Ocean Chemistry & Life
Acidification, deoxygenation, and the unravelling of marine ecosystems
2.1 Ocean Acidification: The Carbonate System
The ocean absorbs approximately 25% of anthropogenic CO\(_2\) emissions. When CO\(_2\) dissolves in seawater, it initiates a series of chemical reactions that increase acidity. The full carbonate equilibrium chain:
\( \text{CO}_2\text{(g)} \rightleftharpoons \text{CO}_2\text{(aq)} + \text{H}_2\text{O} \rightleftharpoons \text{H}_2\text{CO}_3 \rightleftharpoons \text{H}^+ + \text{HCO}_3^- \rightleftharpoons 2\text{H}^+ + \text{CO}_3^{2-} \)
The equilibrium constants governing these reactions (at 25 °C, salinity 35):
\( K_0 = \frac{[\text{CO}_2\text{(aq)}]}{p\text{CO}_2} \approx 3.4 \times 10^{-2}\;\text{mol/(L}\cdot\text{atm)} \)
Henry's law solubility (CO\(_2\) dissolution)
\( K_1 = \frac{[\text{H}^+][\text{HCO}_3^-]}{[\text{CO}_2\text{(aq)}]} \approx 1.4 \times 10^{-6}\;\text{mol/L} \quad (pK_1 = 5.86) \)
First dissociation (carbonic acid to bicarbonate)
\( K_2 = \frac{[\text{H}^+][\text{CO}_3^{2-}]}{[\text{HCO}_3^-]} \approx 1.1 \times 10^{-9}\;\text{mol/L} \quad (pK_2 = 8.92) \)
Second dissociation (bicarbonate to carbonate)
The Bjerrum Plot
The Bjerrum plot shows the relative concentrations of the three dissolved inorganic carbon (DIC) species as a function of pH. At seawater pH (\(\sim 8.1\)), the dominant species is bicarbonate (\(\text{HCO}_3^-\),\(\sim 90\%\)), with carbonate (\(\text{CO}_3^{2-}\), \(\sim 9\%\)) and dissolved CO\(_2\) (\(\sim 1\%\)).
The fractions are derived from the equilibrium constants. Defining total DIC:
\( \text{DIC} = [\text{CO}_2] + [\text{HCO}_3^-] + [\text{CO}_3^{2-}] \)
The fraction of each species as a function of \([\text{H}^+]\):
\( \alpha_0 = \frac{[\text{CO}_2]}{\text{DIC}} = \frac{[\text{H}^+]^2}{[\text{H}^+]^2 + K_1[\text{H}^+] + K_1 K_2} \)
\( \alpha_1 = \frac{[\text{HCO}_3^-]}{\text{DIC}} = \frac{K_1[\text{H}^+]}{[\text{H}^+]^2 + K_1[\text{H}^+] + K_1 K_2} \)
\( \alpha_2 = \frac{[\text{CO}_3^{2-}]}{\text{DIC}} = \frac{K_1 K_2}{[\text{H}^+]^2 + K_1[\text{H}^+] + K_1 K_2} \)
pH Change Since Preindustrial
Ocean surface pH has dropped from approximately 8.21 (preindustrial) to 8.10 (present). This 0.11 unit drop corresponds to:
\( \frac{[\text{H}^+]_{\text{now}}}{[\text{H}^+]_{\text{pre}}} = 10^{8.21 - 8.10} = 10^{0.11} \approx 1.29 \)
A 29% increase in hydrogen ion concentration — often quoted as “30% more acidic.” Simultaneously, carbonate ion concentration has decreased by approximately 16%:
\( [\text{CO}_3^{2-}] \text{ decreased from } \sim 225\;\mu\text{mol/kg to } \sim 190\;\mu\text{mol/kg} \)
Under SSP5-8.5, ocean pH is projected to decline to approximately 7.7 by 2100, representing a 150% increase in H\(^+\) concentration — a rate of change unprecedented in at least 66 million years (since the Paleocene-Eocene Thermal Maximum).
