedesco, and
O. Vaselli (2009), Isotopic and geochemical study of the Nyiragongo and Nyamulagira volcanics in the western rift of the
East African Rift System, Earth Planet. Sci. Lett., in press.
Charlton, S. R., and D. L. Parkhurst (2002), Phreeqc I. A graphical
user interface to the geochemical model PHREEQC, U.S.
Geol. Surv. Fact Sheet, FS-031 02, 2.
Cioni, R., G. Fanelli, M. Guidi, J. K. Kinnyariro, and L. Marini
(1992), Lake Bogoria hot springs (Kenya): Geochemical
features and geothermal implications, J. Volcanol. Geotherm.
Res., 50, 231 246, doi:10.1016/0377-0273(92)90095-U.
Coleman, M. L., T. J. Sheperd, J. E. Rouse, and G. R. Moore
(1982), Reduction of water with zinc for hydrogen isotope analysis, Anal. Chem., 54, 993 995, doi:10.1021/ac00243a035.
Craig, H. (1961), Isotopic variations in meteoric waters, Science,
133, 1702 1703, doi:10.1126/science.133.3465.1702.
Damas, H. (1937), La Stratification Thermique et Chimique
des Lacs Kivu, Edouard et Ndaleger (Congo Belge), Verh.
Int. Ver. Theor. Angew. Limnol., 8, 51 68.
Degens, E. T., and G. Kulbicki (1973), Hydrothermal origin of
metals in some East African Rift Lakes, Miner. Deposita, 8,
388 404, doi:10.1007/BF00207520.
Degens, E. T., R. P. Von Herzen, H. K. Wong, W. G. Deuser,
and H. W. Jannach (1973), Lake Kivu: Structure, chemistry
and biology of an East African Rift Lake, Geol. Rundsch.,
62, 245 277, doi:10.1007/BF01826830.
Deuser, W. G., E. T. Degens, and G. R. Harvey (1973),
Methane in Lake Kivu: New data bearing its origin, Science,
181, 51 54, doi:10.1126/science.181.4094.51.
Doevenspeck, M. (2007), Lake Kivus methane gas: Natural risk,
or source of energy and political security?, Afr. Spectrum, 42,
91 106.
Dumont, H. J. (1986), The Tanganyika sardine in Lake Kava:
Another ecodisaster for Africa?, Environ. Conserv., 13,
143 148.
Ebinger, C. J. (1989), Tectonic development of the western
branch of the East African rift system, Geol. Soc. Am. Bull.,
101, 885 903, doi:10.1130/0016-7606(1989)101<0885:
TDOTWB>2.3.CO;2.
Emrich, K., D. H. Ehhalt, and J. C. Vogel (1970), Carbon isotope
fractionation during the precipitation of calcium carbonate,
Earth Planet. Sci. Lett., 8, 363 371, doi:10.1016/0012821X(70)90109-3.

