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Extreme events are accelerating coastal carbon cycling

Posted by mmaheigan

· Monday, March 1st, 2021

The world is getting stormier, and recent evidence shows significant impacts on coastal carbon cycling. The upticks in extreme weather events such as tropical cyclones have resulted in enhanced delivery of nutrients and organic matter across the land-ocean continuum. Lagoonal estuaries such as the Albemarle-Pamlico Sound (APS) in North Carolina and Galveston Bay in Texas are key coastal environments in which we can observe the long-term carbon cycling consequences of these events. Residence times of these coastal environments are on the order of months to over a year, providing ample opportunity for biogeochemical processing. Emerging from studies of Atlantic and Gulf of Mexico hurricanes in 2016 and 2017 is a clear example of the role of terrestrial dissolved organic carbon (DOC) as a key reactant driving the observed carbon cycling and ecosystem effects ( Figure 1).

Figure. 1. The impact of hurricanes on CO₂ fluxes (top) and terrestrial DOC decay constants (bottom) demonstrate the sustained effect on the coastal carbon cycle caused by extreme weather events. Top panel shows results from Hurricane Matthew in 2016, where date is month and day and Km downstream represents observations taken along the main axis of the Neuse River Estuary and lower Pamlico Sound, eastern North Carolina. F_CO2 is the daily sea-to-air flux of CO₂ estimated from measurements of temperature, salinity, dissolved inorganic carbon, and wind speed. The results indicate the Sound existed as a weak yet sustained CO2 source to the atmosphere well after the storm. Outgassing of CO₂ is driven by the rapid mineralization of terrestrial DOC. Bottom panel shows the high bioreactivity of flood-derived terrestrial DOC indicated by elevated microbial decay constants for Galveston Bay and the coastal Gulf of Mexico in 2017 as compared to high and low latitude coastal environments.

In coastal North Carolina, 36 tropical cyclones (TCs), including three floods of historical significance in the past two decades, have occurred in the past 20 years. The lingering effects of these storms include extensive periods of carbon dioxide (CO₂) supersaturation. For example, Hurricane Matthew in 2016 caused the lower Pamlico Sound to emit CO₂ for months after the passage of the storm. With similar results documented for the Pamlico Sound for storms in 2011 and 2012, there is solid evidence that shifts in the ecosystem state of this mesotrophic estuary from net autotrophic to net heterotrophic are a major effect of this process.

Reactive DOC from the landscape appears to be driving the shift in ecosystem state. Large plumes of brown-colored DOC are observable from space in numerous satellite images of the Atlantic and Gulf coasts following these storms. The color is part of a phenomenon known as “coastal darkening"—spectroscopic, stable isotopic, and biomarker evidence show this darkening is related to the flushing of wetlands in the flood-plain adjacent to the rivers draining into these estuaries.

Along the Texas coast, Hurricane Harvey produced the largest rainfall event recorded in US history and caused extensive flooding in 2017. Similar to results from coastal North Carolina, flood-derived terrestrial DOC in Galveston Bay exhibited high bioreactivity, with decay constants exceeding those observed for terrestrial DOC across coastal environments from high and low latitudes by almost three-fold. The rapid processing of terrestrial DOC was linked to an active microbial community capable of decomposing aromatic compounds that are abundant in colored DOC as indicated by genomic analyses. These recent studies clearly demonstrate the impacts of large storm events on coastal carbon cycling via the transport of reactive terrestrial DOC into coastal waters. Climate-driven increases in the frequency and intensity of such storm events warrant more sustained capacity to monitor episodic deliveries of carbon and nutrients and their impacts on coastal marine ecosystems.

Authors:
Chris Osburn (North Carolina State University) @closburn
Hans Paerl (University of North Carolina, Institute of Marine Sciences)
Ge Yan (Institute of Deep-Sea Science and Engineering, Chinese Academy of Sciences)
Karl Kaiser (Texas A&M University, Galveston Campus)

Citations:

Yan, G., Labonté, J. M., Quigg, A., & Kaiser, K. (2020). Hurricanes accelerate dissolved organic carbon cycling in coastal ecosystems. Frontiers in Marine Science, 7, 248.

Osburn, C. L., Rudolph, J. C., Paerl, H. W., Hounshell, A. G., & Van Dam, B. R. (2019). Lingering carbon cycle effects of Hurricane Matthew in North Carolina's coastal waters. Geophysical Research Letters, 46(5), 2654-2661.

