Guest essay by Phillip Mulholland

Late Carboniferous to Early Permian time (315 mya — 270 mya) is the only time period in the last 600 million years when both atmospheric CO2 and temperatures were as low as they are today (Quaternary Period ). Temperature after C.R. Scotese http://www.scotese.com/climate.htmCO2 after R.A. Berner, 2001 (GEOCARB III) 
In a previous thread on WUWT published on 13 September titled Claim: atmosphere heats the oceans, melts Antarctic ice shelf, Sridhar Anandakrishnan, Professor of Geosciences, at Penn State is reported as saying:-
“Eventually, with all that atmospheric heat, the oceans will heat up.”
Well, that statement may or may not be true, but one thing we can be certain about, it does not apply to the seas around Antarctica.
A former colleague of mine had on the wall of his office a standard map of the World with the continents coloured by surface elevation. Unusually his map showed the icecaps of Greenland and Antarctica, not as featureless white regions, but instead coloured by the true elevation of the ice surface. What his map showed is the dramatic height of this surface, both over the bulk of Greenland and also over the vast majority of Antarctica, with layers of ice piled high into the atmosphere forming a plateau as tall as the mountain ranges of other continents.
His map demonstrated why Antarctica at 2,500m has the greatest average surface elevation of all the continents. With its high surface elevation that reaches a plateau maximum at Dome A of just over 4,000 metres, Antarctica stands taller in the atmosphere than any other landmass. With thin dry transparent air above it and the long months of the Austral winter, the ice surface of Antarctica acts as a gigantic thermal radiator that short circuits the atmospheric greenhouse effect and exhausts surface radiant energy directly into Space.
Throughout the winter season of darkness in Antarctica the thermal cooling of the ice surface generates copious amounts of cold dry dense air, this bitterly cold tropospheric air flows north off the icecap towards the Southern Ocean, descending to sea level as a gale force katabatic wind. The wind that Captain Scott referred to when he wrote “Great God this is an awful place”.
When the dense cold air reaches the coast at the Weddell Sea, its temperature is sufficiently low to flash freeze any open surface sea water, but the wind’s continuous force directs any newly formed ice north, away from the coast, creating a permanent open water gap The Latent Heat Polynya.
Oxygen is a reactive gas vital for the survival of animal life. In the oceans, oxygen can only be created either by biological activity in the surface waters of the photic zone or be directly dissolved from the atmosphere by the turbulent mixing of surface waves. In the planetary ocean sea water is layered by density and cold dense water is found throughout the bulk of the modern deep ocean. One of the challenges for Oceanography is to explain the presence and distribution of dissolved oxygen gas in the ocean deeps, given that it cannot have been formed there.
The explanation for the presence of this deep ocean oxygen lies in the existence of the Latent Heat Polynya in the Weddell Sea and elsewhere along the coast of Antarctica. Here, in the polynya, cold dense sea water is created, chilled and oxygenated by the katabatic winds of Antarctica and salted by the key process of brine rejection – dense salty water expelled from the continuously formed sea ice. This chilled sea water descends into the ocean as a gravity driven flow of high salinity brine that carries the dissolved oxygen vital for deep marine life down into the ocean depths. Truly it can be said that the polar icecaps are the lungs of the deep ocean.
The current climate paradigm recognises two distinct and separate states for world climate, the Icehouse World and the Greenhouse World. The Icehouse World is characterised by low atmospheric carbon dioxide levels, cold ocean deeps with high levels of dissolved oxygen and of course, polar continental icecaps with consequent low global sea levels. The Greenhouse World by contrast is characterised by high atmospheric carbon dioxide levels, warm ocean deeps with low levels of dissolved oxygen, no polar continental icecaps and therefore high global sea levels.
Geology shows us that in the past during the Cretaceous period, at a time when the world did not have any polar continental icecaps and global sea levels were high, the ocean deeps were filled with warm +15C dense salty oxygen-poor water creating the required conditions for global marine anoxia and the deposition of Sapropel, (biological carbon) in deep ocean muds of, for example, the Cretaceous Boreal Ocean. The implication here is clear, because warm sea water has a low dissolved gas carrying capacity, anoxia is preferentially associated with warm world conditions and the presence of sapropel in the Geological record is considered to be diagnostic of a Greenhouse World.
This dichotomy is a fundamental tenet of climate science. That climate can be in one state, either global cold – the Modern world, or global warmth – the Cretaceous world, but not in both states simultaneously. However this tenet is wrong and Geology proves that it is wrong. It is indeed possible to have a world with a massive continental polar ice cap, an Icehouse World diagnostic, and simultaneously anoxic prone warm water ocean deeps, a Greenhouse World diagnostic, and that world was the Carboniferous period.