2.2 The Calcification Crisis
Many marine organisms build shells and skeletons from calcium carbonate (CaCO\(_3\)). The ability to do so depends on the saturation state(\(\Omega\)) of seawater with respect to the mineral form used:
\( \Omega_{\text{aragonite}} = \frac{[\text{Ca}^{2+}][\text{CO}_3^{2-}]}{K_{\text{sp,arag}}} \)
where:
- • \([\text{Ca}^{2+}] \approx 10.3\;\text{mmol/kg}\) — essentially constant in seawater
- • \([\text{CO}_3^{2-}]\) — decreases as ocean absorbs CO\(_2\)
- • \(K_{\text{sp,arag}} \approx 6.5 \times 10^{-7}\;\text{mol}^2/\text{kg}^2\) (at 25 °C, surface)
When \(\Omega > 1\), seawater is supersaturated and calcification is thermodynamically favoured. When \(\Omega < 1\), shells and skeletons begin to dissolve. Current surface ocean values:
Ω ≈ 3.5-4.0
Supersaturated (but declining)
Ω ≈ 2.0-3.0
Moderately supersaturated
Ω ≈ 1.0-1.5
Near undersaturation
Ω < 1
Undersaturated (aragonite dissolves)
Deriving \(\Omega\) vs Atmospheric CO\(_2\)
Since \([\text{Ca}^{2+}]\) is constant, the saturation state tracks carbonate ion concentration, which decreases as CO\(_2\) is absorbed. The relationship can be derived from the Revelle factor \(R\):
\( \frac{\Delta[\text{CO}_3^{2-}]}{[\text{CO}_3^{2-}]} \approx -\frac{\Delta \text{DIC}}{\text{DIC}} \cdot \frac{R-1}{R} \approx -0.016 \cdot \frac{\Delta p\text{CO}_2}{p\text{CO}_2} \)
For a doubling of atmospheric CO\(_2\) (280 to 560 ppm), carbonate ion concentration decreases by approximately 40%, pushing \(\Omega_{\text{arag}}\) from ~4 to ~2.4 in the tropics and below 1 in polar waters.
Organisms at Risk
Pteropods (sea butterflies)
Thin aragonite shells dissolve below Ω = 1.5. Already showing shell thinning in Southern Ocean. Key food for salmon and whales.
Coccolithophores
Calcite plates (coccoliths) affected below Ω_calcite = 2. Major phytoplankton group; decline would alter ocean albedo and carbon export.
Reef-building corals
Calcification rate drops ~30% for each unit decrease in Ω. Below Ω = 3, net reef dissolution exceeds accretion.
Oysters and mussels
Larval stages especially sensitive; hatchery failures already observed in Pacific Northwest (Barton et al. 2012).
2.3 Ocean Deoxygenation
The ocean has lost approximately 2% of its dissolved oxygen since the 1960s, with oxygen minimum zones (OMZs) expanding by 3–8% in volume. Two mechanisms drive this loss:
Solubility Effect (Henry's Law)
Oxygen solubility decreases with temperature. From Henry's law:
\( [\text{O}_2]_{\text{sat}} = K_H(T) \cdot p\text{O}_2 \)
The temperature dependence of the Henry's law constant for O\(_2\) in seawater can be approximated:
\( \ln K_H = A_1 + \frac{A_2}{T} + A_3 \ln T + A_4 T + S \left(B_1 + \frac{B_2}{T} + B_3 T^2\right) \)
where \(T\) is absolute temperature and \(S\) is salinity. A simpler approximation: O\(_2\) solubility decreases by approximately 2% per °C warming. For a 3 °C warming, this alone reduces surface O\(_2\) saturation by ~6%.
Stratification Effect
Warming preferentially heats the upper ocean, strengthening density stratification. The stratification parameter:
\( N^2 = -\frac{g}{\rho_0}\frac{\partial \rho}{\partial z} \)
where \(N\) is the Brunt-Väisälä (buoyancy) frequency. Increased stratification (\(N^2\) increasing) reduces vertical mixing, which:
- • Reduces ventilation of deep waters (less O\(_2\) transported downward)
- • Reduces nutrient upwelling (less primary production at surface in some regions)
- • Expands oxygen minimum zones (OMZs), compressing habitable depth ranges
Habitat Compression Index
The habitat compression index (HCI) quantifies how the vertical range available to aerobic organisms shrinks as oxygen declines and temperatures rise:
\( \text{HCI} = \frac{z_{\text{oxy}} - z_{\text{therm}}}{z_{\text{oxy,ref}} - z_{\text{therm,ref}}} \)
where \(z_{\text{oxy}}\) is the depth of the hypoxic boundary (\([\text{O}_2] < 60\;\mu\text{mol/kg}\)) and \(z_{\text{therm}}\)is the depth of the thermal tolerance limit. As OMZs shoal (shallower) and surface waters warm, the habitable vertical range compresses. For tropical tunas, this compression exceeds 15% in some eastern Pacific regions, concentrating fish in a thinner surface layer.
2.4 Fisheries Under Warming
Marine fisheries are being reorganised by warming. The two standard stock-recruitment models show how warming affects sustainable yield.
Ricker Model
The Ricker model describes spawner-recruit dynamics with density-dependent mortality:
\( R = \alpha S \, e^{-\beta S} \)
where \(R\) is recruitment, \(S\) is spawning stock biomass,\(\alpha\) is productivity (recruits per spawner at low density), and\(\beta\) controls density dependence. The maximum sustainable yield (MSY) occurs at:
\( S_{\text{MSY}} = \frac{1}{\beta}, \quad \text{MSY} = \frac{\alpha}{\beta e} \)
Beverton-Holt Model
The Beverton-Holt model assumes compensatory (not overcompensatory) density dependence:
\( R = \frac{\alpha S}{1 + \beta S} \)
Temperature Effect on MSY
Productivity \(\alpha\) depends on temperature through metabolic scaling. For species near their thermal optimum, further warming decreases \(\alpha\):
\( \alpha(T) = \alpha_{\text{opt}} \cdot \exp\!\left[-\frac{(T - T_{\text{opt}})^2}{2\sigma_T^2}\right] \)
This gives a temperature-dependent MSY. Global analyses (Free et al. 2019) estimate that warming has already reduced maximum sustainable yield of assessed populations by 4.1% on average since 1930. Tropical fisheries show the largest declines (up to 35%), while some high-latitude stocks have temporarily benefited.
