Dissolved Inorganic Carbon Fluxes Research Articles

Dynamics of dissolved inorganic carbon (DIC) and stable C isotope ratios (δ13CDIC) in a tropical watershed with diversified land use in São Paulo State, Brazil

The fluvial transport of dissolved inorganic carbon (DIC) is an important component of the global carbon cycle. Herein, we assessed the dynamics of DIC and the C stable isotopic composition (δ13CDIC) in a watershed with diversified land use in São Paulo State (Brazil), more specifically in the Sorocaba River basin (SRB) and considered the temporal and spatial scales. For this purpose, twelve fluvial samples at each sampling point (e.g., S1, S2, S3, S4 and S5) were collected in the SRB, from June 2009 to May 2010, which represented one complete hydrological cycle that included the extremes of the rainfall and discharge regimes. In addition, the δ13CDIC values were also characterized in the wet and dry season at all sampling points to verify their seasonal variability. The results reflected the seasonal variation in discharges, water temperatures, and electrical conductivities. Most of the DIC was transported in the wet season at all sampling points, where the less negative δ13CDIC values were characterized. The natural sources of DIC are associated with atmospheric/soil CO2 consumption. The anthropogenic impacts on both [DIC] and δ13CDIC are linked to untreated urban sewage that is discharged directly into the Sorocaba River, as well as to aquatic photosynthesis in the Itupararanga Reservoir. From 1970 to 2020, the modeling proposed in this study indicated that the annual flux of DIC (Friver) varied from 9.0 to 78.7 t km−2 a−1, confirming that the El Niño Southern Oscillation (ENSO) controlled Friver in the SRB, with higher and lower Friver values occurring during strong El Niño (EN) and La Niña (LN) years. The average Friver value was 20 t km−2 a−1, which is higher than those obtained in natural several temperate and tropical watersheds due to the influences of urban areas on [DIC] in the SRB.

Contribution of carbonate-derived dissolved inorganic carbon into autochthonous particulate organic carbon in two small temperate Korean rivers (Geum and Seomjin)

In this study, we estimated the contributions of carbonate mineral weathering to dissolved inorganic carbon (DIC) and carbonate-derived DIC to autochthonous particulate organic carbon (POC) in two temperate Korean rivers. We combined stoichiometric and stable carbon isotopic approaches to calculate the contribution of autochthonous POC, considering diverse riverine DIC sources. We collected surface water samples from May 2016 to May 2018 and analyzed the major ion composition of rivers along with the concentrations and stable carbon isotopes of DIC. Our estimates showed that the relative abundances of carbonate mineral weathering (0.41 ± 0.11 in the Geum River and 0.43 ± 0.07 in the Seomjin River) were only slightly lower than those of silicate mineral weathering (0.59 ± 0.1 in the Geum River and 0.57 ± 0.07 in the Seomjin River). The resulting percentage contributions of DIC derived from the carbonate mineral weathering to riverine autochthonous POC, if we consider the additional DIC sources of atmospheric and soil-derived CO2, were 10 ± 3 % in the Geum River and 2 ± 1 % in the Seomjin River. The calculated annual fluxes of carbonate-derived DIC for 2016–2018 were 23.2 ± 0.3 Gg C yr−1 in the Geum River and 1.1 ± 0.4 Gg C yr−1 in the Seomjin River. Moreover, the calculated annual fluxes of carbonate-derived POC were 3.6 ± 0.5 Gg C yr−1 in the Geum River and 0.1 ± 0.7 Gg C yr−1 in the Seomjin River. Accordingly, our study provides the first insight into the contribution of carbonate-derived DIC to riverine autochthonous POC in small temperate Korean river systems, dominated by silicate rocks.

Production and fluxes of inorganic carbon and alkalinity in a subarctic subterranean estuary

