# Ocean acidification

Change in sea water acidity pH caused by anthropogenic CO2 between the 1700s and the 1990s

Ocean acidification is the name given to the ongoing decrease in the pH and increase in acidity of the Earth's oceans, caused by the uptake of anthropogenic carbon dioxide (CO2) from the atmosphere.[1] Generally speaking when the carbon molecules in the air above seawater increase by four molecules one will diffuse into seawater. About a quarter of the carbon dioxide in the atmosphere goes into the sea. As the amount of carbon, measured in parts per million, rose in the atmosphere there was a corresponding rise of carbon going into the ocean. Why we must measure acidity or pH in water instead of dissolved carbon is more complicated (chemical) because unlike oxygen and dissolved oxygen carbon does not last long as carbon dioxide. pH is a measure of acidity ranging from 0-14. The lower the value, the more acidic the environment. Becoming more acidic is a relative shift in pH to a lower value.

When carbon dioxide is absorbed by seawater, chemical reactions occur that reduce seawater pH, carbonate ion concentration, and saturation states of biologically important calcium carbonate minerals. These chemical reactions are termed "ocean acidification" or "OA" for short. Calcium carbonate minerals are the building blocks for the skeletons and shells of many marine organisms. In areas where most life now congregates in the ocean, the seawater is supersaturated with respect to calcium carbonate minerals. This means there are abundant building blocks for calcifying organisms to build their skeletons and shells. However, continued ocean acidification is causing many parts of the ocean to become undersaturated with these minerals, which is likely to affect the ability of some organisms to produce and maintain their shells. Increasing acidity in sea water, pushing it towards soda water, increases the potential of calcium in animals to fizzle. [2] Between 1751 and 1994 surface ocean pH is estimated to have decreased from approximately 8.25 to 8.14,[3] representing an increase of approaching 30% in "acidity" (H+ ion concentration) in the world's oceans.[4][5][6]

## Carbon cycle

The CO2 cycle between the atmosphere and the ocean

The carbon cycle describes the fluxes of carbon dioxide (CO2) between the oceans, terrestrial biosphere, lithosphere,[7] and the atmosphere. Human activities such as the combustion of fossil fuels and land use changes have led to a new flux of CO2 into the atmosphere. About 45% has remained in the atmosphere; most of the rest has been taken up by the oceans,[8] with some also taken up by terrestrial plants.[9]

The carbon cycle involves both organic compounds as well as inorganic carbon compounds such as carbon dioxide and the carbonates. The inorganic compounds are particularly relevant when discussing ocean acidification for it includes the many forms of dissolved CO2 present in the Earth's oceans.[10]

When CO2 dissolves, it reacts with water to form a balance of ionic and non-ionic chemical species: dissolved free carbon dioxide (CO(aq)
2
), carbonic acid (H2CO3), bicarbonate (HCO
3
) and carbonate (CO2−
3
). The ratio of these species depends on factors such as seawater temperature and alkalinity (see the article on the ocean's solubility pump for more detail).

## Acidification

Carbonate system of seawater

Dissolving CO2 in seawater increases the hydrogen ion (H+) concentration in the ocean, and thus decreases ocean pH. Caldeira and Wickett (2003)[1] placed the rate and magnitude of modern ocean acidification changes in the context of probable historical changes during the last 300 million years.

Average surface ocean pH[11]
Time pH pH change Source H+ concentration change
relative to pre-industrial
Pre-industrial (18th century) 8.179 0.000 analysed field[12] 0%
Recent past (1990s) 8.104 -0.075 field[12] + 18.9%
Present levels ~8.069 -0.11 field[4][5][13][6] + 28.8%
2050 (2×CO2 = 560 ppm) 7.949 -0.230 model[11] + 69.8%
2100 (IS92a)[14] 7.824 -0.355 model[11] + 126.5%

Since the industrial revolution began, it is estimated that surface ocean pH has dropped by slightly more than 0.1 units on the logarithmic scale of pH, representing an approximately 29% increase in H+, and it is estimated that it will drop by a further 0.3 to 0.5 pH units (an additional doubling to tripling of today's post-industrial acid concentrations) by 2100 as the oceans absorb more anthropogenic CO2.[1][11][15] These changes are predicted to continue rapidly as the oceans take up more anthropogenic CO2 from the atmosphere. The degree of change to ocean chemistry, including ocean pH, will depend on the mitigation and emissions pathways society takes.[16] Even though the ocean is acidifying its pH is still greater than 7 (that of neutral water), so the ocean could also be described as becoming less basic.

