Overlooked your response sorry.

Here is a better description

“Phytoplankton are the base of the marine food chain, providing food for little sea animals called zooplankton, which in turn feed fish and other creatures. Any change in phytoplankton numbers alters the ocean food chain.

The computer model showed that during El Niño periods, warm waters from the Western Pacific Ocean spread out over much of the ocean basin as upwelling weakens in the Eastern Pacific Ocean. Upwelling brings cool, nutrient-rich water from the deep ocean up to the surface. When the upwelling is weakened, there are less phytoplankton, making food more scarce for zooplankton that eat the ocean plants.

During La Niña conditions as in 1998, the opposite effect occurs as the easterly trade winds pick up and upwelling intensifies bringing nutrients like iron to the surface waters, which increases phytoplankton growth. Sometimes, the growth can take place quickly, developing into what scientists call phytoplankton “blooms.”

In a study published in the January 2005 issue of Geophysical Research Letters, Wendy Wang and colleagues at the University of Maryland Earth System Science Interdisciplinary Center, College Park, Md., found that changes in phytoplankton amounts due to El Niño and La Niña not only affect the food chain, but also influence Earth’s climate.”

http://www.nasa.gov/vision/earth/lookingatearth/plankton_elnino.html

What we are observing is not only the perturbation of the photic region in a local event,this also occurs globally eg in the arctic and antarctic and in semi enclosed basins.

First let us observe a natural law. Living organisms operate in what is described as far from equilibrium.

eg in “Theoretical Biology” E. Bauer confidently stated that biology was not applied physics or chemistry. He also stated that “all special laws, which would be revealed in certain fields of biology would display the general laws of motion, appropriate to living matter” [4, p.8]. The urgent problem of theoretical biology was, according to E. Bauer, the development of general laws of motion for living matter.

“Only living systems never reach equilibrium, for they constantly work against stability” [4, p.43]. According to Bauer, the source of free energy(or” the work of structuring forces” and “structural energy” are the synonyms) is the nonequilibrium of molecular structure of living matter

What is the source of the nonequilibrium of “living matter”? Firstly it is the activation of molecules of food caused by levelling processes. Energy of these molecules maintains nonequilibrium (here the molecules of living matter in “active, deformed state” are considered [4, p.127]. However, the unavoidable result of metabolism is, according to E. Bauer, the lowering of the potential of free energy of nonequilibrium. “The more intensive metabolism is, the higher rates of the free energy depletion are. This free energy of living matter exists because of the deformed nonequilibrium structure of its molecules” [4, p.129]. “During assimilation the structural energy of a system can be used. This energy is necessary for the reconstruction of nonliving substance” [4, p.144].The total amount of energy that can be assimilated is limited. This amount of energy is species-specific parameter of organism (Rubner constant) (see [4, p.131; 37] and is “proportional to the free energy of an ovicell” [4, p.130].

This means that the problem of the source of living matter’s nonequilibrium cannot be reduced to the possibility of nonequilibrium’s replenishment with free energy of food. Another source of nonequilibrium is required. The utilization of this source should regulate the organism’s ability to make up for free energy losses with food. Concerning deeper nonequilibrium one can propose several possibilities of its origination in organism. They might be the following:

- the law of nonincrease (or conservation) of structural energy and transfer of it from generation to generation;

- the possibility of external replenishment of structural energy during the origination or fertilization of the ovicell in addition to an explanation of Bauer’s theory, according to which fetal cells, possessing maximum initial potential, originate due to dying or, in other words, dissimilation of the body tissues” [4, p. 144].

- to reject the idea of the impossibility of structural energy replenishment during the life period, and then to find the ways of such replenishment, for instance, the mechanism of structural energy assimilation by autotrophs and its farther spreading in the biosphere through the food chains.

In the second and third proposals, and in other cases, allowing the structural energy replenishment, the question about the sources of such replenishment remains.
When considering the problem of understanding the stable nonequilibrium principle, another problem arises, that is the search for the sources of nonequilibrium. This problem is connected with time, its flow and becoming. One of the possible hypotheses dealing with this problem’s consideration consists of the substantial time construction [28; 29].

In modeling of biological systems that oscillate from state to state seemingly random in appearance, are actually showing self organization of the ecologic community to variation of resource and both evolution and devolution.

Yakushev, E.V. and Mikhailovsky, G.E., 1995. found biological attenuation (modulation)of ph levels during phytoplankton blooms.

