Monday, April 11, 2016

Peter Ward Plays Pinata

It may be unfair, but when somebunny volunteers as a pinata, who is Eli not to go to Bad Bunny. Peter L. Ward has been spreading nonsense like fertilizer, most recently at Walter Hannah's blog, and neither Ankh nor AT were kind enough to clue Eli in on the fun, so the Rabett will have to simply cut and snip.  To say that Ward is a few drops short of a clue, would be generous.  OTOH, Eli is rather better prepared to deal with the nonsense than most because he has studied and worked in the areas of atomic and molecular physics, physical chemistry, chemical physics, spectroscopy and kinetics so he can recognize climate baff on sight.

It is such a rich display, that were it a buffet the Bunny would have to check in for lap band surgery.  The choice is difficult, but one must start with something Ward gets wrong (and there is little he gets right), perhaps here

Heating of the stratosphere is done primarily by O2 absorbing UV-C and being dissociated. Many other gas molecules are dissociated in the stratosphere including CO2, but their concentrations are very low. We have observed for a long time that the top of the stratosphere averages about 70oC warmer than the tropopause. These facts are not included in typical energy balance efforts by Trenberth and others. Why not?
Let Eli start at the top
Heating of the stratosphere is done primarily by O2 absorbing UV-C and being dissociated. 
Well, as a matter of fact not.  Heating of the stratosphere is initiated by dissociation of O2 (Step 1) but the heating is done primarily by absorption of light and dissociation of ozone (Step 2) followed by regeneration of the ozone (Step 3).  The chain is terminated in Step 4.  The name for this is the Chapman cycle
(1)  O+ hv (< 200 nm) --> O + O
(2)  O + O2 + M  --> O+ M 
(3)  O+ hv (306 < λ < 200 nm)                                       -- >  O + O 
 (4) O + O-> O+ O 


The figure is from Chapter 5 of the Stratospheric Ozone Textbook linked at the top of the sidebar and a good place to look for details.  The key to the good Dr. Ward's confusion is both spectroscopic and kinetic as well as involving the structure of the atmosphere and the solar flux.  The dissociation of oxygen requires light below 200 nm (technically below 243, but the absorption there is very low in the so called Herzberg Band, and does not really pick up until 195 nm or so where the Schumann Runge band kicks in).


Ozone, OTOP, has a bell shaped absorption
between 306 and 200 nm. One also has to understand that a) there are orders of magnitude more oxygen (O2) than ozone (O3) at all levels of the stratosphere, and orders of magnitude more ozone than oxygen atoms.







 Further, the flux of solar radiation falls off rapidly at 200 nm.  Because there is so much O2 in the atmosphere the UV radiation below 200 nm falls to zero quickly at the top of the stratosphere.  A spectrum of the UV actinic flux above the atmosphere can be found at Penn State. The UV between 200 and 300 nm is absorbed by the ozone, which is more concentrated between 25 and 35 km as can be seen in the figure to the right by comparing the fall off with the ozone spectrum above.

Putting this all together, the rate at which O atoms are produced in the photolysis of Step 1, is slow, and primarily occurs at the top of the atmosphere, where all of the radiation that can dissociate O2 is absorbed.  The O atoms rapidly react with O2 (a matter of seconds) to form ozone, O3.  If there was no third body (M standing for nitrogen or another oxygen molecule) then the O3 would have energy above the dissociation limit and simply fall apart again.  However even in the upper stratosphere there are enough oxygen or nitrogen molecules to make this possible.  The chain steps 2 and 3 result in a heating of the stratosphere.  Step 4, the termination, is really slow, but there are additional reactions involving Cl, Br and water that deplete the ozone to an observed level.  Still odd oxygen, O and O3 persists long enough to move down through the stratosphere to 30 km or so, the ozone layer.  A detailed discussion of the kinetics can be found at Harvard and discussion of the solar spectrum at various layers in the atmosphere, aka the actinic flux at Penn State.

The reason why ozone absorption rather than oxygen molecule absorption is responsible for most of the stratospheric heating is simple

Step 1, the photodissociation of oxygen molecules is very slow because the amount of UV radiation below 200 nm is low.  Thus the number of oxygen molecules photodissociated per second is low and the number of O atoms produced per second is low.

Steps 2 and 3 in the Chapman cycle, absorption of a UV photon by ozone followed by dissociation and the cyclical regeneration of the ozone molecule by reaction with oxygen molecules and a third body are repeated myriad times before termination.

Oxygen molecular photodissociation occurs only once




Oh yeah
Many other gas molecules are dissociated in the stratosphere including CO2
Nope, CO2 won't be dissociated in the stratosphere, because it doesn't start absorbing until 180 nm or so.  Absorption by oxygen higher up will stop any of the < 180 nm light from reaching CO2 in the stratosphere.

