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Archive for ocean acidification – Page 2

pH: the secrets that you keep

Posted by mmaheigan

· Monday, September 20th, 2021

The Intergovernmental Panel on Climate Change (IPCC) defines ocean acidification as “a reduction in pH of the ocean over an extended period, typically decades or longer, caused primarily by the uptake of carbon dioxide (CO₂) from the atmosphere” (Rhein et al., 2013, p. 295). Does this mean that a greater change in pH at the ocean surface relative to the subsurface, or at one location relative to another, always indicates greater acidification? Based on this IPCC definition of ocean acidification, the answer is yes. But does that make sense?

Seawater pH is the negative base 10 logarithm of the seawater’s hydrogen ion concentration ([H⁺]) and is a useful way to display a wide range of [H⁺] in a compact form. A change in pH reflects a relative change in [H⁺]. Thus, anytime we speak of pH changes, we are really referring to a relative change in the chemical species of interest ([H⁺]). On the other hand, changes in all the other carbonate system variables that we measure are usually absolute. This characteristic of pH can lead to ambiguity in the interpretation and presentation of rates and patterns of change. Improved understanding comes from also studying changes in [H⁺], which can reveal aspects that studying changes in pH alone may conceal or overemphasize.

A recent Biogeosciences article reviewed the history leading to this unintuitive relationship between changes in pH and changes in [H⁺]. The article provides three real-world examples to display how examining pH changes alone can hide the ocean acidification signals of interest (Figure 1). These examples highlight potential challenges associated with comparing surface and subsurface pH changes across ocean domains without accounting for differences in the initial pH values. The authors recommend reporting both pH and [H⁺] in studies that assess changes in ocean chemistry to improve the clarity of ocean acidification research.

Figure Caption: Data used in this figure come from the GFDL ESM2M model for the combined historical and RCP8.5 experiments. Top: the 1950s surface ocean (left) pH and (right) [H+]. Bottom: the 1950s to 2090s change (Δ) in surface ocean (left) pH and (right) [H+]. The color bar for ΔpH is reversed to ease comparison with patterns of Δ[H+]

Authors:
Andrea J. Fassbender (NOAA Pacific Marine Environmental Laboratory)
Andrew G. Dickson (Scripps Institution of Oceanography, University of California, San Diego)
James C. Orr (LSCE/IPSL, Laboratoire des Sciences du Climat et de l’Environnement)

Acidity across the interface from the ocean surface to sea spray aerosol

Posted by mmaheigan

· Wednesday, March 31st, 2021

The pH of aerosols controls their impact on climate and human health. Sea spray aerosols are one of the largest sources of aerosols globally by mass, yet it has been challenging to measure the pH of fresh sea spray aerosols in the past. A recent study published in PNAS measured sea spray aerosols under controlled conditions, during a sampling intensive called SeaSCAPE, and optimized a pH paper-based technique to measure the aerosol acidity. The authors found that fresh sea spray aerosols can be rapidly acidified by 4 to 6 orders of magnitude relative to the ocean. This acidification is caused by interaction with surrounding acidic gases, changes in relative humidity, and enhanced dissociation of organic acids within the aerosols. This is a critical finding since the pH of aerosols controls key atmospheric chemical reactions including sulfur dioxide oxidation to form particulate sulfate. The results are also important in light of the fact that enzyme activity has been observed in sea spray aerosols, and enzyme activity is pH dependent.

Figure 1. Acidity of nascent sea spray aerosols (SSA) compared to bulk ocean water measured during the 2019 SeaSCAPE sampling intensive. Background artwork by Nigella Hillgarth.

