Ocean acidification means that the average ocean pH value is dropping over time.[1]
Ocean acidification means that the average ocean pH value is dropping over time.[1]
Spatial distribution of global surface ocean pH (Panel a: the annually-averaged surface ocean pH to be approximate for the year 1770; Panel b: the difference between pH in 2000 and 1770 in the global surface ocean).[2]
Spatial distribution of global surface ocean pH (Panel a: the annually-averaged surface ocean pH to be approximate for the year 1770; Panel b: the difference between pH in 2000 and 1770 in the global surface ocean).[2]

Ocean acidification is the reduction in the pH value of the Earth’s ocean. Between 1751 and 2021, the pH value of the ocean surface is estimated to have decreased from approximately 8.25 to 8.14.[3] The root cause of ocean acidification are the human-caused carbon dioxide emissions which have led to atmospheric carbon dioxide (CO2) levels of more than 410 ppm (in 2020). The oceans absorb CO2 from the atmosphere. This leads to the formation of carbonic acid which dissociates into a bicarbonate ion (HCO3) and a hydrogen ion (H+). The free hydrogen ions (H+) decrease the ocean pH of the ocean, causing "acidification" (this does not mean that seawater is acidic yet; it is still alkaline, with a pH higher than 8). The lowered pH causes a decrease in the concentration of carbonate ions, which are the main building block for calcium carbonate (CaCO3) shells and skeletons. It also lowers carbonate mineral saturation states. Marine calcifying organisms, like mollusks, oysters and corals, are particularly affected by this as they rely on calcium carbonate to build shells and skeletons.[4]

The change in pH value from 8.25 to 8.14 represents an increase of almost 30% in hydrogen ion concentration in the world's oceans (the pH scale is logarithmic, so a change of one in pH unit is equivalent to a tenfold change in hydrogen ion concentration).[5] Sea-surface pH and carbonate saturation states can vary depending on ocean depth and location. Colder and higher latitude waters have the capacity to absorb more CO2. This can increase acidification, lowering the pH and carbonate saturation states in these regions. Other factors that affect the atmosphere-ocean CO2 exchange, and therefore impact local ocean acidification, include: ocean currents (upwelling zones), proximity to large continental rivers, sea ice coverage, and atmospheric exchange with nitrogen and sulfur from fossil fuel burning and agriculture.[2][6][7]

Decreased ocean pH has a range of potentially harmful effects for marine organisms. These include reduced calcification, depressed metabolic rates, lowered immune responses, and reduced energy for basic functions such as reproduction.[8] The effects of ocean acidification are therefore impacting marine ecosystems that provide food, livelihoods, and other ecosystem services for a large portion of humanity. Some 1 billion people are wholly or partially dependent on the fishing, tourism, and coastal management services provided by coral reefs. Ongoing acidification of the oceans may therefore threaten future food chains linked with the oceans.[9][10] Ocean alkalinity is not changed by ocean acidification, but over long time periods alkalinity may increase due to carbonate dissolution and reduced formation of calcium carbonate shells.[9][11]

The United Nations Sustainable Development Goal 14 ("Life below Water") has a target to "minimize and address the impacts of ocean acidification".[12] Reducing carbon dioxide emissions (i.e. climate change mitigation measures) is the only solution that addresses the root cause of ocean acidification. Other ocean-based mitigation technologies that can achieve carbon dioxide removal from the ocean (e.g. ocean alkalinity enhancement, enhanced weathering) generally have a low technology readiness level and many risks.[13]: 12–36 

Ocean acidification has occurred previously in Earth's history.[14] The resulting ecological collapse in the oceans had long-lasting effects on the global carbon cycle and climate.

Cause

This diagram of the fast carbon cycle shows the movement of carbon between land, atmosphere, and oceans. Yellow numbers are natural fluxes, and red are human contributions in gigatons of carbon per year. White numbers indicate stored carbon.[15]
This diagram of the fast carbon cycle shows the movement of carbon between land, atmosphere, and oceans. Yellow numbers are natural fluxes, and red are human contributions in gigatons of carbon per year. White numbers indicate stored carbon.[15]
Video summarizing the impacts of ocean acidification. Source: NOAA Environmental Visualization Laboratory.

See also: Oceanic carbon cycle

Present-day (2021) atmospheric carbon dioxide (CO2) levels of around 415 ppm are around 50% higher than preindustrial concentrations.[16]< The current elevated levels and rapid growth rates are unprecedented in the past 55 million years of the geological record. The source for this excess CO2 is clearly established as human driven, reflecting a mix of anthropogenic fossil fuel, industrial, and land-use/land-change emissions. The concept that the ocean acts as a major sink for anthropogenic CO2 has been present in the scientific literature since at least the late 1950s. The ocean takes up roughly a quarter of total anthropogenic CO2 emissions.[17] It is also well understood that the additional CO2 in the ocean results in a wholesale shift in seawater acid-base chemistry toward more acidic, lower pH conditions and lower saturation states for carbonate minerals used in many marine organism shells and skeletons.[17]

Cumulated since 1850, the ocean sink adds up to 175 ± 35 gigatons of carbon, with more than two-thirds of this amount (120 GtC) being taken up by the global ocean since 1960. Over the historical period, the ocean sink increased in pace with the exponential anthropogenic emissions increase. Since 1850, the ocean has removed 26 % of total anthropogenic emissions.[16] Emissions during the period 1850–2021 amounted to 670 ± 65 gigatons of carbon and were partitioned among the atmosphere (41 %), ocean (26 %), and land (31 %).[16]

The carbon cycle describes the fluxes of carbon dioxide (CO
2
) between the oceans, terrestrial biosphere, lithosphere,[18] and atmosphere. The carbon cycle involves both organic compounds such as cellulose and inorganic carbon compounds such as carbon dioxide, carbonate ion, and bicarbonate ion, together referenced as dissolved inorganic carbon (DIC). These inorganic compounds are particularly significant in ocean acidification, as they include many forms of dissolved CO
2
present in the Earth's oceans.[19]

When CO
2
dissolves, it reacts with water to form a balance of ionic and non-ionic chemical species: dissolved free carbon dioxide (CO
2(aq)
), carbonic acid (H
2
CO
3
), bicarbonate (HCO
3
) and carbonate (CO2−
3
). The ratio of these species depends on factors such as seawater temperature, pressure and salinity (as shown in a Bjerrum plot). These different forms of dissolved inorganic carbon are transferred from an ocean's surface to its interior by the ocean's solubility pump. The resistance of an area of ocean to absorbing atmospheric CO
2
is known as the Revelle factor.