Counterintuitive effects of shoreline armoring on estuarine water clarity

Posted by mmaheigan

· Wednesday, February 24th, 2021

Around the world, human-altered shorelines change sediment inputs to estuaries and coastal waters, altering water clarity, especially in areas of dense human population. The Chesapeake Bay estuary is recovering from historically high nutrient and sediment inputs, but water clarity improvement has been ambiguous. Long-term trends show increasing water clarity in terms of deepening light attenuation depth, yet degrading clarity in terms of shallowing Secchi depth over time. High water clarity is needed to support seagrass meadows, which act as nursery habitats for commercially important fish species such as striped bass. How are these opposing water clarity trends possible?

In a recent paper published in Science of the Total Environment, researchers performed experiments with a coupled hydrodynamic-biogeochemical model to test a simulated Chesapeake Bay under realistic conditions, more shoreline erosion, and highly armored shorelines. Comparing the two extreme conditions (Figure 1), there was a striking difference between (a) an estuary experiencing more shoreline erosion and greater resuspension versus (b) a highly armored estuary with decreased resuspension. Reduced erosion yielded improved water clarity in terms of light attenuation depth, but a shallower Secchi depth (reduced visibility). In estuaries, reducing sediment inputs is often proposed as a strategy for improving water quality. This study shows that, under certain conditions in a productive estuary, reduced sediments can have unintended secondary effects on water clarity due to enhanced production of organic particles. This study also highlights the need to consider other sediment sources in addition to rivers, such as seabed resuspension and shoreline erosion, especially at times and locations of low river input.

Figure 1. Schematic of how shoreline armoring causes deepening light attenuation depth (navy) yet shallowing Secchi depth (green) during the spring growing season in the mid-bay central channel.

Authors:
Jessica S. Turner
Pierre St-Laurent
Marjorie A. M. Friedrichs
Carl T. Friedrichs
(all Virginia Institute of Marine Science)

Wildfire impacts on coastal ocean phytoplankton

Posted by mmaheigan

· Wednesday, February 24th, 2021

Wildfire frequency, size, and destructiveness has increased over the last two decades, particularly in coastal regions such as Australia, Brazil, and the western United States. While the impact of fire on land, plants, and people is well documented, very few studies have been able to evaluate the impact of fires on ocean ecosystems. A serendipitously planned research cruise one week after the Thomas Fire broke out in California in December 2017 allowed the authors of this study and their colleagues to sample the adjacent Santa Barbara Channel during this devastating extreme fire event.

In a recent paper published in Journal of Geophysical Research: Oceans, the authors describe the phytoplankton community in the Santa Barbara Channel during the Thomas Fire. Phytoplankton community composition was described using a combination of images of phytoplankton from the Imaging FlowCytobot (McLane Labs) and phytoplankton pigments. Dinoflagellates were the dominant phytoplankton group in the surface ocean during the Thomas Fire, according to both methods (Figure 1).

Figure 1. (A) The fraction of total particle volume imaged by the Imaging FlowCytobot (IFCB) comprised of phytoplankton (green) and detritus (brown). Example IFCB images of ash (counted as part of detritus) particles are outlined in brown. (B) The phytoplankton fraction is then further divided by taxonomy, showing the abundance of nano-sized phytoplankton and especially dinoflagellates during the week of sampling. Example IFCB images of Gonyaulax (outlined in dark green), Prorocentrum (outlined in light green), and Umbilicosphaera (outlined in purple) cells are also shown.

While this study was not able to demonstrate a causal relationship between the Thomas Fire and the presence of dinoflagellates, this result is quite different from previous winters in the Santa Barbara Channel, when picophytoplankton and diatoms typically dominate the winter community. The incidence of dinoflagellates in the Santa Barbara Channel in December 2017 was correlated with the warmer-than-average water temperature during this study, which matched observations from other areas along the Central California coast that winter.

At the time this study was conducted, the Thomas Fire was the largest wildfire in California history. Since then, California fires have increased in danger, destruction, and human mortality; the Mendocino Fire complex (summer 2018) and five separate wildfires in summer 2020 exceeded the impacts of the Thomas Fire. With wildfire severity and frequency increasing not only in California but in coastal regions worldwide, this study gives an important first look at the impact of wildfire smoke and ash on oceanic primary productivity and community composition.

