We carried out 10 field expeditions between 2010 and 2015 in the lowland
part of the Congo River network in the eastern part of the basin (Democratic
Republic of the Congo), to describe the spatial variations in fluvial dissolved
carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O)
concentrations. We investigate the possible drivers of the spatial
variations in dissolved CO2, CH4 and N2O concentrations by
analyzing covariations with several other biogeochemical variables, aquatic
metabolic processes (primary production and respiration), catchment
characteristics (land cover) and wetland spatial distributions. We test the
hypothesis that spatial patterns of CO2, CH4 and N2O are
partly due to the connectivity with wetlands, in particular with a giant
wetland of flooded forest in the core of the Congo basin, the “Cuvette
Centrale Congolaise” (CCC). Two transects of 1650 km were carried out from
the city of Kisangani to the city of Kinshasa, along the longest possible
navigable section of the river and corresponding to 41 % of the total
length of the main stem. Additionally, three time series of CH4 and
N2O were obtained at fixed points in the main stem of the middle Congo
(2013–2018, biweekly sampling), in the main stem of the lower Kasaï
(2015–2017, monthly sampling) and in the main stem of the middle Oubangui
(2010–2012, biweekly sampling). The variations in dissolved N2O
concentrations were modest, with values oscillating around the concentration
corresponding to saturation with the atmosphere, with N2O saturation
level (%N2O, where atmospheric equilibrium corresponds to 100 %)
ranging between 0 % and 561 % (average 142 %). The relatively narrow
range of %N2O variations was consistent with low NH4+
(2.3±1.3µmol L-1) and NO3- (5.6±5.1µmol L-1) levels in these near pristine rivers and streams, with
low agriculture pressure on the catchment (croplands correspond to 0.1 %
of catchment land cover of sampled rivers), dominated by forests
(∼70 % of land cover). The covariations in %N2O,
NH4+, NO3- and dissolved oxygen saturation level
(%O2) indicate N2O removal by soil or sedimentary
denitrification in low O2, high NH4+ and low NO3-
environments (typically small and organic matter rich streams) and N2O
production by nitrification in high O2, low NH4+ and high
NO3- (typical of larger rivers that are poor in organic matter).
Surface waters were very strongly oversaturated in CO2 and CH4
with respect to atmospheric equilibrium, with values of the partial pressure
of CO2 (pCO2) ranging between 1087 and 22 899 ppm (equilibrium
∼400 ppm) and dissolved CH4 concentrations ranging
between 22 and 71 428 nmol L-1 (equilibrium ∼2 nmol L-1). Spatial variations were overwhelmingly more important than
seasonal variations for pCO2, CH4 and %N2O as well as day–night variations for pCO2. The wide range of pCO2
and CH4 variations was consistent with the equally wide range of
%O2 (0.3 %–122.8 %) and of dissolved organic carbon (DOC) (1.8–67.8 mg L-1), indicative of generation of these two greenhouse gases from
intense processing of organic matter either in “terra firme” soils, wetlands or
in-stream. However, the emission rate of CO2 to the atmosphere from
riverine surface waters was on average about 10 times higher than the flux
of CO2 produced by aquatic net heterotrophy (as evaluated from
measurements of pelagic respiration and primary production). This indicates
that the CO2 emissions from the river network were sustained by lateral
inputs of CO2 (either from terra firme or from wetlands). The pCO2 and
CH4 values decreased and %O2 increased with increasing Strahler
order, showing that stream size explains part of the spatial variability of
these quantities. In addition, several lines of evidence indicate that
lateral inputs of carbon from wetlands (flooded forest and aquatic
macrophytes) were of paramount importance in sustaining high CO2 and
CH4 concentrations in the Congo river network, as well as driving
spatial variations: the rivers draining the CCC were characterized by
significantly higher pCO2 and CH4 and significantly lower
%O2 and %N2O values than those not draining the CCC;
pCO2 and %O2 values were correlated to the coverage of flooded
forest on the catchment. The flux of greenhouse gases (GHGs) between rivers and the atmosphere
averaged 2469 mmol m-2 d-1 for CO2 (range 86 and 7110 mmol m-2 d-1), 12 553 µmol m-2 d-1 for CH4 (range
65 and 597 260 µmol m-2 d-1) and 22 µmol m-2 d-1 for N2O (range -52 and 319 µmol m-2 d-1). The
estimate of integrated CO2 emission from the Congo River network
(251±46 TgC (1012 gC) yr-1), corresponding to nearly half the
CO2 emissions from tropical oceans globally (565 TgC yr-1) and was
nearly 2 times the CO2 emissions from the tropical Atlantic Ocean
(137 TgC yr-1). Moreover, the integrated CO2 emission from the
Congo River network is more than 3 times higher than the estimate of
terrestrial net ecosystem exchange (NEE) on the whole catchment (77 TgC yr-1). This shows that it is unlikely that the CO2 emissions from
the river network were sustained by the hydrological carbon export from
terra firme soils (typically very small compared to terrestrial NEE) but most likely,
to a large extent, they were sustained by wetlands (with a much higher
hydrological connectivity with rivers and streams).
Introduction
Emissions to the atmosphere of greenhouse gases (GHGs) such as carbon
dioxide (CO2), methane (CH4) and nitrous oxide (N2O) from
inland waters (rivers, lakes and reservoirs) might be quantitatively
important for global budgets (Seitzinger and Kroeze, 1998; Cole et al., 2007;
Bastviken et al., 2011). Yet, there are very large uncertainties in the
estimates of GHGs emission to the atmosphere from rivers, as reflected in
the wide range of reported values, between 0.2 and 1.8 PgC (1015 gC) yr-1 for CO2 (Cole et al., 2007; Raymond et al., 2013), 2 and 27 TgCH4 (1012 gCH4) yr-1 for CH4 (Bastviken et al., 2011; Stanley et al., 2016), and 32 and 2100 GgN2O-N (109 gN2O-N) yr-1 for N2O (Kroeze et al., 2010; Hu et al., 2016). This
uncertainty is mainly due to the scarcity of data in the tropics that
account for the majority of riverine GHG emissions (∼80 %
for CO2, Raymond et al., 2013; Borges et al., 2015a, b; Lauerwald et al., 2015, 79 % for N2O, Hu et al., 2016; 70 % for CH4, Sawakushi
et al., 2014) but also to scaling procedures of varying complexity that use
different input data (Raymond et al., 2013; Borges et al., 2015b; Lauerwald et
al., 2015), in addition to uncertainty in the estimate of surface area of
rivers (Downing et al., 2012; Raymond et al., 2013; Allen and Pavelsky, 2018)
and the parameterization of the gas transfer velocity (k) (Raymond et al., 2012; Huotari et al., 20013; Maurice et al., 2017; Kokic et al., 2018; McDowell
and Johnson, 2018; Ulseth et al., 2019). The exchange of CO2 between
rivers and the atmosphere is in most cases computed from the air–water
gradient of the CO2 concentration and k parameterized as a function of
stream morphology (e.g., slope or depth) and water flow (or discharge).
However, there can be large errors associated with the computation of the
dissolved CO2 concentration from pH and total alkalinity (TA) for low alkalinity waters in
particular so that high-quality direct
measurements of dissolved CO2 concentration are preferred (Abril et al., 2015), although scarce. In the tropics, research on GHGs in rivers has
mainly focussed on South American rivers and on the central
Amazon in particular (Richey et al., 1988, 2002; Melack et al., 2004; Abril et al., 2014;
Barbosa et al., 2016; Scofield et al., 2016), while until recently African
rivers were nearly uncharted with a few exceptions (Koné et al., 2009,
2010).
There is also a lack of understanding of the drivers of the fluvial
concentrations of GHGs, hence, ultimately of the drivers of their exchange
with the atmosphere. It is unclear to what extent CO2 emissions from
rivers are sustained by in situ net heterotrophy and/or by lateral inputs of
CO2. The global organic carbon degradation by net heterotrophy of
rivers and streams given by Battin et al. (2008) of 0.2 PgC yr-1 is
insufficient to sustain global riverine CO2 emissions given by the most
recent estimates of 0.7–1.8 PgC yr-1 (Raymond et al., 2013; Lauerwald et
al., 2015), suggesting an important role of lateral CO2 inputs in
sustaining emissions to the atmosphere from rivers. In a regional study in
the US, Hotchkiss et al. (2015) estimated that in-stream organic matter
degradation could only sustain 14 % and 39 % of CO2 riverine
emissions in small and large systems, respectively. It is also unclear to
what extent CO2 and CH4 emissions from rivers are sustained by
carbon inputs either from the terrestrial biome (terra firme) or from wetlands (flooded
forests and macrophytes) (Abril and Borges, 2019). This difference has large
implications for our fundamental understanding of carbon cycling in rivers
and their connectivity with respective catchments but also, consequently,
for our capacity to predict how GHG emissions from rivers might be modified
in response to climate change (warming and modification of the hydrological
cycle), water diversion (damming, water abstraction) or land use change on
the catchment (e.g., Klaus et al., 2018). In upland areas, low-order stream
CO2 emissions are undoubtedly related to soil-water and ground-water
CO2 inputs, although CO2 degassing takes place over very short
distances from point sources (≤200 m), is highly variable in space and
seasonally, and mainly occurs during short-lived high-flow events that
promote shallow flow paths (e.g., Duvert et al., 2018). Low-order streams (1–3)
might account for about one-third of the global riverine CO2 emissions (Marx
et al., 2017). Recently acquired datasets allowed us to show that inputs from
riparian wetlands seem to be of paramount importance in sustaining CO2
and CH4 emissions to the atmosphere from large tropical lowland rivers
(Abril et al., 2014; Borges et al., 2015a, b). About half of the global surface
area of wetlands is located in the tropics and subtropics (33∘ N–33∘ S), the rest are in the Northern Hemisphere (Fluet-Chouinard
et al., 2015), and more than half of river surface area is located in the
tropics and subtropics (Allen and Pavelsky, 2018).
The Congo River (∼4400 km length, freshwater discharge
∼44000 m3 s-1) has a large drainage basin (3.7×106 km2) covered by evergreen forest (dense and mosaic)
(∼67 %) and savannah (shrubland and grassland)
(∼30 %), owing to the tropical climate (annual average
precipitation of 1530 mm and air temperature of 23.7 ∘C). The
Congo basin accounts for 89 % of African rainforests. These rainforests
are spread between the Democratic Republic of the Congo (54 %), Gabon
(11 %), Cameroon (10 %) and the Republic of the Congo (10 %), the
remaining 15 % being shared by several other countries. The mean
above-ground biomass of the rainforests in Central Africa (43 kg dry biomass
(db) m-2) is much higher than the mean in Amazonia (29 kgdb m-2) and nearly equals the mean in the notorious high biomass forests
of Borneo (44 kgdb m-2) (Malhi et al., 2013). Current estimates of
carbon transport from the Congo River close to the mouth rank it as the
Earth's second-largest supplier of organic carbon to the oceans (Coynel et
al., 2005). Despite its overwhelming importance, our knowledge of carbon and
nutrient cycling in the Congo river basin is limited to some transport flux
data from the 1980s, reviewed by Laraque et al. (2009) and a number of more
recent small-scale studies (Bouillon et al., 2012, 2014; Spencer et al., 2012;
Lambert et al., 2016), in sharp contrast to the extensive and sustained work
that has been done on the Amazon river basin (Alsdorf et al., 2016). The
Congo basin has a wide range of contrasting tributaries (differing in
lithology, soil characteristics, vegetation, rainfall patterns,
etc.) and extensive flooded forests in its central region, the
“Cuvette Centrale Congolaise” (CCC), with an estimated flooded cover of
360 000 km2, for a total surface area of 1 760 000 km2 (Bwangoy et
al., 2010). Extensive peat deposits are present beneath the swamp forest of
the CCC that store below-ground 31 PgC of organic carbon, a quantity similar
to the above-ground carbon stock of the forests of the entire Congo basin
(Dargie et al., 2017). The tributaries partly drain semi-humid catchments
with alternating dry and wet seasons on both sides of the Equator, resulting
in a relatively constant discharge and water level for the main stem Congo
River (Runge, 2008). Hence, the CCC is an extended zone of year-round
inundation (Bwangoy et al., 2010), in sharp contrast with other large
tropical rivers such as the Amazon where floodplain inundation shows clear
seasonality (Hamilton et al., 2002).
Data of dissolved GHGs (CH4, N2O and CO2) have been reported
in rivers in the western part of the Congo basin in four major river basins
in the Republic of the Congo (Alima, Lefini, Sangha, Likouala-Mossaka) (Mann et
al., 2014; Upstill-Goddard et al., 2017), and we previously reported GHGs data
collected in the eastern part of the basin in the Democratic Republic of
the Congo in the framework of a broad synthesis of riverine GHGs at the scale of
the African continent (Borges et al., 2015a) and a general comparison of
the Congo and the Amazon rivers (Borges et al., 2015b). Here, we describe in
more detail the variability of GHGs based on a dataset collected during 10
field expeditions from 2010 to 2015 (Figs. 1 and 2) (Borges and Bouillon, 2019), in particular with
regards to spatial and seasonal patterns, as well as with regards to the
origin of fluvial CO2 by integrating metabolic measurements (primary
production and respiration), stable isotope ratios of dissolved inorganic
carbon (DIC) and characteristics of the catchments with regards to the
cover of wetlands. Comparison of data obtained in streams within and outside
the giant wetland area of the CCC allows a natural large-scale test of the
influence of the connectivity of wetlands on CO2 and CH4 dynamics
in lowland tropical rivers.