In this study, we focus on the biogeochemical processes that produce both dissolved inorganic carbon (DIC) and total alkalinity (TA) along a subarctic subterranean estuary (STE) located in the Gulf of St. Lawrence (Magdalen Island, Qc, Canada) in order to evaluate the DIC and TA fluxes as well as the buffering capacity of the exported groundwater to coastal waters. DIC and TA do not behave conservatively during mixing along the groundwater flow path and this implies the occurrence of internal redox reactions that control both their production and consumption. In addition, we show that the origin and composition of the organic carbon within the system alter the carbonate parameters by generating low pH conditions (5.9 - 7.2) and contributing to non-carbonate alkalinity (NCA) that accounts for more than 30% of TA. Whereas iron cycling plays a key role in the production of DIC in the fresh and low-salinity groundwaters, the precipitation of sulfide minerals neutralize the acidity produced by the metabolically produced CO2, in the saline groundwater where sulfate is available. The STE pCO2, computed from the DIC-pHNBS pair ranged from a few ppm to 16000 ppm that results in a CO2 evasion rate of up to 310 mol m−2d−1 to the atmosphere. Based on Darcy flow and the mean concentrations of DIC and carbonate alkalinity (Ac = TA - NCA) in the discharge zone, fluxes derived from submarine groundwater discharge were estimated at 1.43 and 0.70 mol m−2d−1 for DIC and Ac, respectively. Despite a major part of the metabolic CO2 being lost along the groundwater flow path, the SGD-derived DIC flux was still greater than the Ac flux, implying that groundwater discharge reduces the buffering capacity of the receiving coastal waters. This site-specific scale study demonstrates the importance of diagenetic reactions and organic matter remineralization processes on carbonate system parameters in STE. Our results highlight that subarctic STEs could be hot spots of CO2 evasion and a source of acidification to coastal waters that should be considered in carbon budgets.

Characterization of the benthic biogeochemical dynamics after flood events in the Rhône River prodelta: a data–model approach

Abstract. At the land–sea interface, the benthic carbon cycle is strongly influenced by the export of terrigenous particulate material across the river–ocean continuum. Episodic flood events delivering massive sedimentary materials can occur, but their short-term impact on carbon cycling is poorly understood. In this paper, we use a coupled data–model approach to estimate the temporal variations in sediment–water fluxes, biogeochemical pathways and their reaction rates during these abrupt phenomena. We studied one episodic depositional event in the vicinity of the Rhône River mouth (NW Mediterranean Sea) during the fall–winter of 2021/22. The distributions of dissolved inorganic carbon (DIC), sulfate (SO42-) and methane (CH4) were measured in sediment porewaters collected every 2 weeks before and after the deposition of a 25 cm sediment layer during the main winter flood event. Significant changes in the distribution of DIC, SO42- and CH4 concentrations were observed in the sediment porewaters. The use of an early diagenetic model (FESDIA) to calculate biogeochemical reaction rates and fluxes revealed that this type of flood event can increase the total organic carbon mineralization rate in the sediment by 75 % a few days after deposition. In this period, sulfate reduction is the main process contributing to the increase in total mineralization relative to non-flood deposition. The model predicts a short-term decrease in the DIC flux out of the sediment from 100 to 55 mmolm-2d-1 after the deposition of the new sediment layer with a longer-term increase by 4 %, therefore implying an initial internal storage of DIC in the newly deposited layer and a slow release over relaxation of the system. Furthermore, examination of the stoichiometric ratios of DIC and SO42- as well as model output over this 5-month window shows a decoupling between the two modes of sulfate reduction following the deposition – organoclastic sulfate reduction (OSR) intensified in the newly deposited layer below the sediment surface, whereas anaerobic oxidation of methane (AOM) intensified at depth below the former buried surface. The bifurcation depth of sulfate reduction pathways, i.e., the sulfate–methane transition zone (SMTZ), is shifted deeper by 25 cm in the sediment column following the flood deposition. Our findings highlight the significance of short-term transient biogeochemical processes at the seafloor and provide new insights into the benthic carbon cycle in the coastal ocean.

Effects of seasonal deposition-erosion cycle on sedimentary organic carbon remineralization and oxygen consumption in a large-river delta-front estuary

Seasonal sediment deposition-erosion events are dominant drivers of particle-solute dynamics in large-river delta-front estuaries (LDEs), but their influence on elemental cycles is not yet fully understood. To better constrain the role of deposition-erosion events on elemental cycling in LDEs, benthic fluxes of dissolved inorganic carbon (DIC), oxygen, and pore-water solute profiles were measured over different seasons in the Changjiang LDE. Benthic DIC efflux (23.4 ± 6.0 mmol C m−2 d−1) was greater than oxygen influx (7.5 ± 2.0 mmol O2 m−2 d−1) in summer but less in winter (7.7 ± 1.2 mmol C m−2 d−1 and 10.1 ± 1.5 mmol O2 m−2 d−1, respectively). The additional oxygen consumption in sediments in winter was likely due to the oxidation of inorganic diagenetic reductive products (IDRP) (e.g., NH4+, Fe2+, and Mn2+) in deeper sediments exposed by erosion, which resulted in the development of an “oxygen debt”. Sedimentary oxygen respiration accounted for at least 48 % of total oxygen consumption (oxygen consumption in both water column and sediment) in winter and was significantly greater than in summer (∼15 %); this highlighted the importance of winter sediment erosion in oxygen depletion. In addition to IDRP oxidation, the remineralization of resuspended sedimentary organic carbon in water column also contributed to the oxygen consumption. The global dataset on benthic DIC and oxygen fluxes provides evidence that the “oxygen debt” is likely to be widespread in LDEs, exerting a significant impact on global carbon and oxygen cycling.

