Ocean Acidification: The Other CO2 Problem

Increased carbon dioxide is changing the chemistry of the earths oceans, threatening marine life Earths atmosphere isnt the only victim of burning fossil fuels. About a quarter of all carbon dioxide emissions are absorbed by the earths oceans, where theyre having an impact thats just starting to be understood.
Over the last decade, scientists have discovered that this excess CO2 is actually changing the chemistry of the sea and proving harmful for many forms of marine life. This process is known as ocean acidification. A more acidic ocean could wipe out species, disrupt the food web and impact fishing, tourism and any other human endeavor that relies on the sea. The change is happening fast -- and it will take fast action to slow or stop it. Over the last 250 years, oceans have absorbed 530 billion tons of CO2, triggering a 30 percent increase in ocean acidity. Before people started burning coal and oil, ocean pH had been relatively stable for the previous 20 million years. But researchers predict that if carbon emissions continue at their current rate, ocean acidity will more than double by 2100. The polar regions will be the first to experience changes. Projections show that the Southern Ocean around Antarctica will actually become corrosive by 2050.

Click the photo above to view a slideshow of corals and learn more about the impact of ocean acidification.

Corrosive Impacts on Sealife

The new chemical composition of our oceans is expected to harm a wide range of ocean life -particularly creatures with shells. The resulting disruption to the ocean ecosystem could have a widespread ripple effect and further deplete already struggling fisheries worldwide.

Increased acidity reduces carbonate -- the mineral used to form the shells and skeletons of many shellfish and corals. The effect is similar to osteoporosis, slowing growth and making shells weaker. If pH levels drop enough, the shells will literally dissolve. This process will not only harm some of our favorite seafood, such as lobster and mussels, but will also injure some species of smaller marine organisms -- things such as pteropods and coccolithophores. Youve probably never heard of them, but they form a vital part of the food web. If those smaller organisms are wiped out, the larger animals that feed on them could suffer, as well.

Disappearing Coral Reefs

Delicate corals may face an even greater risk than shellfish because they require very high levels of carbonate to build their skeletons. Acidity slows reef-building, which could lower the resiliency of corals and lead to their erosion and eventual extinction. The tipping point for coral reefs could happen as soon as 2050. Coral reefs serve as the home for many other forms of ocean life. Their disappearance would be akin to rainforests being wiped out worldwide. Such losses would reverberate throughout the marine environment and have profound social impacts, as well -- especially on the fishing and tourism industries. The loss of coral reefs would also reduce the protection that they offer coastal communities against storms surges and hurricanes -- which might become more severe with warmer air and sea surface temperatures due to global warming.

What Can We Do About It?

Combating acidification requires reducing CO2 emissions and improving the health of the oceans. Creating marine protected areas (essentially national parks for the sea) and stopping destructive fishing practices would increase the resiliency of marine ecosystems and help them withstand acidification. Evidence suggests that coral reefs in protected ocean reserves are less affected by global threats such as global warming and ocean acidification, demonstrating the power of ecosystem protection. Ultimately, though, reducing the amount of carbon dioxide absorbed into the oceans may be the only way to halt acidification. The same strategies needed to fight global warming on land can also help in the seas.

The acidification of our oceans is the hidden side of the worlds carbon crisis, says Lisa Suatoni, an NRDC ocean scientist, and only reinforces that we need to make changes in how we fuel our world -- and we need to do it quickly. 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] About a quarter of the carbon dioxide in the atmosphere goes into the oceans, where it forms carbonic acid. As the amount of carbon has risen in the atmosphere there has been a corresponding rise of carbon going into the ocean. Between 1751 and 1994 surface ocean pH is estimated to have decreased from approximately 8.25 to 8.14,[2] representing an increase of almost 30% in "acidity" (H+ ion concentration) in the world's oceans.[3][4][5] This ongoing acidification of the oceans poses a threat to the food chains connected with the oceans.[6] 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).

[edit] 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 preindustrial

Pre-industrial (18th century)

8.179 0.000

analysed field[12][not in citation

given]

0%

Recent past (1990s)

8.104 0.075

field[12]

+ 18.9%

Present levels

~8.069 0.11

field[3][4][5][13]

+ 28.8%

2050 (2CO2 = 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[16] society takes.[17] 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.[18] 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.[18]
[edit] Rate

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 previously predicted, with consequences for near-shore benthic ecosystems.[19][20] 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."[21] 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 56 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,[22] and the rate of increase is about ten times the rate that preceded the Paleocene-Eocene mass extinction. The current and projected acidification has been described as an almost unprecedented geological event.[23] 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."[24][25] A 2012 paper in the journal Science examined the geological record in an attempt to find a historical analog for current global conditions as well as those of the future. The researchers determined that the current rate of ocean acidification is faster than at any time in the past 300 million years.[26][27] 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:[28] "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." In the 15-year period 19952010 alone, acidity has increased 6 percent in the upper 100 meters of the Pacific Ocean from Hawaii to Alaska.[29]

