3 Article

Geochemistry
G
Volume 10, Number 2
Geophysics 6 February 2009
Q02005, doi:10.1029/2008GC002191
Geosystems
AN ELECTRONIC JOURNAL OF THE EARTH SCIENCES ISSN: 1525-2027
Published by AGU and the Geochemical Society

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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 3
Geophysics
Geosystems G 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 to better understand the risk of limnic eruptions

[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 >50–80 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 0°C 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 lake-
side 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 occur-
rence 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
[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 sub-
basins 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
lake’s bottom; (3) provide a geochemical conceptual
model of the lake by taking into account precipita-
tion and dissolution processes, effects of biological
activity, and inputs of deep-seated fluids.
2. Geographic Location and
Limnological Features
[3] Lake Kivu (located between 1°300 and 2°300S
and 28°500 and 29°230E) was formed in the Pleisto-
cene, 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 [Holzförster and
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 Geochemistry 3
Geophysics
Geosystems G 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 effi-
ciently inhibit vertical mixing. The lake is indeed
meromictic, with an epilimnion, reaching a depth
of 50–80 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 heteroge-
neity of water chemistry in the Main basin, ascrib-
ing 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 physical-
chemical parameters, i.e., density, electrical con-
ductivity, 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 homo-
geneously distributed all over the entire lake.

3. Sampling and Analytical Methods

Figure 1. Map of Lake Kivu with the location of the 3.1. Water and Dissolved Gas Sampling
sampling sites.
[5] The liquid and gas phases were collected during
Schmidt, 2007, and references therein]. Presently, three field campaigns in 2004, 2005, and 2007,
Lake Kivu’s surface waters are maintained at an along profiles from the lake bottom to the surface,
elevation of 1462 – 1463 m asl by the Mururu at regular intervals of 25 m, corresponding to the
hydroelectric plant near Bukavu (Figure 1). The deepest point for each of the five basins of Lake
waters are discharged toward south into the Ruzizi
river and that enter Lake Tanganyika at a rate of
3.2 km3/a. The world’s 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 Figure 2. Three-dimensional bathymetric map of Lake
and OSAE, 1998]. Kivu.
3 of 22
 Geochemistry 3
Geophysics
Geosystems G tassi et al.: water and gas chemistry at lake kivu (drc)
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 associ-
ated 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 accu-
rately 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 chromatogra-
phy (Dionex DX-120 and Metrohm 761), respec-
tively. Reduced sulfur species (hereafter reported as
SS2), i.e., those deriving from dissolved H2S,
HS, S2, polysulfide, and metal-sulfide com-
plexes, 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-
10.1029/2008GC002191
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 500°C [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 solid-
liquid 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 dis-
solved gas compounds (CO2, N2, O2 and Ar) stored
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 Geochemistry 3
Geophysics
Geosystems G tassi et al.: water and gas chemistry at lake kivu (drc)
in the headspace of the sampling flasks was deter-
mined by a Shimadzu 15A gas chromatograph
equipped with a Thermal Conductivity Detector
(TCD). The analysis of dissolved light hydrocar-
bons (CH4, C2H6, C3H8, n-C4H10 and i-C4H10) was
performed with a Shimadzu 14A gas chromato-
graph equipped with a Flame Ionization Detector
(FID) [Tassi et al., 2004]. The complete composi-
tion of dissolved gas compounds was calculated on
the basis of the Henry’s law constants, regulating
the liquid-gas equilibrium for each volatile com-
pound [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 deter-
mination 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 deter-
mined by mass spectrometry by the methods de-
scribed by Poreda and Farley [1992]. The gas
samples were purified in a high vacuum line con-
structed of stainless steel and Corning-1724 glass to
minimize He diffusion. Water vapor and CO2 were
cryogenically trapped at 90 and 195°C, respec-
tively, 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 233°C, 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 concen-
trations were analyzed on a VG 5400 Rare Gas
Mass Spectrometer fitted with a Faraday cup (res-
olution 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 com-
pletely separated from HD+, with a baseline sepa-
ration 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 com-
position (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, suggest-
ing 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 differ-
ences do exist among the various basins at increas-
ing 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,
Mg, HCO 2 
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
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 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
Sampling
Geophysics

Basin Depth Date F B dD

Geosystems

pH Na+ K+ Mg2+ Ca2+ HCO3 CO32 Cl SO42 Li+ NH4+ Br NO3 S2 SiO2 TDS d 18O d 13CDIC d 13CDICcalc
Geochemistry

Kabuno 0 2/19/2004 8.88 148 107 111 27 1050 40 24 25 0.04 <0.01 2.05 0.05 0.23 0.32 0.03 28 1493 20.16 1.24 1.00
G

