Carbonate chemistry and carbon sequestration driven by inorganic carbon outwelling from mangroves and saltmarshes.

Mangroves and saltmarshes are biogeochemical hotspots storing carbon in sediments and in the ocean following lateral carbon export (outwelling). Coastal seawater pH is modified by both uptake of anthropogenic carbon dioxide and natural biogeochemical processes, e.g., wetland inputs. Here, we investigate how mangroves and saltmarshes influence coastal carbonate chemistry and quantify the contribution of alkalinity and dissolved inorganic carbon (DIC) outwelling to blue carbon budgets. Observations from 45 mangroves and 16 saltmarshes worldwide revealed that >70% of intertidal wetlands export more DIC than alkalinity, potentially decreasing the pH of coastal waters. Porewater-derived DIC outwelling (81 ± 47 mmol m-2 d-1 in mangroves and 57 ± 104 mmol m-2 d-1 in saltmarshes) was the major term in blue carbon budgets. However, substantial amounts of fixed carbon remain unaccounted for. Concurrently, alkalinity outwelling was similar or higher than sediment carbon burial and is therefore a significant but often overlooked carbon sequestration mechanism.

Greenhouse gas emissions from African lakes are no longer a blind spot.

Natural lakes are thought to be globally important sources of greenhouse gases (CO2, CH4, and N2O) to the atmosphere although nearly no data have been previously reported from Africa. We collected CO2, CH4, and N2O data in 24 African lakes that accounted for 49% of total lacustrine surface area of the African continent and covered a wide range of morphology and productivity. The surface water concentrations of dissolved CO2 were much lower than values attributed in current literature to tropical lakes and lower than in boreal systems because of a higher productivity. In contrast, surface water-dissolved CH4 concentrations were generally higher than in boreal systems. The lowest CO2 and the highest CH4 concentrations were observed in the more shallow and productive lakes. Emissions of CO2 may likely have been substantially overestimated by a factor between 9 and 18 in African lakes and between 6 and 26 in pan-tropical lakes.

Under pressure: Rapid lavaka erosion and floodplain sedimentation in central Madagascar.

Lavaka (gullies) are often considered as the prime indication of a currently ongoing human-induced environmental crisis in Madagascar's highlands. Yet, lavaka are known to have existed long before human arrival and account for the majority of the long-term sediment input into the highland rivers and floodplains. The role of anthropogenic disturbances in their formation therefore remains highly debated and it is unclear whether lavaka erosion has recently increased. Here, we address these questions by evaluating the dynamics of lavaka in the Lake Alaotra region (central Madagascar). An overall birth to stabilization ratio of 6.1 indicates a rapid lavaka population growth over the period 1949-2010s. Using data on lavaka development we calculated a mean lavaka population age of 410 ± 40 years and estimate that the disequilibrium started at 870 ± 430 cal. BP. Floodplain sedimentation starts to increase around 1000 cal. BP and peaks over the last 400 years, thereby independently confirming this time frame of increased lavaka activity. Lavaka population dynamics modelling shows that a strong increase in environmental pressure over the last centuries is needed to attain current disequilibrium levels. A general drying of the climate since 950 cal. BP in combination with the introduction of cattle and growing human presence around 1000 cal. BP will likely have triggered the increase in lavaka erosion. However, the recent acceleration cannot be explained by climatic changes alone and seems to be linked to increased anthropogenic pressure on the environment. As such, we offer a fresh and quantitatively supported perspective on lavaka dynamics and human impact in central Madagascar, where our methodology can be used in other locations where similar questions on geomorphic equilibrium need to be answered.

Nitrate-dependent anaerobic methane oxidation and chemolithotrophic denitrification in a temperate eutrophic lake.

While the emissions of methane (CH4) by natural systems have been widely investigated, CH4 aquatic sinks are still poorly constrained. Here, we investigated the CH4 cycle and its interactions with nitrogen (N), iron (Fe) and manganese (Mn) cycles in the oxic-anoxic interface and deep anoxic waters of a small, meromictic and eutrophic lake, during two summertime sampling campaigns. Anaerobic CH4 oxidation (AOM) was measured from the temporal decrease of CH4 concentrations, with the addition of three potential electron acceptors (NO3-, iron oxides (Fe(OH)3) and manganese oxides (MnO2)). Experiments with the addition of either 15N-labeled nitrate (15N-NO3-) or 15N-NO3- combined with sulfide (H2S), to measure denitrification, chemolithotrophic denitrification and anaerobic ammonium oxidation (anammox) rates, were also performed. Measurements showed AOM rates up to 3.8 µmol CH4 L-1 d-1 that strongly increased with the addition of NO3- and moderately increased with the addition of Fe(OH)3. No stimulation was observed with MnO2 added. Potential denitrification and anammox rates up to 63 and 0.27 µmol N2 L-1 d-1, respectively, were measured when only 15N-NO3- was added. When H2S was added, both denitrification and anammox rates increased. Altogether, these results suggest that prokaryote communities in the redoxcline are able to efficiently use the most available substrates.

