• what is the carbon situation? Where is all carbon stored and how much of it is circulating?
• reservoir or pipe? do we need to treat the CO2 in air as a reservoir or as a pipe connecting all living things?
• is the level of carbon dioxide rising? What evidence exists that CO2 in air is rising?
• where is the CO2 in the oceans? the oceans and the sea soil form a massive store of CO2.
• is carbondioxide absorbed by the sea? CO2 takes part in the normal exchange but is it being sequestered?
• how acidic are the oceans? what is the normal acidity of the oceans and by how much does it vary?
• are oceans becoming more acidic? what evidence exists that the oceans are becoming more acidic?
• the Bjerrum plot of the carbonate system: much value is attached to classical carbonate theory but does it stick?
• so why is acidification a problem? the main fear is that increased acidity would erode shells and coral reefs.
• is CO2 a potent fertiliser? Land plants are seriously limited by a dearth of CO2, but what is the situation in the sea?
• are coral reefs threatened? All alarmist publications agree that corals will soon be extinct due to coral bleaching and dissolution of coral skeletons, but what does factual science say?
• natural CO2 vents  A recent study found that biodiversity decreased near natural CO2 vents. What does it mean?
• phytoplankton calcification  A recent study finds that CO2 improves calcification in coccolithophores, as we predicted.
• crustose coralline agae affected by raised levels of CO2? A much-hailed study with severe deficiencies.
• declining coral calcification: Porites corals show a sudden and unknown reduction in calcification towards their skins, but the study is a fraud.
• Guinotte & Fabry: an overview article about ocean acidification, frequently cited by others, almost entirely fictional.
• further studies: a mix of further studies debunking the fear of ocean acidification. Summaries only.

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What is the carbon situation? Over the past two decades scientists gained a fair understanding of where all carbon is found and how much of it circulates between atmosphere, land and sea, although significant differences can be found among authors. As one can see, the human contribution is about 8Pg carbon per year (8Gt, billions of tons) against a global respiration rate of about 100-250Pg/y (fossil fuel alone: 2%, some say 3%). It is thought that this contribution is the cause of the observed increase in the concentration of CO2 in the atmosphere from a supposed 180ppm pre-industrial to a present-day 400ppm. So there is good certainty that the amount of CO2 in the air is rising. The critical question remains why? Many scientists believe it is caused by the burning of fossil fuels and other human activities, but considering the presence of a huge reservoir of carbondioxide in the ocean, one should ask whether the tail is wagging the dog (see box below). [for more about where the carbon is locked up on land, look at soil54.gif ]

This diagram shows the latest figures (after Holmen, 2000) with residence times and today's atmospheric carbon at 700Gt.  The land has been split in two compartments and the oceans in three. Apparently plants assimilate 122Gt/y in photosynthesis, with leaves dying after 5 years, and their stems and decaying wood estimated at 1100Gt, decaying in 20 years while returning 60Gt back to the air. Of the total, only 2Gt is sequestered. From this less than 0.1Gt is sequestered for 1000y in fossil fuels and shales. The oceans have been split into three compartments, with mainly the surface ocean interacting with the atmosphere, photosynthesising and respiring/decaying 100GtC/y while sequestering 2 GtC/y. Only 0.3 GtC/y rains down in the form of carbonate oozes of marine sediments of which a massive 30 million GtC exists, to be circulated to the surface through ocean floor spreading, subduction and volcanic activity, which takes 100 million years.

I have some reservations about this diagram:

• of the plants, their soils have been neglected, including the fast turnover of CO2 between them. Batjes (1996) estimates soil carbon at 2200GtC ("the soil is the largest terrestrial pool of organic carbon"), a substantial addition to above diagram.
• a cycle of 122 Gt on a living biomass of 70Gt living plant matter cannot result in residency time of 5y
• fossil oil and shales come from the sea, not the land but peat and coal do.
• the figures differ too much from previously published ones.
• values for sequestration are guessed at, being the small difference between two large figures.
• residence time of CO2 in atmosphere is highly contentious, estimated between 2 and 20 years
• residence times for deep ocean water have been measured to be less than thousand years, not 100,000.
• carbon exchange with sea soil is not shown.
• river deposits into the sea are not shown
• forest burning and habitat change are not shown.
• deep carbon clathrate deposits are not taken account of.

Compare this diagram of global carbon dioxide fluxes and reservoirs with the previous one and notice the large differences.

What all this means is that we know very little for sure about the most important process on Earth.
 

Compare the poor world during last ice age with today's rich world

The relationship between ocean temperature and CO2 in the atmosphere is shown here, as graphed by Prof Lance Endersbee (www.atse.org.au), showing a near-linear relationship with little deviation from it (R2=0.996, a measure of match). As temperature rises, so does the concentration of CO2 in the atmosphere. Note that this graph does not prove who drives whom, but as atmospheric temperature stabilised and even declined in the years 1998-2008, while oceans continued to warm, it becomes defensible that rising ocean temperature is the driving force behind rising concentrations of CO2, as explained above. However, critics argue that the 21-year averaging of temperature will always give a straight line of sorts, but to simulate deep warming from surface variations, by long-term averaging is entirely proper. Note that a rise of 0.1 ºC corresponds to an increase of about 15ppmv in the atmosphere (150ppmv per ºC ~ 300Gt/ ºC carbon. [compare with our estimate above] ). Cumulative anthropogenic emission over the industrial age is estimated at about 140ppmv over two centuries, which is about the same as an ocean warming of 1 ºC.Note that Endersbee's figure is a blessing in disguise, because it is impossible to calculate or estimate CO2 outgassing from the solubility in water. For instance: the effect of salt and other minerals on solubility is not known the effective depth of the warming sea contributing to outgassing is not known the effect needs to be integrated over the entire globe, taking account of local sea temperatures the effect of the carbon pump through the deep sea is unknown as cold seas absorb CO2 while warm seas expel it. For instance, assuming a rate of 3%/ºC degassing at global average temperature (see part1), and an amount of 38,000Gt (C) dissolved CO2, the amount outgassed for the whole ocean would be 1,140Gt/ºC (Carbon) or 635ppmv/ºC for the whole ocean. The surface 100m with 600Gt C is perturbed a few times per year, contributing almost instantly to warming, or 18 Gt/ºC (carbon), or 10ppmv/ºC. Remember 10ppm/ºC for each 100m of ocean depth. Endersbee's figure of ~300 lies comfortably between 18 and 1140. Reader, as you may notice, there is a lot of uncertainty here. The 'Keeling curve' from Mauna Loa may eventually dip again. One thing is certain: as long as the oceans warm up, it outgasses CO2. Thus the oceans, while warming, do not absorb the extra CO2 from fossil fuel, but they do recycle it. One cannot have it both ways. See also Fred Goldberg www.heartland.org/custom/semod_policybot/pdf/25543.pdf  who comes to the same conclusion, following a different logic. Update Aug 2011: Endersbee's curve is heavily contested mainly because he took a period in which both temperature and CO2 were rising. However when earlier data is included to 1960, the linearity distorts. More important, the new measurements of missing oxygen climate4#missing_oxygen lead to the conclusion that seas have been absorbing CO2 for several decades, rather than exhaling it.

"Eighty percent of inputs from land to sea are deposited here [in coastal margins], and 85% of organic carbon and 45% of inorganic carbon are buried in the ocean margin sediments (Gattuso et al., 1998a; Wollast, 1998; Chen et al., 2003)". This suggests that carbon from the terrestrial biosphere finds its way to the sea, carried by rain water and rivers,  not shown in the diagram.

"Carbonate accumulation in coral reef environments alone accounts for an estimated 20–30% of the global ocean accumulation (Milliman and Droxler, 1996)".

"Ocean margins are also heavily impacted by human activities, as nearly 40% of the global population lives within 100 km of the coastline (Cohen et al., 1997). Since the onset of the Industrial Revolution, burning of fossil fuels and land-use changes have caused substantial increases in both atmospheric CO2 concentration and in the delivery of organic matter and nutrients to ocean margins (Mackenzie, 2003). Such changes could alter the role of this system and considerably affect important processes such as air-sea CO2 exchange".
 

As the sea warms, the warmer water remains on top because it is lighter, which results in a layer of warm water above a thermocline, below which the colder water is found. Thus the water above the thermocline, also called the mixed layer, is more in contact with the atmosphere than the water below it, which cannot reach the surface. This map shows the depth of the mixed layer, with the warm tropics being very shallow and the cold subantarctic very deep. Notice the rather strange false colour scale below it. It so happens that warm water breathes CO2 out whereas cold water breathes it in. Notice also that the mixed layer depth changes with the seasons. The next question is: how does temperature affect the in- and ex-haling of CO2?