Authors:
Sasha Kramer (University of California Santa Barbara)
Kelsey Bisson (Oregon State University)
Alexis Fischer (University of California Santa Cruz)

Ice sheets mobilize trace elements for export downstream

Posted by mmaheigan

· Thursday, January 7th, 2021

Trace elements are essential micronutrients for life in the ocean and also serve as valuable fingerprints of chemical weathering. The behaviour of trace elements in the ocean has gained interest because some of these elements are found at vanishingly low concentrations that limit ecosystem productivity. Despite delivering >2000 km³ yr^-1 of freshwater to the polar oceans, ice sheets have largely been overlooked as major trace element sources. This is partly due to a lack of data on meltwater endmember chemistry beneath and emerging from the Greenland and Antarctic ice sheets, which cover 10% of Earth’s land surface area, and partly because meltwaters were previously assumed to be dilute compared to most river waters.

In a study published in PNAS, authors analysed the trace element composition of meltwaters from the Mercer Subglacial Lake, a hydrologically active subglacial lake >1000 m below the surface of the Antarctic Ice Sheet, and a meltwater river emerging from beneath a large outlet glacier of the Greenland Ice Sheet (Leverett Glacier). These subglacial meltwaters (i.e., water travelling along the ice-rock interface beneath an ice mass) contained much higher concentrations of trace elements than anticipated. For example, typically immobile elements like iron and aluminium were observed in the dissolved phase (<0.45 µm) at much higher concentrations than in mean river or open ocean waters (up to 20,900 nM for Fe and 69,100 nM for Al), but exhibited large size fractionation between colloidal/nanoparticulate (0.02 – 0.45 µm) and soluble (<0.02 µm) size fractions (Figure 1). Subglacial physical and biogeochemical weathering processes are thought to mobilize many of these trace elements from the bedrock and sediments beneath ice sheets and export them downstream. Antarctic subglacial meltwaters were more enriched in dissolved trace elements than Greenland Ice Sheet outflow, which is likely due to longer subglacial residence times, lack of dilution from surface meltwater inputs, and differences in underlying sediment geology.

These results indicate that ice sheet systems can mobilize large quantities of trace elements from the land to the ocean and serve as major contributors to regional elemental cycles (e.g., coastal Southern Ocean). In a warming climate with increasing ice sheet runoff, subglacial meltwaters will become an increasingly dynamic source of micronutrients to coastal oceanic ecosystems in the polar regions.

Figure caption: Leverett Glacier (Greenland Ice Sheet) and Mercer Subglacial Lake (Antarctic Ice Sheet) dissolved elemental concentrations (<0.45 µm) normalized to mean non-glacial riverine trace element concentrations (Gaillardet et al., 2014) and major element concentrations (Martin and Meybeck, 1979). Grey regions indicate ±50 % of the riverine mean. Although major elements can be significantly depleted compared to non-glacial rivers, trace elements are commonly similar to or enriched.

Authors:
Jon R. Hawkings (Florida State Univ and German Research Centre for Geosciences)
Mark L. Skidmore (Montana State Univ)
Jemma L. Wadham (Univ of Bristol, UK)
John C. Priscu (Montana State Univ)
Peter L. Morton (Florida State Univ)
Jade E. Hatton (Univ of Bristol, UK)
Christopher B. Gardner (Ohio State Univ)
Tyler J. Kohler (École Polytechnique Fédérale de Lausanne, Switzerland)
Marek Stibal (Charles University, Prague, Czech Republic)
Elizabeth A. Bagshaw (Cardiff Univ, UK)
August Steigmeyer (Montana State Univ)
Joel Barker (Univ of Minnesota)
John E. Dore (Montana State Univ)
W. Berry Lyons (Ohio State Univ)
Martyn Tranter (Univ of Bristol, UK)
Robert G. M. Spencer (Florida State Univ)
SALSA Science Team

Water clarity impacts temperature and biogeochemistry in Chesapeake Bay

Posted by mmaheigan

· Thursday, December 3rd, 2020

Estuarine water clarity is determined by suspended materials in the water, including colored dissolved organic matter, phytoplankton, sediment, and detritus. These constituents directly affect temperature because when water is opaque, sunlight heats only the shallowest layers near the surface, but when water is clear, sunlight can penetrate deeper, warming the waters below the surface. Despite the importance of accurately predicting temperature variability, many numerical modeling studies do not adequately parameterize this fundamental relationship between water clarity and temperature.