Imagine a world with no South Atlantic Ocean, instead South America is joined directly to Africa, a world with no Southern Ocean, instead Antarctica is joined directly to Australia and also no Indian Ocean with instead the Indian landmass (along with Madagascar) filling the jigsaw puzzle gap between South America/Africa/Arabia and Australia/Antarctica. This southern continent is called Gondwana by Geologists. Imagine this gigantic Gondwana continent covered with an ice sheet that at its maximum extended from the South Pole across an area equivalent to all of Antarctica, Southern Australia, India, Madagascar, south & east Africa and southern South America combined. This continental icecap existed throughout the Carboniferous period. The modern world’s single polar ice continent of Antarctica is puny in size compared to this ice monster.
Victorian geologists were very interested in the Carboniferous period; the coal won from these rocks powered their industrial world. Studies of the Carboniferous strata in north Yorkshire demonstrated the existence of Cyclothems, repeated patterns of marine sedimentation that start with a coal seam, the remains of an equatorial forest being drowned and then often overlain by marine limestone. The limestones were then in turn overlain by river delta sediments as the coast moved seaward and the shallow sea retreated. Eventually the swamp forests regrew and another coal seam was created. The Victorians recognised that this rhythmic depositional cycle seen in the Yoredale deposits of Yorkshire was controlled by eustatic sea level change. That is global sea level variations controlled by the waxing and waning of a major continental icecap. We now know that the icecap responsible for the Carboniferous cyclothems was located on the Gondwana continent.
So the deep oceans of the Carboniferous world were filled with cold oxygenated seawater created by the katabatic winds of the Gondwana icecap, just like those from the modern world’s Antarctica? Well no actually the deep ocean of the Carboniferous world was anoxic just like the later Cretaceous ocean. Again thanks to the Victorian geologists who studied the Culm deposits of Devon they recognised that the Carboniferous Culm contained radiolarian chert, pseudomorphs of calcite and abundant organic carbon. They concluded correctly that Culm was a deep ocean deposit, and although they did not recognise the true size of the ocean they were studying, we know because of their work, that the muds were bathyal sediments deposited below the carbonate compensation depth far from land. The carbon content of Culm proves that the Carboniferous world ocean was anoxic and that abundant marine sapropel was created and deposited in Carboniferous marine sediments which now form part of the oil and gas shale resource which supplies the hydrocarbon fuel used to power our modern industry and commerce.
So how can we resolve this paradox of the Carboniferous with its simultaneous continental icecap of Gondwana and an anoxia prone global ocean? In Geology, the present is often the key to the past, and we have a key to unlock this conundrum. That key is the modern Red Sea.
The Red Sea is situated in the northern hemisphere tropics between Africa and Arabia. Under modern climatic conditions, located beneath the Hadley Cell, the Red Sea experiences high insolation, high evaporation and low fresh water input. These features combine to produce a Red Sea marine bottom water with the highest temperature (21.7C) and salinity (40.6 psu) in the modern world, even with its current low carbon dioxide atmospheric conditions.
Although the outflow volume of Red Sea high temperature bottom water into the Indian Ocean does not impact the modern deep water temperatures of the World Ocean, the key point is that Red Sea deep water produced under a modern tropical climate has a higher density at 1028.579 kg/m3 than any of the cold deep water currently produced in Antarctica by the modern world’s polar climate. For example Antarctic Bottom Water has a minimum temperature of -0.8C, a peak salinity of 34.6 psu and a consequent density of 1027.880 kg/m3.
If these two bottom waters, cold oxygenated polar deep water and warm high salinity low-oxygen carrying tropical bottom water, were allowed to meet, the density stratification principle requires that the densest marine water will occupy the deepest part of the ocean. Red Sea bottom water is denser than the coldest water Antarctica can produce. In a straight contest between the Red Sea and the Weddell Sea, the Red Sea wins every time.
So consider now the Carboniferous period with its shallow tropical seas and vast coastal equatorial coal swamps and remember that half of the surface area of our planet is located between 30 degrees North and 30 degrees South. The shallow seas of the tropics are huge solar energy collectors producing warm dense marine brines. Even in the Carboniferous with its gigantic Gondwana icecap the world was warm because in Oceanography marine water salinity trumps marine water temperature every time.
The Carboniferous shows us that with open ocean conditions the natural state of the world’s climate is as follows-
A polar continental icecap that produces cold oxygenated mid-level ocean water. This sea water is less dense and therefore is layered above the warm dense saline and anoxia-prone tropical water of the bathyal ocean depths.