Main effects

The ocean’s chemistry is changing due to the uptake of anthropogenic carbon dioxide (CO2).[2][20]: 395  Ocean pH, carbonate ion concentrations ([CO32−]), and calcium carbonate mineral saturation states (Ω) have been declining as a result of the uptake of approximately 30% of the anthropogenic carbon dioxide emissions over the past 270 years (since around 1750). This process is commonly referred to as “ocean acidification”. Ocean acidification is making it harder for marine calcifiers to build a shell or skeletal structure, endangering coral reefs and the broader marine ecosystems.[2]

Ocean acidification has been called the "evil twin of global warming"and "the other CO2 problem".[21][22] Increased ocean temperatures and oxygen loss act concurrently with ocean acidification and constitute the "deadly trio" of climate change pressures on the marine environment.[23] The impacts of this will be most severe for coral reefs and other shelled marine organisms,[24][25] as well as those populations that depend on the ecosystem services they provide.

Reduction in pH value

Dissolving CO
2
in seawater increases the hydrogen ion (H+
) concentration in the ocean, and thus decreases ocean pH, as follows:[26]

CO2 (aq) + H2O ⇌ H2CO3 ⇌ HCO3 + H+ ⇌ CO32− + 2 H+.

In shallow coastal and shelf regions, a number of factors interplay to affect air-ocean CO2 exchange and resulting pH change.[27][28] These include biological processes, such as photosynthesis and respiration,[29] as well as water upwelling.[30] Also, ecosystem metabolism in freshwater sources reaching coastal waters can lead to large, but local, pH changes.[27]

Freshwater bodies also appear to be acidifying, although this is a more complex and less obvious phenomenon.[31][32]

Decreased calcification in marine organisms

Various types of foraminifera observed through a microscope using differential interference contrast.
Various types of foraminifera observed through a microscope using differential interference contrast.
Bjerrum plot: Change in carbonate system of seawater from ocean acidification
Bjerrum plot: Change in carbonate system of seawater from ocean acidification

Changes in ocean chemistry can have extensive direct and indirect effects on organisms and their habitats. One of the most important repercussions of increasing ocean acidity relates to the production of shells out of calcium carbonate (CaCO
3
).[33] This process is called calcification and is important to the biology and survival of a wide range of marine organisms. Calcification involves the precipitation of dissolved ions into solid CaCO
3
structures, structures for many marine organisms, such as coccolithophores, foraminifera, crustaceans, mollusks, etc. After they are formed, these CaCO
3
structures are vulnerable to dissolution unless the surrounding seawater contains saturating concentrations of carbonate ions (CO32−).

Given the current pH of the ocean (around 8.14), of the extra carbon dioxide added into the ocean, very little remains as dissolved carbon dioxide. The majority dissociates into additional bicarbonate and free hydrogen ions. The increase in hydrogen is larger than the increase in bicarbonate,[34] creating an imbalance in the reaction HCO3 ⇌ CO32− + H+. To maintain chemical equilibrium, some of the carbonate ions already in the ocean combine with some of the hydrogen ions to make further bicarbonate. Thus the ocean's concentration of carbonate ions is reduced, removing an essential building block for marine organisms to build shells, or calcify: Ca2+ + CO32− ⇌ CaCO3.

The increase in concentrations of dissolved carbon dioxide and bicarbonate, and reduction in carbonate, are shown in the Bjerrum plot.

Decrease in saturation state

The saturation state (known as Ω) of seawater for a mineral is a measure of the thermodynamic potential for the mineral to form or to dissolve, and for calcium carbonate is described by the following equation:

Here Ω is the product of the concentrations (or activities) of the reacting ions that form the mineral (Ca2+ and CO2−3), divided by the apparent solubility product at equilibrium (Ksp), that is, when the rates of precipitation and dissolution are equal.[35] In seawater, dissolution boundary is formed as a result of temperature, pressure, and depth, and is known as the saturation horizon.[33] Above this saturation horizon, Ω has a value greater than 1, and CaCO
3
does not readily dissolve. Most calcifying organisms live in such waters.[33] Below this depth, Ω has a value less than 1, and CaCO
3
will dissolve. The carbonate compensation depth is the ocean depth at which carbonate dissolution balances the supply of carbonate to sea floor, therefore sediment below this depth will be void of calcium carbonate.[36] Increasing CO2 levels, and the resulting lower pH of seawater, decreases the concentration of CO32− and the saturation state of CaCO
3
therefore increasing CaCO
3
dissolution.

Calcium carbonate most commonly occurs in two common polymorphs (crystalline forms): aragonite and calcite. Aragonite is much more soluble than calcite, so the aragonite saturation horizon, and aragonite compensation depth, is always nearer to the surface than the calcite saturation horizon.[33] This also means that those organisms that produce aragonite may be more vulnerable to changes in ocean acidity than those that produce calcite.[37] Ocean acidification and the resulting decrease in carbonate saturation states raise the saturation horizons of both forms closer to the surface.[38] This decrease in saturation state is one of the main factors leading to decreased calcification in marine organisms because the inorganic precipitation of CaCO
3
is directly proportional to its saturation state and calcifying organisms exhibit stress in waters with lower saturation states.[39]

Observations and predictions

Detailed diagram of the carbon cycle within the ocean
Detailed diagram of the carbon cycle within the ocean