And finally from Peter L. Ward we have
We have observed for a long time that the top of the stratosphere averages about 70oC warmer than the tropopause. These facts are not included in typical energy balance efforts by Trenberth and others. Why not?
And from Kevin Trenberth


Maybe because they were.  Trenberth's energy balance is referenced to the top of the atmosphere which is ABOVE the stratosphere and based on satellite measurements such as ERBE.  Buns can not understand the numbers without dealing with the vertical structure of ozone, water vapor and temperature.  For the hard of hinting, the energy absorbed by the atmosphere from the solar radiation includes energy absorbed by O2 and O3

33 comments:

Russell Seitz said...

Eli should ask if anybody in his academic neighborhood keeps condensed O3 as a lab pet- you don't get to see dark blue metallic-looking liquids every day

Look, but don't smell.

EliRabett said...

The bunny has seen too many labs fracked by ozone driven explosions to want to play.

Brandon R. Gates said...

Eli, thanks for the small treatise on ozone heating. Bookmarked for further knoodling and reference.

I've typically interpreted the middle layer of the energy budget cartoons as doings near the tropopause, always keeping in the back of my mind that the real vertical structure is more complex. Somebunnies do tend to assume that if it isn't crammed into the simplified schematic, it wasn't considered in the analysis. I would think, however, that Dr. Ward wouldn't be the sort to have not RTFP.

Brandon R. Gates said...

It's worse than I thought:

Greenhouse warming theory also assumes that the heated air radiates energy back to Earth’s surface, and that this return flow of heat energy warms Earth. The problem with this is that the [lower atmosphere is] colder than Earth’s surface. Heat cannot physically flow from cold to hot. You do not stand next to a cold stove to get warm.

He's a slayer. How does a guy with a PhD from Columbia in geophysics write such bilge with a straight face?

JohnMashey said...

He and his friend had a booth at AGU2015 (i.e., spent the money), and I stopped by and picked up brochures, but did not talk to them. One of the brochures stated:

“There has been a fundamental misunderstanding in physics about what radiant energy is and how it should be calculated. Natural philosophers and scientists have debated for 2400 years whether light travels as waves or as particles. New observations show that light and other forms of electromagnetic radiation travel simply as frequency, in a manner similar to the signal from your cellphone or a radio station, and that the thermal energy involved is simply equal to frequency times a constant, representing the energy of the atomic oscillators which are the sources of radiation. It turns out that the energy of ultraviolet B radiation is actually 48 times greater -48 times “hotter”- than the energy of infrared radiation, confirming common experience. There simply is not enough energy involved with greenhouse gases for them to play a significant role in global warming.”

So there. While my physics is rusty, that was enough for me.

andthentheresphysics said...

nor AT were kind enough to clue Eli in on the fun

Sorry :-)

I notice how Peter Ward made plenty of claims alone the lines of

How much of this is from Earth versus how much is from UV heating of the stratosphere is not known yet because people have not been thinking this way.

There are apparently lots of examples of things that people weren't considering, despite plenty of indications that they either were considering these things, or Peter Ward had completely misunderstood the significance of the things they were supposedly not considering.

davidp said...

Typo alert: I think the sentence "The dissociation of ozone requires light below 200 nm " is referring to oxgen, not ozone.

Walter Hannah said...

Eli,

Thanks for the detailed info on this, I'm not an expert on stuff that high up.

Peter Ward would have a much better chance of making sense to us if he could work his ideas into a new surface energy balance figure like the Trenberth diagram. All his talk about dissociation processes is such a waste of time in the larger picture of what he claims to be able to refute.

Walter

andthentheresphysics said...

Walter,
I suspect that there is a very good reason why he is reluctant to produce some kind of surface energy flux diagram based on his theory. He can't; at least he can't produce one that would be remotely consistent with observations.

Hank Roberts said...

Well, other numbers to consider, you know where these are from:
...
10 points for each claim that quantum mechanics is fundamentally misguided (without good evidence).
...
10 points for offering prize money to anyone who proves and/or finds any flaws in your theory....

I haven't tried to add up all that.

I did suggest over there that PLW ask his Field Medal friend to propose an experimental test of PLW's revision of quantum mechanics.

So far it's "can't be CO2, therefore must be O3, therefore quantum mechanics must be amended" -- backwards reasoning?

Just a spectator here myself.

MartinM said...

I suspect Ward would reply that, because the photons which cause O2 to disassociate are higher-frequency than those for ozone, they must be primarily responsible for heating the stratosphere. He seems to reject the mainstream understanding of concepts like 'flux', 'intensity', and 'two things with positive energy have more energy than either on its own'.

8c7793aa-15b2-11e5-898a-67ca934bd1df said...