Bay
3

Kabuno 25 2/19/2004 8.58 328 297 530 88 4225 81 70 <0.1 0.10 6.93 2.60 0.15 0.20 3.62 0.11 136 5548 5.08 2.46 2.91
Bay
Kabuno 50 2/19/2004 7.32 385 345 710 78 5272 81 <0.1 0.11 9.50 2.75 0.20 0.35 4.17 0.30 145 6884 10.00 2.44 2.06 4.86
Bay
Kabuno 75 2/19/2004 7.25 365 357 760 80 5638 83 <0.1 0.11 10.30 1.88 0.20 0.30 4.42 0.33 154 7295 2.53 2.40 2.25 5.38
Bay
Kabuno 100 2/19/2004 7.12 375 359 780 77 5955 84 <0.1 0.12 9.83 2.70 0.25 0.35 4.58 0.32 154 7643 3.59 2.58 2.70 7.48
Bay
Kabuno 125 2/19/2004 6.90 485 396 920 70 6626 91 <0.1 0.14 9.66 2.60 0.20 0.30 4.42 0.34 161 8601 4.58 2.45 3.16 6.23
Bay
Kabuno 140 2/19/2004 6.70 460 402 925 67 6669 93 <0.1 0.14 10.15 2.65 0.30 0.20 4.54 0.35 166 8629 7.24 2.66 3.29 6.04
Bay
Main 0 2/21/2004 8.76 108 83 84 7 781 23 21 16 0.03 0.32 1.57 0.08 <0.01 2.07 0.05 11 1102 29.69 1.17 3.35
Main 25 2/21/2004 8.68 111 85 84 7 778 19 21 15 0.03 0.19 1.57 0.09 <0.01 2.36 0.05 10 1102 26.81 1.85 3.45
Main 50 2/21/2004 8.56 117 85 87 8 805 15 21 16 0.04 0.13 1.60 0.09 <0.01 2.69 0.05 11 1141 26.83 2.20 1.65
Main 75 2/21/2004 7.48 143 102 99 25 1025 28 10 0.05 2.32 1.82 0.10 0.18 2.75 0.08 20 1436 27.20 2.02 1.21
Main 100 2/21/2004 6.89 188 116 134 53 1507 44 11 0.07 7.25 2.26 0.10 0.28 3.38 0.15 33 2063 24.95 2.11 1.12 0.17
Main 125 2/21/2004 6.77 219 155 152 68 1730 52 15 0.08 9.83 2.75 0.15 0.30 3.52 0.19 41 2405 25.13 1.04 1.25
Main 150 2/21/2004 6.71 226 162 161 72 1827 53 16 0.09 10.62 2.60 0.10 0.18 3.49 0.20 47 2530 25.87 1.25 1.00 2.00
Main 175 2/21/2004 6.64 229 166 169 73 1913 55 15 0.09 11.59 2.58 0.10 <0.01 3.65 0.21 51 2634 24.95 1.11 0.52
Main 200 2/21/2004 6.52 247 169 171 78 1986 56 6 0.10 12.72 2.60 0.15 0.13 4.01 0.24 54 2729 26.58 1.65 1.12 2.63
Main 225 2/21/2004 6.53 283 196 195 88 2239 65 13 0.13 18.03 2.72 0.20 0.15 4.11 0.27 54 3099 21.94 2.02 0.56
Main 250 2/21/2004 6.45 280 193 200 91 2258 65 13 0.13 18.03 2.70 0.20 1.78 4.44 0.24 55 3122 23.57 2.12 0.88 1.71
tassi et al.: water and gas chemistry at lake kivu (drc)

Main 275 2/21/2004 6.33 302 211 236 119 2486 69 9 0.14 21.57 2.78 0.25 0.13 4.44 0.29 66 3456 25.05 1.65 0.88
Main 300 2/21/2004 6.35 428 277 334 122 3753 88 15 0.20 47.65 3.35 0.20 0.18 5.97 0.47 93 5068 13.85 1.22 3.31 2.32
Main 325 2/21/2004 6.24 452 293 344 127 3795 90 15 0.20 48.29 3.36 0.25 0.32 6.55 0.43 95 5168 15.25 1.31 3.23
Main 350 2/21/2004 6.18 470 317 374 135 4082 97 15 0.21 54.09 3.33 0.40 0.20 6.95 0.45 103 5548 13.43 1.70 4.62 3.21
Main 375 2/21/2004 6.15 488 320 380 130 4198 97 15 0.22 55.38 3.34 0.35 <0.01 7.20 0.44 105 5687 12.79 1.25 3.69 2.56
Main 400 2/21/2004 6.07 478 326 394 129 4259 98 9 0.21 56.66 3.20 0.37 <0.01 7.25 0.42 100 5753 11.59 0.31 3.92 2.65
Main 425 2/21/2004 6.08 482 336 390 135 4314 99 12 0.21 56.66 3.15 0.35 0.25 7.70 0.46 103 5828 12.15 0.55 3.74 3.32
Main 450 2/21/2004 6.11 490 334 392 130 4326 102 10 0.20 57.31 3.18 0.30 0.00 7.75 0.42 102 5845 12.27 0.50 3.66 3.95
Main 478 2/21/2004 6.02 492 325 468 117 4344 101 5 0.21 58.92 3.15 0.35 0.25 7.81 0.44 103 5915 11.44 0.72 3.71 4.11
Kalehe 0 6/15/2005 9.47 103 80 82 8 738 109 28 15 0.03 0.01 1.64 0.07 0.06 0.06 14 1057 20.80 2.41
10.1029/2008GC002191

