Carbon and Carbonate

Guest Post by Willis Eschenbach

I’ve spent a good chunk of my life around, on, and under the ocean. I worked seasonally for many years as a commercial fisherman off of the western coast of the US. I’ve frozen off my begonias setting nets in driving sleet up in the Bering Sea. I’m also a blue-water sailor with a Pacific crossing under my belt, and a surfer, and both a sport and a commercial diver.

Plus I’m eternally curious, so I have read about and studied the ocean all my life.

Based on both my experience and my knowledge, I have written a number of posts regarding what I see as the astounding responsiveness and adaptability of the creatures that live in the ocean (links below). I’ve said repeatedly that the minor neutralization of the oceans due to more atmospheric CO2 was meaningless, that the oceanic creatures would not be bothered by such a change.

So I laughed out loud when I saw the latest study in Science magazine, which involves coccolithophores. These are calcifying plants, which form the most delicate and intricate skeletons out of calcium carbonate which they precipitate from the seawater.

coccolithoporesCoccolithophore. Image Source

Puts me in mind of the old song, “A wheel in a wheel, way up in the middle of the air”. Beautiful.

The study says that coccolithophore abundance in the North Atlantic has increased by about ten-fold in recent years. In other words, instead of finding coccolithophores in ~ 2% of their plankton trawls, they now find them in about 20% of the trawls. They did a multi-variable analysis, and their conclusion was that increases in CO2 are a main cause of the increase in coccolithophore abundance. The study is entitled “Multidecadal increase in North Atlantic coccolithophores and the potential role of rising CO2”, paywalled here.

This study is important because the state of the ocean is one of the latest targets of the serially failed climate doomcasters. The alarmists’ claim is that the slight neutralization of the ocean will make it harder for calcifying organisms to form their calcium shells, substrates, and skeletons. However, the study shows that for coccolithophores, this is not the case. From the magazine:

Passing an acid test

Calcifying marine organisms will generally find it harder to make and maintain their carbonate skeletons as increasing concentrations of atmospheric CO2 acidify the oceans. Nevertheless, some types of organisms will be damaged more than others, and some may even benefit from higher CO2 levels. Coccolithophores are a case in point, because their photosynthetic ability is strongly carbon-limited. Rivero-Calle et al. show that the abundance of coccolithophores in the North Atlantic has increased by up to 20% or more in the past 50 years (see the Perspective by Vogt). Thus, this major phytoplankton functional group may be able to adapt to a future with higher CO2 concentrations.

Science, this issue p. 1533; see also p. 1466

Abstract

As anthropogenic carbon dioxide (CO2) emissions acidify the oceans, calcifiers generally are expected to be negatively affected. However, using data from the Continuous Plankton Recorder, we show that coccolithophore occurrence in the North Atlantic increased from ~2 to more than 20% from 1965 through 2010. We used random forest models to examine more than 20 possible environmental drivers of this change, finding that CO2 and the Atlantic Multidecadal Oscillation were the best predictors, leading us to hypothesize that higher CO2 levels might be encouraging growth. A compilation of 41 independent laboratory studies supports our hypothesis. Our study shows a long-term basin-scale increase in coccolithophores and suggests that increasing CO2 and temperature have accelerated the growth of a phytoplankton group that is important for carbon cycling.

I’ve said it before, and I’ll say it again. Regarding the ocean I have a rule of thumb;

In the ocean, chemistry doesn’t rule life—instead, life rules chemistry

And this rule of thumb has a corollary:

Life is sneaky and will find a way to grow through stone

This is a perfect example. Life has a habit of making chemical reactions go in unexpected directions and at speeds unseen anywhere outside of living creatures. Despite the chemical reality of increased CO2 making the precipitation of CaCO3 slightly harder, the coccolithophores pay little attention to how steep the energetic hill is. They just keep cranking, and in this case, even speed up.

I find this very important because according to the study, coccolithophores are estimated to be responsible for about half of all precipitation of calcium carbonate (CaCO3) in the ocean. Half. That’s a lot.

And following that chain of effects to its next logical step, the rate at which CO2 is precipitated from the ocean as CaCO3 has an effect on the amount of neutralization of the ocean due to increased atmospheric CO2.

Paraphrasing Mark Twain, my conclusion is that the rumors of the oceans’ death from increased CO2 are greatly exaggerated.

My best wishes to all of you,

w.

My Usual Request: If you disagree with me or anyone, please quote the exact words you disagree with. I can defend my own words. I cannot defend someone’s interpretation of my words.

My Other Request: If you think that e.g. I’m using the wrong method on the wrong dataset, please educate me and others by demonstrating the proper use of the right method on the right dataset. Simply claiming I’m wrong doesn’t advance the discussion.

Previous Posts On This Topic:

The Electric Oceanic Acid Test 2010-06-19

I’m a long-time ocean devotee. I’ve spent a good chunk of my life on and under the ocean as a commercial and sport fisherman, a surfer, a blue-water sailor, and a commercial and sport diver. So I’m concerned that the new poster-boy of alarmism these days is sea-water “acidification” from…

The Reef Abides 2011-10-25

I love the coral reefs of the planet. In my childhood on a dusty cattle ranch in the Western US, I decorated my mental imaginarium of the world with images of unbelievably colored reefs below white sand beaches, with impossibly shaped fish and strange, brilliant plants. But when I finally…

The Ocean Is Not Getting Acidified 2011-12-27

There’s an interesting study out on the natural pH changes in the ocean. I discussed some of these pH changes a year ago in my post “The Electric Oceanic Acid Test“. Before getting to the new study, let me say a couple of things about pH. The pH scale measures…

The Reef Abides … Or Not 2014-07-06

I’ve written a few times on the question of one of my favorite hangouts on the planet, underwater tropical coral reefs. Don’t know if you’ve ever been down to one, but they are a fairyland of delights, full of hosts of strange and mysterious creatures. I’ve seen them far from…

pH Sampling Density 2014-12-30

A recent post by Anthony Watts highlighted a curious fact. This is that records of some two and a half million oceanic pH samples existed, but weren’t used in testimony before Congress about ocean pH. The post was accompanied by a graph which purported to show a historical variation in ocean…

A Neutral View of Oceanic pH 2015-01-02

Following up on my previous investigations into the oceanic pH dataset, I’ve taken a deeper look at what the 2.5 million pH data points from the oceanographic data can tell us. Let me start with an overview of oceanic pH (the measure of alkalinity/acidity, with neutral being a pH of…

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Jimmyy
January 30, 2016 8:12 pm

Ezekiel 1:4. UFOs in the Bible.
[??? .mod]

a happy little debunker
Reply to  Jimmyy
January 30, 2016 8:38 pm

I too, want to believe – but, gosh darn it – Chris Carter, just keeps making it harder and harder.

Reply to  Jimmyy
January 31, 2016 4:49 am

Ezekiel saw the wheel;
Way up in the middle of the air.
Now Ezekiel saw the wheel in a wheel;
Way in the middle of the air. . .

—Trad.

Sad Lassie
Reply to  L. E. Joiner
January 31, 2016 5:57 am

And there was me thinking it might be a circle in a spiral, a wheel within a wheel … and fretting that WE had ‘Windmills in his mind”.

AndrewZ
Reply to  Jimmyy
January 31, 2016 6:50 am

.mod, the song that Willis refers to in his post is an old folk song about the Book of Ezekiel, in which Ezekiel has some very strange visions. Jimmyy is referring to the fact that some UFO enthusiasts have suggested that Ezekiel was really seeing alien spaceships.

Berényi Péter
Reply to  AndrewZ
January 31, 2016 11:39 am

Puts me in mind of the old song, “A wheel in a wheel, way up in the middle of the air”. Beautiful.

LOUIS ARMSTRONG lyrics — Ezekiel Saw The Wheel
[youtube https://www.youtube.com/watch?v=tUt7JGU9sq4&w=420&h=315%5D

Paul Westhaver
Reply to  Jimmyy
January 31, 2016 7:25 am

Mod…I think maybe Jimmyy is referring to the wheels within wheels architecture of the carbonate skeleton of the diatoms? UFO enthusiasts sometimes point to Ezekiel as “evidence” of ancestral extraterrestrial visitations.. but I am speculating.
look at this image. I chopped the “http” to suppress the image in the blog, but if you are curious…
whatshotn.files.wordpress.com/2013/07/ezekiel-14.jpg
That all being said, aren’t the ovular layers patterns a wonder to see?

Reply to  Jimmyy
January 31, 2016 8:23 am


13 The appearance of the living creatures was like burning coals of fire or like torches. Fire moved back and forth among the creatures; it was bright, and lightning flashed out of it. 14 The creatures sped back and forth like flashes of lightning.
15 As I looked at the living creatures, I saw a wheel on the ground beside each creature with its four faces. 16 This was the appearance and structure of the wheels: They sparkled like topaz, and all four looked alike. Each appeared to be made like a wheel intersecting a wheel. 17 As they moved, they would go in any one of the four directions the creatures faced; the wheels did not change direction as the creatures went. 18 Their rims were high and awesome, and all four rims were full of eyes all around.
19 When the living creatures moved, the wheels beside them moved; and when the living creatures rose from the ground, the wheels also rose. 20 Wherever the spirit would go, they would go, and the wheels would rise along with them, because the spirit of the living creatures was in the wheels. 21 When the creatures moved, they also moved; when the creatures stood still, they also stood still; and when the creatures rose from the ground, the wheels rose along with them, because the spirit of the living creatures was in the wheels.
Ezekiel 1, 13-21

Ernest Bush
Reply to  Jimmyy
January 31, 2016 5:43 pm

For the moderator: read the description of the vehicle that took Ezekiel straight to heaven. Years ago a NASA engineer read that description and concocted a workable alien space vehicle using fusion generators for the power, one for each pod using contra-rotating helicopter blades.

Ernest Bush
Reply to  Jimmyy
January 31, 2016 6:03 pm

For the moderator: The biblical reference was for the lyric Willis quoted: ” wheel within a wheel.” Ezekiel got a ride to heaven while still alive in a vehicle described in Ezekiel 1. I see Willis’s quote with respect to the photo as being right on the money.

January 30, 2016 8:15 pm

no evidence that ocean acidification [is] related to fossil fuel emissions
http://papers.ssrn.com/sol3/papers.cfm?abstract_id=2669930

Lance Wallace
Reply to  Jamal Munshi
January 30, 2016 8:39 pm

Jamal Munshi
I’ve been hugely enjoying your papers on statistical analyses of various CAGW assumptions. Would you consider collecting them, perhaps doing a guest post for Anthony? (If he approves, of course).

dennisambler
Reply to  Jamal Munshi
January 31, 2016 12:34 am

No evidence of ocean acidification.
http://quadrant.org.au/opinion/qed/2016/01/fishy-science-ocean-acidification/
“Here’s what NOAA’s Dr Shallin Busch had to say, privately, to her NOAA colleague Madelyn Applebaum on September 30 about the draft. They had been asked by the New York Times to sex it up with some specific hurts allegedly being caused by all this acidification. The editor asked,
It’s very interesting, but in order to work for us it needs to be geared more toward the general reader. Can the authors give us more specific, descriptive images about how acidification has already affected the oceans? Is the situation akin to the acid rain phenomenon that hit North America? What can be done to counteract the problem?
Dr Busch, who works for NOAA’s Ocean Acidification Program and Northwest Fisheries Science Center at Seattle, responded to Ms Applebaum:
Unfortunately, I can’t provide this information to you because it doesn’t exist. As I said in my last email, currently there are NO areas of the world that are severely degraded because of OA or even areas that we know are definitely affected by OA right now. If you want to use this type of language, you could write about the CO2 vent sites in Italy or Polynesia as examples of things to come. Sorry that I can’t be more helpful on this!”

Duster
Reply to  dennisambler
February 1, 2016 10:37 am

Scientific honesty vs. the press. Which will win, and why is the general reader in need of being alarmed?

Mark luhman
January 30, 2016 8:17 pm

Only idiots would thing the [main] driver of long term storage of CO2 would slow down with higher CO2. The logical thought would be they would accelerate the long term storage of CO2 since they have more CO2 to work with. The depth of stupidity know no bounds with educated idiots.