What I am left wondering is why not one but two science bloggers would give an obvious idiot emeritus gigliologist the time of day, let alone a comprehensive blog post. Is this be nice to science cranks day or what?

Windchasers said...

I almost feel sorry for the guy. Really. Some snippets from hannahlab blog:

Ward: "Flux is calculated by integrating spectral radiance as a function of wavelength (wavenumber or frequency). Watts, in this formulation, is on the y-axis, so y is the amount of watts available at each frequency. But watts is a function of frequency (E=hv) and no matter how much IR you have, you will not be as hot as a little UV."

Ward: "But thermal energy is not additive."

The guy is getting the energy of individual photons confused with the energy flux. I.... wow.

It reminds me of this. No, seriously, watch it:
https://www.youtube.com/watch?v=Qwr6_015ROo

Walter Hannah said...

@8c7793aa-15b2-11e5-898a-67ca934bd1df

My idea for that post and others like it was to just have a clear/simple explanation of skeptic errors to help fight the online information war and avoid personal attacks. The post about Peter Ward shows up at the top of the second page of the google search results for "Peter Ward Climate", which seems pretty good considering how much stuff he has written online. I would hope pages like these could eventually fill up the first page of search results, so anyone looking for info on someone's crazy ideas will at least have some alternate viewpoints to consider.

Tt also serves to address common misconceptions that people have. I know there are plenty of sites with the same info out there (with better written articles) but it can't hurt to have more explanations out there.

Maybe it's a fool's errand, idk.

andthentheresphysics said...

My idea for that post and others like it was to just have a clear/simple explanation of skeptic errors to help fight the online information war and avoid personal attacks.

That was the motivation behind my blog, when I started it.


I know there are plenty of sites with the same info out there (with better written articles) but it can't hurt to have more explanations out there.


Absolutely. The more the merrier.


Maybe it's a fool's errand, idk.


Depends on your goal. If you're hoping to convert the unconvertable, then, IMO, yes it is. If your goal is to simply provide another site with credible information to counter all the nonsense out there, then no it is not.

Walter Hannah said...

OpenID andthentheresphysics said... "That was the motivation behind my blog, when I started it."

So is that not the motivation for your blog now?

andthentheresphysics said...

So is that not the motivation for your blog now?

Yes, it still is, although I've somewhat expanded what I write (there's only so many times you can rebut what's promoted on "skeptic" sites).

What I should have said in my response is that it was my motivation and I thought that nice simple explanations would convince those who seemed to dispute the mainstream position. The latter is the bit that I no longer regard as viable. I guess I can't say how it might have influenced lurkers, but I don't think I've ever encountered someone who publicly disputed the mainstream positions, who's then changed their mind after reading something I've written.

Windchasers said...

I guess the logical question for Ward would be to ask him how he'd calculate an energy flux, given a set of frequencies and their intensities.

If the known equations are wrong, then what's the right one? How would you convert between (wavelengths + intensities) and energy?

Walter Hannah said...

Windchasers said...
I guess the logical question for Ward would be to ask him how he'd calculate an energy flux, given a set of frequencies and their intensities.


Peter would say that intensity is a linear function of frequency only, and some other nonsense about addition doesn't make sense.

andthentheresphysics said...

Windchaser,
You should read the comment thread on Walter's post. This was tried. Ward claims it's simply not possible due to flaws in our current understanding of radiative physics.

EliRabett said...

8C

As RayP said about Lindzen, some people are always wrong, but some of them are wrong in interesting ways. Ward's perambutations provide a platform for interesting explications which are hopefully useful to otherbunnies.

8c7793aa-15b2-11e5-898a-67ca934bd1df said...

A useful wrong hypothesis is something like the Younger Dryas impact hypothesis, which wrong or right has propelled several diverse fields in geophysics, paleontology and condensed physics forward dramatically.

With regards to ozone, every academic crackpot should consult wiki first, which could save them a lot of embarrassment. The only really interesting result I could find in this field is here. The rest of it is just splitting very thin greenhouse gas forcing and feedback hairs.

It's amazing what a small amount of ozone can do, but it's transient.

Hank Roberts said...

Disambiguation is important for 'oogling, remember.

"Peter L. Ward" and climate -- will find you one Peter Ward
"Peter Ward" and "Green Sky" and climate -- will find you a different Peter Ward

Under the "Search Tools" button change to "Verbatim" to improve on that.

When 'oogling, be very careful you don't Peiser yourself.

Hank Roberts said...

Or, to embrace a wider field of bad examples:
When 'oogling don't P yourself ...

Yeah, other searches turn up .... stuff. I found a New Z. zoology BA who believes the flashes from atmospheric nuclear tests were so much brighter than sunlight that they made self-sustaining persistent ozone holes that, over decades, slowly migrated to Antarctica. But he left out the quantum part.