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 Geophysics
Geosystems
Geochemistry

Table 1. (continued)
3

Sampling
Basin Depth Date pH Na+ K+ Mg2+ Ca2+ HCO3 CO32 Cl SO42 Li+ NH4+ F Br NO3 S2 B SiO2 TDS dD d 18O d 13CDIC d 13CDICcalc

Kalehe 25 6/15/2005 9.31 103 80 80 8 738 76 27 16 0.03 0.41 1.52 0.12 <0.01 0.06 13 1054 22.85 2.55
Kalehe 50 6/15/2005 9.14 107 82 84 9 753 52 26 15 0.03 0.43 1.52 0.05 <0.01 0.06 14 1078 24.51 2.67
Kalehe 75 6/15/2005 8.19 116 90 96 16 847 23 14 0.04 1.07 1.62 0.05 <0.01 0.09 21 1206 20.51 2.33
Kalehe 100 6/15/2005 7.24 157 116 119 40 1156 44 13 0.05 15.47 2.24 0.05 0.02 0.17 42 1662 18.22 2.17 2.81
Kalehe 125 6/15/2005 6.96 191 139 141 61 1477 54 12 0.06 10.31 2.69 0.06 <0.01 0.20 54 2089 21.02 1.97 2.97
Kalehe 150 6/15/2005 7.11 212 155 156 77 1662 60 13 0.07 16.86 2.92 0.10 <0.01 0.24 68 2355 23.12 2.30 2.92
Kalehe 175 6/15/2005 7.05 220 163 165 79 1742 64 14 0.07 19.51 3.04 0.09 <0.01 0.25 71 2471 24.99 2.66 3.18
Kalehe 200 6/12/2007 6.78 231 173 154 86 1861 55 12 0.07 25.15 3.01 0.11 <0.01 0.21 55 2600 24.53 2.06 4.19
Bukavu 0 6/12/2007 9.09 95 79 67 9 732 45 24 15 0.03 0.01 1.56 0.07 0.36 0.04 9 1023 31.31 3.27
Bukavu 25 6/12/2007 8.95 96 81 69 11 732 33 24 15 0.03 0.10 1.66 0.04 0.10 0.04 9 1030 31.19 3.14
Bukavu 50 6/12/2007 8.61 96 80 71 12 763 16 24 14 0.03 0.14 1.67 0.05 0.05 0.05 10 1062 32.21 3.21
Bukavu 75 6/12/2007 8.55 97 82 71 11 750 13 25 14 0.03 0.07 1.53 0.04 0.02 0.05 11 1051 30.42 3.50
Bukavu 90 6/12/2007 8.36 91 87 71 13 769 9 24 13 0.03 0.33 1.55 0.05 0.02 0.06 13 1071 32.36 3.19
Ishungu 0 6/12/2007 8.90 96 81 72 10 750 30 24 15 0.03 <0.01 1.60 0.04 0.02 0.06 14 1050 32.41 3.42
Ishungu 25 6/12/2007 9.02 96 82 73 12 756 40 24 15 0.03 <0.01 1.69 0.07 <0.01 0.05 14 1060 29.68 3.40
Ishungu 50 6/12/2007 9.00 95 87 71 13 781 39 24 15 0.03 <0.01 1.54 0.03 0.07 0.06 13 1088 27.27 3.23
Ishungu 75 6/12/2007 8.60 96 84 76 15 799 16 26 14 0.03 0.20 1.55 0.04 <0.01 0.07 15 1112 31.53 3.25
Ishungu 100 6/12/2007 7.39 123 105 90 30 1025 32 11 0.04 6.79 2.13 0.05 <0.01 0.12 30 1426 28.48 2.91 2.14
Ishungu 125 6/12/2007 6.98 200 156 121 67 1635 47 11 0.07 16.01 2.82 0.07 0.05 0.22 59 2255 27.88 2.50 2.21
Ishungu 150 6/12/2007 6.57 204 154 138 69 1641 48 13 0.07 18.67 2.78 0.06 <0.01 0.23 63 2288 25.01 2.39 2.41
tassi et al.: water and gas chemistry at lake kivu (drc)