Understanding the linkage between regional climatology and cave geochemical parameters to calibrate speleothem proxies in Madagascar.

Robust reconstructions of paleoclimate and paleoenvironmental changes using stalagmite proxy records critically depend on detailed observations of the transfer function between the regional climate/environment, the karst aquifer hydrology, and finally the cave microclimate via monitoring, which is currently lacking in Madagascar. This paper reports the first monitoring study performed in Anjohibe Cave, in Mahajanga, NW Madagascar to understand the linkage between regional climatological changes and cave responses to such changes. In this research, we monitored (1) the drip water pH, TDS, EC, temperature, δ13CDIC, δ18Ow, δ2Hw, and elemental (Ca, Mg, Sr) composition, and (2) the cave atmosphere pCO2, relative humidity (RH) and temperature. Three significant findings were drawn from the results. First, the data show that air-to-air transfer is fast, and the internal parameters closely vary with the regional climatology. Second, rainfall to drip signal transfer is not immediate, and it can take few months to one season for the signals to be detected in the drip water due to the "epikarst storage effect". Lastly, CaCO3 precipitation is likely to occur during the winter-summer transition, during which prior carbonate precipitation was detected. Since the growth of speleothems is influenced by numerous cave-specific factors, this study, although preliminary, indicates that Anjohibe Cave drip waters are capable of registering changes in its surrounding environment. Such information is ultimately archived in speleothems to reconstruct paleoclimate and paleoenvironmental changes. Results from this research will be of high significance for those working on speleothems within Madagascar, and for those working on understanding the transfer of climatic variations to cave deposits.

Publisher Correction: East Siberian Arctic inland waters emit mostly contemporary carbon.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

East Siberian Arctic inland waters emit mostly contemporary carbon.

Inland waters (rivers, lakes and ponds) are important conduits for the emission of terrestrial carbon in Arctic permafrost landscapes. These emissions are driven by turnover of contemporary terrestrial carbon and additional pre-aged (Holocene and late-Pleistocene) carbon released from thawing permafrost soils, but the magnitude of these source contributions to total inland water carbon fluxes remains unknown. Here we present unique simultaneous radiocarbon age measurements of inland water CO2, CH4 and dissolved and particulate organic carbon in northeast Siberia during summer. We show that >80% of total inland water carbon was contemporary in age, but pre-aged carbon contributed >50% at sites strongly affected by permafrost thaw. CO2 and CH4 were younger than dissolved and particulate organic carbon, suggesting emissions were primarily fuelled by contemporary carbon decomposition. Our findings reveal that inland water carbon emissions from permafrost landscapes may be more sensitive to changes in contemporary carbon turnover than the release of pre-aged carbon from thawing permafrost.

Terrestrial contributions to Afrotropical aquatic food webs: The Congo River case.

Understanding the degree to which aquatic and terrestrial primary production fuel tropical aquatic food webs remains poorly understood, and quantifying the relative contributions of autochthonous and allochthonous inputs is methodologically challenging. Carbon and nitrogen stable isotope ratios (δ 13C, δ 15N) can provide valuable insights about contributions of terrestrial resources and trophic position, respectively, but this approach has caveats when applied in typical complex natural food webs.Here, we used a combination of C, N, and H (δ 2H) stable isotope measurements and Bayesian mixing models to estimate the contribution of terrestrial (allochthonous) and aquatic (autochthonous) inputs to fish and invertebrate communities in the Congo River (and some tributaries).Overall, our results show that we gained power to distinguish sources by using a multiple tracer approach and we were able to discriminate aquatic versus terrestrial sources (esp. including hydrogen isotopes). Fish δ 2H values were clearly correlated with their food preferences and revealed a high level of variation in the degree of allochthony in these tropical aquatic communities.At the community level, it is clear that terrestrial C3 plants are an important source fueling the Congo River food web. However, in order to better constrain source contribution in these complex environments will require more robust constraints on stable isotope values of algal and methane-derived C sources.