Much effort has been spent travelling the world's ocean to measure the net flux (flow) of CO2 in and out of the ocean, and the map here shows its result. Where the water warms and wells up from the deep, the release of CO2 is dominant. Conversely where the water cools and sinks, CO2 dissolves into the water. The figures are in trillions of grams or billions of kg or millions of tons carbon (MtC) per 4x5 degree area. Note that these 'squares' become significantly smaller towards the poles, and also that the pattern changes with the seasons. Most importantly, from the complex dataset it cannot be determined whether the oceans are over-all breathing in or breathing out, let alone by how much. A quick impression is that there is more blue and purple (CO2 in) than yellow and red (CO2 out).

Note that scientists cannot actually measure the flow of CO2. They measure the partial pressure of CO2 (pCO2aq) in the water and above it where pCO2 is equal to ppmv CO2, and then computers do the rest. Whether this is true to nature, is not known, also because wind plays a role.

Reader did you notice the high level of uncertainty here?

The graph shows how ecologists see the growth of populations. The green curve shows growth in biomass over time, from a near-zero beginning in a world without limitations. The rate of growth here depends only on how much offspring survives, and follows an exponential (explosive) curve. However, gradually some important resource becomes inadequate to sustain this growth, and the population grows ever more slowly until it reaches a maximum for which the resource (right hand scale) is zero. Of course this cannot happen in real life because populations regulate their sizes by their longevity, fecundity, disease and predation. Besides it costs more and more energy to find the last left-overs of the resource, scattered here and there (this is NOT the case for CO2). The right-hand side plots (red) growth rate against resource use, showing high growth rate at 100% and rapid decrease towards 0% (top). Note, however, that each population and each species and each individual within a species has its own growth curve. Note also that this graph has more value as a thought experiment than reflecting the real-world situation.

For populations of warm-blooded animals it is impossible to live near exhaustion of their resources because they need so much energy even while sleeping. But cold-blooded animals (insects, worms) do much better. Best of all do the plants because they don't even move, building their biomass up gradually while living long lives. They live from a different source of food, from the energy of the sun which comes to them only at the cost of dehydration. So they are able to live even in low levels of their most important resource, CO2. Note that CO2 in air is rare. Whereas one in five molecules is oxygen, only one in 3000 is CO2. It is a miracle that plants do so well in such a depleted resource. But CO2 was once six times richer in the age of the dinosaurs (2000ppmv), while the climate was also warmer. Now that the concentration of CO2 is increasing again, we see plants doing well, expected to grow exponentially (ever faster) in reaction to CO2 (see diagram).

• The amount of CO2 in air is very small (0.03%), much like that of a pipe compared to a reservoir (100%).
• An increase in (partial) pressure results in an increase of plant growth which results in an increase in gas exchange (flow).
• In a dead world, CO2 concentrations would be in perfect equilibrium betwen air, sea and land. However, a living world pumps it around, absorbing it into plant life and exhaling it again from animal life and decomposition while also reacting to global temperature, sunshine and CO2 concentration changes.
• Depending on changes in temperature, sea and land act as reservoirs (1800Gt and 38,000Gt) connected by a narrow pipe (700Gt) with a high throughput (200Gt/y). When the earth and the sea warm up, CO2 is released and absorbed by land life. When the earth cools, the reverse takes place.
• High volume pipes exist but are ignored by atmospheric scientists because they do not connect through air, even though they store much carbon (see diagram below).

• some measurements rely on radioactive carbon (made from nitrogen by high energy radiation). However, the air is polluted by man-made CO2 which has no radioactive carbon (because it sat underground and lost it over time), and by nuclear tests which cause high concentrations of it. To make matters worse, the production of radioactive carbon is not constant. Nuclear 14-C indeed had a residence time of about 5 years.
• one method relies on the dilution of radioactive carbon by man-made carbon, assuming that we know the precise origin, quantity and decay of each and the role the oceans play in this.
• all methods assume that CO2 is evenly spread through the atmosphere and that it cycles equally fast in all atmospheric layers, which is unlikely.
• alll methods assume a single 'average' cycle, however nature is bound to have both very fast and very slow cycles (see diagram below).
• all methods assume a dead planet where life does not react to concentrations in CO2 or temperature, and does not influence the flow rate.
• the methods used cannot detect fast cycles, as these return the same carbon that was absorbed a short time before.
• some CO2 dissolves rapidly in rain and is washed out of the air in a matter of days.

Main carbon pathways on land and in the sea The diagram shows how an imaginary carbon pipe connects all living creatures and also to some extent with the inanimate sea water into which CO2 dissolves so easily. As can be seen, the highest flow is found outside the atmosphere, inside the soil on land and the photic (sun-lit) zone in the sea. CO2 escaping direct from the soil is also likely to be trapped first by the overlying canopy, resulting in a residence time of hours rather than years. Although leaf litter and animal wastes take months to recycle, the residence time here is still a fraction of a year.  The sea circulates faster still: because plankton cells are so small, growth rates in the sea are extraordinarily high. For instance, the rise and fall of a plankton bloom can happen within a week, and dead plankton fully recycled within a month (most of which is returned within a week), resulting in a residence time of less than one month rather than 5 years. But recycling with the deep sea bottom takes hundreds of years. Likewise, the CO2 found in the upper atmosphere is not likely to play a role, resulting in long residence times. It is therefore wrong to think of an 'average' residence time in air.

When oceans expel CO2 as they warm up, the new CO2 charges the carbon pipe, resulting in faster turnover in coastal seas and on land where vegetation is not severely limited by other factors. The human CO2 also charges the carbon pipe.
 
 

Reader please note that some of this we discovered here at Seafriends in 2005, as explained in the DDA chapter. The planktonic decomposers and the way symbiotic decomposition transfers CO2 direct to the plant as a significant source of carbon dioxide, is a discovery that has not (yet) been confirmed by mainstream science.

Is the level of carbon dioxide in air rising? The diagram shows the growth in population and our use of resources. The vertical scale is logarithmic, which shows exponential growth best. In the top left one sees three lines for a 5,10 and 100 times growth rate per century. It brings the shocking reality that population (p) still grows at the rate of 10x per century, all energy use (e) at close to 100x per century. Ironically, the top brown curve for CO2 (h) does not keep up with these trends, and by comparison, appears to be levelling off. In other words, the relationship between increased CO2 levels in air, and the growing use of energy, is rather weak. Then again, a doubling in 30 years would imply an underlying growth rate of close to ten times per century, still far removed from the actual rate of increase in fossil fuel burning. Reader, note that in climate chapter 4, a strong relation between CO2 in air and human emisions is defended. Note also that the world is still doing relatively well, as measured by GDP per person (gp), and even the use of water per person is still climbing, but not for long (wp). An interesting fact is that the total energy (e) until 1800 consisted of burning biomass (sustainable). In 1800 the use of coal took off, later flattening off (b) because by 1870 oil replaced it and later still, gas.

A high CO2 world There is a lot of panic about CO2 levels rising to 400ppm and above, but in the history of the planet, CO2 has often been much higher, and the present low levels of CO2 could be considered an anomaly. At the time of the great dinosaurs, carbon dioxide levels were five times higher still (2000ppm) and life as we know, was prolific back then. Evolution towards diversity also thrived. The work of Budyko has been replicated and refined, and essentially been confirmed, see diagram and further below. To understand ancient epochs, read our Geologic Timetable.

The general consensus is that the concentration of CO2 in the atmosphere is increasing. Very accurate measurements at mount Mauna Loa in Hawaii and independently at Baring Head in New Zealand, show a steadily growing CO2 concentration [see note2 below]. But the data before 1960 remains sketchy. The IPCC attaches high value to CO2 measurements from air bubbles trapped in ice which indicated that the pre-industrial concentration was about 270ppm. Knowing the age of each point by the year rings in the ice, the brown curve resulted from the Siple Dome in West Antarctica (drilling 1996-2005, 990m deep). However, this curve did not join up with that of Mauna Loa, so it was arbitrarily shifted right by 83 years, and also down a little. The reason for doing so is that the first part of the core, containing compressed snow or firn, is still 'open' to atmospheric influences, see dotted brown curve with question marks, and the box below.

Some scientists [Jaworowsky, Segalstad] mention that the method is flawed, since CO2 does dissolve into ice and it even escapes. For instance, the starting pressure at the top of the curve is already 5 bar and increases to 15 bar at the bottom.
Already since about 1750, chemistry scientists have done CO2 measurements in a more classical way, and the tens of thousands of data points join up quite well (green curve), even though many measurements were taken in industrial cities. The green curve shows that perhaps the CO2 concentration was not all that ideal both inside the industrial age and before. Note how it eventually joined up with Mauna Loa.
 