Authors
Kyle Angle (University of California, San Diego)
Daniel Crocker (University of California, San Diego)
Rebecca Simpson (University of California, San Diego)
Kathryn Mayer (University of California, San Diego)
Lauren Garofalo (Colorado State University, Fort Collins)
Alexia Moore (University of California, San Diego)
Stephanie Mora Garcia (University of California, San Diego)
Victor Or (University of California, San Diego)
Sudarshan Srinivasan (University of California, San Diego)
Mahum Farhan (University of California, San Diego)
Jonathan Sauer (University of California, San Diego)
Christopher Lee (University of California, San Diego)
Matson Pothier (Colorado State University, Fort Collins)
Delphine Farmer (Colorado State University, Fort Collins)
Todd Martz (University of California, San Diego)
Timothy Bertram (University of Wisconsin, Madison)
Christopher Cappa (University of California, Davis)
Kimberly Prather (University of California, San Diego)
Vicki Grassian (University of California, San Diego)

Joint post with Surface Ocean – Lower Atmosphere Study (SOLAS)

Does ocean acidification make marine fish grow differently? What about sex-specific effects?

Posted by mmaheigan

· Monday, February 8th, 2021

The question of whether ocean acidification (OA) will impact the growth of marine fish remains surprisingly uncertain. The bulk of available evidence in the form of laboratory experiments suggests that most fish are not impacted by OA-relevant CO₂ levels, but many studies suffer from the inherent methodical constraints of rearing marine fish in captivity. For example, most experiments cover a small fraction of a species’ lifespan and do not employ restricted feeding regimes which may enable fish to increase feeding to offset metabolic deficits associated with high-CO₂ acclimation.

To address these methodological shortcomings, authors of a recent publication in PLOS One synthesized three years of multiple long-term, food-controlled experiments that reared large populations of the model forage fish Menidia menidia (Atlantic silverside) from fertilization to about a third of their lifespan. Results showed modest but consistent negative, temperature-dependent growth effects, in which silversides from high-CO₂ treatments were shorter (-3% to -9%) and weighed less (-6% to -18%) than ambient-CO₂ conspecifics. However, sometimes it takes more than just looking at means and standard deviations to elucidate these effects. Hence, the authors employed powerful shift functions to analyze how the size distributions of experimental populations shifted to smaller quantiles under future CO₂ conditions.

Figure caption: The length of juvenile Atlantic silversides reared from fertilization under control (blue dots) and high-CO₂ treatments (red dots). Exposure to OA conditions imposed a universal shift to a smaller body size across the size frequency distribution. Black vertical bars overlaying each distribution indicate the .1, .25, .5, .75, and .9 quantiles and quantile shifts are indicated by connecting lines.

It took over 100 days of continuous high-CO₂ exposure until size differences were detectable. This means that long-term CO₂effects could exist in other tested species but are missed in relatively short experiments. Furthermore, the authors sexed several thousand fish to enable a rare sex-specific analysis of CO₂ effects. Both sexes were similarly affected by high CO₂, and the hormonal pathways that mediate environmental sex determination in this species are not impacted by CO₂ level. Our results confirm that Atlantic silversides are relatively tolerant of future OA conditions. But even in this robust estuarine species, high CO₂ can reduce growth. This could have cascading effects on population dynamics by impacting size-dependent traits like reproductive success and over-wintering survival of this widespread and ecologically important prey species.

Authors
Christopher S. Murray (University of Washington)
Hannes Baumann (University of Connecticut)

Warming counteracts acidification in temperate crustose coralline algae communities

Posted by mmaheigan

· Friday, November 6th, 2020

Seawater carbonate chemistry has been altered by dramatic increases in anthropogenic CO₂ release and global temperatures, leading to significant changes in rocky shore habitats and the metabolism of most marine organisms. There has been recent interest in how these anthropogenic stresses affect crustose coralline algae (CCA) communities because CCA photosynthesis and calcification are directly influenced by seawater carbonate chemistry. CCA is a foundation species in temperate macroalgal communities, where species succession and rocky shore community structure are particularly susceptible to anthropogenic disturbance. In particular, the disappearance of turf and foliose macroalgae caused by climate change and herbivore pressure results in the dominance of CCA (Figure 1a).

Figure 1: (a) Examples of crustose coralline algae (CCA)-dominated seaweed bed in the East Sea of Korea showing barren ground dominated by CCA (bright white and pink color on the rock; see arrows) on a rocky subtidal zone grazed by sea urchins. (b) Specific growth rate of marginal encrusting area under future climate conditions.

