skip to main content

Title: Particle Triggered Reactions as an Important Mechanism of Alkalinity and Inorganic Carbon Removal in River Plumes

The effects of heterogeneous reactions between river‐borne particles and the carbonate system were studied in the plumes of the Mississippi and Brazos rivers. Measurements within these plumes revealed significant removal of dissolved inorganic carbon (DIC) and total alkalinity (TA). After accounting for all known DIC and TA sinks and sources, heterogeneous reactions (i.e., heterogeneous CaCO3precipitation and cation exchange between adsorbed and dissolved ions) were found to be responsible for a significant fraction of DIC and TA removal, exceeding 10% and 90%, respectively, in the Mississippi and Brazos plume waters. This finding was corroborated by laboratory experiments, in which the seeding of seawater with the riverine particles induced the removal of the DIC and TA. The combined results demonstrate that heterogeneous reactions may represent an important controlling mechanism of the seawater carbonate system in particle‐rich coastal areas and may significantly impact the coastal carbon cycle.

more » « less
Award ID(s):
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
DOI PREFIX: 10.1029
Date Published:
Journal Name:
Geophysical Research Letters
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    The marine carbonate system is influenced by anthropogenic CO2uptake, biogeochemical processes, and physical changes that involve freshwater input and removal. Two frequently used parameters to quantify seawater carbonate system are total alkalinity (TA) and total dissolved inorganic carbon (DIC). To account for the physical changes, both TA and DIC are usually normalized to a reference salinity (i.e., nTA and nDIC), and then the relationship between nTA and nDIC is used to identify major biogeochemical processes that regulate the carbonate system, based on process‐specific reaction stoichiometry. However, the theoretical basis of this interpretation has not been holistically examined. In this study, we validated this method under  idealized conditions and discussed the associated assumptions and limitations. Furthermore, we applied this method to interpret field TA and DIC data from a lagoonal estuary in the northwestern Gulf of Mexico. Our results demonstrated that evaluating field data that encompass multiple stations and time periods could be problematic. In addition, various combinations of biogeochemical processes can lead to the same nTA–nDIC relationship, even though the relative importance of each individual process may vary significantly. Therefore, the stoichiometric relationship relying solely on TA and DIC data is not a definitive approach for uncovering dominant biogeochemical processes. Instead, measurements of process‐specific parameters are necessary.

    more » « less
  2. Abstract

    High‐accuracy spectrophotometric pH measurements were taken during a summer cruise to study the pH dynamics and its controlling mechanisms in the northern Gulf of Mexico in hypoxia season. Using the recently available dissociation constants of the purified m‐cresol purple (Douglas & Byrne, 2017,; Müller & Rehder, 2018,, spectrophotometrically measured pH showed excellent agreement with pH calculated from dissolved inorganic carbon (DIC) and total alkalinity over a wide salinity range of 0 to 36.9 (0.005 ± 0.016,n= 550). The coupled changes in DIC, oxygen, and nutrients suggest that biological production of organic matter in surface water and the subsequent aerobic respiration in subsurface was the dominant factor regulating pH variability in the nGOM in summer. The highest pH values were observed, together with the maximal biological uptake of DIC and nutrients, at intermediate salinities in the Mississippi and Atchafalaya plumes where light and nutrient conditions were favorable for phytoplankton growth. The lowest pH values (down to 7.59) were observed along with the highest concentrations of DIC and apparent oxygen utilization in hypoxic bottom waters. The nonconservative pH changes in both surface and bottom waters correlated well with the biologically induced changes in DIC, that is, per 100‐μmol/kg biological removal/addition of DIC resulted in 0.21 unit increase/decrease in pH. Coastal bottom water with lower pH buffering capacity is more susceptible to acidification from anthropogenic CO2invasion but reduction in eutrophication may offset some of the increased susceptibility to acidification.