Ishungu 170 6/12/2007 6.55 226 168 145 82 1806 54 13 0.07 21.93 2.98 0.07 0.20 0.25 70 2518 24.20 2.26 0.22
a
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.
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Table 2. Concentrations of Trace Elements in the Main and Kabuno Bay Basins, Lake Kivu, Democratic Republic
of the Congoa
Basin Depth Al Ba Ce Co Cr Cs Cu Fetot Mntot Nb Ni P Rb Sr V Y Zn Zr

Kabuno Bay 0 18 45 0.05 0.10 0.8 3 104 7 0.1 2 359 46 556 1.3 0.03 7 0.5
Kabuno Bay 25 21 580 0.07 0.14 0.6 55 359 784 9.4 24 722 109 3568 5.7 0.10 83 13.7
Kabuno Bay 50 6 132 0.02 0.70 368 0.9 23 687 376 13.0 5 311 174 4243 24.2 0.02 9 42.6
Kabuno Bay 75 5 163 0.01 0.44 393 0.6 26 498 348 12.5 23 243 179 4748 26 0.02 7 40.6
Kabuno Bay 100 10 164 0.02 0.41 447 0.6 20 394 5 12.0 5 540 187 4716 33.6 0.04 8 47.1
Kabuno Bay 125 16 292 0.01 0.63 278 0.6 22 530 256 12.4 8 302 209 6477 27.1 0.02 10 15.6
Kabuno Bay 140 7 230 0.01 0.63 489 0.5 24 539 171 14.8 6 983 213 5809 32.4 0.07 10 60.5
Main 0 59 25 0.08 0.18 72 1.2 7 403 3 0.1 3 142 58 185 1.7 0.06 23 0.4
Main 25 24 22 0.06 0.17 20 1.3 79 430 2 0.1 2 69 57 182 1.4 0.04 74 0.5
Main 50 19 29 0.02 0.15 12 1.2 153 423 54 0.1 6 80 57 222 0.4 0.04 136 0.6
Main 75 9 103 0.01 0.18 40 1.8 29 292 643 0.5 3 143 67 800 1.2 0.01 99 0.2
Main 100 55 252 0.07 0.12 9 2.6 114 1022 606 1.3 2 1540 93 1739 1.7 0.10 91 1.5
Main 125 108 313 0.07 0.22 8 3.5 107 413 481 1.7 1 1692 103 2305 1 0.11 74 1.9
Main 150 25 331 0.14 177 3.8 22 313 418 2.1 1 1336 110 2580 0.6 0.03 17 2.6
Main 175 14 327 0.01 0.12 173 3.7 16 367 385 1.9 2 980 112 2665 0.03 10 2.2
Main 200 19 368 0.21 167 4.4 17 328 414 2.3 1512 117 2892 0.3 0.04 13 2.3
Main 225 39 465 0.05 0.39 12 5.9 75 449 374 1.6 2 2628 129 3527 0.09 56 1.3
Main 250 38 465 0.05 0.31 7 5.7 108 274 365 2.1 2718 126 3514 0.14 75 2.2
Main 275 14 488 0.30 182 6.3 33 298 362 3.1 3225 138 3836 0.2 0.05 22 4.5
Main 300 22 578 0.53 245 8.5 29 392 398 4.9 1 4629 191 5131 2.4 0.05 12 7.9
Main 325 17 450 0.54 281 8.4 50 246 286 4.9 5286 195 4584 3.6 0.04 12 7.5
Main 350 13 497 0.64 295 9.1 53 340 300 5.3 5899 206 4789 3 0.02 4 8.7
Main 375 18 652 0.01 0.70 294 9.8 47 564 411 5.5 6669 211 5346 3.1 0.09 20 9.2
Main 400 16 653 0.01 0.70 197 9.4 27 388 399 5.1 1 7065 207 5215 2.1 0.09 14 6.9
Main 425 6 516 0.46 280 9.2 16 243 272 5.1 1 5304 203 4887 2.6 0.03 2 9.5
Main 450 13 618 0.66 239 9.0 20 464 371 5.3 5012 207 5135 1.6 0.05 10 7.9
Main 478 10 514 0.52 281 8.5 15 222 271 4.9 1 4829 209 4712 2.4 0.02 4 8.3
a
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 homo-
geneity of the vertical water column.
[14] With respect to the minor chemical com-
pounds, 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 concen-
trations are relatively low, not exceeding 0.44 and
Figure 4. Vertical profiles of the TDS values (in mg/L)
0.21 mg/L, respectively. In contrast, F concen- of the Main, Kalehe, Ishungu, Kabuno Bay, and Bukavu
trations are remarkably high, up to 3.36 mg/L, from basins, Lake Kivu, Democratic Republic of the Congo
to the leaching of the F-rich volcanic rocks of the (DRC).
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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
Na K Mg Ca HCO3 Cl SO42 Li NH4 F Br NO3 S2 B Si Mntot Fetot Sr Ba Rb