Freshwater discharge (m3 s-1) of the Congo River at
Kinshasa from 2010 to 2015, with an indication of field expedition duration
(thick lines).
Map showing the sampling stations of the 10 field expeditions in
the Congo River network.
Material and methodsField expeditions and fixed monitoring
Samples were collected during a total of 10 field expeditions (Figs. 1 and
2). Three were done from a medium sized boat (22 m long) on which we
deployed the equipment for continuous measurements of the partial pressure
of CO2 (pCO2) (total n=30490) as well as the field laboratory
for conditioning water samples. Sampling in the main stem and large
tributaries was made from the medium sized boat, while sampling in smaller
tributaries was made with a pirogue. These large-scale field expeditions
covered the Kisangani–Kinshasa transect twice (3–19 December 2013 and
10–30 June 2014) and the Kwa river up to Ilebo (16 April–6 May 2015).
During the other cruises, the field laboratory was installed in a base camp
(typically in a village along the river), and traveling and sampling was
made with small pirogues on which it was not possible to deploy the
apparatus for continuous measurements of pCO2. Three cruises covered
the section from Kisangani to the mouth of the Lomami River
(20 November–8 December 2012; 17–26 September 2013; 13—21 March 2014), one cruise covered the
section from Kisangani to the mouth of the Itimbiri River
(8 May–6 June 2010) and three cruises (previously reported by Bouillon et
al., 2012, 2014) covered the Oubangui river network around the city of
Bangui (21–23 March 2010, 20–23 March 2011, and 20–24 November 2012).
Fixed sampling was carried out in the Congo main stem in proximity of the
city of Kisangani (10 December 2012–16 April 2018), the Oubangui main stem
in
proximity of the city of Bangui (20 March 2010–31 March 2012) and the Kasaï
main stem in proximity of the village of Dima, close to the city of Bandundu
(14 April 2015–15 May 2017). Sampling was carried out at regular intervals,
every 15 d in the Congo and Oubangui main stems and every month in the
Kasaï main stem. Data from the Oubangui catchment were previously
reported by Bouillon et al. (2012, 2014).
Continuous measurements
Continuous measurements (1 min interval) of pCO2 were made with an
equilibrator designed for turbid waters (Frankignoulle et al., 2001) coupled
to a nondispersive infra-red gas analyzer (IRGA) (Li-Cor 840). The
equilibrator consisted of a Plexiglas cylinder (height of 70 cm and internal
diameter of 7 cm) filled with glass marbles; pumped water flowed from the
top to the bottom of the equilibrator at a rate of about 3 L min-1;
water residence time within the equilibrator was about 10 s, while 99 %
of equilibration was achieved in less than 120 s (Frankignoulle et al., 2001). This type of equilibrator system was shown to be the fastest among
commonly used equilibration designs (Santos et al., 2012). In parallel to the
pCO2 measurements, water temperature, specific conductivity, pH,
dissolved oxygen saturation level (%O2), and turbidity were measured
with an YSI multiparameter probe (6600) and position was measured with a Garmin
geographical position system (Map 60S) portable probe. Water was pumped to
the equilibrator and the multiparameter probe (on deck) with a 12V powered
water pump (LVM105) attached on a wooden pole to the side of the boat at
about 1 m depth. We did not observe bubble entrainment in water circuit to
the equilibrator, as the sailing speed was low (maximum speed 12 km h-1). Instrumentation was powered by 12 V batteries that were recharged
in the evening with power generators.
Discrete sampling
In smaller streams, sampling was done from the side of a pirogue with a 1.7 L
Niskin bottle (General Oceanics) for gases (CO2, CH4, N2O)
and a 5 L polyethylene water container for other variables. Water
temperature, specific conductivity, pH and %O2 were measured
in situ with a YSI multiparameter probe (ProPlus). pCO2 was measured
with a Li-Cor Li-840 IRGA based on the headspace technique with four polypropylene syringes (Abril et al., 2015). During two cruises
(20 November–8 December 2012; 17–26 September 2013, n=38), a PP Systems EGM-4 was used
as an IRGA instead of the Li-Cor Li-840. During one of the cruises
(13–21 March 2014, n=20) the equilibrated headspace was stored in
pre-evacuated 12 mL Exetainer (Labco) vials and analyzed in our home
laboratory with a gas chromatograph (GC) (see below). Similarly, the
equilibrated headspace was stored in pre-evacuated 12 mL Exetainer (Labco)
vials for pCO2 analysis from the fixed sampling in Kisangani. This
approach was preferred to the analysis of pCO2 from the samples for
CH4 and N2O analysis, as the addition of HgCl2 to preserve
the water sample from biological alteration led to an artificial increase in
CO2 concentrations most probably related to the precipitation of
HgCO3 (Supplement Fig. S1).
Both YSI multiparameter probes were calibrated according to manufacturer's
specifications, in air for %O2 and with standard solutions for other
variables: commercial pH buffers (4.00 and 7.00), a 1000 µS cm-1
standard for conductivity and a 124 nephelometric turbidity unit (NTU)
standard for turbidity. The turbidity data from the YSI 6600 compared
satisfactorily with discrete total suspended matter (TSM) measurements (Fig. S2), so hereafter we will refer to TSM for both discrete samples and sensor
data. The Li-Cor 840 IRGAs were calibrated before and after each cruise with
ultrapure N2 and a suite of gas standards (Air Liquide Belgium), with
CO2 mixing ratios of 388, 813, 3788 and 8300 ppm. The overall precision
of pCO2 measurements was ±2.0 %.
Metabolism measurements
Primary production (PP) was measured during 2 h incubations along a gradient
of light intensity using 13C-HCO3- as a tracer, as described
in detail by Descy et al. (2017). Data were integrated vertically with PAR
profiles made with a Li-Cor Li-193 underwater spherical sensor and at daily
scale with surface PAR data measured during the cruises with a Li-190R
quantum sensor. In order to extend the number of PP data points we developed
a very simple model as a function of chlorophyll a concentration (Chl a) and of
Secchi depth (Sd):
PP=-4.4+0.166×Sd+3.751×Chla,
where PP is in mmol m-2 d-1, Sd in cm and Chl a in µg L-1
This approach is inspired from empirical models such as the one developed by
Cole and Cloern (1987) that accounts for phytoplankton biomass given by
Chl a, light extinction given by the photic depth and daily surface
irradiance. We use Sd as a proxy for photic depth and, in order to
simplify the computations, we did not include in the model daily surface
irradiance, since it is nearly constant year round in our study region close
to the Equator. The model satisfactorily predicts the PP (Fig. S3), except at
very low Chl a values at which the model overestimates PP (due to the
Sd term). In order to overcome this, we assumed a zero PP value for
Chl a concentrations < 0.3 µg L-1.
Pelagic community respiration (CR) was determined from the decrease in
O2 in 60 mL biological oxygen demand bottles (Wheaton) over
∼24 h incubation periods. The bottles were kept in the dark
and close to in situ temperature in a cooler filled with in situ water.
The O2 decrease was determined from triplicate measurements at the
start and the end of the incubation with an optical O2 probe (YSI
ProODO). At the end of incubation the sealed samples were homogenized with a
magnetic bar prior to the measurement of O2. Depth integration was made
by multiplying the CR in surface waters by the depth measured at the station
with a portable depth meter (Plastimo Echotest-II).
For methane oxidation measurements, seven 60 mL borosilicate serum bottles
(Wheaton) were filled sequentially from the Niskin bottle and immediately
sealed with butyl stoppers and crimped with aluminum caps. The butyl
stoppers were cleaned of leachable chemicals by boiling in deionized water
during 15 min in our home laboratory. The first and the last bottle to
be filled were then poisoned with a saturated solution of HgCl2 (100 µL) injected through the butyl stopper with a polypropylene syringe
and a steel needle, corresponding to the initial concentration of the
incubation (T0). The other bottles were stored in a cooler full of in situ
water (to keep samples close to in situ temperature and in the dark) and
were poisoned approximately 12 h after T0 (T1) and then approximately every
24 h after T0 (T2, T3, T4 and T5). The difference between the two T0 samples
was close to the typical precision of measurements showing that the water
was homogeneous within the Niskin bottle with regards to CH4
concentration, and no measurable loss of CH4 occurred when filling the
seven vials. Methane oxidation was computed from the linear decrease in
CH4 concentration with time.
Sample conditioning and laboratory analysis
Samples for CH4 and N2O were collected from the Niskin bottle with
a silicone tube in 60 mL borosilicate serum bottles (Wheaton), poisoned with
200 µL of a saturated solution of HgCl2 and sealed with a butyl
stopper and crimped with aluminum cap. Measurements were made with the
headspace technique (Weiss, 1981) and a GC (SRI 8610C) with a flame
ionization detector for CH4 (with a methanizer for CO2) and
electron capture detector for N2O calibrated with
CO2 : CH4 : N2O : N2 gas mixtures (Air Liquide Belgium) with
mixing ratios of 1, 10, and 30 ppm for CH4; 404, 1018, and 3961 ppm for
CO2; and 0.2, 2.0, and 6.0 ppm for N2O. The precision of
measurements based on duplicate samples was ±3.9 % for CH4 and
±3.2 % for N2O. The CO2 concentration is expressed as
partial pressure in parts per million (ppm) and CH4 as dissolved
concentration (nmol L-1), in accordance with convention in existing
topical literature and because both quantities were systematically and
distinctly above saturation level (400 ppm and 2–3 nmol L-1,
respectively). Variations in N2O were modest and concentrations
fluctuated around atmospheric equilibrium, so data are presented as percent
of saturation level (%N2O, where atmospheric equilibrium corresponds
to 100 %), computed from the global mean N2O air mixing ratios given
by the Global Monitoring Division (GMD) of the Earth System Research
Laboratory (ESRL) of the National Oceanic and Atmospheric Administration
(NOAA) (https://www.esrl.noaa.gov/gmd/hats/combined/N2O.html, last access: 15 August 2018) and using the
Henry's constant given by Weiss and Price (1980).
The flux (F) of CO2 (FCO2), CH4 (FCH4) and N2O
(FN2O) between surface waters and the atmosphere was computed according
to Liss and Slater (1974):
F=kΔG,
where k is the gas transfer velocity (cm h-1) and ΔG is the
air–water gradient of a given gas.
Atmospheric pCO2 data from Mount Kenya station (NOAA ESRL GMD) and a
constant atmospheric CH4 partial pressure of 2 ppm were used.
Atmospheric mixing ratios given in dry air were converted to water-vapor-saturated air, using the water vapor formulation of Weiss and Price (1982)
as a function of salinity and water temperature. The k normalized to a Schmidt
number of 600 (k600 in cm h-1) were derived from the
parameterization as a function slope and stream water velocity given by
Eq. 5 of Raymond et al. (2012):
k600=8.42+11838×VS,
where V is stream velocity (m s-1) and S is slope (unitless).
We chose this parameterization because it is based on the most
exhaustive compilation to date of k values in streams derived from tracer experiments
and was used in the global riverine CO2 efflux estimates of Raymond et
al. (2013) and Lauerwald et al. (2015). Values of V and S were derived from a
geographical information system (GIS), as described in Sect. 2.6.
During the June 2014 field expedition, samples for the stable isotope
composition of CH4 (δ13C-CH4) were collected and
preserved similarly to those described above for the CH4 concentration. The
δ13C-CH4 was determined with a custom developed interface,
whereby a 20 mL He headspace was first created and CH4 was flushed out
through a double-hole needle, non-CH4 volatile organic compounds were
trapped in liquid N2, CO2 was removed with a soda lime trap,
H2O was removed with a magnesium perchlorate trap, and the CH4 was
quantitatively oxidized to CO2 in an online combustion column similar
to that of an elemental analyzer. The resulting CO2 was subsequently
pre-concentrated by immersion of a stainless steel loop in liquid N2,
passed through a micropacked GC column (Restek HayeSep Q 2 m length, 0.75 mm
internal diameter) and finally measured on a Thermo DeltaV Advantage
isotope ratio mass spectrometer (IRMS). Calibration was performed with
CO2 generated from certified reference standards (IAEA-CO-1 or NBS-19
and LSVEC) and injected in the line after the CO2 trap. Reproducibility
of measurements based on duplicate injections of samples was typically better
than ±0.5 ‰.
The fraction of CH4 removed by methane oxidation (Fox) was calculated
with a closed-system Rayleigh fractionation model (Liptay et al., 1998)
according to
ln(1-Fox)=lnδ13C-CH4_initial+1000-lnδ13C-CH4+1000/[α-1],
where δ13C-CH4_initial is the signature of
dissolved CH4 as produced by methanogenesis in sediments, δ13C-CH4 is the signature of dissolved CH4 in situ and
α is the fractionation factor.
We used a value of 1.02 for α based on field measurements in a
tropical lake (Morana et al., 2015). For δ13C-CH4_initial, we used a value of
-60.2 ‰, which we measured in bubbles from the sediment
trapped with a funnel on one occasion in a river dominated by Vossia cuspidata wetlands
(16 April–6 May 2015). The model we used to compute Fox applies for closed
systems, implying that CH4 is assumed not to be exchanged with
surroundings in contrast to open-system models. Running river water
corresponds to a system that is intermediate between closed and open
chemical systems, since it is open to the atmosphere and the sediments, but,
on the other hand, the water parcel can be partly viewed as a closed system
being transported downstream with the flow. As such, the water parcel
receives a certain amount of CH4 from sediments and then is transported
downstream away from the initial input of CH4. We also applied two
common open-system models to estimate Fox given by Happel et al. (1994) and
by Tyler et al. (1997) that have also been applied in lake systems
(Bastviken et al., 2002). However, both open-system models gave Fox values
> 1 in many cases (data not shown) since the difference between
δ13C of the CH4 source and measured δ13C in
dissolved CH4 was often much higher than expected from the assumed
isotopic fractionation (1.02). The same observation (Fox > 1) was
also reported with open-system models in the lakes studied by Bastviken et
al. (2002). Since Fox values > 1 are not conceptually possible, we
preferred to use the results from the closed-system model instead, although
we acknowledge that flowing waters are in fact intermediary systems between
closed and open and that, consequently, the computed Fox values are likely
underestimated.