Robert B
Reply to  Mark luhman
January 31, 2016 12:23 am

I’ve seen this often. My G and K still have H and J between them. What am I missing? Is it voice recognition (a bit like pre-emptive testicles?)
[??? .mod]

Robert B
Reply to  Robert B
January 31, 2016 1:17 am

thing/think

Hugs
Reply to  Robert B
January 31, 2016 11:18 am

Normal sound/ finger movement based typo. -ing is both a usual ending plus g is sometimes like k as a sound.

Mark luhman
January 30, 2016 8:20 pm

main driver not may driver, although May driving in May up north when spring actually brings warm temperatures is nice.
[English is difficult for new learners: “May you drive up north with May, in order that May maying flowers in May may bring them with her for May Day in Cape May.” may be a proper sentence. .mod]

Tucci78
January 30, 2016 8:31 pm

I’ve said it before, and I’ll say it again. Regarding the ocean I have a rule of thumb;

In the ocean, chemistry doesn’t rule life—instead, life rules chemistry

And this rule of thumb has a corollary:

Life is sneaky and will find a way to grow through stone

This is a perfect example. Life has a habit of making chemical reactions go in unexpected directions and at speeds unseen anywhere outside of living creatures. Despite the chemical reality of increased CO2 making the precipitation of CaCO3 slightly harder, the coccolithophores pay little attention to how steep the energetic hill is. They just keep cranking, and in this case, even speed up.
I find this very important because according to the study, coccolithophores are estimated to be responsible for about half of all precipitation of calcium carbonate (CaCO3) in the ocean. Half. That’s a lot.
And following that chain of effects to its next logical step, the rate at which CO2 is precipitated from the ocean as CaCO3 has an effect on the amount of neutralization of the ocean due to increased atmospheric CO2.
Paraphrasing Mark Twain, my conclusion is that the rumors of the oceans’ death from increased CO2 are greatly exaggerated.

There’s the takeaway. This defines an obvious and certainly productive line of investigation which will not be pursued by the catastrophe-dependent “scientists” invested in the “consensus” precisely because your supposition is almost certain to find verification by way of such investigation.
How does one get funding to prove that there’s not only nothing the politicians need be worried about but that there’s nothing the politicians can do to affect the mechanisms’ outcomes?

Robert B
Reply to  Tucci78
January 31, 2016 12:34 am

I would appreciate a biochemist writing something on this. All I know is that organisms have enzymes that turn CO2 and water into bicarbonate rapidly with the reverse reaction being very slow, so that acid has a much less of an effect than an increase in CO2 (hence, demonstrations of the impending Armageddon use other acids rather than adding CO2/H2CO2). The acid increases the concentration of H2CO2 but because of the enzymes, the equilibrium is heavily towards formation of bicarbonate, with diffusion of CO2 to the site rate limiting.

Robert B
Reply to  Robert B
January 31, 2016 12:51 am

While I read up more on it – here is the Wikipedia entry
https://en.wikipedia.org/wiki/Carbonic_anhydrase

Reply to  Robert B
January 31, 2016 2:15 am

Robert B,
Coccoliths use bicarbonates as raw material, which makes that more bicarbonate increases production…
The main reaction is here:
http://www.noc.soton.ac.uk/soes/staff/tt/eh/biogeochemistry.html
and very interesting pages on coccoliths in general:
http://www.soes.soton.ac.uk/staff/tt/

Robert B
Reply to  Robert B
January 31, 2016 1:43 pm

Thanks, Ferdinand.
(correction to above H2CO3)

Robert B
Reply to  Robert B
January 31, 2016 1:48 pm

Ca + 2HCO3 —> CaCO3 + H2O + CO2

I might look for a better source (I’m just an anonymous commentator so I’m allowed to screw up the formula)

StephanF
January 30, 2016 8:34 pm

In order to make CaCO3, doesn’t one need carbonic acid in the first place? So maybe the increase in CO2 actually helps these creatures. Any other evidence on that?

zemlik
Reply to  StephanF
January 31, 2016 4:58 am

looking at the pretty pictures there is this which seems to say so.
http://www.co2.ulg.ac.be/peace/intro.htm

Steve in SC
January 30, 2016 8:39 pm

“Coccolithophores are a case in point, because their photosynthetic ability is strongly carbon-limited. Rivero-Calle et al. show that the abundance of coccolithophores in the North Atlantic has increased by up to 20% or more in the past 50 years (see the Perspective by Vogt). Thus, this major phytoplankton functional group may be able to adapt to a future with higher CO2 concentrations.”
Notice that these cats use the term photosynthesis. If I remember my grade school science correctly, that is where the plant gobbles up the CO2 and produces Oxygen in return. But all that CO2 can’t be in the ocean because the ocean is so warm the CO2 comes out of solution and into the atmosphere. So there can’t be an increase of carbonic acid because all the CO2 is fleeing to the atmosphere. Then again, maybe the ocean is not really warming at all and is really soaking up all the CO2 out of the atmosphere.
Color me confused.

Don K
Reply to  Steve in SC
January 30, 2016 9:54 pm

Steve,
The chemistry of Carbonates in sea water is insanely complex. I don’t remotely understand it and I wouldn’t be surprised if no one really understands it. But it’s highly probable that more CO2 in the atmosphere will result in more Carbon Dioxide being exchanged into the sea where it will presumably eventually be precipitated either organically or inorganically as Calcium Carbonate. That’ll presumably drop Calcium levels and thus make it tougher for shell forming plants and animals to form shells.
… or not.
Note that all that is temperature and pressure dependent.
And also note that, unlike say salt, Carbonate in general is less soluble in warm water than in cold.
Confusing? You bet.

RoHa
Reply to  Don K
January 31, 2016 1:21 am

“That’ll presumably drop Calcium levels and thus make it tougher for shell forming plants and animals to form shells.”
So we should be pouring milk and cheese into the oceans?

RWTurner
Reply to  Don K
January 31, 2016 10:53 am

Carbonate sedimentologists have a much better grasp on marine carbonate chemistry than the lot that has jumped onto the OA bandwagon. The OA bandwagon has some truly laughable papers, i.e. http://scrippsscholars.ucsd.edu/aandersson/content/dissolution-carbonate-sediments-under-rising-pco2-and-ocean-acidification-observations-devil, where they treat the ocean like a closed system and make other classic OA alarmist false claims.
The paper in the link, for example, estimates dissolution rates of carbonate sediments under elevated carbonic acid, which is fine. But then they go off the rail by not considering the ions being added back into to the water by this dissolution, as if they magically disappeared in a one-way chemical reaction, which is a mind boggling assumption for any scientist. Then their inexperience with marine carbonates shows (a common theme in OA paper) when they conflate carbonate sediments with the living and growing shells of marine organisms.
Any carbonate sedimentologist would tell you that the shells of the living organisms cannot be treated the same as broken shell fragments comprising the sediments left behind from these creatures. This is because almost all living organisms have a nifty trick called biomineralization control. With this nifty trick, organisms have been precipitating mineral polymorphs for about one billion years in conditions that these precipitates would not form naturally.
Organisms use organic compounds, i.e. mucus, to facilitate the creation of a mosaic network of their preferred mineral polymorph and organic material such as chitin, as well as for protection from biofouling and low pH upwellings. When the organisms die, this biomineral control ceases, the organic materials within the shells are destroyed, and the shells are then subject to a substantially heightened chance for dissolution. In many cases, this dissolution is facilitated by other organsisms that produce in situ acids much more aggressive than carbonic acid, i.e. red algae.
The dissolution of these carbonate sediments, no longer protected by the biologic processes that created them, is the ion supply for the next generation of marine calcifiers. If you increase dissolved CO2 and thereby H2CO3, it will be the carbonate sediments that react first in order to reestablish equilibrium, and there are enough sediments to provide the sea water with all the salts it needs. Furthermore, increased atmospheric CO2 will cause higher rates of carbonate dissolution on land, increasing dissolved salt load delivered to the sea via rivers.

Reply to  Don K
January 31, 2016 3:20 pm

RWT, thanks. I vaguely knew marine organisms shaped their environment, but did not appreciate biomineralization control. Something to study up on. And another soundbite in the global warming political wars.

Reply to  Steve in SC
January 31, 2016 2:30 am

Steve in SC,
There is more CO2 in different forms in the oceans than in the atmosphere. In the upper few hundred meters (the “mixed” layer) in close contact with the atmosphere, the total inorganic carbon content is ~1000 GtC, in the atmosphere around 800 GtC.
The change in CO2 solubility is about 16 ppmv/°C in equilibrium (Henry’s law). The ocean surface warming since the LIA is about 0.8°C, that is good for ~13 ppmv increase. The real increase was about 110 ppmv. That means that the main CO2 driving force was from the atmosphere into the ocean surface.
The ~30% CO2 increase in the atmosphere did increase the free (gaseous) CO2 level in the ocean with 30% per Henry’s law, but free CO2 is only 1% of all inorganic carbon in ocean water. Due to ocean chemistry, the rest of the carbon species (bicarbonates and carbonates) only increased with 3%. That is the Revelle/buffer factor.
As that is mostly bicarbonates and the coccoliths use bicarbonates as raw material, they show more growth…

Reply to  Steve in SC
January 31, 2016 12:08 pm

The poles are cold and the Artic has a lot of open cold sea water in the summer. The heated water is down where el Nino resides.

Richard Petschauer
January 30, 2016 8:41 pm

Is this one of the reasons that CO2 concentration in the atmosphere is growing at only about one half of the rate that emissions increase (about 0.5% per year vs. 1%).

eyesonu
January 30, 2016 9:17 pm

That pic of a Coccolithophore looks like it could be pretty tasty if you could get it to grow to the size of a gumball. Would it be crunchy and fizzy on the outside and chewy on the inside? Yummy.

Don K
Reply to  eyesonu
January 30, 2016 9:40 pm

Crunchy might be a bit of an understatement. It’d likely break your teeth. There are probably exceptions, but in general, the practice when dealing with marine critters with Calcium Carbonate shells — clams, oysters, mussels, snails — is to somehow extract the soft parts for dinner and to discard the shells.

davideisenstadt
Reply to  Don K
January 30, 2016 11:16 pm

tums.

StephanF
January 30, 2016 9:51 pm

To Steve: There is a balance with regard to the partial pressure of CO2 in the atmosphere, the temperature of the ocean water and the dissolved CO2 in the ocean. So, yes, if we increase the temperature of the ocean and don’t add CO2 from other sources to the atmosphere, then CO2 would escape from the ocean’s top surface and increase atmospheric concentrations of CO2.
If the temperature of the oceans were kept constant but atmospheric CO2 would increase due to other sources, then the ocean would absorb some of the CO2. If the oceans would warm up at the same time, then it depends on the partial pressure of CO2 in the atmosphere and the solubility of CO2 in water at that temperature.
The solubility of CO2 in water goes pretty linear with partial atmospheric pressure, i.e. with atmospheric concentration. The temperature coefficient is negative and non-linear. The approximate linear coefficient at 25C is about -5% per degree C for the solubility.
If we change the ocean temperature by +1C then the atmospheric CO2 would rise by 5% to achieve equilibrium (given an infinite ocean volume), did I do this right?
Regards,
Stephan

Nimrod
January 30, 2016 10:04 pm

Seems these researchers have discovered that if you mix more CO2 into water you will stimulate plants that use photosynthesis and calcification. I nominate them for the Noble prize in chemistry! They are true geniuses. Perhaps these organisms will turn out to be the saviours of the Planet?

Dudley Horscroft
January 30, 2016 10:14 pm

If they keep on precipitating Calcium Carbonate, and the precipitation increases with increased Carbon Dioxide, where are they getting the Calcium from? Is the sea an ocean of Calcium Hydroxide? [Or is the ocean a sea of Calcium Hydroxide?]

StephanF
Reply to  Dudley Horscroft
January 30, 2016 10:26 pm

Or it is this way: increase of CO2 in the ocean increases the solubility of Ca by forming Ca-bicarbonate thus increasing the bioavailability of Ca for the coccolithophore!