Observed pH value changes

Time series of atmospheric CO2 at Mauna Loa (in parts per million volume, ppmv; red), surface ocean pCO2 (µatm; blue) and surface ocean pH (green) at Ocean Station ALOHA in the subtropical North Pacific Ocean.[40]
Time series of atmospheric CO2 at Mauna Loa (in parts per million volume, ppmv; red), surface ocean pCO2 (µatm; blue) and surface ocean pH (green) at Ocean Station ALOHA in the subtropical North Pacific Ocean.[40]
Estimated change in seawater pH caused by anthropogenic impact on CO2 levels between the 1700s and the 1990s, from the Global Ocean Data Analysis Project (GLODAP) and the World Ocean Atlas
Estimated change in seawater pH caused by anthropogenic impact on CO
2
levels between the 1700s and the 1990s, from the Global Ocean Data Analysis Project (GLODAP) and the World Ocean Atlas

Between 1751 (the beginning of the industrial revolution) and 2021, the pH value of the ocean surface is estimated to have decreased from approximately 8.25 to 8.14.[3][41] This represents an increase of almost 30% in hydrogen ion concentration in the world's oceans (the pH scale is logarithmic, so a change of one in pH unit is equivalent to a tenfold change in hydrogen ion concentration).[5] For example, in the 15-year period 1995–2010 alone, acidity has increased 6 percent in the upper 100 meters of the Pacific Ocean from Hawaii to Alaska.[42]

The IPCC Sixth Assessment Report in 2021 stated that "present-day surface pH values are unprecedented for at least 26,000 years and current rates of pH change are unprecedented since at least that time.[43]: 76  The pH value of the ocean interior has declined over the last 20-30 years everywhere in the global ocean.[43]: 76  The report also found that "pH in open ocean surface water has declined by about 0.017 to 0.027 pH units per decade since the late 1980s".[44]: 716 

The rate of decline differs by region due to the "complex interplay between physical and biological forcing mechanisms".[44]: 716 :

The rate at which ocean acidification will occur may be influenced by the rate of surface ocean warming, because warm waters will not absorb as much CO2.[45] Therefore, greater seawater warming could limit CO2 absorption and lead to a smaller change in pH for a given increase in CO2.[45] The difference in changes in temperature between basins is one of the main reasons for the differences in acidification rates in different localities.

Current rates of ocean acidification have been likened to the greenhouse event at the Paleocene–Eocene boundary (about 56 million years ago), when surface ocean temperatures rose by 5–6 degrees Celsius. In that event, surface ecosystems experienced a variety of impacts, but bottom-dwelling organisms in the deep ocean actually experienced a major extinction.[46] Currently, the rate of carbon addition to the atmosphere-ocean system is about ten times the rate that occurred at the Paleocene–Eocene boundary.[47]

Extensive observational systems are now in place or being built for monitoring seawater CO2 chemistry and acidification for both the global open ocean and some coastal systems.[17]

Acidification rates in different marine regions
Location Change in pH units per decade Period Data source Year of publication
Iceland[48] minus 0.024 1984 – 2009 Direct measurements 2009
Drake Passage[49] minus 0.018 2002 – 2012 Direct measurements 2012
Canary (ESTOC)[50] minus 0.017 1995 – 2004 Direct measurements 2010
Hawaii (HOT)[51] minus 0.019 1989 – 2007 Direct measurements 2009
Bermuda (BATS)[52] minus 0.017 1984 – 2012 Direct measurements 2012
Coral Sea[53] minus 0.002 ~1700 – ~1990 Proxy reconstruction 2005
Eastern Mediterranean[54] minus 0.023 1964 – 2005 Proxy reconstruction 2016
Rates of pH change for some regions of the world (many more regions available in source table)[55]: Table 5.SM.3 
Station, region Study period pH change (per decade)
Equatorial Pacific TAO 2004-2011 minus 0.026
Indian Ocean IO-STPS 1991-2011 minus 0.027
Mediterranean Dyfamed (43.42°N, 7.87°E) 1995-2011 minus 0.03
North Atlantic Iceland Sea (68°N, 12.67°W) 1985-2008

1985-2010

minus 0.024

minus 0.014

North Atlantic Irminger Sea (64.3°N, 28°W) 1983-2004 minus 0.026
North Pacific NP-STSS 1991-2011 minus 0.01
Southern Ocean PAL-LTER, west Antarctic Peninsula 1993-2012 plus 0.02

Predicted future pH value changes

In situ CO2 concentration sensor (SAMI-CO2), attached to a Coral Reef Early Warning System station, utilized in conducting ocean acidification studies near coral reef areas (by NOAA (AOML))
In situ CO
2
concentration sensor (SAMI-CO2), attached to a Coral Reef Early Warning System station, utilized in conducting ocean acidification studies near coral reef areas (by NOAA (AOML))
A moored autonomous CO2 buoy used for measuring CO2 concentration and ocean acidification studies (NOAA (by PMEL))
A moored autonomous CO
2
buoy used for measuring CO
2
concentration and ocean acidification studies (NOAA (by PMEL))

Earth System Models project that, by around 2008, ocean acidity exceeded historical analogues.[56] In combination with other ocean biogeochemical changes, this could undermine the functioning of marine ecosystems and disrupt the provision of many goods and services associated with the ocean beginning as early as 2100.[57] Current ocean acidification is now on a path to reach lower pH levels than at any other point in the last 300 million years.[58][59] The rate of ocean acidification is also estimated to be unprecedented over that same time scale.[60][14] The expected changes are considered unprecedented in the geological record.[61][62][63]

The extent of further chemistry changes, including ocean pH, will depend on climate change mitigation efforts taken by nations and their governments.[43] Different scenarios of projected socioeconomic global changes are modelled by using the Shared Socioeconomic Pathways (SSP) scenarios.

If the 'business as usual' model for human activity persists (where little effort is made to curb greenhouse gas emissions, leading to a very high emission scenario called SSP5-8.5), model projections estimate that surface ocean pH could decrease by as much as 0.44 units compared to the present day by the end of the century.[64]: 608  This would mean a pH as low as about 7.7, and represents a further increase in H+ concentrations of two to four times beyond the increase to date.