Samples for the stable isotope composition of DIC (δ13C-DIC)
were collected from the Niskin bottle with a silicone tube in 12 mL
Exetainer vials (Labco) and poisoned with 50 µL of a saturated
solution of HgCl2. Prior to the analysis of δ13C-DIC, a 2 mL helium headspace was created and 100 µL of phosphoric acid
(H3PO4, 99 %) was added in the vial in order to convert
CO32- and HCO3- to CO2. After overnight
equilibration, up to 1 mL of the headspace was injected with a gastight
syringe into a coupled elemental analyzer – IRMS (EA-IRMS, Thermo FlashHT or
Carlo Erba EA1110 with DeltaV Advantage). The obtained data were corrected
for isotopic equilibration between dissolved and gaseous CO2, as
described by Gillikin and Bouillon (2007). Calibration was performed with
certified standards (NBS-19 or IAEA-CO-1 and LSVEC). Reproducibility of
measurements based on duplicate injections of samples was typically better
than ±0.2 ‰.
Water was filtered on Whatman glass fiber filters (GF/F grade, 0.7 µm
porosity) for TSM (47 mm diameter), particulate organic carbon (POC) and
particulate nitrogen (PN) (25 mm diameter) (precombusted at 450 ∘C
for 5 h) and Chl a (47 mm diameter). Filters for TSM and POC were stored dry
and filters for Chl a were stored frozen at -20 ∘C. Filters for POC
analysis were decarbonated with HCl fumes for 4 h and dried before
encapsulation into silver cups; POC and PN concentration and carbon stable
isotope composition (δ13C-POC) were analyzed on an EA-IRMS
(Thermo FlashHT with DeltaV Advantage), with a reproducibility better than
±0.2 ‰ for stable isotopic composition and better
than ±5 % for bulk concentration of POC and PN. Data were
calibrated with certified (IAEA-600: caffeine) and in-house standards
(leucine and muscle tissue of Pacific tuna) that were previously calibrated
versus certified standards. The Chl a samples were analyzed by high-performance liquid chromatography according to Descy et al. (2005), with a
reproducibility of ±0.5 % and a detection limit of 0.01 µg L-1. Part of the Chl a data were previously reported by Descy et al. (2017).
The water filtered through GF/F Whatman glass microfiber filters was collected
and further filtered through polyethersulfone syringe encapsulated filters
(0.2 µm porosity) for stable isotope composition of O of H2O
(δ18O-H2O), TA, dissolved organic carbon (DOC), major
elements (Na+, Mg2+, Ca2+, K+ and dissolved silicate,
Si), nitrate (NO3-), nitrite (NO2-) and ammonium
(NH4+). Samples for δ18O-H2O were stored at
ambient temperature in polypropylene 8 mL vials and measurements were
carried out at the International Atomic Energy Agency (IAEA, Vienna), where
water samples were pipetted into 2 mL vials and measured twice on different
laser water isotope analyzers (Los Gatos Research or Picarro). Isotopic
values were determined by averaging isotopic values from the last four out
of nine injections, along with memory and drift corrections, with final
normalization to the VSMOW/SLAP scales by using two-point lab standard
calibrations, as fully described in Wassenaar et al. (2014) and Coplen and
Wassenaar (2015). The long-term uncertainty for standard δ18O
values was ±0.1 ‰. Samples for TA were stored at
ambient temperature in polyethylene 55 mL vials and measurements were
carried out by open-cell titration with HCl 0.1 mol L-1 according to
Gran (1952), and data quality was checked with certified reference material
obtained from Andrew Dickson (Scripps Institution of Oceanography,
University of California, San Diego, USA), with a typical reproducibility
better than ±3µmol kg-1. DIC was computed from TA and
pCO2 measurements using the carbonic acid dissociation constants for
freshwater of Millero (1979) using the “CO2sys” package. Samples to determine
DOC were stored at ambient temperature and in the dark in 40 mL brown
borosilicate vials with polytetrafluoroethylene (PTFE)-coated septa and
poisoned with 50 µL of H3PO4 (85 %), and DOC
concentration was determined with a wet oxidation total organic carbon
analyzer (IO Analytical Aurora 1030W), with a typical reproducibility better
than ±5 %. Part of the DOC data were previously reported by Lambert
et al. (2016). Samples for major elements were stored in 20 mL scintillation
vials and preserved with 50 µL of HNO3 (65 %). Major elements
were measured with inductively coupled plasma MS (ICP-MS; Agilent 7700x)
calibrated with the following standards: SRM1640a from National Institute of
Standards and Technology, TM-27.3 (lot 0412) and TMRain-04 (lot 0913) from
Environment Canada, and SPS-SW2 Batch 130 from Spectrapure Standard. Limit
of quantification was 0.5 µmol L-1 for Na+, Mg2+, and
Ca2+; 1.0 µmol L-1 for K+; and 8 µmol L-1
for Si. Samples were collected during four cruises (8 May–6 June 2010,
20 November–8 December 2012, 3–19 December 2013, and 16 April–6 May 2015) for NO3-,
NO2- and NH4+ and were stored frozen (-20 ∘C)
in 50 mL polypropylene vials. NO3- and NO2- were
determined with the sulfanilamide, colorimetric was determined with the vanadium reduction
method (APHA, 1998) and NH4+ was determined with the
dichloroisocyanurate-salicylate-nitroprussiate colorimetric method (SCA,
1981). Detection limits were 0.3, 0.01 and 0.15 µmol L-1 for
NH4+, NO2- and NO3-, respectively. Precisions
were ±0.02, ±0.02
and ±0.1µmol L-1 for NH4+, NO2- and
NO3-, respectively.
GIS
The limits of the river catchments and Strahler order of rivers and streams
were determined from the geospatial HydroSHEDS dataset
(https://hydrosheds.cr.usgs.gov/, last access: 27 September 2018) using ArcGIS® (10.3.1). Land
cover data were extracted from the global land cover (GLC) 2009 dataset
(http://due.esrin.esa.int/page_globcover.php, last access: 11 January 2019) from the
European Space Agency GlobCover 2009 project for the following classes:
croplands, mosaic cropland/vegetation, dense forest, flooded dense forest,
open forest/woodland, shrublands, mosaic forest or shrubland/grassland,
grasslands, flooded grassland, and water bodies. Shrubland and grassland classes
were aggregated for the estimate of savannah. Theoretical contribution of
C4 vegetation were extracted based on the vegetation δ13C
isoscape for Africa from Still and Powell (2010) but corrected for
agro-ecosystems according to the method of Powell et al. (2012).
The geospatial and statistical methods to compute river width, length,
Strahler stream order, surface area, slope, flow velocity and discharge
throughout the Congo River network are described in detail in the
Supplement.
Statistical analysis
Statistical tests were carried out using GraphPad Prism®
software at 0.05 level, and the normality of the distribution was tested with
the D'Agostino–Pearson omnibus normality test.
Results and discussion
This section starts with the description of the
spatial variations in general limnological variables as well as GHGs along
the two main transects (Kinsangani–Kinshasa and Kwa) and as a function of
stream order and the presence of the CCC. The following parts of this section deal with
the seasonal variability and the drivers of CO2 dynamics, based on one
hand on the metabolic measurements and on the other hand on stable isotopic
composition of DIC. The final part of this section deals with fluxes of GHGs between the
river and the atmosphere that are presented and discussed firstly as areal
fluxes and finally as integrated fluxes at the scale of the basin and at
global scale.
Spatial variations along the Kisangani–Kinshasa transect of general
limnological variables and dissolved GHGs
Figures 3 and 4 show the spatial distribution of variables in surface waters
of the main stem
Congo River and confluence with tributaries along the
Kisangani–Kinshasa transect during high water (HW, December 2013) and
falling water (FW, June 2014) periods (Figs. 1 and 2). Numerous variables
show a regular pattern in the main stem (increase or decrease) due to the
gradual inputs from tributaries with a different (higher or lower) value
than the main stem. Specific conductivity, TA, δ13C-DIC, pH,
%O2, %N2O, TSM, pH and δ18O-H2O
decreased, while pCO2 and DOC increased in the main stem along the
Kisangani–Kinshasa transect. Numerous tributaries had black-water
characteristics (low conductivity, TA, pH, %O2, TSM and high DOC)
while the main stem had generally white-water characteristics. The
black-water tributaries were mainly found in the region of the CCC, while
tributaries upstream or downstream of the CCC had in general more
white-water characteristics. The differences between black-waters and
white-waters were apparent in the patterns of continuous measurements of
pCO2, showing a negative relationship with %O2, TSM, pH and
specific conductivity (Fig. S4).
Specific conductivity in the main stem Congo River decreased from 48.3 (HW) and 78.9 (FW) µS cm-1 in Kisangani to 26.5 (HW) and 32.7 (FW) µS cm-1 in Kinshasa (Figs. 3 and 4). This decreasing pattern was related
to a gradual dilution with tributary water with lower conductivities, on
average 27.6±9.9 (HW) and 31.9±17.8 (FW) µS cm-1.
The lowest specific conductivity was measured in the Lefini River that is
part of the Téké Plateau, where rainwater infiltrates into deep
aquifers across thick sandy horizons leading to water with a low
mineralization (Laraque et al., 1998). TA in the main stem decreased from 344
(HW) and 697 (FW) µmol kg-1 in Kisangani to 195 (HW) and 269 (FW) µmol kg-1 in Kinshasa, with an average in tributaries of
141±119 (HW) and 136±141 (FW) µmol kg-1. δ13C-DIC roughly followed the patterns of TA, decreasing in the
main stem from -7.9 (HW) and -13.8 (FW) ‰ in Kisangani to
-11.8 (HW) and -17.8 (FW) ‰ in Kinshasa, with an average
in tributaries of -21.7±3.2 (HW) and -20.9±4.3 (FW) ‰. TSM in the main stem decreased from 92.9 (HW) and 23.2
(FW) mg L-1 in Kisangani to 45.4 (HW) and 18.2 (FW) mg L-1 in
Kinshasa, with an average in tributaries of 9.3±13.4 (HW) and 8.5±9.3 (FW) mg L-1. The highest TSM values were recorded in the
Kwa (44.4 (HW) and 15.8 (FW) mg L-1) and in the Nsele, a small stream-draining savannah and flowing into pool Malebo (71.4 [HW] and 34.8 [FW] mg L-1). pH in the main stem decreased from 6.73 (HW) and 7.38 (FW) in
Kisangani to 6.11 (HW) and 6.29 (FW) in Kinshasa, with an average in
tributaries of 5.44±0.88 (HW) and 4.91±1.05 (FW). %O2
values in the main stem
decreased from 89.2 (HW) and 92.6 (FW) % in
Kisangani to 57.8 (HW) and 79.7 (FW) % in Kinshasa, with an average in
tributaries of 36.7±33.3 (HW) and 43.7±35.8 (LW) %. DOC
increased from 5.9 (HW) and 5.1 (FW) mg L-1 in Kisangani to 11.9 (HW) and 9.4 (FW) mg L-1 in Kinshasa, with an average in tributaries of
16.1±10.6 (HW) and 17.9±15.2 (FW) mg L-1. Extremely low pH
values were recorded in rivers draining the CCC, with values as low as 3.6,
coinciding with nearly anoxic conditions (%O2 down to 0.3 %) in
surface waters and very high DOC content (up to 67.8 mg L-1). δ18O-H2O in the main stem decreased from -2.2 (HW) and -1.6 (FW) ‰ in Kisangani to -2.9 (HW) and -2.2 (FW) ‰ in Kinshasa, with an average in the tributaries of
-2.7±0.9 (HW) and -2.2±0.8 ‰ (FW). Temperature
increased in the main stem from 26.0 (HW) and 27.1 (FW) ∘C in
Kisangani to 27.8 (HW) and 27.3 (FW) ∘C in Kinshasa, due to
exposure in the uncovered main stem to solar radiation, as temperature was
lower in tributaries with an average of 26.0±1.1 (HW) and 26.1±1.7 (FW) ∘C due to more shaded conditions (forest cover).
Variation in surface waters of the specific conductivity (µS cm-1), water temperature (∘C), oxygen stable isotope
composition of H2O (δ18O-H2O in ‰), total suspended matter (TSM in mg L-1), total alkalinity (TA in
µmol kg-1), dissolved organic carbon (DOC in mg L-1),
carbon stable isotope composition of dissolved inorganic carbon (δ13C-DIC in ‰), pH, partial pressure of CO2
(pCO2 in ppm), dissolved O2 saturation level (%O2 in
%), dissolved CH4 concentration (nmol L-1) and dissolved N2O
saturation level (%N2O in %) as a function of the distance
upstream of Kinshasa along a transect along the Congo River from Kisangani
(3–19 December 2013, n=10505). Grey and black symbols indicate samples
from the main stem and green samples from tributaries.