Although the largest changes are expected in the future,[11] a report from NOAA scientists found large quantities of water undersaturated in aragonite are already upwelling close to the Pacific continental shelf area of North America.[17] Continental shelves play an important role in marine ecosystems since most marine organisms live or are spawned there, and though the study only dealt with the area from Vancouver to northern California, the authors suggest that other shelf areas may be experiencing similar effects.[17]

### Rate of Acidification

Similarly, one of the first detailed datasets examining temporal variations in pH at a temperate coastal location found that acidification was occurring at a rate much higher than that previously predicted, with consequences for near-shore benthic ecosystems.[18][19] Thomas Lovejoy, former chief biodiversity advisor to the World Bank, has suggested that "the acidity of the oceans will more than double in the next 40 years. This rate is 100 times faster than any changes in ocean acidity in the last 20 million years, making it unlikely that marine life can somehow adapt to the changes."[20]

Current rates of ocean acidification have been compared with the greenhouse event at the Paleocene-Eocene boundary (about 55 million years ago) when surface ocean temperatures rose by 5-6 degrees Celsius. No catastrophe was seen in surface ecosystems, yet bottom-dwelling organisms in the deep ocean experienced a major extinction. The current acidification is on a path to reach levels higher than any seen in the last 65 million years,[21] and the rate of increase is about ten times the rate that preceded Paleocene-Eocene mass extinction. The current and projected acidification has been described as an almost unprecedented geological event.[22] A National Research Council study released in April 2010 likewise concluded that "the level of acid in the oceans is increasing at an unprecedented rate."[23][24]

A review by climate scientists at the RealClimate blog, of a 2005 report by the Royal Society of the UK similarly highlighted the centrality of the rates of change in the present anthropogenic acidification process, writing:[25]

"The natural pH of the ocean is determined by a need to balance the deposition and burial of CaCO3 on the sea floor against the influx of Ca2+ and CO2−
3
into the ocean from dissolving rocks on land, called weathering. These processes stabilize the pH of the ocean, by a mechanism called CaCO3 compensation...The point of bringing it up again is to note that if the CO2 concentration of the atmosphere changes more slowly than this, as it always has throughout the Vostok record, the pH of the ocean will be relatively unaffected because CaCO3 compensation can keep up. The [present] fossil fuel acidification is much faster than natural changes, and so the acid spike will be more intense than the earth has seen in at least 800,000 years."

A July 2010 article in Scientific American quoted marine geologist William Howard of the Antarctic Climate and Ecosystems Cooperative Research Center in Hobart, Tasmania stating that "the current rate of ocean acidification is about a hundred times faster than the most rapid events" in the geologic past.[26] Research at the University of South Florida has shown that 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.[27]

## Calcification

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 and plates out of calcium carbonate (CaCO3).[15] 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 CaCO3 structures, such as coccoliths. After they are formed, such structures are vulnerable to dissolution unless the surrounding seawater contains saturating concentrations of carbonate ions. The saturation state of seawater for a mineral (known as Ω) is a measure of the thermodynamic potential for the mineral to form or to dissolve, and is described by the following equation${\Omega} = \frac{\left[Ca^{2+}\right] \left[CO_{3}^{2-}\right]}{K_{sp}}$

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 product of the concentrations of those ions when the mineral is at equilibrium (Ksp), that is, when the mineral is neither forming nor dissolving.[28] In seawater, a natural horizontal boundary is formed as a result of temperature, pressure, and depth, and is known as the saturation horizon, or lysocline.[15] Above this saturation horizon, Ω has a value greater than 1, and CaCO3 does not readily dissolve. Most calcifying organisms live in such waters.[15] Below this depth, Ω has a value less than 1, and CaCO3 will dissolve. However, if its production rate is high enough to offset dissolution, CaCO3 can still occur where Ω is less than 1. The carbonate compensation depth occurs at the depth in the ocean where production is exceeded by dissolution.[29]

Calcium carbonate occurs in 2 common polymorphs: aragonite and calcite. Aragonite is much more soluble than calcite, with the result that the aragonite saturation horizon is always nearer to the surface than the calcite saturation horizon.[15] This also means that those organisms that produce aragonite may possibly be more vulnerable to changes in ocean acidity than those that produce calcite.[11] Increasing CO2 levels and the resulting lower pH of seawater decreases the saturation state of CaCO3 and raises the saturation horizons of both forms closer to the surface.[30] This decrease in saturation state is believed to be one of the main factors leading to decreased calcification in marine organisms, as it has been found that the inorganic precipitation of CaCO3 is directly proportional to its saturation state.[31]

