Kivu Lake Chemistry

Water and gas chemistry at Lake Kivu (DRC): Geochemical evidence of...
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Volume 10, Issue 2
February 2009
Water and gas chemistry at Lake Kivu (DRC): Geochemical evidence of

vertical and horizontal heterogeneities in a multibasin structure
F. Tassi, O. Vaselli, D. Tedesco, G. Montegrossi, T. Darrah, E. Cuoco, M. Y. Mapendano, R. Poreda,
A. Delgado Huertas
First published:
6 February 2009
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DOI:
10.1029/2008GC002191
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15 articles
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Abstract
[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 CO 2 , responsible of the huge CO 2 (CH4 )-rich reservoir hosted within
the deep lake water; (2) spatial variations of the biomass distribution and/or speciation; and (3) solutes
from water-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.
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
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volcanically active Western Branch (Albertine Rift) of the East African Rift System (EARS) [e.g.,
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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 CO 2 (CH4 )-rich composition. In 2004, the
calculated total amounts of CO 2 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 lake's 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 130 and 230S and 2850 and 2923E) 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 [ Holzfrster and Schmidt , 2007, and
references therein]. Presently, Lake Kivu's surface waters are maintained at an elevation of 14621463 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 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 and OSAE , 1998].
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Figure 1.
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Map of Lake Kivu with the location of the sampling sites.
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Figure 2.

Three-dimensional bathymetric map of Lake Kivu.
[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 CO 2 - 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 physical-chemical 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

3.1. Water and Dissolved Gas Sampling
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[5] The liquid and gas phases were collected during three field campaigns in 2004, 2005, and 2007, along
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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 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 Rilsan (a plastic material impermeable to both water and gas)
tubes (6 mm in diameter) connected by steel connectors. At the surface, the Rilsan 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.
Figure 3.

Schematic drawing of the gas and water sampling equipment.
3.2. Chemical and Isotopic ( 18 O, D, and 13 C DIC ) Analysis of Water

