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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)

The past, present, and future of the ocean carbon cycle: A global data product with regional insights

Posted by mmaheigan

· Tuesday, January 21st, 2020

A new study published in Scientific Reports debuts a global data product of ocean acidification (OA) and buffer capacity from the beginning of the Industrial Revolution to the end of the century (1750-2100 C.E.). To develop this product, the authors linked one of the richest observational carbon dioxide (CO₂) data products (6^th version of the Surface Ocean CO₂ Atlas, 1991-2018, ~23 million observations) with temporal trends modeled at individual locations in the global ocean. By linking the modeled pH trends to the observed modern pH distribution, the climatology benefits from recent improvements in both model design and observational data coverage, and is likely to provide more accurate regional OA trajectories than the model output alone. The authors also show that air-sea CO₂ disequilibrium is the dominant mode of spatial variability for surface pH, and discuss why pH and calcium carbonate mineral saturation states (Omega), two important metrics for OA, show contrasting spatial variability. They discover that sea surface temperature (SST) imposes two large but cancelling effects on surface ocean pH and Omega, i.e., the effects of SST on (a) chemical speciation of the carbonic system; and (b) air-sea exchange of CO₂ and the subsequent DIC/TA ratio of the seawater. These two processes act in concert for Omega but oppose each other for pH. As a result, while Omega is markedly lower in the colder polar regions than in the warmer subtropical and tropical regions, surface ocean pH shows little latitudinal variation.

Figure 1. Spatial distribution of global surface ocean pH_T (total hydrogen scale, annually averaged) in past (1770), present (2000) and future (2100) under the IPCC RCP8.5 scenario.

This data product, which extends from the pre-Industrial era (1750 C.E.) to the end of this century under historical atmospheric CO₂ concentrations (pre-2005) and the Representative Concentrations Pathways (post-2005) of the Intergovernmental Panel on Climate Change (IPCC)’s 5^th Assessment Report, may be helpful to policy-makers and managers who are developing regional adaptation strategies for ocean acidification.

The published paper is available here: https://www.nature.com/articles/s41598-019-55039-4

The data product is available here: https://www.nodc.noaa.gov/oads/data/0206289.xml

Authors:
Li-Qing Jiang (University of Maryland and NOAA NCEI)
Brendan Carter (NOAA PMEL and University of Washington JISAO)
Richard Feely (NOAA PMEL)
Siv Lauvset, Are Olsen (University of Bergen and Bjerknes Centre for Climate Research, Norway)

A role for tropical nitrogen fixers in glacial CO2 drawdown

Posted by mmaheigan

· Wednesday, December 4th, 2019

Iron fertilization of marine phytoplankton by Aeolian dust is a well-established mechanism for atmospheric carbon dioxide (CO₂) drawdown by the ocean. When atmospheric CO₂ decreased by 90-100 ppm during previous ice ages, fertilization of iron-limited phytoplankton in the high latitudes was thought to have contributed up to ¹/₃ (30 ppm) of the total CO₂ drawdown. Unfortunately, recent modeling studies suggest that substantially less CO₂ (only 2-10 ppm) is sequestered by the ocean in response to high latitude fertilization.

The limited capacity for high latitude CO₂sequestration in response to iron enrichment motivated the authors of a new study published in Nature Communications to address how lower latitude phytoplankton could contribute to CO₂ drawdown. The authors used an ocean model to show that in response to Aeolian iron fertilization, dinitrogen (N₂) fixers, specialized phytoplankton that introduce bioavailable nitrogen to tropical surface waters, drive the sequestration of an additional 7-16 ppm of CO₂ by the ocean.