Estimated past and future global mean surface pH for different emission scenarios[43]: values estimated from Figure TS.11 (d) 
Time period pH value (approx.)
Pre-industrial (1850) 8.18
Now (2021) (assessed observational change spans 1985–2019) 8.14
Future (2100) with low emission scenario (SSP 1-2.6) 8.0
Future (2100) with very high emission scenario (SSP 5-8.5) 7.7

Ocean acidification in the geologic past

Three of the big five mass extinction events in the geologic past were associated with a rapid increase in atmospheric carbon dioxide, probably due to volcanism and/or thermal dissociation of marine gas hydrates.[65] Elevated CO2 levels impacted biodiversity.[66] Decreased CaCO3 saturation due to seawater uptake of volcanogenic CO2 has been suggested as a possible kill mechanism during the marine mass extinction at the end of the Triassic.[67] The end-Triassic biotic crisis is still the most well-established example of a marine mass extinction due to ocean acidification, because (a) carbon isotope records suggest enhanced volcanic activity that decreased the carbonate sedimentation which reduced the carbonate compensation depth and the carbonate saturation state, and a marine extinction coincided precisely in the stratigraphic record,[68][69][70] and (b) there was pronounced selectivity of the extinction against organisms with thick aragonitic skeletons,[68][71][72] which is predicted from experimental studies.[73] Ocean acidification has also been suggested as a one cause of the end-Permian mass extinction[74][75] and the end-Cretaceous crisis.[59] Overall, multiple climatic stressors, including ocean acidification, was likely the cause of geologic extinction events.[65]

The most notable example of ocean acidification is the Paleocene-Eocene Thermal Maximum (PETM), which occurred approximately 56 million years ago when massive amounts of carbon entered the ocean and atmosphere, and led to the dissolution of carbonate sediments across many ocean basins.[76] Relatively new geochemical methods of testing for pH in the past indicate the pH dropped 0.3 units across the PETM.[77][78] One study that solves the marine carbonate system for saturation state shows that it may not change much over the PETM, suggesting the rate of carbon release at our best geological analogy was much slower than human-induced carbon emissions. However, stronger proxy methods to test for saturation state are needed to assess how much this pH change may have affected calcifying organisms.

Distribution of (A) aragonite and (B) calcite saturation depth in the global oceans[79]
Distribution of (A) aragonite and (B) calcite saturation depth in the global oceans[79]
This map shows changes in the aragonite saturation level of ocean surface waters between the 1880s and the most recent decade (2006–2015). Aragonite is a form of calcium carbonate that many marine animals use to build their skeletons and shells. The lower the saturation level, the more difficult it is for organisms to build and maintain their skeletons and shells. A negative change represents a decrease in saturation.[80]
This map shows changes in the aragonite saturation level of ocean surface waters between the 1880s and the most recent decade (2006–2015). Aragonite is a form of calcium carbonate that many marine animals use to build their skeletons and shells. The lower the saturation level, the more difficult it is for organisms to build and maintain their skeletons and shells. A negative change represents a decrease in saturation.[80]

Impacts on oceanic calcifying organisms

See also: Marine biogenic calcification

A normally-protective shell made thin, fragile and transparent by acidification
A normally-protective shell made thin, fragile and transparent by acidification

Complexity of research findings

The full ecological consequences of the changes in calcification due to ocean acidification are complex but it appears likely that many calcifying species will be adversely affected by ocean acidification.[17][20]: 413  Increasing ocean acidification makes it more difficult for shell-accreting organisms to access carbonate ions, essential for the production of their hard exoskeletal shell.[41] Oceanic calcifying organism span the food chain from autotrophs to heterotrophs and include organisms such as coccolithophores, corals, foraminifera, echinoderms, crustaceans and molluscs.[57][81]

Overall, all marine ecosystems on Earth will be exposed to changes in acidification and several other ocean biogeochemical changes.[82] Ocean acidification may force some organisms to reallocate resources away from productive endpoints n order to maintain calcification.[83] For example, the oyster Magallana gigas is recognized to experience metabolic changes alongside altered calcification rates due to energetic tradeoffs resulting from pH imbalances.[84]

Under normal conditions, calcite and aragonite are stable in surface waters since the carbonate ions are supersaturated with respect to seawater. However, as ocean pH falls, the concentration of carbonate ions also decreases. Calcium carbonate thus becomes undersaturated, and structures made of calcium carbonate are vulnerable to calcification stress and dissolution.[85] In particular, studies show that corals,[86][87] coccolithophores,[81][27][88] coralline algae,[89] foraminifera,[90] shellfish and pteropods[91] experience reduced calcification or enhanced dissolution when exposed to elevated CO2. Even with active marine conservation practices it may be impossible to bring back many previous shellfish populations.[92]

Some studies have found different responses to ocean acidification, with coccolithophore calcification and photosynthesis both increasing under elevated atmospheric pCO2,[93] and an equal decline in primary production and calcification in response to elevated CO2,[94] or the direction of the response varying between species.[95]

Similarly, the sea star, Pisaster ochraceus, shows enhanced growth in waters with increased acidity.[96]

Reduced calcification from ocean acidification may affect the ocean's biologically driven sequestration of carbon from the atmosphere to the ocean interior and seafloor sediment, weakening the so-called biological pump.[59] Seawater acidification could also reduce the size of Antarctic phytoplankton, making them less effective at storing carbon.[97] Such changes are being increasingly studied and synthesized through the use of physiological frameworks, including the Adverse Outcome Pathway (AOP) framework.[84]

Coccolithus pelagicus, a species of coccolithophore sampled from the North Atlantic Ocean.
Coccolithus pelagicus, a species of coccolithophore sampled from the North Atlantic Ocean.