Variation in surface waters of the specific conductivity (µS cm-1), water temperature (∘C), oxygen stable isotope
composition of H2O (δ18O-H2O in ‰), total suspended matter (TSM in mg L-1), total alkalinity (TA in
µmol kg-1), dissolved organic carbon (DOC in mg L-1),
carbon stable isotope composition of dissolved inorganic carbon (δ13C-DIC in ‰), pH, partial pressure of CO2
(pCO2 in ppm), dissolved O2 saturation level (%O2 in
%), dissolved CH4 concentration (nmol L-1) and dissolved N2O
saturation level (%N2O in %) as a function of the distance
upstream of Kinshasa along a transect along the Congo River from Kisangani
(10–30 June 2014, n=12968). Grey and black symbols indicate samples from
the main stem and green samples from tributaries.
The pCO2 values in the main stem increased from 2424 (HW) and 1670 (FW) ppm in Kisangani to 5343 (HW) and 2896 (FW) ppm in Kinshasa, with an average
in tributaries of 8306±4089 (HW) and 8039±5311 (FW) ppm.
pCO2 in tributaries was in general higher than in the main stem with a
few exceptions, namely in rivers close to Kinshasa (1582 to 1903 [HW] and
1087 to 2483 [FW] ppm), due to degassing at waterfalls upstream of the
sampling stations, as the terrain is more mountainous in this area than in
more gently sloping catchments upstream and also possibly due to a larger
contribution of savannah to the catchment cover. The highest pCO2
values (up to 16 942 ppm) were observed in streams draining the CCC.
CH4 in the main stem decreased from 85 (HW) and 63 (FW) nmol L-1 in
Kisangani to 24 (HW) and 22 (FW) nmol L-1 just before Kinshasa and then
increased again in the Malebo pool (82 [HW] and 78 [FW] nmol L-1),
possibly related to the shallowness (∼3 m in Malebo pool
versus ∼30 m depth at station just upstream). The general
decreasing pattern of CH4 in the main stem resulted from CH4
oxidation, as indicated by 13C-enriched values in the main stem (-38.1 ‰
to -49.4 ‰) with regards to sediment CH4 (-60.2 ‰) and the increasing 13C enrichment along the
transect (Fig. 5). The calculated fraction of oxidized CH4 ranged
between 0.43 and 0.68 in the main stem and also increased downstream along
the transect (Fig. S5). CH4 in the tributaries showed a very large
range of CH4 concentration (68 to 51 839 nmol L-1 (HW) and 102 to
56 236 nmol L-1 (FW)). CH4 in the tributaries showed a variable
degree of 13C enrichment compared to sediment CH4 (δ13C-CH4 between -19.3 ‰ and -56.3 ‰, Fig. 5),
and the calculated fraction of oxidized CH4 ranged between 0.18 and
0.88 (Fig. S5). Unlike the large rivers of the Amazon where a loose negative
relation has been reported (Sawakuchi et al., 2016), the δ13C-CH4 values in the Congo River were unrelated to dissolved
CH4 concentrations, and a relatively high 13C enrichment (δ13C-CH4 up to -19.3 ‰) was observed even at
high CH4 concentrations (correspondingly 3118 nmol L-1) (Fig. 5).
This lack of correlation between concentration and isotope composition of
CH4 was probably related to spatial heterogeneity of sedimentary (and
corresponding water column) CH4 content over a very large and
heterogeneous sampling area. The highest CH4 concentrations were
observed at the mouths of small rivers in the CCC. At the confluence with
the Congo main stem, the flow is slowed down, leading to the development of
shallow delta-type systems with very dense coverage of aquatic macrophytes
(in majority Vossia cuspidata with a variable contribution of Eichhornia crassipes but also other species, Fig. S6). Such sites are favorable for intense sediment methanogenesis but, due
to the stable environment related to near stagnant waters, also very
favorable for the establishment of a stable methanotrophic bacterial
community in the water column and associated with the root system of floating
macrophytes that sustain intense methane oxidation (Yoshida et al., 2014;
Kosten et al., 2016). Indeed, we found a very strong relation between
CH4 oxidation and CH4 concentration on a limited number of
incubations carried out in the Kwa river network in April 2015 (Fig. S7).
Such conditions can explain the apparently paradoxical combination of high
CH4 concentrations in some cases associated with a high degree of
CH4 oxidation. Microbial oxidation of CH4 might also explain the
occurrence of samples with extremely 13C depleted POC (δ13C-POC down to -39.0 ‰) observed in low
%O2 and high CH4 environments (Fig. 6) located in small streams
of the CCC that were also characterized by low POC and TSM values (not
shown) and high POC : Chl a ratios (excluding the possibility that in situ PP would
be at the basis of the 13C depletion). This suggests that in these
environments poor in particles (typical of black-water streams) but with
high CH4 concentrations, methanotrophic bacteria that are able to
incorporate 13C-depleted CH4 into their biomass contribute
substantially to POC. While such patterns have been reported at the
oxic–anoxic transition zone of lakes with high hypolimnetic CH4
concentrations such as Lake Kivu (Morana et al., 2015), this has never been
reported in surface waters of rivers.
Carbon stable isotope composition of CH4 (δ13C-CH4 in ‰) in surface waters of the Congo
River main stem (black symbols) and tributaries (green symbols) as a
function of dissolved CH4 concentration (nmol L-1) and as a function
of the distance upstream of Kinshasa, obtained along a longitudinal transect
along the Congo River from Kisangani (10–30 June 2014). The dotted line
indicates linear regression.
Carbon stable isotope composition of particulate organic carbon
(δ13C-POC in ‰) in surface waters of the
Congo River network as a function of dissolved O2 saturation level
(%O2 in %) and dissolved CH4 concentration (nmol L-1).
Grey lines indicate average (full line) and standard deviation (dotted
lines) of average soil organic carbon stable isotope composition with a
dominance of C4 (-15.5±0.8 ‰) and C3
plants (-28.4±0.7 ‰) (Bird and Pousai, 1997).
Data with δ13C-POC < -30 ‰ were
associated with significantly lower %O2 and higher CH4 than data
with δ13C-POC > -30 ‰
(Mann–Whitney p<0.0001 for both tests).
%N2O decreased from 198 (HW) and 139 (FW) % in Kisangani to 168
(HW) and 153 (FW) % in Kinshasa, and in most cases %N2O was lower
in tributaries, on average 114±73 (HW) and 120±69 (FW) %. The
undersaturation in N2O was observed in streams with high DOC, low
%O2 and relatively low NO3- and is most probably
related to denitrification of N2O, as also reported in the Amazon river
(Richey et al., 1988) and in temperate rivers (Baulch et al., 2011).
Denitrification could have occurred in river sediments or soils, although
the lowest %N2O (and %O2) occurred in the CCC dominated by
flooded soils in the flooded forest. Indeed, there was a general negative
relationship between %N2O and %O2 (Fig. 7), with an average
%N2O of 78.5±59.3 % for %O2 < 25 % and an
average %N2O of 155.7±57.7 % for %O2 > 25 % (Mann–Whitney p<0.0001). The decreasing pattern of
NH4+ : DIN and increasing pattern of NO3- : DIN with
%O2 indicated the occurrence of nitrification in oxygenated (typical
of high Strahler stream order) rivers and prevalence of NH4+ in
the more reducing and lower oxygenated (typical of low Strahler order)
streams draining the CCC in particular, where NO3- was probably
also removed from the water by sedimentary or soil denitrification (Fig. 7).
In addition, in black-water rivers and streams, low pH (down to 4) might have
led to the inhibition of nitrification (Le et al., 2019) and also
contributed higher NH4+:DIN values. Furthermore, the positive
relation between %N2O and NO3- : DIN and the negative
relation between %N2O and NH4+ : DIN (Fig. 8) support the
hypothesis of N2O removal by denitrification in O2-depleted
environments (either in stream sediments or soils), while in more oxygenated
rivers N2O was produced by nitrification. In the main stem of the
Congo, there might, in addition, be a loop of nitrogen recycling
(ammonification-nitrification) sustained by phytoplankton growth and decay
that contributed to maintain oversaturation of N2O with respect to
atmospheric equilibrium, as phytoplankton growth was only observed in the
main stem (Descy et al., 2017). The generally low %N2O values in the
Congo River network were probably due to the near pristine nature of these
systems with low NH4+ (2.3±1.3µmol L-1) and
NO3- (5.6±5.1µmol L-1) levels, typical of
rivers and streams draining a large fraction (∼70 %) of
forests. Croplands only represented at most 17 %, on average, of the land
cover of the studied river catchments where traditional agriculture is
practised with little use of artificial fertilizers. This corresponds to an
upper bound of cropland surface area since it was estimated aggregating the
“cropland” and “mosaic cropland/vegetation” GLC 2009 categories, the
latter corresponding to mixed surfaces with < 50 % of cropland.
The “cropland” GLC 2009 category only accounts for 0.1 %, on average, of
the land cover of the studied river catchments. Nitrogen inputs from waste
water can also sustain N2O production in impacted rivers and streams
(Marwick et al., 2014), but the largest cities along the Congo River main stem
are of relatively modest size such as Kisangani (1 600 000 habitants) and
Mbandaka (350 000 habitants), especially considering the large dilution due
to the massive discharge of the main stem (sampling was done upstream of the
influence of the megacity of Kinshasa with 11 900 000 habitants).
Dissolved N2O saturation level (%N2O in %), ratio
of NH4+ to dissolved inorganic nitrogen
(DIN =NH4++NO2-+NO3-) (µmol : µmol) and ratio of NO3- to DIN (µmol : µmol) in surface waters of the Congo River network as a function of dissolved
O2 saturation level (%O2 in %). Outliers (red dots) were
identified with a Cook's distance procedure and removed prior to linear
regression analysis (solid line).
Dissolved N2O saturation level (%N2O in %), as a
function of the ratio of NH4+ to dissolved inorganic nitrogen
(DIN =NH4++NO2-+NO3-) (µmol : µmol) and of the ratio of NO3- to DIN (µmol : µmol) in surface waters of the Congo River network. Outliers (red
dots) were identified with a Cook's distance procedure and removed prior
to linear regression analysis (solid line).
The input of the Kwa led to distinct changes of TA, δ18O-H2O (decrease) and TSM (increase) of main stem values
(comparing values upstream and downstream of the Kwa mouth) (Figs. 3–4). In
the main stem, continuous measurements of pCO2, pH, %O2 and
conductivity showed more variability compared to discrete samples acquired
in the middle of channel, in particular in the region of CCC (Figs. 3–4).
These patterns were related to gradients across the section of channel, as
the boat sailed either along the mid-channel or closer to shore. The water
from the tributaries flowed along the riverbanks and did not mix with
main stem middle channel waters, as visible in natural color remotely sensed
images (Fig. S8), leading to strong gradients across the section of main stem
channel. During the June 2014 field expedition, this was investigated in
more detail by a series of six transects perpendicular to the river main stem
channel (Fig. 9). In the upper part (1590 km from Kinshasa), the variables
showed little cross section gradients except for a decrease in conductivity
towards the right bank due to inputs from the Lindi River that had
distinctly lower specific conductivities (27.2 [HW] and 35.1 [FW] µS cm-1) than the main stem (48.3 [HW] and 78.9 [FW] µS cm-1).
At 795 km from Kinshasa, marked gradients appeared in all variables, with the
presence of black-water characteristics close to the right bank (higher
pCO2 and lower %O2, pH, specific conductivity, temperature, and
TSM values). This feature was related to inputs from large right-bank
tributaries such as the Aruwimi and the Itimbiri (Supplement Table S1). Upstream of
this section the only major left-bank tributary is the Lomami, which had
white-water characteristics, relatively similar to those of the main stem
(Figs. 3–4). The presence of black-water characteristics became apparent
also on the left bank, from cross sections at 307 and 254 km upstream of
Kinshasa, where the river is particularly wide (> 6 km wide) and
received the inputs from the Ruki, the second-largest left-bank tributary
(Table S1) with black-water characteristics. The cross section gradients
became less marked at 203 km upstream from Kinshasa, as in this region the
river becomes more narrow (2 km wide) leading to increased currents and more
lateral mixing. The cross section gradients nearly disappeared at 158 km
upstream of Kinshasa (and 30 km downstream of the Kwa mouth) due to
homogenization by the large Kwa inputs (nearly 20 % of total freshwater
discharge from the Congo River, Table S1) into a relatively narrow river section
(∼1 km).
Variations in surface water of the partial pressure of CO2
(pCO2 in ppm), dissolved oxygen saturation level (%O2 in %),
pH, specific conductivity (µS cm-1), water temperature
(∘C) and total suspended matter (TSM in mg L-1) along
perpendicular transects to the main stem Congo River as a function of distance
from the left bank (m) and at a variable distance from Kinshasa
(10–30 June 2014).