Figure 1: Scenarios of Fe supply to the tropical Pacific. In the low iron scenario, analogous to the modern climate, N₂ fixation (yellow zone and dots) is concentrated in the Northwest and Southwest subtropical Pacific where aeolian dust deposition is greatest. Non-limiting PO₄ concentrations (green zone and dots) exist within the tropics and spread laterally from the area of upwelling near the Americas and at the equator (blue zone). In the high Fe scenario, analogous to the glacial climate, N₂ fixation couples to the upwelling zones in the east Pacific, enabling strong utilisation of PO₄, the vertical expansion of suboxic zones (grey bubbles) and a deeper injection of carbon-enriched organic matter (downward squiggly arrows).

These results provide evidence of a tropical ocean CO₂ sequestration pathway, the mere existence of which is hotly debated. Importantly, the study describes an additional mechanism of CO₂ drawdown that is complementary to the high latitude mechanism. When combined, their contributions elevate iron-driven CO₂ drawdown towards the expected 30 ppm, making iron fertilization a driver of a stronger biological pump on a global scale.

Authors:
Pearse Buchanan (University of Liverpool, University of Tasmania, CSIRO Oceans and Atmosphere, ARC Centre of Excellence in Climate System Science)
Zanna Chase (University of Tasmania)
Richard Matear (CSIRO Oceans and Atmosphere, ARC Centre of Excellence in Climate Extremes)
Steven Phipps (University of Tasmania)
Nathaniel Bindoff (University of Tasmania, CSIRO Oceans and Atmosphere, ARC Centre of Excellence in Climate Extremes, Antarctic Climate and Ecosystems Cooperative Research Centre)

The ecology of the biological carbon pump

Posted by mmaheigan

· Tuesday, October 15th, 2019

Plankton in the surface ocean convert CO₂ into organic biomass thereby fueling marine food webs. Part of this organic biomass sinks down into the deep ocean, where the surface-derived organic carbon, or respired CO₂, is locked in for decades to millennia. Without the biological carbon pump, atmospheric CO₂ would be ~200 ppm higher than it is today. We know that ecological processes in the surface ocean plankton communities have a paramount importance on the efficiency of the biological carbon pump. Unfortunately, however, the mechanisms how ecology determines sinking fluxes are poorly understood.

A recent study in Global Biogeochemical Cycles used large-scale in situ mesocosms to explore how the ecological interplay within plankton communities affects the downward flux of organic material. Organic biomass tends to sink faster when produced by smaller organisms because the sinking material they generate forms dense aggregates. Conversely, larger organisms produce relatively porous particles that sink more slowly.

Figure: Flow chart illustrating how plankton community structure affects the properties of sinking organic particles and ultimately the strength and efficiency of the biological carbon pump. The thick arrows at the bottom indicate that flux attenuation depends on the properties of particulate matter formed in the surface ocean. For example, slow-sinking porous aggregates containing large amounts of easily degradable organic substances will decay faster (right side) than dense aggregates of more refractory organic matter (left side).

The key finding of this study was the unexpectedly large influence that plankton community composition has on the degradation rate of sinking organic biomass. In fact, degradation rates changed maximally 15-fold over the course of the study while sinking speed changed only 3-fold. Degradation rate of sinking material, measured in oxygen consumption assays, was quite variable and tended to be higher for more easily degradable fresh organic matter. The rate was lower during harmful algal blooms, which produce toxic substances that inhibit organisms that feed on aggregates thereby reducing degradation rates. These findings are an important step forward as they show that our predictive understanding of the biological carbon pump could be improved substantially when linking degradation rates of sinking material with ecological processes in surface ocean plankton communities.

Authors:
L. T. Bach (University of Tasmania)
P. Stange, J. Taucher, E. P. Achterberg, M. Esposito, U. Riebesell (GEOMAR)
M. Algueró‐Muñiz (Alfred-Wegener-Institut Helmholtz)
H. Horn (NIOZ and Utrecht University)

Suddenly shallow: A new aragonite saturation horizon will soon emerge in the Southern Ocean

Posted by mmaheigan

· Monday, May 27th, 2019

Earth System Models (ESMs) project that by the end of this century, the aragonite saturation horizon (the boundary between shallower, saturated waters and deeper, undersaturated waters that are corrosive to aragonitic shells) will shoal all the way to the surface in the Southern Ocean, yet the temporal evolution of the horizon has not been studied in much detail. Rather than a gradual shoaling, a new shallow aragonite saturation horizon emerges suddenly across many locations in the Southern Ocean between now and the end of the century (Figure 1, left), as detailed in a new study published in Nature Climate Change.