Samples
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[7] The determination of pH and the concentration of HCO 3 (acidimetric titration with 0.01 N HCl) were
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carried out in the field. Water samples were analyzed for major cations (Na, K, Ca, Mg, NH4 , and Li) and
anions (Cl , SO 4 2 , NO 3 , 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 S 2 ), i.e., those deriving from dissolved H2 S, HS , S 2 , polysulfide, and
metal-sulfide complexes, were determined as SO 4 2 , after oxidation with H2 O 2 , by ion chromatography
(Metrohm 761) using the Cd-IC sampling and analytical procedure described by
Montegrossi et al. [2006]. Boron and SiO 2 were determined by molecular spectrophotometry. 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 18 O/ 16 O and 2 H/ 1 H isotopic ratios (expressed as 18 O and 2 H 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 CO 2 H2 O equilibration method proposed by
Epstein and Mayeda [1953]. Hydrogen isotopic ratios were measured on H2 after the reaction of 10
L of water with metallic zinc at 500C [ Coleman et al. , 1982]. The experimental error was +0.1 and
+1 for 18 O and 2 H 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 13 C DIC 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 CO 2 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 13 C DIC was 0.05.
3.3. Chemical and Isotopic ( 13 C CO2strip and 3 He/ 4 He) Analysis of Dissolved
Gas Compounds
[10] The composition of the main inorganic dissolved gas compounds (CO 2 , N2 , O 2 and Ar) stored 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 , C 2 H6 , C 3 H8 ,
n-C 4 H10 and i-C 4 H10 ) 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 Henry's law constants, regulating the liquid-gas equilibrium for each
volatile compound [ Vaselli et al. , 2006; Tassi et al. , 2008].
[11] The
13
C/ 12 C ratios of dissolved CO 2 (
13
C CO2 ) were determined on the basis of those measured in
the separated gas phase stored in the headspace of the dissolved gas flasks (
13
C CO2strip ). 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 13 C dic 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 3 He/ 4 He 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 CO 2 were cryogenically trapped
at 90 and 195C, respectively, whereas N2 and O 2 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
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Gas Mass Spectrometer fitted with a Faraday cup (resolution of 200) and a Johnston electron multiplier
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(resolution of 600) for sequential analyses of the 4 He (F-cup) and 3 He (multiplier) beams. On the axial
collector (resolution of 600) 3 He + was completely separated from HD + , with a baseline separation of <2%
of the HD + peak. The contribution of HD + to the 3 He 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 10 4 Amps/torr), the 3 He signal averaged 2500 ions/s with a
background signal of 15 cps, due to either scattered 4 He ions or the formation of 4 He ions at lower
voltage potentials within the source of the mass spectrometer. The analytical error for the determination of
3
He/ 4 He (hereafter expressed as R/R air , where R is the measured 3 He/ 4 He ratio and R air is that of the air:
1.39 10 6 [ 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 Rilsan 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 C i b /C i s ratio (where C i b and C i s 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 3 , SO 4 2 ,
and Cl , are listed. At the Main, Kalehe, and Ishungu basins, Ca, whose C i b /C i s ratio is up to 16.7,
represents the ion with the highest relative increase with depth, whereas at Kabuno Bay the strongest
variation among the dissolved species along the vertical water column is that of Mg (C i b /C i s = 8.4). All
the stratified basins are also characterized by remarkable increases of HCO 3 concentrations (C i b /C i s
ratio up to 6.4). Sulfate concentrations tend to decrease with depth (C i b /C i s < 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 S 2 concentrations increase with depth with a C i b /C i s ratio is 3.8 and 14.2 at the Main
and Kabuno Bay basins, respectively. The C i b /C i s ratios of the main chemical compounds of the Bukavu
basin are 1, indicating a substantial compositional homogeneity of the vertical water column.
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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).
Table 1. Chemical Composition and pH, Total Dissolved Solids, D, 18 O, 13 C DIC , and
13 C DICcalc Values of the Main, Kabuno Bay, Kalehe, Ishungu, and Bukavu Basins, Lake
Kivu, Democratic Republic of the Congoa
Basin
Depth
Sampling Date
pH
Na +
K+
Mg 2+
Ca 2+
HCO 3
CO 3
Kabuno Bay
2/19/2004
8.88
148
107
111
27
1050
40
Kabuno Bay
25
2/19/2004
8.58
328
297
530
88
4225
81
a Ion concentrations and total dissolved solids (TDS) are in mg/L; D and 18 O values are in V-SMOW; 13 C DIC and
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Basin
Depth
Sampling Date
pH
Na +
K+
Mg 2+
Ca 2+
HCO 3
CO 3
Kabuno Bay
50
2/19/2004
7.32
385
345
710
78
5272
Kabuno Bay
75
2/19/2004
7.25
365
357
760
80
5638
Kabuno Bay
100
2/19/2004
7.12
375
359
780
77
5955
Kabuno Bay
125
2/19/2004
6.90
485
396
920
70
6626
Kabuno Bay
140
2/19/2004
6.70
460
402
925
67
6669
Main
2/21/2004
8.76
108
83
84
781
23
Main
25
2/21/2004
8.68
111
85
84
778
19
Main
50
2/21/2004
8.56
117
85
87
805
15
Main
75
2/21/2004
7.48
143
102
99
25
1025
Main
100
2/21/2004
6.89
188
116
134
53
1507
Main
125
2/21/2004
6.77
219
155
152
68
1730
Main
150
2/21/2004
6.71
226
162
161
72
1827
Main
175
2/21/2004
6.64
229
166
169
73
1913
Main
200
2/21/2004
6.52
247
169
171
78
1986
Main
225
2/21/2004
6.53
283
196
195
88
2239
Main
250
2/21/2004
6.45
280
193
200
91
2258
Main
275
2/21/2004
6.33
302
211
236
119
2486
Main
300
2/21/2004
6.35
428
277
334
122
3753
Main
325
2/21/2004
6.24
452
293
344
127
3795
Main
350
2/21/2004
6.18
470
317
374
135
4082
Main
375
2/21/2004
6.15
488
320
380
130
4198
Main
400
2/21/2004
6.07
478
326
394
129
4259
Main
425
2/21/2004
6.08
482
336
390
135
4314
Main
450
2/21/2004
6.11
490
334
392
130
4326
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Basin
Depth
Sampling Date
pH
Na +
K+
Mg 2+
Ca 2+
HCO 3
CO 3
Main
478
2/21/2004
6.02
492
325
468
117
4344
Kalehe
6/15/2005
9.47
103
80
82
738
109
Kalehe
25
6/15/2005
9.31
103
80
80
738
76
Kalehe
50
6/15/2005
9.14
107
82
84
753
52
Kalehe
75
6/15/2005
8.19
116
90
96
16
847
Kalehe
100
6/15/2005
7.24
157
116
119
40
1156
Kalehe
125
6/15/2005
6.96
191
139
141
61
1477
Kalehe
150
6/15/2005
7.11
212
155
156
77
1662
Kalehe
175
6/15/2005
7.05
220
163
165
79
1742
Kalehe
200
6/12/2007
6.78
231
173
154
86
1861
Bukavu
6/12/2007
9.09
95
79
67
732
45
Bukavu
25
6/12/2007
8.95
96
81
69
11
732
33
Bukavu
50
6/12/2007
8.61
96
80
71
12
763
16
Bukavu
75
6/12/2007
8.55
97
82
71
11
750
13
Bukavu
90
6/12/2007
8.36
91
87
71
13
769
Ishungu
6/12/2007
8.90
96
81
72
10
750
30
Ishungu
25
6/12/2007
9.02
96
82
73
12
756
40
Ishungu
50
6/12/2007
9.00
95
87
71
13
781
39
Ishungu
75
6/12/2007
8.60
96
84
76
15
799
16
Ishungu
100
6/12/2007
7.39
123
105
90
30
1025
Ishungu
125
6/12/2007
6.98
200
156
121
67
1635
Ishungu
150
6/12/2007
6.57
204
154
138
69
1641
Ishungu
170
6/12/2007
6.55
226
168
145
82
1806
Table 2. Concentrations of Trace Elements in the Main and Kabuno Bay Basins, Lake Kivu,
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Democratic Republic of the Congoa