In a recent study published in Marine Pollution Bulletin, the authors conducted a mesocosm experiment to investigate the sensitivity of temperate CCA Chamberlainium sp. to future climate stressors, as simulated by three experimental treatments: 1) Acidification: doubled CO₂; 2) Warming: +5ºC; and 3) Greenhouse: doubled CO₂ and +5ºC. After a 47-day acclimation period, when compared with present-day (control: 490 μatm and 20ºC) conditions, the Acidification treatment showed decreased photosynthesis rates of Chamberlainium sp, whereas the Warming treatment showed increased photosynthesis. The Acidification treatment also showed reduced encrusting growth rates relative to the Control, but when acidification was combined with warming in the Greenhouse treatment, encrusting growth rates increased substantially (Figure 1b). Taken together, these results suggest that the negative ecophysiological responses of Chamberlainium sp to acidification are ameliorated by elevated temperatures in a greenhouse world. In other words, if the foliose macroalgal community responses negatively in the greenhouse environment, the dominance of CCA will increase further, and the biodiversity of the algae community will be reduced.

Authors:
Ju-Hyoung Kim (Faculty of Marine Applied Biosciences, Kunsan National University)
Il-Nam Kim (Department of Marine Science, Incheon National University)

Multiyear predictions of ocean acidification in the California Current System

Posted by mmaheigan

· Thursday, August 20th, 2020

The California Current System is a highly productive coastal upwelling region that supports commercial fisheries valued at $6 billion/year. These fisheries are supported by upwelled waters, which are rich in nutrients and serve as a natural fertilizer for phytoplankton. Due to remineralization of organic matter at depth, these upwelled waters also contain large amounts of dissolved inorganic carbon, causing local conditions to be more acidic than the open ocean. This natural acidity, compounded by the dissolution of anthropogenic CO₂ into coastal waters, creates corrosive conditions for shell-forming organisms, including commercial fishery species.

A recent study in Nature Communications showcases the potential for climate models to skillfully predict variations in surface pH—thus ocean acidification—in the California Current System. The authors evaluate retrospective predictions of ocean acidity made by a global Earth System Model set up similarly to a weather forecasting system. The forecasting system can already predict variations in observed surface pH fourteen months in advance, but has the potential to predict surface pH up to five years in advance with better initializations of dissolved inorganic carbon (Figure 1). Skillful predictions are mostly driven by the model’s initialization and subsequent transport of dissolved inorganic carbon throughout the North Pacific basin.

Figure 1. Forecast of annual surface pH anomalies in the California Current Large Marine Ecosystem for 2020. Red colors denote anomalously basic conditions for the given location and blue colors indicate anomalously acidic conditions.

These results demonstrate, for the first time, the feasibility of using climate models to make multiyear predictions of surface pH in the California Current. Output from this global prediction system could serve as boundary conditions for high-resolution models of the California Current to improve prediction time scale and ultimately help inform management decisions for vulnerable and valuable shellfisheries.

Authors:
Riley X. Brady (University of Colorado Boulder)
Nicole S. Lovenduski (University of Colorado Boulder)
Stephen G. Yeager (National Center for Atmospheric Research)
Matthew C. Long (National Center for Atmospheric Research)
Keith Lindsay (National Center for Atmospheric Research)

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)

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)

What really controls deep-seafloor calcite dissolution?

Posted by mmaheigan

· Monday, December 16th, 2019

On time scales of tens to millions of years, seawater acidity is primarily controlled by biogenic calcite (CaCO₃) dissolution on the seafloor. Our quantitative understanding of future oceanic pH and carbonate system chemistry requires knowledge of what controls this dissolution. Past experiments on the dissolution rate of suspended calcite grains have consistently suggested a high-order, nonlinear dependence on undersaturation that is independent of fluid flow rate. This form of kinetics has been extensively adopted in models of deep-sea calcite dissolution and pH of benthic sediments. However, stirred-chamber and rotating-disc dissolution experiments have consistently demonstrated linear kinetics of dissolution and a strong dependence on fluid flow velocity. This experimental discrepancy surrounding the kinetic control of seafloor calcite dissolution precludes robust predictions of oceanic response to anthropogenic acidification.