Figure 1: Maximum step-change in the depth of the aragonite saturation horizon (left), timing of the step-change (center), and cause of the change (right). Xs on the time axis (center) indicate when the shallow horizon emerges in each ensemble member. (click image to enlarge)

The emergence of the shallow aragonite saturation horizon is apparent in each member of an ensemble of climate projections from an ESM, but the step change occurs during different years (Figure 1, center). The shoaling is driven by the gradual accumulation of anthropogenic CO₂ in the Southern Ocean thermocline, where the carbonate ion concentration exhibits a local minimum and approaches undersaturation (Figure 1, right).

The abrupt shoaling of the Southern Ocean aragonite saturation horizon occurs under both business-as-usual and emission-stabilizing scenarios, indicating an inevitable and sudden decrease in the volume of suitable habitat for aragonitic organisms such as shelled pteropods, foraminifers, cold-water corals, sea urchins, molluscs, and coralline algae. Widespread reductions in these habitats may have far-reaching consequences for fisheries, economies, and livelihoods.

Authors:
Gabriela Negrete-García (Scripps Institution of Oceanography)
Nicole Lovenduski (University of Colorado Boulder)

See also OCB2019 plenary session: Carbon cycle feedbacks from the seafloor (Wednesday, June 26, 2019)

Antarctic Ocean CO2 helped end the ice age

Posted by mmaheigan

· Tuesday, April 2nd, 2019

Many scientists have long hypothesized that the ocean around Antarctica was responsible for changing CO₂ levels during ice ages, but lacked definitive evidence. A new study in Nature provides the most direct evidence of this process to date and provides crucial evidence of the mechanisms—including changing sea ice cover and bipolar seesaw (warming in the Southern Hemisphere during cooling in the Northern Hemisphere) events—that controlled CO₂ and climate during the ice ages.

Using samples of fossil deep-sea corals collected from 1000 m in the Drake Passage (Figure 1a), the authors were able to reconstruct the CO₂ content of the deep ocean. They found that the deep ocean CO₂ record was the “mirror image” of CO₂ in the atmosphere (Figure 1b), with the ocean storing CO₂ during an ice age and releasing it back to the atmosphere during deglaciation. CO₂ rise during the last ice age occurred in a series of steps and jumps associated with intervals of rapid climate change.

As well as helping scientists better understand the ice ages, the new findings also provide context to current CO₂ rise and climate change. Although the CO₂ rise that helped end the last ice age was dramatic in geological terms, CO₂ rise due to human activity over the last 100 years is even larger and about 100 times faster. CO₂ rise at the end of the ice age helped drive major melting of ice sheets resulting in sea level rise of >100 meters. These results bolster the idea that if we want to prevent dangerous levels of global warming and sea level rise in the future, we need to reduce CO₂ emissions as quickly as possible

Authors:
J. W. B. Rae (University of St Andrews, UK)
A. Burke (University of St Andrews, UK)
L. F. Robinson (University of Bristol, UK)
J. F. Adkins (California Institute of Technology)
T. Chen (University of Bristol, UK, Nanjing University, China)
C. Cole (University of St Andrews, UK)
R. Greenop (University of St Andrews, UK)
T. Li (University of Bristol, UK, Nanjing University, China)
E. F. M. Littley (University of St Andrews, UK)
D. C. Nita (University of St Andrews, UK, Babes-Bolyai University, Romania)
J. A. Stewart (University of St Andrews, UK, University of Bristol, UK)
B. J. Taylor (University of St Andrews, UK)

Ocean’s heat cycle shows that atmospheric carbon may be headed elsewhere

Posted by hbenway

· Thursday, August 16th, 2018

Studies over the past 25 years have supported the existence of a large net land biosphere CO₂ sink of 0.5–2 PgC yr^-1. Significant uncertainties remain, however, regarding the long-term partitioning between northern, tropical, and southern land sinks, in part connected to the uncertain ocean carbon sink. These uncertainties limit our capacity to predict earth system response to anthropogenic changes and design effective mitigation strategies.