I leave you with this conclusion. The Carboniferous was a warm ocean world, with low gas solubility in the deep sea. This produced an atmosphere suitable for land plants as they had an abundance of carbon dioxide gas to consume. Not for nothing does this period of Earth’s geological history have as its name the Carboniferous and yet in the mid-ocean above the deep abyssal anoxia, the pelagic fish also had an abundance of dissolved oxygen to breathe thanks to the presence of the Gondwana icecap and its coastal latent heat polynya.
This essay proposes that a fundamental tenet of climate science, that the world’s climate can be in one of two separate and distinct modes, either the Icehouse world or the Greenhouse world, is false.
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Stephen Rasey says:
October 8, 2013 at 1:59 pm
@phlogiston 9:25 am
Ok. Birds have the same physiology as pterosaurs ( a hypothesis ). Hopefully in 100 MY of evolution birds have made some physiological improvements on pterosaurs.
So… where are the birds who are as big as were the pterosaurs?
Where today are the dragonflies with 26 inch wing spans?
OK I accept there might have been higher [O2] in the past especially to explain those big insects. How high does [O2] have to get in the atmosphere before a single flash of lightning will burn down any vegetation that is not currently being rained on?
milodonharlani 2:34 pm
The teratorns & other large volant birds existed fairly recently, ie in the Pliocene to Pleistocene. …. They achieved up to seven meter wingspans, versus the 10 to 15 m of the azhdarchid pterosaurs: http://en.wikipedia.org/wiki/Argentavis
Dragonflies were huge in the Carboniferous Period (not the Mesozoic Era) more because of high oxygen content than total air P much denser than now. Pressure was higher then, but not five to 20 bar.
Ok, now we are getting somewhere.
You agree the pressure was higher in the Carboniferous. I don’t know if it was as high as 20 atm (the upper end of my range). 5 atm might be high for a low side. I can come down to 3 atm.
2 atm is a bit hard to do. Here’s why:
The biggest birds today are somewhere between 1/2 to 1/3 the DIMENSION of the biggest pterosaurs. Mass goes with Dimension as the cube. Let’s say that the biggest Condors are only 1/2 of size of the pterosaurs. That means the pterosaurs were at least 8 times the weight, and maybe not as flight efficient as a condor. So go back to Eq. 17. 8 times the weight is hard to do without at least 8 times the density of air. Even if somehow the pterosaur somehow scales by area and not volume, it must still be 4 times the density. Split the difference and you are at 6. These are conservative estimates, starting from the observation/hypothesis that today’s bird’s wingspans are as big as 1/2 of the pterosaurs.
Go back to that 26 inch dragonfly in the Carboniferous.. You can’t get there just by more oxygen partial pressure. 26 inches is 5 times today’s biggest dragon fly. Scale it up not by volume ( power of 3) but by the power of 2.5. It is over 50 times heavier than today’s bug. How can you do that without about 50 times denser atmosphere? The only way I see it is you don’t just raise the partial pressure of O2 from 0.21 bar to 0.3 bar, but raise it to 1.0 bar which potentially gives an organism of 5 times the power potential for equal weight. Therefore you could get such a dragon fly with a 10 bar atmosphere with 10% oxygen, 1.0 bar O2.
Stephen Rasey says:
October 8, 2013 at 3:55 pm
We’re not getting anywhere. We’re right back where we were.
It’s hard even to get to two bar as the Carboniferous maximum air pressure, let alone three or five to twenty. I keep asking where you think all the N2 went, then as now the major component of earth’s atmosphere, & you keep not answering.
Studies of the Carboniferous atmosphere find falling CO2, taken up by plants, while O2 increased. The lack of fungi contributed to the formation of coal swamps.
The spontaneous-combustion-set upper limit on O2, around 35%, may well have been reached during the Carboniferous. However scientists researching the Period have found no evidence for a doubling, tripling or 20-fold increase in N2:
http://jeb.biologists.org/content/201/8/1043.full.pdf
“Concomitant with this reduction in carbon dioxide
concentration, the oxygen concentration of the late Paleozoic
atmosphere may have risen to as high as 35 % (Berner and
Canfield, 1989; see Fig. 1), a remarkable value compared with
the 20.9 % of the contemporary atmosphere. This elevation of
oxygen partial pressure occurred against the background of a
constant nitrogen partial pressure (Hart, 1978; Holland, 1984),
yielding an increased total pressure of the atmosphere.”
Now, that constant N2 may have been somewhat higher than now, but not enough even in combo with fifteen percentage points higher O2 concentration & trace gases, even to double total air P.
So even making the generous assumption that N2 increased as much as O2, for which there is no evidence, we’re talking 1.3 bar, not 2.0, 3.0, 5.0 or 20.