## Possible impacts

Although the natural absorption of CO2 by the world's oceans helps mitigate the climatic effects of anthropogenic emissions of CO2, it is believed that the resulting decrease in pH will have negative consequences, primarily for oceanic calcifying organisms. These span the food chain from autotrophs to heterotrophs and include organisms such as coccolithophores, corals, foraminifera, echinoderms, crustaceans and molluscs. As described above, under normal conditions, calcite and aragonite are stable in surface waters since the carbonate ion is at supersaturating concentrations. However, as ocean pH falls, so does the concentration of this ion, and when carbonate becomes undersaturated, structures made of calcium carbonate are vulnerable to dissolution. Even if there is no change in the rate of calcification, therefore, the rate of dissolution of calcareous material increases.[32]

Research has already found that corals,[33][34][35] coccolithophore algae,[36][37][38][39] coralline algae,[40] foraminifera,[41] shellfish[42] and pteropods[11][43] experience reduced calcification or enhanced dissolution when exposed to elevated CO2. The Royal Society of London published a comprehensive overview of ocean acidification, and its potential consequences, in June 2005.[15] However, some studies have found different response to ocean acidification, with coccolithophore calcification and photosynthesis both increasing under elevated atmospheric pCO2,[44][45][46] an equal decline in primary production and calcification in response to elevated CO2[47] or the direction of the response varying between species.[48] Recent work examining a sediment core from the North Atlantic found that while the species composition of coccolithophorids has remained unchanged for the industrial period 1780 to 2004, the calcification of coccoliths has increased by up to 40% during the same time.[46] While the full ecological consequences of these changes in calcification are still uncertain, it appears likely that many calcifying species will be adversely affected. When exposed in experiments to pH reduced by 0.2 to 0.4, larvae of a temperate brittlestar, a relative of the common sea star, fewer than 0.1 percent survived more than eight days.[27] There is also a suggestion that a decline in the coccolithophores may have secondary effects on climate, contributing to global warming by decreasing the Earth's albedo via their effects on oceanic cloud cover.[49]

Aside from calcification, organisms may suffer other adverse effects, either directly as reproductive or physiological effects (e.g. CO2-induced acidification of body fluids, known as hypercapnia), or indirectly through negative impacts on food resources.[15] Ocean acidification may also force some organisms to reallocate resources away from productive endpoints such as growth in order to maintain calcification.[50] It has even been suggested that ocean acidification will alter the acoustic properties of seawater, allowing sound to propagate further, increasing ocean noise and impacting animals that use sound for echolocation or communication.[51] However, as with calcification, as yet there is not a full understanding of these processes in marine organisms or ecosystems.[52]

Leaving aside direct biological effects, 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.[53] This will cause an elevation of ocean alkalinity, leading to the enhancement of the ocean as a reservoir for CO2 with moderate (and potentially beneficial) implications for climate change as more CO2 leaves the atmosphere for the ocean.[54]

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## References

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5. "Ocean acidification and the Southern Ocean" by the Australian Antarctic Division of the Australian Government
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13. EPA weighs action on ocean acidification post at official blog of EPOCA, the European Project on Ocean Acidification
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15. Raven, J. A. et al. (2005). Ocean acidification due to increasing atmospheric carbon dioxide. Royal Society, London, UK.
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19. "Ocean Growing More Acidic Faster Than Once Thought; Increasing Acidity Threatens Sea Life". Science Daily. 2008-11-26. Retrieved 26 November 2008.
20. UN: Oceans are 30 percent more acidic than before fossil fuels
21. Rate of ocean acidification the fastest in 65 million years
22. An Ominous Warning on the Effects of Ocean Acidification
23. Report: Ocean acidification rising at unprecedented rate
24. The Acid Ocean – the Other Problem with CO2 Emission
25. Ancient Ocean Acidification Intimates Long Recovery from Climate Change
26. How Acidification Threatens Oceans from the Inside Out
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29. The Royal Society. Ocean Acidification Due To Increasing Atmospheric Carbon Dioxide, The Clyvedon Press Ltd. (2005): 11.
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40. Phillips, Graham; Chris Branagan (2007-09-13). "Ocean Acidification – The BIG global warming story". ABC TV Science: Catalyst (Australian Broadcasting Corporation). Retrieved 2007-09-18.
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50. Acid In The Oceans: A Growing Threat To Sea Life by Richard Harris. All Things Considered, 12 August 2009.
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