Coccolithophores

Further information: Coccolithophore

A coccolithophore is a unicellular, eukaryotic phytoplankton (alga). Understanding calcification changes in coccolithophores may be particularly important because a decline in the coccolithophores may have secondary effects on climate: it could contribute to global warming by decreasing the Earth's albedo via their effects on oceanic cloud cover.[98] A study in 2008 examining a sediment core from the North Atlantic found that while the species composition of coccolithophorids remained unchanged for the industrial period 1780 to 2004, the calcification of coccoliths has increased by up to 40% during the same time.[93]

Corals

Further information: Coral and Coral reef

Warm water corals are clearly in decline, with losses of 50% over the last 30-50 years due to multiple threats from ocean warming, ocean acidification, pollution and physical damage from activities such as fishing, and these pressures are expected to intensify.[99][20]: 416 

The fluid in the internal compartments (the coelenteron) where corals grow their exoskeleton is also extremely important for calcification growth. When the saturation state of aragonite in the external seawater is at ambient levels, the corals will grow their aragonite crystals rapidly in their internal compartments, hence their exoskeleton grows rapidly. If the saturation state of aragonite in the external seawater is lower than the ambient level, the corals have to work harder to maintain the right balance in the internal compartment. When that happens, the process of growing the crystals slows down, and this slows down the rate of how much their exoskeleton is growing. Depending on the aragonite saturation state in the surrounding water, the corals may halt growth because pumping aragonite into the internal compartment will not be energetically favorable.[100] Under the current progression of carbon emissions, around 70% of North Atlantic cold-water corals will be living in corrosive waters by 2050–60.[101]

Acidified conditions primarily reduce the coral’s capacity to build dense exoskeletons, rather than affecting the linear extension of the exoskeleton. The density of some species of corals could be reduced by over 20% by the end of this century.[102]

An in situ experiment, conducted on a 400 m2 patch of the Great Barrier Reef, to decrease seawater CO2 level (raise pH) to near the preindustrial value showed a 7% increase in net calcification.[103] A similar experiment to raise in situ seawater CO2 level (lower pH) to a level expected soon after the 2050 found that net calcification decreased 34%.[104]

However, a field study of the coral reef in Queensland and Western Australia from 2007 to 2012 found that corals are more resistant to the environmental pH changes than previously thought, due to internal homeostasis regulation; this makes thermal change (marine heatwaves), which leads to coral bleaching, rather than acidification, the main factor for coral reef vulnerability due to climate change.[105]

Studies at carbon dioxide seep sites

In some places carbon dioxide bubbles out from the sea floor, locally changing the pH and other aspects of the chemistry of the seawater. Studies of these carbon dioxide seeps have documented a variety of responses by different organisms.[106] Coral reef communities located near carbon dioxide seeps are of particular interest because of the sensitivity of some corals species to acidification. In Papua New Guinea, declining pH caused by carbon dioxide seeps is associated with declines in coral species diversity.[107] However, in Palau carbon dioxide seeps are not associated with reduced species diversity of corals, although bioerosion of coral skeletons is much higher at low pH sites.

Pteropods and brittle stars

Pteropods and brittle stars both form the base of the Arctic food webs and are both seriously damaged from acidification. Pteropods shells dissolve with increasing acidification and the brittle stars lose muscle mass when re-growing appendages.[108] For pteropods to create shells they require aragonite which is produced through carbonate ions and dissolved calcium and strontium. Pteropods are severely affected because increasing acidification levels have steadily decreased the amount of water supersaturated with carbonate.[109] The degradation of organic matter in Arctic waters has amplified ocean acidification; some Arctic waters are already undersaturated with respect to aragonite.[110][111][112]

In the North Pacific and North Atlantic, saturation states are also decreasing (the depth of saturation is getting more shallow). Additionally the brittle star's eggs die within a few days when exposed to expected conditions resulting from Arctic acidification.[113] Similarly, when exposed in experiments to pH reduced by 0.2 to 0.4, larvae of a temperate brittle star, a relative of the common sea star, fewer than 0.1 percent survived more than eight days.[57]

Other impacts on ecosystems and ocean chemistry

Other biological impacts

Aside from the slowing and/or reversal of calcification, organisms may suffer other adverse effects, either indirectly through negative impacts on food resources, or directly as reproductive or physiological effects.[33] For example, the elevated oceanic levels of CO2 may produce CO
2
-induced acidification of body fluids, known as hypercapnia.[114]

Acoustic properties

Increasing acidity has been observed to reduce metabolic rates in jumbo squid[115] and depress the immune responses of blue mussels.[116] This is possibly because ocean acidification may alter the acoustic properties of seawater, allowing sound to propagate further, and increasing ocean noise.[117] This impacts all animals that use sound for echolocation or communication.[118] Atlantic longfin squid eggs took longer to hatch in acidified water, and the squid's statolith was smaller and malformed in animals placed in sea water with a lower pH.[119] However, these studies are ongoing and there is not yet a full understanding of these processes in marine organisms or ecosystems.[120]

Algae and seagrasses

Another possible effect would be an increase in harmful algal bloom events, which could contribute to the accumulation of toxins (domoic acid, brevetoxin, saxitoxin) in small organisms such as anchovies and shellfish, in turn increasing occurrences of amnesic shellfish poisoning, neurotoxic shellfish poisoning and paralytic shellfish poisoning.[121] Although algal blooms can be harmful, other beneficial photosynthetic organisms may benefit from increased levels of carbon dioxide. Most importantly, seagrasses will benefit.[122] Research found that as seagrasses increased their photosynthetic activity, calcifying algae's calcification rates rose, likely because localized photosynthetic activity absorbed carbon dioxide and elevated local pH.[122]

Fish larvae

Ocean acidification can also have affects on marine fish larvae. It internally affects their olfactory systems, which is a crucial part of their development, especially in the beginning stage of their life. Orange clownfish larvae mostly live on oceanic reefs that are surrounded by vegetative islands.[105] With the use of their sense of smell, larvae are known to be able to detect the differences between reefs surrounded by vegetative islands and reefs not surrounded by vegetative islands.[105] Clownfish larvae need to be able to distinguish between these two destinations to have the ability to locate an area that is satisfactory for their growth. Another use for marine fish olfactory systems is to help in determining the difference between their parents and other adult fish in order to avoid inbreeding.