The high O2 helped flight metabolism & the slightly denser air made flying a bit easier, but that’ it. So we’ve gotten nowhere.
The best physical evidence now available suggests at most two bar in the distant past, ~2.7 Ba, with decline to near present density before the Paleozoic Era 543 Ma. The constituent components change within narrow ranges, with high CO2 in the Cambrian Period replaced by even higher O2 by the Carboniferous, but overall atmospheric surface pressure hasn’t altered all that much.
As noted, for instance, oxygen fell down to around 15% in the Early Triassic, after the End Permian Mass Extinction Event, then rose during that Period in which the first small pterosaurs evolved, & continued doing so in the Jurassic, when birds developed. But I’m repeating myself, although with more numbers.
phlogiston says:
October 8, 2013 at 3:38 pm
As above, 35% O2 concentration makes fires easy to start & hard to stop. So the giant Carboniferous dragonflies probably enjoyed oxygen levels a little lower than that, but higher than present 21%.
milodonharlani says: @ur momisugly October 8, 2013 at 3:08 pm
>>>>>>>>>>>>>
Thanks
It does get a bit murky. I think there is also another point below which plants do not have enough energy to reproduce. Perhaps that was the 180 to 200 ppm. Also it probably differs from species to species a bit. (I am a chemist not a biologist BTW)
It’s not straight-forward since CO2 can’t be taken in isolation, but other factors such as temperature, water, sunlight, elevation, growing season, total air pressure, etc. naturally also figure into overall growth & plant health:
http://www.ncbi.nlm.nih.gov/pubmed/19017126
It’s safe to say that under glacial conditions, 150 ppm is starvation for most C3 plants. As you note, the plant itself could survive just barely, but not have enough energy or resources to reproduce, like yard plants when I don’t water them enough & they don’t flower. Eventually years of such mistreatment will kill them, too.
@milodonharlani 4:23 pm
We’re right back where we were.
I don’t know about you, but I’ve made progress. This has been a thought provoking discussion and I thank you.
As I understand your argument,
1. Atmospheric pressures have changed,
2. but only by a fraction of a bar
3. [O2] has changed, but in the range of 15%(hypooxic) to 35%(spontaneous combustion)
4. [N2] has remained constant. There is no mechanism to gain or loose significant amounts of N2 from the atmosphere.
5. [CO2] has been under 0.5% in the Phanerozoic and as such is insignificant in terms of pressure.
6. No other gases move the needle.
So the only changes to air density come from changes of +/- 0.1 bar of O2 and maybe a minor loss of N2 escaping to space.
I’ve been coming at it from an aerodynamic point of view.
1. Atmospheric pressurs have change,
2. and have been on a long term decline.
2a. We loose gas to space, preferentially loosing lighter molecules
3. [O2] has changed, but in the range of hypooxic to hyperoxic – spontaneous combustion. Gaia is in charge when it comes to Oxygen.
4. Hmmm. The Amount of N2 in the atmosphere is a hard nut to crack. If the earth can retain H2O, it should retain N2.
http://abyss.uoregon.edu/~js/ast121/lectures/lec14.html>
4b. NH3 isn’t an escape vector, it is only a little lighter than H2O.
4c. Nitrogen doesn’t make up minerals.
4d. Nitrogen isn’t not as big a component of biology as is C and O2.
5. [CO2] has been under 0.5% in the Phanerozoic and as such is insignificant in terms of pressure. — Wait a minute!
5a. How do we know that?
Really? Only 12 times more than today?
How much carbon is accounted for in CO2 in the atmosphere compared to other places: (See Wiki: Carbon Cycle) in gigatons
Atmosphere: 720 GT
Fossil Fuels: 4,130 GT (90% coal and peat)
Terrestrial biosphere: 2,000 GT (living and dead)
Ocean organic: 1,000 GT
Ocean inorganic: 37,400 GT
Lithosphere Kerogens: 15,000,000 GT
Lithosphere Carbonates: more than 60,000,000
There is 100,000 times more carbon locked in terrestrial Kerogen and carbonates than is in the current atmosphere. These are all BIOLOGIC and for the most part formed in the Phanerozoic. Where did all that carbon (and oxygen!) come from if it wasn’t in the atmosphere/hydrosphere 700 Mya?
Today’s [CO2] has a partial pressure of 0.0004 bar. If we unlock all those carbonates and kerogens and return them to the atmosphere, the partial pressure would be 40 bar.
Ok, that was a real rough back-of-the-envelope guesstimate. We can hide some of that in the oceans, maybe all of it. Max solubility is 3 g / kg of water.