Land sinks from atmospheric inversion (1990-2010 average) with two different ocean/river fluxes: (top) previous ocean inversion-based carbon fluxes; and (bottom) updated pCO2-based air-sea flux with a scaled-up river flux of 0.78 PgC /yr.

In a recent study published in Nature Geoscience, Resplandy et al. (2018) used models and field observations to demonstrate that the world’s oceans transport heat between the northern and southern hemispheres in the same way that carbon is transported. The transport of heat, however, is easier to observe. By tracking this heat, they showed that the Southern Ocean — while still a substantial carbon sink —may not take up as much carbon as previously thought, and that ocean currents might transport 20 to 100% more carbon from the northern to the southern hemisphere. To maintain this additional transport of carbon, they showed that the amount of carbon entering the ocean from rivers may be as much as 70% higher than estimated in previous global carbon budget studies. These changes in the ocean and river carbon transport imply that up to 40% of the world’s atmospheric carbon absorbed by land ecosystems needs to be reallocated from existing estimates.

Authors
L. Resplandy, Princeton University
Ralph Keeling, Scripps Institution of Oceanography/ UCSD
Christian Rödenbeck, Max Planck Institute
Briton Stephens, NCAR
Matthew Long, NCAR
Samar Khatiwala, University of Oxford
Keith Rodgers, Princeton University
Laurent Bopp, ENS Paris
Pieter Tans, NOAA’s ESRL

Arctic surface waters release methane but also absorb 2,000 times the CO2 for a net cooling effect

Posted by mmaheigan

· Thursday, September 28th, 2017

A recent study by Pohlman et al. published in PNAS showed that ocean waters near the surface of the Arctic Ocean absorbed 2,000 times more carbon dioxide (CO₂) from the atmosphere than the amount of methane released into the atmosphere from the same waters. The study was conducted near Norway’s Svalbard Islands, which overly numerous seafloor methane seeps.

Methane is a more potent greenhouse gas than CO₂, but the removal of CO₂from the atmosphere where the study was conducted more than offset the potential warming effect of the observed methane emissions. During the study, scientists continuously measured the concentrations of methane and CO₂ in near-surface waters and in the air just above the ocean surface. The measurements were taken over methane seeps fields at water depths ranging from 260 to 8530 feet (80 to 2600 meters).

Figure 1. Ocean waters overlying shallow-water methane seeps (white dots) offshore from the Svalbard Islands absorb substantially more atmospheric carbon dioxide than the methane that they emit to the atmosphere. Colors indicate the strength of the negative greenhouse warming potential associated with carbon dioxide influx to these surface waters relative to the positive greenhouse warming potential associated with the methane emissions. Gray shiptracks have background values for the relative greenhouse warming potential.

Analysis of the data confirmed that methane was entering the atmosphere above the shallowest (water depth of 260-295 feet or 80-90 meters) Svalbard margin seeps. The data also showed that significant amounts of CO₂ were being absorbed by the waters near the ocean surface, and that the cooling effect resulting from CO₂ uptake is up to 230 times greater than the warming effect expected from the methane emitted.

Most previous studies have focused only on the sea-air flux of methane overlying seafloor seep sites and have not accounted for the drawdown of CO₂that could offset some of the atmospheric warming potential of the methane. Phytoplankton appeared to be more active in the near-surface waters overlying the seafloor methane seeps, which would explain why so much carbon dioxide was being absorbed. Physical and biogeochemical measurements of near-surface waters overlying the seafloor methane seeps showed strong evidence of upwelling of cold, nutrient-rich waters from depth, stimulating phytoplankton activity and increasing CO₂ drawdown. This study was the first to document this CO₂ drawdown mechanism in a methane source region.