Kabuno Bay 3.1 3.8 8.4 2.5 6.4 3.9 3.5 1.3 6.0 0.9 14.2 12 6.0 25 5.2 10 5.1 4.7
Main 4.6 3.9 5.6 16.7 5.6 4.8 0.3 7.0 183 2.0 4.7 3.8 8.1 9.4 54 0.6 25 20 3.6
Kalehe 2.2 2.2 1.9 10.5 2.5 2.0 0.8 2.8 3609 1.8 1.7 3.6 3.9 95 3.9 10 12 1.6
Bukavu 1.0 1.1 1.1 1.4 1.1 1.0 0.9 1.0 65 1.0 0.7 0.1 1.5 1.5 19 0.7 1.3 2.0 1.0
Ishungu 2.4 2.1 2.0 7.8 2.4 2.2 0.9 2.3 1.9 2.0 11.1 4.4 5.0 77 1.6 17 21 1.9
a
Cib and Cis are the concentrations of the i compound at lake bottom and surface, respectively. Main chemical compounds are Na, K, Ca, Mg,
HCO 2
3 , SO4 and Cl .


area [Gerasimoskiy and Savinova, 1969] and/or the
input of F – rich geothermal fluids from the Nyir-
agongo 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 precipita-
tion that limits Ca enrichment with depth without
significantly affecting Sr concentrations. Alumi-
num, 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 pos-
itive shift of both the oxygen and hydrogen isoto-
pic 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 charac-
terizes 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 concentra-
tion 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 vari-
ous 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 (50–60%), (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
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 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
Lake Depth CO2 Ar O2 N2 N2/Ar CO2/Ar CH4 C2H6 C3H8 n-C4H10 i-C4H10 Gas Total d 13CCO2strip d 13CCO2 R/Ra He/Ne
Geophysics
Geosystems
Geochemistry

Kabuno Bay 0 0.01 0.01 0.28 0.58 38.49 0.99 <0.001 0.88
Kabuno Bay 50 32.18 0.01 0.05 0.34 42.25 4049 0.387 32.96 9.60 10.79
G
3

Kabuno Bay 75 36.68 0.01 0.08 0.39 41.31 3849 0.500 37.67 10.02 11.21 5.33 2.15
Kabuno Bay 100 41.43 0.01 0.16 0.53 39.25 3049 0.732 42.87 12.00 13.19
Kabuno Bay 125 47.18 0.02 0.17 0.73 38.93 2499 0.960 49.05 10.72 11.91
Kabuno Bay 140 52.12 0.01 0.07 0.33 40.78 6511 1.518 54.05 10.29 11.48 5.54 2.78
Main 0 0.01 0.01 0.27 0.57 38.84 1.0 <0.001 0.87
Main 50 0.04 0.04 0.10 1.56 40.53 1.0 <0.001 1.73
Main 100 8.27 0.04 0.39 1.52 41.14 224 1.886 0.00140 12.11 4.74 5.93 2.10 1.55
Main 150 14.64 0.06 0.65 2.13 38.60 266 3.060 0.00186 20.56 6.20 7.39
Main 200 21.33 0.08 0.38 3.25 39.28 258 3.769 0.00286 28.85 6.29 7.48 2.32 2.13
Main 250 31.79 0.12 0.28 4.96 40.29 258 4.915 0.00316 42.09 4.84 6.03 2.40 2.55
Main 300 55.03 0.15 0.05 6.17 41.60 371 7.980 0.00435 0.00057 0.00004 0.00011 69.37 5.31 6.50 2.58 2.48
Main 350 58.89 0.20 0.88 8.03 40.86 300 10.604 0.00476 0.00070 0.00006 0.00017 78.61 6.23 7.42 2.49 2.15
Main 375 61.98 0.24 0.14 9.82 41.26 260 11.335 0.00491 0.00086 0.00006 0.00020 83.52 5.48 6.67
Main 400 69.07 0.24 0.10 10.04 42.11 290 11.507 0.00584 0.00095 0.00007 0.00023 90.96 5.39 6.58
Main 425 86.07 0.25 0.04 9.74 38.79 343 11.825 0.00728 0.00105 0.00006 0.00025 107.93 5.66 6.85
Main 450 102.87 0.27 0.12 11.62 42.78 379 12.256 0.00808 0.00076 0.00016 127.14 5.95 7.14
Main 470 136.89 0.41 0.20 16.26 39.57 333 16.977 0.01105 0.00099 0.00021 170.75 5.60 6.79 3.17 35.2
Kalehe 50 0.02 0.07 0.85 2.96 41.30 0.26 0.001 3.91 2.35 2.05
Kalehe 100 22.97 0.07 0.13 2.50 38.42 353 4.250 0.00243 29.91 5.30 6.49 2.21 28.6
Kalehe 125 29.55 0.04 0.05 1.81 42.44 691 4.495 0.00369 35.96 5.45 6.64 2.24 92.8
Kalehe 150 31.21 0.03 0.04 1.37 41.78 953 3.845 0.00309 36.49 5.47 6.66 2.49 7.83
Kalehe 175 34.76 0.02 0.03 0.99 41.40 1459 2.722 0.00337 38.51 5.61 6.80 2.28 78.9
Kalehe 200 42.47 0.02 0.05 0.94 42.47 1922 2.749 0.00370 46.23 6.36 7.55 2.59 82.2
Bukavu 50 0.01 0.04 0.36 1.55 38.75 0.2 0.002 1.96
tassi et al.: water and gas chemistry at lake kivu (drc)