The dramatic increase in atmospheric carbon dioxide (CO2) concentrations observed during the past decades can be associated with the natural climatic oscillations or/and with anthropogenic influence. Concern about the potential role of CO2 as a “greenhouse gas” had led to necessity of investigation of this element global biogeochemical cycle peculiarities. The oceans play an important role in this cycle, containing large reservoirs of dissolved inorganic carbon as gaseous CO2(g), bicarbonate (HCO3-) and carbonate (CO32-) ions. Because of it, the ocean ultimately determines the atmosphere’s CO2 content (Siegenthaler, Sarmiento, 1993). Information about the CO2 system behavior can be obtained by investigations of the processes which affect the carbonate system parameters distribution and variability.

One of the most interesting aspect of this problem is the role of marine biota. When we speak about this, we consider the aggregation of gaseous CO2 into particulate organic carbon (POC), which can be transported into the deeper layers, sedimented on the bottom and thereby excluded from the global cycle and also of the POC mineralization and respiration processes (so-called “soft tissue pump” (Gruber et al, 1996) . However during the phytoplankton bloom the decrease of CO2 is accompanied by disbalance of the system which can initialize the activity of the other “pumps”: (“solubility pump” – ocean-atmosphere CO2 exchange, and “carbonate pump” – and formation dissolution of calcium carbonates).

During the bloom the consummation of gaseous CO2 by phytoplankton leads to the disbalance of the carbonate system equilibrium. This results in increased pH values and therefore in changes in the carbonate system balance toward increases in carbonates and additional decreases in gaseous CO2. In other words, during the bloom the upper layer gaseous carbon dioxide decreases for two reasons – consummation of the organic matter synthesis and transformation from gaseous CO2 to CO3, initiated by pH changes.

In this case during the bloom period one can observe decrease of TCO2 and dissolved CO2 while the value of carbonate alkalinity (AlkC) remains constant to fulfill the sea water electricity neutrality equation (Millero, 1995, Dickson, 1992).

eg http://i255.photobucket.com/albums/hh133/mataraka/Image62.gif

The ocean is not an empty “beaker” 65% of the biosphere lives in or under the ocean.

I think I see the source of your confusion…the H-H equation gives you pH at equilibrium. So you need to use the equilibrium calculations to determine [HCO3-] and [CO2] (or [H2CO3]) before you use the H-H equation. It doesn’t seem like you are doing the equilibrium calculations before you plug in your concentrations and just trying to rationalize what will happen. The other complication is that at a pH~8.1 you are right between the pKa of Ka1 (for H2CO3) and Ka2 (for HCO3-), so there is a significant contribution from each equilibrium to the concentrations of each species in solution. By focusing only on Ka1, you are neglecting the effects of changes in H+ on the concentrations in the second equilbrium equation. It really helps to do the math instead of shooting from the hip. You would save yourself a lot of time and understand things a lot better!

Your calculation was fine, but your reasoning of the effects of an increase in CO2* on the rest of the system was off, having not performed the calculations.

Thanks, Chris. Maybe I’ll see if I can make the calculations using H2CO3 as the input, instead of specifying pH then calculating the species – as it appears you might have done? – “you’ll get these concentrations for DIC species at pHsws = 8.05, 7.95, 7.85″

And, again just shooting from the hip, another one of my problems is that looking at your pH calculations, they are all too low, at least if you use the H.-H. calculation as per human acid-base chemistry where [H2CO3] can be ignored, change in [CO2] is often the culprit/driver, and:

pH = 6.1 + log [HCO3]/[dissolved CO2]

But I’ll give it a rest!

Your calculation for of the ratio K1/K2 = [HCO3-]^2/{[H2CO3][CO3=]} is fine. I think the point that is confusing you is that, since the concentration of HCO3- is so high an increase of X in [H2CO3] results in only a proportionally small increase in HCO3-.

For example, @ 35 ppt, 1 atm, 25 C, 2300 ueq/kg TA (standard sea water) you’ll get these concentrations for DIC species at pHsws = 8.05, 7.95, 7.85 (K1 and K2 from Dickson and Millero, 1987; K2 for HSO4- from Dickson1990):

All conc. in umol/kg
pHsws = 8.05
CO2* = 10.79
HCO3- = 1761.60
CO3= = 219.03

pHsws = 7.95
CO2* = 14.28
HCO3- = 1851.07
CO3= = 182.82

pHsws = 7.85
CO2* = 18.73
HCO3- = 1928.75
CO3= = 151.31

For all sets you get the same K1/K2 = 1312.71. From pHsws = 8.05 to pHsws = 7.85 the concentration of CO2* increases by only 7.94 umol/kg while HCO3- increases by 167.14 umol/kg. However, CO2* increases by 74% while HCO3- only increases by 9%.

