Carbon dioxide emissions to the atmosphere from inland waters-streams, rivers, lakes and reservoirs-are nearly equivalent to ocean and land sinks globally. Inland waters can be an important source of methane and nitrous oxide emissions as well, but emissions are poorly quantified, especially in Africa. Here we report dissolved carbon dioxide, methane and nitrous oxide concentrations from 12 rivers in sub-Saharan Africa, including seasonally resolved sampling at 39 sites, acquired between 2006 and 2014. Fluxes were calculated from published gas transfer velocities, and upscaled to the area of all sub-Saharan African rivers using available spatial data sets. Carbon dioxide-equivalent emissions from river channels alone were about 0.4 Pg carbon per year, equivalent to two-thirds of the overall net carbon land sink previously reported for Africa. Including emissions from wetlands of the Congo river increases the total carbon dioxide-equivalent greenhouse-gas emissions to about 0.9 Pg carbon per year, equivalent to about one quarter of the global ocean and terrestrial combined carbon sink. Riverine carbon dioxide and methane emissions increase with wetland extent and upland biomass. We therefore suggest that future changes in wetland and upland cover could strongly a ect greenhouse-gas emissions from African inland waters.C limate predictions necessitate a full and robust account of natural and anthropogenic greenhouse-gas (GHG) fluxes, especially for CO 2 (refs 1-3), CH 4 (ref. 4) and N 2 O (ref. 5), which together accounted for 94% of the anthropogenic global radiative forcing by well-mixed GHGs in 2011 relative to 1750 (ref. 6). Inland waters (streams, rivers, lakes and reservoirs) are increasingly recognized as important sources of GHGs to the atmosphere, with global CO 2 and CH 4 emissions estimated at 2.1 PgC yr −1 (ref.3) and 0.7 PgC yr −1 (CO 2 -equivalents; CO 2 e) (ref. 4) (1 Pg = 10 15 g), respectively. Considering that the oceanic and land carbon (C) sinks correspond to ∼1.5 and ∼2.0 PgC yr −1 (ref. 7), respectively, the GHG flux from inland waters is significant in the global C budget.In a recent global compilation of inland CO 2 data 3 , <20 data points (out of 6,708, that is, <0.3%) represented African inland waters (with the exception of South Africa, which has been densely sampled), even though they account for ∼12% of both global freshwater discharge 8 and riverine surface area 3 , and include some of the largest rivers and lakes in the world. Equally for the global CH 4 database, there is a strong under-representation of tropical inland waters, whereby a recent synthesis 4 resorted to extrapolating CH 4 fluxes from temperate rivers.The prevailing large uncertainty involved in GHG flux estimates for inland waters, essentially due to the paucity of available data, is coupled to a poor understanding of underlying processes, both of which preclude gauging of future fluxes in response to human pressures. In particular, there is a need to further understand the link between inland water GHG fluxes and ...

Iron-rich (ferruginous) ocean chemistry prevailed throughout most of Earth’s early history. Before the evolution and proliferation of oxygenic photosynthesis, biological production in the ferruginous oceans was likely driven by photoferrotrophic bacteria that oxidize ferrous iron {Fe(II)} to harness energy from sunlight, and fix inorganic carbon into biomass. Photoferrotrophs may thus have fuelled Earth’s early biosphere providing energy to drive microbial growth and evolution over billions of years. Yet, photoferrotrophic activity has remained largely elusive on the modern Earth, leaving models for early biological production untested and imperative ecological context for the evolution of life missing. Here, we show that an active community of pelagic photoferrotrophs comprises up to 30% of the total microbial community in illuminated ferruginous waters of Kabuno Bay (KB), East Africa (DR Congo). These photoferrotrophs produce oxidized iron {Fe(III)} and biomass, and support a diverse pelagic microbial community including heterotrophic Fe(III)-reducers, sulfate reducers, fermenters and methanogens. At modest light levels, rates of photoferrotrophy in KB exceed those predicted for early Earth primary production, and are sufficient to generate Earth’s largest sedimentary iron ore deposits. Fe cycling, however, is efficient, and complex microbial community interactions likely regulate Fe(III) and organic matter export from the photic zone.