Basin
Depth
Al
Ba
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Ce
Co
Cr
Cs
Cu
Fe tot
Mn tot
Nb
Kabuno Bay
18
45
0.05
0.10
0.8
104
0.1
Kabuno Bay
25
21
580
0.07
0.14
0.6
55
359
784
9.4
Kabuno Bay
50
132
0.02
0.70
368
0.9
23
687
376
13.0
Kabuno Bay
75
163
0.01
0.44
393
0.6
26
498
348
12.5
Kabuno Bay
100
10
164
0.02
0.41
447
0.6
20
394
12.0
Kabuno Bay
125
16
292
0.01
0.63
278
0.6
22
530
256
12.4
Kabuno Bay
140
230
0.01
0.63
489
0.5
24
539
171
14.8
Main
59
25
0.08
0.18
72
1.2
403
0.1
Main
25
24
22
0.06
0.17
20
1.3
79
430
0.1
Main
50
19
29
0.02
0.15
12
1.2
153
423
54
0.1
Main
75
103
0.01
0.18
40
1.8
29
292
643
0.5
Main
100
55
252
0.07
0.12
2.6
114
1022
606
1.3
Main
125
108
313
0.07
0.22
3.5
107
413
481
1.7
Main
150
25
331
0.14
177
3.8
22
313
418
2.1
Main
175
14
327
0.12
173
3.7
16
367
385
1.9
Main
200
19
368
0.21
167
4.4
17
328
414
2.3
Main
225
39
465
0.05
0.39
12
5.9
75
449
374
1.6
Main
250
38
465
0.05
0.31
5.7
108
274
365
2.1
Main
275
14
488
0.30
182
6.3
33
298
362
3.1
Main
300
22
578
0.53
245
8.5
29
392
398
4.9
Main
325
17
450
0.54
281
8.4
50
246
286
4.9
Main
350
13
497
0.64
295
9.1
53
340
300
5.3
Main
375
18
652
0.70
294
9.8
47
564
411
5.5
0.01
0.01
a Trace elements are measured in g/L.
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Basin
Depth
Al
Ba
Ce
Co
Cr
Cs
Cu
Fe tot
Mn tot
Nb
0.01
0.70
197
9.4
27
388
399
5.1
Main
400
16
653
Main
425
516
0.46
280
9.2
16
243
272
5.1
Main
450
13
618
0.66
239
9.0
20
464
371
5.3
Main
478
10
514
0.52
281
8.5
15
222
271
4.9
a Trace elements are measured in g/L.
Table 3. Values of the C i b /C i s Ratio of the Main Chemical Compounds in the Main,
Kabuno Bay, Kalehe, Ishungu, and Bukavu Basins, Lake Kivu, Democratic Republic of the
Congoa
Na
Mg
Ca
HCO 3
Cl
SO 4 2
Li
Kabuno Bay
3.1
3.8
8.4
2.5
6.4
3.9
Main
4.6
3.9
5.6
16.7
5.6
4.8
0.3
7.0
Kalehe
2.2
2.2
1.9
10.5
2.5
2.0
0.8
Bukavu
1.0
1.1
1.1
1.4
1.1
1.0
Ishungu
2.4
2.1
2.0
7.8
2.4
2.2
a Ci
and C i
NH 4
3.5
Br
1.3
6.0
183
2.0
4.7
2.8
3609
1.8
1.7
0.9
1.0
65
1.0
0.7
0.9
2.3
1.9
2.0
are the concentrations of the i compound at lake bottom and surface, respectively. Main chemical compounds are Na,
[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 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
(C i b /C i s ratio between 65 and 3609) while NO 3 has low and variable concentrations in the lake. The
contents of Fe tot , Mn tot , 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 CaCO 3 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 g/L) at Kabuno Bay, while increasing with depth at the Main basin (from 1.2 to 8.5
g/L) (Table 2).
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4.2. Water Isotopic ( O 18 and 2 H) Composition

