Engelbeen on why he thinks the CO2 increase is man made (part 3)

About carbon isotopes and oxygen use…

1. The different carbon isotopes in nature.

The carbon of CO2 is composed of different isotopes. Most is of the lighter type: 12C, which has 6 protons and 6 neutrons in its nucleus. About 1.1% is the heavier 13C which has 6 protons and 7 neutrons in the nucleus. There also is a tiny amount of 14C which has 6 protons and 8 neutrons in the nucleus. 14C is continuously formed in the upper stratosphere from the collisions of nitrogen with cosmic rays particles. This type of carbon (also formed by above-ground atomic bomb experiments in the 1950′s) is radio-active and can be used to determine the age of fossils up to about 60,000 years.

One can measure the 13C/12C ratio and compare it to a standard. The standard was some type of carbonate rock, called Pee Dee Belemnite (PDB). When the standard rock was exhausted, this was replaced by a zero definition in a Vienna conference, therefore the new standard is called the VPDB (Vienna PDB). Every carbon containing part of any subject can be measured for its 13C/12C ratio. The comparison with the standard is expressed as d13C in per thousand (the term mostly used is per mil):

(13C/12C)sampled – (13C/12C)standard
————————————————————— x 1.000
(13C/12C)standard

Where the standard is defined as 0.0112372 part of 13C to 1 part of total carbon. Thus positive values have more 13C, negative values have less 13C. Now, the interesting point is that vegetation growth in general uses by preference 12C, thus if you measure d13C in vegetation, you will see that it has quite low d13C values. As fossil fuels were formed from vegetation (or methanogenic bacteria, with similar preferences), these have low d13C values too.  Most other carbon sources (oceans, carbonate rock wearing, volcanic degassing,…) have higher d13C values. For a nice introduction of the isotope cycle in nature, see the web page of Anton Uriarte Cantolla ( http://homepage.mac.com/uriarte/carbon13.html ).


This is an interesting feature, as we can determine whether changes of CO2 levels in the atmosphere (observed to be currently -8 per mil VPDB) were caused by vegetation decay or fossil fuel burning (both about -24 per mil) or by ocean degassing (0 to +4 per mil).

2. Trends in carbon isotope ratios, the 13C/12C ratio.

From different CO2 baseline stations, we not only have CO2 measurements, but also d13C measurements. Although only over a period of about 25 years, the trend is clear and indicates an extra source of low d13C in the atmosphere.


Recent trends in d13C from direct measurements of ambient air at different baseline stations.

Data from http://cdiac.ornl.gov/trends/co2/contents.htm

ALT=Alert; BAR=Barrow; LJO=La Jolla; MLO=Mauna Loa; CUM=Cape Kumukahi; CHR=Christmas Island; SAM=Samoa; KER=Kermadec Island; NZD=New Zealand (Baring Head); SPO=South Pole.

Again, we see a lag in the trends with altitude and NH/SH border transfer and less variability in the SH. Again, this points to a source in the NH. If that is from vegetation decay (more present in the NH than in the SH) and/or from fossil fuel burning (90% in the NH) is solved in the investigation of Battle ea. http://www.sciencemag.org/cgi/reprint/287/5462/2467.pdf
More up-to-date (Bender e.a.) and not behind a paywall:
http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf

Where it is shown that there is less oxygen used than can be calculated from fossil fuel burning. Vegetation thus produces O2, by incorporating more CO2 than is formed by decaying vegetation (which uses oxygen). This means that more 12C is incorporated, and thus more 13C is left behind in the atmosphere. Vegetation is thus a source of 13C and is not the cause of decreasing d13C ratios.

And we have several other, older measurements of d13C in the atmosphere: ice cores and firn (not completely closed air bubbles in the snow/ice). These align smoothly with the recent air measurements. There is a similar line of measurements from coralline sponges and sediments in the upper oceans. Coralline sponges grow in shallow waters and their skeleton is built from CO2 in the upper ocean waters, without altering the 13C/12C ratio in seawater at the time of building. The combination of atmospheric/firn/ice and ocean measurements gives a nice history of d13C changes over the past 600 years:


Figure from http://www.agu.org/pubs/crossref/2002/2001GC000264.shtml gives a comparison of upper ocean water and atmospheric d13C changes.

What we can see, is that the d13C levels as well as in the atmosphere as in the upper oceans start to decrease from 1850 on, that is at the start of the industrial revolution. In the 400 years before, there is only a small variation, probably caused by the temperature drop in the Little Ice Age.

In comparison, over the whole Holocene, the variation of d13C was only 0.4 per mil:

http://www.nature.com/nature/journal/v461/n7263/full/nature08393.html

And the change in d13C from the coldest part of the last glacial to the warm Holocene Optimum was only 0.7 per mil, slightly over the recent d13C change:

http://epic.awi.de/Publications/Khl2004e.pdf

The decrease of d13C in the atmosphere cannot be caused by some extra outgassing from the oceans, as that would INcrease the d13C ratios of the atmosphere (even including the fractionation at the ocean-air border), while we see a DEcrease both in the oceans and the atmosphere. This effectively excludes the oceans as the main cause of the increase.