Your calculation was fine, but your reasoning of the effects of an increase in CO2* on the rest of the system was off, having not performed the calculations.

Well, there’s really been a whole lot of discussion about nothing here hasn’t there. The chemistry works just as expected, and is easily replicated at whatever set of conditions one likes. It’s a bit perplexing that it’s taken so much ‘debate’ to get to this point, but at least we got here.

Also, @ Alan Wilkinson: good on ya. We need more folks like yourself.

Best,

Chris

Thanks, Pete, I might be wrong. But right now I don’t see how “the math” avoids the math problem that K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-] presents, given that at pHsoln > 6.1, adding H2CO3 results in more HCO3 formed net than H2CO3 remains after its addition – HCO3 increases more than H2CO3 – since at pHsoln > 6.1, H2CO3 is more than half dissociated, and likewise for any more added H2CO3, making the net increase in [H2CO3] necessarily more “neglible” than the increase in [HCO3]. So that to keep K constant, [CO3] must increase.

This is a math problem, too. Maybe these “neglibles” don’t really count in calculating or describing [CO3], but K says they do. Instead, do we just ignore K?

So an increase in acidity has 400 x the impact of an equivalent increase in dissolved CO2 and therefore forces carbonate lower. This is amplified further by the high degree of dissociation of H2CO3 in seawater.

Yes, I understand that this is “their” argument – “increase in acidity” forces H + CO3 to the net formation of HCO3 with a decrease in CO3 – but I don’t see how they overcome mine, that K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-] must remain constant, and when adding CO2/H2CO3 to solution at pH > 6.1, more HCO3 is formed than H2CO3 results, meaning [CO3] must increase if K is to remain constant.

Another wrinkle from http://chimge.unil.ch/En/ph/1ph67.htm, slightly modified, i.e. H3O to H3O-1 and H3O-2, and adding 1] and 2] as notations:

Both protons of Carbonic Acid, H2CO3 are weakly acidic:
1] H2CO3 + H2O = HCO3 + H3O-1 pKa1 = 6.1
2] HCO3 + H2O = CO3 + H3O-2 pKa2 = 10.3

What is the pH of a solution of carbonic acid ?

The hydrogenocarbonate ion HCO3- is amphoteric [able to both donate and receive H+ effectively], thus

pH = 1/2[pKa1 + pKa2] = [6.1 + 10.3]/2 = 8.2 [near Oceans']

independently of the concentration of Carbonic Acid!

pH doesn’t change regardless of Carbonic Acid concentration.

“Their” argument is that with the addition of CO2/H2CO3, H3O-1/”acidity” increases ~ “a lot”, causing the H3O-2 component to combine with CO3 so as to decrease [CO3], also because pKa of HCO3 = 10.3 [btw, which is nothing new to the interactions].

Still, if pH doesn’t change, “their” argument seems to make sense – increased H has to go somewhere – except that it contradicts the constancy of K, where, according to my argument, [CO3] must increase if CO2/H2CO3 is added at pHsoln > 6.1.

So what happens to the added H3O-1 instead of acting to decrease [CO3] net, which allows pH and K to remain constant, and [CO3] to increase net as per K?

I say it just forms H2O:

H3O + OH = 2H2O

In other words, I essentially don’t care about the extra “acidity”/H+ – unless it results from a source of acid other than CO2/H2CO3. I’m saying K must remain constant, so that the extra H from H2CO3 must simpy form H2O – that is, enough to keep pH constant, while allowing a net increase in CO3.

Also, imo, “their” argument also seems to state that decreasing CO2/H2CO3 in solution increases CO3.

You are confusing yourself. Use the equilibria and work out the algebra.