Regeneration of sedimentary phosphorus and iron in a large seasonally hypoxic estuary deciphered by 224Ra/228Th disequilibria

Using a 224Ra/228Th disequilibrium approach, we demonstrate in this study that benthic fluxes of dissolved inorganic phosphorus (DIP) in the seasonally hypoxic Yangtze River Estuary were largely manipulated by two counteracting processes: the decomposition of sedimentary organic matter and adsorption of DIP onto iron (Fe) oxides. The decomposition rate of sedimentary organic matter rose exponentially with bottom water dissolved oxygen (DO) concentration multiplied by the amplification factor of sediment surface area (ξ), a variable used to describe the intensity of bio-irrigation and physical reworking in the sediment deposit. In the summer of 2020, the Yangtze River catchment encountered the largest flood event in the past 20 years. As a result of enhanced physical reworking of the seabed, dissolved inorganic carbon (DIC) flux increased by approximately 4-fold as compared to the summer of 2019 (657 vs. 154 mmol m−2 d−1). DIP flux exhibited similar inter-annual variations to DIC flux, indicating that changes in the decomposition rate of sedimentary organic matter were the main cause of the inter-annual differences in DIP flux (1.5 mmol m−2 d−1 in 2020 vs. 0.3 mmol m−2 d−1 in 2019). On the other hand, benthic dissolved Fe fluxes declined exponentially with rising DO concentration because of re-oxidation of Fe2+ in porewater into Fe oxides. As a consequence, approximately 90% of DIP sourced from the decomposition of sedimentary organic matter was retained within the sediment when the bottom water was well oxygenated (DO >125 μmol l−1). Our results imply that regeneration of sedimentary P and Fe may be efficient only within a very narrow redox window where DO concentrations are below a threshold value of ∼60 μmol l−1, but bio-irrigation or physical reworking is still active.

Assessing biogeochemical controls on porewater dissolved inorganic carbon cycling in the gas hydrate-bearing sediments of the Makran accretionary wedge, Northeastern Arabian Sea off Pakistan

Quantitatively assessing the porewater dissolved inorganic carbon (DIC) cycling in methane-enriched marine sediments is crucial to understanding the contributions of different carbon sources to the global marine carbon pool. In this study, Makran accretionary wedge was divided into Zone 1 (high methane flux area) and Zone 2 (background area). Porewater geochemical compositions (Cl–, SO42–, NH4+, Mg2+, Ca2+, Ba2+, DIC and δ13C-DIC) and a reaction-transport model were used to determine the DIC source and calculate the DIC flux through carbonate precipitation and releasing into overlying seawater in sediments. Zone 1 is characterized by the shallower depth of sulfate-methane transition (SMT), where most of porewater sulfate was consumed by anaerobic oxidation of methane (AOM). In contrast, a relatively low flux of methane diffusion in Zone 2 results in a deeper SMT depth and shallow sulfate is predominantly consumed by organoclastic sulfate reduction (OSR). Based on the porewater geochemical profiles and δ13C mass balance, the proportions of porewater DIC originating from methane were calculated as 51% in Zone 1 and nearly 0% in Zone 2. An increase of porewater DIC concentration leads to authigenic carbonate precipitation. Solid total inorganic carbon (TIC), X-ray diffractometry (XRD) and scanning electron microscopy (SEM) analysis display that carbonate content increases with depth and aragonite appears at or below the depths of SMT. Meanwhile, the flux of DIC released from sediments calculated by the reaction-transport model is 51.3 ~ 90.4 mmol/m2·yr in Zone 1, which is significantly higher than that in Zone 2 (22.4 mmol/m2·yr). This study demonstrates that AOM serves as the dominant biogeochemical process regulating the porewater DIC cycle, which has an important impact on the authigenic carbonate burial and the seawater carbonate chemistry.

