Toxic Seawater Fraud

[Note: some understanding of chemistry (approximately A-Level) is necessary to understand this post, and it will be helpful to read the background in the previous post Ocean Acidification Scam.]

The theory behind the ‘toxic ocean acidification’ scam proceeds like this: as the concentration of CO₂ in the atmosphere increases, the concentration in the oceans also increases due to dissolution [true – all other things being equal]. CO₂ dissolved in water reacts with water to form carbonic acid, making the seas acidic [a half truth – they become very slightly less alkaline]. This acidity dissolves the shells of marine life causing mass extinction [an utter falsehood].

As a matter of fact, seawater is alkaline. Dissolving the carbon dioxide from all the world’s known fossil fuel reserves would never make the sea acidic. The climate alarmists coined the phrase “ocean acidification” to make it sound alarming, whereas the process is actually what is known as neutralization. The term ‘acidification’ of course sounds more scary than talking about the oceans becoming slightly less alkaline or a little more neutral.

To put this into perspective, the pH of seawater is, on average, around pH 8.2. Pure water is pH 7.0, and clean rainwater is pH 5.6. What is more, seawater is a highly buffered solution – it can take up a huge amount of dissolved inorganic carbon without significant effect on pH. There is not the slightest possibility that the alkalinity of the oceans could approach the neutral pH of pure water even if all the fossil fuel reserves in the world were burned, so all talk of ‘acid’ oceans is utter nonsense. What sort of change are we talking about? Possibly a change of pH of 0.2 units this century, say from 8.2 to 8.0. That would mean by definition that there were still no more than 10% of the ‘acidic’ H⁺ ions than there are in pure water.

The so-called science behind this ‘acid ocean’ scare is complete baloney. Firstly, an increasing concentration of CO₂ in the water improves the efficiency of photosynthesis in the oceans (as it does on the land), and so increases the growth of plant life in the ocean, including phytoplankton, upon which ‘graze’ zooplankton, which is food for a vast range of sea animals, including whales.

Secondly, it’s not possible through lifeless inorganic chemistry to predict what is happening with living processes. Fish pump huge quantities (hundreds of millions of tonnes annually) of available carbonate in the oceans as a byproduct of the systems that enable them to survive in high salinity. This is using the energy of life processes to buck the normal dissolved inorganic carbon equilibria. The calcium carbonate (limestone) of dead calcifying organisms dissolves naturally in seawater. What stops a sea creature’s shell from dissolving away is the living creature’s continually producing more calcium carbonate, just like a land animal continually produces skin cells to replace those that are lost to the environment.

Thirdly, an increasing concentration of dissolved inorganic carbon (e.g. dissolved carbon dioxide, bicarbonate ions, carbonate ions) makes the process of laying down calcium carbonate in shells efficient. This is because there is a far greater supply of calcium ions (441ppm) in seawater than dissolved inorganic carbon (90ppm) and any increase in dissolved carbon dioxide simply pushes the equilibrium balance towards the production of carbonate ions. The reactions are reversible and in equilibria:

CO₂ + H₂O <=> H₂CO₃ <=> H⁺ + HCO₃^- <=> H⁺ + H⁺ + CO₃^2-

Add more CO₂ at the left and the equilibrium balance is driven to the right – liberating more carbonate, which can combine with the superabundant calcium ions to form calcium carbonate. Note that as the reaction is driven to the right by the dissolution of additional CO₂ there is increased production of H⁺ ions, so acidity is increasing (= decreasing pH) but the absolute carbonate concentration is increasing as well.

Fourthly, the situation is completely different from the case where pH is artificially lowered by adding, say, hydrochloric acid, where there would be no addition of dissolved inorganic carbon. Unfortunately, many scientists have failed to understand this basic chemistry and have conducted crude experiments on shellfish by adding mineral acids to seawater. Whilst this duly lowers the pH, it drives the equilibrium reactions in the opposite direction, so is completely invalid as an experimental model. In the equilibrium equation above, introducing mineral acid (which introduces no additional dissolved inorganic carbon) adds H⁺ ions on the right of the equilibrium equation, which drives the equilibrium to the left, and removes carbonate. The increase in H⁺ ions (equivalent to lower pH), arises because the experimenter is tipping in mineral acid and is thereby forcing the reaction to reduce carbonate and to increase dissolved carbon dioxide, which will come out of solution into the atmosphere as bubbles, decarbonizing the seawater. But if increasing atmospheric CO₂ is the driver, the reaction is forced the other way and the carbonates go up; if mineral acid is the driver, the pH goes down and carbonates also go down. Looking at pH tells us absolutely nothing about the concentrations of carbonates, bicarbonates, dissolved CO₂, equilibria, reaction rates or reaction directions. As a matter of fact, calcium carbonate dissolves in alkaline seawater (pH 8.2) 15 times faster than in pure water (pH 7.0), so it is silly, meaningless nonsense to focus on pH.

