Search

We present a one-dimensional reactive transport model to estimate benthic fluxes of dissolved inorganic carbon (DIC) and alkalinity (AT) from coastal marine sediments. The model incorporates the transport processes of sediment accumulation, molecular diffusion, bioturbation and bioirrigation, while the reactions included are the redox pathways of organic carbon oxidation, re-oxidation of reduced nitrogen, iron and sulfur compounds, pore water acid-base equilibria, and dissolution of particulate inorganic carbon (calcite, aragonite, and Mg-calcite). The coastal zone is divided into four environmental units with different particulate inorganic carbon (PIC) and particulate organic carbon (POC) fluxes: reefs, banks and bays, carbonate shelves and non-carbonate shelves. Model results are analyzed separately for each environment and then scaled up to the whole coastal ocean. The model-derived estimate for the present-day global coastal benthic DIC efflux is 126 Tmol yr-1, based on a global coastal reactive POC depositional flux of 117 Tmol yr-1. The POC decomposition leads to a carbonate dissolution from shallow marine sediments of 7 Tmol yr-1 (on the order of 0.1 Pg C yr-1). Assuming complete re-oxidation of aqueous sulfide released from sediments, the effective net flux of alkalinity to the water column is 29 Teq. yr-1, primarily from PIC dissolution (46%) and ammonification (33%). Because our POC depositional flux falls in the high range of global values given in the literature, the reported DIC and alkalinity fluxes should be viewed as upper-bound estimates. Increasing coastal sea-water DIC to what might be expected in year 2100 due to the uptake of anthropogenic CO2 increases PIC dissolution by 2.3 Tmol yr-1 and alkalinity efflux by 4.8 Teq. yr-1. Our reactive transport modeling approach not only yields global estimates of benthic DIC, alkalinity and nutrient fluxes under variable scenarios of ocean productivity and chemistry, but also provides insights into the underlying processes. [ABSTRACT FROM AUTHOR]

We present a one-dimensional reactive transport model to estimate benthic fluxes of dissolved inorganic carbon (DIC) and alkalinity (AT) from coastal marine sediments. The model incorporates the transport processes of sediment accumulation, molecular diffusion, bioturbation and bioirrigation, while the reactions included are the redox pathways of organic carbon oxidation, re-oxidation of reduced nitrogen, iron and sulfur compounds, pore water acid-base equilibria, and dissolution of particulate inorganic carbon (calcite, aragonite, and Mg-calcite). The coastal zone is divided into four environmental units with different particulate inorganic carbon (PIC) and particulate organic carbon (POC) fluxes: reefs, banks and bays, carbonate shelves and non-carbonate shelves. Model results are analyzed separately for each environment and then scaled up to the whole coastal ocean. The model-derived estimate for the present-day global coastal benthic DIC efflux is 126 Tmolyr-1 , based on a global coastal reactive POC depositional flux of 117 Tmolyr-1. The POC decomposition leads to a carbonate dissolution from shallow marine sediments of 7 Tmolyr-1 (on the order of 0.1 PgCyr-1). Assuming complete re-oxidation of aqueous sulfide released from sediments, the effective net flux of alkalinity to the water column is 29 Teqyr-1 , primarily from PIC dissolution (46 %) and ammonification (33%). Because our POC depositional flux falls in the high range of global values given in the literature, the reported DIC and alkalinity fluxes should be viewed as upper-bound estimates. Increasing coastal seawater DIC to what might be expected in year 2100 due to the uptake of anthropogenic CO2 increases PIC dissolution by 2.3 Tmolyr-1 and alkalinity eflux by 4.8 Teqyr-1. Our reactive transport modeling approach not only yields global estimates of benthic DIC, alkalinity and nutrient fluxes under variable scenarios of ocean productivity and chemistry, but also provides insights into the underlying processes. [ABSTRACT FROM AUTHOR]