Diffusive and advective cross-frontal fluxes of inorganic nutrients and dissolved inorganic carbon in the Barents Sea in autumn

The Atlantic Water, entering the Arctic through the Barents Sea and Fram Strait, is the main source of nutrients in the Arctic Ocean. The Barents Sea is divided by the Polar Front into an Atlantic-dominated domain in the south, and an Arctic-dominated domain in the north. The Polar Front is a thermohaline structure, which is topographically-steered at sub-surface, and influenced by the seasonal sea ice edge near the surface. Exchanges of nutrients between the inflowing Atlantic Water and the surrounding waters are key for the primary production in the Barents Sea. In October 2020, we measured nutrients (nitrate, phosphate and silicic acid), dissolved inorganic carbon (DIC), ocean stratification, currents and turbulence in the vicinity of the Polar Front in the Barents Sea within the framework of the Nansen Legacy project, allowing estimates of horizontal and vertical advective fluxes and turbulent fluxes of nitrate and DIC. We studied the autumn situation when primary production was declining. We found a substantial transfer of nitrate and DIC across the Polar Front from the Atlantic domain to the Arctic domain. Up to one quarter of the replenishment of the nitrate in the mixed layer during winter could be attributed to vertical mixing during wind events, shared approximately equally between advective and turbulent fluxes. The vertical turbulent fluxes bring nutrients from the subsurface Atlantic Water to the surface. We also identified an export of nitrate and DIC from the Barents Sea to the Nordic Seas occurring along the eastern shelf of Svalbard. Our study shows the role of vertical fluxes in fall and winter to precondition for the following spring bloom.

Carbon Outgassing in the Antarctic Circumpolar Current Is Supported by Ekman Transport From the Sea Ice Zone in an Observation‐Based Seasonal Mixed‐Layer Budget

AbstractDespite its importance for the global cycling of carbon, there are still large gaps in our understanding of the processes driving annual and seasonal carbon fluxes in the high‐latitude Southern Ocean. This is due in part to a historical paucity of observations in this remote, turbulent, and seasonally ice‐covered region. Here, we use autonomous biogeochemical float data spanning 6 full seasonal cycles and with circumpolar coverage of the Southern Ocean, complemented by atmospheric reanalysis, to construct a monthly climatology of the mixed layer budget of dissolved inorganic carbon (DIC). We investigate the processes that determine the annual mean and seasonal cycle of DIC fluxes in two different zones of the Southern Ocean—the Sea Ice Zone (SIZ) and Antarctic Southern Zone (ASZ). We find that, annually, mixing with carbon‐rich waters at the base of the mixed layer supplies DIC which is, in the ASZ, either used for net biological production or outgassed to the atmosphere. In contrast, in the SIZ, where carbon outgassing and the biological pump are weaker, the surplus of DIC is instead advected northward to the ASZ. In other words, carbon outgassing in the southern Antarctic Circumpolar Current (ACC), which has been attributed to remineralized carbon from deep water upwelled in the ACC, is also due to the wind‐driven transport of DIC from the SIZ. These results stem from the first observation‐based carbon budget of the circumpolar Southern Ocean and thus provide a useful benchmark to evaluate climate models, which have significant biases in this region.

Air-sea CO2 fluxes and cross-shelf exchange of inorganic carbon in the East China Sea from a coupled physical-biogeochemical model

The East China Sea (ECS) has been reported to be a significant sink of atmospheric CO2, but less is known about horizontal transport of dissolved inorganic carbon (DIC) across the shelf. A coupled physical-biogeochemical model has been implemented for the ECS to simulate the inorganic carbon system and estimate CO2 fluxes and cross-shelf DIC transport in the ECS. A 6-year model hindcast (2013–2018) was performed and assessed. Multiple existing datasets from in-situ observations are used to constrain and validate the model. The model reproduces the spatial and temporal patterns of nitrogen, chlorophyll and CO2 parameters in general agreement with observations. Modeling estimation reveals that the ECS takes up CO2 at an annual mean rate of about 8.20 ± 3.13 mmol m−2 d−1, and experiences substantial seasonal variability. The total annual CO2 uptake in the ECS is about 21.55 Tg C yr−1. Modeling estimation suggests that the biological processes contribute to about 15 % of the shelf CO2 uptake in the ECS, leaving ~80 % of the shelf uptake contributed by other physical-chemical processes, e.g., physical pump and/or solubility pump. The horizontal fluxes of DIC between the ECS and the adjacent ocean are more than two orders of magnitude larger than the air-sea CO2 flux on the ECS and result in a net DIC export of about ~33.8 ± 14.87 Tg C yr−1 from the shelf area. Modeling results suggest that this conveyance of DIC to the open ocean is equivalent to about 70 % of the inorganic carbon inflow from riverine and atmospheric pathways in the annual scale.