Mike McMillan
Reply to  Dudley Horscroft
January 30, 2016 11:34 pm

Regardless, they must be stopped.

Reply to  Dudley Horscroft
January 31, 2016 7:37 am

The sea has a virtually unlimited amount of sodium, calcium, and magnesium chlorides. Sodium chloride (ordinary salt) of course predominates. They come from weathering of andesitic continental rocks, the most common of which is the feldspar group. These ocean minerals are constantly replenished by ‘freshwater’ runoff that carries the weathering product from the continents to the sea. Coccolithophores, among other organisms, recycle them into for example limestone (calcium carbonate) and dolomite (magnesium carbonate). If tectonics pushes those seafloor strata up forming sedimentary continental rock (e.g major portions of the eaatern Alps like the Dolomitan, or the Appenines in Italy, or the Uplands in Wisconsin) then the weathering recycling is that much more direct, the eventual ocean mineral products being the oxides rather than chlorides.

Reply to  Dudley Horscroft
February 1, 2016 7:47 am

Calcium is a chemical element with symbol Ca and atomic number 20. Calcium is a soft gray alkaline earth metal, fifth-most-abundant element by mass in the Earth’s crust. The ion Ca2+ is also the fifth-most-abundant dissolved ion in seawater by both molarity and mass, after sodium, chloride, magnesium, and sulfate. Calcium

Which means there is a lot of Calcium in the oceans and more gets added every time rain hits the soil. We would never live long enough to see the oceans depleted of calcium and if we did see the oceans depleted of calcium we wouldn’t live long.

January 30, 2016 10:51 pm

The warmth of the Cretaceous period has been blamed on extremely high CO2, yet coccolithophores dominated the oceans producing the massive chalk deposits that gave the Cretaceous its name.
Another twist in keeping with your truism that life governs the oceans chemistry, when coccolithophores produce their coccoliths, they create CO2 and pump alkalinity to depth.

Gloateus Maximus
Reply to  jim Steele
January 31, 2016 8:04 am

The GCMs can’t model the Cretaceous Hot House. They need to assume preposterously high ECS to do so.

RWTurner
Reply to  Gloateus Maximus
January 31, 2016 11:25 am

Because the GCM creators are willfully ignorant of the first order control on global climate, the global tectonic cycle.
http://www.sciencedirect.com/science/article/pii/S0012821X15006081
http://openearthsystems.org/data/readings/FridaySeminars/2012-02-10-Linda-Carbonates/StanleyandHardie1998-Secular%20oscillations%20in%20the%20carbonate%20mineralogy%20of%20reef-building%20and%20sediment-producing%20organisms%20driven%20by%20tectonically%20forced%20shifts%20in%20seawater%20chemistry.pdf
No model will work if you fail to include the first order controls that bound the climate system into a specific regime. Hence, a little CO2 is predicted to cause runaway warming with no end in sight, and you should run for the hills says Chicken Little.

Gloateus Maximus
Reply to  Gloateus Maximus
January 31, 2016 1:04 pm

Yup.
CO2 isn’t even the fine tuning knob on climate, let alone its control knob.
Beyond the minimum level needed to sustain photosynthesis, CO2 is more an effect than a cause. Water vapor is the GHG that matters.

Reply to  Gloateus Maximus
February 1, 2016 1:20 pm

Yes. I should have been more clear. Models can only re-create the Cretaceous hothouse via non-sensical concentrations of CO2 that are not supported by proxy data.

mickgreenhough
January 30, 2016 10:55 pm

see theeuroprobe.org 2015 – 134 Carbon dioxide in a nutshell and why we need more not less. Mick |G
m: Watts Up With That?
To: mickgreenhough@yahoo.co.uk Sent: Sunday, 31 January 2016, 3:51 Subject: [New post] Carbon and Carbonate #yiv6309682140 a:hover {color:red;}#yiv6309682140 a {text-decoration:none;color:#0088cc;}#yiv6309682140 a.yiv6309682140primaryactionlink:link, #yiv6309682140 a.yiv6309682140primaryactionlink:visited {background-color:#2585B2;color:#fff;}#yiv6309682140 a.yiv6309682140primaryactionlink:hover, #yiv6309682140 a.yiv6309682140primaryactionlink:active {background-color:#11729E;color:#fff;}#yiv6309682140 WordPress.com | Willis Eschenbach posted: “Guest Post by Willis EschenbachI’ve spent a good chunk of my life around, on, and under the ocean. I worked seasonally for many years as a commercial fisherman off of the western coast of the US. I’ve frozen off my begonias setting nets in driving sle” | |

Hoser
January 30, 2016 11:34 pm

CO2 in the ocean is not the point. The alkalinity vastly outweighs the temporary carbonic acid produced. CO2 comes, it goes. It’s far more interesting to think about is where the alkalinity comes from. That would be a product of nitrogen fixation. What happens in N2 fixation?
http://algaeenergy.weebly.com/uploads/2/6/4/4/26444126/6178930_orig.jpg
Here the reaction appears simple, but you see acid is consumed in the process. In reality, ATP is consumed too, since breaking the N≡N triple bond requires a lot of energy. But when there isn’t any other N nutrient around, and you are the only game in town, you have some serious advantages. The energy cost is worth it.comment image
But what’s this? It claims to be the Nitrogenase catalyzed nitrogen fixation reaction too. But here they show the ATP consumption. And another thing you might notice. The end product appears to be acid. No acid consumed, but acid produced? How could that be? And where did the oxygen atoms in the water go?
The answer is in the 12 Pi. Inorganic phosphate loves to suck up protons (H+). The water molecules break the phosphdiester bond converting ATP to ADP + Pi. Pi has a pKa of 12, and certainly, the Pi will be at least HPO42- in vast excess over PO43-. And so in hydrolysis, the Pi keeps one H from water. There are 12 H+. 8 of these are shown to be attached to N, partially neutralized by 6e-. 4 H+ left. pKa2 is 6.8. And there are 12 HPO42-. In first year chemistry, you will calculate about 40% of the HPO4 is protonated to H2PO4, or 5 of the 12. This last proton comes from water, and the reaction increases alkalinity.
This is clearly not a rigorous treatment of the problem, but it should nevertheless be clear the net effect of nitrogen fixation is an increase in alkalinity, since the OH- produced tends to cause transient carbonic acid to become stable bicarbonate. The vast majority of CO2 dissolved in water is CO2 and not carbonic acid.
Then if nitrogen fixation increases alkalinity, say in the ocean, why do we have to worry about ocean acidification? I’d say CO2 has nothing to do with the problem other than being captured and stored as bicarbonate in the ocean. If alkalinity is falling, it is more likely due to less N fixation. What could cause that? An external supply of N nutrients delivered to the ocean. An obvious candidate for such a supply is agricultural run off and drainage into the ocean.
Higher atmospheric CO2 is unlikely to have any significant impact on ocean chemistry, but do look at the consequences of possible over-use of N fertilizers. Higher N nutrients will give other species an ability to grow in competition with nitrogen fixers, and thus, less nitrogen fixation will occur. Consequently, ocean pH can fall, at least until the free soluble N nutrients are used up.

Reply to  Hoser
January 31, 2016 1:18 am

I think you need to spell out
1. What nitrogen fixation process you are talking about
2. On what scale is it occurring relative to CO2 production, and also photosynthesis
3. What happens when NH3 is subsequently oxidised.

Reply to  Hoser
January 31, 2016 1:35 pm

Nitrogen fertlizers (and N from livestock and municipal waste) is primarily a near-shore problem. CO2 is everywhere. In the open ocean, micro-nutrients may be the limiting factor.

Reply to  opluso
January 31, 2016 2:26 pm

I should modify my own comment above with the fact that Nitrous Oxides from human activities could contribute to open ocean deposition (although I don’t know by how much). To quote S Mosher against myself: Think more, comment less.

Hoser
January 30, 2016 11:37 pm

Rats. The <sup> tag doesn’t work. So above, e.g. HPO4 (2-). I think you’ll figure it out.

January 30, 2016 11:47 pm

There is a fairly broad review of recent papers on this topic at CO2science here. It starts with a 2004 paper of Riebesell, in which he describes the competing effects of augmented photosynthesis vs difficulty in forming CaCO3, and says that, while emphasising that it’s too early to be conclusive:
” These findings suggest large differences in CO2-sensitivity between major phytoplankton taxonomic groups. CO2-sensitive taxa, such as the calcifying coccolithophorids, should therefore benefit more from the present increase in atmospheric CO2 compared to the non-calcifying diatoms and Phaeocystis.”
It seems that an aspect of the trade-off is that the organisms maintain a proton pump to control the pH near calcification. The pump has to work harder when ambient pH drops; on the other hand the enhanced photosynthesis makes more energy available.

michael hart
Reply to  Nick Stokes
January 31, 2016 4:01 am

I’ll agree with you there, NS.
What is also often not mentioned is that the pH is generally lower inside living cells than it is in the ocean. Therefore the organism should have to do less work to maintain internal pH as the external pH falls.

ferdberple
Reply to  Nick Stokes
January 31, 2016 6:33 am

calcium carbonate (limestone) is shell. Here is the basic chemistry.
2Ca + 2CO2 + O2 yields 2CaCO3
in other words:
calcium + carbon dioxide + oxygen yields shell (limestone).
The oceans already have plenty of calcium and oxygen. Add carbon dioxide and you will get limestone (shell).
Organisms NEED CO2 to make shell. When you increase the concentration of material on the left, it increases the concentration of items on the right. In other words, adding CO2 to the ocean will make more limestone (shell), not less.
Nature will of course use many different pathways to achieve this, and thereby lower the activation energy, but the basic chemistry remains the same.

Reply to  ferdberple
January 31, 2016 8:43 am

“Here is the basic chemistry.
2Ca + 2CO2 + O2 yields 2CaCO3”

No, there is no oxidation. And there are plenty of carbonate ions in solution, so the equilibrium
Ca++ + CO3– ⇌ CaCO3
can be shifted either way by a change in concentration. There is no need for CO2 to be supplied, and no oxidation.
Your diagram below has it right. There is a general acid-base equilibrium which you can experiment with here. Adding CO2 shifts in the acid direction:
CO2+CO3– +H2O ⇌ 2HCO3-
and ultimately
CO2 +CaCO3 +H2O ⇌ Ca++ + 2HCO3-
One added molecule of CO2 dissolves one of CaCO3. You can write with H+ intermediates, but it is a Lewis acid-base reaction, in which CO2 shares an electron pair which originates from the CaCO3. CO2 is the acid, CaCO3 the base.

mebbe
Reply to  ferdberple
January 31, 2016 9:50 am

I think proton pumps are more about maintaining gradients across a membrane and acting like a capacitor, rather than maintaining a concentration on one side or the other of a membrane. Obviously, the two are related but mitochondria membranes are studded with proton pump proteins, far removed from the outer environment. Plasma membrane pumps serve to import metabolites.

Reply to  ferdberple
January 31, 2016 10:18 am

“I think proton pumps are more about maintaining gradients across a membrane and acting like a capacitor”
There’s actual pumping to be done. The reaction
Ca++ + CO3– ⇒ CaCO3
removes the base end of he solution acid-base equilibrium (CO2 ~ HCO3- ~ CO3–), and leaves a more acid solution behind. The proton pump has to remove this acidity, else the pH will drop.

RWTurner
Reply to  ferdberple
January 31, 2016 11:37 am

Nick, there won’t be any biomineralization from photosythetic organisms without CO2 so there is a very big need for CO2 to be supplied.
Also, dissolved salts are constantly supplied via rivers, and if increased CO2 shifts equilibrium in shallow sea chemistry, salts will be supplied via sediment dissolution.

mebbe
Reply to  ferdberple
January 31, 2016 4:14 pm

Nick; “The proton pump has to remove this acidity, else the pH will drop.”
Proton pumps are ubiquitous in biology and come in different versions. Some pump with the gradient and use the energy to build ATP, some pump against the gradient and expend ATP to do so. Mitochondria re-import the protons that they expel, performing phosphorylation. It’s the relative H concentrations across the membrane that creates the gradient that is the membrane potential, rather than a specific pH in the cytoplasm. The organism would be pumping protons even if it weren’t forming a shell.