Spatial variations along the Kwa transect
Spatial features of biogeochemical variables along the transect in the Kwa
River network (Fig. 10) showed some similarities with two Kisangani–Kinshasa
transects along the Congo main stem (Figs. 3–4). The main stem Kwa had a higher
specific conductivity than the tributaries (25.1±4.2 versus 21.2±11.5µS cm-1), higher TA (281±64 versus 119±118µmol kg-1), higher temperatures (27.7±0.7 versus
26.3±2.2∘C), higher TSM (40.1±8.9 versus
15.2±35.1 mg L-1), higher pH (6.1±0.2 versus 4.5±0.7), higher %O2 (67.0±7.0 versus 37.9±26.8 %),
higher δ13C-DIC (-16.5±1.2 versus -22.6±3.4 ‰) and lower DOC (5.2±1.4 versus 13.0±8.5 mg L-1). Unlike the Kisangani–Kinshasa transects along the Congo
main stem, the δ18O-H2O was lower in the main stem Kwa
(-4.3±0.3 ‰) than in the tributaries
(-3.3±0.6 ‰). Note that both the main upstream
branches of the Kwa (Kasai and Sankuru) had low δ18O-H2O
values. The δ18O-H2O values of the upper Kasai and Sankuru
(-4.4 ‰ and -4.7 ‰, respectively) were lower than those
of the Lualaba (Congo at Kisangani) (-2.2 [HW] and -1.6 [FW] ‰). This difference can be in part explained by the
spatial patterns of δ18O-H2O in rainwater, as the annual
averages over of river catchments are -3.1 ‰ and -4.2 ‰, for the Lualaba and the Kasai, respectively, based on
the global grids of the O isotope composition of precipitation given by
Bowen et al. (2005). The river δ18O-H2O was close to
those of rain for the Kasai but less depleted in 18O for the Lualaba.
This was probably related to the lower evapotranspiration over the
catchments of the upper Kasai and Sankuru than those of Lualaba (Bultot,
1972), leading to more 18O-depleted water (e.g., Simpson and Herczeg,
1991). Additionally, the catchment of Kwa has a high fraction of
unconsolidated sedimentary (41.4 %) and siliciclastic sedimentary
(44.3 %) rocks than the catchment of the Lualaba that is dominated by
metamorphic rocks (68.4 %). Unconsolidated sedimentary and siliciclastic
sedimentary rocks are more favorable to the infiltration of water and
development of aquifers that will minimize evaporation and 18O
enrichment, unlike catchments dominated by metamorphic rocks. Note that the
tributaries with the lowest δ18O-H2O values were situated
downstream of the Kwa and upstream of Kinshasa (Figs. 3–4) and are part of
the Téké Plateau. These rivers are fed by deep aquifers derived from
infiltration of rain through sandy soils (Laraque et al., 1998).
Variation in surface waters of the specific conductivity (µS cm-1), water temperature (∘C), oxygen stable isotope
composition of H2O (δ18O-H2O in ‰), total suspended matter (TSM in mg L-1), total alkalinity (TA in
µmol kg-1), dissolved organic carbon (DOC in mg L-1),
carbon stable isotope composition of dissolved inorganic carbon (δ13C-DIC in ‰), pH, partial pressure of CO2
(pCO2 in ppm), dissolved O2 saturation level (%O2 in
%), dissolved CH4 concentration (nmol L-1) and dissolved N2O
saturation level (%N2O in %) as a function of the distance
upstream of the Kwa mouth along a transect along the Kwa River
(16 April–6 May 2015, n=7017). Grey and black symbols indicate samples from
the main stem and green samples from tributaries.
Another difference with the Kisangani–Kinshasa transects along the Congo
main stem relates to N2O values that were closer to saturation in the
Kwa main stem (110.1±8.8 %), while surface waters oscillated from
undersaturation to oversaturation in the tributaries (122.4±59.5 %). This difference could be due to variations in biogeochemical cycling
or in physical settings leading to changes in k. The latter seems more likely
due to the strong flow in the Kwa that probably led to high gas transfer
velocities and strong degassing of N2O to the atmosphere. In the Kwa
main stem, pCO2 (3473±974 ppm) and CH4 (255±150 nmol L-1) values were lower than in tributaries (8804±5108 ppm,
6783±16479 nmol L-1). The highest pCO2 and CH4
values of the entire dataset in the Congo River network were observed in a
tributary of the Fimi (22 899 ppm and 71 428 nmol L-1) that is bordered
by very extensive meadows of the aquatic macrophyte Vossia cuspidata and unrelated to
inputs from the shallow Lake Mai Ndombé that showed lower pCO2 and
CH4 values (3,143 ppm and 250 nmol L-1, respectively).
Spatial variations as a function of stream order and as a function of
the influence of the CCC
The large differences in pCO2, CH4, %O2 and %N2O
(Figs. 3, 4, 10) among the various sampled tributaries of the Congo River can
be analyzed in terms of size classes as given by Strahler order (Fig. 11).
There were distinct patterns in CH4 and pCO2 versus Strahler
order, with a decrease in the central value (median and average) for both
quantities as a function of Strahler order in streams draining and not
draining the CCC (Fig. 11). For nearly all the stream orders, the streams
draining the CCC had significantly higher pCO2 and CH4 values than
streams not draining the CCC (Fig. 11). The %O2 values per Strahler
order did not show any distinct pattern (increase or decrease) in the
streams not draining the CCC, but the streams draining the CCC showed an
increasing pattern as a function of Strahler order. The %O2 values
were significantly lower in the streams draining the CCC than those not
draining the CCC (Fig. 11). For %N2O, the tendency of the central
value (median and average) as a function of Strahler order did not show a
clear pattern for streams not draining the CCC; however, there was a clear
increasing pattern with Strahler order for streams draining the CCC. In
addition, the %N2O values were significantly lower for half of the
cases, in streams draining the CCC compared to those not draining it (Fig. 11).
Box plot as a function of Strahler stream order of the partial
pressure of CO2 (pCO2 in ppm), dissolved CH4 concentration
(nmol L-1), dissolved N2O saturation level (%N2O in %),
and dissolved O2 saturation level ( %O2 in %) for rivers and
streams of the Congo River network draining and not draining the Cuvette
Centrale Congolaise. The box represents the first and third quartile,
the horizontal line corresponds to the median, the cross corresponds to the average, the error
bars correspond to the maximum and minimum, and the symbols show all data points. A
Mann–Whitney test was used to test statistical differences: ns represents not
significant, ****=p<0.0001; ***=p<0.001;
**=p<0.01; *=p<0.05.
In US rivers, a decreasing pattern as a function of Strahler order has
previously been reported for pCO2 (Butman and Raymond, 2001; Liu and
Raymond, 2018). This has been interpreted as reflecting inputs of soil-water
enriched in terrestrial respired CO2 that have a stronger impact in
smaller and lower Strahler order systems, in particular headwater streams,
followed by degassing of CO2 in higher Strahler order rivers (Hotchkiss
et al., 2015), although soil-water CO2 inputs in headwater streams are
seasonally variable and spatially heterogeneous (Duvert et al., 2018).
Nevertheless, all of the low-Strahler-order streams we sampled were in
lowlands, so the decreasing pattern of pCO2 as a function of Strahler
order could alternatively reflect the stronger influence of riparian
wetlands on smaller streams, rather than larger systems. The mechanism
remains the same, a high ratio of lateral inputs to water volume in small
streams that is related to soil-water in temperate streams such as in the
US but related in addition to riparian wetlands in tropical systems such as
those sampled in the Congo River network.
The influence of riparian wetlands on stream pCO2, CH4 and
%N2O can be also highlighted when data were separated into rivers
draining or not draining the CCC but aggregating into systems smaller or
larger than Strahler order 5 to account simultaneously for the effect of
stream size (Fig. 12). The pCO2 values were statistically higher in
rivers draining the CCC than those not draining it, with median values more
than 2-fold higher in both small and large rivers. Conversely, %O2
levels were statistically lower in rivers draining the CCC than those not
draining it, with median values 11-fold and 2-fold lower in small and large
rivers, respectively. Additional evidence on the influence of the
connectivity of wetlands with rivers in sustaining high pCO2 and low
%O2 values was provided by the positive relationship between
pCO2 and flooded dense forest cover and the converse negative
relationship between %O2 and flooded dense forest cover (Fig. 13).
These patterns were also consistent with the positive relation between DOC
concentration and flooded dense forest reported by Lambert et al. (2016).
Note that aquatic macrophytes (Vossia cuspidata) also most probably strongly contributed, in
addition to flooded forest, to high pCO2 and low %O2 levels,
based on visual observations of dense coverage (Fig. S9), although macrophytes have
not been systematically mapped and GIS data are unavailable (as for flooded
dense forest).
Box plot of the partial pressure of CO2 (pCO2 in ppm),
dissolved O2 saturation level (%O2 in %), dissolved CH4
concentration (nmol L-1), and dissolved N2O saturation level
(%N2O in %) in surface waters of rivers and streams of the Congo
river network draining and not draining the Cuvette Centrale Congolaise for
small and large systems (Strahler stream order 5≤ and > 5,
respectively) (3–19 December 2013; 10–30 June 2014). The box represents
the first and third quartile, the horizontal line corresponds to the median, the
cross corresponds to the average, the error bars correspond to the maximum and minimum, and the
symbols show all data points. A Mann–Whitney test was used to test
statistical differences: ****=p<0.0001; ***=p<0.001; **=p<0.01.
Partial pressure of CO2 (pCO2 in ppm) and dissolved
O2 saturation level (%O2 in %) in surface waters of rivers
and streams of the Congo River network as a function of the flooded dense
forest over the respective catchment (GLC, 2009). Grey open
dots are individual data points, and black full dots are binned averages
(± standard deviation) by intervals of 20 %.
Wetlands coverage had also a major importance on CH4 distribution, as
the CH4 values were statistically higher in rivers draining the CCC
than those not draining it (Fig. 12), with median values 10-fold and 2-fold
higher in small and large rivers, respectively. %N2O was also
statistically lower in rivers draining the CCC than those not draining it,
with median values 2.7-fold lower in small rivers but 1.4-fold higher in
large rivers. The pattern of %N2O followed the one of %O2,
and the very low to null N2O values were observed in the systems
draining the CCC where the lowest %O2 values (close to 0) were also
observed due to sedimentary or soil organic matter degradation, leading to a
decrease in O2 and N2O in surface waters (consumption of N2O
by denitrification).
The CH4 : CO2 molar ratio ranged between 0.0001 and 0.1215, with a
mean of 0.0097±0.018. Such ratios were distinctly higher than those
typically observed in marine waters (0.0005) and in the atmosphere (0.005).
The CH4 : CO2 molar ratio strongly increased with the decrease in
%O2 and was significantly higher in small rivers draining the CCC
(Fig. 14). These patterns were probably related to inputs of organic matter
from wetlands and in particular aquatic macrophytes that lead to important
organic matter transfer to sediments and high sedimentary degradation of
organic matter. This led to %O2 decrease in surface waters and a
large fraction of organic matter degradation by anaerobic processes compared
to aerobic degradation, leading to an increase in the CH4 : CO2
ratio. The decrease in O2 and increase in CO2 in the water in
presence of floating macrophytes was probably in part also related to
autotrophic root respiration and not fully related to microbial
heterotrophic respiration.
Ratio of dissolved CH4 and CO2 concentration (µmol:µmol) plotted as a function of O2 saturation level
(%O2 in %) and plotted in box plots draining and not draining the
Cuvette Centrale Congolaise for small and large systems (Strahler stream
order 5≤ and > 5, respectively) (3–19 December 2013;
10–30 June 2014). The box represents the first and third quartile,
the horizontal line corresponds to the median, the cross corresponds to the average, the error
bars correspond to the maximum and minimum, and the symbols show all data points. A
Mann–Whitney test was used to test statistical differences: ns=not
significant; ****=p<0.0001.
Primary production (measured and modeled) (mmol m-2 d-1) as a function of community respiration (mmol m-2 d-1)
and air–water CO2 fluxes (FCO2 in mmol m-2 d-1) as a
function of community respiration (mmol m-2 d-1) and net community
production (mmol m-2 d-1) in surface waters of rivers and streams
of the Congo River network. Insets show the data on a linear scale (instead
of a log–log scale).
Drivers of CO2 dynamics – metabolic
measurements and daily variations in CO2
We compared the balance of depth-integrated planktonic PP to water column CR
and compared it to FCO2 to test if in situ net heterotrophy was sufficient to
sustain the emissions of CO2 to the atmosphere (Fig. 15), or if
alternatively fluvial CO2 had a lateral origin (soils or wetlands). A
detailed description of spatial and seasonal variations in PP as well as
main phytoplankton communities is given by Descy et al. (2017). In brief,
phytoplankton biomass was mainly confined to the main stem and was low in
most tributaries. The PP values in the Congo River ranged between 0.0 and
57.5 mmol m-2 d-1 and were higher than previously reported in
tropical river channels, whereas in other tropical rivers phytoplankton
production mainly occurred in the floodplain lakes. This is due to generally
lower TSM values in the Congo and to its relative shallowness that allows
net phytoplankton growth in the mainstream unlike other deeper and more
turbid tropical rivers such as the Amazon. Measured CR was lower than PP 3 out of 49 times, and on average the PP : CR ratio was 0.28. Volumetric rates of
CR ranged between 0.7 and 46.6 mmol m-3 d-1, while integrated
rates of CR ranged between 3.1 and 790.4 mmol m-2 d-1. CR was
unrelated to TSM, POC, NH4+ and Chl a but showed a positive
relation with DOC after binning the data (Fig. S10). The same pattern
emerged when using modeled PP, to extend the number of data points, with PP higher than CR
2 out of 169 times and a PP : CR ratio of 0.15 on average. This
indicates that a generalized and strongly net heterotrophic metabolism was
encountered in the sampled sites. Yet, in 174 out of 187 cases, FCO2 was
higher than CR, and in 162 out of 169 cases, FCO2 was higher than net
community production (NCP). CR averaged 81 mmol m-2 d-1, NCP
averaged -75 mmol m-2 d-1 and the corresponding average FCO2
was 740 mmol m-2 d-1. The FCO2 : CR ratio was higher in lower-order streams than in higher-order streams, with median values ranging between
21 and 139 in stream orders 2–5 and between 3 and 17 in stream orders 6–10
(Fig. 16). This indicates a prevalence of lateral CO2 inputs either
from soil-water or riparian wetlands in sustaining FCO2 in lower-order
streams over higher-order streams where in-stream CO2 production from
net heterotrophy is more important. These patterns are in general agreement
with the conceptual framework developed by Hotchkiss et al. (2015), although
lateral CO2 inputs were exclusively attributed by these authors to
soil-water or ground-water inputs and riparian wetlands were not considered.