High‐frequency variability of carbon dioxide fluxes in tidal water over a temperate salt marsh

AbstractExisting analyses of salt marsh carbon budgets rarely quantify carbon loss as CO2 through the air–water interface in inundated marshes. This study estimates the variability of partial pressure of CO2 (pCO2) and air–water CO2 fluxes over summer and fall of 2014 and 2015 using high‐frequency measurements of tidal water pCO2 in a salt marsh of the U.S. northeast region. Monthly mean CO2 effluxes varied in the range of 5.4–25.6 mmol m−2 marsh d−1 (monthly median: 4.8–24.7 mmol m−2 marsh d−1) during July to November from the tidal creek and tidally‐inundated vegetated platform. The source of CO2 effluxes was partitioned between the marsh and estuary using a mixing model. The monthly mean marsh‐contributed CO2 effluxes accounted for a dominant portion (69%) of total CO2 effluxes in the inundated marsh, which was 3–23% (mean 13%) of the corresponding lateral flux rate of dissolved inorganic carbon (DIC) from marsh to estuary. Photosynthesis in tidal water substantially reduced the CO2 evasion, accounting for 1–86% (mean 31%) of potential CO2 evasion and 2–26% (mean 11%) of corresponding lateral transport DIC fluxes, indicating the important role of photosynthesis in controlling the air–water CO2 evasion in the inundated salt marsh. This study demonstrates that CO2 evasion from inundated salt marshes is a significant loss term for carbon that is fixed within marshes.

Dissolved fluxes of nutrients and carbon at the sediment-water interface in the Adriatic Sea: review of early data and methods from the Italian National Research Council (CNR)

We report the measurement of the Fluxes of Dissolved Compounds at the Sediment-Water Interface (DFSWIs), obtained by analyzing data collected in the Italian Exclusive Economic Zone (EEZ) of the Northern and Central Adriatic Sea from 1982. We also describe the methods, honed by Italy’s Consiglio Nazionale delle Ricerche (CNR), employed to measure and calculate DFSWIs, including benthic chambers and landers, sediment-water interface micro-profiling, on-board incubation, and pore water modeling. Data analysis demonstrated that in situ measurements are the most reliable approaches, but that on-board collected data also supply interesting results. The DFSWI data allowed to divide the Adriatic seafloor into areas with similar DFSWI types and intensities and to define the role of sediments as sources or sinks of chemicals such as nutrients, Dissolved Inorganic Carbon (DIC), and metals. DFSWIs mainly depend on dissolved and solid river inputs, Marine Organic Matter (mOM) production, and sediment reworking. They show a seasonal temperature-related trend, which in summer induces increased chemical reaction kinetics and microbial activity. DFSWIs decline from the Po River mouths southward, along the Holocene mud wedge. North of the Po River Delta, the DFSWIs are weaker and confined to the areas in front of the major river mouths, due to poor Organic Matter (OM) inputs and strong reworking of bottom sediments. The area south of the Po Delta cusp is characterized by strong DFSWIs, due to the high deposition of solid inputs from the Po River, strong primary production, and protection from the Western Adriatic Current and Bora storms; in summer, higher temperatures, and calm hydrodynamic conditions generate near-bottom hypoxic to anoxic environments in this area. In Northern and Central Adriatic offshore areas, negative DIC and phosphate fluxes are due to poorly reactive OM reaching this area and to the mainly carbonate composition and oxic environment of local bottom sediments. DFSWI data analysis highlighted the important contribution of sediments to marine carbon and nutrient cycles. This is particularly important for carbon, which plays a major role in seawater acidification and global climate change. The study also provides average DFSWI data for each diagenetic area, which allow calculating the carbon and nutrient budgets in the Adriatic Sea.

Tracing terrestrial groundwater discharge and porewater exchange derived dissolved carbon export in a tropical estuary using multiple isotopes

Coastal terrestrial groundwater discharge and porewater exchange are two different submarine groundwater discharge (SGD) pathways. The contribution of both pathways in dissolved carbon export to the coastal water remains almost unknown. Here, we investigated terrestrial groundwater discharge, porewater exchange, and dissolved carbon export in a tropical estuary (Moyangjiang, China) using stable water (δ2H and δ18O) and radioactive (222Rn, 224Ra, and 228Th) isotopes. The average terrestrial groundwater discharge was estimated to be (3.2±0.2) × 106 m3 d−1 by a three end-member mixing model of δ18O and salinity. The porewater exchange was estimated to be 11.3±0.14 cm d−1 by the 224Ra/228Th disequilibrium method. Accordingly, dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) fluxes from terrestrial groundwater discharge were estimated to be (1.19±0.10) × 107 and (3.23±0.25) × 105 mol d−1, respectively. In comparison, when upscaling to the whole estuary, DIC and DOC export fluxes from porewater exchange were estimated to be (1.56±0.21) × 105 and (2.12±0.29) × 105 mol d−1, respectively. Terrestrial groundwater discharge derived DIC flux was two orders of magnitude greater than that from porewater exchange, and was three times greater than that from river discharge. Terrestrial groundwater discharge was recognized as a significant contributor to DIC export. Porewater exchange played a disproportionately important role in the delivery of DOC to the ocean, and its contribution to DOC needed to be emphasized. Overall, both pathways contributed a large amount of dissolved carbon export to the coastal water, and play an important role in delivering terrestrial carbon across land-ocean interface. Evaluating the contributions of different pathways of SGD to terrestrial solutes will help to improve the accuracy of SGD associated terrestrial solute fluxes.

