• 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.

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.