The latest bit of idiocy at WUWT is from someone who goes by the name of James R. Barrante, Ph.D. A Google search shows that for many years now, young James has been trying to convince whoever is silly enough to take any notice of him that it's the oceans that are causing atmospheric CO2 to increase or something like that. He's a very mixed up chappie and can't seem to keep his story straight. Today at WUWT he wrote how burning hydrocarbons doesn't produce CO2, or words to that effect:...if the measurement of ocean pH were not so complicated, and we had that data for the last 150 years, I would bet that we could show exactly that the increase in atmospheric CO2 from 280 ppmv to 380 ppmv in the last 150 years is an ocean temperature effect and not at all related to burning fossil fuels.
Wow! Just think that this is someone who says he used to teach physical chemistry to poor unsuspecting students. They must be thanking their lucky stars that he wasn't trying to teach organic chemistry. He'd flunk his own tests.
Anthony Watts wouldn't know a hydrocarbon from a water molecule, and he no longer advocates the greenhouse effect. You can't blame him for being dazzled by an emeritus professor urging his readers to "believe" that burning hydrocarbons doesn't produce CO2.
The even more peculiar thing is that James is arguing that although as he states the oceans have become more acidic with a pH drop from 8.2 to 8.1, he's still arguing that the oceans have been emitting CO2. He reckons it's because the oceans have got hotter. Just what's caused the seas to heat up he doesn't say. He skipped over that rather important step.
It's really weird to come across someone who used to teach chemistry at university level write such utter bunkum.
From the WUWT comments
There are only two so far. Both asked similar questions. Alex asks about James' assertion that the oceans have become more acidic. Yes James did say this, but blamed it on hotter oceans:
March 21, 2016 at 5:20 am
Is it really well-known that pH has decreased from 8.2 to 8.1?
"...if the measurement of ocean pH were not so complicated, and we had that data for the last 150 years, I would bet that ..."
ReplyDeleteI love that weaselly sentence. Read: there is not any data so I can make up whatever I want.
After having spent my alotted time at WUWT yesterday, I wasn't going back again today, but I did see that pH headline and think: WTF are they going on about now? I just couldn't force myself to go read it.
ReplyDeleteBarrante is the author of a book I own, "Global Warming for Dim Wits" and a signer of Happer's "300 scientists" letter to help Lamar Smith harass NOAA.
ReplyDeleteSee the end of my comment at ATTP, which links to his participation in a thread at RealClimate, and a 25-page excerpt from his book.
I quote from the book's 25-page excerpt, p.16:
Delete"‘As a physical scientist and somewhat knowledgeable in the physical chemistry of the atmosphere, I am going to re-define a “dim wit” as someone who believes that greenhouse gases, and in particular carbon dioxide, could actually control the climate. Such individuals generally fabricate their own version of science to fit their own agenda. When it comes to dim wits, there is a lot of truth to the old saying, “in one ear and out the other!”’
So, he's a gone-emeritus professor, with zero peer-reviewed publications in climate. and actually, not a lot of publications in a 42-year career (S CT State U offers BS and MS, not PhD, so to be fair, there's much more emphasis on teaching than research) ... but the Dunning-Kruger is strong.
Indeed, the Journal publishing career of Prof Barrante seems to run from 1961 to 1968.
DeleteOh, FFS!
ReplyDeleteConverting human CO2 emissions to atmospheric mole-fraction values (and then trivially to PPM in the atmosphere) is all you need to do to prove that humans *must* be responsible for the increasing atmospheric CO2 levels.
That should be a very straightforward high-school science homework assignment! (I should qualify myself here: straightforward for students who are lot smarter than Anthony Watts and his followers.)
And like I said, "Oh, FFS!".
Oh bless, what terrible timing for the poor man. Just today the Guardian reports that the current rate of release of CO2 into the atmosphere is unprecedented in at least 66m years.
ReplyDelete"It revealed that at the start of the PETM, no more than 1bn tonnes of carbon was being released into the atmosphere each year. In stark contrast, 10bn tonnes of carbon are released into the atmosphere every year by fossil fuel-burning and other human activity."
I am also a physical chemist. I was interested in the solubility of CO2 in brine at various temperatures, so I looked up the Henry's law data and found it in an old USA Bureau of Mines publication, "The solubility of methane, carbon dioxide, and oxygen in brines..." by Stephen D. Cramer. O2 solubility in water is very temperature sensitive, as anglers well know. I wanted to know the effect of ionic strength on solubility in brines. It took some bit of minor math work, and there was some inconsistency between various data regarding solubility, but the data was pretty clear regarding temperature effects. As brine temperature increases, CO2 becomes less soluble, as one would expect. In addition, I calculated that, were the partial pressure of CO2(g) to remain constant, global warming would have reduced the amount of CO2 dissolved in the oceans by less than ten percent relative to 1950; that is, warming oceans would outgas CO2 were temperature increasing alone. But of course, the partial pressure of CO2 is also increasing, and produces an increase in CO2(aq) despite the increase in the Henry's Law constant in brine. That is, the increase in atmospheric CO2 is increasing dissolved CO2. And yes, it is correct to refer to the corresponding decrease in ocean pH as acidification.