Reply to  ferdberple
January 31, 2016 6:01 pm

Every calcifying marine organism generates CO2!!
The complete formula is Ca2+ + 2HCO3− → CaCO3 + CO2 + H2O

Reply to  ferdberple
January 31, 2016 7:10 pm

“The complete formula”
And what then happens to the CO2? It’s in a buffer solution where the balance is very much on the carbonate side of HCO3-. So
Ca2+ + 2HCO3− → CaCO3 + CO2 + H2O
and
CO2 + CO3−- +H20 → 2HCO3-
yields
Ca++ + CO3– ⇒ CaCO3

Reply to  ferdberple
February 1, 2016 1:18 pm

Nick Stokes,
I am not are what you are trying to argue. But when CO2 is released by the formation of coccoliths, if it produces a partial pressure greater than the atmospheric partial pressure, CO2 will escape to the atmosphere, Simultaneously CO2 will interact with the water to from bicarbonates which are preferentially absorbed by most phytoplankton. During plankton blooms there is typically a scarcity CO2/bicarbonates to allow photosynthesis. A general overview suggests that the biosphere will control the ocean chemistry as Willis suggests. Accordingly any claims about ocean acidification thmost models that assume present and past pH is the result of an imagined equilibrium with atmospheric CO2 concentrations are woefully in adequate!

ferdberple
Reply to  Nick Stokes
January 31, 2016 6:37 am
ferdberple
Reply to  ferdberple
January 31, 2016 6:41 am

In the above diagram, adding CO2 to the water INCREASES the CaCO3 precipitated. In other words, adding CO2 makes it easier to make shell, not harder.
It is the worst kind of numbskull science to focus on the “acid” dissolving limestone. The oceans are not acidic.

Don K
Reply to  ferdberple
January 31, 2016 2:45 pm

Good chart Ferd, although someone other than me should review it. I took my last Physical Chemistry class in 1959 or 1960. May have forgotten a bit.
Two things though.
First. as RWTurner points out, organisms fixing CaCO3 may be able to accelerate reactions or even push them in reverse to some extent if doing so serves their purposes.
Second, not every reaction in the diagram takes place predominantly in the same place and same time under the same temperature, pressure and reactant concentration conditions.
That is to say if you put sea water in a flask, dump some limestone in and then add CO2 to the air in the flask, you may not replicate what will happen in nature very well.

Mike McMillan
January 30, 2016 11:50 pm
Reply to  Mike McMillan
January 31, 2016 5:10 am

Iglesias-Rodriguez is as QED as it gets. Marine calcifers love CO2-rich diets.

Louis
January 31, 2016 1:35 am

“Rivero-Calle et al. show that the abundance of coccolithophores in the North Atlantic has increased by up to 20% or more in the past 50 years”

Boy is that a vague statement. Which is it, “up to 20%,” or “more” than 20%? If more, how much more? Is it 30%, 50%, 100%, or, as Willis says, “increased by about ten-fold in recent years,” which would be about 1000%. I hope their language is more precise elsewhere in the study than in this abstract because I have no idea what they really mean. When you say “up to 20% or more,” you could mean anything from 0 to infinity.

“we show that coccolithophore occurrence in the North Atlantic increased from ~2 to more than 20% from 1965 through 2010.”

Here they say it in a different way but, again, the language is ambiguous. When they say “~2 to more than 20%,” are they saying that the increase was somewhere between about 2% and 20%? Or are they saying that cocolithophore occurrence began at 2% and increased to more than 20% during that time period? I can’t tell from the language being used.

Willis states: “The study says that coccolithophore abundance in the North Atlantic has increased by about ten-fold in recent years. In other words, instead of finding coccolithophores in ~ 2% of their plankton trawls, they now find them in about 20% of the trawls.”

I have to assume Willis got that from elsewhere in the paywalled study because the quoted abstract does not mention plankton trawls. It doesn’t even mention what the 20% refers to. Assuming Willis got it right, as he usually does, is there a way to estimate how much CO2 coccolithophores precipitate from the ocean as CaCO3? If so, how much additional CO2 are they using now compared with 1965? And how does that compare with increases in human generated CO2 during the same time period? Is it just a small fraction or a significant amount?
It seems to me that if they have increased ten-fold in recent years, that is greater than the amount CO2 has increased during those same years. At that rate, how long would they have to multiply before they entirely offset yearly increases in CO2? Could that even be possible?

Jit
Reply to  Louis
January 31, 2016 5:04 am

If the Coccolithophores appeared in 2% of trawls and now appears in 20% of trawls, that is an increase in frequency, not abundance!

Don K
Reply to  Jit
January 31, 2016 2:34 pm

“If the Coccolithophores appeared in 2% of trawls and now appears in 20% that is an increase in frequency, not abundance.”
Yes, but if you assume random sampling and no change in sampling procedures and think about it i think you’ll probably convince yourself that for SMALL percentage increases, (up to maybe 20-30%) changes in frequency of detection should track changes of abundance fairly well.

Reply to  Louis
January 31, 2016 5:17 am

There are only a few places of the oceans where they monitor the precipitation of organic and inorganic material from the surface layer into the depth. That gives a rough indication of the amounts. Besides that they monitor DIC (total inorganic carbon). pH, density, total alkalinity,… at the same places. For the latter the measurements at Bermuda:
http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf

bit chilly
Reply to  Ferdinand Engelbeen
February 1, 2016 3:02 am

a few places, just like a few trees ferdinand .
The trend line is hindcast for seawater carbonate chemistry in
Fig. 8 into the 1970s, but the actual trend in the 1970s would
likely follow the nonlinear trend of the atmospheric pCO2
record. A final caveat in showing the GEOSECS/TTO data
is that these data are adjusted (Tanhua and Wallace, 2005) to
account for measurement biases and not adjusted for seasonality,
so some caution is urged in comparing these data with
those from BATS/Hydrostation S. Notwithstanding these issues,
the trends established at BATS/Hydrostation S appear
to extend back to the early 1970s, constituting a nearly continuous
40 year record of changing seawater carbonate chemistry
and ocean acidification indicators.
i reckon that part of the conclusion gives me a full house in climateball bingo. we have hindcasting , a likely trend unsupported by evidence, adjusted data to account for measurement biases but no adjustments for seasonality (i wonder why 😉 ) yet it all adds up to a near continuous 40 year record,lol.
they can pull the other one, it has bells on it.

January 31, 2016 1:41 am

Willis:
Thankyou for the trip down memory lane!
Decades ago, when showing visitors round the lab. I would always demo. a scanning electron microscope (SEM). Commonly, I would ‘explore’ the surface of a Au-sputter-coated sample of chalk and ‘find’ a coccolithophore because they are pretty (as the SE micrograph in your essay shows).
Chalk is an important indicator of effect of elevated atmospheric CO2 concentration.
Chalk is very pure limestone (i.e. calcium carbonate) and originates from the calcite shells of marine algae which – as you say – are called coccoliths. Much calcite precipitated in warm, tropical seas during the Cretaceous Period about 100 million years ago. Subsequently, the deposits compacted and formed solid rock that comprises, for example, the White Cliffs of Dover.
Clearly, the White Cliffs of Dover demonstrate that biota had no difficulty forming shells during the Cretaceous when atmospheric CO2 levels are estimated to have been from 3.7 to 14.7 times the asserted modern pre-industrial value of 285 ppm . The precipitation of calcite was obviously immense at those elevated levels of atmospheric CO2.
It is difficult to equate the existence of the White Cliffs of Dover with assertions that a doubling of atmospheric CO2 concentration would inhibit the ability of oceanic biota to form shells.
Richard

Reply to  richardscourtney
January 31, 2016 7:46 am

Terrific comment. Makes a great soundbite.
If ocean acidification is a problem, then how did the White Cliffs of Dover form during the Cretaceous when CO2 levels were several times higher than today?

bit chilly
Reply to  ristvan
February 1, 2016 3:07 am

+1. i always look forward to richardscourtney commenting on this type of technical thread. an education in making a very good point in an interesting manner. being a bit of a cretin i often have trouble with that.

Patrick MJD
Reply to  richardscourtney
January 31, 2016 6:04 pm

Very well said Richard. But it’s not limited to the White Cliffs of Dover. Almost all of the south east and south cost of England is made from the same stuff. So the amount of biota activity to lay down such sediments was truly staggering. And with all that CO2 too!

Reply to  Patrick MJD
February 1, 2016 5:19 am

Patrick MJD:
Oh, it certainly is “not limited to the White Cliffs of Dover”. The limestone strata crosses much of southern England so, for example, forms the Cotswold Hills. And Cretaceous limestone exists in many places not only in Britain.
Richard

Gloateus Maximus
Reply to  Patrick MJD
February 1, 2016 5:49 am

The same system as the North Downs, which formation contains the White Cliffs, extends across the Channel into the Alabaster Coast of France. Similar chalk cliffs are found on Danish and German islands in the Baltic Sea. The Cretaceous Period takes its name from these layers of coccolith deposits.

January 31, 2016 1:48 am

“THE BIG WHIMPER”
Damned coccolithophores – they’ll be the death of us all.
I posted the following musings, starting on 30Jan2009.
My question: Am I correct is saying the following, and if so, approximately when will it happen?
“During an Ice Age, atmospheric CO2 concentrations drop to very low levels due to solution in cold oceans, etc. Below a certain atmospheric CO2 concentration, terrestrial photosynthesis slows and shuts down. I suppose life in the oceans can carry on but terrestrial life is done.
So when will this happen – in the next Ice Age a few thousand years hence, or the one after that ~100,000 years later, or the one after that?
In geologic time, we are talking the blink of an eye before terrestrial life on Earth ceases due to CO2 starvation.”
Regards, Allan
http://wattsupwiththat.com/2015/03/14/matt-ridley-fossil-fuels-will-save-the-world-really/#comment-1883937
I have no time to run the numbers, but I do not think we have millions of years left for carbon-based life on Earth.
Over time, CO2 is ~permanently sequestered in carbonate rocks, so concentrations get lower and lower. During an Ice Age, atmospheric CO2 concentrations drop to very low levels due to solution in cold oceans, etc. Below a certain atmospheric CO2 concentration, terrestrial photosynthesis slows and shuts down. I suppose life in the oceans can carry on but terrestrial life is done.
So when will this happen – in the next Ice Age a few thousand years hence, or the one after that ~100,000 years later, or the one after that?
In geologic time, we are talking the blink of an eye before terrestrial life on Earth ceases due to CO2 starvation.
________________________
I wrote the following on this subject on 18Dec2014, posted on Icecap.us:
On Climate Science, Global Cooling, Ice Ages and Geo-Engineering:
[excerpt]
Furthermore, increased atmospheric CO2 from whatever cause is clearly beneficial to humanity and the environment. Earth’s atmosphere is clearly CO2 deficient and continues to decline over geological time. In fact, atmospheric CO2 at this time is too low, dangerously low for the longer term survival of carbon-based life on Earth.
More Ice Ages, which are inevitable unless geo-engineering can prevent them, will cause atmospheric CO2 concentrations on Earth to decline to the point where photosynthesis slows and ultimately ceases. This would devastate the descendants of most current [terrestrial] life on Earth, which is carbon-based and to which, I suggest, we have a significant moral obligation.
Atmospheric and dissolved oceanic CO2 is the feedstock for all carbon-based life on Earth. More CO2 is better. Within reasonable limits, a lot more CO2 is a lot better.
As a devoted fan of carbon-based life on Earth, I feel it is my duty to advocate on our behalf. To be clear, I am not prejudiced against non-carbon-based life forms, but I really do not know any of them well enough to form an opinion. They could be very nice. 🙂
Best, Allan
http://wattsupwiththat.com/2009/01/30/co2-temperatures-and-ice-ages/#comment-79524
[excerpts from my post of 2009]
Questions and meanderings:
A. According to para.1 above:
During Ice ages, does almost all plant life die out as a result of some combination of lower temperatures and CO2 levels that fell below 200ppm (para. 2 above)? If not, why not? [updated revision – perhaps 150ppm not 200ppm?]
When all life on Earth comes to an end, will it be because CO2 permanently falls below 200ppm as it is permanently sequestered in carbonate rocks, hydrocarbons, coals, etc.?
Since life on Earth is likely to end due to a lack of CO2, should we be paying energy companies to burn fossil fuels to increase atmospheric CO2, instead of fining them due to the false belief that they cause global warming?
Could T.S. Eliot have been thinking about CO2 starvation when he wrote:
“This is the way the world ends
Not with a bang but a whimper.”
Regards, Allan 🙂

urederra
Reply to  Allan MacRae
January 31, 2016 10:24 am

Maybe this is what is missing in your analysis:
http://www.columbia.edu/~vjd1/carbon.htm