Or we need 330 GT water for each GT of CO2. We’d have 75,000,000 GT = 250,000,000 GT CO2. So we need 90,000,000,000 GT = 9.0E+10 GT water to dissolve it.
Mass of the Ocean (Hypertextbook): 1.37 × 10^21 kg = 1.4E+18 ton = 1.4E+09 GT
So we can dissolve only about 1.5% of the CO2 in the ocean.
I still have a 40 bar CO2 atmosphere untill we can start creating carbonates.
The problem isn’t how do we get N2 concentrations to jump un and down, but how do we account for all this Carbon, which is probably in CO2, before we lock it up in carbonates? How does life operate in a hyperbaric mix of CO2 and O2?
So, how the heck can we have a 0.5% CO2 atmosphere at the start of the Phanerozoic before we have created carbonates in mass and organic kerogens buried in sedimentary rocks. Was the carbon locked up in algal mats and stromatalite mounds?
Stephen Rasey says:
October 8, 2013 at 10:43 pm
I’m glad you’ve found our discussion worthwhile.
How much N2 might leak to space I don’t know, but seems not a lot. A possible mechanism for removal of a little I noted above, ie combination with “excess” oxygen during the catastrophic K/T impact event atmosphere, but that would be just a fraction at most & might have been returned to the air during the Cenozoic.
I haven’t addressed your aerodynamic arguments, since I feel the links to pterosaur research I’ve posted adequately address those issues. Giant Carboniferous arthropods IMO are explained by high O2, not a much denser atmosphere. It wasn’t just flying insects but ground-dwelling & burrowing arthropods as well which grew enormous.
While there has been geologic uptake of CO2 during the Phanerozoic, the main force drawing down the gas from atmospheric concentrations on the order of 10,000 ppm to 100 ppm has been land & sea photosynthesizers, plus cooler oceans.
There just hasn’t ever been enough CO2 in earth’s air for about the past 2.7 billion years to get total pressure much higher than twice present density. In the early eons, it was taken up by rocks & later by life, despite additions from volcanism. It might have regained the 10% level during Snowball Earth intervals, but I don’t know how much physical evidence there is for that, as opposed to purely hypothetical.
IMO the raindrop study’s finding of a max of 2.0 bar 2.7 Ba makes sense. Sure I’d like to see confirmatory studies, but the picture of atmospheric evolution which it paints cannot be easily falsified, or at least hasn’t yet been, that I’ve found.
But it’s good to have people challenging every emerging orthodoxy.
@milodonharlani 8:19 am
There just hasn’t ever been enough CO2 in earth’s air for about the past 2.7 billion years to get total pressure much higher than twice present density. In the early eons, it was taken up by rocks
That’s the part I’m challenging. How do we know the partial pressure of CO2 at the start of the Phanerozoic was less than 0.01 bar?
Photosynthetic life created oxygen and the Banded Iron Formations of the Archean. Here is an interesting page on Chapter 11: Climate Regulation and Atmosphere Evolution through Geologic Time
A couple of quotes about that caught my eye:
Point 1 is weak evidence. We don’t see evidence of high acidic rain. We don’t know a lot about the Archean. What else is in the atmosphere to buffer the solution? But it is an issue I cannot ignore.
Point 2 is interesting. If life is necessary to fix hydrogen to oxygen to form water, and thereby keep from losing H2 to space, it is profound. I guess it follows from life isn’t necessary to combine oxygen and hydrogen, but the oxygen is rare without life to make it available to hydrogen.
Point 3 is the killer. Black shales. I guess I found my Archean carbon sink. I cannot contest that there will be long term preservation — the oceans will be very hypoxic. These Black shales will be subducted and the carbon will return via volcanism later. But it is a very real avenue to remove CO2 from the atmosphere, sink the carbon and hydrogen and liberate oxygen for the formation of minerals, thus reducing the atmospheric pressure.
So I’ll have to reduce my range of paleoatmospheric pressures. I’m not ready to discard the aerodynamic argument yet. But I’ll have to give greater weight to the proposition that O2 Partial pressure today the limiting factor on flight and not total atmospheric density.
Thanks for the conversation.
Stephen Rasey says:
October 9, 2013 at 12:54 pm
As you know, there is a wide range of error bars on Cambrian CO2 estimates from paleosols & other data, but 7000 ppm is the usually cited best guess.
You’re welcome. Thank you.
Stephen Rasey, October 8, 2013 at 10:43 pm
milodonharlani, October 9, 2013 at 1:11 pm
An interesting conversation. Thanks for the collection of useful parameters Stephen, I particularly liked the comment about the Archean black shales acting as a carbon sink.