    more » « less
  3. Abstract

    In coastal regions and marginal bodies of water, the increase in partial pressure of carbon dioxide (pCO2) in many instances is greater than that of the open ocean due to terrestrial (river, estuarine, and wetland) influences, decreasing buffering capacity and/or increasing water temperatures. Coastal oceans receive freshwater from rivers and groundwater as well as terrestrial-derived organic matter, both of which have a direct influence on coastal carbonate chemistry. The objective of this research is to determine if coastal marshes in Georgia, USA, may be “hot-spots” for acidification due to enhanced inorganic carbon sources and if there is terrestrial influence on offshore acidification in the South Atlantic Bight (SAB). The results of this study show that dissolved inorganic carbon (DIC) and total alkalinity (TA) are elevated in the marshes compared to predictions from conservative mixing of the freshwater and oceanic end-members, with accompanying pH around 7.2 to 7.6 within the marshes and aragonite saturation states (ΩAr) <1. In the marshes, there is a strong relationship between the terrestrial/estuarine-derived organic and inorganic carbon and acidification. Comparisons of pH, TA, and DIC to terrestrial organic material markers, however, show that there is little influence of terrestrial-derived organic matter on shelf acidification during this period in 2014. In addition, ΩArincreases rapidly offshore, especially in drier months (July). River stream flow during 2014 was anomalously low compared to climatological means; therefore, offshore influences from terrestrial carbon could also be decreased. The SAB shelf may not be strongly influenced by terrestrial inputs to acidification during drier than normal periods; conversely, shelf waters that are well-buffered against acidification may not play a significant role in mitigating acidification within the Georgia marshes.

    more » « less
  4. Abstract

    Coastal ecosystems are highly dynamic areas for carbon cycling and are likely to be negatively impacted by increasing ocean acidification. This research focused on dissolved inorganic carbon (DIC) and total alkalinity (TA) in the Mississippi Sound to understand the influence of local rivers on coastal acidification. This area receives large fluxes of freshwater from local rivers, in addition to episodic inputs from the Mississippi River through a human‐built diversion, the Bonnet Carré Spillway. Sites in the Sound were sampled monthly from August 2018 to November 2019 and weekly from June to August 2019 in response to an extended spillway opening. Prior to the 2019 spillway opening, the contribution of the local, lower alkalinity rivers to the Sound may have left the study area more susceptible to coastal acidification during winter months, with aragonite saturation states (Ωar) < 2. After the spillway opened, despite a large increase in TA throughout the Sound, aragonite saturation states remained low, likely due to hypoxia and increased CO2concentrations in subsurface waters. Increased Mississippi River input could represent a new normal in the Sound's hydrography during spring and summer months. The spillway has been utilized more frequently over the last two decades due to increasing precipitation in the Mississippi River watershed, which is primarily associated with climate change. Future increases in freshwater discharge and the associated declines in salinity, dissolved oxygen, and Ωarin the Sound will likely be detrimental to oyster stocks and the resilience of similar ecosystems to coastal acidification.

    more » « less
  5. Abstract Measuring, reporting, and verification (MRV) of ocean-based carbon dioxide removal (CDR) presents challenges due to the dynamic nature of the ocean and the complex processes influencing marine carbonate chemistry. Given these challenges, finding the optimal sampling strategies and suite of parameters to be measured is a timely research question. While traditional carbonate parameters such as total alkalinity (TA), dissolved inorganic carbon (DIC), pH, and seawater pCO2 are commonly considered, exploring the potential of carbon isotopes for quantifying additional CO2 uptake remains a relatively unexplored research avenue. In this study, we use a coupled physical-biogeochemical model of the California Current System (CCS) to run a suite of Ocean Alkalinity Enhancement (OAE) simulations. The physical circulation for the CCS is generated using a nested implementation of the Regional Ocean Modeling System (ROMS) with an outer domain of 1/10 ̊ (~10 km) and an inner domain of 1/30 ̊ (~3 km) resolution. The biogeochemical model, NEMUCSC, is a customized version of the North Pacific Ecosystem Model for Understanding Regional Oceanography (NEMURO) that includes carbon cycling and carbon isotopes. The CCS is one of four global eastern boundary upwelling systems characterized by high biological activity and CO2 concentrations. Consequently, the CCS represents an essential test case for investigating the efficacy and potential side effects of OAE deployments. The study aims to address two key questions: (1) the relative merit of OAE to counter ocean acidification versus the additional sequestration of CO2 from the atmosphere, and (2) the footprint of potentially harmful seawater chemistry adjacent to OAE deployments. We plan to leverage these high-resolution model results to competitively evaluate different MRV strategies, with a specific focus on analyzing the spatiotemporal distribution of carbon isotopic signatures following OAE. In this talk, we will showcase our initial results and discuss challenges in integrating high-resolution regional modeling into models of the global carbon cycle. More broadly, this work aims to provide insights into the plausibility of OAE as a climate solution that maintains ocean health and to inform accurate quantification of carbon uptake for MRV purposes. 
    more » « less