Coastal North Carolina (USA) has experienced 35 tropical cyclones over the past 2 decades; the frequency of these events is expected to continue in the foreseeable future. Individual storms had unique and, at times, significant hydrologic, nutrient-, and carbon (C)-loading impacts on biogeochemical cycling and phytoplankton responses in a large estuarine complex, the Pamlico Sound (PS) and Neuse River Estuary (NRE). Major storms caused up to a doubling of annual nitrogen and tripling of phosphorus loading compared to non-storm years; magnitudes of loading depended on storm tracks, forward speed, and precipitation in NRE-PS watersheds. With regard to C cycling, NRE-PS was a sink for atmospheric CO 2 during dry, storm-free years and a significant source of CO 2 in years with at least one storm, although responses were storm-specific. Hurricane Irene (2011) mobilized large amounts of previously-accumulated terrigenous C in the watershed, mainly as dissolved organic carbon, and extreme winds rapidly released CO 2 to the atmosphere. Historic flooding after Hurricanes Joaquin (2015) and Matthew (2016) provided large inputs of C from the watershed, modifying the annual C balance of NRE-PS and leading to sustained CO 2 efflux for months. Storm type affected biogeochemical responses as C-enriched

In 2016, Hurricane Matthew accounted for 25% of the annual riverine C loading to the Neuse River Estuary‐Pamlico Sound, in eastern North Carolina. Unlike inland watersheds, dissolved organic carbon (DOC) was the dominant component of C flux from this coastal watershed and stable carbon isotope and chromophoric dissolved organic matter evidence indicated the estuary and sound were dominated by wetland‐derived terrigenous organic matter sources for several months following the storm. Persistence of wetland‐derived DOC enabled its degradation to carbon dioxide (CO2), which was supported by sea‐to‐air CO2 fluxes measured in the sound weeks after the storm. Under future increasingly extreme weather events such as Hurricane Matthew, and most recently Hurricane Florence (September 2018), degradation of terrestrial DOC in floodwaters could increase flux of CO2 from estuaries and coastal waters to the atmosphere.

Riverine loading of nutrients and organic matter act in concert to modulate CO2 fluxes in estuaries, yet quantitative relationships between these factors remain poorly defined. This study explored watershed‐scale mechanisms responsible for the relatively low CO2 fluxes observed in two microtidal, lagoonal estuaries. Air‐water CO2 fluxes were quantified with 74 high‐resolution spatial surveys in the neighboring New River Estuary (NewRE) and Neuse River Estuary (NeuseRE), North Carolina, which experience a common climatology but differ in marine versus riverine influence. Annually, both estuaries were relatively small sources of CO2 to the atmosphere, 12.5 and 16.3 mmol C m−2 d−1 in the NeuseRE and NewRE, respectively. Large‐scale pCO2 variations were driven by changes in freshwater age, which modulates nutrient and organic carbon supply and phytoplankton flushing. Greatest pCO2 undersaturation was observed at intermediate freshwater ages, between 2 and 3 weeks. Biological controls on CO2 fluxes were obscured by variable inputs of river‐borne CO2, which drove CO2 degassing in the river‐dominated NeuseRE. Internally produced CO2 exceeded river‐borne CO2 in the marine‐dominated NewRE, suggesting that net ecosystem heterotrophy, rather than riverine inputs, drove CO2 fluxes in this system. Variations in riverine alkalinity and inorganic carbon loading caused zones of minimum buffering capacity to occur at different locations in each estuary, enhancing the sensitivity of estuarine inorganic C chemistry to acidification. Although annual CO2 fluxes were similar between systems, watershed‐specific hydrologic factors led to disparate controls on internal carbonate chemistry, which can influence ecosystem biogeochemical cycling, trophic state, and response to future perturbations.

A comprehensive carbon budget was constructed to quantify carbon flows through the freshwater‐marine continuum of a temperate, microtidal estuary. We performed coordinated measurements of dissolved inorganic carbon and total organic carbon fluxes to resolve spatial variability between and along the channel and shoals and diel variability across the entire estuary for 2 yr. Net ecosystem metabolism (NEM) was the most significant control on carbon flow within estuary regions. However, metabolic rates were spatially coupled such that counteracting fluxes across the channel‐shoal gradient or along the river‐ocean gradient resulted in system‐wide NEM that was closely in balance (–3.0 ± 3.3 to 1.1 ± 4.4 molC m−2 yr−1). Similarly, large diel and seasonal variability in air–water CO2 fluxes were observed during 72 spatial surveys, but these short‐term variations generally cancelled out when aggregated to annual budget terms. Although atmospheric exchanges were small (–0.2 ± 0.1 to 2.0 ± 0.4 molC m−2 yr−1), they were subject to large errors (± 4 molC m−2 yr−1) if diel variability was neglected. Internal mechanisms that maintained balanced carbon flows were strongly impacted by river discharge and were only apparent by separately quantifying channel and shoal fluxes. Notably, metabolic responses of the shoal to river forcing outweighed the responses of the channel, and the net impact was contrary to prior relationships derived from synthesis of lower‐resolution carbon budgets. Our budget demonstrates that resolution of carbon fluxes at appropriate scales, including channel‐shoal and diel variability, is critical to characterizing ecosystem function and the fate of carbon within the river‐ocean continuum.

Decadal-scale pH trends for the open ocean are largely monotonic and controlled by anthropogenic CO 2 invasion. In estuaries, though, such long-term pH trends are often obscured by a variety of other factors, including changes in net metabolism, temperature, estuarine mixing, and riverine hydrogeochemistry. In this study, we mine an extensive biogeochemical database in two North Carolina estuaries, the Neuse River estuary (NeuseRE) and New River estuary (NewRE), in an effort to deconvolute decadal-scale trends in pH and associated processes. By applying a Generalized Additive Mixed Model (GAMM), we show that temporal changes in NewRE pH were insignificant, while pH decreased significantly throughout much of the NeuseRE. In both estuaries, variations in pH were accompanied by increasing river discharge, and were independent of rising temperature. Decreases in bottom-water pH in the NeuseRE coincided with elevated primary production in surface waters, highlighting the importance of eutrophication on long-term acidification trends. Next, we used a simple mixing model to illustrate the impact of changing river discharge on estuarine carbonate chemistry. We found that increased riverine alkalinity loads to the NewRE likely buffered the impact of CO 2-intrusion-induced acidification. In the NeuseRE, however, elevated dissolved inorganic carbon loads further decreased the buffering capacity, exacerbating the effects of CO 2-intrusion-driven acidification. Taken together, the findings of this study show that future trajectories in estuarine pH will be shaped by complex interactions among global-scale changes in climate, regional-scale changes in precipitation patterns, and local-scale changes in estuarine biogeochemistry.