Archive for estuary

The curious role of organic alkalinity in seawater carbonate chemistry

Posted by mmaheigan 
· Wednesday, August 5th, 2020 

The marine chemistry community has measured organic alkalinity in coastal and estuarine waters for over two decades. While the common perception is that any unaccounted alkalinity should enhance seawater buffer capacity, the effects of organic alkalinity on this buffering capacity, and hence the potential CO2 uptake by coastal and estuarine systems are still not well quantified.

In a thought experiment recently published in Aquatic Geochemistry, the author added organic alkalinity to model seawater (salinity=35, temperature=15˚C, pCO2=400 µatm) in the form of 1) organic acid (HOA) and 2) its conjugate base (OA–). Results suggest that the weaker organic acid/conjugate base pair (pKa ~8.2-8.3) yields the greatest buffering capacity under the simulation conditions. However, the HOA addition first displaces dissolved inorganic carbon (DIC) and causes CO2 degassing; the resultant seawater buffer capacity can be greater or less than the original seawater, depending on the pKa. In comparison, OA– addition leads to CO2 uptake and elevated seawater buffer capacity. As the organic anions are remineralized via biogeochemical processes, a “charge transfer” results in quantitative conversion to carbonate alkalinity (CA), which is overpowered by the concomitant CO2 production (∆DIC>∆CA). Overall, the complete process (organic alkalinity addition and remineralization) results in a net CO2 release from seawater, regardless of whether it is added in the form of HOA or OA–.

Figure caption: A schematic illustration of the role of organic alkalinity on seawater carbonate chemistry in an open system (constant CO2 partial pressure). Organic acid (HOA) addition leads to CO2 degassing and varying seawater buffer (greater or lower than the original seawater) as a function of Ka. Organic base (OA–) addition causes initial CO2 uptake and overall elevated seawater buffer. Regardless, upon complete remineralization, more CO2 is produced than the amount of net gain in carbonate alkalinity (OA– addition only). Therefore, the complete process (organic acid/base addition and its ultimate remineralization) should result in net CO2 degassing.

While the presence of organic alkalinity may increase seawater buffer capacity to some extent (depending on the pKa values of the organic acid), CO2 degassing from the seawater, because of both the initial organic acid addition and eventual remineralization of organic molecules, should be the net result. However, modern alkalinity analysis precludes the bases of stronger organic acids (pKa < 4.5). This fraction of “potential” alkalinity, especially from river waters, remains a relevant topic for future alkalinity cycle studies. The potential alkalinity can be converted to bicarbonate through biogeochemical reactions (or charge transfer at face value), although it is unclear how significant this potential alkalinity is in rivers that flow into the ocean.

 

A backstory
The author used an example of vinegar and limewater (calcium hydroxide solution), which is employed by many aquarists to dose alkalinity and calcium in hard coral saltwater tanks, to demonstrate the conversion of organic base (acetate ion) to bicarbonate and CO2 via complete remineralization. It is also known the added vinegar helps microbes to remove excess nitrate. This procedure had been in the author’s memory for the past nine years, ever since his previous research life when he participated in a study at a coral farm in a suburb of Columbus, Ohio. A strong vinegar odor would arise every now and then at the facility. However, a recent communication with the facility owner suggests that this memory was totally false and the owner simply used vinegar to get rid of lime (CaCO3) buildup in the water pumps. Nonetheless, the chemistry in this paper should still hold, with that false memory serving as the inspiration.

 

Author:
Xinping Hu (Texas A&M University-Corpus Christi)

Impacts of atmospheric nitrogen deposition and coastal nitrogen fluxes on oxygen concentrations in Chesapeake Bay

Posted by mmaheigan 
· Tuesday, April 30th, 2019 

How do atmospheric and oceanic nutrients impact oxygen concentrations in the Chesapeake Bay? Generally, researchers focus on how terrestrial nutrients impact hypoxia. The relative importance of river, atmosphere, and ocean inputs have not been quantified, largely because estimates of nitrogen fluxes from the atmosphere and ocean are limited.