3. The 14C/12C ratio

14C is a carbon isotope that is produced in the atmosphere by the impact of cosmic rays. It is an unstable (radioactive) isotope and breaks down with a half-life time of less than 6,000 years. 14C is used for radiocarbon dating of not too old fossils (maximum 60,000 years). The amount of 14C in the atmosphere is variable (depends of the sun’s activity), but despite that, it allows for a reasonable good dating method. Until humans started to burn fossil fuels…

The amounts of 14C in the atmosphere and in vegetation is more or less in equilibrium (as is the case for 13C: a slight depletion, due to 12C preference of the biological reactions). But about half of it returns to the atmosphere within a year, by the decay of leaves. Other parts need more time, but a lot goes back into the atmosphere within a few decades. For the oceans, the lag between 14C going into the oceans (at the North Atlantic sink place of the great conveyor belt) is 500-1500 years, which gives a slight depletion of 14C, together with some very old carbonate going into solution which is completely 14C depleted. In pre-industrial times, there was an equilibrium between cosmogenic 14C production and oceanic depletion.

Fossil fuels at the moment of formation (either wood for coal or plankton for oil) incorporated some 14C, but as these are millions of years old, there is virtually no 14C anymore left. Just as is the case for 13C, the amount of CO2 released from fossil fuel burning dilutes the 14C content of the atmosphere. This caused problems for carbon dating from about 1890 on. Therefore a correction table is used to correct samples after 1890.

In the 1950′s another human intervention caused trouble for carbon dating: nuclear bomb testing induced a lot of radiation, which nearly doubled the atmospheric 14C content. Since then, the amount is fast decreasing, as the oceans replace it with “normal” 14C levels. The half life time of the excess 14C caused by this refresh rate is about 5 years.

This adds to the evidence that fossil fuel burning is the main cause of the increase of CO2 in the atmosphere…

T4. Trends in oxygen use.

To burn fossil fuels, you need oxygen. As for every type of fuel the ratio of oxygen use to fuel use is known, it is possible to calculate the total amount of oxygen which is used by fossil fuel burning. At the other hand, the real amount of oxygen which is used can be measured in the atmosphere. This is quite a challenging problem, as the change in atmospheric O2 from year to year is quite low, compared to the total amount of O2 (a few ppmv in over 200,000 ppmv). Moreover, as good as for CO2 as for oxygen, there is the seasonal to year-by-year influence of vegetation growth and decay. Only since the 1990′s, oxygen measurements with sufficient resolution are available. These revealed that there was less oxygen used than was calculated from fossil fuel use. This points to vegetation growth as source of extra O2, thus vegetation is a sink of CO2, at least since 1990.

This effectively excludes vegetation as the main cause of the recent increase.

The combination of O2 and d13C measurements allowed Battle e.a. to calculate how much CO2 was absorbed by vegetation and how much by the oceans (see the references above). The trends of O2 and CO2 in the period 1990-2000 can be combined in this nice diagram:


O2-CO2 trends 1990-2000, figure from the IPCC TAR

http://www.grida.no/climate/IPCC_tar/wg1/pdf/TAR-03.PDF
This doesn’t directly prove that all the CO2 increase in the atmosphere is from fossil fuel burning, but as both the oceans and vegetation are not the cause, and even show a net uptake, and other sources are much slower and/or smaller (rock weathering, volcanic outgassing,…), there is only one fast possible source: fossil fuel burning.

Engelbeen on why he thinks the CO2 increase is man made (part 3)

About carbon isotopes and oxygen use…

  1. The different carbon isotopes in nature.

The carbon of CO2 is composed of different isotopes. Most is of the lighter type: 12C, which has 6 protons and 6 neutrons in its nucleus. About 1.1% is the heavier 13C which has 6 protons and 7 neutrons in the nucleus. There also is a tiny amount of 14C which has 6 protons and 8 neutrons in the nucleus. 14C is continuously formed in the upper stratosphere from the collisions of nitrogen with cosmic rays particles. This type of carbon (also formed by above-ground atomic bomb experiments in the 1950′s) is radio-active and can be used to determine the age of fossils up to about 60,000 years.

One can measure the 13C/12C ratio and compare it to a standard. The standard was some type of carbonate rock, called Pee Dee Belemnite (PDB). When the standard rock was exhausted, this was replaced by a zero definition in a Vienna conference, therefore the new standard is called the VPDB (Vienna PDB). Every carbon containing part of any subject can be measured for its 13C/12C ratio. The comparison with the standard is expressed as d13C in per thousand (the term mostly used is per mil):

(13C/12C)sampled – (13C/12C)standard
————————————————————— x 1.000
(13C/12C)standard

Where the standard is defined as 0.0112372 part of 13C to 1 part of total carbon. Thus positive values have more 13C, negative values have less 13C. Now, the interesting point is that vegetation growth in general uses by preference 12C, thus if you measure d13C in vegetation, you will see that it has quite low d13C values. As fossil fuels were formed from vegetation (or methanogenic bacteria, with similar preferences), these have low d13C values too.  Most other carbon sources (oceans, carbonate rock wearing, volcanic degassing,…) have higher d13C values. For a nice introduction of the isotope cycle in nature, see the web page of Anton Uriarte Cantolla ( http://homepage.mac.com/uriarte/carbon13.html ).