In this post I have concentrated on the point that cold water absorbs gas from the atmosphere, and only alluded to the converse point that warm water expels gas back into the air, without giving any details of how this process is achieved for the carbon dioxide that is chemically bound in sea water. Atmospheric carbon dioxide gas dissolves readily in cold fresh water (for example raindrops) and forms the mild acid, carbonic acid. The standard chemical test for carbon dioxide is to bubble a sample of gas through lime water, which is a solution of the alkali chemical calcium hydroxide.
Carbonic acid combines with lime water to form a milky white precipitate of the insoluble salt calcium carbonate (acid plus base forms a crystalline salt plus molecular water). If however you continue the test and bubble more carbon dioxide gas into the cloudy water, another change occurs, the milky white precipitate of calcium carbonate disappears as water soluble calcium bicarbonate is formed.
Limestone is unusual among the sedimentary rocks in that its mineral calcite is formed by precipitation as dissolved calcium bicarbonate in seawater is converted to insoluble calcium carbonate with the expulsion of a carbon dioxide molecule. This geochemical process readily occurs in warm agitated sea water, such as the beach swash zone of a tropical coral island, where oolitic carbonate sand grains are abundantly created. Although we primarily think of limestone as being an organic deposit, in fact half of the limestone rock found in sedimentary strata is inorganic in origin. Nature has merely adopted the chemical process of calcite mineral precipitation for its own purposes.
I need to revise a previous essay about carbonate rocks that was posted elsewhere and develop this theme more fully.
@Philip Mulholland 5:00 pm
I look forward to reading about the inorganic carbonate processes.
The same time as I was mulling over the potential 40 bar CO2 atmosphere, I checked the mineralogy of the Banded Iron Formation. What I found was that the non-iron bands were sands and cherts instead of carbonates.
There are two pregnant questions here.
First, why not inorganic carbonate between the iron bands? Was it Ph? At what Ph ranges does inorganic carbonate deposit, probably dependent upon some other parameter, like temperature.
Second, the banding of the formation illustrates many thousands of climate changes that starts and stops the deposition of iron. The time frame of this would be fascinating. Is this going on during the acid rain, leaching continents with seasonal fluxes of eroded minerals.
Philip Mulholland says:
October 9, 2013 at 5:00 pm
I’m glad that our discussion on past atmospheric pressures arising from Mesozoic pterosaur & Paleozoic dragonfly flight has been of some use to your work on carbonate rocks, in particular Stephen’s comment on Archean black shales. This is an example of how blogs can help advance science, whether amateur or professional.
A closing reflection:
This is a chart of Paleo atmospheric composition over the whole history of the earth.
I have some technical problems with it. The overlap of the Water Vapor and Carbon Dioxide areas screws up the Nitrogen areas.
But the biggest problem with this and other similar composition charts gets back to the overall discussion on atmospheric pressure. This type of chart boxes you into thinking about constant pressure and all that is changing is the relative composition. The present is NOT the key to the past; it only hints at the past. Just because today it is 1 atm, shouldn’t lock you into thinking it was always 1 atm.
My enlightenment this week has been in the mineralization of the Archean CO2. I am going to have to accept that by the beginning of the Phanerozoic the atmospheric pressure is probably under 5 atm and likely under 2.5 atm. But I’m probably more convinced than ever that at the beginning of the Archean, at the dawn of photosynthetic life, we see partial pressures of CO2 in the 10 – 80 bar range. Our atmosphere didn’t escape into space — life turned CO2 from gas into solid by transforming CO2 into hydrocarbons, oxides, silicates and free oxygen. The end of the Archean is less an end of high CO2 partial pressures, but an end of the acidic – neutral oceans as life-generated free oxygen precipitated out the cat-ions from the oceans. In the Proterozoic, CO2 partial pressures can (must?) continue to fall as life continues to generate O2 and lock up C in Carbonates.
So Atmospheric Composition charts needs to be created in a stacked area chart of partial pressures or by TeraTons. (Partial pressure (at sea level) would be preferable, but sea level adds noise to the calculation.) In this chart, we have 1/2 of a Venusian atmosphere at the beginning of the Archean (60 bar) and over 2.5 billion years it drops to under 2-4 bar by the beginning of the Pherozoic.
A companion chart of ocean composition (pH, O2, sulfur, metals, isotope ratios) should parallel the atmospheric chart.
Viewed in this light, a fall of CO2 partial pressures and total atmospheric pressures with corresponding drop in temperatures via lapse rates, a Snowball Earth scenario is not only possible, but maybe inevitable.
Refs:
Grotzinger 2010, “PreCambrian Carbonates: Evolution of Understanding”
Grotzinger 2009, Archean Oceans cooler, better for origin of life
Hydrogen deuterium ratio in Archean cherts is lighter than today. Loss of H2 to space over time to change the ratio.