By elementary chemistry, adding CO₂ to a CO₂/carbonate equilibrium will always drive the reaction towards the production of more carbonate, irrespective of any associated reduction in pH arising from the shift in equilibrium itself. So if atmospheric CO₂ increases, leading to increased dissolution of CO₂, we can be sure that there will be a higher concentration of carbonate available for combination with calcium – the complete opposite of what the scare mongers are telling us. It’s a no brainer. It seems that those creating the ‘ocean acidification’ scare don’t know the basics about chemical equilibria, buffer solutions and Le Chatelier’s principle. Or maybe they hope we don’t know and understand them, so that they can hoodwink us. They would like us to believe that a reduction in pH is analogous to tipping mineral acid in the oceans, which would indeed be damaging, and would liberate CO₂ from the oceans, whereas the effect of increasing dissolution of CO₂ is wholly beneficial both to marine plants and animals.

To see what muddled thinking and ignorance of chemistry there is, it is sufficient to examine the report by the Royal Society, Ocean acidification due to increasing atmospheric carbon dioxide. As usual, what comes from the Royal Society these days is special pleading and phoney science. They state

Carbonic acid is an acid because it can split up into its constituents, releasing an excess of H⁺ to solution and so driving pH to lower values. Carbonic acid splits up by adding one H⁺ ion to solution along with HCO₃^- (a bicarbonate ion)…This increase in H⁺ causes some CO₃^2- (called carbonate ions) to react with H⁺ to become HCO₃^-…Thus the net effect of the dissolution of CO₂ in seawater is to increase concentrations of H⁺, H₂CO₃ and HCO₃^- , while decreasing concentrations of CO₃^2-

This is breathtakingly stupid chemistry – they have muddled up absolute and relative concentrations. What’s more, the equations given in the Royal Society paper show one-way reactions rather than two-way equilibria. They are treating the process as a titration rather than an equilibrium reaction with increasing concentration of dissolved inorganic carbon.

The faulty reasoning in the Royal Society’s paper (and many others) is that because addition of carbon dioxide causes more acidity, the increasing H⁺ ions will eventually force the reaction to the left. But where are the H⁺ ions coming from in the first place? As a result of the reaction moving to the right! The reasoning of fraudulent science is that as the reaction proceeds to the right and liberates H⁺ ions it must subsequently swing back to the left (which would create higher CO₂ in the water as well). Equilibrium processes don’t work in this unstable, oscillatory way: the H⁺ ions that are generated become a brake on the reaction proceeding too far to the right, and a new equilibrium point is reached with lower pH and higher carbonate.

Whilst the relative concentration of CO₃^2- (carbonate) with respect to the increasing concentration of HCO₃^- (bicarbonate) may reduce, the absolute concentration of carbonate in seawater will increase as more CO₂ dissolves. We can demonstrate this principle by a simple experiment. Consider a beaker of pure water, pH 7.0. The beaker contains nothing but H₂O molecules and its dissociated ions H⁺ and OH^-. If carbon dioxide is bubbled through the water for some hours and the system left to rest and establish equilibrium the pH will go down, perhaps to pH 5. There will be now be some dissolved CO₂, some bicarbonate ions and some carbonate ions in solution and many more H⁺ ions than there were before. Carbonate ions have thus increased because there were literally none before, yet pH has gone down and the absolute quantity of H⁺ ions has increased considerably. So, in absolute terms, carbonate ions increase as dissolved CO₂ increases.

In fact, at pH 8, seawater is supersaturated with carbonate. Why does this excess carbonate not precipitate out as calcium carbonate, since there are so many free calcium ions in the water? This seldom happens (except when forced to do so by the calcification processes in living organisms) because of the presence of magnesium ions in seawater that preferentially ion pair with the carbonate in solution. With ion pairing, the reaction moves further to the right than would be the case without magnesium ions, yet without precipitation of magnesium and calcium carbonate salts, and this ensures there is an abundance of dissolved carbonate ions available for living organisms in spite of the low alkalinity. Moreover, phosphorus and dissolved organic compounds permit high levels of carbonate to exist without precipitation. Seawater is a truly marvelous and complex chemical system, which includes non-volatile borate, phosphate and silicate buffers.