• Large data-set of CO 2 , CH 4 , and N 2 O in the surface waters of the Meuse River We report a data-set of CO 2 , CH 4 , and N 2 O concentrations in the surface waters of the Meuse river network in Belgium, obtained during four surveys covering 50 stations (summer 2013 and late winter 2013, 2014 and 2015), from yearly cycles in four rivers of variable size and catchment land cover, and from 111 groundwater samples. Surface waters of the Meuse river network were over-saturated in CO 2 , CH 4 , N 2 O with respect to atmospheric equilibrium, acting as sources of these greenhouse gases to the atmosphere, although the dissolved gases also showed marked seasonal and spatial variations. Seasonal variations were related to changes in freshwater discharge following the hydrological cycle, with highest concentrations of CO 2 , CH 4 , N 2 O during low water owing to a longer water residence time and lower currents (i.e. lower gas transfer velocities), both contributing to the accumulation of gases in the water column, combined with higher temperatures favourable to microbial processes. Inter-annual differences of discharge also led to differences in CH 4 and N 2 O that were higher in years with prolonged low water periods. Spatial variations were mostly due to differences in land cover over the catchments, with systems dominated by agriculture (croplands and pastures) having higher CO 2 , CH 4 , N 2 O levels than forested systems. This seemed to be related to higher levels of dissolved and particulate organic matter, as well as dissolved inorganic nitrogen in agriculture dominated systems compared to forested ones. Groundwater had very low CH 4 concentrations in the shallow and unconfined aquifers (mostly fractured limestones) of the Contents lists available at ScienceDirectScience of the Total Environment j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / s c i t o t e n vMeuse basin, hence, should not contribute significantly to the high CH 4 levels in surface riverine waters. Owing to high dissolved concentrations, groundwater could potentially transfer important quantities of CO 2 and N 2 O to surface waters of the Meuse basin, although this hypothesis remains to be tested.

Abstract. 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±1.3 µmol L−1) and NO3- (5.6±5.1 µmol 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).

Some prokaryotes are known to be specialized in the use of phytoplankton-derived dissolved organic carbon (DOCp) originated by exudation or cell lysis; however, direct quantification measurements are extremely rare. Several studies have described bacterial selectivity based on DOCp quality, but very few have focused on the quantity of DOCp, and the relative importance of each of these variables (for example, quantity versus quality) on prokaryote responses. We applied an adapted version of the MAR-FISH (microautoradiography coupled with catalyzed reporter deposition fluorescence in situ hybridization) protocol using radiolabelled exudates from axenic algal cultures to calculate a specialization index (d') for large bacterioplankton phylogenetic groups using DOCp from different phytoplankton species and at different concentrations to elucidate to what extent the bacterial response to DOCp is driven by resource quantity (different DOCp concentrations) or by quality (DOCp from different phytoplankton species). All bacterial phylogenetic groups studied had lower d' at higher DOCp concentration, indicating more generalist behavior at higher resource availabilities. Indeed, at increasing resource concentrations, most bacterial groups incorporated DOCp indiscriminately, regardless of its origin (or quality). At low resource concentrations, only some specialists were able to actively incorporate the various types of organic matter effectively. The variability of bacterial responses to different treatments was systematically higher at varying concentrations than at varying DOCp types, suggesting that, at least for this range of concentrations (10-100 μM), DOCp quantity affects bacterial responses more than quality does. Therefore, resource quantity may be more relevant than resource quality in the bacterial responses to DOCp and affect how bacterioplankton use phytoplankton-derived carbon.

The impact of human activities on the concentrations and composition of dissolved organic matter (DOM) and particulate organic matter (POM) was investigated in the Walloon Region of the Meuse River basin (Belgium). Water samples were collected at different hydrological periods along a gradient of human disturbance (50 sampling sites ranging from 8.0 to 20,407 km 2 ) and during a 1.5 year monitoring of the Meuse River at the city of Liège. This dataset was completed by the characterization of the DOM pool in groundwaters. The composition of DOM and POM was investigated through elemental (C:N ratios), isotopic (d 13 C) and optical measurements including excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC). Land use was a major driver on fluvial OM composition at the regional scale of the Meuse Basin, the composition of both fluvial DOM and POM pools showing a shift toward a more microbial/algal and less plant/soil-derived character as human disturbance increased. The comparison of DOM composition between surface and groundwaters demonstrated that this pattern can be attributed in part to the transformation of terrestrial sources by agricultural practices that promote the decomposition of soil organic matter in agricultural lands and subsequent microbial inputs in terrestrial sources. In parallel, human land had contrasting effects on the autochthonous production of DOM and POM. While the in-stream generation of fresh DOM through biological activity was promoted in urban areas, summer autochthonous POM production was not influenced by land use. Finally, soil erosion by agricultural management practices favored the transfer of terrestrial organic matter via the particulate phase. Stable isotope data suggest that the hydrological transfer of terrestrial DOM and POM in humanimpacted catchment are not subject to the same controls, and that physical exchange between these two pools of organic matter is limited.