Emission and oxidation of methane in a meromictic, eutrophic and temperate lake (Dendre, Belgium).

We sampled the water column of the Dendre stone pit lake (Belgium) in spring, summer, autumn and winter. Depth profiles of several physico-chemical variables, nutrients, dissolved gases (CO2, CH4, N2O), sulfate, sulfide, iron and manganese concentrations and δ13C-CH4 were determined. We performed incubation experiments to quantify CH4 oxidation rates, with a focus on anaerobic CH4 oxidation (AOM), without and with an inhibitor of sulfate reduction (molybdate). The evolution of nitrate and sulfate concentrations during the incubations was monitored. The water column was anoxic below 20 m throughout the year, and was thermally stratified in summer and autumn. High partial pressure of CO2 and CH4 and high concentrations of ammonium and phosphate were observed in anoxic waters. Important nitrous oxide and nitrate concentration maxima were also observed (up to 440 nmol L-1 and 80 µmol L-1, respectively). Vertical profiles of δ13C-CH4 unambiguously showed the occurrence of AOM. Important AOM rates (up to 14 µmol L-1 d-1) were observed and often co-occurred with nitrate consumption peaks, suggesting the occurrence of AOM coupled with nitrate reduction. AOM coupled with sulfate reduction also occurred, since AOM rates tended to be lower when molybdate was added. CH4 oxidation was mostly aerobic (∼80% of total oxidation) in spring and winter, and almost exclusively anaerobic in summer and autumn. Despite important CH4 oxidation rates, the estimated CH4 fluxes from the water surface to the atmosphere were high (mean of 732 µmol m-2 d-1 in spring, summer and autumn, and up to 12,482 µmol m-2 d-1 in winter).

Divergent biophysical controls of aquatic CO2 and CH4 in the World's two largest rivers.

Carbon emissions to the atmosphere from inland waters are globally significant and mainly occur at tropical latitudes. However, processes controlling the intensity of CO2 and CH4 emissions from tropical inland waters remain poorly understood. Here, we report a data-set of concurrent measurements of the partial pressure of CO2 (pCO2) and dissolved CH4 concentrations in the Amazon (n = 136) and the Congo (n = 280) Rivers. The pCO2 values in the Amazon mainstem were significantly higher than in the Congo, contrasting with CH4 concentrations that were higher in the Congo than in the Amazon. Large-scale patterns in pCO2 across different lowland tropical basins can be apprehended with a relatively simple statistical model related to the extent of wetlands within the basin, showing that, in addition to non-flooded vegetation, wetlands also contribute to CO2 in river channels. On the other hand, dynamics of dissolved CH4 in river channels are less straightforward to predict, and are related to the way hydrology modulates the connectivity between wetlands and river channels.

Pelagic photoferrotrophy and iron cycling in a modern ferruginous basin.

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.

Carbon cycling of Lake Kivu (East Africa): net autotrophy in the epilimnion and emission of CO2 to the atmosphere sustained by geogenic inputs.

We report organic and inorganic carbon distributions and fluxes in a large (>2000 km2) oligotrophic, tropical lake (Lake Kivu, East Africa), acquired during four field surveys, that captured the seasonal variations (March 2007-mid rainy season, September 2007-late dry season, June 2008-early dry season, and April 2009-late rainy season). The partial pressure of CO2 (pCO2) in surface waters of the main basin of Lake Kivu showed modest spatial (coefficient of variation between 3% and 6%), and seasonal variations with an amplitude of 163 ppm (between 579±23 ppm on average in March 2007 and 742±28 ppm on average in September 2007). The most prominent spatial feature of the pCO2 distribution was the very high pCO2 values in Kabuno Bay (a small sub-basin with little connection to the main lake) ranging between 11,213 ppm and 14,213 ppm (between 18 and 26 times higher than in the main basin). Surface waters of the main basin of Lake Kivu were a net source of CO2 to the atmosphere at an average rate of 10.8 mmol m(-2) d(-1), which is lower than the global average reported for freshwater, saline, and volcanic lakes. In Kabuno Bay, the CO2 emission to the atmosphere was on average 500.7 mmol m(-2) d(-1) (∼46 times higher than in the main basin). Based on whole-lake mass balance of dissolved inorganic carbon (DIC) bulk concentrations and of its stable carbon isotope composition, we show that the epilimnion of Lake Kivu was net autotrophic. This is due to the modest river inputs of organic carbon owing to the small ratio of catchment area to lake surface area (2.15). The carbon budget implies that the CO2 emission to the atmosphere must be sustained by DIC inputs of geogenic origin from deep geothermal springs.