CO2 glaciology depends on the following unproved assumptions, which in fact, have been proved wrong [Prof. Zbigniew Jaworowski 1992; see also reference [1] below]:

• No liquid phase occurs in the ice at mean annual temperatures below -24ºC
• The way air is entrapped in ice is a mechanical process and does not differentiate between gas components (fractionation)
• The air inclusions represent the original atmospheric air composition
• High pressure of the ice does not influence the makeup of entrapped gases and does not dissolve CO2 into ice in the form of clathrates.
• The age of gases in the air bubbles is much younger than the age of the ice in which they are entrapped, ranging from decades to millennia.
• Drilling the ice core does not pollute it
• Relaxation of the ice core after its pressure drops from hundreds of bar to one, does not influence its content by forming cracks. (one bar per 12 metre)

Measurements of gases, temperature and volcanic activity are done by measuring proxies, such as the amount of dust in a core for volcanic activity, and the ratios of radioactive elements for temperature and carbon dioxide. In all cases, a consistent record is obtained for the distant past, but this never seems to join up with the situation of today and the past two centuries. An inconvenient discontinuity remains. So we can't be sure whether the proxies are right. The fact that the past does not join up with the present, is in fact proof that there is something wrong. If only the top of the ice core or sediment core would agree with today, the methods would gain more credibility. So far, they don't. The graph shown here illustrates the point: scientists (of the IPCC) have abutted three different proxies to the reliable measurements of Mauna Loa, without expressing doubt about the scientific validity of it. For instance, has anyone tried to grow plants and seedlings at 180ppm? It suggests that life on Earth during the ice ages was much less than half of what we have today and very much less productive too.

Mauna Loa measurements representative? The CO2 measurements at Mauna Loa (Hawaii) and Baring Head (New Zealand) both measure CO2 concentrations over the Pacific Ocean, the world's largest ocean. As such they are representative only of CO2 above the ocean at their respective latitudes, and will almost certainly not represent CO2 concentrations found above land. This graph, plotting CO2 levels against wind speed is not from Mauna Loa but from Diekirch, Luxemburg. Notice the wide spread (320-560ppm) in CO2 levels. The red baseline is arbitrarily chosen to represent 'maximal atmospheric mixing'. We would have liked to see such a graph from Mauna Loa [3] and also the original raw (unfiltered and uncorrected) data. See notes [2] and [3] below. Apparently there are now some 100 CO2 monitoring stations world-wide. Note the large amount of uncertainty and thus scope for arbitrary 'adjustments' and fraud, because it is unthinkable that the Keeling Curve one day may dip downward steeply. Since 2008 the Keeling curve has been flattening and may begin to dip soon as a result of cooling oceans. Who knows. See also climate chapter4.

[1] Prof. Zbigniew Jaworowski: Climate Change: Incorrect information on pre-industrial CO2. March 19, 2004. Statement of Prof. Zbigniew Jaworowski, Chairman, Scientific Council of Central Laboratory for Radiological Protection Warsaw, Poland. http://www.middlebury.net/op-ed/Jawoworski%20CO2%202004.doc
[2] Note re Mauna Loa and Baring Point: these two places also 'cherry-pick' their results from natural variations in their measurements. At Mauna Loa the low points are selected in order to avoid measuring CO2 from nearby volcanoes. Thus the wind direction is important in their measurements, as it is also at Baring Point. Both sites measure the CO2 concentration above the ocean, thus are not representative of CO2 over land, or 'world average' CO2.
[3] Ferdinand Engelbeen (Belgium) has a very good page with data and graphs, studying whether the increase of CO2 is from human sources and also the raw data of Mauna Loa, and much more: http://www.ferdinand-engelbeen.be/klimaat/co2_measurements.html We agree, the human signature is found wherever CO2 is found or used, but there is no hard proof that the rising level of CO2 in air is caused by humans and that this causes a rise in temperature. The noise on the Mauna Loa signal is about 4 ppm CO2. The noise in the picture above is over 200ppm, so we are skeptical about the ML noise of only 4ppm.
[4] Fred Goldberg (2010?): Rate of increasing concentrations of atmospheric carbon dioxide controlled by natural temperature variations , looks at the only reliable data, yearly human emissions and yearly CO2 increases as per Mauna Loa, and concludes that temperature variations come from elsewhere (ENSO, volcanoes) and this drives the level of CO2 emitted or absorbed by the oceans. There is no human signature. www.heartland.org/custom/semod_policybot/pdf/25543.pdf
[5] www.ferdinand-engelbeen.be/klimaat/jaworowski.html  Ferdinand Engelbeen rebuts Jaworoski's criticism. The science is not settled.
[6] www.21stcenturysciencetech.com/2006_articles/IceCoreSprg97.pdf  Zbigniew Jaworowski (1997): Ice Core Data Show No Carbon Dioxide Increase. Jaworowski explains in detail what is going on in ice as it ages under pressure in ice sheets.

Where is the CO2 in the oceans? There is a difference between CO2 from burning wood and that from fossil fuels in the amount of radioactive carbon. Weak cosmic rays are capable of changing a normal nitrogen atom into radioactive carbon. So a very small percentage of the air we breathe is radioactive. When plants incorporate this CO2 into their woody tissues, it is locked in place while its radioactivity slowly decays to zero. On the basis of this, scientists are able to measure the date of anything that has been made by life. However, in the course of millions of years, the remaining radioactivity can no longer be determined, as in fossil coal and oil. CO2 from burning coal is thus entirely non-radioactive.

With great difficulty the amount of fossil CO2 can be calculated from the total CO2 encountered:

• the amount of non-radioactive CO2 is large, and that of the radioactive part is small.
• only a very small amount of non-radioactive CO2 originated from fossil fuel.
• one cannot tell from the reduced radioactivity whether this was caused by age or by dispersion into the rest of the ocean which is also rather old, or by the amount of human-made CO2.

The question now remains whether this CO2 caused the oceans to become more acidic. But first we need to know how acidic the oceans normally are.

How much CO2 is absorbed by the oceans? We have rough estimates of how much carbon dioxide is recycled by the oceans (40-100GtC/y), but no hard data as to how much is permanently absorbed by it. The whole question about whether CO2 causes global warming or global warming causing CO2 has not been solved either. With nearly 40,000 GtC in the oceans, of which about half would escape for 10 degrees warming, means that a very small warming of 0.1 degree would still release 200 GtC to the air, or 25 years of human consumption. Global warming protagonists insist that more warming has happened than that, since the industrial revolution.

From sediment cores, scientists were able to obtain a record of past carbon dioxide levels, and these were very high for about 200 million years, with some 50 million years of low levels, and earlier still, very high indeed. So where did all that carbon come from and where did it go to?
From the blue line one can see clearly two sequestration periods, one in the Carbon/Devonian 350-400 million years ago, and this was when coal was laid down in the freshwater marshes (a vast quantity). During the dip at the end of the Cretacious (K), all oil was laid down in the middle seas while Gondwana was breaking up. Presumably all this CO2 came from volcanic activity.

It is important to remember that in order for the oceans to permanently fix more CO2 (which is true also for plants on land), the level of CO2 in the air needs to be higher than it was before the industrial revolution (the hockey stick for global temperatures). Sequestration at previous CO2 levels is not possible.

It is widely claimed that the oceans absorb (sequester) up to 30% of anthropogenic (man-made) CO2, but this cannot be measured.
 

Ocean CO2 sinks and sources The Joint Global Ocean Flux (JGOFS) survey has substaniated that the oceans absorb CO2 in cold seas while expelling it in warm seas, as shown in the above map. Although much of it (if not all) can be attributed to the fact that CO2 dissolves better in cold water, which can also contain more of it, there is also the biological pump. The sea is an ecosystem in which phytoplankton absorb CO2 as the beginning of the food chain which ends in top predators. When they die, they sink to the bottom, thus continually pumping CO2 towards the bottom of the oceans. In ocean upwellings, this CO2 reappears at the surface. There are two areas of high productivity: the southern oceans and the equator, but the one is a source, as the other is a sink for CO2. So the ocean pump draws CO2 down in cold seas while expelling it in warm seas. Reader please note that it cannot be ascertained whether the oceans as a whole absorb or emit CO2.

The seasonal greening of Earth Satellite scans from NASA show seasonal changes in the chlorophyll greenness of land and sea. In the northern summer the ice and snow covering the boreal conifer forests has melted, and the deciduous trees of temperate climates have sprung into leaf. It is a massive change from winter. By comparison, the southern hemisphere in its summer, does not have much change to show for, mainly due to the fact that there is little temperate and boreal land, but the Southern Ocean does spring into bloom. From just over one decade of observations, it was calculated that Earth's greening increased about 6% or about 0.5% per year, mainly at the fringes of forests. These maps cannot show that forests also become denser. However, 0.5% of 70Gt living plant matter = 0.35Gt, compared to 8Gt human emissions. Note that sequestration by plants can occur only in places with enough moisture and nutrients.

To understand ancient epochs, read our Geologic Timetable.