“If what we observed near Svalbard occurs more broadly at similar locations around the world, it could mean that methane seeps have a net cooling effect on climate, not a warming effect as we previously thought,” said USGS biogeochemist John Pohlman, the paper’s lead author. “We are looking forward to testing the hypothesis that shallow-water methane seeps are net greenhouse gas sinks in other locations.”

Authors:
John W. Pohlman (USGS Woods Hole Coastal & Marine Science Center)
Jens Greinert (GEOMAR, Univ. of Tromsø, Royal Netherlands Institute for Sea Research)
Carolyn Ruppel (USGS Woods Hole Coastal & Marine Science Center)
Anna Silyakova (Univ. of Tromsø)
Lisa Vielstädte (GEOMAR)
Michael Casso (USGS Woods Hole Coastal & Marine Science Center)
Jürgen Mienert (Univ. of Tromsø)
Stefan Bünz (Univ. of Tromsø)

Scientists reveal major drivers of aragonite saturation state in the Gulf of Maine, a region vulnerable to acidification

Posted by mmaheigan

· Thursday, May 11th, 2017

The Gulf of Maine (GoME) is a shelf region that is especially vulnerable to ocean acidification (OA). GoME’s shelf waters display the lowest mean pH, aragonite saturation state (Ω-Ar), and buffering capacity of the entire U.S. East Coast. These conditions are a product of many unique characteristics and processes occurring in the GoME, including relatively low water temperatures that result in higher CO₂ solubility; inputs of fresher, low-alkalinity water that is traceable to the rivers discharging into the Labrador Sea to the north, as well as local inputs of low-pH river water; and its semi-enclosed nature (long residence time >1 year), which enables the accumulation of respiratory products, i.e. CO₂.

A recent study by Wang et al. (2017) is the first to assess the major oceanic processes controlling seasonal variability of aragonite saturation state and its linkages with pteropod abundance in the GoME. The results indicate that surface production was tightly coupled with remineralization in the benthic nepheloid layer during highly productive seasons, resulting in occasional aragonite undersaturation. Mean water column Ω-Ar and abundance of large thecosomatous pteropods show some correlation, although discrete cohort reproductive success likely also influences their abundance. Photosynthesis-respiration is the primary driving force controlling Ω-Ar variability over the seasonal cycle. However, calcium carbonate (CaCO₃) dissolution appears to occur at depth in fall and winter months when bottom water Ω-Ar is generally low but slightly above 1. This is accompanied by a decrease in pteropod abundance that is consistent with previous CaCO₃ flux trap measurements.

Figure. Changes of aragonite saturation states (ΔΩ) between three consecutive cruises from April – July 2015 as a function of changes in salinity-normalized DIC (ΔenDIC, including correction of freshwater inputs) (a) and changes in salinity-normalized TA (ΔenTA, including correction of freshwater inputs) (b). The data points circled in (b) represent potential alkalinity sources from CaCO3 dissolution and/or anaerobic respiration. Solid lines are theoretical lines of ΔΩ vs. ΔenDIC and ΔΩ vs. ΔenTA expected if only photosynthesis and respiration/remineralization occur. Dashed lines are theoretical lines if only calcification and dissolution of CaCO3 occur.

Under the current rate of OA, the mean Ω-Ar of the subsurface and bottom waters of the GoME will approach undersaturation (Ω-Ar < 1) in 30-40 years. As photosynthesis and respiration are the major driving mechanisms of Ω-Ar variability in the water column, any biological regime changes may significantly impact carbonate chemistry and the GoME ecosystem, including the CaCO₃ shell-building capacity of organisms that are critical to the GoME food web.

Author:

Zhaohui Aleck Wang (Woods Hole Oceanographic Institution)

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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