Rapid losses of surface elevation following tree girdling and cutting in tropical mangroves.

The importance of mangrove forests in carbon sequestration and coastal protection has been widely acknowledged. Large-scale damage of these forests, caused by hurricanes or clear felling, can enhance vulnerability to erosion, subsidence and rapid carbon losses. However, it is unclear how small-scale logging might impact on mangrove functions and services. We experimentally investigated the impact of small-scale tree removal on surface elevation and carbon dynamics in a mangrove forest at Gazi bay, Kenya. The trees in five plots of a Rhizophora mucronata (Lam.) forest were first girdled and then cut. Another set of five plots at the same site served as controls. Treatment induced significant, rapid subsidence (-32.1±8.4 mm yr-1 compared with surface elevation changes of +4.2±1.4 mm yr-1 in controls). Subsidence in treated plots was likely due to collapse and decomposition of dying roots and sediment compaction as evidenced from increased sediment bulk density. Sediment effluxes of CO2 and CH4 increased significantly, especially their heterotrophic component, suggesting enhanced organic matter decomposition. Estimates of total excess fluxes from treated compared with control plots were 25.3±7.4 tCO2 ha-1 yr-1 (using surface carbon efflux) and 35.6±76.9 tCO2 ha-1 yr-1 (using surface elevation losses and sediment properties). Whilst such losses might not be permanent (provided cut areas recover), observed rapid subsidence and enhanced decomposition of soil sediment organic matter caused by small-scale harvesting offers important lessons for mangrove management. In particular mangrove managers need to carefully consider the trade-offs between extracting mangrove wood and losing other mangrove services, particularly shoreline stabilization, coastal protection and carbon storage.

Disproportionate Contribution of Riparian Inputs to Organic Carbon Pools in Freshwater Systems.

A lack of appropriate proxies has traditionally hampered our ability to distinguish riverine organic carbon (OC) sources at the landscape scale. However, the dissection of C4 grasslands by C3-enriched riparian vegetation, and the distinct carbon stable isotope signature (δ13C) of these two photosynthetic pathways, provides a unique setting to assess the relative contribution of riparian and more distant sources to riverine C pools. Here, we compared δ13C signatures of bulk sub-basin vegetation (δ13CVEG) with those of riverine OC pools for a wide range of sites within two contrasting river basins in Madagascar. Although C3-derived carbon dominated in the eastern Rianala catchment, consistent with the dominant vegetation, we found that in the C4-dominated Betsiboka basin, riverine OC is disproportionately sourced from the C3-enriched riparian fringe, irrespective of climatic season, even though δ13CVEG estimates suggest as much as 96% of vegetation cover in some Betsiboka sub-basins may be accounted for by C4 biomass. For example, δ13C values for river bed OC were on average 6.9 ± 2.7‰ depleted in 13C compared to paired estimates of δ13CVEG. The disconnection of the wider C4-dominated basin is considered the primary driver of the under-representation of C4-derived C within riverine OC pools in the Betsiboka basin, although combustion of grassland biomass by fire is likely a subsidiary constraint on the quantity of terrestrial organic matter available for export to these streams and rivers. Our findings carry implications for the use of sedimentary δ13C signatures as proxies for past forest-grassland distribution and climate, as the C4 component may be considerably underestimated due to its disconnection from riverine OC pools.

Contrasting biogeochemical characteristics of the Oubangui River and tributaries (Congo River basin).

The Oubangui is a major tributary of the Congo River. We describe the biogeochemistry of contrasting tributaries within its central catchment, with watershed vegetation ranging from wooded savannahs to humid rainforest. Compared to a 2-year monitoring record on the mainstem Oubangui, these tributaries show a wide range of biogeochemical signatures, from highly diluted blackwaters (low turbidity, pH, conductivity, and total alkalinity) in rainforests to those more typical for savannah systems. Spectral analyses of chromophoric dissolved organic matter showed wide temporal variations in the Oubangui compared to spatio-temporal variations in the tributaries, and confirm that different pools of dissolved organic carbon are mobilized during different hydrological stages. δ(13)C of dissolved inorganic carbon ranged between -28.1‰ and -5.8‰, and was strongly correlated to both partial pressure of CO2 and to the estimated contribution of carbonate weathering to total alkalinity, suggesting an important control of the weathering regime on CO2 fluxes. All tributaries were oversaturated in dissolved greenhouse gases (CH4, N2O, CO2), with highest levels in rivers draining rainforest. The high diversity observed underscores the importance of sampling that covers the variability in subcatchment characteristics, to improve our understanding of biogeochemical cycling in the Congo Basin.