These patterns are also in agreement with the results reported by Ward et
al. (2018), who show that in large high-order rivers of the lower Amazon,
in-stream production of CO2 from respiration is sufficient to sustain
CO2 emissions to the atmosphere.
Ratio of air–water CO2 fluxes (FCO2 in mmol m-2 d-1) and community respiration (mmol m-2 d-1) as a function
of Strahler stream order for rivers and streams of the Congo River network.
The box represents the first and third quartile, the horizontal line corresponds
to the median, the cross corresponds to the average, the error bars correspond to the
maximum and minimum, and the symbols show all data points. Inset shows on a log
scale the median of FCO2 : CR and an exponential fit (r2=0.88).
CR was estimated from measurements of O2 concentration decrease in
bottles that were not rotated, and this has been shown to lead to an
underestimation of CR up to a factor of 2 (Richardson et al., 2013; Ward
et al., 2018). The underestimation of our CR measurements due to the absence
of rotation is most likely not as severe as in the Richardson et al. (2013)
and Ward et al. (2018) studies, as the organic matter in our samples was
mostly in dissolved form (median DOC of 8.6 mg L-1), with a low
particulate load (median TSM of 14 mg L-1 and POC of 1.3 mg L-1),
while the median of TSM at the sites studied by Ward et al. (2018) in the
Amazon was higher (28.5 mg L-1 based on data reported by Ward et al., 2015). We acknowledge that our CR measurements might be underestimated due
to bottle effects and lack of rotation up to a factor of 2 based on the
studies of Richardson et al. (2013) and Ward et al. (2018); nevertheless, it
seems unrealistic to envisage an underestimation of CR by a factor of 10 that
would allow reconciling the CR (and NCP) estimates with those of
FCO2. Although we did not measure sediment respiration, the average
value reported by Cardoso et al. (2014) of 21 mmol m-2 d-1 for
tropical rivers and streams does not allow accounting for the imbalance
between FCO2 and NCP. This then suggests that the emission of CO2
from the Congo lowland river network is to a large extent sustained by
lateral inputs rather than by in-stream production of CO2 by net
heterotrophy. It remains to be determined to what extent this lateral input
of CO2 is sustained by riparian wetlands or soil-groundwater from
terra firme.
The low PP : CR ratio of 0.15 to 0.28 on average, and generally low PP values
(on average 12 mmol m-2 d-1) were also reflected in the low
diurnal variations in pCO2. We did not carry out dedicated 24 h cycles
to look at the day–night variability of pCO2, due to lack of
opportunity given the important navigation time to cover large distances,
but we compared the data acquired at the anchoring site on shore (typically
around 17:00 universal time, UT, just before dusk) with the data on the
same spot the next day (typically around 04:30 UT, just after dawn) (Fig. S11). Unsurprisingly, water temperature measured just before dusk was
significantly higher than just after dawn (on average 0.5 ∘C
higher), while specific conductivity was not significantly different,
indicating that the same water mass was sampled at dusk and dawn (Fig. S11).
The pCO2 and O2 concentration measured just before dusk were not
significantly different than just after dawn, showing that daily variability
in these variables was low (Fig. S11). The difference between pCO2 at
dusk and dawn ranged between -2307 and 1186 ppm and averaged 39 ppm
(n=39). The wide range of values of the difference of pCO2 at dusk
and at dawn might reflect occasional small-scale variability of pCO2,
as the boat anchored for the night close to shore, frequently in
close proximity to riparian vegetation. Nevertheless, the average difference is
not of the expected sign (in the case of a strong diurnal change of
pCO2 due to PP and CR, pCO2 should have been lower at dusk than
dawn, so the difference should have been negative). This difference was also
very small compared to the overall range of spatial variations in pCO2
(1087 to 22 899 ppm). Day–night variations in pCO2 have been reported
in temperate headwater and low-order streams and in one lowland river with
an amplitude from ∼50 to ∼700 ppm (Lynch et
al., 2010; Dinsmore et al., 2013; Peter et al., 2014; Crawford et al., 2017;
Reiman and Xu, 2019), although daily signals of pCO2 were not
systematically observed and were absent for instance in streams covered by
forest canopy (Crawford et al., 2017). In a low turbidity and very shallow
low-order stream of the Tana River network, Tamooh et al. (2013) reported on
one occasion day–night variation in pCO2 with an amplitude of
∼400 ppm, and in the Zambezi river, during the dry season,
corresponding to very low TSM values (< 10 mg L-1), Teodoru et
al. (2015) reported day–night pCO2 variation in the range of 475 ppm.
In both cases, the day–night variations were also small compared to spatial
variations of 300 to 5204 ppm in the Tana and 300 to 14 004 ppm in the
Zambezi. In floodplain lakes of the Amazon, daily variations in pCO2
can be intense (with an amplitude up to ∼2000 ppm) during
cyanobacterial blooms (Abril et al., 2013; Amaral et al., 2018) but have not
been documented in the river channels of the Amazon. Our data show that in
nutrient-poor and light-limited lowland tropical rivers such as the Congo
River, where pelagic PP is low, day–night variations in pCO2 were
negligible compared to spatial variations in pCO2. We conclude that
accounting for day–night variations in pCO2 should not lead to a
dramatic revision of global CO2 emissions, unlike the recent claim
based on data from a lowland temperate river by Reiman and Xu (2019), given
that tropical rivers account for 80 % of CO2 emissions (Raymond et
al., 2013; Borges et al., 2015a, b; Lauerwald et al., 2015).
Drivers of CO2 dynamics – stable isotope
composition of DIC
The stable isotope composition of DIC can provide information on the origin
of CO2, although the signal depends on the combination of the
biological processes that remove or add CO2 to the water column (CR and
PP), rock weathering that adds HCO3-, and outgassing, which removes
CO2 that is 13C-depleted relative to HCO3-. The variable
contribution to DIC in time and in space of CO2 relative to
HCO3- complicates the interpretation of δ13C-DIC
data. The stable isotope composition of DIC due to rock weathering will
depend on the type of rock (silicate or carbonate) and on the origin of the
CO2 involved in rock dissolution (either CO2 from the atmosphere
or from respiration of soil organic matter). The stable isotopic composition
of DIC due to the degradation of organic matter will depend in part on
whether the organic matter is derived from terrestrial vegetation following
the C3 photosynthetic pathway (woody plants and trees, temperate
grasses; δ13C∼-27 ‰)
compared to the less fractionating C4 photosynthetic pathway (largely
tropical and subtropical grasses; δ13C∼-13 ‰) (Hedges et al., 1986; Bird et al., 1994). Spatial
and temporal changes of δ13C are related to the change of the
relative abundance of HCO3- over CO2. The degassing of
CO2 to the atmosphere and the addition of HCO3- from rock
weathering lead to δ13C-DIC values becoming dominated by those
related to HCO3-. Since CO2 is isotopically depleted relative
to HCO3-, CO2 degassing leads to a gradual enrichment of the
remaining DIC pool (e.g., Doctor et al., 2008; Deirmendjian and Abril, 2018).
The combination of these processes can lead to spatial changes of δ13C-DIC that covary with CO2 and HCO3- concentrations.
For instance, in the Tana River network, an altitudinal gradient of δ13C-DIC was attributed to a downstream accumulation of HCO3-
due to rock weathering combined to CO2 degassing (Bouillon et al., 2009;
Tamooh et al., 2003). Figure 17 shows δ13C-DIC as a function of
the TA : DIC ratio in the rivers and streams of the Congo, with a general
increase in δ13C-DIC from TA : DIC = 0 (all of the DIC is in the
form of CO2) towards TA : DIC = 1 (nearly all of the DIC is in the form
of HCO3-). This pattern reflects the mixing of two distinct types
of rivers and streams: the lowland systems draining the CCC with low rock
weathering due to dominance of deep organic soils (low HCO3-) and
high CO2 from respiration leading to TA : DIC close to 0 with low δ13C-DIC and the systems draining highland regions (Lualaba and
Kasaï) with high rock weathering and lower generation of CO2 from
respiration and/or higher CO2 degassing leading to TA : DIC close to 1
with high δ13C-DIC. The plots of TA:Na+ and
Mg2+:Na+ versus Ca2+:Na+ (Fig. 18) showed aggregation of
data close to what would be expected for silicate rock weathering based on
the average values proposed by Gaillardet et al. (1999). This is in
agreement with the dominance of silicate rocks over carbonate rocks in the
Congo basin (Nkounkou and Probst, 1987). Note that TA values from the Congo
are generally very low compared to other large rivers globally (Meybeck,
1987), due to the large proportion of relatively insoluble rocks on the
catchment (70 % of metamorphic rocks) and a small proportion of low
soluble rocks such as siliciclastic sedimentary rocks (10 % mainly as sand
stone), unconsolidated sediments (17 % as sand and clays) and a very
small proportion of highly soluble volcanic rocks (1 %). The high TA values
in the Lualaba are due to a larger proportion of volcanic rocks in high-altitude areas, such as the Virunga region, which is rich in volcanic rocks
(including basalts) and has been shown to be a hotspot of chemical
weathering (Balagizi et al., 2015).
Carbon stable isotope composition of dissolved inorganic carbon
(DIC) (δ13C-DIC in ‰) as a function of the
total alkalinity (TA) to DIC ratio (µmol : µmol) and as a function
of the partial pressure of CO2 (pCO2 in ppm) for a TA:DIC ratio
equal to zero in surface waters of rivers and streams of the Congo River
network. Open dots indicate individual data points, full dots indicate
binned averages (± stand deviation) (bins < 5000,
5000–10 000 and > 10 000 ppm). Horizontal dotted lines indicate
the δ13C values of atmospheric CO2 and of average soil
organic carbon stable isotope composition with a dominance of C4
(-15.5±0.8 ‰) and C3 plants (-28.4±0.7 ‰) (Bird and Pousai, 1997). Dotted red line provides
polynomial fit (δ13C-DIC =-22.5+21.37× TA : DIC -6.97× (TA : DIC)2, r2=0.76).
Total alkalinity (TA) and Mg2+ as a function of Ca2+ of
the surface waters of rivers and streams of the Congo River network, in
Na+ normalized plots (µmol : µmol) showing the composition
fields for rivers draining different lithologies from a global compilation
of the 60 largest rivers in the world (Gaillardet et al., 1999).
At TA : DIC = 0, the δ13C-DIC values are exclusively related to
those of CO2 and might be indicative of the source of mineralized
organic matter. The δ13C-DIC values ranged between -28.2 ‰ and
-15.9 ‰ and averaged -24.1 ‰ (Fig. 17) indicating that CO2 was produced from the degradation of mixture of
organic matter from C3 and C4 origin. Furthermore, δ13C-DIC was positively related to pCO2 (Fig. 17), indicating that
in the streams with high pCO2 values, the CO2 was generated from
the degradation organic matter with a higher contribution from C4
plants. The δ13C-DIC values were unrelated to the contribution
of C4 vegetation on the catchment (terra firme), as modeled by Still and Powell (2010), and the cover by savannah on the catchment given by GLC2009 (Fig. S12). Further, the most enriched δ13C-DIC values (> -21 ‰), corresponded on average to a low contribution
of C4 vegetation on the catchment (7.4 %) and low contribution of
savannah cover on the catchment (0.8 %). These patterns are inconsistent
with an origin from terra firme of the C4 material that led to high pCO2 in
streams (Fig. 17) but is rather more consistent with a larger contribution
of degradation of C4 aquatic macrophyte material in high CO2
streams.
Seasonal variations
The difference between the HW and FW in the main stem along the
Kisangani–Kinshasa transects (Figs. 3 and 4) were relatively modest with
higher specific conductivity, TA, δ13C-DIC, and TSM (at
Kisangani); biogeochemical signatures of higher surface run-off during the
HW sampling (December 2013); and water flows from deeper soil horizons (or
ground-water) during the FW sampling (June 2014). The comparison of
tributaries that were sampled during both HW and FW periods along the
Kisangani–Kinshasa transects shows that pCO2 was significantly higher
(Wilcoxon match-pairs signed rank test p=0.078) during HW for large
systems (freshwater discharge ≥300 m3 s-1, Table S1) but not
significantly different for small systems (freshwater discharge < 300 m3 s-1), irrespective of whether it was from the left or right bank (Fig. 19).
However, no significant differences among the HW and FW periods occurred in
%O2, CH4 and %N2O for either small of large systems,
irrespective of whether they were taken from the left or right bank (Fig. 19). This indicates that
across the basin, spatial differences among tributaries are more important
than seasonal variations within a given tributary. The average difference
for large rivers between HW and FW was on average only 1745 ppm for
pCO2 when the respective range of variation for the whole dataset was
from 1087 to 22 899 ppm.