A recent study in Journal of Geophysical Research: Oceans quantified the relative impacts of atmospheric and oceanic nitrogen inputs on dissolved oxygen (DO) in the Chesapeake Bay. The authors combined a 3-D biogeochemical model and estimates of atmospheric deposition from the Community Multiscale Air Quality model and interpolations of nitrogen concentrations along the continental shelf from the Ocean Acidification Data Stewardship Project. Atmospheric nitrogen deposition and coastal nitrogen fluxes most impact Chesapeake Bay DO concentrations during the summer when surface waters are depleted in nitrogen. Overall, atmospheric nitrogen deposition has about the same gram-for-gram impact on Chesapeake Bay DO as riverine loading. Although all three nutrient sources vary spatially and temporally, in the central bay, where summer hypoxia is most prevalent, coastal nitrogen fluxes and atmospheric nitrogen fluxes have roughly the same impact on bottom oxygen as a ~10% change in riverine nitrogen loading (Figure 1).

Figure caption: (Left) Four-year (2002–2005) average increase in DO in the summer by removing the atmospheric nitrogen deposition (AtmN), reducing the riverine loading (ΔRiverN) by ~10% (roughly equivalent to turning off the atmospheric deposition), and removing the nitrogen fluxes from the continental shelf (CoastalN). (Right) Relative impacts of the three nitrogen modification scenarios on summertime bottom DO.

These results indicate that two often-neglected sources of nitrogen—direct atmospheric deposition and fluxes of nitrogen from the continental shelf—substantially impact Chesapeake Bay DO, especially in the summer. Future study is needed to investigate the long-term trend of these relative impacts by continued coordination between modeling and observational work, such as applying higher-resolution atmospheric deposition products and integrating more in situ data along the model ocean boundary when they are available. These efforts will improve our understanding of the impacts of different nutrient sources on biogeochemical cycles in coastal water bodies.

 

Authors:
Fei Da (VIMS, College of William & Mary)
Marjorie A. M. Friedrichs (VIMS, College of William & Mary)
Pierre St-Laurent (VIMS, College of William & Mary)

Biological and physical controls on estuarine nitrous oxide emissions

Posted by mmaheigan 
· Tuesday, February 5th, 2019 

Nitrous oxide (N2O) is a potent greenhouse gas with rising atmospheric concentrations. Atmospheric emissions of N2O are predicted to increase with continued anthropogenic perturbation of the nitrogen cycle, yet the magnitude of these emissions is uncertain, particularly in coastal systems where N2O fluxes are poorly constrained. How do N2O emissions from a eutrophic estuary vary in space and time?

Figure 1: Depth profiles of nitrous oxide (N2O) (circles), salinity (dashed line), and dissolved oxygen (solid line) in the Chesapeake Bay at three stations. Solid circles indicate oversaturation of N2O with respect to equilibrium with the atmosphere, and open circles indicate undersaturation.

In a recent publication in Estuaries and Coasts, Laperriere et al. (2018) examined how physical and biological processes influence the distribution of N2O in Chesapeake Bay using dissolved gas measurements (N2O and N2/Ar) and stable isotope tracer incubations. During stratified summer conditions, the mesohaline region of the Chesapeake Bay was always a source of N2O to the atmosphere. The highest N2O concentrations occurred in the pycnocline at the interface between reducing bottom waters and oxygenated surface waters (Figure 1). Vertical mixing of surface waters across the pycnocline caused elevated rates of ammonia oxidation, a biological source of N2O, and resulted in the accumulation of nitrite (NO2–) below the pycnocline. During periods of weak mixing, ammonia oxidation rates and N2O concentrations were lower, and low dissolved oxygen concentrations below the pycnocline set the stage for N2O consumption via denitrification (Figure 1). The interplay between biological and physical processes controlling fluctuations in N2O concentration was examined using a mass balance approach. Mass balance estimates indicated that both biological processes and physical transport contribute to local changes in N2O concentration. The authors suggest that the fate of N2O during stratified summer conditions is governed by vertical mixing across the pycnocline, controlling whether N2O is released to the atmosphere or consumed at depth.

 

Authors:
Sarah M. Laperriere (University of California, Santa Barbara)
Nicholas J. Nidzieko (University of California, Santa Barbara)
Rebecca J. Fox (Washington College)
Alexander W. Fisher (University of California, Santa Barbara)
Alyson E. Santoro (University of California, Santa Barbara)

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