How acidic are the oceans? As this map suggests, ocean pH measurements have been done all over the world and in the most unlikely places. The false colour scale on the right suggests a range from 7.9 to 8.2 (personally I have measured a wider range from 7.8 to 8.3). The lowest pH occurs in upwelling areas whereas highest pH occurs in the centres of ocean gyres. From this extensive mix it would be difficult to state what the 'average' pH is for the oceans, let alone whether the oceans have become more or less acidic. Note that upwelling areas are more acidic because high-CO2 bottom water surfaces, warms up and makes CO2 more readily available, a bonus for photosynthesis by marine plankton.

My own measurements (see DDA) showed that the resulting pH is a tug-of-war between photosynthesisers that scavenge hydrogen ions to such extent that some lakes in summer and rock pools can go as high as 9.0, and decomposers that decompose living and nonliving biomatter to unlikely levels of 5.0 in putrid mud. pH is relatively low in eutrophied (overnourished) seas that can only be called sick. This implies that the degrading state of our coastal seas must have been accompanied by a decrease in pH. However, none of the scientific papers I read even mentioned this.
 
 

Acidity variation in the South China Sea Researchers [1] used the radioactive Boron-11 isotope in fossil corals to reconstruct a Holocene history of sea surface pH variations for the South China Sea. It showed that alkalinity varied between a pH of 7.91 and 8.29 during the past seven thousand years. Such variability far overshadows the fear of 0.3 pH change in two centuries. It must be noted, however, that most of the variation was towards 'healthier' values above 8.2. [1] Liu, Y et al. (2011): Reconstructing seawater pH in the South China Sea. Geochimica et Cosmochimica Acta 73: 1264-1272.

The Bermuda Atlantic Time-series Study (BATS) There exist very few time series of ocean measurements. The longest are HOTS (Hawaii Ocean Time Series, since 1990, does not measure pH) and BATS (Bermuda Atlantic Time-series Study, since 1984). Shown here is BATS for twenty years, with total dissolved inorganic carbon (DIC, mmol/kg), TA (Total Alkalinity), CO2 concentration (ppmv) and pH. One can see that there is quite a high degree of variability, with total carbon varying by 50mmol/kg (1.4%), CO2 all over the place, varying 100ppmv (25%) and the pH by 0.12 (32% hydrogen ions). With some difficulty a slanting line can be drawn for -0.03 pH (7%H) and +20ppm CO2 (5.9%) in 20 years. In the same period Mauna Loa measured an increase from 345 to 375ppm (8.6%). Before one can say that the decline in pH was caused by carbondioxide, one needs to prove that it was not caused by other acid gases, land-based effluent and eutrophication/degradation were not the cause. This has not been attempted. Note that the time series does not show any cyclic effect from El Niño (temperature variation) or any other cycle and is therefore too short to draw any certain conclusions from. Note that the pH makes large excursions that must have been caused by life. Note also that the pH makes large excursions downward but not upward, as if it reaches a maximum. This agrees with our observations that a high pH is limiting plankton growth: as plankton blooms, it scavenges hydrogen ions (and CO2 which is practically a mirror image), which causes the pH to rise until a dearth of (lack of) hydrogen ions becomes limiting, while there is still plenty of CO2 for photosynthesis (300-320ppm)! It also shows that measuring pH without first disabling all life in the sample, does not make much sense.

The Monterey Bay marine aquariums have been monitoring seawater parameters (temperature, pH, salinity, ammonia, nitrite, nitrate, phosphorus) for over a decade, and the graph here shows average monthly pH from 1995 to 2009. Because of the depth of the intake, near the thermocline, most parameters fluctuate wildly between surface and deep water quality. In a single day the temperature may vary regularly by 2ºC and sometimes by 4ºC, considering that winter to summer varies by only 2-3ºC. Compare this to the oceanic BATS data above, and it becomes clear that coastal water varies considerably from day to day, season to season and year to year. The important message here is, that when people talk about 'THE average pH' of THE ocean, they do not know what they are talking about.

Those familiar with science know that a single experiment cannot be hailed as conclusive, as it needs to be replicated by others, and also shown to be true over a representative extent of ocean. But the situation becomes worse, if one knows that an increase in hydrogen ions of pH=-0.1also makes the sea 20% more productive, leading to 20% more biomass if nutrients were sufficiently available. Such is the case in all coastal seas above continental shelves and far beyond due to rampant soil erosion.

In 2003 a paper appeared by Caldeira & Wickett which is based on computer simulations. They claim that already the oceans have acidified by 0.1 pH units. No actual measurements to back this up, and no mention of the calcium ion and carbonate buffering of sediments and no mention of eutrophication either. The 0.1pH amounts to 21% more hydrogen ions. This paper is interested in the possibility of injecting CO2 into the deep sea, a technological 'solution' to reduce emissions.

In 2005 a paper by Jacobson appeared, who calculated pH from dissociation constants, assuming that the ocean is in equilibrium with the air.  In his paper he includes dissociation constants of over 50 possible ion species in seawater, a truly complex system with enough scope for error. He claims that in 1751 ocean pH was 8.25 and now 8.14, a difference of 0.11 pH units or 22% more hydrogen ions. We wonder why the measurements in 1751 were so accurate and reliable. He goes further by claiming that when CO2 reaches 750ppm, the ocean will eventually settle at a pH=7.88, or a drop of 0.37 or an increase in hydrogen ions('acidity') of nearly 60%.

Reader please note that around 1750 electricity was about to be invented by Benjamin Franklin (see our timetable of human inventions), and pH could be determined only by the method of titration (litmus test?), and it is not possible to get more accurate than 0.2pH unit with this, regardless of the amount of sampling and averaging. Even today it is difficult to guarantee this kind of absolute exactness, considering the state of pH sensors and calibration buffers. In addition, the pH of the sea changes night to day, from day to day and winter to summer and from place to place. In fact, after our discoveries (DDA), natural alkalinity of the water can be established only after first disabling all life in the sample, and this has never before been considered. For Jacobson to claim an average ocean pH of 8.25 in 1751 is rather naive, if not fraudulent. His paper builds further on this by extrapolating:
 

Did he verify this with tests? No. The interacting chemistry of seawater is just too complicated to fully understand and even the carbonate part of it is not fully understood.
Although time series are still too short, other stations report increases of 0.4 to 2.2 µmol/y, equating to a decrease in pH of around 0.0012 per year. Note that because pH is a logarithmic scale, this annual decrease cannot be extended far into the future by multiplying it with the number of years.

The Bjerrum plot of the carbonate system Much ado is being made of the Bjerrum Plot, named after N Bjerrum (1914) who invented the diagram for visually representing the equilibrium between the three carbonate species CO2, HCO3 and CO3. With very precise equations, corrected for temperature, this system is well defined for the ideal situation (distilled water). What the plot says, is that for instance at a pH of 8.1 for the ocean, the three carbonate species are given by the intersection of the dashed vertical with each of the curves, giving 0.02, 2.05 and 0.12 mmol/kg for each (note that the drawing above is not accurate). By making the sample more acidic, hydrogen ions out-compete the hydroxyl ions, which results in more CO2 in solution, less CO3 and an inconsequential change in HCO3 (the FAT arrows). No problems here, but scientists now claim that an increase in CO2 is the same, and this cannot be true as an increase in CO2 simply lifts all three curves a little higher.  Note the relative concentrations CO2 : HCO3 : CO3 = 0.02 : 2.05 : 0.12 = 1 : 100 : 6

Le Chatelier's Principle: Adding CO2 to a CO2/carbonate equilibrium (including carbonate rock) will drive the reaction towards the formation of MORE carbonates, not less.

But there is more wrong:

• the plot doesn't explain the difference in pH between rain water and sea water. Neither does it explain the wide range in the pH of lakes.
• the plot does not take account of other mineral ions, of which calcium is the most important. These ions compete for hydrogen or hydroxyl ions and even for ions of the carbonate system.
• the plot does not include stabilising carbonate deposits.
• the plot has never been proved experimentally for the complex sea water system.
• what the Bjerrum plot DOES show is that if the sea becomes acidic for other reasons than CO2 (acid rain, runoff, eutrophication, warming, artificial addition of acids), CO2 levels WILL increase even if atmospheric CO2 does not increase.

So why is acidification considered a problem? This brings us to some questionable science that was looking for an excuse (Victoria Fabry in James C Orr et al. 2005). By examining certain shell forming plankton species like pteropods (wing-foots, pelagic snails that swim with their foot), it was found that some had minor damage to their shells. Apart from being inconclusive, these results were then hailed as proof that higher acidity in the sea would dissolve shells faster and that eventually the snails would not be able to make their shells fast enough, and that this would lead to extensive ecosystem changes and extinction of species. Also coral reefs would dissolve and weaken and combined with global warming, disappear from the face of the ocean. Oops. Correct me from being wrong, but there is something very fishy here. It is known that CO2 dissolved in rain water, makes it more acidic (pH=5.5-6), thus capable of dissolving limestone at a very slow rate, which takes a dripstone stalagmite thousands of years to grow a few kg.  CO2 + CaCO3 + H2O => 2(HCO3)- + 2Ca2+ (note the one way reaction => because water is transported away) So it is thought that more CO2 in ocean water would do the same. Apart from the fact that a pH=6 has 100 times more hydrogen ions than a pH=8, and does not seem to worry freshwater snails in lakes, sea water is almost saturated with calcium (Ca).