In an experimental aquarium facility, clownfish were sustained in non-manipulated seawater that obtained a pH of 8.15 ± 0.07 which is similar to our current ocean's pH.[105] To test for effects of different pH levels, seawater was manipulated to three different pH levels, including the non-manipulated pH. The two opposing pH levels correspond with climate change models that predict future atmospheric CO2 levels.[105] In the year 2100 the model predicts that we could potentially acquire CO2 levels at 1,000 ppm, which correlates with the pH of 7.8 ± 0.05.

Results of this experiment show that when larvae is exposed to a pH of 7.8 ± 0.05 their reaction to environmental cues differs drastically to larvae's reaction to cues in a non-manipulated pH.[105] At the pH of 7.6 ± 0.05 larvae had no reaction to any type of cue. However, a meta-analysis published in 2022 found that the effect sizes of published studies testing for ocean acidification effects on fish behavior have declined by an order of magnitude over the past decade and have been negligible for the past five years.[123]

Compounded effects of acidification, warming and deoxygenation

Further information: Effects of climate change on oceans and Ocean deoxygenation

Drivers of hypoxia and ocean acidification intensification in upwelling shelf systems. Equatorward winds drive the upwelling of low dissolved oxygen (DO), high nutrient, and high dissolved inorganic carbon (DIC) water from above the oxygen minimum zone. Cross-shelf gradients in productivity and bottom water residence times drive the strength of DO (DIC) decrease (increase) as water transits across a productive continental shelf.[124][125]
Drivers of hypoxia and ocean acidification intensification in upwelling shelf systems. Equatorward winds drive the upwelling of low dissolved oxygen (DO), high nutrient, and high dissolved inorganic carbon (DIC) water from above the oxygen minimum zone. Cross-shelf gradients in productivity and bottom water residence times drive the strength of DO (DIC) decrease (increase) as water transits across a productive continental shelf.[124][125]

There is a substantial body of research showing that a combination of ocean acidification and elevated ocean temperature have a compounded effect on marine life and the ocean environment. This effect far exceeds the individual harmful impact of either.[126] In addition, ocean warming, along with increased productivity of phytoplankton from higher CO2 levels exacerbates ocean deoxygenation. Deoxygenation of ocean waters is an additional stressor on marine organisms that increases ocean stratification therefore limiting nutrients over time and reducing biological gradients.[127][128]

Meta analyses have quantified the direction and magnitude of the harmful effects of combined ocean acidification, warming and deoxygenation on the ocean.[129][130] These meta-analyses have been further tested by mesocosm studies that simulated the interaction of these stressors and found a catastrophic effect on the marine food web: thermal stress more than negates any primary producer to herbivore increase in productivity from elevated CO2.[131][132]

Upwelling

Already now large quantities of water undersaturated in aragonite are upwelling close to the Pacific continental shelf area of North America, from Vancouver to Northern California.[133] These continental shelves play an important role in marine ecosystems, since most marine organisms live or are spawned there. Other shelf areas may be experiencing similar effects.[133]

Carbonate compensation depth

At depths of 1000s of meters in the ocean, calcium carbonate shells begin to dissolve as increasing pressure and decreasing temperature shift the chemical equilibria controlling calcium carbonate precipitation.[134] The depth at which this occurs is known as the carbonate compensation depth. Ocean acidification will increase such dissolution and shallow the carbonate compensation depth on timescales of tens to hundreds of years.[134] Zones of downwelling are being affected first.[135]

Carbonate sediments

It is expected that ocean acidification in the future will lead to a significant decrease in the burial of carbonate sediments for several centuries, and even the dissolution of existing carbonate sediments.[136] This will cause an elevation of ocean alkalinity, leading to the enhancement of the ocean as a reservoir for CO2, which would cause further invasion of CO2 from the atmosphere to the ocean.[137]

Impacts on the economy and societies

The increase of ocean acidity decelerates the rate of calcification in salt water, leading to smaller and slower growing coral reefs which supports approximately 25% of marine life.[138][139] Impacts are far-reaching from fisheries and coastal environments down to the deepest depths of the ocean.[140] The increase in ocean acidity in not only killing the coral, but also the wildly diverse population of marine inhabitants which coral reefs support.[141]

Fishing industry

The threat of acidification includes a decline in commercial fisheries and the coast-based tourism industry. Several ocean goods and services are likely to be undermined by future ocean acidification potentially affecting the livelihoods of some 400 to 800 million people depending upon the emission scenario.[57]

Arctic

In the Arctic, commercial fisheries are threatened because acidification harms calcifying organisms which form the base of the Arctic food webs (pteropods and brittle stars, see above).  Acidification threatens Arctic food webs from the base up. Arctic food webs are considered simple, meaning there are few steps in the food chain from small organisms to larger predators. For example, pteropods are "a key prey item of a number of higher predators – larger plankton, fish, seabirds, whales".[142] Both pteropods and sea stars serve as a substantial food source and their removal from the simple food web would pose a serious threat to the whole ecosystem. The effects on the calcifying organisms at the base of the food webs could potentially destroy fisheries.

US commercial fisheries

An adult American lobster rests on the sea floor. Rhode Island, Dutch Island, Newport County.
An adult American lobster rests on the sea floor. Rhode Island, Dutch Island, Newport County.