In a recent study published in Estuaries and Coasts, the authors quantified the impact of a more realistic representation of water clarity in a hydrodynamic-biogeochemical model of the Chesapeake Bay by comparing two simulations: (1) water clarity is constant in space and time for the calculation of solar heating vs. (2) water clarity varies with modeled concentrations of light-attenuating materials. In the variable water clarity simulation (2), the water is more opaque, particularly in the northern region of the Bay. During the spring and summer months, the lower water clarity in the northern Bay is associated with warmer surface temperatures and colder bottom temperatures. Warmer surface temperatures encourage phytoplankton growth and nutrient uptake near the head of the Bay, thus fewer nutrients are transported downstream. These conditions are exacerbated during high-river flow years, when differences in temperature, nutrients, phytoplankton, and zooplankton extend further seaward.

Figure 1: Top row: Difference in the light attenuation coefficient for shortwave heating, kh[m-1] (variable minus constant light attenuation simulation). June, July, and August average for (A) 2001, (B) average of 2001-2005, and (C) 2003; difference in bottom temperatures [oC] (variable minus constant). Bottom row: Difference in June, July, and August average bottom temperature for (D) 2001, (E) average of 2001-2005, and (F) 2003. Data for 2001 are representative of low river discharge, and 2003 are representative high river discharge years.

This work demonstrates that a constant light attenuation scheme for heating calculations in coupled hydrodynamic-biogeochemical models underestimates temperature variability, both temporally and spatially. This is an important finding for researchers who use models to predict future temperature variability and associated impacts on biogeochemistry and species habitability.

Authors:
Grace E. Kim (NASA, Goddard Space Flight Center)
Pierre St-Laurent (VIMS, William & Mary)
Marjorie A.M. Friedrichs (VIMS, William & Mary)
Antonio Mannino (NASA, Goddard Space Flight Center)

A new Regional Earth System Model of the Mediterranean Sea biogeochemical dynamics

Posted by mmaheigan

· Thursday, November 19th, 2020

The Mediterranean Sea is a semi-enclosed mid-latitude oligotrophic basin with a lower net primary production than the global ocean. A west-east productivity trophic gradient results from the superposition of biogeochemical and physical processes, including the biological pump and associated carbon and nutrient (nitrogen, phosphorus) fluxes, the spatial asymmetric distribution of nutrient sources (rivers, atmospheric deposition, coastal upwelling, etc.), the estuarine inverse circulation associated with the inflow of Atlantic water through the Gibraltar Strait. The complex and highly variable interface between land and sea throughout this basin add a further layer of complexity in the Mediterranean oceanic and atmospheric circulation and on the associated biogeochemistry dynamics, emphasizing the need for high-resolution truly integrated Regional Earth System Models to track and understand fine-scale processes and ecosystem dynamics.

In a recent paper published in the Journal of Advances in Modeling Earth System, the authors introduced a new version of the Regional Earth System model RegCM-ES and evaluated its performance in the Mediterranean region. RegCM-ES fully integrates the regional climate model RegCM4, the land surface scheme CLM4.5 (Community Land Model), the river routing model HD (Hydrological Discharge Model), the ocean model MITgcm (MIT General Circulation model) and the Biogeochemical Flux Model BFM.

A comparison with available observations has shown that RegCM-ES was able to capture the mean climate of the region and to reproduce horizontal and vertical patterns of chlorophyll-a and PO₄(the limiting nutrient in the basin) (Figure 1). The same comparison revealed a systematic underestimation of simulated dissolved oxygen (which will be fixed by the use of a new parametrization of oxygen solubility), and an overestimation of NO₃, possibly due to uncertainties in initial and boundary conditions (mostly traced to river and Dardanelles nutrient discharges) and an overly vigorous vertical mixing simulated by the ocean model in some parts of the Basin.

Figure.1 Distributions of chlorophyll-a mg/m³ (top) and PO₄ mmol/m³ (bottom) in the Mediterranean Sea as simulated by RegCM-ES.

Overall, this analysis has demonstrated that RegCM-ES has the capabilities required to become a powerful tool for studying regional dynamics and impacts of climate change on the Mediterranean Sea and other ocean basins around the world.