Bukavu 75 0.05 0.05 0.45 1.97 39.40 1.0 0.003 2.53
Bukavu 90 0.88 0.07 0.63 2.89 41.29 13 0.018 4.48 1.21 0.51
Ishungu 100 6.70 0.15 1.07 4.58 30.53 45 0.083 12.59 6.77 7.96
Ishungu 125 7.44 0.16 1.33 4.71 29.44 47 1.757 15.39 7.39 8.58
Ishungu 150 8.70 0.20 0.58 7.01 35.05 44 1.518 18.01 7.29 8.48 2.19 3.90
Ishungu 170 10.62 0.02 0.01 5.10 255.00 531 4.908 20.65 4.94 6.13
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the one atmosphere solubility levels at the temper-
ature 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 in-
voked 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 north-
ern and southern lake borders are indeed charac-
terized by presence of several fluid discharges (i.e.,
Rambo, Kankule, Muganzo), likely having a com-
position 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 Henry’s 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 isobu-
tane), 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 ¼ d13 CCO2  d13 CCO2strip ¼ ð0:0049 * TÞ  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 mantle-
derived CO2 [e.g., Hoefs, 1973; Rollinson, 1993],
although distinct from the d 13CCO2 values of the
summit fumaroles of Nyiragongo (3 to 4% V-
PBD) (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 determina-
tion of the d 13CDIC values that vary from 4.62 to
3.45 and from 3.29 to 1.00% V-PBD, respec-
tively (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 atmospheric-
derived gases dissolved in lake water directly or
dissolved into groundwater during precipitations
recharging the aquifer that are subsequently dis-
charged 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
ð1Þ [25] The compositional and isotopic features of the
Lake Kivu water, as well as its permanent stratifi-
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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 com-
bination of (1) mineral dissolution-deposition pro-
cesses, (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].
5.1.1. Mineral Dissolution and Deposition
[26] Water-rock interaction involving both ground-
water and hydrothermal fluids plays a significant
role in major and minor solute chemistry of the
lake. Mineral dissolution of the strongly undersat-
urated 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 referen-
ces therein]:
Ca0:3 Mg0:1 Fe0:4 Al0:3 SiO3:25 þ 2:5CO2
2þ 2þ
þ 3:25H2 O ! 0:3Ca þ 0:1Mg
þ 0:4Fe 2þ
þ 0:3Al 3þ
þ H2 SiO4 þ 2:5HCO
3 ð2Þ
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
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) alkali-
olivine 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,
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.
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 Geochemistry 3
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Ce, Nb, and Rb) seem to behave concordantly with
the outcropping lava flows indicating a clear input of
cations deriving from water-rock interactions. Nio-
bium, 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 Nyiragon-
go [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 nor-
mally 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 car-
bonate 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 con-
centrations, 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 over-
saturated, whereas boehmite is undersaturated.
Most secondary minerals (e.g., beidellite-Mg, cela-
donite, 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. Musco-
vite and phyrophyllite are mostly oversaturated to
slightly above saturation. Among the main and
accessory minerals, only K-feldspar is character-
ized by SI values >1, whereas albite, anorthite,
diospide, enstatite, nepheline, forsterite, and mon-
ticellite 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 cyano-
bacteria, with lower abundances of diatoms [Hecky
and Kling, 1987]. The effect and degree of bacte-
rial activity on the water chemistry of Lake Kivu
strongly affects the distribution of S and N com-
pounds. 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 pro-
duce 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 ver-
tical patterns of NH+4 , a product of reducing mi-
crobial and bacteria activity, show increases by up
to three orders of magnitude in all the stratified
13 of 22
 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]
Depth (m) Albite Anorthite Beidellite-Mg Calcite Celad-onite Clino-ptilolite Diopside Enstatite Hematite Illite K-Feldspar Kao-linite Magn-esite Montmor-Mg
Geophysics
Geosystems
Geochemistry