Remember the CO2 equilibrium equations that end in carbonate CO3^2- of 0.12 mmol/kg compared to that of Ca²⁺ of 10.4 mmol/kg? This means that there is not enough carbonate in the water to combine with the free calcium, and any increase in CO2 would mean that laying down a limestone skeleton becomes easier rather than more difficult. An increase in carbonate leads to calcification of CaCO3, just the opposite of what is being claimed! In other words, the vast store of calcium in the oceans has a buffering effect. Notice in this respect also the way salts precipitate when making table salt from sea water (/oceano/seawater.htm), with CaCO3 the first to settle out, followed by gypsum CaSO4.

Sarma et al. (1971) reported an increase in alkalinity of about 11 µmol/kg when DIC (CO2 species as Dissolved Inorganic Carbon) increased by about 20µmol/kg, which should create some inconvenient doubt.
 
 

Calcite and aragonite saturation There is a vast discussion going on and many experiments focusing on 'aragonite saturation', meaning that normal sea water should be in balance with the limestone in sea shells, oversaturated even. However, in practice all sea shells dissolve back into sea water, which means that the concept of aragonite saturation and calcite saturation may live only in our minds. Here is what's behind this idea:

 

On the surface of the ocean all dissolved gases are in balance with those in air. But in the water, with the help of sunlight, plants produce oxygen while consuming CO2. So oxygen concentrations are higher and carbon dioxide concentrations lower than in air. As one goes deeper, the beneficial effect of photosynthesis decreases, and CO2 increases due to breathing and decomposition. In theory at least, the water becomes more acidic with depth, to the point that the thin skeletons of plankton critters (coccolithophores, pteropods, foraminifers, etc) could begin to dissolve. This is called the aragonite saturation horizon (0.5-2.5km). Below it, the shells dissolve, whereas above it, they supposedly don't. As we have shown above, this is a dubious concept (Sarma et al, 1971). There is likewise also a calcite saturation horizon (1.5-5km). The concept 'explains' why clay deposits without limestone occur deeper than those with limestone as carbonate ooze. The diagram shows actually measured values for the carbonate ion CO32-  versus depth (red line). Below 2km the concentration is rather static although it decreases further with pressure. Where it crosses the (hypothetical) aragonite saturation horizon, sea shells will be dissolved gradually, and below where it crosses the calcite horizon, calcite will dissolve as well. It is thought that increased CO2, and thus acidity is the cause of this. Sadly actual pH is missing from this graph (why was it not measured or published?).

These hypothetical horizons are very dependent on temperature and pressure: the higher the pressure, the more readily calcite dissolves. Lower temperatures also increase the solubility of the water, and temperature decreases with depth. Hence it is not clear whether acidity or pressure or temperature are the main drivers. For this reasons the cold oceans like the Southern ocean are most likely to become under-saturated, one of the main scares.

What must also be remembered that the act of dissolving CaCO3 (limestone) into seawater also increases the pH. Thus the huge amount of ocean sediment will neutralise any acidification. It is estimated that ocean sediments amount to 30,000,000Gt carbon, a massive reservoir. But since most of it is in the deepest parts of the oceans, it may take a millennium to become effective.
 
 

0708135: a smooth tiger shell (Maurea tigris) has almost completely dissolved back into seawater, showing its spire made from  more dissolution-resistant nacre (mother-of-pearl). It took just over a year from live animal to this stage.

f012810: after about 6 months the fragile shell of a paper nautilus becomes too brittle to handle. In 12 months it has dissolved completely in clear seawater. Aluminium cans dissolve in 5-10 years!

Our own discoveries (DDA) show that the sea does not at all work as expected, and that marine plants (and corals) depend more or less on symbiotic decomposition. We have shown that a lowering of the pH is beneficial to overall productivity and biomass.

As far as measuring the effect of raised CO2 levels on marine animals, the situation is complicated because CO2 rapidly becomes toxic, with symptoms of depression of physiological functions, depressed metabolic rate + activity + growth, followed by a collapse in circulation. Remember that free CO2 amounts to only 1% of the total CO2 'bonded' to the water and that it takes some time for equilibrium with the other CO2 species to happen. It is thus too easy to overdose the free CO2 by increasing the CO2 in the air above. In other words, it is nearly impossible to mimic the natural situation truthfully in an experiment.

1. coral bleaching: coral bleaching by which a coral loses its symbiotic algae, may cause death. It is loosely linked to exceptional warm water. In case the Earth warms further, there is a chance that corals may not survive.
2. rising seas: seas may rise so fast due to the expansion of the water column and due to the melting of ice caps, that corals may not keep up. They will end up in deeper, darker water, which could mean death or at least a major ecological turmoil.
3. ocean acidification: corals make their limestone skeletons from the calcium and carbonate ions in the water. If higher CO2 levels in the atmosphere cause the sea to become more acidic, they may no longer be able to do so, while also their (dead) skeletons dissolve faster back into the sea. Reefs may become a thing of the past.

1. coral bleaching: scientists discovered that corals are not picky about the type of symbiotic alg (a dinoflagellate) they host, and are capable of adopting temperature-hardier variants of symbiodinium in a process named symbiont-shuffling. In fact, corals may have some hardier variants already as part of their customary algal lodgers. Once a coral recovers from bleaching, it proves to be hardier and not as easily bleached. So coral reefs adapt in a matter of months to years. Corals also respond favourably to warmer water by also growing faster (3-5% for one degree Celsius).
2. rising seas: many reefs are already limited in their growth by falling dry during spring low tides. Also fresh water floating on the surface, limits their growth. Fossil cores have shown that reefs have kept up with rising and falling seas during the ice ages and long before that. Most corals grow much faster than the worst-case predicted rise in sea level.
3. ocean acidification: because corals are encapsulated by live tissue within which the concentrations of minerals are controlled by the coral polyp, they are not very sensitive to acids outside. However, since their metabolism depends on that of their algal symbionts (who provide the food), they react favourably to raised levels of CO2, also producing skeleton faster. Warmth and CO2 work together, resulting in rapid growth, rather than decay.

[1] Idso, Craig D (2009): CO2, global warming and coral reefs: prospects for the future. http://scienceandpublicpolicy.org/originals/co2_coral_warming.html  free PDF (81 pages). An excellent review of published science confirming that corals adapt well to warmer seas, rising seas and acid oceans. In fact, they love it! Must-read!
[2] Idso, Craig D (2010): A new propaganda film by the NRDC fails the acid test of real world data. SPPI Institute. Free PDF (53 pages).

In the BBC report (http://news.bbc.co.uk/2/hi/science/nature/7437862.stm), the following quote appears: "I can't count the number of times that scientific talks end with 'responses have not yet been documented in the field'," said Elliott Norse, president of the Marine Conservation Biology Institute (MCBI), "This paper puts that to rest for several ecologically important marine groups."
"The reason that the oceans are becoming more acidic is because of the CO2 emissions that we are producing from burning fossil fuels," observed Dr Turley, "Add CO2 to seawater and you get carbonic acid; it's simple chemistry, and therefore certain. This means that the only way of reducing the future impact of ocean acidification is the urgent, substantial reduction in CO2 emissions."  - Oops, what is so simple about ocean chemistry?

However, we have some reservations about this work, since science is not only about measuring a correlation between supposed effect and cause, but also about proving that the correlation is not caused by anything else, which is what these scientists omitted. The CO2 vents were found towards the main coast and the coastal gradient extended outward from this coast (co-inciding with an increase in pH). Along such a gradient one also finds a change in water clarity, sediment deposition, shelter from waves (exposure), and human influences like sewage and run-off. It was telling that the measurements done at the northern side of the islet were not reported. Loss of biodiversity accompanied with a loss of coralline algae, urchins, limpets and others, can also be observed anywhere in the world in a gradient from an estuary to an outlying promontory, which is essentially the situation at the location of study. However, the fact that most changes happened within 25 metres, suggests that they were indeed caused by CO2.
More important, down to a pH of 7.6 (4x more acidic), no measurable effect was found and minor loss of biodiversity. Thus a doubling (pH=7.9) or quadrupling (pH=7.6) of CO2 concentrations in the atmosphere is not going to have any measurable effect on marine life. This was not mentioned in the article. In fact, the conclusion above is somewhat at odds with it.

Our main criticism with the study concerns the fact that water with a pH of 6.0 contains over 100 times the natural amount of CO2, and this is poisonous enough to kill almost all water-breathing organisms. The fact that animals went from perfectly healthy to completely dead within 25 metres, means that the study can in no way be assumed to have any relationship to the real-world situation. Researchers claimed to have calculated 'tipping points' for various organisms, but in this case one cannot meaningfully calculate 'average' CO2 concentrations. To understand this, study the results in the box below.
 
