coastal ocean :: Ocean Carbon & Biogeochemistry

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Archive for coastal ocean – Page 2

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

Chesapeake Bay acidification partially offset by submerged aquatic vegetation

Posted by mmaheigan

· Wednesday, September 30th, 2020

Ocean acidification is often enhanced by eutrophication and subsequent hypoxia and anoxia in coastal waters, which collectively threaten marine organisms and ecosystems. Acidification is particularly of concern for organisms that form shells and skeletons from calcium carbonate (CaCO₃) such as commercially important shellfish species. Given that CaCO₃ mineral dissolution can increase the total alkalinity of water and neutralize anthropogenic and metabolic CO₂, it is important to include CaCO₃ cycle in the coastal water acidification study. However, very few studies have linked CaCO₃ dissolution to the timing and location of its formation in coastal waters. A recent study from the Chesapeake Bay published in Nature Geoscience reveals the occurrence of a bay-wide pH-buffering mechanism resulting from spatially decoupled CaCO₃ mineral cycling (Figure 1). Photosynthesis by submerged aquatic vegetation at the head of the Bay and in other shallow, nearshore waters can remove nutrient pollution from the Bay, generate very high pH, and elevate the carbonate mineral saturation state (Figure 1). This facilitates the formation of CaCO₃ minerals, which are then transported downstream along with other biologically produced carbonate shells into acidic subsurface waters, where they dissolve. This dissolution of carbonate minerals helps “buffer” the water against pH decreases and even drive pH increases. This finding has great ecological and natural resource management significance, in that coastal nutrient management and reduction via the resurgence of submerged aquatic vegetation can help mitigate low oxygen and acidification stress for these environments and organisms.

Figure 1: Conceptual model of the self-regulated pH-buffering mechanism in the Chesapeake Bay. Calcium carbonate is formed within the high-pH submerged aquatic vegetation beds in shallow waters (top left and upper part of diagram, all Shoals with SAV), where it could be subsequently transported longitudinally and/or laterally into the deep main channel of the mid and lower bay (center) and upon dissolution, increase pH buffering capacity and alleviate coastal acidification (lower section).

Authors:
Jianzhong Su (University of Delaware, Xiamen University)
Wei-Jun Cai (University of Delaware)
Jean Brodeur (University of Delaware)
Baoshan Chen (University of Delaware)
Najid Hussain (University of Delaware)
Yichen Yao (University of Delaware)
Chaoying Ni (University of Delaware)
Jeremy Testa (University of Maryland Center for Environmental Science)
Ming Li (University of Maryland Center for Environmental Science)
Xiaohui Xie (University of Maryland Center for Environmental Science, Second Institute of Oceanography)
Wenfei Ni (University of Maryland Center for Environmental Science)
K. Michael Scaboo (University of Delaware)
Yuanyuan Xu (University of Delaware)
Jeffrey Cornwell (University of Maryland Center for Environmental Science)
Cassie Gurbisz (St. Mary’s College of Maryland)
Michael S. Owens (University of Maryland Center for Environmental Science)
George G. Waldbusser (Oregon State University)
Minhan Dai (Xiamen University)
W. Michael Kemp (University of Maryland Center for Environmental Science)

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)

A Methane-Charged Carbon Pump in Shallow Marine Sediments

Posted by mmaheigan

· Wednesday, June 3rd, 2020

Ocean margins are often characterized by the transport of methane, a potent greenhouse gas, entering from the subsurface and moving towards the seafloor. However, a significant portion of subsurface methane is consumed within shallow sediments via microbial driven anaerobic oxidation of methane (AOM). AOM converts the methane carbon to dissolved inorganic carbon (DIC) and reduces the amount of sulfate that diffuses down from the seafloor towards a sediment interval known as the sulfate-methane transition zone (SMTZ). The SMTZ is where the upward flux of methane encounters the downward diffusive sulfate flux (Figure 1). While the mechanisms of methane production and consumption have been extensively studied, the fate of the DIC that is produced in methane-charged sediments is not well constrained.

In a recent study published in Frontiers in Marine Science, authors used existing reports of methane and sulfate flux values to the SMTZ and synthesized a carbon flow model to quantify the DIC cycling in diffusive methane flux sites globally. They report an annual average of 8.7 Tmol (1 Tmol = 10¹² moles) of DIC entering the diffusive methane-charged shallow marine sediments due to sulfate reduction coupled with AOM and organic matter degradation, as well as DIC input from depth (Figure 1). Approximately 75% (average of 6.5 Tmol year^–1) of this DIC pool flows upward toward the water column, making it a potential contributor to oceanic CO₂and ocean acidification. Further, an average of 1.7 Tmol year^–1DIC precipitates as methane-derived authigenic carbonates. This synthesis emphasizes the importance of the SMTZ, not only as a methane sink but also an important biogeochemical front for global DIC cycling.

Figure 1: A simplified representation of DIC cycling at diffusive methane charged settings.

The study highlights that regions characterized by diffusive methane fluxes can contribute significantly to the oceanic inorganic carbon pool and sedimentary carbonate accumulation. DIC outflux from the methane-charged sediments is comparable to ~20% global riverine DIC flux to oceans. Methane-derived authigenic carbonate precipitation is comparable to ~15% of carbonate accumulation on continental shelves and in pelagic sediments, respectively. These pathways must be included in coastal and geologic carbon models.