The Carbon Cycle
The primary source of carbon/CO2 is outgassing from the Earth’s interior at midocean ridges, hotspot volcanoes, and subduction-related volcanic arcs. Much of the CO2 released at subduction zones is derived from the metamorphism of carbonate rocks subducting with the ocean crust. Much of the overall outgassing CO2, expecially as midocean ridges and hotpot volcanoes, was stored in the mantle when the Earth formed. Some of the outgassed carbon remains as CO2 in the atmosphere, some is dissolved in the oceans, some carbon is held as biomass in living or dead and decaying organisms, and some is bound in carbonate rocks. Carbon is removed into long term storage by burial of sedimentary strata, especially coal and black shales that store organic carbon from undecayed biomass and carbonate rocks like limestone (calcium carbonate).

and…

Metamorphism of Carbonates
Some of this carbon is returned to the atmosphere via metamorphism of limestone at depth in subduction zones or in orogenic belts
CaCO3 + SiO2 -> CO2 + CaSiO3
followed by outgassing at the volcanic arc.

urederra
Reply to  urederra
January 31, 2016 10:26 am

Oh… I see your are already discussing the subject below, my bad.

AndyE
January 31, 2016 1:52 am

Never worry – Gaia will fix it.

Reply to  AndyE
January 31, 2016 2:06 am

Allan MacRae and AndyE:
Not Gaia but tectonic subduction will ‘unlock’ carbon sequestered as carbonate rocks.
All sulphur would have become sequestered in rocks long ago were it not for melting of subducted rocks then the sulphur and carbon of the melted rocks being returned to the atmosphere by volcanism.
Richard

ferdberple
Reply to  richardscourtney
January 31, 2016 6:59 am

tectonic subduction will ‘unlock’ carbon sequestered as carbonate rocks.
========================================
limestone + water + iron + heat + pressure === natural gas + iron rich rock

Reply to  richardscourtney
January 31, 2016 7:10 am

Thank you Richard for your comment; very nice to hear from you.
However, will tectonic subduction of carbonates and volcanism be of sufficient magnitude to overcome the impacts of oceanic CO2 sequestration?
My impression is that volcanism may not suffice, since atmospheric CO2 concentrations have been trending downwards for millennia, and the current CO2 spike to ~400ppm will not last, especially in a cooling world.
Atmospheric CO2 reportedly dropped as low as ~180ppm during the last Ice Age, close to an extinction event (reportedly at ~150ppm)..
https://sites.google.com/a/sheffield.ac.uk/djb-group/ecosystem-co2-starvation/joe-quirk
I suppose that as the world cools in the next Ice Age, photosynthesis (and atmospheric CO2 demand) will slow and volcanism could predominate, but it does seem a rough and risky ride for terrestrial carbon-based life on our planet.
Best, Allan
,

Reply to  richardscourtney
January 31, 2016 9:41 am

Postscript:
To be clear…
I do expect that after such a (hypothesized) low-atmospheric-CO2 extinction event, life will continue in the oceans, and some form of complex terrestrial life might ultimately establish itself over the millennia.
That extinction scenario does not give me much comfort – I prefer the terrestrial life we have now. I can also accept the slow evolutionary changes in current life forms – no issues there.
What concerns me is the BIG WHIMPER – a terrestrial-life extinction event that appears probable, and “within the blink-of-an-eye” in geologic time.
I confess to a strong emotional prejudice in favour of carbon=based life on Earth, and hope it will continue for many millions of years to come.

Reply to  richardscourtney
February 1, 2016 6:09 am

Allan MacRae:
Thankyou for your clarification. You say

I suppose that as the world cools in the next Ice Age, photosynthesis (and atmospheric CO2 demand) will slow and volcanism could predominate, but it does seem a rough and risky ride for terrestrial carbon-based life on our planet.

It has always been “a rough and risky ride for terrestrial carbon-based life on our planet” as e.g. the mass extinctions at the K/T boundary demonstrate.
We are in a warm phase of an Ice Age now. The warm phase is very likely to end with return to glacial conditions. And whatever future generation is confronted with that transition will have real and serious problems; not imaginary ones like AGW.
Richard

Reply to  AndyE
January 31, 2016 5:20 am

Or change it.

January 31, 2016 2:36 am

Willis,
Again nice read… In fact no wonder that coccoliths have no problem with adapting to increased CO2 levels, as they evolved in the Cretaceous with much higher CO2 levels in atmosphere and oceans. Much of that CO2 was disposed by coccoliths as can be seen in the many thick carbonate layers all over the world like the white cliffs of Dover (UK) and France (Normandy).
With many new generations each year, no problem to adapt to the ancient CO2 levels again…

Reply to  Ferdinand Engelbeen
January 31, 2016 2:53 am

Strange. I twice made posts which said that (with reference, link and data) but both vanished (possibly in the bin).

Alex
Reply to  richardscourtney
January 31, 2016 3:34 am

I’m having some problems with posting innocuous comments too. (on the previous thread). Perhaps there is a different moderator..

Alex
Reply to  richardscourtney
January 31, 2016 3:35 am

problem somewhere

Alex
Reply to  richardscourtney
January 31, 2016 3:36 am

tried twice on another thread

Alex
Reply to  richardscourtney
January 31, 2016 3:37 am

seems to post if you use simple sentences like this

Alex
Reply to  richardscourtney
January 31, 2016 3:50 am

Maybe I’m just boring

ferdberple
Reply to  Ferdinand Engelbeen
January 31, 2016 7:02 am

as they evolved in the Cretaceous with much higher CO2 levels in atmosphere
==============
just about every living thing on earth evolved when CO2 levels were higher than today. the white cliffs of Dover are fossilized CO2, as is coal, as is oil, as is natural gas. The carbon in fossil fuels came from ancient CO2.

Gloateus Maximus
Reply to  Ferdinand Engelbeen
January 31, 2016 7:07 am

They evolved in the Late Triassic (more than 200 Ma), but proliferated in the Cretaceous (from 145 Ma), when the oceans were as hot as they’ve ever been in the entire Phanerozoic Eon and at least the late Precambrian.

Reply to  Ferdinand Engelbeen
January 31, 2016 9:20 am

Ferdinand,
The ocean is constantly in contact with solid CaCO3, as at Dover. So it should be saturated with CaCO3, whatever the CO2 level. And calcifying organisms can deposit CaCO3 by doing a small amount of work to shift the equilibrium locally.
But the CO2 is added in one place, and the CaCO3 reserve is in another. It takes a long time for that saturation to be recovered when CO2 is added. And the work the organisms have to do to calcify depends on how far from CaCO3 saturation their part of the ocean is. Organisms can handle slow change where CaCO3 near-saturation is maintained.

Reply to  Nick Stokes
January 31, 2016 12:48 pm

Nick,
Coccoliths don’t need carbonate, they use bicarbonates to build their shells, independent of the carbonate level (indirectly that does affect the bicarbonate level too). Of course, the saturation level of carbonates need to be taken into account, but as far as I remember, the saturation depth is at around 2,000 meters, still far from a problem. Many algal blooms are mid-ocean, far from any carbonate rocks…

Reply to  Nick Stokes
January 31, 2016 1:54 pm

Organisms can handle slow change where CaCO3 near-saturation is maintained.

Calcium dependent organisms (e.g., corals) can also handle extremely rapid changes in CO2/acidity.
It seems obvious that the genetic flexibility of ocean organisms was influenced during times with quite a bit more CO2 in the atmosphere than today’s level.

Reply to  Nick Stokes
January 31, 2016 4:45 pm

Ferdinand,
“independent of the carbonate level”
I don’t think it is independent. The bio mechanism uses HCO3-, but it is governed by the solubility equilibrium because:
1. The CaCO3 once formed has to remain solid and not be re-dissolved
2. The reaction with HCO3 releases an acid species
Ca++ + HCO3- -> CaCO3 + H+
and in a CO3–/HCO3- buffer, that then reacts
H+ + CO3– -> HCO3-
So the net reaction is removal of carbonate.
” far from any carbonate rocks”
Yes, that is my point. When CO2 dissolves, it will be eventually “neutralised” by CaCO3. But that may take a long time, and meanwhile there is disequilibrium with unsaturated CaCO3.

Reply to  Nick Stokes
January 31, 2016 5:12 pm

Surface waters are generally supersaturated with respect to CaCO3. However it is rare for CaCO3 to precipitate inorganically because of complex ion-ion interactions, which inhibit
the Ca2+ ion. Magnesium (Mg2+) is one of the “competing” ions that depresses a spontaneous inorganic formation of CaCO3 as expected from thermodynamics (e.g. Rushdi et al., 1992). Thus it is through biological processes that CaCO3(s) is formed in the ocean.

http://www.biogeosciences.net/6/2421/2009/bg-6-2421-2009.pdf

Reply to  Nick Stokes
January 31, 2016 9:05 pm

“Coccoliths don’t need carbonate, they use bicarbonates to build their shells”
Furthermore, phytoplankton that don’t use HCO3 may be CO2 limited. (Reisbell et al 1993)
The bottom line is that these critters have been been around all those hundreds of millions of years through thick and thin CO2, through warmer and colder climes, because they are not one trick ponies.

Don K
January 31, 2016 3:39 am

The study says that coccolithophore abundance in the North Atlantic has increased by about ten-fold in recent years.

Shouldn’t that raise a few flags? Exponential growth with a vengance. After all, if coccoliths continue to grow in numbers at that rate, pretty soon we’ll be knee deep in coccoliths and ships won’t be able to leave port and we’re all gonna die. Seems unlike the Science/Smithsonian/National Geographic crowd to leave a potential catastrophe buried in an obscure abstract.

Jit
Reply to  Don K
January 31, 2016 5:15 am

Commenting from a position of ignorance here, having not read the paper, but: it was mentioned that the Coccolithophores occur in 20% of trawls now instead of 2% of trawls in the dim and distant. On the face of it that is a change in frequency, as I commented above (e.g. there may be a general low abundance but spread thinly). The commentary does not give detail on what fraction of plankton is now Coccolithophores, and whether other groups (Dinoflagellates, Diatoms) have decreased in frequency.
Has the overall abundance of plankton changed? This can be measured as mass of photosynthetic pigment per unit volume of H2O.
Plankton are often limited by a suite of factors (sunlight in higher latitudes, trace elements). This gives rise to a seasonal pattern in plankton abundance and species composition – well mixed water high in nutrients in winter gives rise to rapid growth of plankton in spring as sunlight returns, followed by nutrient depletion; zooplankton etc time their lifecycles to take advantage of this spring bloom. Point is, dissolved CO2 is only one factor among a great many affecting plankton communities.

January 31, 2016 3:42 am

From what I’ve read, CO2 is not responsible for ocean warming, it’s man’s activities that had the most important role in the ocean warming process: http://oceansgovernclimate.com/man-made-ocean-warming-yes-but-its-not-co2/.

January 31, 2016 4:05 am

I have a truly dumb question: If the calcium is not bound to carbonate, what other form does it take in Nature?
I means its all very well to have an organism that binds CO2 to form calcite, but where does it get the calcium from and what gets released as a byproduct? I.e., if it’s calcium sulphate or calcium chloride you would expect sulphur/chlorine (rather acidic) to be released, etc.