Baseline levels and trophic transfer of persistent organic pollutants in sediments and biota from the Congo River Basin (DR Congo).

The present study aimed to evaluate the occurrence of persistent organic pollutants (POPs: (PCBs, PBDEs, DDTs, HCHs, CHLs and HCB) in sediments and biota from the middle Congo River Basin (CRB) and to investigate their trophic transfer through the aquatic food web using nitrogen stable isotope ratios. To our knowledge, no data on levels of POPs in sediment and biota from the CRB are present in the literature, and studies on trophic transfer and biomagnification profiles of POPs using δ(15)N are scarce in tropical regions. POP levels in the sediment and biota were low, with exception of total PCB levels found in fish from the Itimbiri River (1.4 to 44ng/g ww). Compared to concentrations found in fish from pristine to relatively industrial developed areas, the ∑PCB levels in fish from the Itimbiri were high, indicating the presence of a local PCB contamination source in this catchment. Based on minimum risk level criteria formulated by ATSDR, the consumption of PCB contaminated fish from the Itimbiri river poses a potential risk for humans. The POP levels in biota were not significantly related to the POP levels in sediments, and the BSAF concept (Biota-Sediment Accumulation Factor) was found to be a poor predictor of the bioavailability and bioaccumulation of environmental pollutants in the present study. With increasing trophic levels, a significant increase in PCB 95, 101, 110, 138, 146, 149, 153, 174, 180 & 187 and p,p'-DDT in Itimbiri and BDE 47 & 99 in Itimbiri, Aruwimi & Lomami river basins was observed. Trophic magnification factors were higher than 1, indicating that biomagnification occurs through the tropical food web.

Variation in physiological indicators in Bathymodiolus azoricus (Bivalvia: Mytilidae) at the Menez Gwen Mid-Atlantic Ridge deep-sea hydrothermal vent site within a year.

Bathymodiolus azoricus, thriving at Mid-Atlantic Ridge deep vents, benefits from a symbiosis with methane- and sulphide-oxidising (MOX and SOX) bacteria, and feeds on particulate and dissolved organic matter. To investigate the temporal evolution in their nutrition adult mussels were collected from one location at the Menez Gwen vent site (817 m depth) on four occasions between 2006 and 2007 and studied using different techniques, including stable isotope analyses and FISH. Gill and mantle tissues delta13C and delta15N signatures varied by 2-3 per thousand during the year and these variations were linked to fluctuations in tissue condition index, C and N contents and SOX/MOX volume ratios as quantified by 3D-FISH. October and January mussels presented a particularly poor condition, possibly related with the prolonged summer period of low sea-surface primary production and/or with the stress of the transplant to acoustically retrievable cages for the October mussels, and with their reproductive state in January mussels, since they were spawning. Our results point to the possibility that May mussels benefited from a pulse of sinking sea-surface plankton material. Results underline the dependency of stable isotopic signatures on the physiological state of the mussel at the time of collection, and on the type of tissue analyzed.

The role of biogenic structures on the biogeochemical functioning of mangrove constructed wetlands sediments--a mesocosm approach.

Benthic metabolism (measured as CO(2) production) and carbon oxidation pathways were evaluated in 4 mangrove mesocosms subjected daily to seawater or 60% sewage in the absence or presence of mangrove trees and biogenic structures (pneumatophores and crab burrows). Total CO(2) emission from darkened sediments devoid of biogenic structures at pristine conditions was comparable during inundation (immersion) and air exposure (emersion), although increased 2-7 times in sewage contaminated mesocosms. Biogenic structures increased low tide carbon gas emissions at contaminated (30%) and particularly pristine conditions (60%). When sewage was loaded into the mesocosms under unvegetated and planted conditions, iron reduction was substituted by sulfate reduction and contribution of aerobic respiration to total metabolism remained above 50%. Our results clearly show impacts of sewage on the partitioning of electron acceptors in mangrove sediment and confirm the importance of biogenic structures for biogeochemical functioning but also on greenhouse gases emission.