Authors:
Sajjad Akam (Texas A&M University-Corpus Christi)
Richard Coffin (Texas A&M University-Corpus Christi)
Hussain Abdulla (Texas A&M University-Corpus Christi)
Timothy Lyons (University of California, Riverside)

Global change impacts soil carbon storage in blue carbon ecosystems

Posted by mmaheigan

· Wednesday, May 20th, 2020

Vegetated coastal “blue carbon” ecosystems, including sea grasses, mangroves, and salt marshes, provide valuable ecosystem services such as carbon sequestration, storm protection, critical habitat, etc.. Many of these services are supported by the ability of blue carbon ecosystems to accumulate soil organic carbon over thousands of years. Rapidly changing climate and environmental conditions will impact decomposition and thus the global reservoir of organic carbon in coastal soils. A recent Perspective article published in Nature Geoscience focused on the biogeochemical factors affecting decomposition in coastal soils, such as mineral protection, redox zonation, water content and movement, and plant-microbe interactions. The authors explored the spatial and temporal scales of these decomposition mechanisms and developed a conceptual framework to characterize how they may respond to environmental disturbances such as land-use change, nutrient loading, warming, and sea-level rise.

Figure caption: Temperate salt marshes (MA, USA). Healthy salt marshes have lush stands of grasses (top). Storms can expose peat deposits that have been buried for thousands of years (bottom). The fate of this soil carbon is unknown, but some fraction will be respired by microbes and returned to the atmosphere as CO₂.

Improved estimates of soil organic carbon in blue carbon systems will require better characterization of these processes from sustained data sets. Furthermore, incorporation of these decomposition mechanisms into ecosystem evolution models will improve our capacity to quantify and predict changes in these soil carbon reservoirs, which could facilitate their inclusion in global budgets and management tools.

Temperate salt marshes (MA, USA). Healthy salt marshes have lush stands of grasses (left/top). Storms can expose peat deposits that have been buried for thousands of years (right/bottom). The fate of this soil carbon is unknown, but some fraction will be respired by microbes and returned to the atmosphere as CO₂.

Authors:
Amanda C Spivak (University of Georgia)
Jon Sanderman (Woods Hole Research Center)
Jennifer Bowen (Northeastern University)
Elizabeth A. Canuel (Virginia Institute of Marine Science)
Charles S Hopkinson (University of Georgia)

An Important Biogeochemical Link between Organic and Inorganic Carbon Cycling: Contributions of Organic Alkalinity

Posted by mmaheigan

· Wednesday, April 8th, 2020

As a part of dissolved organic carbon (DOC), organic acid charge groups can contribute significantly to total alkalinity (TA) in natural waters. Such a contribution is termed as organic alkalinity (OrgAlk). Beyond being part of TA, OrgAlk represents an important biogeochemical linkage between organic and inorganic carbon cycling. In other words, the biogeochemical cycling of organic acid charge groups – i.e. their sources, sinks, and biogeochemical behaviors – directly impacts pH and carbonate speciation, which may ultimately influence air-water CO₂ exchange and inorganic carbon fluxes. However, the effects of OrgAlk is often ignored or treated as a calculation uncertainty in many aquatic CO₂ studies. How we treat and study OrgAlk may need a new paradigm under biogeochemical cycles.

Based on direct titration data of OrgAlk, the authors of a recent study conducted a comprehensive assessment of OrgAlk variability, sources, and characteristics in a sub-estuary of Waquoit Bay (Massachusetts). The sub-estuary is influenced by a salt marsh, groundwater input, and offshore water. Both the salt marsh and groundwater OrgAlk contributed up to 4.3% of the TA across all sampled seasons. Estuarine OrgAlk:DOC ratios varied across space and time, which suggests that their abundances are controlled by different biogeochemical processes. In addition, the study demonstrates the insufficiency of using a fixed proportion of DOC to account for OrgAlk, as well as the challenge of using measured pH, TA, and dissolved inorganic carbon (DIC) to estimate OrgAlk. The effects of OrgAlk in these waters are equivalent to a pH change of ~ 0.03 – 0.26, or a pCO₂ change of ~30–1600 matm. If extrapolating OrgAlk results to other coastal systems ranging from estuaries to continental shelves, OrgAlk would exert a strong control on both carbonate speciation and, ultimately, air-sea CO₂ fluxes. This study provides a new conceptual framework for cycling of OrgAlk species and associated links between DOC and DIC pools in coastal systems (Figure 1).

Figure caption: A conceptual model of organic alkalinity cycling in coastal systems. BioP and ChemP represent in-situ biological production and chemical production of organic acid charge groups, respectively. Alk denotes total alkalinity. Arrows with dashed lines indicate processes that were not studied in the present study. The values in the boxes of pH, pCO₂, and buffer capacity represent the magnitude of OrgAlk effects on pH, pCO₂, and buffer capacity in the range of OrgAlk% in TA observed in this study (0.9 – 4.3%).

Authors
Shuzhen Song (East China Normal University)
Zhaohui Aleck Wang (Woods Hole Oceanographic Institution)
Meagan Eagle Gonneea (U. S. Geological Survey)
Kevin D. Kroeger (U. S. Geological Survey)

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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