[15] The
18
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O and 2 H 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 CO 2 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 CO 2 (5060%), (2)
relatively high N2 and O 2 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 CO 2 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 CO 2 increase (up to 19.6%) at the bottom of the basin at a
depth of 90 m.
Table 4. Chemical Composition of Dissolved Gas and 13 C CO2strip , 13 C CO2 , and R/R air
Values in the Main, Kabuno Bay, Kalehe, Ishungu, and Bukavu Basins, Lake Kivu,
Democratic Republic of the Congo
Lake
Depth
CO 2
Ar
O2
N2
N 2 /Ar
CO 2 /Ar
CH 4
Kabuno Bay
0.01
0.01
0.28
0.58
38.49
0.99
<0.001
Kabuno Bay
50
32.18
0.01
0.05
0.34
42.25
4049
0.387
Kabuno Bay
75
36.68
0.01
0.08
0.39
41.31
3849
0.500
Kabuno Bay
100
41.43
0.01
0.16
0.53
39.25
3049
0.732
Kabuno Bay
125
47.18
0.02
0.17
0.73
38.93
2499
0.960
Kabuno Bay
140
52.12
0.01
0.07
0.33
40.78
6511
1.518
C2H6
C3H
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Lake
Depth
CO 2
Ar
O2
N2
N 2 /Ar
CO 2 /Ar
CH 4
C2H6
C3H
Main
0.01
0.01
0.27
0.57
38.84
1.0
<0.001
Main
50
0.04
0.04
0.10
1.56
40.53
1.0
<0.001
Main
100
8.27
0.04
0.39
1.52
41.14
224
1.886
0.00140
Main
150
14.64
0.06
0.65
2.13
38.60
266
3.060
0.00186
Main
200
21.33
0.08
0.38
3.25
39.28
258
3.769
0.00286
Main
250
31.79
0.12
0.28
4.96
40.29
258
4.915
0.00316
Main
300
55.03
0.15
0.05
6.17
41.60
371
7.980
0.00435
0.00057
Main
350
58.89
0.20
0.88
8.03
40.86
300
10.604
0.00476
0.00070
Main
375
61.98
0.24
0.14
9.82
41.26
260
11.335
0.00491
0.00086
Main
400
69.07
0.24
0.10
10.04
42.11
290
11.507
0.00584
0.00095
Main
425
86.07
0.25
0.04
9.74
38.79
343
11.825
0.00728
0.00105
Main
450
102.87
0.27
0.12
11.62
42.78
379
12.256
0.00808
0.00076
Main
470
136.89
0.41
0.20
16.26
39.57
333
16.977
0.01105
0.00099
Kalehe
50
0.02
0.07
0.85
2.96
41.30
0.26
0.001
Kalehe
100
22.97
0.07
0.13
2.50
38.42
353
4.250
0.00243
Kalehe
125
29.55
0.04
0.05
1.81
42.44
691
4.495
0.00369
Kalehe
150
31.21
0.03
0.04
1.37
41.78
953
3.845
0.00309
Kalehe
175
34.76
0.02
0.03
0.99
41.40
1459
2.722
0.00337
Kalehe
200
42.47
0.02
0.05
0.94
42.47
1922
2.749
0.00370
Bukavu
50
0.01
0.04
0.36
1.55
38.75
0.2
0.002
Bukavu
75
0.05
0.05
0.45
1.97
39.40
1.0
0.003
Bukavu
90
0.88
0.07
0.63
2.89
41.29
13
0.018
Ishungu
100
6.70
0.15
1.07
4.58
30.53
45
0.083
Ishungu
125
7.44
0.16
1.33
4.71
29.44
47
1.757
Ishungu
150
8.70
0.20
0.58
7.01
35.05
44
1.518
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Lake
Ishungu
Depth
170
CO 2
10.62
Ar
O2
N2
0.02
0.01
5.10
N 2 /Ar
255.00
CO 2 /Ar
531
CH 4
C2H6
C3H
4.908
[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 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 40 Ar/ 36 Ar 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 CO 2 -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 CO 2 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 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 isobutane), although at relatively low amounts (Table 4), represents a
peculiar compositional feature. Both the O 2 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 CO 2 ( 13 C CO2 ) and DIC