Comparison of the partial pressure of CO2 (pCO2 in
ppm), dissolved CH4 concentration (nmol L-1), dissolved O2
saturation level (%O2 in %), and dissolved N2O saturation level
(%N2O in %) in surface waters of the Congo River tributaries
sampled during both high water (3–19 December 2013) and falling water
periods (10–30 June 2014). Tributaries were separated into left and right
bank, as well as into large and small systems, with a freshwater discharge
(Q) <and ≥300 m3 s-1, respectively.
Yearly cycles of CH4 and N2O were established on the Lualaba (6 years), the Oubangui (2 years) and the Kasaï (2 years) (Figs. 20 and 21),
while pCO2 is only available during 2 years in the Lualaba. In the
Oubangui and the Kasaï, CH4 concentration peaked with the onset of
rising water and decreased as water level continued to increase. The
decrease in CH4 as discharge peaked in the Oubangui and the Kasaï
is most probably related to dilution by surface runoff, as also testified by
the decrease in specific conductivity and TA (not shown). The increase at
the onset of rising water could be related to initial flushing of soil
atmosphere enriched in CH4 as rain penetrates superficial layers of
soils. In the Lualaba the CH4 seasonal variations seem to follow more
closely those of freshwater discharge (for instance in 2014). Unlike the
Kasaï and the Oubangui, the Lualaba has very extensive permanent
marshes and swamps such as the Upemba wetland system (inundated area of
18 000 km2) and the Luama swamps (inundated area of 6000 km2)
(Hughes and Hughes, 1992). Yet, it remains to be determined if the
seasonality of CH4 observed in Lualaba can be attributed to higher
inputs during high water from these major wetlands located, respectively,
1000 and 600 km upstream of Kisangani. Even so, there are numerous more
modest marshes and swamps that border upstream tributaries of the Lualaba
closer to Kisangani (Hughes and Hughes, 1992). The seasonal amplitude of
dissolved CH4 in the Oubangui was about 10 times higher than in the
Kasaï and the Oubangui, and the seasonal amplitude of CH4 in these
three rivers seemed to be related to the relative seasonal amplitude of
freshwater discharge, as indicated by the positive relation with the ratio of
maximum and minimum of freshwater discharge (Fig. 22).
Time series of dissolved CH4 concentration (nmol L-1)
in surface waters and freshwater discharge (grey line) in the Congo
(at Kisangani, 2013–2018), the Oubangui (at Bangui, 2010–2012) and the
Kasaï (at Dima, 2015–2017) rivers. The black line shows a five sample running
average. Time series of the partial pressure of CO2 (pCO2 in ppm)
in surface waters was also obtained in the Congo River (at Kisangani,
2017–2018). Data in the Oubangui were previously reported by Bouillon et al. (2012, 2013).
The seasonal cycles of %N2O show patterns that were consistent with
those CH4, with a loose parallelism of %N2O and discharge in
the Lualaba, an inverse relation in the Kasaï, and peak of %N2O
during rising waters (although delayed with respect to the CH4 peak) in
the Oubangui. In addition to the seasonal cycle there seemed to be a longer-term decrease in the annual average of N2O in the Lualaba (Fig. S13).
There were no significant long-term changes of the annual average of other
variables such as POC and PN (not shown). So the observed decrease in annual
N2O is probably unrelated to changes in terrestrial productivity (Zhou
et al., 2014) or nitrogen content of terrestrial vegetation (Craine et al., 2018) that act at longer timescales (several decades) and seem to be
related to long-term changes in climate (precipitation). Freshwater
discharge showed an increasing pattern during the time period (Fig. S13). An
increasing discharge could lead to increased gas transfer velocities and a
loss of N2O to the atmosphere. Water temperature in the Congo River is
already close to the optimum of denitrification (∼27∘C, Canion et al., 2014), so an enhancement of denitrification
with increase in temperature is unlikely. Water temperature did not show a
clear pattern, but freshwater discharge increased during the 2013–2018
period, excluding the year 2017. It is likely that the decreasing trend in
N2O during the 2013–2018 period is a transient feature in response to
inter-annual fluctuations in hydrology that led to a period of sustained
increase in freshwater discharge.
Time series of dissolved N2O saturation level (%N2O
in %) in surface waters and freshwater discharge (grey line) in the Congo
(at Kisangani, 2013–2018), the Oubangui (at Bangui, 2010–2012) and
the Kasaï (at Dima, 2015–2017) rivers. The black line shows a five sample
running average. Data in the Oubangui were previously reported by Bouillon
et al. (2012, 2013).
Seasonal amplitude of dissolved CH4 concentration (ΔCH4 in nmol L-1) in surface waters as a function of the ratio of
seasonal maximum and minimum of freshwater discharge (Qmax:Qmin) in the
Congo (at Kisangani, 2013–2018), the Oubangui (at Bangui, 2010–2012)
and the Kasaï (at Dima, 2015–2017) rivers (Fig. 20).
The pCO2 time series in the Lualaba at Kisangani is shorter than for
CH4, but a general positive relationship between pCO2 and
discharge was observed (Fig. S14). A similar positive relationship between
pCO2 and discharge was also observed in the Oubangui (Bouillon et al., 2012) and the Madeira River (Almeida et al., 2017), as well in several rivers
in the Amazon (Richey et al., 2002) based on pCO2 calculated from pH and
TA. Such pCO2 discharge patterns were interpreted as resulting from
higher connectivity during high water between the river main stem and the
floodplains and wetlands. In large temperate rivers, a negative relationship
between pCO2 and discharge was observed in the Meuse (Borges et al., 2018) and in more than half of the US rivers analyzed by Liu and Raymond (2018). The difference in the relationship of pCO2 versus discharge
between tropical and temperate large rivers might be related to lower
interactions between river and floodplains in temperate rivers, particularly
in highly human-impacted and channelized rivers such as the Meuse. This is
in agreement with the analysis of Aho and Raymond (2019), who reported, in
the Salmon River network, positive relationships between pCO2 and flow
in water watersheds with a high presence of wetlands and negative
relationships between pCO2 and flow in watersheds with low presence of
wetlands. Also, in temperate rivers, temperature covaries strongly with
discharge in temperate rivers, so that the warmer months that promote
biological production of CO2 are also characterized by lower discharge
(Borges et al., 2018).
The seasonal amplitude of CH4 (∼50 nmol L-1 in the
Kasaï and the Congo, versus 200–400 nmol L-1 in the Oubangui) and
%N2O (20 %–90 % in the 3 rivers) was overall much lower than the
spatial gradients across the basin of 22 and 71 428 nmol L-1 for
CH4 and 0 and 561 % for N2O.
Variability of GHG fluxes in the Congo river network
Since pCO2 and CH4 and N2O concentrations followed distinct
patterns as a function of Strahler stream order (Fig. 11) we used
k600 and stream surface area as a function of Strahler stream order
(Fig. S15) to compute the air–water GHG fluxes and to integrate them at
basin scale. This was done separating data for streams draining and not
draining the CCC since pCO2 and CH4 and N2O patterns were
very different (Figs. 11 and 12). The stream surface area decreased
regularly with increasing Strahler stream order but showed a large increase
for Strahler stream order 9 (Fig. S15). The latter mainly corresponds to the
Congo main stem that downstream of Kisangani is characterized by anastomosing
river channels with extended sand bars and numerous islands (Runge, 2008;
O'Loughlin et al., 2013). In particular along the about 500 km
long section between the Mbandaka and Kwa mouths, the main stem river channel undergoes a
general expansion and width increases from ∼4 to
∼10 km. This corresponds to the area of CCC depression with a
corresponding decrease in the slope from 6 to 3 cm km-1 (O'Loughlin et
al., 2013). The calculated k600 decreased regularly with increasing
Strahler stream order, as previously reported (Butman and Raymond, 2011;
Raymond et al., 2012; Deirmendjian and Abril, 2018; Liu and Raymond, 2018), due
to higher turbulence in low-order streams associated with higher stream flow
due to steeper slopes. HydroSHEDS stream order classification is missing at
least 1 stream order because small streams are not correctly represented
(Benstead and Leigh, 2012; Raymond et al., 2013). Hence, to correct this bias,
we added 1 to stream orders determined by HydroSHEDS, meaning that the
lowest stream order to which GHG were attributed was 2. We then extrapolated
pCO2 and CH4 and N2O concentrations to stream order 1,
separating streams draining and not draining the CCC, using a linear
regression with higher orders or by using the same value as for order 2
(Fig. S16).
An error analysis on the GHG flux computation and upscaling was carried out
by error propagation of the GHG concentration measurements, the k value
estimates and the estimate of surface areas of river channels to scale the
areal fluxes, using a Monte Carlo simulation with 1000 iterations. The
uncertainty in the GHG concentrations led to an uncertainty of areal fluxes
of ±1.2 %, ±2.3 % and ±7.1 % for CO2,
CH4 and N2O, respectively. The uncertainty in k derived from tracer
experiments is typically ±30.0 % (Ulseth et al., 2019). This leads
to a cumulated uncertainty of areal fluxes of ±17.6 %, ±17.9 % and ±19.0 % for CO2, CH4 and N2O,
respectively. The uncertainty of the river and stream surface areas based on GIS
analysis of Allen and Pavelsky (2018) is estimated to ±10 %
leading to an overall uncertainty of integrated fluxes of ±18.3 %,
±18.3 % and ±19.6 % for CO2, CH4 and N2O,
respectively.
The calculated FCO2 ranged between 86 and 7110 mmol m-2 d-1,
averaging 2469±435 mmol m-2 d-1 (weighted by surface area
of Strahler stream order), encompassing the range FCO2 reported by Mann
et al. (2014) (312 to 1429 mmol m-2 d-1) in 25 sites during a
single period (November 2010) from four major river basins in the Republic
of the Congo (Alima, Lefini, Sangha, Likouala-Mossaka). The pCO2 values
ranged between 1087 and 22 899 ppm, also encompassing the values reported
by Mann et al. (2014) (2600 to 15 802 ppm) that were not measured directly
but computed from pH and DIC measurements, although pH measurements in
black-water rivers can be biased by the presence of humic-dissolved organic
matter (Abril et al., 2015) and the addition of HgCl2 seems to alter
the CO2 content of samples (Fig. S1). The calculated FCH4 ranged
between 65 and 597 260 µmol m-2 d-1, averaging
12553±2247µmol m-2 d-1 (weighted by surface area
of Strahler order), encompassing the range FCH4 reported by
Upstill-Goddard et al. (2017) (33 to 48 705 µmol m-2 d-1)
in 41 sites draining the Congo basin in the Republic of the Congo (November 2010
and August 2011) in the same four river basins sampled by Mann et al. (2014). The CH4 values ranged between 22 and 71 428 nmol L-1, also
encompassing the values reported by Upstill-Goddard et al. (2017) (11 to
9553 nmol L-1). The calculated FN2O ranged between -52 and 319 µmol m-2 d-1, averaging 22±4µmol m-2 d-1 (weighted by surface area of Strahler order), encompassing the
range FN2O reported by Upstill-Goddard et al. (2017) (-19 to 67 µmol m-2 d-1). The %N2O values ranged between 0 % and 561 %, also encompassing the values reported by Upstill-Goddard et al. (2017)
(6 % to 266 %). The wider ranges of GHGs and respective fluxes we report
compared to those of Mann et al. (2014) and Upstill-Goddard et al. (2017)
reflect the larger number of river systems sampled over a wider geographical
area (n=25 versus n=278 for pCO2 and n=41 versus n=367 for CH4 and N2O),
hence, representing a wider range of river types, morphologies, catchment
characteristics and wetland densities.
Information on the seasonal variability of concurrent FCO2, FCH4 and
FN2O values was only available in the Lualaba (at Kisangani), where the
three GHGs were measured simultaneously (Fig. S17). FCO2, FCH4 and
FN2O were loosely positively correlated with freshwater discharge, as
the seasonal variations in k600 were small (ranging between 23.4 and
30.3 cm h-1), and although pCO2 was correlated to freshwater
discharge (Fig. S14) this was not the case for CH4 and N2O
concentrations (Figs. 20 and 21). The range of seasonal variations at
Kisangani of FCO2 (234 and 948 mmol m-2 d-1), FCH4 (116
and 876 µmol m-2 d-1) and FN2O (-2 and 40 µmol m-2 d-1) was small compared to the range of spatial variations in
FCO2 (86 and 7,110 mmol m-2 d-1), FCH4 (65 and 597 260 µmol m-2 d-1) and FN2O (-52 and 319 µmol m-2 d-1).
Significance of integrated GHG fluxes at basin and global scales
The FCO2 and FCH4 decreased with increasing Strahler order, as given
by surface area, and also when integrated by surface area of the streams
(Table 1). Strahler orders 1-2 accounted for nearly 80 % of the integrated
FCO2 (79.6 %) and FCH4 (77.0 %), while Strahler orders 1–4
accounted for > 90 % of the integrated FCO2 (90.7 %) and
FCH4 (91.9 %). Strahler orders 5–10 only accounted for 9.3 % of
integrated FCO2 and 8.1 % of integrated FCH4. The rivers draining
the CCC contributed to 6 % of the basin-wide emissions for CO2 and
22 % for CH4, although the contribution in stream surface area was
only 11 %. The low contribution of FCO2 from the CCC to the basin-wide
emissions was due to the lower k600 values, although pCO2 values
were higher than the rest of the basin (Table 1). In the case of
FCH4, the much higher CH4 concentrations in the CCC overcome the
lower k600 values. FN2O per surface area in rivers and streams
outside the CCC were relatively similar for Strahler orders 10 to 3 and
increased for Strahler orders 1 and 2 (Table 1). FN2O per surface area
in rivers and streams draining the CCC steadily decreased from Strahler
order 8 to 1, with rivers of orders 5, 3, 2 and 1 acting as sinks for
N2O. Consequently, the relative contribution per Strahler order of
integrated FN2O was less skewed than for integrated FCO2 and
FCH4. Strahler orders 1–4 contributed 69.9 % of integrated FN2O
compared to > 90 % for FCO2 and FCH4.