Assessing the Deep Carbon Release in an Active Volcanic Field Using Hydrochemistry, δ13CDIC and Δ14CDIC

AbstractVolcanic activities have great implications on the geological carbon cycle, and ascertaining the deep carbon contribution in the Earth's surface that runs along the volcanic edifices is important to understand the relationship between solid Earth degassing and global climate change. This study reports analytical results of major dissolved ions concentrations, carbon isotopic compositions (δ13CDIC and Δ14CDIC) of dissolved inorganic carbon (DIC) of rivers, cold springs, and hot springs from Changbaishan volcanic area, Northeast China. The hydrothermal fluids had a significant impact on solutes budgets, as well as carbon isotopes for the rivers. The changes in concentrations of major ions are mainly controlled by mixing of high‐temperature water/rock interaction and low‐temperature water/rock interaction, and low‐temperature water/rock interaction can be explained by the change of chemical composition between volcanic cone (trachyte) and basaltic shield. Because Δ14CDIC is conservative to CO2 outgassing, we used Δ14CDIC to figure out the contributions of deep carbon and surface carbon. While δ13CDIC is sensitive to CO2 outgassing, we thus estimated the minimum deep CO2 outgassing yield (1.24 × 104 t C yr−1) based on DIC flux corrected for outgassing by a Rayleigh model. In the Changbaishan volcanic area, deep carbon release flux was higher than CO2 consumption flux by silicate weathering, while the deep CO2 outgassing flux was an underestimate, consistent with the hypothesis that deep CO2 release regulates climate on geological timescales. This study calls for a better understanding of the effects of volcanic activities on Earth's surface carbon cycling, which has great implications on studying global climate change.

Elevated River Inputs of the Total Alkalinity and Dissolved Inorganic Carbon in the Northern Adriatic Sea

The response of coastal systems to global acidification depends strongly on river inputs, which can alter the total alkalinity (AT) and dissolved inorganic carbon (DIC) in seawater. The northern Adriatic Sea (NAd) is a shallow continental shelf region that currently receives about 15% of the total freshwater input in the Mediterranean Sea, where the role of riverine discharges on the carbonate system has been poorly studied. In particular, river discharges can alter the carbonate system in the sea, affecting both the equilibrium chemistry and biological processes. For the main rivers flowing into the NAd (the Po, Adige, Brenta, Piave, Livenza, Tagliamento, Isonzo, Timavo and Rižana), data were collected for the pH, concentrations of the total alkalinity (AT), Ca2+ and Mg2+ and the isotopic ratio of stable carbon in the dissolved inorganic carbon (δ13CDIC). The DIC fluxes were estimated using the THINCARB (THermodynamic modeling of INOrganic CARBon) model for the compilation of the AT and pH data. The results show that the total transport of the AT in the rivers was 205 Gmol yr−1 while the transport of the DIC was 213 Gmol yr−1, of which about 70% was from the Po River. About 97% of the DIC in the river waters was in the form of bicarbonates. The high Mg2+/Ca2+ ratios indicate that dolomite weathering is predominant in the Adige, Piave, and Livenza river basins, while lower ratios in the Timavo and Rižana rivers indicate a greater proportion of calcite. The mean δ13C-DIC value was estimated to be −10.0 ± 1.7 ‰, a value nowadays considered typical for the DIC flux inputs in oceanic carbon cycle modeling. The DIC flux depends on the mineral weathering and biological activity in each river basin. However, these natural processes can be modified by anthropogenic disturbances that should be better quantified.

