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Abstract Variations in estuarine carbonate chemistry can have critical impacts on marine calcifying organisms, yet the drivers of this variability are difficult to quantify from observations alone, due to the strong spatiotemporal variability of these systems. Terrestrial runoff and wetland processes vary year to year based on local precipitation, and estuarine processes are often strongly modulated by tides. In this study, a 3D-coupled hydrodynamic-biogeochemical model is used to quantify the controls on the carbonate system of a coastal plain estuary, specifically the York River estuary. Experiments were conducted both with and without tidal wetlands. Results show that on average, wetlands account for 20–30% of total alkalinity (TA) and dissolved inorganic carbon (DIC) fluxes into the estuary, and double-estuarine CO₂outgassing. Strong quasi-monthly variability is driven by the tides and causes fluctuations between net heterotrophy and net autotrophy. On longer time scales, model results show that in wetter years, lower light availability decreases primary production relative to biological respiration (i.e., greater net heterotrophy) resulting in substantial increases in CO₂outgassing. Additionally, in wetter years, advective exports of DIC and TA to the Chesapeake Bay increase by a factor of three to four, resulting in lower concentrations of DIC and TA within the estuary. Quantifying the impacts of these complex drivers is not only essential for a better understanding of coastal carbon and alkalinity cycling, but also leads to an improved assessment of the health and functioning of coastal ecosystems both in the present day and under future climate change. 

Abstract Alongside global climate change, many freshwater ecosystems are experiencing substantial shifts in the concentrations and compositions of salt ions coming from both land and sea. We synthesize a risk framework for anticipating how climate change and increasing salt pollution coming from both land and saltwater intrusion will trigger chain reactions extending from headwaters to tidal waters. Salt ions trigger ‘chain reactions,’ where chemical products from one biogeochemical reaction influence subsequent reactions and ecosystem responses. Different chain reactions impact drinking water quality, ecosystems, infrastructure, and energy and food production. Risk factors for chain reactions include shifts in salinity sources due to global climate change and amplification of salinity pulses due to the interaction of precipitation variability and human activities. Depending on climate and other factors, salt retention can range from 2 to 90% across watersheds globally. Salt retained in ecosystems interacts with many global biogeochemical cycles along flowpaths and contributes to ‘fast’ and ‘slow’ chain reactions associated with temporary acidification and long-term alkalinization of freshwaters, impacts on nutrient cycling, CO₂, CH₄, N₂O, and greenhouse gases, corrosion, fouling, and scaling of infrastructure, deoxygenation, and contaminant mobilization along the freshwater-marine continuum. Salt also impacts the carbon cycle and the quantity and quality of organic matter transported from headwaters to coasts. We identify the double impact of salt pollution from land and saltwater intrusion on a wide range of ecosystem services. Our salinization risk framework is based on analyses of: (1) increasing temporal trends in salinization of tributaries and tidal freshwaters of the Chesapeake Bay and freshening of the Chesapeake Bay mainstem over 40 years due to changes in streamflow, sea level rise, and watershed salt pollution; (2) increasing long-term trends in concentrations and loads of major ions in rivers along the Eastern U.S. and increased riverine exports of major ions to coastal waters sometimes over 100-fold greater than forest reference conditions; (3) varying salt ion concentration-discharge relationships at U.S. Geological Survey (USGS) sites across the U.S.; (4) empirical relationships between specific conductance and Na⁺, Cl⁻, SO₄²⁻, Ca²⁺, Mg²⁺, K⁺, and N at USGS sites across the U.S.; (5) changes in relationships between concentrations of dissolved organic carbon (DOC) and different salt ions at USGS sites across the U.S.; and (6) original salinization experiments demonstrating changes in organic matter composition, mobilization of nutrients and metals, acidification and alkalinization, changes in oxidation–reduction potentials, and deoxygenation in non-tidal and tidal waters. The interaction of human activities and climate change is altering sources, transport, storage, and reactivity of salt ions and chain reactions along the entire freshwater-marine continuum. Our salinization risk framework helps anticipate, prevent, and manage the growing double impact of salt ions from both land and sea on drinking water, human health, ecosystems, aquatic life, infrastructure, agriculture, and energy production. 

Abstract Continuous measurements of dissolved oxygen (DO) are useful for quantifying ecosystem metabolism, which is critical for understanding estuarine biogeochemistry and ecology, but current methods applied to these data may lead to estimates that are physically impossible and poorly constrained errors. Here, we present a new approach for estimating estuarine metabolism: Estuarine BAyesian Single‐station Estimation (EBASE). EBASE applies a Bayesian framework to a simple process‐based model and DO observations, allowing the estimation of critical model parameters, specifically light efficiency and respiration, as informed by a set of prior distributions. EBASE improves upon the stream‐based model from which it was derived by accommodating missing DO data and allowing the user to set the time period over which parameters are estimated. We demonstrate that EBASE can recover known metabolic parameters from a synthetic time series, even in the presence of noise (e.g., due to tidal advection) and when prior distributions are uninformed. Optimization periods of 7 and 30 d are more preferable than 1 d. A comparison with the more‐conventional method of Odum reveals the ability of EBASE to avoid unphysical results (such as negative photosynthesis and respiration) and improves when the DO data are detided. EBASE is available using open‐source software (R) and can be readily applied to multiple years of long‐term monitoring data that are available in many estuaries. Overall, EBASE provides an accessible method to parameterize a simple metabolic model appropriate for estuarine systems and will provide additional understanding of processes that influence ecosystem status and condition. 

Abstract Global carbon dioxide (CO₂) evasion from inland waters (rivers, lakes, and reservoirs) and carbon (C) export from land to oceans constitute critical terms in the global C budget. However, the magnitudes, spatiotemporal patterns, and underlying mechanisms of these fluxes are poorly constrained. Here, we used a coupled terrestrial–aquatic model to assess how multiple changes in climate, land use, atmospheric CO₂concentration, nitrogen (N) deposition, N fertilizer and manure applications have affected global CO₂evasion and riverine C export along the terrestrial‐aquatic continuum. We estimate that terrestrial C loadings, riverine C export, and CO₂evasion in the preindustrial period (1800s) were 1,820 ± 507 (mean ± standard deviation), 765 ± 132, and 841 ± 190 Tg C yr⁻¹, respectively. During 1800–2019, multifactorial global changes caused an increase of 25% (461 Tg C yr⁻¹) in terrestrial C loadings, reaching 2,281 Tg C yr⁻¹in the 2010s, with 23% (104 Tg C yr⁻¹) of this increase exported to the ocean and 59% (273 Tg C yr⁻¹) being emitted to the atmosphere. Our results showed that global inland water recycles and exports nearly half of the net land C sink into the atmosphere and oceans, highlighting the important role of inland waters in the global C balance, an amount that should be taken into account in future C budgets. Our analysis supports the view that a major feature of the global C cycle–the transfer from land to ocean–has undergone a dramatic change over the last two centuries as a result of human activities.