( 13 C DIC )
[22] To obtain the 13 C values of dissolved CO 2 ( 13 C CO2 ) from the measured 13 C CO2strip values, the
carbon isotopic fractionation can be quantified by using the 1 factor for the gas-water equilibrium [
Zhang et al. , 1995], as follows:
Both the measured 13 C CO2strip and the calculated 13 C CO2 values are listed in Table 4. The isotopic
analysis of those samples with dissolved CO 2 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 13 C CO2 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 CO 2
[e.g., Hoefs , 1973; Rollinson , 1993], although distinct from the 13 C CO2 values of the summit
fumaroles of Nyiragongo (3 to 4 V-PBD) (D. Tedesco et al., manuscript in preparation, 2008). At
Kabuno Bay the 13 C CO2 values range between 13.19 to 10.79 V-PBD, indicating either a different
CO 2 source or the occurrence of isotopic fractionation processes as CO 2 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
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13
13
C DIC values that vary from 4.62 to 3.45 and from 3.29 to 1.00 V-PBD, respectively (Table 1). The
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C dic values of these two basins abruptly decrease with depth as the dissolved CO 2 increases.
4.5. Helium Isotopic Composition
[24] The R/R air 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/R air values up
to 5.54. In comparison, the Bukavu basin displays the lowest R/R air 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 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
stratification, 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].
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 CO 2 , as described by the following
general basalt weathering reaction [ Navarre-Sitchler and Brantley , 2007, and references therein]:
Accordingly, SiO 2 concentrations in lake water show a strong correlation with dissolved CO 2 , 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 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., Fe tot ,
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Mn tot , Si, and Ni and, to a lesser extent, Mg, Ca, Ba, Sr, V, Y, Zn, and Zr, with respect to the volcanic rocks
Go To
(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, 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 g/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 CO 2 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).
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Go To
Figure 5.