The value of fish caught from US commercial fisheries in 2007 was valued at $3.8 billion and of that 73% was derived from calcifiers and their direct predators.[143] Other organisms are directly harmed as a result of acidification. For example, decrease in the growth of marine calcifiers such as the American lobster, ocean quahog, and scallops means there is less shellfish meat available for sale and consumption.[144] Red king crab fisheries are also at a serious threat because crabs are also calcifiers. Baby red king crab when exposed to increased acidification levels experienced 100% mortality after 95 days.[145] In 2006, red king crab accounted for 23% of the total guideline harvest levels and a serious decline in red crab population would threaten the crab harvesting industry.[146]

Indigenous peoples

See also: Climate change and indigenous peoples

Acidification will affect the way of life of indigenous peoples. Sport fishing and hunting are both culturally important to Arctic Indigenous peoples.The rapid decrease or disappearance of marine life could also affect the diet of Indigenous peoples. For example, in Washington State and California (United States), Native American communities report potential damage to shellfish resources due to sea level rise and ocean acidification.[147]

Possible responses

Climate change mitigation

Main article: Climate change mitigation

Reducing carbon dioxide emissions (i.e. climate change mitigation measures) is the only solution that addresses the root cause of ocean acidification. Increasing the land devoted to forests and encouraging the growth of CO2-breathing sea plants could help to slow down ocean acidification.[148]

Technologies to remove carbon dioxide from the ocean

Main articles: Carbon dioxide removal and Carbon sequestration § Sequestration techniques in oceans

Other technologies that can achieve carbon dioxide removal (CDR) are being developed (e.g. direct air capture (DAC), bioenergy with carbon capture and storage (BECCS)). These might slow the rate of acidification. Scientists are also investigating strategies that use the ocean for carbon dioxide removal which might help with local ocean acidification adaptation (e.g. ocean alkalinity enhancement, enhanced weathering).[149] These technologies are generally expensive, have many risks and side effects and have a low technology readiness level.[13]: 12–36 

Approaches that remove carbon dioxide from the ocean include ocean nutrient fertilization, artificial upwelling/downwelling, seaweed farming, ecosystem recovery, ocean alkalinity enhancement, and electrochemical processes. All of these methods use the ocean to remove CO2 from the atmosphere to store it in the ocean. However, a few of the methods have the additional positive effect, or a co-benefit, of mitigating ocean acidification. The research field for all CDR methods has grown a lot since 2019.[149]

In principle, carbon can be stored in ocean reservoirs. This can be done with the processes of ocean fertilisation, ocean alkalinity enhancement or enhanced weathering.[13]: 12–36  These methods could assist with mitigation but they can have side-effects on marine life and they currently have a low technology readiness level.

In total, "ocean-based methods have a combined potential to remove 1–100 gigatons of CO2 per year".[150]: TS-94  Their costs are in the order of USD40–500 per ton of CO2. For example, enhanced weathering could remove 2–4 gigatons of CO2 per year. This technology comes with a cost of 50-200 USD per ton of CO2.[150]: TS-94 

Ocean nutrient fertilization

Ocean fertilization or ocean nourishment is a type of technology for carbon dioxide removal from the ocean based on the purposeful introduction of plant nutrients to the upper ocean to increase marine food production and to remove carbon dioxide from the atmosphere.[151][152] Ocean nutrient fertilization, for example iron fertilization, of the ocean could stimulate photosynthesis in phytoplankton. The phytoplankton would convert the ocean's dissolved carbon dioxide into carbohydrate and oxygen gas, some of which would sink into the deeper ocean before oxidizing. More than a dozen open-sea experiments confirmed that adding iron to the ocean increases photosynthesis in phytoplankton by up to 30 times.[153]

This is one of the more well-researched carbon dioxide removal (CDR) approaches, however this approach would only sequester carbon on a timescale of 10-100 years dependent on ocean mixing times. While surface ocean acidity may decrease as a result of nutrient fertilization, when the sinking organic matter remineralizes, the deep ocean acidity will increase. A 2021 report on CDR indicates that there is medium-high confidence that the technique could be efficient and scalable at low cost, with medium environmental risks.[154] One of the key risks of nutrient fertilization is nutrient robbing, a process by which excess nutrients used in one location for enhanced primary productivity, as in a fertilization context, are then unavailable for normal productivity downstream. This could result in ecosystem impacts far outside the original site of fertilization.[154]

Ocean alkalinity enhancement

See also: Enhanced weathering

Ocean alkalinity enhancement (OAE) is defined as "a proposed carbon dioxide removal (CDR) method that involves deposition of alkaline minerals or their dissociation products at the ocean surface".[155]: 2241  The process would increase surface total alkalinity. It would work to accelerate Earth’s geologic carbon regulator. The process involves increasing the amount of bicarbonate (HCO3-) through accelerated weathering (enhanced weathering) of rocks (silicate, limestone and quicklime).[149]: 181  This process mimics the silicate-carbonate cycle, and will ultimately draw down CO2 from the atmosphere into the ocean. The CO2 will either become bicarbonate, and be stored in the ocean in that form for more than 100 years, or may precipitate into calcium carbonate (CaCO3). When the calcium carbonate is buried in the deep ocean, it can store the carbon for approximately one million years when utilizing silicate rocks as the means to increase alkalinity.

In addition to sequestering CO2, alkalinity addition buffers the pH of the ocean therefore reducing the degree of ocean acidification. However, little is known about how organisms will respond to added alkalinity, even from natural sources.[149] For example, weathering of some silicate rocks could release a large amount of potentially trace metals into the ocean at the site of enhanced weathering. In addition, the cost and the energy consumed by implementing ocean alkalinity enhancement (mining, pulverizing, transport) is high compared to other CDR techniques. Overall, OAE is scalable, and highly efficient at removing carbon dioxide.[149]

The cost of ocean alkalinity enhancement is estimated to be 20–50 USD per ton of CO2 (for "direct addition of alkaline minerals to the ocean").[13]: 12–50 

Electrochemical processes

Electrochemical methods, or electrolysis, can strip carbon dioxide directly from seawater.[149] Some methods focus on direct CO2 removal (in the form of carbonate and CO2 gas) while others increase the alkalinity of seawater by precipitating metal hydroxide residues, which absorbs CO2 in a matter described in the ocean alkalinity enhancement section. The hydrogen produced during direct carbon capture can then be upcycled to form hydrogen for energy consumption, or other manufactured laboratory reagents such as hydrochloric acid. Electrolysis is a classic chemical technique that dates back to the 19th century. However, implementation of electrolysis for carbon capture is expensive and the energy consumed for the process is high compared to other CDR techniques.[149] In addition, research to assess the environmental impact of this process is ongoing. Some complications include toxic chemicals in wastewaters, and reduced DIC in effluents; both of these may negatively impact marine life. Similar to OAE, recent reports show electrochemical processes are scalable and highly efficient at removing carbon dioxide.[149]