Kabuno Bay 0 0.57 4.25 1.53 1.53 6.90 6.63 0.86 0.05 12.26 3.49 3.25 1.38 2.01 3.32
Kabuno Bay 50 2.66 3.47 6.25 0.99 7.42 16.85 2.77 1.62 14.00 7.18 5.44 4.89 1.76 6.84
G
3

Kabuno Bay 75 2.63 3.59 6.29 0.95 7.33 16.92 2.97 1.71 13.71 7.17 5.45 4.91 1.74 6.86
Kabuno Bay 100 2.88 3.13 7.10 0.81 7.32 17.72 3.50 1.96 13.45 7.87 5.68 5.64 1.63 7.34
Kabuno Bay 125 3.01 3.20 7.55 0.55 7.02 18.02 4.33 2.32 13.63 8.18 5.75 6.06 1.48 7.55
Kabuno Bay 140 2.15 4.97 5.93 0.31 5.81 15.12 5.09 2.69 13.52 6.42 4.91 4.71 1.26 6.27
Main 0 0.20 4.48 1.55 0.81 5.46 2.21 0.95 0.64 13.50 3.40 2.50 1.89 1.73 2.69
Main 50 0.65 5.37 0.81 0.72 4.61 0.63 1.63 1.00 13.59 2.52 2.02 1.30 1.58 2.02
Main 100 1.08 3.50 6.07 0.08 3.63 9.09 6.25 3.65 12.19 6.44 3.68 5.67 0.27 5.31
Main 150 0.64 5.03 4.73 0.05 3.11 8.22 6.48 3.79 13.07 5.05 3.31 4.38 0.19 4.44
Main 200 0.02 6.54 3.38 0.12 2.17 6.23 7.07 4.09 12.97 3.58 2.66 3.21 0.01 3.42
Main 250 0.13 6.43 3.63 0.12 2.21 6.62 7.21 4.16 12.73 3.80 2.78 3.42 0.02 3.58
Main 300 0.16 7.54 2.79 0.01 2.41 7.42 6.93 3.97 12.94 2.97 2.79 2.45 0.25 3.28
Main 350 0.55 9.17 1.24 0.16 1.47 5.10 7.43 4.21 12.62 1.34 2.09 1.11 0.08 2.12
Main 375 0.48 9.12 1.40 0.21 1.49 5.37 7.54 4.26 13.01 1.48 2.15 1.24 0.06 2.23
Main 400 0.88 9.80 0.73 0.33 0.95 3.91 7.88 4.42 12.59 0.77 1.77 0.71 0.04 1.67
Main 425 1.21 10.51 0.12 0.29 0.65 2.81 7.81 4.39 12.18 0.06 1.44 0.03 0.03 1.08
Main 450 0.76 9.63 0.86 0.26 1.14 4.32 7.71 4.34 12.78 0.93 1.88 0.80 0.02 1.80
Main 478 1.18 10.53 0.07 0.45 0.62 2.87 8.03 4.43 12.01 0.07 1.45 0.13 0.04 1.20
Kalehe 50 1.05 6.39 1.37 1.14 5.36 0.62 0.12 0.79 1.64 0.78 2.00 0.93
Kalehe 100 0.86 4.32 4.67 0.26 4.25 4.79 2.88 5.32 3.54 4.25 0.52 4.69
Kalehe 125 1.06 4.35 5.16 0.21 4.06 9.99 5.46 3.28 12.03 5.62 3.74 4.62 0.36 5.01
Kalehe 150 1.76 3.36 6.06 0.51 5.18 12.79 4.56 2.85 11.97 6.64 4.43 5.23 0.60 5.91
Kalehe 175 1.16 4.65 4.70 0.47 4.51 10.79 4.74 2.94 10.25 5.27 3.84 4.06 0.58 4.92
Kalehe 200 0.16 6.20 3.23 0.22 2.83 6.85 6.03 3.61 10.73 3.63 2.85 3.00 0.26 3.50
Bukavu 50 0.24 4.14 1.91 0.93 5.09 2.28 1.36 1.00 10.93 3.62 2.49 2.26 1.53 2.79
tassi et al.: water and gas chemistry at lake kivu (drc)