SiO 2 (in mg/L) versus CO 2 (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.
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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.
[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 CO 2 that produces
HCO 3 , significantly lowers the pH of lake water and moves the lake system out of the stability field for
calcite and magnesite.
Table 5. 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
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Depth (m)
Albite
Anorthite
Beidellite-Mg
Calcite
Celad-onite
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Clino-ptilolite
Kabuno Bay
0.57
4.25
1.53
1.53
6.90
6.63
Kabuno Bay
50
2.66
3.47
6.25
0.99
7.42
16.85
Kabuno Bay
75
2.63
3.59
6.29
0.95
7.33
16.92
Kabuno Bay
100
2.88
3.13
7.10
0.81
7.32
17.72
Kabuno Bay
125
3.01
3.20
7.55
0.55
7.02
18.02
Kabuno Bay
140
2.15
4.97
5.93
0.31
5.81
15.12
Main
0.20
4.48
1.55
0.81
5.46
2.21
Main
50
0.65
5.37
0.81
0.72
4.61
0.63
Main
100
1.08
3.50
6.07
0.08
3.63
9.09
Main
150
0.64
5.03
4.73
0.05
3.11
8.22
Main
200
0.02
6.54
3.38
0.12
2.17
6.23
Main
250
0.13
6.43
3.63
0.12
2.21
6.62
Main
300
0.16
7.54
2.79
0.01
2.41
7.42
Main
350
0.55
9.17
1.24
0.16
1.47
5.10
Main
375
0.48
9.12
1.40
0.21
1.49
5.37
Main
400
0.88
9.80
0.73
0.33
0.95
3.91
Main
425
1.21
10.51
0.12
0.29
0.65
2.81
Main
450
0.76
9.63
0.86
0.26
1.14
4.32
Main
478
1.18
10.53
0.07
0.45
0.62
2.87
Kalehe
50
1.05
6.39
1.37
1.14
5.36
Kalehe
100
0.86
4.32
4.67
0.26
4.25
Kalehe
125
1.06
4.35
5.16
0.21
4.06
9.99
Kalehe
150
1.76
3.36
6.06
0.51
5.18
12.79
Kalehe
175
1.16
4.65
4.70
0.47
4.51
10.79
Kalehe
200
0.16
6.20
3.23
0.22
2.83
6.85
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Depth (m)
Albite
Anorthite
Beidellite-Mg
Calcite
Celad-onite
Clino-ptilolite
Bukavu
50
0.24
4.14
1.91
0.93
5.09
2.28
Bukavu
75
0.20
4.28
1.95
0.84
5.07
2.60
Bukavu
90
0.16
4.32
2.27
0.77
4.86
3.18
Ishungu
100
0.78
3.80
4.89
0.28
4.29
8.08
Ishungu
125
1.72
3.19
6.48
0.31
4.75
12.43
Ishungu
150
0.04
6.65
3.28
0.17
2.33
6.73
Ishungu
170
0.24
6.47
3.52
0.09
2.54
7.55
[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 CO 2 . 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 CO 2
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, SO 4 2 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 (S 2 ) as well as elemental sulfur [e.g.,
Kallistova et al. , 2006, and references therein]. Accordingly, S 2 concentrations at both the Kabuno
Bay and Main basins show marked increases with depth (Table 1). Similarly, the vertical patterns of NH4 + ,
a product of reducing microbial and bacteria activity, show increases by up to three orders of magnitude in
all the stratified 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).
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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.
Go To
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 CO 2 -dominated gas reservoir of the
deep lake strata [e.g., Tietze et al. , 1980; Schoell et al. , 1988]. According to this hypothesis, the 2 H
and
18
O 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.
Figure 7.