Alex
Reply to  Leo Smith
January 31, 2016 4:19 am

probably hydroxide

Alex
Reply to  Leo Smith
January 31, 2016 4:20 am

lots of O and H in water

Don K
Reply to  Leo Smith
January 31, 2016 4:49 am

Calcium ions (Ca++). Since they are just bouncing around in the sea water solution, they aren’t bound to any particular anion unless and until the solution they are in becomes so concentrated that the Calcium starts to precipitate out as some solid. Calcium compounds that sometimes precipitate in nature include Calcium Carbonate (two crystal forms–aragonite and calcite), Calcium Sulfate (gypsum), and Calcium-Magnesium Carbonate (dolomite).

Gary Pearse
Reply to  Leo Smith
January 31, 2016 6:03 am

Leo Smith: First, calcium is ubiquitous. It occurs in hundreds of minerals which make up major rock units on land which are being broken down by mechanical and chemical weathering eventually to reach the sea. Limestone and dolomite is one of the most abundant of sedimentary rocks on land and in the ocean (sea muds, coral reefs, etc.). Basalts make up oceanic crust and are continously being discharged by volcanoes around and under the sea. Basalts average 10% CaO. There is no chance of a shortage of calcium for reactions in the ocean, although this fact seems to be conveniently not mentioned by the worry warts.

ferdberple
Reply to  Gary Pearse
January 31, 2016 7:28 am

Basalts average 10% CaO.
===================
interesting. CaO is a predicted end product from the reduction of limestone in the presence of iron to produce natural gas. Lending support to the theory that natural gas is not from decomposition, but rather from subduction of limestone. the limestone.
CaCO3 + 2Fe + 2H2O === CH4 + CaO + 2FeO2
Since the limestone is largely created by an organic process, it is technically correct to say that natural gas is a fossil fuel. But it is not the result of decomposition. It is a much longer process, whereby the fossilized CO2 rocks of the ocean are subducted and reduced by iron to yield hydrocarbons.

Reply to  Gary Pearse
January 31, 2016 7:59 am

FB, most natural gas is biogenic, from thermal catagenesis of marine kerogen (algal remains). Abiogenic gas is known. There are some proven seeps in Spain, Italy, and Turkey. Not commercilizable. The only major abiogenic deposit known is the methane clathrate on the floor of the Framm Strait. The result of unusual geology there (slow seafloor speading, iron rich basalt intrusion). Not commercializable.
Abiogenic oil is a myth. The Swedish experiment was trace drilling mud contamination from the mud pumps. The so called Russian discovery in the Ukraine was simply mistaken geology, missing the complex igneous overthrust.

Reply to  Gary Pearse
January 31, 2016 1:04 pm

Thanks for that.

Don K
Reply to  Gary Pearse
January 31, 2016 1:04 pm

ristvan, Certainly, most natural gas served up to customers is biogenic simply because people who are going to invest millions of dollars in drilling a hole almost always drill where geologists say hydrocarbons are likely to be found which is mostly into the same sediments where other people are finding gas and oil. I should think that (almost) all oil would be biogenic if for no other reason that the high temperatures of crustal rocks at depth will tend to crack long chain hydrocarbons down to gas given enough time. (“oil window”). I do think that abiogenic gas seeps from basalts in the deep ocean basins might be hard to detect without an intensive and sophisticated search effort. My bet would be that if they exist, they probably will have little or no commercial value unless there is some reason for the gas to collect in large, exploitable pockets.

Editor
January 31, 2016 5:06 am

Great post, Willis…
I often wonder if the authors of these papers ever took any courses in stratigraphy and carbonate geology.
This was built by coccolithophores over 60 million years ago…
http://www.discoveringfossils.co.uk/dover_geological_panoramic.jpg
Nothing built by man will ever compare to this.
When presented with abundances of CO2, the oceans precipitate carbonate rocks.
http://i90.photobucket.com/albums/k247/dhm1353/Cretaceous.png
The more CO2, the faster the process…

Lisa L. Robbins1, Kimberly K. Yates1
(1) U. S. Geological Survey, St. Petersburg, FL
Abstract: Microbial calcification: implications for marine whitings and inorganic carbon cycling
Microbial calcification has been identified as a significant source of carbonate sediment production in modern marine and lacustrine environments around the globe. This process has been linked to the production of modern whitings and large, micritic carbonate deposits throughout the geological record. Recent research has advanced our understanding of the microbial calcification mechanism as a photosynthetically driven process. However, little is known of the effects of this process on inorganic carbon cycling or of the effects of changing atmospheric CO2 concentrations on microbial calcification mechanisms.
Direct measurements of air:sea CO2 gas fluxes and carbonate sediment production rates were measured in whitings located on the Great Bahama Bank and in laboratory cultures of calcifying cyanobacteria and unicellular green algae. In situ gas flux measurements showed a reduction in atmospheric CO2 relative to adjacent waters outside of whitings. Similar results were also observed in laboratory cultures. Calcification rates in whitings and laboratory cultures ranged from approximately 0.06 to 34.5 g CaCO3m-3h-1. These results suggest that production of microbial carbonates may serve as a sink for inorganic carbon. Laboratory cultures of calcifying microbes were subjected to biological buffers to examine the role of photosynthetic uptake of inorganic carbon species in calcification. Results from these experiments indicate that microbial calcification mechanisms depend upon the species of inorganic carbon available to cells for photosynthesis and, thus, atmospheric CO2 concentrations. These results suggest fluctuations in Phanerozoic dominance trends for calcareous cyanobacteria and algae may be linked to fluctuations in atmospheric CO2.
AAPG Search and Discovery Article #90914©2000 AAPG Annual Convention, New Orleans, Louisiana

For a more in depth discussion of microbial lime muds and climate change, see Yates & Robbins, 2001.

ferdberple
Reply to  David Middleton
January 31, 2016 7:06 am

When presented with abundances of CO2, the oceans precipitate carbonate rocks. The more CO2, the faster the process.
================
exactly. adding CO2 to the oceans creates more limestone (shell) not less. the worry warts have their chemistry backwards.

Reply to  David Middleton
January 31, 2016 9:25 am

“When presented with abundances of CO2, the oceans precipitate carbonate rocks.”
No, when presented with an abundance of dissolved carbonate, the oceans precipitate rocks. Converting CO2 to carbonate requires an abundance of some base. Not so easy.

Gary Pearse
January 31, 2016 6:16 am

” according to the study, coccolithophores are estimated to be responsible for about half of all precipitation of calcium carbonate (CaCO3) in the ocean. Half. That’s a lot.”
Moreover, if they are in ascendancy, it must be surpassing more than half as we speak. These critters are the inconvenient truth regarding OA. I hate it that they give these AGW characters earth science accreditation and they don’t seem to know about the enormous production of limestones during periods of……elevated CO2 in the atmosphere!!!
The ‘ocean acidification’ and other terminal diseases are what come to ‘light’ when ignoramus activist sit around and speculate all day long on how to tie CO2 to our worst nightmares because the UN enviros have asked for the vilification of CO2. That’s all it is. Speculation. When the ‘pause’ was the problem, speculation gave us 60+ reasons for it and finally, the true nature of the beast arose and they simply cancelled the pause.

Gary Pearse
Reply to  Gary Pearse
January 31, 2016 6:23 am

Oops! My rant took over. I had intended to thank Willis for another of his gems. This was one was short and sweet like a knock on the head that makes you see.

Gloateus Maximus
January 31, 2016 6:47 am

Coccolithophores are not technically plants, but phytoplankton, ie algae. The common Ehux is for example a single-celled, photosynthetic organism. Not all members of the groups to which they belong form shells.
They’ve been around for well over 200 million years, so have survived waters much warmer and CO2 levels much higher than now.

Eliza
January 31, 2016 6:49 am

IF you are young you believe in AGW, socialism, communism, Hitler, Che Guevara, UFO’s.ect… as you get older you don’t. Fortunately!

Steve in SC
January 31, 2016 7:33 am

I must apologize to the crowd for my lack of chemistry knowledge, unfortunately I can’t add much to the discussion other than to display my ignorance.
I would like to thank Willis for his gem of a post, very stimulating.
I would also like to thank all the commenters for their inciteful comments, they are very illuminating.
Anthony, you should be pleased as this is an illustration of what a well informed and expert readership you have.

Marcus
January 31, 2016 8:13 am

…And now for the Sunday Funnies……more great science talk from the liberal left !!!
http://video.foxnews.com/v/4722257009001/rapper-bob-insists-earth-is-flat-in-series-of-twitter-posts/?#sp=show-clips

January 31, 2016 8:52 am

Thanks, Willis. What an informative post.
“coccolithophore abundance in the North Atlantic has increased by about ten-fold in recent years.”
And this is a sign of other kinds of algae anthropogenic extinction by CO2?
This CO2 warming cult is even more versatile than CO2 itself.

Retired Engineer John
January 31, 2016 8:53 am

Willis, thank you for the post. I recall reading an article many years ago about the tropical ocean bubbling on a still hot night. Have you ever seen or heard about this action?

Don B
January 31, 2016 8:54 am

We can not find understanding from the pages of the NY Times. An article on ocean accidification was supposedly the result of expert input from a NOAA scientist. However, a FOIA request showed that the scientist specifically told the NYT writer that no evidence existed of OA damage – a message which did not appear in the article.
https://notalotofpeopleknowthat.wordpress.com/2015/12/23/fois-reveal-how-noaa-spin-lies-about-ocean-acidification/

January 31, 2016 9:02 am

Coccolithophores are responsible for 50% of CO2 drawdown from the ocean.
And now there are 10x more coccolithophores.
So that means a 500% increase in CO2 drawdown from the oceans.
OK if it’s only the North Atlantic, and the oceans account for only half of CO2 drawdown, then the increase will be less than 500%.
But it’s still a big increase. On the face of it a nice negative feedback acting against CO2 increase.
Inless of course their data is a load of crap.

Reply to  belousov
January 31, 2016 9:26 am

“On the face of it a nice negative feedback acting against CO2 increase.”
But CO2 is increasing.

Reply to  Nick Stokes
January 31, 2016 9:50 am

Exactly. So something doesn’t quite add up.

Gloateus Maximus
Reply to  Nick Stokes
January 31, 2016 10:41 am

Thank God or Man for that!
Another 120 ppm increase would be even better for life on our planet.

Reply to  Nick Stokes
January 31, 2016 2:21 pm

An informative presentation of CO2 observations is the ratio of annual CO2 increase in the air divided by annual fossil fuel CO2 emissions, the “airborne fraction”. This airborne fraction, clearly, is not increasing. Thus the net ocean plus terrestrial sink for carbon emissions has increased by a factor of 3-4 since 1958, accommodating the emissions increase by that factor.

Hansen, et al., 2013

Gary Pearse
Reply to  Nick Stokes
January 31, 2016 5:13 pm

Nick, yes but the plankton haven’t closed shop (see picture of Cliffs of Dover for what actually happens). If the coccos are now taking up half of the CO2 and they are expanding in number, then we are on our way to 60%, 70%… I know you know better but I’m always surprised in general at the simple concepts that seem to not make the cut in peoples’ thinking. The other one is, you have the planet recently and notably greening, both older forest growth but more significantly NEW PLANTS around the fringes of arid regions like the Sahel. This promotes concentric ‘fringing’ inwards as it changes the micro-climate of the fringe. This looks like an exponential function of carbon uptake to me.

Reply to  belousov
January 31, 2016 9:53 am

I would suggest that the bulk of the observed increase is due to more accurately counting coccolithophores. Does the paywall article explain any differences in counting methodologies?