If you start with the values listed by Alan Wilkinson (16:15:09) and increase the amount of dissolved CO2 by 10% (by increasing [H2CO3] to 2.20e-5 M), you get an increase in [H+] to 1.79e-8 M (pH = 7.75 as opposed to the initial pH = 7.79). This is accompanied by a negligible increase in [HCO3-] (because it is so high to begin with), but also by a significant decrease in [CO3=] from 1.20e-4 to 1.09e-4. Alan is right about doing the math. Equilbrium for multiprotic acids in a buffered system can be difficult to think about without doing the math!

d( [CO3=] ) = (K1 * K2 / [H+]^2 * ( d( [H2CO3] ) – ( [H2CO3] / 3 * [H+] ) * d( [H+] )

In seawater ballpark values are:

[HCO3-] 1.86E-03
[CO3=] 1.20E-04
[H+] 1.62E-08
[H2CO3] 2.00E-05
K1 1.45E-06
K2 1.09E-09

So [H2CO3] / 3 * [H+] = 411

And K1 * K2 / [H+]^2 = 5.97

So an increase in acidity has 400 x the impact of an equivalent increase in dissolved CO2 and therefore forces carbonate lower. This is amplified further by the high degree of dissociation of H2CO3 in seawater.

This was the calculation I was going to use to show J Lo the error of his ways but instead it convinced me I should do the math next time before I open my mouth!

Simon Evans (04:42:45)

“El Nino also drastically reduced the amount of carbon dioxide this ocean region adds to the atmosphere. Unlike most parts of the world’s oceans, the equatorial Pacific is normally a major contributor to atmospheric carbon dioxide due to the carbon-dioxide-rich deep ocean waters brought to the surface here and the relatively low levels of biological activity….

I’ve added some bold! Besides which it’s rather obvious, isn’t it, that CO2-rich waters upwelling will increase the acidification pressure at surface levels and decrease the exposure of CO2 to the sea floor carbon buffer? How on earth is the observation of ENSO behaviiour supposed to answer the point that ocean floor buffering is globally a very slow process whilst near-surface CO2 absorption is developing rapidly?

Pete D (11:45:37) :

J Peden, Foinavon:

If there is still debate on this, a little General Chem…

1) H2CO3 = H+ + HCO3- with Ka1 = [HCO3-][H+]/[H2CO3] = 4.2E-7
2) HCO3- = H+ + CO32- with Ka2 = [H+][CO32-]/[HCO3-] = 4.8E-11

overall equilibrium constant, K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-]

K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-]

Pete D, try out this argument:

pKa = pH at which an Acid is exactly one half dissociated. In other words, at pKa, concentration of Acid = concentration of Conjugate Base formed from the Acid. They are “half and half”, existing in a ratio of 1:1.

pKCarbonic Acid/H2CO3 = 6.1

Therefore, at pH of solution = 6.1, [H2CO3] = [HCO3]. In other words at pH = 6.1, H2CO3 has exactly half-dissociated to produce an equal concentration of HCO3 – and it will stay exactly half-dissociated as long as pHsoln. = 6.1.

But at pHsoln. greater than 6.1, H2CO3 is more than half-dissociated. In other words, as the pH of the total solution increases, decreasing total [H+], existing H2CO3 more readily donates a proton H+, and so as to also produce more HCO3-.

Such that, [HCO3] >> [H2CO3]

Now looking at your equation, K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-]

For H2CO3 at pHsoln. > 6.1, [HCO3] > [H2CO3]

Therefore, [CO3] must increase in order to keep K constant when more H2CO3 is added to the solution, again, because any added H2CO3 at pHsoln > 6.1 will end up more than half-dissociated. Effectively, more HCO3 is added to the solution than H2CO3 at any pHsoln. > 6.1.

So for every addition of H2CO3 to a solution of pH > 6.1, in particular by increasing dissolved CO2, [CO3] must increase – in order for K to remain constant.

Therefore, in the Oceans, where pH = 8.1, addition of more dissolved CO2 must increase CO3.

Imo, once again, when more H2CO3 is added to a solution of pH > 6.1, it is simply not possible to get more net H2CO3 formed/added than HCO3 formed, because at these pH’s, H2CO3 more than half-dissociates, so more HCO3 is formed net than H2CO3 is increased.

Therefore, by equation K, CO3 must increase net to keep K constant, regardless of the “strength” of equation 2 in tending to form HCO3 from CO3 and H.

That’s what K says [to me], in solutions of H2CO3 whose pH’s are > 6.1.