The 2 H versus
18
O 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;
2 H = 8 18 O + 10. Symbols as in Figure 5.
[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;
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Pflumio et al. , 1994] and those of Lake Bogoria, Kenya [ Cioni et al. , 1992]. The relative increases
Go To
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 contribution may also be responsible, at least partially, of the SiO 2 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
CO 2 /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., CO 2 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 13 C CH4 and D CH4 values (58 V-PDB
and 218 SMOW, respectively) and the 14 C 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 (6070%) produced by reduction of CO 2 and, to a lesser extent (3040%), by acetate
fermentation. Schoell's hypothesis for CH4 origin is also supported by the CH4 /(C 2 H6 + C 3 H8 ) 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 bacteriadriven 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 CO 2 , but no insights on the ultimate source of the carbon dioxide are provided.
[35] The 13 C CO2 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 CO 2 is mainly deriving from a magmatic source. Considering that the carbon isotopic
fractionation factor between solid calcium carbonate and gaseous CO 2 is 10.2 at 20C [
Emrich et al. , 1970], the 13 C CO2 values of the Main basin ( 13 C 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 13 C 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 13 C (Table 4). Moreover, at Kabuno Bay dissolved CO 2 is not in
equilibrium with calcite, the latter having a
13
C 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 CO 2 altered by (1)
removal or scrubbing processes as CO 2 interacts with groundwater, and (2) a possible addition of
isotopically light biogenic carbon. The Kabuno Bay basin waters have CO 2 /Ar ratios up to 6.5 10 3 , up to
10 to 20 times greater than those of the other basins, with the exception of the deepest Kalehe water
whose CO 2 /Ar ratio is only 3 times lower. Assuming that the CO 2 /Ar ratio of the mantle-related fluids is
represented by the fumarolic discharges from the Nyiragongo crater, i.e., up to 1 10 4 (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 CO 2 /Ar may be lowered by CO 2
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scrubbing (removal) and therefore becoming less abundant in the gases directly discharged into the lake.
Go To
[36] In the Main, Ishungu, and Kalehe basins CO 2 does not exhibit the same degree of carbon
fractionation as Kabuno Bay, and a more significant addition of crustal He is shown. The R/R air values and
the CO 2 /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/R air = 1.21) and CO 2
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 CO 2 /Ar ratio (44) (Table 4). This finding implies that input of deep fluids in this area can likely
be regarded as negligible. In addition, the 13 C 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].
[37] The apparent decoupling of CO 2 ( 13 C CO2 10 V-PDB) and He (R/R air 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 CO 2 -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 13 C CO2 values of the fluids
of these areas in that the addition of thermally generated CO 2 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
13 C CO2 values show only a little difference from that of CO 2 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 13 C CO2 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) CO 2 scrubbing in the lake neutral-alkaline water [e.g.,
Vogel et al. , 1970; Mook et al. , 1974], (2) bacterial conversion of CO 2 to CH4 , and (3) isotopic
exchange.
[38] The negative 13 C DIC values of Kabuno Bay water also supports the
13
C CO2 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
follows:
13
C DIC values are produced by combining the
13
C values of the main carbon species, as
where [CO 2 ] (dissolved CO 2 ), [HCO 3 ] and [CO 3 2 ] are in mmol/L. As shown in Table 1, the CO 3 2
concentrations ([CO 3 2 ]) are negligible with respect to those of HCO 3 ([HCO 3 ]). Thus, equation (3) can
be expressed as follows:
Isotopic fractionation due to the reaction between dissolved CO 2 and HCO 3 can be quantified by the 2
enrichment factor [ Mook et al. , 1974], as follows:
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where T is the water temperature in K.
[39] Therefore, by combining equations (4) and (5) the relation between 13 C DIC and
The
13
Go To
13
C CO2 is
C DIC values calculated with equation (6) ( 13 C DICcalc ), 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 CO 2 , continuously discharged into the lake from the
sublacustrine emissions, and the dissolved carbonate species (i.e., CO 2 , HCO 3 , and CO 3 2 ).
Conversely, at the Main basis the measured and calculated 13 C DIC 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 13 C DIC 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 13 C DIC
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 CO 2 (Figure 8a) and CH4 (Figure 8b)
at the Main basin are consistent with those measured in 1974 [ Tietze , 1978] and 2004 [
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 artifacts
conflicts with the general agreement among the CO 2 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 CO 2 -CH4 conversion [ Schmid et al. , 2005]. This intriguing hypothesis, although reasonable,
does not explain the significant differences among the CO 2 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 CO 2 vertical profiles measured in the last decades (Figure 8a). Owing to the fact that the
dissolved CO 2 is mainly derived from mantle degassing [e.g., Schoell et al. , 1988;
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Schmid et al. , 2005], the spatial distribution should be depending on the location of the sublacustrine
Go To
discharges, which are likely controlled by the tectonic setting of the area. Nevertheless, a direct relation
between the distribution of dissolved CO 2 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 West , 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 CO 2 concentrations
constitute a permanent and dangerous feature the this basin (Figure 8a). The sublacustrine vents
discharging CO 2 -rich fluids into the Kabuno Bay basin, whose CO 2 /CH4 and CO 2 /Ar ratios are one order
of magnitude higher with respect to those of the other basins (Table 4), have a particularly high flux. The
CO 2 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.
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Go To
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Figure 8.
Go To
Vertical profiles of (a) CO 2 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.
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 CO 2 -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 CO 2 /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 CO 2 scrubbing by interaction with groundwater, produces an extremely negative 13 C-CO 2
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 CO 2 concentrations at a shallow level and the
presence of a CO 2 gradient with depth suggest a CO 2 flux that could be detected at the lake surface.
Systematic flux measurement could provide useful information on variations of CO 2 input at depth. The
Bukavu basin, whose chemistry seems to be exclusively regulated by water-rock interaction and
carbonate 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 CO 2 -, 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.
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Acknowledgments
Go To
[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 19941995, 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 defenseless
population. Our thought is to the GVO personnel and their families.
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Water and gas chemistry at Lake Kivu (DRC): Geochemical evidence of...