10.1029/2008GC002191

Epstein, S., and T. K. Mayeda (1953), Variation of the 18O/16O ratio

in natural waters, Geochim. Cosmochim. Acta, 4, 213 224,
doi:10.1016/0016-7037(53)90051-9.
Evans, W. C., G. W. Kling, M. L. Tuttle, G. Tanyileke, and
L. D. White (1993), Gas build-up in Lake Nyos, Cameroon:
The recharge process and its consequences, Appl. Geochem.,
8, 207 221, doi:10.1016/0883-2927(93)90036-G.
Evans, W. C., L. D. White, and J. B. Rapp (1998), Geochemistry of some gases in hydrothermal fluids from the southern
San Juan de Fuca ridge, J. Geophys. Res., 15, 305 313.
Furman, T. (2007), Geochemistry of East African Rift System
basalts: An overview, J. Afr. Earth Sci., 48, 147 160,
doi:10.1016/j.jafrearsci.2006.06.009.
Gerasimoskiy, V. I., and Y. N. Savinova (1969), Fluorine contents of volcanic rocks in the rift zone of East Africa, Geochem. Int., 6, 1124 1128.
Giggenbach, W. F. (1991), Chemical techniques in geothermal
exploration, in Application of Geochemistry in Geothermal
Reservoir Development, edited by F. DAmore, pp. 253 273,
U. N. Inst. for Training and Res., New York.
Gold, T., and S. Soter (1980), The deep-earth gas hypothesis,
Sci. Am., 242, 154 161.
Haberyan, K. A., and R. E. Hecky (1987), The late Pleistocene
and Holocene stratigraphy and paleolimnology of Lakes Kivu
and Tanganyika, Palaeogeogr. Palaeoclimatol. Palaeoecol.,
61, 169 197, doi:10.1016/0031-0182(87)90048-4.
Hecky, R. E., and H. J. Kling (1987), Phytoplankton ecology
of the great lakes in the rift valleys of Central Africa, Arch.
Hydrobiol. Beit. Ergebn. Limnol., 25, 197 228.
Hoefs, J. (1973), Stable Isotope Geochemistry, 140 pp.,
Springer, Berlin.
Holzforster, F., and U. Schmidt (2007), Anatomy of a river
drainage reversal in the Neogene Kivu-Nile Rift, Quat. Sci.
Rev., 26, 1771 1789, doi:10.1016/j.quascirev.2007.04.018.
Imboden, D. M., and A. Wuest (1995), Mixing mechanisms in
lakes, in Physics and Chemistry of Lakes, edited by A. Lerman,
D. Imboden, and J. Gat, pp. 83138, Springer, New York.
Isumbisho, M., M. Kaningini, J. Dercy, and E. Baras (2004),
Seasonal and diel variations in diet of the young stages of
the fish limnothrissa miodon in Lake Kava, eastern Africa,
J. Trop. Ecol., 20, 73 83, doi:10.1017/S0266467403001056.
Jagoutz, E., H. Palme, H. Baddenhausen, K. Blum, M. Cendales,
G. Dreibus, B. Spettel, V. Lorenz, and H. Waenke (1979),
The abundances of major, minor and trace elements in the Earths
mantle as derived from primitive ultramafic nodules, in Proceedings of the Lunar and Planetary Science Conference, edited by
R. B. Merrill et al., pp. 20312050, Pergamon, New York.
Johnson, J., G. Anderson, and D. Parkhurst (2000), Database
thermo.com.V8.R6.230, Rev. 1.11, Lawrence Livermore
Natl. Lab., Livermore, Calif.
Kallistova, A. Y., M. V. Kevbrina, N. V. Pimenov, I. I. Rusanov,
D. Y. Rogozin, B. Wehrli, and A. N. Nozhevnikova (2006),
Sulfate reduction and methanogenesis in the Shira and Shunet
meromictic lakes (Khakasia, Russia), Microbiology, 75,
720 726, doi:10.1134/S0026261706060166.
Kling, G. W., M. A. Clark, H. R. Compton, J. D. Devine, W. C.
Evans, A. M. Humphrey, E. J. Koenigsberg, J. P. Lockwood,
M. L. Tuttle, and G. N. Wagner (1987), The 1986 Lake Nyos
gas disaster in Cameroon, West-Africa, Science, 236(4798),
169 175, doi:10.1126/science.236.4798.169.
Lahmeyer International and OSAE (1998), Bathymetric survey
of Lake Kivu, final report, 18 pp., Dir. of Energy and Hydrocarbons, Repub. of Rwanda Minist. of Public Work, Kigali.
Lorke, A., K. Tietze, M. Halbwachs, and A. Wuest (2004),
Response of Lake Kivu stratification to lava inflow and climate warning, Limnol. Oceanogr., 49(3), 778 783.
20 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