 

The graph shows the essence of the study. From left to right the transect distance along the rocky shore, moving landward towards the field of CO2 bubblers on right. In this field the pH varies considerably between 6.0 and 7.5 (30-fold). Note that the gas was nearly pure CO2, capable of acidifying the water locally 1000-fold to a pH of 5. However, mixing through turbulence, currents and waves soon dilutes the acid, even though an area of over 50m remains consistently highly acidic. Within a distance of a mere 25m, average acidity changes from 6.5 to 7.7, accompanied by a critical change in the environment, affecting in particular grazing sea urchins, snails and limpets. In their absence while fed by higher CO2 levels, non-calcareous (edible) algae multiply. The early decline of calcareous algae may not be entirely due to CO2 but also to competition with the edible algae and normal coastal degradation. The problem with this study is that it does not reflect a real-world situation where CO2 levels rise slowly, evenly spread over all oceans. This study looks more like a local CO2 Chernobyl with fatal fall-out wafting unpredictably here and there, such that it becomes meaningless to talk of average pH. Note that humans die at a 50-fold increase in CO2, and the situation here comes pretty close to this, if not far worse. For instance, what is the average between 1 and 100? Is it 50? 10? 90? It depends on what the numbers mean (weighted). If the numbers mean food, then the average lies close to one, because hunger (=no food) kills. If the numbers mean threat, then the average lies close to 100, because threats kill.  It is also important to note that nature is affected more by bad times than by good times, because during bad times, one is more likely to die. Thus a killer cloud of pH 6.2 wafting over, can be quite decisive, even though it may happen sporadically, not affecting the average. Particularly affected are the young (recruits) of all species. But the long-lived creatures are disadvantaged more than the short-lived ones. It so happens that many of the long-lived ones live in limestone houses.  See also our chapter on the principles of degradation.

[1] http://www.nature.com/nature/journal/vaop/ncurrent/full/nature07051.html Volcanic carbon dioxide vents show ecosystem effects of ocean acidification by Jason M. Hall-Spencer, Riccardo Rodolfo-Metalpa, Sophie Martin, Emma Ransome1, Maoz Fine, Suzanne M. Turner, Sonia J. Rowley, Dario Tedesco & Maria-Cristina Buia. Unfortunatelly this publication is not free and sets you back by US$32.

See also photos of natural CO2 vents at Dobu Island, taken by Bob Halstead, on Jenifer Marohasy's web site: http://jennifermarohasy.com/blog/2008/07/ocean-acidification-photographs-from-bob-halstead-and-a-note-from-floor-anthoni/

• a doubling of particulate organic carbon, a doubling of size and calcite shell
• slightly slower growth rates but photosynthetic health unaffected
• near-constant C:N ratio (6.8-8.3), an indication of food value for grazers
• the deep cores showed an increase in coccolith mass of about 40% in the past 220 years, which roughly agrees with experiments. The curve has a hockey-stick appearance, climbing more steeply in the past 25 years (~25%).

The graph shown here illustrates how coccolith mass was derived from deep sea core RAPID 21-12-B, dating back to before 1800. Also shown is the IPCC curve for CO2 concentrations in the atmosphere. The past 25 years of coccolith growth suggests that it follows the rapid increase in CO2 concentration in air. For a 20% increase in CO2, size increased about 30%. In laboratory experiments, however, coccolith size and calcification increased mainly betwen 400 and 600 ppm CO2, which has not happened in the sea yet. Could temperature be a driving factor?

[1] Phytoplankton Calcification in a High-CO2 World: M. Debora Iglesias-Rodriguez, Paul R. Halloran, Rosalind E. M. Rickaby, Ian R. Hall, Elena Colmenero-Hidalgo, John R. Gittins, Darryl R. H. Green, Toby Tyrrell, Samantha J. Gibbs, Peter von Dassow, Eric Rehm, E. Virginia Armbrust, Karin P. Boessenkool. Science 230, 336-340, 18 Apr 2008. Available for US$10 from Sciencemag.com, but freely downloadable from http://www.sb-roscoff.fr/Phyto/index.php?option=com_docman&task=doc_details&gid=418&Itemid=112
 
 

Owing to anthropogenic emissions, atmospheric concentrations of carbon dioxide could almost double between 2006 and 2100 according to business-as-usual carbon dioxide emission scenarios. Because the ocean absorbs carbon dioxide from the atmosphere, increasing atmospheric carbon dioxide concentrations will lead to increasing dissolved inorganic carbon and carbon dioxide in surface ocean waters, and hence acidification and lower carbonate saturation states. As a consequence, it has been suggested that marine calcifying organisms, for example corals, coralline algae, molluscs and foraminifera, will have difficulties producing their skeletons and shells at current rates, with potentially severe implications for marine ecosystems, including coral reefs. Here we report a seven-week experiment exploring the effects of ocean acidification on crustose coralline algae, a cosmopolitan group of calcifying algae that is ecologically important in most shallow-water habitats Six outdoor mesocosms were continuously supplied with sea water from the adjacent reef and manipulated to simulate conditions of either ambient or elevated seawater carbon dioxide concentrations. The recruitment rate and growth of crustose coralline algae (CCA) were severely inhibited in the elevated carbon dioxide mesocosms. Our findings suggest that ocean acidification due to human activities could cause significant change to benthic community structure in shallow-warm-water carbonate ecosystems.

...Although previous work examined the effects of calcium carbonate saturation state on calcification rates of corals and coral communities in realistic mesocosm studies, none has examined how community structure may change under increasing degree of ocean acidification. ....
... Under high conditions, CCA recruitment rate and percentage cover decreased by 78% and 92%, respectively, whereas non-calcifying algae increased by 52% (Fig. 2) relative to controls. ....
... we did not attempt to replicate the natural compliment of herbivores found on Hawaiian reef flats, and thus only microherbivores (for example sea hares and amphipods) were in abundance. ...
... Under all proposed scenarios, continuous anthropogenic emissions of CO2 to the atmosphere will result in a continuous decline in the pH and calcium carbonate saturation state of ocean waters, with all the ecological implications of such a change in a major Earth-surface-system carbon reservoir. The only way to slow or prevent the continuing acidification of surface ocean waters is to reduce the emissions of CO2 from human activities to the atmosphere; however, because of the slow mixing rate of the oceans, they will continue to be a major sink of anthropogenic CO2 emissions well into the future, and ocean acidification will continue to intensify. ... [sigh]

These scientists placed two times three plastic cages (mesocosms) of 1x1x0.5m under water at shallow depth. The advantage of this method is that the study mimics as closely as possible the natural situation, including day-night light rhythm. In one set of three they manipulated acidity to reflect a doubling of CO2 to 800ppm. Then they placed perspex cylinders in each to see what would happen. In the control set they were encrusted by crustose calcareous algae (CCA), whereas in the CO2-rich set they were encrusted by fleshy green algae. The differences between the two sets were quite dramatic as shown by the photograph and graphic. The conclusion is that man-made CO2 is bad, and that major ecosystem changes can be expected. A final blow to the acid ocean skeptics. End of debate. Period. ... Unless we examine the fine print and do some detective work.

Crustose calcareous algae or pink paint as divers call it, is a group of the most astounding organisms on our planet. If you were told about stones that grew and replicated, you would disbelieve. Yet it is true. CCA is living limestone, physically a red seaweed but without any flesh or vessels. It grows in the shallows, exposed to ultraviolet and low tide, yet forming extensive rocky platforms with caves and tunnels in a mere 6000 years. On coral reefs it is the glue between corals, forever scraped and nibbled at by urchins and fish, yet surviving and growing. When algae peter out at the deep end of the photic zone, there is still CCA and at twice that depth too. A boulder in a rock pool may be turned by a storm, leaving its CCA cover buried in darkness. Yet turned back upright after two months, the bleached CCA soon turns pink again, resuming business as usual. When going from healthy waters to extremely degraded environments, CCA is one of the last to give up. So come-on, why can this sturdy creature not handle a little extra CO2? What is wrong we must ask? We have some serious misgivings about this work for a variety of reasons.