Poleward Redistribution
Marine species are shifting poleward at a rate of approximately 70 km per decade (Poloczanska et al. 2013), far faster than terrestrial species (~17 km/decade). This has profound geopolitical implications:
- • Winners: High-latitude nations (Norway, Iceland, Russia) gaining species and productivity
- • Losers: Tropical nations (many developing countries) losing catch potential by 40–60% under SSP5-8.5
- • Conflict zones: Transboundary stocks crossing national EEZ boundaries create disputes
2.5 Deep Ocean Carbon Storage
The ocean stores approximately 38,000 GtC — 50 times the atmosphere. Two major mechanisms transport carbon to the deep ocean:
The Biological Pump
Photosynthesis in the surface ocean fixes CO\(_2\) into organic matter. A fraction (the export ratio, typically 5–25%) sinks below the mixed layer as dead organisms, faecal pellets, and marine snow. The Martin curve describes the attenuation of sinking particulate organic carbon (POC) with depth:
\( F(z) = F_{100} \left(\frac{z}{100}\right)^{-b} \)
where \(F_{100}\) is the flux at 100 m depth, \(z\) is depth in metres, and \(b \approx 0.86\) (Martin et al. 1987). This means approximately 90% of exported organic carbon is remineralised (converted back to CO\(_2\)) in the upper 1000 m.
Thermohaline Circulation
The solubility pump works through the thermohaline (overturning) circulation. Cold, dense water forming at high latitudes is enriched in CO\(_2\) (higher solubility) and sinks to the abyss. The residence time of deep ocean carbon:
\( \tau_{\text{deep}} = \frac{V_{\text{deep}} \cdot [\text{DIC}]_{\text{deep}}}{F_{\text{overturning}}} \approx \frac{1.0 \times 10^{18}\;\text{m}^3 \times 2.3\;\text{mol/m}^3}{20\;\text{Sv}} \approx 800{-}1200\;\text{years} \)
where 1 Sv = \(10^6\;\text{m}^3/\text{s}\). This long residence time means that anthropogenic CO\(_2\) absorbed today will influence ocean chemistry for centuries to millennia.
Climate change weakens both pumps: warming reduces solubility (less CO\(_2\) absorbed), stratification reduces both mixing and nutrient supply (weakening the biological pump), and potential slowdown of the Atlantic Meridional Overturning Circulation (AMOC) reduces deep water formation. These feedbacks could reduce the ocean carbon sink by 20–40% by 2100 under high-emission scenarios.
Bjerrum Plot: Carbonate Species vs pH
The relative abundance of dissolved inorganic carbon species as a function of seawater pH:
Bjerrum plot for the seawater carbonate system at 25 °C, salinity 35. At seawater pH (~8.1), bicarbonate dominates (~90%). The shift from pH 8.2 to 7.7 dramatically reduces carbonate ion availability for shell-building organisms.
Computational Simulations
Ocean pH and Aragonite Saturation Projections
PythonClick Run to execute the Python code
Code will be executed with Python 3 on the server
Fisheries Stock-Recruitment Under Warming
PythonClick Run to execute the Python code
Code will be executed with Python 3 on the server
References
- • Doney, S.C. et al. (2009). Ocean acidification: The other CO\(_2\) problem. Annual Review of Marine Science, 1, 169–192.
- • Orr, J.C. et al. (2005). Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms. Nature, 437, 681–686.
- • Keeling, R.F., Körtzinger, A. & Gruber, N. (2010). Ocean deoxygenation in a warming world. Annual Review of Marine Science, 2, 199–229.
- • Free, C.M. et al. (2019). Impacts of historical warming on marine fisheries production. Science, 363(6430), 979–983.
- • Poloczanska, E.S. et al. (2013). Global imprint of climate change on marine life. Nature Climate Change, 3, 919–925.
- • Martin, J.H. et al. (1987). VERTEX: Carbon cycling in the northeast Pacific. Deep Sea Research, 34(2), 267–285.
- • Barton, A. et al. (2012). The Pacific oyster, Crassostrea gigas, shows negative correlation to naturally elevated carbon dioxide levels. Limnology and Oceanography, 57(3), 698–710.
- • Zeebe, R.E. & Wolf-Gladrow, D. (2001). CO\(_2\) in Seawater: Equilibrium, Kinetics, Isotopes. Elsevier Oceanography Series.
- • IPCC, 2019: Special Report on the Ocean and Cryosphere in a Changing Climate.