Policies and goals

Demonstrator calling for action against ocean acidification at the People's Climate March (2017)
Demonstrator calling for action against ocean acidification at the People's Climate March (2017)

Global policies

As awareness about ocean acidification grows, policies geared towards increasing monitoring efforts of ocean acidification have been drafted.[156] Previously in 2015, ocean scientist Jean-Pierre Gattuso had remarked that "The ocean has been minimally considered at previous climate negotiations. Our study provides compelling arguments for a radical change at the UN conference (in Paris) on climate change".[157]

International efforts, such as the UN Cartagena Convention (entered into force in 1986),[158] are critical to enhance the support provided by regional governments to highly vulnerable areas to ocean acidification. Many countries, for example in the Pacific Islands and Territories, have constructed regional policies, or National Ocean Policies, National Action Plans, National Adaptation Plans of Action and Joint National Action Plans on Climate Change and Disaster Risk Reduction, to help work towards SDG 14. Ocean acidification is now starting to be considered within those frameworks.[159]

UN Ocean Decade

The UN Ocean Decade Action "OARS: Ocean Acidification Research for Sustainability” was proposed by the Global Ocean Acidification Observing Network (GOA-ON) and its partners, and has been formally endorsed as a program of the UN Decade of Ocean Science for Sustainable Development.[160][161] The OARS programme builds on the work of GOA-ON to further develop the science of ocean acidification by enhancing ocean acidification capacity, increasing observations of ocean chemistry changes, identifying the impacts on marine ecosystems on local and global scales, and providing society and decision makers with the information needed to mitigate and adapt to ocean acidification.

Global Climate Indicators

The importance of ocean acidification is reflected in its inclusion as one of seven Global Climate Indicators.[162] These Indicators are a set of parameters that describe the changing climate without reducing climate change to only rising temperature. The Indicators include key information for the most relevant domains of climate change: temperature and energy, atmospheric composition, ocean and water as well as the cryosphere. The Global Climate Indicators have been identified by scientists and communication specialists in a process led by Global Climate Observing System (GCOS).[163] The Indicators have been endorsed by the World Meteorological Organization (WMO). They form the basis of the annual WMO Statement of the State of the Global Climate, which is submitted to the Conference of Parties (COP) of the United Nations Framework Convention on Climate Change (UNFCCC). Additionally, the Copernicus Climate Change Service (C3S) of the European Commission uses the Indicators for their annual "European State of the Climate".

Sustainable Development Goal 14

In 2015, the United Nations adopted the 2030 Agenda and a set of 17 Sustainable Development Goals (SDG), including a goal dedicated to the ocean, Sustainable Development Goal 14,[12] which calls to "conserve and sustainably use the oceans, seas and marine resources for sustainable development". Ocean acidification is directly addressed by the target SDG 14.3. The full title of Target 14.3 is: "Minimize and address the impacts of ocean acidification, including through enhanced scientific cooperation at all levels".[164] This target has one indicator: Indicator 14.3.1 which calls for the "Average marine acidity (pH) measured at agreed suite of representative sampling stations".[165] 

The Intergovernmental Oceanographic Commission (IOC) of UNESCO was identified as the custodian agency for the SDG 14.3.1 Indicator. In this role, IOC-UNESCO is tasked with developing the SDG 14.3.1 Indicator Methodology, the annual collection of data towards the SDG 14.3.1 Indicator and the reporting of progress to the United Nations.[166][167]

Policies at country level

United States

In the United States, robust ocean acidification policy supports sustained government coordination, such as the National Oceanic Atmospheric Administration’s Ocean Acidification Program.[168][169] In 2015, USEPA denied a citizens petition that asked EPA to regulate CO2 under the Toxic Substances Control Act of 1976 in order to mitigate ocean acidification.[170][171] In the denial, the EPA said that risks from ocean acidification were being "more efficiently and effectively addressed" under domestic actions, e.g., under the Presidential Climate Action Plan, and that multiple avenues are being pursued to work with and in other nations to reduce emissions and deforestation and promote clean energy and energy efficiency.[172]

History

Research into the phenomenon of ocean acidification, as well as awareness raising about the problem, has been going on for several decades. For example, research in 2010 found that in the 15-year period 1995–2010 alone, acidity had increased 6 percent in the upper 100 meters of the Pacific Ocean from Hawaii to Alaska.[42]

The "First Symposium on the Ocean in a High-CO2 World" took place in France in 2004.[173]

In 2009, members of the InterAcademy Panel called on world leaders to "Recognize that reducing the build up of CO2 in the atmosphere is the only practicable solution to mitigating ocean acidification".[174] The statement also stressed the importance to "Reinvigorate action to reduce stressors, such as overfishing and pollution, on marine ecosystems to increase resilience to ocean acidification".[175]

According to a statement in July 2012 by Jane Lubchenco, head of the U.S. National Oceanic and Atmospheric Administration "surface waters are changing much more rapidly than initial calculations have suggested. It's yet another reason to be very seriously concerned about the amount of carbon dioxide that is in the atmosphere now and the additional amount we continue to put out."[176]

A 2013 study found acidity was increasing at a rate 10 times faster than in any of the evolutionary crises in Earth's history.[177]

The "Third Symposium on the Ocean in a High-CO2 World" took place in Monterey, California, in 2012. The summary for policy makers from the conference stated that "Ocean acidification research is growing rapidly".[178]

In a synthesis report published in Science in 2015, 22 leading marine scientists stated that CO2 from burning fossil fuels is changing the oceans' chemistry more rapidly than at any time since the Great Dying (Earth's most severe known extinction event).[157] Their report emphasized that the 2 °C maximum temperature increase agreed upon by governments reflects too small a cut in emissions to prevent "dramatic impacts" on the world's oceans.[157]

See also

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