[edit] 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 ) is a measure of the thermodynamic potential for the mineral to form or to dissolve, and is described by the following equation:

Here 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.[30] 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, has a value greater than 1, and CaCO3 does not readily dissolve. Most calcifying organisms live in such waters.[15] Below this depth, 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 is less than 1. The carbonate compensation depth occurs at the depth in the ocean where production is exceeded by dissolution.[31] Calcium carbonate occurs in two 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.[32] 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.[33]

[edit] 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.[34] Research has already found that corals,[35][36][37] coccolithophore algae,[38][39][40][41] coralline algae,[42] foraminifera,[43] shellfish[44] and pteropods[11][45] experience reduced calcification or enhanced dissolution when exposed to elevated CO2. The Royal Society 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,[46][47][48] an equal decline in primary production and calcification in response to elevated CO2[49] or the direction of the response varying between species.[50] 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.[48] 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.[29] 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.[51] 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.[52] 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.[53] However, as with calcification, as yet there is not a full understanding of these processes in marine organisms or ecosystems.[54] 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.[55] 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.[56] When we spew carbon dioxide into our air, it eventually ends up in our oceans, too absorbed to the tune of about 22 million tons per day. This results in global warmings evil twin: ocean acidification. As oceans absorb carbon dioxide, or CO2, seawater chemistry changes and the water becomes

more acidic. According to scientists, the oceans have become about 30 percent more acidic due to human CO2 emissions and this spells trouble for ocean life. First of all, ocean acidification depletes seawater of the compounds that organisms need to build shells and skeletons, impairing the ability of corals, crabs, seastars, sea urchins, plankton and other marine creatures to build the protective armor they need to survive. To make matters worse, fish and other ocean organisms may be adversely affected from the rise in acidity in their ocean habitat. Fish are common ocean prey, and plankton are at the base of the ocean food chain, so when these animals suffer, so do the countless animals that eat them. Ocean acidification could disrupt the entire marine ecosystem. Since ocean acidification is one of the gravest threats to marine biodiversity, the Center is tackling it head on, and has launched an initiative to protect our oceans from CO2 pollution. The Clean Water Act is the nations strongest law protecting water quality, and were using the tools provided by this law to stop pollution causing ocean acidification as well as to improve waterquality standards and monitoring for pH. In 2007, we petitioned eight coastal states to declare ocean waters impaired under the Clean Water Act due to ocean acidification, which would require those states to limit CO2 pollution entering waters under their jurisdiction, helping to reduce the devastating effects of ocean acidification. The same year, we also petitioned the U.S. Environmental Protection Agency to impose stricter pH standards for ocean water quality and publish guidance to help states protect U.S. waters from acidification. Finally, in spring 2009, the agency for the first time invoked the Clean Water Act to address the acidification crisis, calling for data to use for evaluating water-quality criteria under the Act. But when it failed to take action against ocean acidification in Washington state waters which are in violation of the states already lax water-quality standard for pH we were forced to sue the agency in spring 2009. Thanks to our landmark lawsuit, the next year the EPA recommended that coastal states begin addressing ocean acidification under the Clean Water Act. We also advocate for the protection of species affected by ocean acidification, most notably elkhorn coral and staghorn coral, which make up much of the rapidly declining coral reefs of Florida and the Caribbean. These corals were listed as endangered under the Endangered Species Act in 2006 as a result of a Center petition, and in September 2007, we sued the National Marine Fisheries Service to speed designation of critical habitat. While elkhorn and staghorn corals are the first species to be listed because of vulnerability to global warming, they unfortunately wont be the last. The Center will contBy burning fossil fuels and clearing forests for agriculture, industry and cities in ever greater extent, humans are releasing vast amounts of CO into the atmosphere. In the last century, atmospheric CO has risen about 30 percent, to 393 parts per million. Approximately one quarter of the excess CO is absorbed by land plants and another quarter by the oceans, which cover some 70 percent of Earth's surface. Once dissolved in the ocean, a carbon atom will stay there on average more than 500 years. The excess CO from the atmosphere reacts with seawater to form carbonic acid. Over time, this mild acid is neutralized by fossilized carbonate shells on the sea floor. But if CO goes into the oceans too quickly, as it is now, it can deplete the carbonate ions that corals, mollusks and some plankton in the seafood chain need for reef and shell-building.

In the early 1990s, scientists used a deep-drilling ship to extract sediment cores from deep in the seabed off Antarctica. They found a layer of mud from the PETM period wedged between thick deposits of white plankton fossils. Because seawater chemistry is partly controlled by temperature, sediments and fossil shells retain a signature of the ambient temperatures under which they formed.
inue to defend our oceans life and fight to curb the pollution that threatens it.