Stephen Rasey says:
October 10, 2013 at 11:26 am
From the Oct 4, 2013 edition of Science:
http://www.sciencemag.org/content/342/6154/101.short
“Understanding the atmosphere’s composition during the Archean eon is fundamental to unraveling ancient environmental conditions. We show from the analysis of nitrogen and argon isotopes in fluid inclusions trapped in 3.0- to 3.5-billion-year-old hydrothermal quartz that the partial pressure of N2 of the Archean atmosphere was lower than 1.1 bar, possibly as low as 0.5 bar, and had a nitrogen isotopic composition comparable to the present-day one. These results imply that dinitrogen did not play a significant role in the thermal budget of the ancient Earth and that the Archean partial pressure of CO2 was probably lower than 0.7 bar.”
This finding comports well with the raindrop study, which put maximum atmospheric pressure 2.7 Ba at two bar.
@milodonharlani 8:52 am
RE: Marty et al. 2013, Nitrogen Isotopic Composition and Density of the Archean Atmosphere
Bernard Marty, Laurent Zimmermann, Magali Pujol, Ray Burgess, and Pascal Philippot
Science 4 October 2013: 101-104.Published online 19 September 2013
Thanks. And Wow. But check out the pod cast at
http://www.sciencemag.org/content/suppl/2013/09/18/341.6152.1409-b.DC1/SciencePodcast_130920.pdf (171 KB) from 18:56 to 27:21.
(11:30 am continued)
Earlier in the podcast transscript there is this:
From this, there seems to be a leap of faith that what they measured was indicative of surface water in saturation equilibrium with the atmosphere. But they may be measuring the composition of the gasses in the hydrothermal water as H4SiO4 precipitates out as silica as the water gradually cools and/or reduces pressure. See. The Quartz Page
Also, why didn’t they measure CO2 directly? Or at least Carbon content? Was the ratio of N2/Ar important to the process, and therefore a critical assumption?
Stephen Rasey says:
October 11, 2013 at 11:30 am
On WUWT, you’ll find extensive discussion of why the supposed paradox of a weak early sun & liquid watery earth isn’t so paradoxical. Very high levels of GHGs don’t need to be invoked.
That said, CO2 at 0.7 bar in an atmosphere no denser than 2.0 bar is still a lot of CO2 to be drawn down geologically & biologically to perhaps 7000 ppm in less thick air by 543 Ma from 2700 Ma.
@milodonharlani 11:49 am
Going on the rough calculations from 10/8 10:43 pm>,
Atmosphere: 720 GT Carbon with CO2 at 400 ppm = about 0.4 mbar.
so roughly 1800 GT Carbon per mb CO2.
So, 7000 ppm is about 7 mbar or about 12,000 GT Carbon. (at begining of Phanerozoic)
700 mb would be 1,200,000 GT Carbon in the atmosphere.
But locked up in rocks today is about 75,000,000 GT of Carbon in carbonates and kerogens. Most of this carbon was in the biosphere from the start of time, and probably in the form of CH4 and CO2. I think we need to account for this mass in the Archean when oceans were ferrous and oxygen starved, beforee the Banded Iron Formation are precipitating out.
Going from 700 mb to about 7 mb or 1,200,000 GT to 12,000 GT Carbon in 1200 Ma in the mid-Archean to Proterozoic is child’s play compared going from 75,000,000 GT of carbon (somewhere) to 1,200,000 GT (atmoshpere) in the first 800 Ma of the Early-mid Archean.
(repost of 1:24 pm)
@milodonharlani 11:49 am
Going on the rough calculations from 10/8 10:43 pm,
Atmosphere: 720 GT Carbon with CO2 at 400 ppm = about 0.4 mbar.
Roughly 1800 GT Carbon (atmosphere) per mb CO2.
So, 7000 ppm is about 7 mbar or about 12,000 GT Carbon. (at begining of Phanerozoic) 700 mb would be 1,200,000 GT Carbon in the atmosphere.
But locked up in rocks today is about 75,000,000 GT of Carbon in carbonates and kerogens. Most of this carbon was in the biosphere from the start of time, and probably in the form of CH4 and CO2. I think we need to account for this mass in the Archean when oceans were at pH 6 to 7.5 while the Banded Iron Formation are precipitating out.
Going from 700 mb to about 7 mb or 1,200,000 GT to 12,000 GT Carbon in 1200 Ma in the mid-Archean to Proterozoic is child’s play compared going from 75,000,000 GT of carbon (somewhere) to 1,200,000 GT in the first 800 Ma of the Archean.