The Bay of Marseille (BoM), located in the northwestern Mediterranean Sea, is affected by various hydrodynamic processes (e.g., Rhône River intrusion and upwelling events) that result in a highly complex local carbonate system. In any complex environment, the use of models is advantageous since it allows us to identify the different environmental forcings, thereby facilitating a better understanding. By combining approaches from two biogeochemical ocean models and improving the formulation of total alkalinity, we develop a more realistic representation of the carbonate system variables at high temporal resolution, which enables us to study air–sea CO 2 fluxes and seawater p CO 2 variations more reliably. We apply this new formulation to two particular scenarios that are typical for the BoM: (i) summer upwelling and (ii) Rhône River intrusion events. In both scenarios, our model was able to correctly reproduce the observed patterns of p CO 2 variability. Summer upwelling events are typically associated with a p CO 2 decrease that mainly results from decreasing near-surface temperatures. Furthermore, Rhône River intrusion events are typically associated with a p CO 2 decrease, although, in this case, the p CO 2 decrease results from a decrease in salinity and an overall increase in total alkalinity. While we were able to correctly represent the daily range of air–sea CO 2 fluxes, the present configuration of Eco3M_MIX-CarbOx does not allow us to correctly reproduce the annual cycle of air–sea CO 2 fluxes observed in the area. This pattern directly impacts our estimates of the overall yearly air–sea CO 2 flux as, even if the model clearly identifies the bay as a CO 2 sink, its magnitude was underestimated, which may be an indication of the limitations inherent in dimensionless models for representing air–sea CO 2 fluxes. [ABSTRACT FROM AUTHOR]

Ocean alkalinity enhancement (OAE) is an emerging approach for atmospheric carbon dioxide removal (CDR). The net climatic benefit of OAE depends on how much it can increase CO 2 sequestration relative to a baseline state without OAE. This so-called "additionality" can be calculated as follows: Additionality = C OAE - Δ C baseline. So far, feasibility studies on OAE have mainly focussed on enhancing alkalinity in the oceans to stimulate CO 2 sequestration (COAE) ; however, the primary focus has not been on how such anthropogenic alkalinity would modify the natural alkalinity cycle and associated baseline CO 2 sequestration (ΔCbaseline). Here, I present incubation experiments in which materials considered for OAE (sodium hydroxide, steel slag, and olivine) are exposed to beach sand to investigate the influence of anthropogenic alkalinity on natural alkalinity sources and sinks. The experiments show that anthropogenic alkalinity can strongly reduce the generation of natural alkalinity, thereby reducing additionality. This is because the anthropogenic alkalinity increases the calcium carbonate saturation state, which reduces the dissolution of calcium carbonate from sand, a natural alkalinity source. I argue that this "additionality problem" of OAE is potentially widespread and applies to many marine systems where OAE implementation is considered – far beyond the beach scenario investigated in this study. However, the problem can potentially be mitigated by dilute dosing of anthropogenic alkalinity into the ocean environment and the avoidance of OAE in natural alkalinity cycling hotspots, such as in marine sediments. Understanding a potential slowdown of the natural alkalinity cycle through the introduction of an anthropogenic alkalinity cycle will be crucial for the assessment of OAE. [ABSTRACT FROM AUTHOR]