Surface ocean carbon budget in the 2017 south Georgia diatom bloom: Observations and validation of profiling biogeochemical argo floats

Estimates of the partial pressure of CO2 (pCO2) derived from biogeochemical Argo floats have the potential to improve our knowledge of the highly variable and partially observed Southern Ocean carbon sink through sampling at improved temporal and spatial resolution. Here we use the data from six biogeochemical Argo floats to characterise near-surface dissolved inorganic carbon (DIC) concentrations and fluxes at the site of an intense (Chl-a >3 mg m−3) mesoscale diatom bloom situated northwest of South Georgia. Concurrently, we provide independent analysis and validation of the methodology used by the Southern Ocean Carbon and Climate Observational and Modelling (SOCCOM) project for deriving surface pCO2 from float-based pH and oxygen measurements. We compare the float observations with co-located ship data from bottle samples over a month-long period. When compared to data sampled within 24 h and 25 km of each float profile, we find good agreement with a mean offset of −0.005 ± 0.018 (1σ) between float pH and bottle-derived pH. This translates to comparable pCO2 estimates between ship measurements and floats with a mean difference of 2.6 ± 12.8 (1σ) μatm, providing support for the use of biogeochemical Argo float data to supplement shipboard pCO2 measurements in the Southern Ocean. Based on float-derived pCO2 we calculate a sizeable local flux of CO2 of 24 ± 7 mmol C m−2 d−1 (over a 27-day period) from the atmosphere into the surface mixed layer, driven by a large air-sea pCO2 gradient and strong but variable winds. Despite the considerable air-sea flux, the local mixed layer carbon budget appears to be dominated by entrainment and detrainment of carbon-rich waters into and out of the mixed layer. However, given the large uncertainties associated with these fluxes and the significant challenges associated with closing the mixed layer budget, further research is required to refine float-based mixed layer DIC fluxes.

An unusual carbon cycle budget of a small stream in a mountain silicate terrain: The case of the Gravona river (Corsica)

AbstractThe current research of carbon cycling in inland waters lacks a sound knowledge of carbon outgassing from small streams. As a consequence, these compartments of the terrestrial water cycle might still be seriously underrepresented in estimates of global carbon transfer budgets from land surfaces. This study investigated carbon sources and sinks of a mountain river in a silicate catchment. For this purpose, the high‐relief Gravona river, in the western part of the island of Corsica (France) in the Western Mediterranean, was investigated for field parameters, dissolved inorganic carbon (DIC) and its stable carbon isotopes (δ13CDIC). The source region was characterized by low DIC contents and high δ13CDIC values that decreased further downstream due to increasing soil respiration. Associated increasing DIC concentrations and elevated seasonality in the lower river section also indicated more respiration and subsequent DIC‐input by weathering. The aqueous partial pressure (pCO2(aq)) was lowest at the source of the Gravona river and samples from the cold season even showed undersaturation that led to uptake of atmospheric CO2. Further downstream, the seasonality of pCO2(aq) increased and was particularly pronounced near the river mouth where CO2 degassing took place. Average DIC flux along the river was 0.129 Gg C year−1 and was almost equal to CO2 degassing from the river surface with 0.128 Gg C year−1. Our study showed that on an annual basis the river is an overall weak to medium source of CO2 to the atmosphere even though headwater parts of the river seasonally act as CO2 sinks.

Nitrogen cycling in sediments on the NW African margin inferred from N and O isotopes in benthic chambers

Benthic nitrogen cycling in the Mauritanian upwelling region (NW Africa) was studied in June 2014 from the shelf to the upper slope where minimum bottom water O2 concentrations of 25 µM were recorded. Benthic incubation chambers were deployed at 9 stations to measure fluxes of O2, dissolved inorganic carbon (DIC) and nutrients (NO3-, NO2-, NH4+, PO43-, H4SiO4) along with the N and O isotopic composition of nitrate (δ15N-NO3- and δ18O-NO3-) and ammonium (δ15N-NH4+). O2 and DIC fluxes were similar to those measured during a previous campaign in 2011 whereas NH4+ and PO43- fluxes on the shelf were 2 – 3 times higher and possibly linked to a long-term decline in bottom water O2 concentrations. The mean isotopic fractionation of NO3- uptake on the margin, inferred from the loss of NO3- inside the chambers, was 1.5 ± 0.4 ‰ for 15/14N (15ϵapp) and 2.0 ± 0.5 ‰ for 18/16O (18ϵapp). The mean 18ϵapp:15ϵapp ratio on the shelf (< 100 m) was 2.1 ± 0.3, and higher than the value of 1 expected for microbial NO3-reduction. The 15ϵapp are similar to previously reported isotope effects for NO3- respiration in marine sediments but lower than determined in 2011 at a same site on the shelf. The sediments were also a source of 15N-enriched NH4+ (9.0 ± 0.7 ‰). A numerical model tuned to the benthic flux data and that specifically accounts for the efflux of 15N-enriched NH4+ from the seafloor, predicted a net benthic isotope effect of N loss (15ϵsed) of 3.6 ‰; far above the more widely considered value of ~0‰. This result is further evidence that the assumption of a universally low or negligible benthic N isotope effect is not applicable to oxygen-deficient settings. The model further suggests that 18ϵapp:15ϵapp trajectories > 1 in the benthic chambers are most likely due to aerobic ammonium oxidation and nitrite oxidation in surface sediments rather than anammox, in agreement with published observations in the water column of oxygen deficient regions.