Mamyrin, B. A., and I. N. Tolstikhin (1984), Helium Isotopes

in Nature, 273 pp., Elsevier, Amsterdam.
McDonough, W. F., and F. A. Frey (1989), REE in upper
mantle rocks, in Geochemistry and Mineralogy of Rare
Earth Elements, edited by B. Lipin and G. R. McKa,
pp. 99 145, Mineral. Soc. of Am., Chelsea, Mich.
Montegrossi, G., F. Tassi, O. Vaselli, E. Bidini, and A. Minissale
(2006), A new rapid and reliable method for the determination
of reduced sulphur (S2) species in natural water discharges,
Appl. Geochem., 21, 849 857, doi:10.1016/j.apgeochem.
2006.02.007.
Mook, W. G., J. C. Bommerson, and W. H. Staverman (1974),
Carbon isotope fractionation between dissolved bicarbonate
and gaseous carbon dioxide, Earth Planet. Sci. Lett., 22,
169 176, doi:10.1016/0012-821X(74)90078-8.
Murthy, C. R. (1976), Horizontal diffusion characteristics in
Lake Ontario, Phys. Oceanogr., 6, 76 84, doi:10.1175/
1520-0485(1976)006<0076:HDCILO>2.0.CO;2.
Navarre-Sitchler, A., and S. Brantley (2007), Basalt weathering across scales, Earth Planet. Sci. Lett., 261, 321 334,
doi:10.1016/j.epsl.2007.07.010.
Oppenheimer, C. (1992), Sulphur eruptions at Volcan Poas,
Costa Rica, J. Volcanol. Geotherm. Res., 49, 1 21,
doi:10.1016/0377-0273(92)90002-U.
Parkhurst, D. L., and C. A. J. Appelo (1999), Users guide to
PHREEQC (version 2). A computer program for speciation,
batch-reaction, one-dimensional transport, and inverse geochemical calculations, U.S. Geol. Surv. Water Resour. Invest.
Rep., 99 4259, 312 pp.
Pearce, J. A. (1982), Trace element characteristics of lavas
from destructive plate boundaries, in Andesites: Orogenic
Andesites and Related Rocks, edited by R. S. Thorpe,
pp. 526 547, John Wiley, Chichester, U. K.
Peeters, F., A. Wuest, G. Piepke, and D. M. Imboden (1996),
Horizontal mixing in lakes, J. Geophys. Res., 101, 18,361
18,375, doi:10.1029/96JC01145.
Pflumio, C., J. Boule`gue, and J. J. Tiercelin (1994), Hydrothermal
activity in the northern Tanganyika Rift, East Africa, Chem.
Geol., 116, 85 109, doi:10.1016/0009-2541(94)90159-7.
Platz, T., S. F. Foley, and L. Andre (2004), Low-pressure fractionation of the Nyiragongo volcanic rocks, Virunga Province,
D. R. Congo, J. Volcanol. Geotherm. Res., 136, 269 295,
doi:10.1016/j.jvolgeores.2004.05.020.
Poreda, R. J., and K. A. Farley (1992), Rare gases in Samoan
xenoliths, Earth Planet. Sci. Lett., 113, 129 144.
Rollinson, H. (1993), Using Geochemical Data, 352 pp.,
Longman, London.
Salata, G. G., L. A. Roelke, and L. A. Cifuentes (2000), A
rapid and precise method for measuring stable carbon isotope ratios of dissolved inorganic carbon, Mar. Chem., 69,
153 161, doi:10.1016/S0304-4203(99)00102-4.
Santo, A. P., B. Capaccioni, D. Tedesco, and O. Vaselli (2002/
2003), Petrographic and geochemical features of the 2002
Nyiragongo lava flows, Acta Vulcanol., 14 15, 63 66.
Sarmento, H., M. Isumbisho, and J. P. Descy (2006), Phytoplankton ecology of Lake Kivu (eastern Africa), J. Plankton
Res., 28, 815 829, doi:10.1093/plankt/fbl017.
Sarmento, H., M. Leitao, M. Stoyneva, P. Compe`re, A. Coute,
M. Isumbisho, and J. P. Descy (2007), Species diversity of
pelagic algae in Lake Kivu (East Africa), Cryptogam.,
Algol., 28, 246 269.
Schmid, M., K. Tietze, M. Halbwachs, A. Lorke, D. McGinnis,
and A. Wuest (2004), How hazardous is the gas accumulation in Lake Kivu? Arguments for a risk assessment in light
of the Nyiragongo Volcano eruption of 2002, Acta Vulcanol.,
14 15, 115 121.