Reply to  belousov
January 31, 2016 11:59 am

belousov wrote, “On the face of it a nice negative feedback acting against CO2 increase.”
Yes: CO2 increase -> coccolithophore increase -> CO2 reduction
i.e., a classic negative (stabilizing / attenuating) feedback.
That doesn’t surprise me, but the magnitude certainly does.
About ten weeks ago, the AP’s most notoriously extreme resident climate alarmist, Seth Borenstein, wrote an article ranking U.S. Presidential candidates for their conformity with the Revealed Truth about Climate Change. He recruited a list of eight climate scientists, starting with Michael Mann, and asked them to rate the correctness of the candidates’ statements on climate change. I didn’t know much about some of the scientists, so I did some googling, and concluded that, of the eight scientists, the only one who appeared to be doing more serious science than alarmist activism was Prof. Louisa Bradtmiller of Macalester College. In the course of that searching, by happenstance I stumbled across something she’d written about a topic I was interested in (quantification of the “greening” effect of anthropogenic CO2, esp. relative to ocean absorption of CO2), and I emailed her about it. She replied helpfully & cordially, and I followed up with a question about the then-breaking coccolithophore story. Some here might be interested in that exchange, so here it is.
I asked Dr. Bradtmiller:

The strangest report I’ve seen in the last few weeks is this:
“Coccolithophores… have been increasing in relative abundance in the North Atlantic over the last 45 years, as carbon input into ocean waters has increased. Their relative abundance has increased 10 times, or by an order of magnitude, during this sampling period.”
https://archive.is/UjZ4k#selection-1153.233-1153.339
What do you make of that? An order of magnitude?? That seems very surprising. Do you believe it?

She replied:

I don’t see any reason not to believe it, as it is based on decades of observational data by well respected scientists/institutions. I agree that it is very surprising, for reasons noted within the article. They summed up my reaction nicely, actually: ““What is worrisome,” he said, “is that our result points out how little we know about how complex ecosystems function.” The result highlights the possibility of rapid ecosystem change, suggesting that prevalent models of how these systems respond to climate change may be too conservative, he said.”

Don K
Reply to  daveburton
January 31, 2016 4:02 pm

“Me, I look at the complex systems and ecosystems of the climate that have kept it within bounds for a half-billion years, I’m comforted.”
Things did get pretty ugly 250 million years ago around the end of the Permian, when 96% of all marine species died off. https://en.wikipedia.org/wiki/Permian%E2%80%93Triassic_extinction_event Personally, I think humanity would have some difficulty pulling that off today even using nuclear weapons. But I suppose it does support the argument that life may not be infinitely resilient

Reply to  daveburton
January 31, 2016 9:28 pm

Don K
OK, I guess that any day a mass extinction could break out. However 250 million years ago there was at least one contributing factor: half of modern day Russia was a continuous open volcano – the Siberian Traps, the biggest flood basalt volcanism in earth’s history. And no – this was not anthropogenic.
In any case five mass extinctions over the Phanerozoic gives a one in 100 million chance per year. This means every morning a 1 in 40 billion chance of a mass extinction. Is this small enough to justify getting out of bed in the morning? (Well I’m still in bed here in Europe).
Willis – I like the pyramid analogy. It would be even more accurate if moving the tourists back from the pyramid just happened to herd them right close to a row of souvenir shops owned by the alarmed person’s old school friend.

bit chilly
Reply to  daveburton
February 1, 2016 8:44 am

the good doctor may want to examine the temperature trend in the north atlantic over the same timescale for possible clues as to the changing plankton demographic as measured by the continuous plankton recorder project.
just like el nino , the fish populations of the various ocean regions give the biggest clue as to what is happening at any given time. the gadoid outburst was a good example of this.

K. Kilty
January 31, 2016 9:37 am

Willis, you say “…In the ocean, chemistry doesn’t rule life—instead, life rules chemistry…”
Indeed! A friend of mine, a physical chemist, brought me a short article from Science about ten years ago, probably, regarding some bacteria thriving in an environment at pH of -40 or something. Now, a pH of -40 sounds impossible as a pH of zero brings to mind a bowlful of protons–how could there be a greater concentration? I think the paradox is resolved by looking at pH as a measure of proton activity not concentration. These bacteria use some enzyme with a highly active but very specific protonating purpose. Life runs some reactions that look absolutely silly from the standpoint of inorganic chemistry.

Reply to  K. Kilty
February 1, 2016 3:47 am

A pH of -40 is impossible, that represents a [H+] of 10^40 mole/L, higher than the density at the center of a black hole!

January 31, 2016 9:50 am

At least Science magazine got one thing right,
“Coccolithophores are a case in point, because their photosynthetic ability is strongly carbon-limited.”
But they missed the big picture that all life that relies on photosynthesis and which is not CO2 limited is limited by either the lack of water (desert) or lack of sunshine (polar).
You would think that the UN/IPCC would be on board with increased agricultural productivity to help feed the world, except that the benefits of CO2 contradict their agenda of pursuing redistributive economics under the guise of climate reparations.

Reply to  co2isnotevil
January 31, 2016 10:09 am

‘co2isnotevil’ is correct as usual. The UN had a clear choice to make: either tell the truth, and acknowledge that the rise in CO2 is a net benefit, with no observed downside, or prevaricate with the cAGW narrative.
They chose the narrative. That choice will cause increased suffering by those least able to afford it. But no matter, you have to break a few eggs to make the omelet, no?
The UN’s agenda is revealed in its actions; the ‘dangerous man-made global warming’ scare requires the demonizing of harmless, beneficial CO2. So that’s what they do.

Haverwilde
January 31, 2016 9:56 am

I attended a lecture recently in which the speaker discussed the effect of CO2 in Puget Sound on geoducks (huge clams with penis-like necks). A pH of 8.2 is optimal for spawning, and the water was 7.9 so the spawn failed. The speaker runs a hatchery and the water in our neighborhood was 7.9 as well. He brought seawater into the vat added some algae and nutrients. Four hours later the pH was 8.3. It’s amazing what a little alga can do. His spawn rate was phenomenal.
Clearly there is an impact of increased CO2 concentrations in the oceans. Unfortunately, the cataclysmic-hysteria gets in the way of an honest systematic evaluation, and the development of minor mitigation that could be implemented.

Reply to  Haverwilde
January 31, 2016 10:16 am

Clearly there is an impact of increased CO2 concentrations in the oceans.
That is a local effect. The intake pipe for the Monterey bay aquarium is located well offshore. It monitors pH, among other variables. There has been no increase in ocean pH since the aquarium opened for business many years ago.
It would require more than a one part in ten thousand rise in CO2 in order to see a change in ocean pH.
The tail doesn’t wag the dog. Oceans affect the atmosphere much more than vice-versa. Any local change in pH is being caused by something other than the rise in atmospheric CO2. Otherwise, the change in pH would be observed everywhere.

Haverwilde
Reply to  dbstealey
January 31, 2016 10:44 am

You are correct, it is a local effect not a global one. Given Puget Sound with its 40 inches of rain (pH of 5.6) and our 140 inches of rain but closer to the open ocean it is not surprising that we have seawater that is less alkaline than water not that far off shore. Nonetheless, it does have an effect on spawning shellfish.

bit chilly
Reply to  dbstealey
February 1, 2016 8:54 am

sometimes a bigger effect is removing raw effluent and waste from the waterways ,an enhanced source of nutrients that have increased biodiversity by orders of magnitude over those naturally occurring in some localised areas. in one case (the clyde estuary) quite a large localised area. removing these sources (along with the necessary removal of industrial waste) has had the opposite effect in some areas to that which was originally intended.

January 31, 2016 10:00 am

“The alarmists’ claim is that the slight neutralization of the ocean will make it harder for calcifying organisms to form their calcium shells, substrates, and skeletons. However, the study shows that for coccolithophores, this is not the case.”
Is the success of one species a reason to dismiss the threat from ocean acidification. I’d quote from the abstract from Impacts of ocean acidification on marine shelled molluscs (PDF Download Available). Available from: https://www.researchgate.net/publication/236597535_Impacts_of_ocean_acidification_on_marine_shelled_molluscs
“The effects of ocean acidification on the growth and shell production by juvenile and adult molluscs are variable among species and even within the same species, precluding the drawing of a general picture. This is, however, not the case for pteropods, with all species tested so far, being negatively impacted by ocean acidification.”
Your conclusion, drawn from a study of one type of marine organism, that “the rumors of the oceans’ death from increased CO2 are greatly exaggerated.” misleads in two ways.
It overemphasises a study of one species, and misleads the public as to what exactly the impact of ocean acidification has been predicted to have.
It is hardly a reason for you to draw a general picture from the success of one organism.

Reply to  Neo Biognosis
January 31, 2016 4:36 pm

NB, Willis’ pictured E. Huxleyi is but one of many such species. And you also overlook the major recent Nature comment on a paper showing many “ocean acidification” aquarium studies have severe methodological problems. Your comment amounts to GIGO.

January 31, 2016 10:01 am

The fundamental assumption of IPCC AR5 Figure 6.1 Carbon/CO2 balance is that they cannot locate any natural source/sink processes (they are/have been static for millennia) that explain the increased atmospheric CO2 concentration between 1750 and 2011 therefore the increase must be attributed to anthropogenic sources.
On the other hand IPCC AR5 Table 6.1 tabulates the partitioning of anthropogenic contributions by those same sources/sinks that couldn’t explain the increase, but can explain the 57%/43% sequestered/retained anthropogenic contribution. The uncertainties associated with this partitioning range as high as +/- 50%.
This sudden discovery of the ocean’s ability to source/sink carbon/CO2 pretty much refutes the entire assumption that natural source/sinks can’t explain the 1750 to 2011 increase.
What else do they have yet to discover?

Reply to  Nicholas Schroeder
January 31, 2016 11:50 am

Nicholas,
The oceans are proven net sinks for CO2. The biosphere as a whole (plants in oceans and on land and plant eaters all together) is a net sink for CO2. Humans emitted about twice the amounts of CO2 which are measured as increase in the atmosphere…
Thus in what way is the CO2 increase in the atmosphere not caused by human emissions?

Reply to  Ferdinand Engelbeen
January 31, 2016 3:49 pm

My point is that considering the huge uncertainties in the reservoirs/sources/sinks as tabulated in IPCC AR5 Table 6.1 and Figure 6.1 the CO2 concentration increase between 1750/2011 could easily fall within the boundaries of natural variability. Basically nobody really knows.
And IMHO IPCC dry lab-bed the partitioning of the anthropogenic contribution among the sources/sinks to make the sequestered/retained, 57%/43%, coincidentally and most conveniently exactly match the increase. Make the data fit the desired results, verdict first, trial later.
See my other postings: 1) anthro CO2 is trivial, 2) CO2 RF is trivial, 3) GCMs are useless.

Reply to  Ferdinand Engelbeen
January 31, 2016 8:38 pm

F E,
Please explain what happened in 1965. If this new sink had existed in 1965 CO2 would have diminished since then. A sink which grows/proportionately increases in step with emissions, wow, what could it be???
The oceans are not proven net sinks for CO2 and you know this.
Do you make money for denying this mystery?
Why are you constantly on here?

Reply to  Ferdinand Engelbeen
February 1, 2016 2:46 am

Michael Moon on January 31, 2016 at 8:38 pm
F E,
Please explain what happened in 1965. If this new sink had existed in 1965 CO2 would have diminished since then. A sink which grows/proportionately increases in step with emissions, wow, what could it be???
The oceans are not proven net sinks for CO2 and you know this.
Do you make money for denying this mystery?
Why are you constantly on here?

When the oceans cool, they are net sinks. When they warm, they are net sources. The most clear recent evidence for a net sink period is for ca 1945-1960. See MacFarling-Meure, 2006.

Reply to  Ferdinand Engelbeen
February 1, 2016 7:03 am

“The oceans are proven net sinks for CO2.”
When you run the numbers on Fig 6.1 prior to 1750 there was balance, no significant net sink or source.

January 31, 2016 10:32 am

I was born and grew up in an area where ‘karst’ is predominant rock. My family owes a large plot of land with a hill about 200m high from the base. According to local legend, (I am a bit doubtful about that) in the Roman times the top was covered by oak forest which was cut down for various purposes, and never re-established itself. Subsequently rain erosion got rid of all the soil, with only rocks and deep crevices left exposed. During centuries past rain water dissolved rock to such an extent that most of them are now covered with incredible sharp ridges and grooves up to 10 cm deep.
Very similar to this
http://media-cdn.tripadvisor.com/media/photo-s/02/4a/f6/4b/small-stone-forest.jpg
After the last summer visit to the area I was intrigued about whole process and after short search came across this illustrationcomment image
looks interesting and plausible, but I am sceptical about the atmospheric CO2 role.
It would be appreciated if any of the experts in the field might wish to comment.
Thanks

Reply to  vukcevic
January 31, 2016 11:16 am

Vuc, a karst landscape or terrain is essentially chemically weathered carbonate rock –limestone or dolomite formed in the marine environment by calcifying organisms like coccoliths, then tectonically upthrust to become continental rock. The chemical weathering is simply because rainwater is acidic, pH around 5.6 in the absence of additional NOx and sulfate aerosol pollution, which makes it more acidic (‘acid rain’ is slowly dissolving the Parthenon in Athens, since it was constructed from the metamorphosed limestone known as marble). Rain is acidic because rainwater is partial pressure CO2 saturated (Henry’s law). The dissolved CO2 forms carbonic acid.
Karst formation is part of what replenishes ocean calcium, allowing coccoliths to continue doing their thing.