Long-term trends of streamflow, sediment load and nutrient fluxes from the Mississippi River Basin: Impacts of climate change and human activities

Under the influences of global climate change and intense human activities, the hydrological and biogeochemical processes have been undergoing profound changes in most of the world's watersheds. However, the long-term changes in streamflow, sediment load, and nutrient fluxes, and quantitative attribution of these changes from a basin-wide perspective are incompletely understood. Here we examined the trends of streamflow, sediment load, and total nitrogen (TN), total phosphorus (TP), and dissolved inorganic carbon (DIC) fluxes in the Mississippi River Basin (MRB) and its four major tributary basins during the 1930s-2010s, and major causes for streamflow, sediment load and nutrient fluxes changes were quantified. The streamflow increased significantly (p < 0.05) in the entire basin except for the Arkansas River Basin, while the sediment load significantly decreased except in the Arkansas River Basin and Upper MRB. Generally, the TN flux reduced except for an increasing trend in the Upper MRB. While the TP flux rose except for a decrease in the Ohio River Basin, and the DIC flux increased significantly. The strength of the relationship between nutrient flux and streamflow/sediment load showed four binary patterns, and in general the nutrient fluxes were more strongly correlated with streamflow compared to sediment load. Over the past 80 years, the increasing precipitation in the MRB has made the most contribution (67 % on average) to the river discharge increase, whereas human activities contribute the most (>58 %) to the changes in the sediment load and nutrient fluxes. The sediment yield coefficient decreased linearly with the increasing impermeable area proportion, river revetment length, and dam storage capacity (p < 0.05) in the MRB. The decrease in TN flux probably resulted from sedimentation and denitrification in reservoirs and wetlands, and increases in farm fertilizer and manure use were the two main factors contributing to the increased TP flux. In addition, the agricultural practices, increased precipitation, and raised temperature jointly led to an increase in the DIC flux. This study provides quantitative results of water–sediment-nutrient variations in the entire watershed system, which facilitates development of watershed management strategies.

Dissolved inorganic carbon export from rivers of Great Britain: Spatial distribution and potential catchment-scale controls

Dissolved inorganic carbon (DIC) fluxes from the land to ocean have been quantified for many rivers globally. However, CO2 fluxes to the atmosphere from inland waters are quantitatively significant components of the global carbon cycle that are currently poorly constrained. Understanding, the relative contributions of natural and human-impacted processes on the DIC cycle within catchments may provide a basis for developing improved management strategies to mitigate free CO2 concentrations in rivers and subsequent evasion to the atmosphere. Here, a large, internally consistent dataset collected from 41 catchments across Great Britain (GB), accounting for ∼36% of land area (∼83,997 km2) and representative of national land cover, was used to investigate catchment controls on riverine dissolved inorganic carbon (DIC), bicarbonate (HCO3−) and free CO2 concentrations, fluxes to the coastal sea and annual yields per unit area of catchment. Estimated DIC flux to sea for the survey catchments was 647 kt DIC yr−1 which represented 69% of the total dissolved carbon flux from these catchments. Generally, those catchments with large proportions of carbonate and sedimentary sandstone were found to deliver greater DIC and HCO3− to the ocean. The calculated mean free CO2 yield for survey catchments (i.e. potential CO2 emission to the atmosphere) was 0.56 t C km−2 yr−1. Regression models demonstrated that whilst river DIC (R2 = 0.77) and HCO3− (R2 = 0.77) concentrations are largely explained by the geology of the landmass, along with a negative correlation to annual precipitation, free CO2 concentrations were strongly linked to catchment macronutrient status. Overall, DIC dominates dissolved C inputs to coastal waters, meaning that estuarine carbon dynamics are sensitive to underlying geology and therefore are likely to be reasonably constant. In contrast, potential losses of carbon to the atmosphere via dissolved CO2, which likely constitute a significant fraction of net terrestrial ecosystem production and hence the national carbon budget, may be amenable to greater direct management via altering patterns of land use.