In a recent study published in Geochimica et Cosmochimica Acta, authors have reconciled these divergent experimental results through an equation for the mass balance of the carbonate ion at the sediment-water interface (SWI), which equates the rate of production of that ion via dissolution and its diffusion in sediment porewaters to the transport across the diffusive sublayer (DBL) at the SWI. If the rate constant derived from suspended-grain experiments is inserted into this balance equation, the rate of carbonate ion supply to the SWI from the sediment (sediment-side control) is much greater in the oceans than the rate of transfer across the DBL (water-side control). Thus, calcite dissolution at the seafloor, while technically under mixed control, is strongly water-side dominated. Consequently, a model that neglects boundary-layer transport (sediment-side control alone) invariably predicts CaCO₃-versus-depth profiles that are too shallow compared to available data (Figure 1). These new findings will inform future attempts to model the ocean’s response to acidification.

Figure 1: Plots of the calcite (CaCO₃) content of deep-sea sediments as a function of oceanic depth. Left panel: data from the Northwestern Atlantic Ocean. Right panel: data from the Southwest Pacific Ocean. The blue line represents predicted CaCO₃ content assuming no boundary-layer effects (pure sediment-side control). The red line is the prediction that includes both sediment and water effects (mixed control), and the green line is the prediction with pure water-side control. The agreement between the red and green lines signifies that calcite dissolution is essentially water-side controlled at the seafloor. These results are duplicated for all tested regions of the oceans.

Authors:
Bernard P. Boudreau (Dalhousie University)
Olivier Sulpis (University of Utrecht)
Alfonso Mucci (McGill University)

Upwelling and solubility drive global surface dissolved inorganic carbon (DIC) distribution

Posted by mmaheigan

· Tuesday, August 20th, 2019

What drives the latitudinal gradient in open-ocean surface DIC concentration? Understanding the processes that drive the distribution of carbon in the surface ocean is essential to the study of the ocean carbon cycle and future predictions of ocean acidification and the ocean carbon sink.

Authors of a recent study in Biogeosciences investigated causes of the observed latitudinal trend in DIC and salinity-normalized DIC (nDIC) (Figure 1). The latitudinal trend in nDIC is not driven solely by the latitudinal gradient in temperature (through its effects on solubility), as is commonly assumed. Careful analysis using the Global Ocean Data Analysis Project version 2 (GLODAPv2) database revealed that physical supply from below (upwelling, entrainment in winter) at high latitudes is another major driver of the latitudinal pattern. The contribution of physical exchange explains an otherwise puzzling observation: Surface waters are lower in nDIC in the high-latitude North Atlantic than in other basins. This cannot be accounted for by temperature difference but rather is explained by a difference in the carbon content of deeper waters (lower in the subarctic North Atlantic than in the subarctic North Pacific or Southern Ocean) that are mixed up into the surface during winter months.

Figure caption: (Top) spatial distributions of surface ocean DIC and (bottom) salinity-normalised (nDIC). Both, most notably nDIC, increase towards the poles. Values are normalised to year 2005 to remove bias from changing levels of atmospheric CO2 in some observations before and after 2005. Data are from GLODAPv2.

These results also suggest that the upwelling/entrainment of water that is high in alkalinity generates a large and long-lasting effect on DIC, one that persists beyond the timescale of CO₂ gas exchange equilibration with the . That is to say, the impact of changes in upwelling on the ocean’s carbon source-sink strength depends not only on the DIC content of the upwelled water but also on its TA content.

Authors:
Yingxu Wu (University of Southampton)
Mathis Hain (University of California, Santa Cruz)
Matthew Humphreys (University of East Anglia and University of Southampton)
Sue Hartman (National Oceanography Centre, Southampton)
Toby Tyrrell (University of Southampton)

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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