Reply to  ristvan
January 31, 2016 12:20 pm

Thanks, I will look further into the processes you describe, despite the chemistry wasn’t my forte.

Mike McMillan
Reply to  ristvan
January 31, 2016 1:50 pm

Karst isn’t upthrust, it’s just flat land that started getting sinkholes, then eventually you had more sinkhole than flat land, leaving the spiky terrain. The Arecibo radio telescope in Puerto Rico was built on Karst terrain.

Reply to  ristvan
January 31, 2016 3:17 pm

Thanx again, halite (salt rock, sodium chloride) is apparently one of the more common minerals. Would you know how often it appears as a volcanic sublimate?

Reply to  ristvan
January 31, 2016 4:43 pm

V. Halite volcanic? Never. Thick salt geological beds are always associated with evaporation from shallow cut off seas or equivalent (Great Salt Lake in Utah being an example of the later, as is the US Salton Flats). Shallow and cut off thanks to plate tectonics. Salt thanks to andesitic rock chemical weathering over billions of years.

Alan Robertson
Reply to  vukcevic
January 31, 2016 11:27 am

vukcevic January 31, 2016 at 10:32 am
“My family owes a large plot of land…”
—————-
That’s a typical scenario for “owning” a large plot of land in this country, too.

Reply to  Alan Robertson
January 31, 2016 12:24 pm

the little ‘n’ makes difference between being OK or broke. Fortunately, plenty of woodland left, and vineyards have done extremely well on the lower slopes, i.e. the ‘n’ is in.

Reply to  vukcevic
January 31, 2016 3:30 pm

Vuc:
You should import a few Crowned Lemurs from Madagascar and create a tax-exempt wildlife preserve.
Eulemur coronatus

It can even be seen delicately moving through some of the knife-edged karst “tsingys” that occur within its range, especially in the Ankarana region.

Julian Flood
January 31, 2016 10:56 am

Willis, have a look at what’s happening to the diatom populations. If mankind has increased the dissolved silica runoff then the ocean spring bloom should have a longer diatom run until the silica is exhausted. If that is the case, the biology of the diatom carbon fixation pathway* has some intriguing implications.
JF.
*C4-like

Alan Robertson
Reply to  Julian Flood
January 31, 2016 11:43 am

Paraphrasing a farmer friend, “every time I bust the crust, I’m losing soil to the ocean”. The US agriculture industry recognizes my friend’s truism and is turning more and more to low till/no till agriculture. Whether diminished ag erosion supplants increased erosion due to construction, etc., the topic bears examination.

January 31, 2016 12:16 pm

Willis thankyou for your post. As always fun to read and a wealth of information in the comments as folk mull over what you’ve said. It’s sort of like sitting around the campfire at a truly interesting science retreat.

January 31, 2016 12:41 pm

Phytoplankton blooms in the Arctic spring melt is a major factor in controlling the annual cycle of atmospheric CO2 concentrations. They will consume all the CO2 that they can get. This makes the unfrozen Arctic ocean an unlimited sink that absorbs nearly all the CO2 that is delivered to it’s surface. Phytoplankton have “inorganic” shells of carbonates or silicates with an organic inner body. In their growth, they separate the 12 and 13 isotopes, The organic portion is lighter than sea water while the shell is heavier. While the organic portion is alive, it keeps the shell afloat near the surface to get sunlight. They travel with the currents, some of which deliver them to the tropics where they may die.
They then decay releasing 13 C depleted CO2. The shell with the higher concentration of 13 C falls as the observed“snow” in the deeper tropical oceans. It becomes the zero standard used in calculating the 12/13 index. So higher production of phytoplankton in the Arctic can contribute to greater emissions of CO2 in the tropics as well as emissions of more negative 12/13 index values. So how much do anthropogenic emissions contribute to this cyclic process? Possibly about 5%.

Reply to  fhhaynie
January 31, 2016 1:09 pm

fhhaynie,
You have the order of what happens with CO2 and the δ13C levels over the seasons in the NH in reverse: in spring most of the extra CO2 uptake is by land plants, as good as the increase in δ13C levels:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/seasonal_CO2_d13C_MLO_BRW.jpg
If the algal growth was the cause, the ice melt in Antarctica would give at least as much change in CO2 and δ13C levels over the seasons, but the levels hardly show any change in the SH. the NH is 70% land with a lot of forests while the SH is 70% oceans…
Moreover the overall carbon balance from the biosphere is more CO2 uptake than release, thus the biosphere as a whole increases the δ13C levels…

ulriclyons
January 31, 2016 2:24 pm

A warm AMO significantly reduces CO2 uptake for the North Atlantic.
http://www.nature.com/ngeo/journal/v6/n2/abs/ngeo1680.html

ulriclyons
Reply to  ulriclyons
January 31, 2016 5:49 pm

“We used random forest models to examine more than 20 possible environmental drivers of this change, finding that CO2 and the Atlantic Multidecadal Oscillation were the best predictors, leading us to hypothesize that higher CO2 levels might be encouraging growth. A compilation of 41 independent laboratory studies supports our hypothesis. Our study shows a long-term basin-scale increase in coccolithophores and suggests that increasing CO2 and temperature have accelerated the growth of a phytoplankton group that is important for carbon cycling.”
Unless there’s a new species of flying phytoplankton, it must be due to temperature, as the North Atlantic is a weaker CO2 sink when warmer.

HankHenry
January 31, 2016 5:28 pm

I assumed that CO2 fertilizes the growth of the shelled creatures of the oceans in the same way it fertilizes photosynthetic plants. I live in Northern Illinois. Underneath me are Ordovician carbonates hundreds of feet thick. Based on this I think the earth must have a great capacity for extracting CO2 from the atmosphere. There is a reason that there is a measly .04% CO2 in the air.

January 31, 2016 5:52 pm

Ii mentioned this study a few weeks ago at ClimateEtc, when it first was published in the paper edition. I am happy to see that it is getting a good press. Like all studies, it requires replication before it acquires believers.

Jimmy Finley
January 31, 2016 7:30 pm

Love the discussion of carbonate sequestration in sediments, possibly awaiting return to the atmosphere through the process of subduction and subsequent volcanic activity. Unfortunately, the earth eats CO2 and packs it away with impressive finality (all those massive carbonate beds and coal and lignite beds on the continental terra are not going to be subducted; it’s only sea floor sediments that get that treatment). Also, one suspects that 4 BY on from the initiation of plate tectonics, that the rate of that process is rather slower than initially, and beginning to enter into a long-term decline (it has been a long time since komaiites have been erupted on the earth’s surface). Thus, there is a real chance that CO2 depletion will become the killer of life as we know it here. Fortunately, just next door, in astrophysical terms, we have a fantastic ore deposit, as it it were, of CO2: the atmosphere of Venus. Great subject for a science fiction novel – siphoning off the atmosphere of Venus to save the world.

Jimmy Finley
Reply to  Jimmy Finley
January 31, 2016 7:31 pm

Correction: “komatiites” not “komaiites”.

Reply to  Jimmy Finley
February 1, 2016 3:01 am

Thank you Jimmy for your comments.
As I wrote above:
“My impression is that Volcanism may not suffice, since atmospheric CO2 concentrations have been trending downwards for millennia…”
As I wrote in 2009:
“Since life on Earth is likely to end due to a lack of CO2, should we be paying energy companies to burn fossil fuels to increase atmospheric CO2, instead of fining them due to the false belief that they cause [dangerous] global warming?”
Here’s a thought:
Instead of importing CO2 from Venus, maybe we should continue to burn fossil fuels as a source of energy AND CO2 for our carbon-based-life-rich blue-water planet.
In their misguided attempts to “fight global warming”, it is ironic that our politicians are spending trillions of dollars of scarce global resources to degrade our energy systems AND also attempting to counteract the hugely beneficial impacts of increasing atmospheric CO2.
The following numbers are from the 2015 BP Statistical Review of World Energy, for the year 2014:
http://www.bp.com/content/dam/bp/pdf/energy-economics/statistical-review-2015/bp-statistical-review-of-world-energy-2015-primary-energy-section.pdf
Global Primary Energy Consumption by Fuel is
86% Fossil Fuel (Oil, Coal and Natural Gas),
4% Nuclear,
7% Hydro,
and 2% Renewables – largely intermittent, unreliable wind and solar power.
Conclusions:
Cheap, abundant reliable energy is the lifeblood of civilization.
Fossil fuels keep our families from freezing and starving to death.
More atmospheric CO2 is good; within limits, a lot more is better.
It IS that simple.
It is truly remarkable how so many politicians, scientists and business leaders could get it so wrong.
When misinformed politicians fool with energy systems, innocent people suffer and die.
Regards to all, Allan

Reply to  Allan MacRae
February 1, 2016 12:48 pm

Allan MacRae:
You suggest

Here’s a thought:
Instead of importing CO2 from Venus, maybe we should continue to burn fossil fuels as a source of energy AND CO2 for our carbon-based-life-rich blue-water planet.

For sake of argument I will assume that is necessary.
If it be necessary then please don’t forget release of sequestered CO2 by cement manufacture.
Cement (mostly calcium oxide: CaO) is made from limestone (calcium carbonate: CaCO3) by heating it in a kiln to ‘drive off’ CO2.
Portland cement is manufactured by crushing, milling and proportioning the following materials:
Lime or calcium oxide, CaO: from limestone, chalk, shells, shale or calcareous rock
Silica, SiO2: from sand, old bottles, clay or argillaceous rock
Alumina, Al2O3: from bauxite, recycled aluminum, clay
Iron, Fe2O3: from from clay, iron ore, scrap iron and fly ash
Gypsum, CaSO4.2H20: found together with limestone
Richard

Reply to  Allan MacRae
February 6, 2016 4:59 am

Thank you for your comment Richard, It led me to revisit the Chicxulub (Yucatan Mexico) impact that reportedly caused the K-T extinction event 66 million years ago. One of those “really bad days” for the dinosaurs.
My comment concerns timing – Earth probably experienced a low-CO2 near-extinction period during the last Ice Age, which only ended about 10,000 years ago. We are going to enter another Ice Age, probably in a few thousand years or less – less than “the blink of an eye” in geologic time, and probably experience another such low-CO2 period.
Meanwhile, our “world leaders” and “great thinkers” are obsessing about too much atmospheric CO2, in the false belief that climate sensitivity to CO2 is ten or more times higher than the evidence suggests.
Global warming alarmism has taken on the qualities of fantasy and farce.

Steve R
February 2, 2016 2:33 pm

It is frustrating to see climate scientists begin to dabble into subjects which they appear to know little about, under the mistaken assumption that they are breaking new ground. In fact these disciplines already have a well established theoretical understanding developed over decades of study.

Steve R
Reply to  Willis Eschenbach
February 2, 2016 4:05 pm

Willis,
Good point…One that I should have caught with even a cursory proofread. In general, I was bemoaning the relatively recent concern that CO2 is going to acidify the worlds oceans.

Steve R
February 2, 2016 5:13 pm

Really, for all of the talk about increased CO2 affecting the oceans, all that can really be stated is that the calcite and aragonite compensation depths might become a LITTLE bit shallower as the partial pressure of CO2 in the atmosphere increases. Since these depths are WAY below the photic zone anyway (4 to 5 KM depth), photosynthetic life is still free to consume as much CO2 as they wish, and their production of calcite, aragonite and siliceous tests can continue as long as the required minerals are available in solution.