I suspect in hindsight we'll observe that
-- extremely expensive hand-lettering preserved civilization but inhibited its spread;
-- moderately expensive letterpress-to-Linotype printing favored widespread literacy and progress; and
-- electronic media drowned civilization in an overwhelming froth of ignorance and nastiness.

It's so hard to get these balances right.
As Arthur Clarke wrote, "I remember Babylon"

Russell Seitz said...

Heat cannot physically flow from cold to hot. You do not stand next to a cold stove to get warm.

IT'S COLD TODAY; I THINK I'LL GO WARM MY HANDS OVER THE BACK OF THE REFRIGERATOR

8c7793aa-15b2-11e5-898a-67ca934bd1df said...

If it's cold, Russell, why are you running a freon compressor?

Hank Roberts said...

PPS, indeed thanks to Eli for the brief and clear explanation.
I'd like to be able to find it later -- it ought to be pinned somewhere.
It should be a supplement to Weart's AIP History, which doesn't explain this bit.

Brandon R. Gates said...

Windchasers,

And then there are things that weigh the same as other things which float on water.

Hank Roberts,

I haven't tried to add up all that.

You can't. Points aren't additive.

Hank Roberts said...

Omigosh, there's a third P in the cautionary "when 'oogling, don't P yourself collection.
-----

> points aren't additive

Extra credit for doing your own addition for yourself

Hank Roberts said...

Entirely aside to Eli -- sidebar death to report, SomeAreBoojums is now owned by some credit mortgage crap merchant. A link to the Archive copy would be good if it's there.

EliRabett said...

Ankh,

There is a story

http://www.somesnarksareboojums.com/blog/?p=175

Rising from the earth’s damp clutch, shaking off clods and looking around dumbly, the blog attempted to form a thought. “Me … alive?”

If you found your way here, you know that this blog’s domain is now “somesnarksareboojums.com” and not “someareboojums.org.” Long story. Let me just advise that, before you sign up with an ISP run by a guy out of your cousin’s mini-storage, do some comparison shopping, ferchrissake. Live and learn. Anyway, recently I felt the need to re-start this thing. I have a whole herd of new bêtes noire now, and a bunch of them are about to calve. Something had to be done. We all know that I’m not a post-every-day kind of guy, so we’ll see how it goes.

Hank Roberts said...

Thankyouthankyou. I sure hope for more there, there, eventually.

Peter Ward said...

While you have a little of the story right, the issue is do you want to discuss science and learn or just keep your blindfold on and play piñata?

The greatest warming of air in the atmosphere clearly occurs in the stratosphere, heated by solar ultraviolet radiation. The basic reason is that when a molecule of gas is dissociated, the molecular pieces fly apart at high velocity. Since gas temperature is proportional to average kinetic energy of all gas molecules and kinetic energy is proportional to the velocity squared, dissociation converts all of the energy in the bond directly into a temperature increase.

When a gas molecule absorbs energy too low to cause dissociation, that energy is absorbed by the bonds and we need to assume the energy gets converted to kinetic energy via collisions. This conversion does not appear to be efficient. It has never been proven experimentally that greenhouse gases absorbing such energy actually warms air significantly. That is the reason for my climate challenge (whyclimatechanges.com/challenge/).

Radiant energy (E) is well known among atmospheric chemists to equal the Planck constant (h) times frequency (v, Greek letter nu). The highest frequency solar radiation reacts first. It takes high energy to ionize molecules, forming the ionosphere. As we approach the top of the stratosphere the highest energy available is able to dissociate oxygen. The higher the energy, the higher the bond strength, the higher the velocities of molecular pieces, the higher the temperature increase upon dissociation. This is why the upper stratosphere is warmest and why it has trivial amounts of ozone. In your diagram showing actinic flux as a function of wavelength, note that the greatest absorption of energy between 40 and 50 km, the upper part of the stratosphere, is around 242 nm, the “wavelength” of the energy required to dissociate oxygen, which is in the ultraviolet-C range.

As we go lower in the stratosphere, ozone begins to form and be dissociated. This is at a maximum in the ozone layer because an average molecule of ozone only lasts around 8.3 days. The ozone layer is where the Chapman cycle works most efficiently typically absorbing most UV-B solar radiation energetic enough to dissociate ozone. The ozone layer is in the lower part of the stratosphere where the temperatures are lower. The UV-B radiation necessary to dissociate ozone is lower energy that UV-C, so the temperature in the lower stratosphere is cooler than in the upper stratosphere.

The basic problem with the Trenberth diagram is that he shows 333 W/m2 back radiation from greenhouse gases which is twice the 161 W/m2 of radiation coming from sun and absorbed by Earth’s surface. Does this make sense to you? Do you get warmer standing in sunlight or outside at night absorbing back radiation?