10.1029/2008GC002191

Schmid, M., M. Halbwachs, B. Wehrli, and A. Wuest (2005),

Weak mixing in Lake Kivu: New insights indicate increasing
risk of uncontrolled gas eruption, Geochem. Geophys. Geosyst., 6, Q07009, doi:10.1029/2004GC000892.
Schmitz, D. M., and J. Kufferath (1955), Proble`mes posees par
la Presence de Gaz dissous dans les Eaux profondes du Lac
Kivu, Acad. R. Sci. Colon. Bull. Seances, 1, 326 356.
Schoell, M., K. Tietze, and S. Schoberth (1988), Origin of the
methane in Lake Kivu (east-central Africa), Chem. Geol., 71,
257 265, doi:10.1016/0009-2541(88)90119-2.
Sigurdsson, H., J. D. Devine, F. M. Tchoua, T. S. Presser, M. K.
Pringle, and W. C. Evans (1987), Origin of the lethal gas
burst from Lake Monoun, Cameroun, J. Volcanol. Geotherm.
Res., 31, 1 16, doi:10.1016/0377-0273(87)90002-3.
Spigel, R. H., and G. W. Coulter (1996), Comparison of
hydrology and physical limnology of the East African Great
Lakes: Tanganyika, Malawi, Victoria, Kivu and Turkana (with
reference to some North American Great Lakes), in The Limnology, Climatology and Paleoclimatology of the East African
Lakes, edited by T. C. Johnson and E. O. Odada, pp. 103 139,
Gordon and Breach, Toronto, Ontario, Canada.
Spigel, R. H., and J. C. Priscu (1998), Physical limnology of the
McMurdo Dry Valleys lakes, in Ecosystem Dynamics in a
Polar Desert: The McMurdo Dry Valleys, Antarctica, Antartct.
Res. Ser., vol. 72, edited by J. C. Priscu, pp. 153 188, AGU,
Washington, D.C.
Tassi, F., O. Vaselli, L. Giannini, D. Tedesco, A. Nencetti,
G. Montegrossi, and M. M. Yalire (2004), A low-cost and
effective method to collect water and gas samples from stratified crater lakes: The 485 m deep Lake Kivu (DRC), paper
presented at General Assembly, Int. Assoc. of Volcanol. and
Chem. of the Earths Inter., Puchon, Chile.
Tassi, F., O. Vaselli, G. Luchetti, G. Montegrossi, and
A. Minissale (2008), Metodo per la determinazione dei gas
disciolti in acque naturali, internal report, 11 pp., Inst. for
Geosci. and Earth Res., Florence, Italy.
Tazieff, H., and P. Bichet (1979), Nyiragongo: The Forbidden
Volcano, 288 pp., Barrons, New York.
TECHNIP and BRGM (1986), Etudes gaz methane. Programme 1: Mesures sur le gisement de gaz au Cap Rubona,
Final Rep. 5840 Y 01, 53 pp., Repub. of Rwanda Minist. of
Public Work, Kigali.
Tedesco, D., O. Vaselli, P. Papale, S. A. Carn, M. Voltaggio,
G. M. Sawyer, J. Durieux, M. Kasereka, and F. Tassi (2007),
January 2002 volcano-tectonic eruption of Nyiragongo
volcano, Democratic Republic of Congo, J. Geophys. Res.,
112, B09202, doi:10.1029/2006JB004762.
Thonnard, R. L. G., M. E. Denaeyer, and P. Antun (1965),
Carte volcanologique des Virunga, Afrique Centrale, Feuille
1, scale , 1:50,000, Cent. Natl. de Volcanol., Brussels.
Tiercelin, J. J., C. Thouin, K. Tshibangu, and A. Mondenguer
(1989), Discovery of sublacustrine hydrothermal activity and
associated massive sulfides and hydrocarbons in the north
Tanganyika trough, East African Rift, Geology, 17, 1053 1056,
doi:10.1130/0091-7613(1989)017<1053:DOSHAA>2.3.
CO;2.
Tietze, K. (1978), Geophysikalische untersuchung des Kivusees und seiner ungewohnlichen methangaslagersta tteschichtung, Dynamik und Gasgehalt des Seewassers, Ph.D.
thesis, Christian-Albrechts-Univ., Kiel, Germany.
Tietze, K. (1987), Results of the German-Cameroon research
expedition to Lake Nyos (Cameroon), October/November
1986, internal report, 84 pp., Fed. Inst. Geosci. Nat. Res.,
Hannover, Germany.
Tietze, K. (2000), Lake Kivu gas development and promotionrelated issues: Safe and environmentally sound exploitation,
21 of 22

Geochemistry
Geophysics
Geosystems

tassi et al.: water and gas chemistry at lake kivu (drc)

final report, 110 pp., Repub. of Rwanda, Minist. of Energy,

Water and Nat. Res., Kigali.
Tietze, K., M. Geyh, H. Muller, L. Schroder, W. Stahl, and
H. Wehner (1980), The genesis of the methane in Lake Kivu
(Central Africa), Geol. Rundsch., 69, 452 472, doi:10.1007/
BF02104549.
Turner, J. S. (1973), Buoyancy Effects in Fluids, Cambridge
Univ. Press, New York.
Vaselli, O., B. Capaccioni, D. Tedesco, F. Tassi, M. Y. Mapedano,
and C. K. Mahinda (2003), The evil winds (mazukus) at
Nyiragongo volcano (Democratic Republic of Congo), Acta
Vulcanol., 14/15, 123 128.
Vaselli, O., F. Tassi, G. Montegrossi, B. Capaccioni, and
L. Giannini (2006), Sampling and analysis of volcanic gases,
Acta Vulcanol., 18, 65 76.
Vaselli, O., F. Tassi, D. Tedesco, E. Cuoco, B. Nisi, and M. M.
Yalire (2007), Environmental impact of the Nyiragongo

10.1029/2008GC002191

volcanic plume after the January 2002 eruption, paper

presented at 26th Workshop on Active Volcanism and
Continental Rifting, With Special Focus on the Virunga
(North Kivu, DR of Congo), Eur. Cent. for Geodyn. and
Seismol., Walferdange, Luxembourg.
Vogel, J. C., P. M. Grootes, and W. G. Mook (1970), Isotope
fractionation between gaseous and dissolved carbon dioxide,
Z. Phys., 230, 255 258, doi:10.1007/BF01394690.
Whiticar, M. J., and E. Suess (1990), Hydrothermal hydrocarbon gases in the sediments of the King George Basin, Bransfield Strait, Antarctica, Appl. Geochem., 5, 135 147,
doi:10.1016/0883-2927(90)90044-6.
Zhang, J., P. D. Quay, and D. O. Wilbur (1995), Carbon
isotope fractionation during gas-water exchange and dissolution of CO2, Geochim. Cosmochim. Acta, 59, 107 114,
doi:10.1016/0016-7037(95)91550-D.

22 of 22