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Geochemistry, Geophysics, Geosystems

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

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2. Geographic Location and Limnological Features

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3. Sampling and Analytical Methods

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3.2. Chemical and Isotopic ( 18 O, D, and 13 C DIC ) Analysis of Water

C CO2 ) were determined on the basis of those measured in

C CO2strip ). The isotopic

4.1. Water Chemical Composition

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Democratic Republic of the Congoa

a Trace elements are measured in g/L.

a Trace elements are measured in g/L.

4.2. Water Isotopic ( O 18 and 2 H) Composition

4.3. Dissolved Gas Composition

4.4. Carbon Isotope Composition of Dissolved CO 2 ( 13 C CO2 ) and DIC

4.5. Helium Isotopic Composition

5.1. Processes Governing Lake Water Chemistry

5.1.1. Mineral Dissolution and Deposition

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montmorillonite-Mg, nontronite, saponite-Mg, typically related to chemical weathering of basic to ultrabasic

5.1.2. Effect of Bacterial Activity

5.1.3. Sublacustrine Fluid Discharges

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5.2. Origin of Dissolved Gas Compounds

C value of 2.3 V-PDB, i.e., lower than that expected for

C CO2 signature of this basin

C DIC values are produced by combining the

C values of the main carbon species, as

where T is the water temperature in K.

C as a consequence of kinetic fractionation during the gas release. Nevertheless, the

5.3. Temporal and Spatial Behavior of the Gas Reservoir

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