“El Nino also drastically reduced the amount of carbon dioxide this ocean region adds to the atmosphere. Unlike most parts of the world’s oceans, the equatorial Pacific is normally a major contributor to atmospheric carbon dioxide due to the carbon-dioxide-rich deep ocean waters brought to the surface here and the relatively low levels of biological activity.

The researchers calculate that the amount of carbon dioxide released to the atmosphere by the equatorial Pacific during the year of El Nino conditions was 700 million metric tons of carbon less than the previous year. This is equivalent to half of the United States’ total annual carbon dioxide emissions from fossil fuel burning. ”

http://svs.gsfc.nasa.gov/stories/elnino/press.html

Simon Evans,

So, please stop making things up – because I am attempting to have a serious discussion here.

I am referring to your implication that observed ocean circulation expedites mixing to the extent of allowing the sea bed to buffer CO2 uptake at a fast enough rate, as indicated in these posts:

Steven Goddard (06:50:57) :

Secondly, as I have pointed out repeatedly, the existence of La Nina is proof of the rapid interchange of deep and shallow water in the Pacific. Where do you think the cold water came from?

The point is crucial. All discussion of rainwater falling on limestone, etc. etc., is moot if the buffer of the ocean floor is not rapidly exposed to the increasing CO2 concentration. It is not disputed that eventually the buffer would do its stuff, but if the current pace of CO2 increase exceeds the rate of the buffer then there is a change in the system, which is not discounted by the fact of atmospheric CO2 concentration having built to higher levels before at a much slower pace.

Another poster mentioned tritium traces which, as I’ve already said, indicate that ocean mixing to depth is far from ‘rapid’ on the time scales that are of concern in respect of the pace of acidification. In terms of CO2 mixing, see the following paper:

http://www.sciencemag.org/cgi/content/abstract/305/5682/367

– which found that 50% of anthropogenic CO2 is held in the top 400 m despite this making up only about 10% of the ocean volume. Most of the deep waters, especially those 1 km + deep, have yet to receive any anthropogenic CO2.

Waving your hand at ENSO upwelling doesn’t cut it. You might want to believe that the oceans mix fast enough for the buffering to keep pace, but the evidence tells us this is not so.

“As Chris J has said above, anyone who’s followed this thread will be able to figure out who has been talking nonsense, so I rather think it pointless for either of you to keep making the claim.”

The exasperation level is getting high here, and shows no sign of resolution. And yet this dispute, or a large part of it, could easily be resolved if there were an acceptable referee who could make a ruling on it. How about an ad hoc panel of presumptively neutral and high-status chemists + geologists, chosen at random from officials or past officials of their scientific societies? This could be useful in resolving–or at least clarifying–other disputes on this site, and maybe other sites too.

“Here we analyse a 13-year time series of oceanic carbon dioxide measurements from station ALOHA in the subtropical North Pacific Ocean near Hawaii4, and find a significant decrease in the strength of the carbon dioxide sink over the period 1989–2001. We show that much of this reduction in sink strength can be attributed to an increase in the partial pressure of surface ocean carbon dioxide caused by excess evaporation and the accompanying concentration of solutes in the water mass. Our results suggest that carbon dioxide uptake by ocean waters can be strongly influenced by changes in regional precipitation and evaporation patterns brought on by climate variability.”

It appears that the “calculated” ph (although I am still in the dark as to exactly how ph was “calculated” by HOT from 1989 – 2002) may have been too high, influenced by natural variability.
I have some some documentation on how ph is “calculated” at least in 2006:

http://hahana.soest.hawaii.edu/hot/methods/dicalk.html

“(DIC) measured using a Single Operator Multi-parameter Metabolic Analyzer (SOMMA) … Total (titration) alkalinity (Talk) was determined using the modified Gran titration method… ”

Apparently it is possible to calculate a ph from basically from those two values. Normalizing and buffer factors are also required, and it seems all this gets quite complex and maybe a tad arbitrary. Of course,

http://www.bios.edu/Labs/co2lab/research/IntDecVar_OCC.html#tab2

“The anticipated rate of change surface ocean CO2 due to the accumulation of anthropogenic CO2 in the atmosphere and the surface ocean buffer factor (assuming that near-surface waters in the subtropical gyres have residence times long enough to equilibrate entirely with the anthropogenic perturbation in atmospheric CO2) can be theoretically calculated.”

I still don’t think I am way off on my suspicions that the HOT ph graph reflects “predicted” change. Set out to prove something and sooner or later you’ll find a way to do it.