Nitrogen limitation during the Proterozoic has been inferred from the great expanse of ocean anoxia under low-O 2 atmospheres, which could have promoted NO 3 − reduction to N 2 and fixed N loss from the ocean. The deep oceans were Fe rich (ferruginous) during much of this time, yet the dynamics of N cycling under such conditions remain entirely conceptual, as analogue environments are rare today. Here we use incubation experiments to show that a modern ferruginous basin, Kabuno Bay in East Africa, supports high rates of NO 3 − reduction. Although 60% of this NO 3 − is reduced to N 2 through canonical denitrification, a large fraction (40%) is reduced to NH 4 + , leading to N retention rather than loss. We also find that NO 3 − reduction is Fe dependent, demonstrating that such reactions occur in natural ferruginous water columns. Numerical modelling of ferruginous upwelling systems, informed by our results from Kabuno Bay, demonstrates that NO 3 − reduction to NH 4 + could have enhanced biological production, fuelling sulfate reduction and the development of mid-water euxinia overlying ferruginous deep oceans. This NO 3 − reduction to NH 4 + could also have partly o set a negative feedback on biological production that accompanies oxygenation of the surface ocean. Our results indicate that N loss in ferruginous upwelling systems may not have kept pace with global N fixation at marine phosphorous concentrations (0.04-0.13 µM) indicated by the rock record. We therefore suggest that global marine biological production under ferruginous ocean conditions in the Proterozoic eon may thus have been P not N limited.

Abstract. The permanently stratified Lake Kivu is one of the largest freshwater reservoirs of dissolved methane (CH 4 ) on Earth. Yet CH 4 emissions from its surface to the atmosphere have been estimated to be 2 orders of magnitude lower than the CH 4 upward flux to the mixed layer, suggesting that microbial CH 4 oxidation is an important process within the water column. A combination of natural abundance stable carbon isotope analysis (δ 13 C) of several carbon pools and 13 CH 4 -labelling experiments was carried out during the rainy and dry season to quantify (i) the contribution of CH 4 -derived carbon to the biomass, (ii) methanotrophic bacterial production (MBP), and (iii) methanotrophic bacterial growth efficiency (MBGE), defined as the ratio between MBP and gross CH 4 oxidation. We also investigated the distribution and the δ 13 C of specific phospholipid fatty acids (PLFAs), used as biomarkers for aerobic methanotrophs. Maximal MBP rates were measured in the oxycline, suggesting that CH 4 oxidation was mainly driven by oxic processes. Moreover, our data revealed that methanotrophic organisms in the water column oxidized most of the upward flux of CH 4 , and that a significant amount of CH 4 -derived carbon was incorporated into the microbial biomass in the oxycline. The MBGE was variable (2-50 %) and negatively related to CH 4 : O 2 molar ratios. Thus, a comparatively smaller fraction of CH 4 -derived carbon was incorporated into the cellular biomass in deeper waters, at the bottom of the oxycline where oxygen was scarce. The aerobic methanotrophic community was clearly dominated by type I methanotrophs and no evidence was found for an active involvement of type II methanotrophs in CH 4 oxidation in Lake Kivu, based on fatty acids analyses. Vertically integrated over the water column, the MBP was equivalent to 16-60 % of the average phytoplankton particulate primary production. This relatively high magnitude of MBP, and the substantial contribution of CH 4 -derived carbon to the overall biomass in the oxycline, suggest that methanotrophic bacteria could potentially sustain a significant fraction of the pelagic food web in the deep, meromictic Lake Kivu.