Partial pressure of CO2 (pCO2 in ppm); dissolved CH4
concentration (nmol L-1); dissolved N2O saturation level
(%N2O in %); gas transfer velocity (k600 in cm h-1);
air–water fluxes of CO2 (FCO2 in mmol m-2 d-1 and in TgC yr-1), CH4 (FCH4 in µmol m-2 d-1 and in
TgCH4 yr-1), and N2O (FN2O in µmol m-2 d-1 and in GgN2O-N yr-1); stream surface area (S.A. in
km2); and as a function of Strahler stream order (S.O.) in the Congo River
network for rivers and streams draining and not draining the Cuvette
Centrale Congolaise. Values in italic were extrapolated to stream order 1, using a linear regression with higher orders or by using the same value as for stream order 2 (Fig. S16).
S.O.pCO2CH4N2O%N2Ok600Temp.FCO2FCH4FN2OS.A.FCO2FCH4FN2Oppmnmol L-1nmol L-1%cm h-1∘Cmmol m2 d-1µmol m2 d-1µmol m2 d-1km2TgC yr-1TgCH4 yr-1GgN2O-N yr-1Draining the Cuvette Centrale Congolaise 112 30483490.57.326.427.0289261 732-43.13504.40.126-0.154212 3048,3492.744.116.127.0176637 747-15.93352.60.074-0.054311 92374114.977.513.026.1137625 765-5.23242.00.049-0.017412 06594096.5104.512.326.7132333 4310.92911.70.0570.003513 70595332.032.212.527.0152533 255-14.82781.90.054-0.0426783053213.2214.712.227.5834185524.74801.80.0050.1217664350311.3188.811.727.5670158218.21630.50.0020.0308697740112.9219.813.628.7824158128.63661.30.0030.107Not draining the Cuvette Centrale Congolaise 110 71915849.4136.6161.624.115 41766 695107.22235150.90.8712.4492892112759.4135.856.524.1445019 17136.4214341.80.2400.7983722511859.3133.431.124.01972955418.9188316.30.1050.364457667268.5126.321.524.31065409810.117528.20.0420.181541105388.6131.417.225.558924529.616884.40.0240.165619292999.3143.416.825.6239132812.917721.90.0140.233726672209.3153.616.327.5343103015.421683.30.0130.340830102266.7109.212.927.73108372.116962.30.0080.036925211708.7145.710.927.72175338.846394.40.0140.419103445339.4153.120.427.757417819.26461.60.0010.127Total2511.75.1
The rivers and streams draining the CCC were a very small sink of
atmospheric N2O (-0.01 GgN2O-N yr-1) while the rivers and
streams outside the CCC were a source of N2O (5.1 GgN2O-N yr-1). The integrated FN2O for the Congo River network was
5.1±1.0 GgN2O-N yr-1 corresponded to 14 %–17 % of total
riverine emissions of N2O reported by Hu et al. (2016). Note that the
N2O riverine emissions computed by Hu et al. (2016) were indirectly
computed from data on global nitrogen deposition on catchments and on
emission factors rather than derived from direct measurements of dissolved
N2O concentrations. The estimates given by Hu et al. (2016) are more
conservative than older estimates (e.g., Kroeze et al., 2010) because they are
based on revised emission factors and converge with a similar more recent
study by Maavara et al. (2018). Our estimate of the integrated FN2O is
consistent with the range of N2O emissions of 3.8 to 4.3 GgN2O-N yr-1 given by Maavara et al. (2018) for the Congo river network, also
based on an indirect calculation based on nitrogen deposition and emission
factors.
The integrated FCH4 for the Congo River network of 1.7±0.3 TgCH4 yr-1 is nearly 2 times higher than the estimate given by
Bastviken et al. (2011) for all tropical rivers and corresponds to 6 % of
the global emission of CH4 from rivers given by Stanley et al. (2016),
while the surface area of the Congo River network corresponds to a lower
proportion (3 %) of the global riverine surface area (773 000 km2,
Allen and Pavelsky). Note that the meta-analysis of Stanley et al. (2016)
includes part of our dataset from the Congo River, as published by Borges et
al. (2015a). The integrated FCH4 we report for the Congo River network
is also more than 3 times higher than the estimate of CH4 emissions
for Amazonian large rivers reported by Sawakuchi et al. (2014) (0.49 TgCH4 yr-1). The integrated FCH4 we report for the Congo River
network corresponds to 7 % of the emission from the Congo wetlands
inferred from remotely sensed atmospheric CH4 data (Bloom et al., 2010)
(25.7 TgCH4 yr-1). However, the top-down estimate given by Bloom
et al. (2011) includes the CH4 emission from all ecosystems over the
Congo basin and should also include the fluvial emissions. Note that the
CH4 emissions we report for the Congo River basin only include the
diffusive flux component, when the ebullitive CH4 emission component
represents the majority of CH4 emissions from inland waters (Bastviken
et al., 2011), which would be consistent with the gap between our emission
estimates and those from atmospheric CH4 inventories. Finally, note
that the CH4 emissions were only calculated and integrated for the
rivers and streams draining the CCC but not for the actual wetland flooded
area of the CCC. The emission of CH4 from actual wetland flooded area
of the CCC can be estimated to a massive 51 TgCH4 yr-1 by
extrapolating the area averaged FCH4 from the streams (24 468 µmol m-2 d-1, Table 1) to the flooded extent (360 000 km2,
Bwangoy et al., 2010). This corresponds to about 29 % of the CH4
emissions from natural wetlands (∼180 TgCH4 yr-1,
Saunois et al., 2010) and would in this case be higher than the estimate of
CH4 emissions from the Congo wetlands inferred from remotely sensed
atmospheric CH4 data (Bloom et al., 2010).
The integrated FCO2 for the Congo River network is 251±46 TgC yr-1 and is equivalent to the CO2 emission value for rivers
globally given by Cole et al. (2007) and to 14 % and 39 % of the
CO2 emission value for rivers globally given by Raymond et al. (2013)
(18 000 TgC yr-1) and Lauerwald et al. (2015) (650 TgC yr-1),
respectively. The integrated CO2 emission from the Congo River network
corresponds to 44 % of the CO2 emissions from tropical (24∘ N–24∘ S) oceans globally (565 TgC yr-1) and 183 % of
CO2 emissions from the tropical Atlantic Ocean (137 TgC yr-1),
based on the Takahashi et al. (2002) FCO2 climatology. The terrestrial
net ecosystem exchange (NEE) of the watershed of the Congo River can be
estimated based on the NEE estimate of 23 gC m-2 d-1 for savannahs
given by Ciais et al. (2011) and of 20 gC m-2 d-1 for forests
given by Fisher et al. (2013) and based on the respective land cover from
GLC2009 (30 % savannah and 70 % forest). The corresponding terrestrial
NEE of 77 TgC yr-1 is more than 3 times lower than the riverine
CO2 emission from the Congo River. This is extremely surprising since
the hydrological export from terra firme forests of DOC and DIC that are assumed to
sustain fluvial emissions are typically 2 %–3 % compared to terrestrial NEE
(Kindler et al., 2011; Deirmendjian et al., 2018). Hydrological carbon export
is higher compared to NEE in European grasslands (on average 22 %)
(Kindler et al., 2011). We ignore if this is transposable to tropical
grasslands, such as savannahs, although they only occupy 30 % of the Congo
catchment surface. Accordingly, the CO2 emission from the Congo River
network should have been an order of magnitude lower than the estimates of
terrestrial NEE from terra firme biomes rather than more than 3 times higher.
However, in wetlands such as peatlands in Europe, the hydrological export of
DOC and DIC represent 109 % of NEE and is enough to sustain the riverine
CO2 emission that represents 17 % of NEE (Billett et al., 2004).
Indeed, the carbon export from flooded forests to riverine waters of the
Congo basin can be roughly estimated to 396 TgC yr-1 and is in excess
of the integrated FCO2 (calculated from the export per surface area of
flooded forest of 1100 gC m-2 yr-1 reported by Abril et al., 2014, for the central Amazon and surface area of flooded forest of the
CCC, 360 000 km-2, Bwangoy et al., 2010). Altogether, this would then
strongly suggest that the CO2 emission from the lowland Congo River
network is to a large extent sustained by another source of carbon than from
the terrestrial terra firme biome. The most likely alternative source would be wetlands
(flooded forest and aquatic macrophytes), in agreement with the analysis in
the central Amazon River by Abril et al. (2013).
Conclusions
Net heterotrophy in rivers and lakes sustained by inputs of organic matter
from the terrestrial vegetation on the catchments is the prevailing paradigm
to explain oversaturation of CO2 in inland surface waters and
corresponding emissions to the atmosphere, based on process studies, the
earliest in the Amazon (Wissmar et al., 1981) and boreal systems (Del Giorgio
et al., 1999; Prairie et al., 2002), and then generalized at global scales for
lakes (Cole et al., 1994) and rivers (Cole and Caraco, 2001). Yet, the
comparison of 169 measurements of aquatic NCP and FCO2 estimates in the
central Congo River network covering a wide range of size and type of rivers
and streams shows that the aquatic NCP cannot account for fluvial
FCO2. This implies that lateral inputs of CO2 sustain a large part
of the CO2 emissions from rivers and streams in the Congo River
network.
The comparison of the integrated CO2 emission from the Congo River
network with terrestrial terra firme NEE shows that it unlikely that fluvial CO2
emissions are sustained by lateral hydrological transfer of carbon from
terra firme. Indeed, integrated FCO2 from the river network was more than 3 times higher than terrestrial NEE, when forests typically only export a very
small fraction of NEE as carbon to rivers that can sustain fluvial CO2
emissions. It is then likely that the fluvial CO2 emissions from the
central Congo River are sustained by organic matter inputs as well as direct
CO2 inputs from extensive riparian wetlands (flooded forest and aquatic
floating macrophytes). This is consistent with the stable isotopic signature
of DIC, the differences in the spatial distribution of dissolved CO2,
%O2 and CH4 between rivers and streams draining or not
draining the CCC, a large wetland region in the core of the basin, and based
on the correlation between pCO2 levels and the cover of flooded forest
in the catchment. Indeed, the calculated export of carbon from the CCC to
the riverine network is sufficient to sustain the fluvial CO2
emission from the Congo.
The fact that fluvial CO2 emissions in lowland rivers are to a large
extent sustained by carbon inputs from wetlands in addition to those from
terra firme has consequences for the conceptualization of statistical and mechanistic
models of carbon cycling in river networks. While progress has been made in
integrating wetland connectivity in mechanistic regional models (Lauerwald
et al., 2017), this has not been the case so far for statistical global
models that rely on terrestrial (terra firme) productivity (Lauerwald et al., 2015). The
comparison of the output of such a statistical model for the Congo River
with observational data (Fig. S18) shows that the model fails to represent
spatial gradients and the higher pCO2 values of streams
and rivers draining the CCC in particular. This illustrates how ignoring the river–wetland
connectivity can lead to the misrepresentation of pCO2 dynamics in
river networks, in particular tropical ones that account for the vast
majority (80 %) of global riverine CO2 emissions.
Data availability
Full dataset is available at https://zenodo.org/record/3413449 (Borges and Bouillon, 2019).
The supplement related to this article is available online at: https://doi.org/10.5194/bg-16-3801-2019-supplement.
Author contributions
AVB and SB conceived the study. AVB, FD, TL,
ET, ATS, TB, JB, CRT and SB collected field samples. AVB, FD, TL, CM, CRT,
JPD and SB made laboratory analysis. GHA and TL carried out GIS analysis. AVB
drafted the manuscript with substantial inputs from SB. All authors
contributed to the manuscript.
Competing interests
The authors declare that they have no conflict of interest.
Acknowledgements
We thank the Isotope
Hydrology Laboratory of IAEA for analyses of water stable isotope ratios,
which contribute to the Coordinated Research Project CRPF33021 (Application
and development of isotope techniques to evaluate human impacts on water
balance and nutrient dynamics of large river basins) implemented by the
IAEA, Jonathan Richir (University of Liège) for advice about the
statistical analysis, Sandro Petrovic and Marc-Vincent Commarieu (University
of Liège), Bruno Leporcq (UNamur) and Zita Kelemen (KU Leuven) for
analytical assistance, the Régie des Voies Fluviales (RVF, Kinshasa) for
providing water height data, and the two anonymous reviewers for their comments on the
previous version of the paper. Publication costs were partly covered by
European Geosciences Union as part of the 2018 Outstanding Reviewer Award to
Alberto V. Borges. Alberto V. Borges is a senior research associate at the FNRS.
Financial support
This research has been supported by the European Research
Council (grant no. 240002), the Fonds National de la Recherche
Scientifique (grant no. 14711103), the Belgian Federal Science
Policy (BELSPO, grant no. COBAFISH SD/AR/05A), the Research Foundation Flanders
(FWO-Vlaanderen), the Research Council of the KU Leuven and the Fonds
Leopold-III pour l'Exploration et Conservation de la Nature. The
Boyekoli-Ebale-Congo 2010 Expedition was funded by the Belgian Development
Cooperation, BELSPO and Belgian National Lottery.
Review statement
This paper was edited by Ji-Hyung Park and reviewed by two anonymous referees.
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