ReplyDeleteNOTE: The Henry's Law constant is the equilibrium constant for the dissolution reaction (which is presumably exothermic)
CO2(aq) <--> CO2(g) K = P(CO2)/[CO2(aq)] = k_H
so that as the Henry's Law constant increases, a greater gas pressure is required to produce a specific amount of the dissolved species.
I'm disappointed in a fellow physical chemist, but not for the first time. IMO, using actual data beats guessing.
Sorry, I was thinking about the reverse reaction. Dissolving is exothermic, outgassing is endo.
DeleteOnymousGuy has basically made the point that I was going to make: to wit, if oceans were the source of CO₂ then oceans would not be acidifying as they have been observed to be doing - if anything, we'd be seeing ocean deacidification/alkalinisation.
ReplyDeleteBarrante is a tragic example of the triumph of ideologically wishful/motivated thinking over rational analysis.
Plants tend to prefer to incorporate the carbon 12 isotope. This will have something to do with its vibrational frequency being different to the carbon 13 isotope.
ReplyDeleteAn analysis of C12 to C13 ratios in atmospheric CO2 will show that the increase in CO2 of the atmosphere is due to the burning of fossil fuels not some 'natural' source.
Bert
Vibrational frequency? Mass, surely.
DeletePhotosynthesis is mediated by the reaction centre in a complex molecule. To break down CO2 and liberate O2 relies on quantum mechanical effects that is a complex interaction of so called wave functions.
DeleteIt is not the mass but the vibrational frequencies. This of course depends on the mass of the atom.
It has been shown that Cyanide and Almonds produce the same sensation to the human sense of smell. It is not the molecular configuration of the Cyanide molecule or the molecules in the Almonds but the actual vibrational frequency of one atom that is detected by QM.
Bert
@-Bert from Eltham
Delete"Plants tend to prefer to incorporate the carbon 12 isotope. This will have something to do with its vibrational frequency being different to the carbon 13 isotope."
The 'preference' is caused by the fractionation by mass, a process of cumulative small differences in reaction kinetics during metabolic synthesis.
The optimisation for C12 is a response to the selection by mass, the plant metabolism cannot select C12 for teleological reasons.
I can only see the Universe as a Physicist. I could never understand Chemistry. So I bow to you different knowledge.
DeleteWe are describing the same thing are we not.
Reaction kinetics to me means lots of vibrational QM states interacting.
Bert
I met the bloke who got the Nobel prize for the elucidation of the molecular structure of the Photosynthetic Centre in my lab many years ago.
DeleteWe went to lunch and had a very long discussion with our entire group.
I did not know who he was at first as my boss left him in the lab with me to answer an urgent phone call. He was full of questions and listened very carefully to my answers. He was the most humble smart bloke I ever met. His name was Johannes Deisenhofer.
Bert
Out of curiosity I looked up to see why C12 is preferred. It turns out that for most photosynthetic reactions C12 is not particularly preferred. It boils down to just a small number of enzymatic reactions, going by this response from Steve Mack:
DeleteRe: Why do living organisms exhibit a preference for Carbon-12 over Carbon-13?
It covers both mass and energy (bond strength), so I'd say that probably both the physics and chemistry perspectives look correct. I'll leave it to you more informed people to battle it out :)
I'm not sure that the answer given by Steve Mack is a good one, in particular, his statements:
DeleteWhat is even more interesting is the observation that this enrichment seems to be the result of the action of a few key metabolic enzymes that seem to "prefer" 12C to 13C. That is to say that in the case of most (or at least many) enzymes, there does not seem to be a strong preference for 12C over 13C.
and
the reason pyruvate dehydrogenase prefers 12C to 13C is because lower mass 12C atoms are slightly more energetic, or "willing" to participate in reactions.
seem to contradict each other; if 12C atoms are "more energetic" why do only "a few key metabolic enzymes" exhibit a preference?
I think (as a Chemist with some specialist knowledge in this area) I have a better working hypothesis for the 12C preference. More to come ...
(a) The structure of molecules.