Bukavu 75 0.20 4.28 1.95 0.84 5.07 2.60 1.52 1.07 10.34 3.62 2.54 2.26 1.47 2.85
Bukavu 90 0.16 4.32 2.27 0.77 4.86 3.18 2.04 1.37 10.37 3.80 2.63 2.51 1.31 3.03
Ishungu 100 0.78 3.80 4.89 0.28 4.29 8.08 4.69 2.83 11.74 5.64 3.52 4.59 0.54 4.73
Ishungu 125 1.72 3.19 6.48 0.31 4.75 12.43 5.35 3.27 12.14 6.96 4.43 5.71 0.36 5.99
Ishungu 150 0.04 6.65 3.28 0.17 2.33 6.73 6.84 4.00 10.94 3.49 2.73 3.05 0.08 3.46
Ishungu 170 0.24 6.47 3.52 0.09 2.54 7.55 6.75 3.98 10.92 3.72 2.92 3.20 0.06 3.68
10.1029/2008GC002191

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 Geochemistry 3
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Geosystems G tassi et al.: water and gas chemistry at lake kivu (drc)
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
10.1029/2008GC002191
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 differ-
ence 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 NNE–SSW trending faults
that are associated to the rift-related tectonic activ-
ity and is also responsible of the complex mor-
phology 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 subla-
custrine 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 contri-
15 of 22
 Geochemistry 3
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Geosystems G 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 pro-
files 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 tran-
sect 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 dis-
solved gas compounds in Lake Kivu (i.e., CO2 and
CH4) has been extensively debated since the dis-
covery 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] sug-
gested 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, re-
spectively) and the 14C activity, the latter being
considerably lower in CH4 (9% modern) com-
pared 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 (30–40%), by acetate fermentation.
Schoell’s hypothesis for CH4 origin is also sup-
ported 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 bacte-
ria-driven genetic processes occurring at low tem-
peratures 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 frac-
tionation factor between solid calcium carbonate
and gaseous CO2 is 10.2% at 20°C [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 monohy-
drocalcite 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 show-
ing a significant depletion in 13C (Table 4). More-
over, 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 pres-
ence 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 min-
imum 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 frac-
tionation 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 atmo-
spheric He/Ne ratios, and (4) the lowest CO2/Ar
ratio (44) (Table 4). This finding implies that
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 Geochemistry 3
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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 differ-
ence from that of CO2 from the Nyiragongo mag-
matic 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
where [CO2] (dissolved CO2), [HCO 2
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 ¼ d 13 CCO2 * ½CO2  þ d13 CHCO3 * HCO
3
 

= HCO 3 þ ½CO2  ð4Þ
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 ¼ d13 CHCO3  d13 CCO2 ¼ ð9483=T  23:9Þ ð5Þ
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 ¼ d 13 CCO2 þ e2 * HCO 
3 = HCO3 þ ½CO2 
ð6Þ
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 3 ). Conversely, at the Main basis the
measured and calculated d 13CDIC values are
consistent. However, the degassing of the water
of the Nyiragongo crater fumaroles (3.5%
V-PDB) (D. Tedesco et al., manuscript in prepara-
tion, 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 ¼ d13 CCO2 * ½CO2  þ d13 CHCO3 * HCO
3
 

þ d13 CCO3 * CO23
   

= CO2 þ HCO 3 þ ½CO2 
3 those measured in 1974 [Tietze, 1978] and 2004
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. There-
fore, 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 concen-
trations of dissolved CO2 (Figure 8a) and CH4
(Figure 8b) at the Main basin are consistent with
ð3Þ
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 Geochemistry 3
Geophysics
Geosystems G 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 concentra-
tions 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 ex-
planation 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 fast-
growing 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 mea-
sured 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 anthropo-
genic-related contamination, with respect to the
collecting sites of Schmid et al. [2005]. Accord-
ingly, significant differences in terms of phyto-
plankton 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 mea-
sured 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 physic-
chemical processes, not easily modeled from a
single vertical profile [e.g., Murthy, 1976; Imboden
and Wüest, 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 flu-
ids into the Kabuno Bay basin, whose CO2/CH4
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 Geochemistry 3
Geophysics
Geosystems G 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 deep-
originated fluids seems to be negligible.
6. Conclusions
[41] The deep water strata of the five basins
constituting Lake Kivu are characterized by dis-
tinct 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 spe-
cies. 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, produ-
ces 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 domi-
nated by mantle-derived gases, but it is also phys-
ically 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 tech-
niques. 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 prox-
imity to hydrothermal and magmatic fluid dis-
charges, 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 geochem-
ical and isotopic results of this study reveal the
complexity of the spatially and temporally evolv-
ing 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 acknowl-
edged 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
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Geophysics
Geosystems G tassi et al.: water and gas chemistry at lake kivu (drc)
defenseless population. Our thought is to the GVO personnel
and their families.
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