Authors:
Marco Reale (Abdus Salam International Centre for theoretical physics-ICTP, National Institute of Oceanography and Experimental Geophysics-OGS)
Filippo Giorgi (Abdus Salam International Centre for theoretical physics-ICTP)
Cosimo Solidoro (National Institute of Oceanography and Experimental Geophysics-OGS)
Valeria Di Biagio (National Institute of Oceanography and Experimental Geophysics-OGS)
Fabio Di Sante (Abdus Salam International Centre for theoretical physics-ICTP)
Laura Mariotti (National Institute of Oceanography and Experimental Geophysics-OGS)
Riccardo Farneti (Abdus Salam International Centre for theoretical physics-ICTP)
Gianmaria Sannino (Italian National Agency for New Technologies, Energy and Sustainable Economic Development-ENEA)

Estuarine sediment resuspension drives non-local impacts on biogeochemistry

Posted by mmaheigan

· Friday, September 18th, 2020

Sediment processes, including resuspension and transport, affect water quality in estuaries by altering light attenuation, primary productivity, and organic matter remineralization, which then influence oxygen and nitrogen dynamics. In a recent paper published in Estuaries and Coasts, the authors quantified the degree to which sediment resuspension and transport affected estuarine biogeochemistry by implementing a coupled hydrodynamic-sediment transport-biogeochemical model of the Chesapeake Bay. By comparing summertime model runs that either included or neglected seabed resuspension, the study revealed that resuspension increased light attenuation, especially in the northernmost portion of the Bay, which subsequently shifted primary production downstream (Figure 1). Resuspension also increased remineralization in the central Bay, which experienced higher organic matter concentrations due to the downstream shift in primary productivity. When combined with estuarine circulation, these resuspension-induced shifts caused oxygen to increase and ammonium to increase throughout the Bay in the bottom portion of the water column. Averaged over the channel, resuspension decreased oxygen by ~25% and increased ammonium by ~50% for the bottom water column. Changes due to resuspension were of the same order of magnitude as, and generally exceeded, short-term variations within individual summers, as well as interannual variability between wet and dry years. This work highlights the importance of a localized process like sediment resuspension and its capacity to drive biogeochemical variations on larger spatial scales. Documenting the spatiotemporal footprint of these processes is critical for understanding and predicting the response of estuarine and coastal systems to environmental changes, and for informing management efforts.

Figure 1: Schematic of how resuspension affects biogeochemical processes based on HydroBioSed model estimates for Chesapeake Bay.

Authors:
Julia M. Moriarty (University of Colorado Boulder)
Marjorie A. M. Friedrichs (Virginia Institute of Marine Science)
Courtney K. Harris (Virginia Institute of Marine Science)

Also see the Geobites piece “Muddy waters lead to decreased oxygen in Chesapeake Bay” on this publication, by Hadley McIntosh Marcek

The role of nutrient trapping in promoting shelf hypoxia in the southern Benguela upwelling system

Posted by mmaheigan

· Thursday, September 3rd, 2020

The southern Benguela upwelling system (SBUS) off southwest Africa is an exceptionally fertile ocean region that supports valuable commercial fisheries. The productivity of this system derives from the upwelling of nutrient-rich Subantarctic Mode Water, and from the concurrent entrainment of nutrients regenerated proximately on the expansive continental shelf. The SBUS is prone to severe seasonal hypoxic events that decimate regional fisheries, occurrences of which are inextricably linked to the inherent nutrient dynamics. In a study recently published in JGR Oceans, the authors sought to understand the mechanisms sustaining elevated concentrations and seasonally-variable distributions of nutrients in the SBUS, in relation to the subsurface oxygen content. Inter-seasonal measurements of nutrients and nitrate isotope ratios across the SBUS in 2017 revealed that upwards of 48% (summer) and 63% (winter) of the on‐shelf nutrients derived from regeneration in situ. The severity of hypoxia at the shelf bottom, in turn, correlated with the incidence of regenerated nutrients. The accrual of nutrients at the shelf bottom appears to be aided by hydrographic fronts that restrict offshore transport, trapping regenerated nutrients on the SBUS shelf and increasing the pool of nutrients available for upwelling – ultimately contributing to hypoxic events. This study underscores the need – if we are to develop a mechanistic and predictive understanding of hypoxia in the SBUS and elsewhere – to elucidate the role of shelf circulation in promoting the accrual of regenerated nutrients on the continental shelf. The next step is to combine new and existing observations with quantitative simulations to further interrogate the coupled physical-biogeochemical mechanisms that modulate the intensity of hypoxia.

Figure caption: Schematic of proposed nutrient-trapping mechanism: Deep nutrient-rich Subantarctic Mode Water (SAMW) acquires more nutrients as it passes over the shelf sediments from the regeneration of exported particulate organic material (POM). The production of this POM is fueled by nutrients stripped from the surface waters advecting back off-shore. The thickness of the arrows represents nutrient concentrations. Triangles indicate the positions of the Shelf Break Front (SBF) and Columbine Front (CF), coincident with an observed subduction of the Ekman layer and downwelling at the inner front boundary.