Apart from being muddled on the chemistry, the Royal Society ’s paper has this to say:

From our understanding of ocean chemistry and available evidence, it is clear that increasing the acidity of the oceans will reduce the concentration and therefore the availability of carbonate ions. It is expected that calcifying organisms will find it more difficult to produce and maintain their shells and hard structures.

Now, here is a classic trick of the illogical argument, the non sequitur. We are being led to believe from these two sentences that the availability of carbonate ions is important to the production of shells. As a matter of fact, nearly all the literature teaches that the biological process of calcification proceeds from the reaction between calcium ions and bicarbonate ions, and there’s no shortage of either of those. Even the Royal Society says so 12 pages earlier, but you are expected to have forgotten that by now:

two ions of bicarbonate (HCO₃^-) react with one ion of doubly charged calcium (Ca²⁺) to form one molecule of CaCO₃

liberating a carbon dioxide and a water molecule as well. This makes the “availability of carbonate ions” a completely moot point, but you are not supposed to pick up on this false logic. And here comes the classic:

…the lack of a clear understanding of the mechanisms of calcification and its metabolic or structural function means that it is difficult, at present, to reliably predict the full consequences of CO₂-induced ocean acidification on the physiological and ecological fitness of calcifying organisms.

So, let’s consign this report to the waste bin, please, and look at papers by authors who do know what they are talking about. But in this regard, the following assertion given in the Royal Society paper is certainly false, as inspection of the sources below shows:

Published data on corals, coccolithophores and foraminifera all suggest a reduction in calcification by 5–25% in response to a doubling of atmospheric CO₂ from pre-industrial values (from 280 to 560 ppm CO₂)

So, what’s the effect of increasing carbon dioxide in seawater on calcifying organisms? Here are some recently reported findings:

Wood, Spicer, and Widdicombe (2008) found that increasing dissolved CO₂ increases calcification rates and improves the rate of regeneration of damaged body parts [Proc Biol Sci. 2008 August 7]. The following extracts are given at length because of the importance of these findings, which overturn ‘assumptions’ (read, false reasoning and bad science):

…we have investigated the effect of CO₂-induced acidification on the ability of a calcifying organism (the ophiuroid brittlestar Amphiura filiformis) to regenerate calcium carbonate structures (arms).

Amphiura filiformis collected from Plymouth Sound, UK, were maintained in sediment cores (five individuals per core) supplied with filtered seawater of the allocated pH (pH modified using CO₂). Each pH treatment (8.0, 7.7, 7.3 and 6.8) had four cores (20 individuals per pH)…

One of the most surprising results is that there was no decrease in the total amount of calcium carbonate in individuals exposed to acidified water. Indeed, individuals from lowered pH treatments had a greater percentage of calcium in their regenerated arms than individuals from control treatments, indicating a greater amount of calcium carbonate…In regenerated arms, calcium levels were greater in those organisms exposed to acidified seawater than in those held in untreated seawater. This was true for all three levels of acidified seawater…there was actually an increasing rate of calcification with lowered pH. Calcium carbonate in established arms was also affected by lowered pH. At pH 6.8, calcium levels increased and at pH 7.7 and pH 7.3, calcium levels were equal to the control indicating that A. filiformis actively replaced calcium carbonate lost by dissolution.

Rates of oxygen (O₂) uptake (as a measure of metabolic rate), or MO2, were significantly greater at reduced pHs (7.7, 7.3 and 6.8) than in controls (pH 8); However, MO2 was not significantly different between the three lowered pH treatments. Increased rates of physiological processes that require energy are paralleled by an increase in metabolism; this relationship is seen with growth and metabolism here in our results.

Seawater acidification stimulated arm regeneration. After the 40-day exposure, the length of the regenerated arm was greater in acidified treatments than in the controls…This increased rate of growth coincided with increased metabolism. Regeneration was not affected by the number of arms removed, nor was there a significant difference in any of the physiological parameters measured as a result of having two arms regenerating instead of one. The ability to regenerate lost arms faster meant a reduction in the length of time animal function (e.g. burrow ventilation and feeding) was compromised by reduced arm length.

Interestingly, even at high levels of hypercapnia (the 6.8 pH treatment crosses the threshold into acidic water, i.e. pH<7.0) investigated here, no mortality was observed.

These results change the face of predictions for future marine assemblages with respect to ocean acidification. Whereas it was previously assumed that all calcifiers would be unable to construct shells or skeletons, and inevitably succumb to dissolution as carbonate became undersaturated, we now know that this is not the case for every species.