• Whenever a scientific article begins with 'anthropogenic emissions' and 'IPCC', it raises the hairs on my back because these people show to have a bias. Real science is about curiosity in about how things work; not about 'proving' an idea. The experiment took only seven (!) weeks (a student's summer holiday), immediately after which the results were published - and accepted by the 'prestigious' journal Nature! The experiment was not replicated; the cylinders were not swapped; mature CCA was not investigated and so on. Instead these people focused on replicating their publication: dial any of the authors (Kuffner or Jokiel will do) on Google and see how many references and duplications come up. Other publications were quick to refer to this shoddy work which is on a par with a school science project.
• For instance, it is equally interesting to see what halving CO2 levels does, because the claim of 250ppm pre-industrial level may be a myth. Why did the scientists not include a set of enclosures for testing this? Note that this is a general criticism of most studies of the effect of raised CO2.
• The raised level of CO2 was not achieved by adding CO2 to the water but a highly concentrated solution of hydrochloric acid (HCl) that was trickled into the treatment enclosures. This releases CO2 from the HCO3 species as discussed in the Bjerrum Plot above, but this is not like the real world as it also diminishes the shell-building CO3 ion. It also assumes various densities before diluting completely. And even if this happens in the water above the cylinders, it will still influence the plankton and spores and their settlement.
• The experiment was not about death or slow growth but about settlement. Algae have a two-phase life cycle: the mature plant makes asexual spores that hatch into male and female plants, too small to see, but these reproduce sexually, and their 'seeds' grow into the colonies observed on the perspex cores, after first some time in the plankton. Thus settlement is about the minute or hour that a 'seed' decides to attach or not; a flash in a CCA's life. And that is all this experiment was about.
• Settlement is an extremely fickle (not constant, uncertain) process. Put your plastic cores out, together with concrete tiles, and you will see different creatures settle on each type. Put them out today and it may be CCA that dominate. Next week could give barnacles. Next month green algae and limpets, and so on. Settlement experiments are almost impossible to replicate. Which means that they also have little relevance. In the bar chart above, you can see some of that unpredictability.
• Let me take you to the laboratory where these experiments were done, at Kaneohe, Hawaii (photo below). The water here is not blue as one would expect, but green. It is indicative of degradation from eutrophication. Now look at the pH curves in the graph next to it. The green curve shows the daily pH rhythm for the environment there. For starters, average pH is well below 8.2, a sure sign of degradation. The water here is already 50% more acidic than average ocean water. Now look at how pH changes from mid day to mid night -0.3 units or 2x more acidic, another sure sign of degradation. This is caused mainly by decomposing planktonic bacteria, who never sleep. The bacterial activity follows from the down slope of the curve in darkness, amounting to an RoA (bacterial Rate of Attack) of 20-40 hion (see our DDA method), an indication that the environment here is under significant stress. The point here is that all stresses add up, such that the extra stress caused by high CO2, is only part of the whole and cannot be singled out (see our principles of degradation chapter).

Summarising it all: a naive study in a highly stressed already acidic environment, using hydrochloric acid, not replicated and perhaps not reproducible, with the low relevance of a settlement experiment. Their far-reaching conclusions are not warranted by the experiment.

[1]  Ocean acidification impacts on coral reefs: changes in community structure, Ilsa Kuffner, Andreas Andersson, Paul Jokiel, Ku’ulei Rodgers & Fred Mackenzie  http://www.whoi.edu/cms/files/Kuffner_OA_Scripps_34825.pdf [free] a slide show with more information about the work done.

Abstract: Reef-building corals are under increasing physiological stress from a changing climate and ocean absorption of increasing atmospheric carbon dioxide. We investigated 328 colonies of massive Porites corals from 69 reefs of the Great Barrier Reef (GBR) in Australia. Their skeletal records show that throughout the GBR, calcification has declined by 14.2% since 1990, predominantly because extension (linear growth) has declined by 13.3%. The data suggest that such a severe and sudden decline in calcification is unprecedented in at least the past 400 years. Calcification increases linearly with increasing large-scale sea surface temperature but responds nonlinearly to annual temperature anomalies. The causes of the decline remain unknown; however, this study suggests that increasing temperature stress and a declining saturation state of seawater aragonite may be diminishing the ability of GBR corals to deposit calcium carbonate.
As we mentioned in previous articles, when a scientific article begins with a reference to changing climate and increasing carbon dioxide, the authors show to have an agenda, a belief that is bound to affect their studies. The bottom line reaffirms this belief with increasing temperature stress and declining saturation state of seawater aragonite. Over 30% of this abstract is taken up by assertions that are not borne out by the experiment, reason for extreme caution. We begin our critique with this issue because it is exactly what the international press has latched onto, inferring that this experiment proves corals declining BECAUSE of anthropogenic carbon emissions, whereas nothing could be further from the truth. Google for "de'ath coral" to see the massive damage done by these statements that are irrelevant to the experiment.
To take this criticism one step further, these two statements secure the article a place in the 'prestigious' Science journal which over the years has shown itself a firm global warming advocate, together with other 'prestigious' journals such as Nature, Scientific American, New Scientist and a host of others. The two statements are also intended to secure continuation of funding. Reader beware!

f044811: a diver in front of a large 'massive' Porites coral in the clear waters of Niue island. The many christmas tree worms are hardly visible on this scale.

f044135: christmas tree worms on Porites coral. These beautiful fan worms are only a few centimetres tall, showing how small the Porites coral polyps really are. Porites corals often include other organisms like worms and molluscs in their matrix.

What was done?
Previous studies have drilled cores into the 'massive' Porites coral which can grow 'coral bommies' of several metres diameter and several hundreds of years old. These cores from the Coral Core Archive were re-analysed for their calcite (limestone) densities and growth rates, using state-of-the-art scientific techniques of X-ray and gamma densitometry and simple length measurements. Because corals live like plants, their growth rates depend on temperature and the amount of light, both causing yearly bands, much like tree rings. The cores investigated come from all over the north-south extending Great Barrier Reef, allowing investigaters to also study the effect of average temperature.

What was found?
The main finding of the study is shown in this graph for extension (blue, growth rate) (cm/yr) and density (green, g/ml), interpretation of which is confusing. The increasing growth rate since 1900 suggests that the sea has been warming, but it is accompanied by a reduction in density. The product of the two is the calcification rate (red) with a flatter mid-range. Its hockey-stick appearance of dipping down steeply since the late-1990s has been cause for alarm, being clearly 'abnormal' as it has not occurred in 400 years (not shown here). Normal growth of about 1.4cm per year has suddenly dipped to less than 1.3cm/yr, a decline of 14.2% per year, and should this trend continue, the porites coral could disappear by the year 2050.

Conclusion:
The question is now what caused this sudden decline?

• Do all Porites corals always end in an extension dip for the past 6-8 years? After all, this is only 6x1.4= 8.4 cm into the coral and it would be foolish to assume that the live polyps end at 1.4cm depth, where they ended last year. In other words, at 8.4cm depth, calcification may still be on-going, extending the coral colony outward as well, and thus 'pulling' the hocky stick for extension up to 'normal' levels as time proceeds. It is logical that where the polyp occupies space, calcification is correspondingly less. Likewise one would not expect much woody tissue in the shoots of a tree, which also extend over time. Ironically, this suggestion has not been considered by the authors. In this context is is important to know whether exceptions have been encountered, corals that do not have a 'stunted growth' towards the present. See also the authors' comment in next paragraph, suggesting that no exceptions were found. Darke&Barnes [2] found that Porites polyps live on average for 2-3 years with a life expectancy of 5 years. It suggests that some of the hockey stick 'nosedive' is natural.
• Is it caused by degradation from run-off from the land? This possible cause is rejected out of hand by the authors even though coral reefs are severely threatened by human proximity [1]: "Terrestrial runoff and salinity, although potentially affecting inshore reefs, are also unlikely causes because calcification declines at similar rates on offshore reefs away from flood plumes". However, we discovered that eutrophication extends far beyond the reach of river plumes and visible runoff, reaching the outer boundaries of continental shelves. Furthermore, when the water is still deemed 'clear' (15m visibility), degradation has its worst effect on sensitive organisms such as found in healthy reefs. To disprove degradation as cause, coral cores must be extracted from areas remote from human settlement. Note also that the authors are still unaware of our recent discoveries about symbiotic decomposition and how corals derive growth in seas devoid of food (nutrients and phytoplankton).
• Is it caused by warming waters? The graph is contradictory as it confirms that corals do better in warmer water, and also the authors find no evidence along the temperature gradient from north to south along the Great Barrier Reef. Sudden temperature events could do it but these have to be frequent and would not produce a smooth decline as in the graphs.
• Is it caused by ocean acidification? Unfortunately the coral cores do not reveal ancient alkalinity (pH) and there exists no record of pH measurements over the past 100 years. Besides, acidification is supposed to have been a slow process, whereas the hockey stick suggests a sudden disaster that began less than 10 years ago. Furthermore we have shown that increased acidity benefits productivity in the oceans. No problem, let's then introduce the notion of 'tipping point', a gradual GOOD process suddenly becoming VERY BAD ??? Note that degradation can have a tipping point which is different for each species. The difference between thriving and dying is usually small (the tipping point); a company thrives when it makes a profit but goes bankrupt from small losses.