Stephen Rasey says:
October 11, 2013 at 1:24 pm
I don’t know if that much carbon was drawn down during the Archean (between 4 Ba & 2.5 Ba), but I do find atmospheric pressure no more than twice present density by 2.7 Ba convincing at this point.
Don’t recall if you’ve seen this 2010 Cold Springs Harbor study of the early atmospheres:
http://cshperspectives.cshlp.org/content/2/10/a004895
Abstract
“Earth is the one known example of an inhabited planet and to current knowledge the likeliest site of the one known origin of life. Here we discuss the origin of Earth’s atmosphere and ocean and some of the environmental conditions of the early Earth as they may relate to the origin of life. A key punctuating event in the narrative is the Moon-forming impact, partly because it made Earth for a short time absolutely uninhabitable, and partly because it sets the boundary conditions for Earth’s subsequent evolution. If life began on Earth, as opposed to having migrated here, it would have done so after the Moon-forming impact. What took place before the Moon formed determined the bulk properties of the Earth and probably determined the overall compositions and sizes of its atmospheres and oceans. What took place afterward animated these materials. One interesting consequence of the Moon-forming impact is that the mantle is devolatized, so that the volatiles subsequently fell out in a kind of condensation sequence. This ensures that the volatiles were concentrated toward the surface so that, for example, the oceans were likely salty from the start. We also point out that an atmosphere generated by impact degassing would tend to have a composition reflective of the impacting bodies (rather than the mantle), and these are almost without exception strongly reducing and volatile-rich. A consequence is that, although CO- or methane-rich atmospheres are not necessarily stable as steady states, they are quite likely to have existed as long-lived transients, many times. With CO comes abundant chemical energy in a metastable package, and with methane comes hydrogen cyanide and ammonia as important albeit less abundant gases.”
It goes on to discuss the first & second atmospheres. It says the earliest atmosphere consisted of gases from the solar nebula, primarily hydrogen, plus probably simple hydrides such as now found in Jupiter & Saturn, ie water vapor, methane & ammonia. As the solar nebula dissipated, these gases would have escaped, partly driven off by the solar wind.
The second atmosphere consisted largely of nitrogen plus CO2 & inert gases, released by volcanic outgassing, supplemented by gases produced during the late heavy bombardment of Earth by huge asteroids. A major part of the CO2 emissions were soon dissolved in water & built up carbonate sediments, as we agree.
What happened later in the Archean has been hypothesized by Jan Veizer (March 2005) in Geoscience Canada, “Celestial Climate Driver: A Perspective from Four Billion Years of the Carbon Cycle”, sometimes cited in this blog:
http://www.gac.ca/wp/wp-content/uploads/2011/09/GACV32No1Veizer.pdf
I’m well aware of the theory of impact formation of the moon. It is a whole chapter of Rare Earth. And until a few days ago, I thought that was the chief reason for our thinner atmosphere than Venus. It probably still plays a big part in Earth starting off with a leaner atmosphere after the impact. But the carbon mass balance is the problem to be solved.
http://www.gac.ca/wp/wp-content/uploads/2011/09/GACV32No1Veizer.pdf
Figures 5 and 6 pertain to the Phanerozoic, but little about the PreCambrian. No references to iron, Archean. But this caught my attention:
Ten thousand times 0.4 mbar is 40 bar. (How about that!?)
My 40 bar came from a mass balance from estimated mass of rocks. This is a value from what is necessary to warm the earth. (However, the estimated mass of rocks might have been from a circular assumption somewhere).
[1] this is a problem. But we are not dealing with sea water as we know it here. We have a reducing mineral soup before the Banded Iron Formations are deposited by oxygen generated by life. The number of ionic equilibrium equations in play is mind boggling.
Hadian Ocean Carbonate Geochemistry (Morse 1998)
http://www.minersoc.org/pages/Archive-MM/Volume_62A/62a-2-1027.pdf
This paper mentions Na+, Ca+2, Cl-, K+, Mg+2 concentrations makes no comment about Fe+2 or Fe+3, iron, or ferric or ferrous conditions. So I think the paper missed the boat on a major condition of the Archean oceans.
Correction to 2:20 pm
Ten thousand times 0.4 mbar is
404.0 bar.(How about that!?)The questions on my mind at the moment for later is:
How did we get a dissolved iron rich ocean in the first place?
One answer with a CO2 rich atmosphere, we have carbonic acid rain. It falls on continents and dissolves out the metals.
What are the chemical reactions mass balances?
Any chance the carbon is parked on land as a carbonate?
Or even a hydrocarbon like methane?
Was early Earth a Titan atmosphere until life oxidized the iron in the oceans?