Riebesell (2004):

coccolithophores may benefit from the present increase in atmospheric CO2 and related changes in seawater carbonate chemistry…increasing CO₂ availability may improve the overall resource utilization of E. huxleyi and possibly of other fast-growing coccolithophore species…if this provides an ecological advantage for coccolithophores, rising atmospheric CO₂ could potentially increase the contribution of calcifying phytoplankton to overall primary production…a moderate increase in CO₂ facilitates photosynthetic carbon fixation of some phytoplankton groups…CO₂-sensitive taxa, such as the calcifying coccolithophorids, should therefore benefit more from the present increase in atmospheric CO₂…

Iglesias-Rodriguez et al (2008) confirmed Riebesell findings experimentally, concluding that coccolithophores, which account for a third of all marine calcium carbonate production, flourish and calcify much better at higher levels of CO₂:

Here, we present laboratory evidence that calcification and net primary production in the coccolithophore species Emiliania huxleyi are significantly increased by high CO2 partial pressures. Field evidence from the deep ocean is consistent with these laboratory conclusions, indicating that over the past 220 years there has been a 40% increase in average coccolith mass. Our findings show that coccolithophores are already responding and will probably continue to respond to rising atmospheric CO2 partial pressures, which has important implications for biogeochemical modeling of future oceans and climate.

Richardson and Gibbons (2008):

…no observed declines in the abundance of calcifiers with lowering pH have yet been reported…the role of pH in structuring zooplankton communities in the North Sea and further afield at present is tenuous.

Vogt et al (2008), experimenting with atmospheric concentrations up to three times current levels,

…the ecosystem composition, bacterial and phytoplankton abundances and productivity, grazing rates and total grazer abundance and reproduction were not significantly affected by CO₂ induced effects.

Gutowska (2008) subjected cuttlefish larvae to CO₂ concentrations of 6000 ppm (sixteen times current CO₂ concentration), at pH 7.1. Results:

No differences in soft tissue growth performance were measured between cuttlefish incubated at ~4000 and ~6000 ppm CO₂ and controls…Standard metabolic rates of cuttlefish exposed acutely to ~6000 ppm CO₂ showed no significant increase or decrease over time…there were no significant differences between the mantle lengths of control cuttlefish and those incubated at 6000 ppm CO₂…Interestingly, in the ~6000 ppm CO₂ growth trial, the CO₂ incubated animals incorporated significantly more CaCO₃ [calcium carbonate] into their cuttlebones than did the control group…Functional control of the cuttlebones (i.e. buoyancy regulation) did not appear to be negatively affected by low pH conditions.

Chave, K.E., Suess, E., Calcium carbonate saturation in seawater: effects of dissolved organic matter, Limnology and Oceanography 1970, Vol. 15, Issue 4

Gehlen, M., Biogeochemical impacts of ocean acidification – emphasis on carbonate production and dissolution. CIESM workshop: Impacts of acidification on biological, chemical and physical systems in the Mediterranean and Black Seas, Menton, 1 – 4 October 2008.

Gutowska, M.A., Pörtner, H.O. and Melzner, F., Growth and calcification in the cephalopod Sepia officinalis under elevated seawater pCO2. Marine Ecology Progress Series (2008) 373: 303-309.

Iglesias-Rodriguez, M.D., et al., Phytoplankton Calcification in a High-CO2 World, Science 18 April 2008: 336-340

Irving, L., The carbonic acid-carbonate equilibrium and other weak acids in sea water, Journal of Biological Chemistry, 1925

Riebesell, U., Effects of CO2 enrichment on marine phytoplankton. Journal of Oceanography (2004) 60: 719-729.

Richardson, A.J. and Gibbons, M.J., Are jellyfish increasing in response to ocean acidification? Limnology and Oceanography (2008) 53: 2040-2045.

Vogt, M., Steinke, M., Turner, S., Paulino, A., Meyerhofer, M., Riebesell, U., LeQuere, C. and Liss, P., Dynamics of dimethylsulphoniopropionate and dimethylsulphide under different CO2 concentrations during a mesocosm experiment. Biogeosciences (2008) 5: 407-419.

Wangersky, P.J., The control of seawater pH by ion pairing, Limology and Oceanography, Jan 1972.

Wilson, R. W., Millero, F. J., Taylor, J. R., Walsh, P. J., Christensen, V., Jennings, S. M., Grosell, M., Contribution of Fish to the Marine Inorganic Carbon Cycle. Science 16 January 2009: Vol. 323. no. 5912, pp. 359 – 362

Wood, H.L., Spicer, J.I., and Widdicombe, S., Ocean acidification may increase calcification rates, but at a cost. Proc Biol Sci. 2008 August 7; 275 (1644): 1767–1773.

The Royal Society, Ocean acidification due to increasing atmospheric carbon dioxide, 2005