Authors
Raquel Flynn (University of Cape Town)
Julie Granger (University of Connecticut)
Jennifer Veitch (South African Environmental Observation Network)
Samantha Siedlecki (University of Connecticut)
Jessica Burger (University of Cape Town)
Keshnee Pillay (South Africa Department of Environment, Forestry and Fisheries)
Sarah Fawcett (University of Cape Town)

Space-based estimates of estuarine dissolved organic carbon flux to the Mid-Atlantic Bight

Posted by mmaheigan

· Wednesday, August 5th, 2020

Dissolved organic carbon (DOC) is a food supplement that supports microorganism growth and plays a major role in the global carbon cycle via the microbial loop, which integrates DOC into the marine food web. DOC from two major estuaries on the US East Coast, Chesapeake (CB) and Delaware Bay (DB), represent major contributors to the adjacent shelf region’s carbon cycle. In a recent study published in Journal of Geophysical Research: Oceans, the authors combined an integrated tracer flux approach, field and satellite data, machine learning, and a physical circulation model to quantify DOC stocks and export fluxes at the mouths of CB and DB.

Figure 1: Model bathymetry for the CB and DB models (a). Twelve‐year (2003–2014) mean MODIS DOC for DB (b) and CB (c) with ROMS grid lines superposed in white and land mask in black. The white dots across the bay mouths are the grid points used in the flux computation. The squares in (a) correspond to the size (50 km × 50 km) and location of the DB and CB MODIS images shown in (b) and (c). The boxes near DB mouth in (b) delimit the cluster of available in situ data stations. The red star, red square, and red diamond near CB mouth in (c) are the locations of in situ data for validation.

Figure 2: Five‐year averaged cross-sections of DOC concentration (top), velocity, and DOC flux at the mouths of Chesapeake Bay (a–c, respectively) and Delaware Bay (d–f, respectively).

This novel methodology not only improved estimates of combined DB-CB DOC fluxes to the US East Coast, but it also improved quantification of contrasting estuarine properties that affect DOC export such as riverine inputs, timescales of variability, and geomorphology. The combined CB-DB DOC contribution represents 25% of the total organic carbon exported and 27% of the total atmospheric carbon dioxide taken up by the Mid-Atlantic Bight (MAB)—the coastal region extending from Massachusetts to North Carolina. Spatial and, to a lesser extent, temporal covariations of velocity and DOC concentration contributed to the fluxes. The primary drivers of DOC flux differences for these two estuaries are their geomorphologies and volumes of freshwater discharge into the bays (74 billion m³/year for CB and 21 billion m³/year for DB). Terrestrial DOC inputs are similar to the export of DOC at the bay mouths at annual and longer timescales, but diverge significantly at shorter timescales of days to months.

The five-year mean DOC flux for CB and DB are 0.21 (confidence intervals 0.15, 0.27) Tg C/year and 0.05 (0.04, 0.07) Tg C/year, respectively. A flux decomposition analysis showed that temporal and spatial covariations in the DOC flux at the mouth of both bays play a significant role in determining the net export of DOC from the estuaries, which suggests that accurate estimates of estuarine DOC export require information on scales that properly resolve the temporal and spatial variability of water flux and DOC concentration. Neglecting these temporal and spatial covariations in the DOC flux leads to a 40% underestimation of the DOC flux in CB and 28% in DB, which would have a significant impact on the accuracy of carbon budget assessments and the role that these estuaries have on the coastal environment. This combination of satellite and field observations with statistical and numerical models shows great promise for capturing these covariations to better quantify the role of estuaries in the coastal carbon cycle.

Authors:
Sergio R. Signorini (NASA, Goddard Space Flight Center)
Antonio Mannino (NASA, Goddard Space Flight Center)
Marjorie A.M. Friedrichs (VIMS, William and Mary)
Pierre St-Laurent (VIMS, William and Mary)
John Wilkin (Rutgers University)
Aboozar Tabatabai (Rutgers University)
Raymond G. Najjar (The Pennsylvania State University)
Eileen E. Hofmann (Old Dominium University)
Fei Da (VIMS, College of William and Mary)
Hanqin Tian (Auburn University)
Yuanzhi Yao (Auburn University)

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 (pK_a ~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 pK_a. 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 K_a. 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 pK_a 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 (pK_a < 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)

Funding for the Ocean Carbon & Biogeochemistry Project Office is provided by the National Science Foundation (NSF) and the National Aeronautics and Space Administration (NASA). The OCB Project Office is housed at the Woods Hole Oceanographic Institution.

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