"Laboratory experiments and models have predicted negative impacts of rising atmospheric CO2 on the future of calcifying organisms. Our data show that growth and calcification of massive Porites in the GBR are already declining and are doing so at a rate unprecedented in coral records reaching back 400 years. If Porites calcification is representative of that in other reef-building corals, then maintenance of the calcium carbonate structure that is the foundation of the GBR will be severely compromised. Verification of the causes of this decline should be made a high priority. Additionally, if temperature and carbonate saturation are responsible for the observed changes, then similar changes are likely to be detected in the growth records from other regions and from other calcifying organisms. These organisms are central to the formation and function of ecosystems and food webs, and precipitous changes in the biodiversity and productivity of the world’s oceans may be imminent."

Latest update, August 2009 Steve McIntyre at Climate Audit (June 2009) gives a chilling explanation of the Porites slow-growth artefact: it is caused by a lack of data, as the dataset suddenly drops from around 40-50 samples to only two! Besides, there is a mathematical averaging problem that does not show in the long-term raw data. The raw data for average calcification shows a steady improvement in coral growth with a sudden drop around the year 2000, not quite resembling the graphs shown in the Science publication. But look at the pink histogram on right, showing the number of datasets used for calculating this 'average'. Since around 1984, this dataset has been declining to about 10, and in 2005 it dropped even further to 2! So all alarm is based on only two items! Could one call this scientific fraud? Surely honest scientists would have mentioned this in their publications? http://www.climate-skeptic.com/2009/06/how-to-manufacture-the-trend-you-want.html

[1] Mora, Camillo (2008): Coral reefs threatened by human proximity - Humans Have Caused Profound Changes In Caribbean Coral Reefs. [free PDF] Proc. R. Soc. B (2008) 275, 767–773 doi:10.1098/rspb.2007.1472 Published online 8 January 2008
[2] W. M. Darke and D. J. Barnes (1993): Growth trajectories of corallites and ages of polyps in massive colonies of reef-building corals of the genus Porites. Mar. Biol. 117:321-326, 1993

Abstract
Ocean acidification is rapidly changing the carbonate system of the world oceans. Past mass extinction events have been linked to ocean acidification, and the current rate of change in seawater chemistry is unprecedented. Evidence suggests that these changes will have significant consequences for marine taxa, particularly those that build skeletons, shells, and tests of biogenic calcium carbonate. Potential changes in species distributions and abundances could propagate through multiple trophic levels of marine food webs, though research into the long-term ecosystem impacts of ocean acidification is in its infancy. This review attempts to provide a general synthesis of known and/or hypothesized biological and ecosystem responses to increasing ocean acidification. Marine taxa covered in this review include tropical reef-building corals, cold-water corals, crustose coralline algae, Halimeda, benthic mollusks, echinoderms, coccolithophores, foraminifera, pteropods, seagrasses, jellyfishes, and fishes. The risk of irreversible ecosystem changes due to ocean acidification should enlighten the ongoing CO2 emissions debate and make it clear that the human dependence on fossil fuels must end quickly. Political will and significant large-scale investment in clean-energy technologies are essential if we are to avoid the most damaging effects of human-induced climate change, including ocean acidification.

Reader, as you can see, most of the abstract is scaremongering and is not supported by the uncertainties in the research reviewed.
 

From the conclusion
"The scientific knowledge base surrounding the biological effects of ocean acidification is in its infancy and the long-term consequences of changing seawater chemistry on marine ecosystems can only be theorized." ...."In contrast, the potential effects ocean acidification may have for the vast majority of marine species are not known. Research into the synergistic effects of ocean acidification and other human induced environmental changes (e.g., increasing sea temperatures) on marine food webs and the potential transformative effects these changes could have on marine ecosystems is urgently needed." ..... "Future ocean acidification research needs include increased resources and efforts devoted to lab, mesocosm, and in situ experiments, all of which will aid in determining the biological responses of marine taxa to increased pCO2. Mesocosm and in situ experiments may simulate and/or provide more natural conditions than single-species lab experiments, but they have thus far used abrupt changes in seawater chemistry which do not allow for potential acclimation or adaptation by marine organisms." [or for the carbonate ion to develop].... "The shallow continental shelves are some of the most biologically productive areas in the sea and are home to the majority of the world’s fisheries, but accurate carbonate saturation state data do not currently exist for most coastal regions." ..... "The overwhelming volume of scientific evidence collated by the IPCC documenting the dangers of human-induced climate change, of which ocean acidification is only one, should end the lingering CO2 emissions reduction debate."...."The global CO2 experiment which has been under way since the Industrial Revolution and the potentially dire consequences this uncontrolled experiment poses for marine organisms and indeed, all life on Earth, leave no doubt that human dependence on fossil fuels must end as soon as possible. International collaboration, political will, and large-scale investment in clean energy technologies are essential to avoiding the most damaging effects of human-induced climate change."  [sigh . . are we detecting a bias here?]
 

What is the study about?
Taking a hand-picked IPCC projection as an unwavering fact, the authors have hand-picked studies that show a decline in calcification for a wide range of organisms, in higher concentrations of CO2 but not in lower concentrations. To give an indication of their assumptions, study the table below which has been taken in its entirety from the paper, in order to avoid making any mistakes.
 
 

The table is based on our present knowledge of the ocean carbonate chemistry [1,2], superimposed on the IPCC scare scenario. As we have seen before, both are subject to considerable doubt and the ocean's carbonate chemistry is also influenced by life. The columns represent milestones in the time scale from glacial through preindustrial to the present and beyond. The important rows are:

• pCO2 in seawater: the IPCC myth of glacial CO2 concentrations of 180ppm, an equally mythical preindustrial concentration of 280ppm to the present 380ppm (the only point with certainty), and from here on extrapolated to twice and three times present concentration. If the first two assumptions are wrong, the others just amplify the error.
• temperature: from a glacial average global temperature of 15.7ºC (perhaps) through a guessed at preindustrial temperature to the present 19.7ºC and beyond by extrapolation. Notice the disastrous 3ºC global warming!
• total pH: sinking from an extrapolated 8.32 through the present 8.05 to a future 7.76. These figures follow from pCO2 in seawater (above) and are thus equally shaky.
• carbonate ion: decreasing as if inside a laboratory test beaker from an extrapolated 279 through the present 182 to an extrapolated future of 115. The effect of the vast amount of buffering not taken into account and Le Chatelier's principle flouted.

Shell-building phytoplankton organisms (Emiliana huxleyi, Gephyrocapsa, Calcidiscus) -8% to -66% calcification.
Foraminifera (Orbulina, Globigerinoides) -4% to -20% calcification.
Scleractinian corals (Stylophora, Acropora, Porites, Pavona, Fungia, Galaxea, Turbinaria) -14% to -55% calcification
Coralline red algae (Porolithon gardineri) -25% calcification.

What are the uncertainties?
Every scientific account should honestly mention doubts and uncertainties, but this paper mentioned only "but they (scientists) have thus far used abrupt changes in seawater chemistry which do not allow for potential acclimation or adaptation by marine organisms". Yet the whole paper is based on the very shaky predictions by the IPCC, mythical values for the past and extrapolations based on these, a large uncertainty about ocean chemistry, 'fraudulent' tests and selective 'bad news' publications. In other words, the publication was meant to be alarming from the beginning. We wonder when a more balanced account may surface.
 

[1] Marsh, Gerald E : Seawater pH and anthropogenic carbon dioxide. www.gemarsh.com. "In 2005, the Royal Society published a report titled Ocean acidification due to increasing atmospheric carbon dioxide.  The report’s principal conclusion—that average ocean pH could decrease by 0.5 units by 2100—is demonstrated here to be consistent with a linear extrapolation of very limited data.  It is also shown that current understanding of ocean mixing, and of the relationship between pH and atmospheric carbon dioxide concentration, cannot justify such an extrapolation."
[2] There are two conflicting 'knowledges' of ocean chemistry: Pearson&Palmer hold the total of all CO2 species constant whereas Caldeira&Berner hold the CO3 ion constant, resulting in radically different relationships between CO2 concentration and pH. To make matters worse, Le Chatelier principle holds that all CO2 species change, and on top of it all, life has its own influence (growth and decay).

• http://www.co2science.org/data/acidification/acidification.phpOcean Acidification Database containing over 1100 studies.
• http://www.c3headlines.com/are-oceans-becoming-acidic/summaries of dozens of studies, kept uptodate. Begin here.
• Dupont, S., Lundve, B. and Thorndyke, M. (2010). Near future ocean acidification increases growth rate of the lecithotrophic larvae and juveniles of the sea star Crossaster papposus. Journal of Experimental Zoology (Molecular and Developmental Evolution) 314B: 382-389.

The three researchers report that just the opposite of what is often predicted actually happened, as the echinoderm larvae and juveniles were "positively impacted by ocean acidification." More specifically, they found that "larvae and juveniles raised at low pH grow and develop faster, with no negative effect on survival or skeletogenesis within the time frame of the experiment (38 days)." In fact, they state that the sea stars' growth rates were "two times higher" in the acidified seawater; and they remark that "C. papposus seem to be not only more than simply resistant to ocean acidification, but are also performing better."