Estuarine regions are generally considered a major source of atmospheric CO2 , as a result of the high organic carbon (OC) mineralization rates in their water column and sediments. Despite this, the intensity of anaerobic respiration processes in the sediments tempered by the reoxidation of reduced metabolites near the sediment–water interface controls the flux of benthic alkalinity. This alkalinity may partially buffer metabolic CO2 generated by benthic OC respiration in sediments. Thus, sediments with high anaerobic respiration rates could contribute less to local acidification than previously thought. In this study, a benthic chamber was deployed in the Rhône River prodelta and the adjacent continental shelf (Gulf of Lion, northwestern Mediterranean) in late summer to assess the fluxes of total alkalinity (TA) and dissolved inorganic carbon (DIC) from the sediment. Concurrently, in situ O2 and pH micro-profiles, voltammetric profiles and pore water composition were measured in surface sediments to identify the main biogeochemical processes controlling the net production of alkalinity in these sediments. Benthic TA and DIC fluxes to the water column, ranging between 14 and 74 and 18 and 78 mmol m -2 d -1 , respectively, were up to 8 times higher than dissolved oxygen uptake (DOU) rates (10.4±0.9 mmol m -2 d -1) close to the river mouth, but their intensity decreased offshore, as a result of the decline in OC inputs. In the zone close to the river mouth, pore water redox species indicated that TA and DIC were mainly produced by microbial sulfate and iron reduction. Despite the complete removal of sulfate from pore waters, dissolved sulfide concentrations were low and significant concentrations of FeS were found, indicating the precipitation and burial of iron sulfide minerals with an estimated burial flux of 12.5 mmol m -2 d -1 near the river mouth. By preventing reduced iron and sulfide reoxidation, the precipitation and burial of iron sulfide increases the alkalinity release from the sediments during the spring and summer months. Under these conditions, the sediment provides a net source of alkalinity to the bottom waters which mitigates the effect of the benthic DIC flux on the carbonate chemistry of coastal waters and weakens the partial pressure of CO2 increase in the bottom waters that would occur if only DIC was produced. [ABSTRACT FROM AUTHOR]

Enhanced release of alkalinity from the seafloor, principally driven by anaerobic degradation of organic matter under low-oxygen conditions and associated secondary redox reactions, can increase the carbon dioxide (CO2) buffering capacity of seawater and therefore oceanic CO2 uptake. The Baltic Sea has undergone severe changes in oxygenation state and total alkalinity (TA) over the past decades. The link between these concurrent changes has not yet been investigated in detail. A recent system-wide TA budget constructed for the past 50 years using BALTSEM, a coupled physical–biogeochemical model for the whole Baltic Sea area revealed an unknown TA source. Here we use BALTSEM in combination with observational data and one-dimensional reactive-transport modeling of sedimentary processes in the Fårö Deep, a deep Baltic Sea basin, to test whether sulfate (SO42-) reduction coupled to iron (Fe) sulfide burial can explain the missing TA source in the Baltic Proper. We calculated that this burial can account for up to 26 % of the missing source in this basin, with the remaining TA possibly originating from unknown river inputs or submarine groundwater discharge. We also show that temporal variability in the input of Fe to the sediments since the 1970s drives changes in sulfur (S) burial in the Fårö Deep, suggesting that Fe availability is the ultimate limiting factor for TA generation under anoxic conditions. The implementation of projected climate change and two nutrient load scenarios for the 21st century in BALTSEM shows that reducing nutrient loads will improve deep water oxygen conditions, but at the expense of lower surface water TA concentrations, CO2 buffering capacities and faster acidification. When these changes additionally lead to a decrease in Fe inputs to the sediment of the deep basins, anaerobic TA generation will be reduced even further, thus exacerbating acidification. This work highlights that Fe dynamics plays a key role in the release of TA from sediments where Fe sulfide formation is limited by Fe availability, as exemplified by the Baltic Sea. Moreover, it demonstrates that burial of Fe sulfides should be included in TA budgets of low-oxygen basins. [ABSTRACT FROM AUTHOR]

Recently, it has been proposed that alkalinity release from sediments can play an important role in the carbonate dynamics on continental shelves, lowering the pCO2 of seawater and hence increasing the CO2 uptake from the atmosphere. To test this hypothesis, sedimentary alkalinity generation was quantified within permeable and muddy sediments across the North Sea during two cruises in September 2011 (basinwide) and June 2012 (Dutch coastal zone). Benthic fluxes of alkalinity (AT) and dissolved inorganic carbon (DIC) were determined using shipboard closed sediment incubations. These results show that sediments can be an important source for alkalinity, particularly in the shallow southern North Sea, where high AT and DIC fluxes were recorded in near shore sediments of the Belgian, Dutch and German coastal zone. In contrast, fluxes of AT and DIC are substantially lower in the deeper, seasonally stratified, northern part of the North Sea. Overall, our results show that sedimentary alkalinity generation should be considered an important factor in the CO2 dynamics of shallow coastal systems. [ABSTRACT FROM AUTHOR]