DeleteMolecules have a structure, atoms located in space relative to each other which can be characterised by bond lengths and angles. The theoretical equilibrium values of these properties should be determined by the interaction of the charged sub-atomic species, protons and electrons, i.e they should be isotopically invariant. In fact, the determination of molecular structure (by Microwave spectroscopy) is often done by substituting isotopes, assuming the bond lengths do not change - these are reported as r(s) structures (s=substitution) rather than the theoretical r(e) (e=equilibrium) values. However, extensive use of isotopes (Townes & Schawlow illustrate this with the molecule O=C=S) shows that the assumption of isotopic invariance is only partially good. The explanation is that real molecules are never in an equilibrium structure - they have zero point vibrational modes, and the vibration depends on the mass of the nuclei in the molecule.
(b) Molecular charge distribution and hydrogen bonds.
DeleteMolecules (genrally) have uneven charge distribution. H2O is shaped like a V with the oxygen at the bottom and the H at the top. The electron PDF for the molecule bond is concentrated along the sides, and is pulling slightly towards the O atom. This makes the "top" of the V slightly positive (with hydrogen proton nuclei slightly exposed) and correspondingly the bottom slightly negative. Since the H nuclei are positive, they tend to form weak "inter-molecular" interactions with slightly neagtive areas of other molecules. These interactions are called "hydrogen bonds" because hydrogen atoms within molecules are, by far, the nuclei most denuded of the electron PDF.
(c) How enzymes work
DeleteGiven (b) above, we can imagine that you could "build" a molecule that has area of where the charge distibution is a mirror image of the water molecule - and then water molecules would come and "nestle" in that spot forming hydrogen bonds. Now imagine that molecule also has a site that matches the charge distribution of another molecule that you wish to react with the water and whatsmore, the charged sites place the two reactants in close proximity to each other. Furthermore imagine that the charge sites aren't a perfect fit, they are close enough, but stretch the molecule in a way that weakens the bond(s) that need to cleave for the reaction to take place. The energy required to force the reaction to happen (the potential barrier) is lowered (see here https://en.wikipedia.org/wiki/Energy_profile_%28chemistry%29 This is my understanding of how enzymes catalyse a reaction.
We can see that since the effect of an enzyme depends on the spatial distribution of charges matching the spatial distribution of charges on the reactant, and we know (from section a) that the structure of charges on the reactant depends (slightly) on the isotopic composition of the molecule. The implication is that some (but only some) enzymes have a chage distribution that better matches the 12C isotopic reactant than the 13C one. And, of course, natural selection would de-select enzymes that work better for 13C and would only weakly select for enzymes that have a charge distribuiton that would hold both isotopic variants equally well.
So there is it - as I said - a working hypothesis: not an explanation. I hope it was clear though, and would, of course, welcome any cogent rebuttal or alternative explanation ! (The posting widget wouldn't let me post this as one, so I had to split it up - sorry about that)
The guy is a twofer contrarian.
ReplyDeleteOne -- he doesn't believe excess atmospheric CO2 is due to burning fossil fuels.
Two -- CO2 is not a greenhouse gas anyways.
Very Salby-like
Yes, and another similarity is the level of total disdain for researchers in the field, who Barrante thinks are "dim wits."
DeleteFor comparison, see my review of Salby's book.
''`Historically, students of the atmosphere and climate have had proficiency in one of the physical disciplines that underpin the topic, but not in the others. Under the fashionable umbrella of climate science, many today do not have proficiency in even one. What is today labeled climate science includes everything from archaeology of the Earth to superficial statistics and a spate of social issues. Yet, many who embrace the label have little more than a veneer of insight into the physical processes that actually control the Earth-atmosphere system, let alone what is necessary to simulate its evolution reliably.'
they have all bases covered - heads they win tails you lose
ReplyDeletepinning these nutters down is like tying to nail jelly to a wall
Well, you see, that's easy. If you already *know* that humans can't be responsible for rising temperatures, then you've done all the hard work. The easy part is just in forcing all the data to line up with your beliefs.
DeleteSo: CO2 is at its highest in a million years? Totally irrelevant. The ocean is acidifying? Meh, it can still be a source of CO2, too.
Who needs consistency or evidence when you've already made up your mind?
I am delighted this issue has prompted such an in-depth response, however off-topic!
ReplyDeleteI stand corrected and acknowledge I was wrong about mass being the key criteria that explains the selective predominance of C12 in plants. The case for the vibrational modes of the molecule being the selective feature is well made and convincing.
My unwarranted suspicion that it was probably down to mass affecting reaction kinetics and diffusion lengths (not vibrational frequencies) was mistaken.
Although I was really objecting to the use of 'prefer' as a dangerous anthropomorphic metaphor for features of the chemical processes of metabolism that imply choice when what is happening is contingent.
In the end the evidence as put up by much smarter people than me has given us all a better insight into the selection of C12 over C13 by plants. As we all know plants are not very intelligent. So how do they know?
ReplyDeleteI can see why izen does not like the anthropomorphic metaphor. It makes us all look rather silly. Plants are much smarter than us. Bert