This is an interesting feature, as we can determine whether changes of CO2 levels in the atmosphere (observed to be currently -8 per mil VPDB) were caused by vegetation decay or fossil fuel burning (both about -24 per mil) or by ocean degassing (0 to +4 per mil).

  1. Trends in carbon isotope ratios, the 13C/12C ratio.

From different CO2 baseline stations, we not only have CO2 measurements, but also d13C measurements. Although only over a period of about 25 years, the trend is clear and indicates an extra source of low d13C in the atmosphere.


Recent trends in d13C from direct measurements of ambient air at different baseline stations.

Data from http://cdiac.ornl.gov/trends/co2/contents.htm

ALT=Alert; BAR=Barrow; LJO=La Jolla; MLO=Mauna Loa; CUM=Cape Kumukahi; CHR=Christmas Island; SAM=Samoa; KER=Kermadec Island; NZD=New Zealand (Baring Head); SPO=South Pole.

Again, we see a lag in the trends with altitude and NH/SH border transfer and less variability in the SH. Again, this points to a source in the NH. If that is from vegetation decay (more present in the NH than in the SH) and/or from fossil fuel burning (90% in the NH) is solved in the investigation of Battle ea. http://www.sciencemag.org/cgi/reprint/287/5462/2467.pdf
More up-to-date (Bender e.a.) and not behind a paywall:
http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf

Where it is shown that there is less oxygen used than can be calculated from fossil fuel burning. Vegetation thus produces O2, by incorporating more CO2 than is formed by decaying vegetation (which uses oxygen). This means that more 12C is incorporated, and thus more 13C is left behind in the atmosphere. Vegetation is thus a source of 13C and is not the cause of decreasing d13C ratios.

And we have several other, older measurements of d13C in the atmosphere: ice cores and firn (not completely closed air bubbles in the snow/ice). These align smoothly with the recent air measurements. There is a similar line of measurements from coralline sponges and sediments in the upper oceans. Coralline sponges grow in shallow waters and their skeleton is built from CO2 in the upper ocean waters, without altering the 13C/12C ratio in seawater at the time of building. The combination of atmospheric/firn/ice and ocean measurements gives a nice history of d13C changes over the past 600 years:


Figure from
http://www.agu.org/pubs/crossref/2002/2001GC000264.shtml gives a comparison of upper ocean water and atmospheric d13C changes.

What we can see, is that the d13C levels as well as in the atmosphere as in the upper oceans start to decrease from 1850 on, that is at the start of the industrial revolution. In the 400 years before, there is only a small variation, probably caused by the temperature drop in the Little Ice Age.

In comparison, over the whole Holocene, the variation of d13C was only 0.4 per mil:

http://www.nature.com/nature/journal/v461/n7263/full/nature08393.html

And the change in d13C from the coldest part of the last glacial to the warm Holocene Optimum was only 0.7 per mil, slightly over the recent d13C change:

http://epic.awi.de/Publications/Khl2004e.pdf

The decrease of d13C in the atmosphere cannot be caused by some extra outgassing from the oceans, as that would INcrease the d13C ratios of the atmosphere (even including the fractionation at the ocean-air border), while we see a DEcrease both in the oceans and the atmosphere. This effectively excludes the oceans as the main cause of the increase.

  1. The 14C/12C ratio

14C is a carbon isotope that is produced in the atmosphere by the impact of cosmic rays. It is an unstable (radioactive) isotope and breaks down with a half-life time of less than 6,000 years. 14C is used for radiocarbon dating of not too old fossils (maximum 60,000 years). The amount of 14C in the atmosphere is variable (depends of the sun’s activity), but despite that, it allows for a reasonable good dating method. Until humans started to burn fossil fuels…

The amounts of 14C in the atmosphere and in vegetation is more or less in equilibrium (as is the case for 13C: a slight depletion, due to 12C preference of the biological reactions). But about half of it returns to the atmosphere within a year, by the decay of leaves. Other parts need more time, but a lot goes back into the atmosphere within a few decades. For the oceans, the lag between 14C going into the oceans (at the North Atlantic sink place of the great conveyor belt) is 500-1500 years, which gives a slight depletion of 14C, together with some very old carbonate going into solution which is completely 14C depleted. In pre-industrial times, there was an equilibrium between cosmogenic 14C production and oceanic depletion.

Fossil fuels at the moment of formation (either wood for coal or plankton for oil) incorporated some 14C, but as these are millions of years old, there is virtually no 14C anymore left. Just as is the case for 13C, the amount of CO2 released from fossil fuel burning dilutes the 14C content of the atmosphere. This caused problems for carbon dating from about 1890 on. Therefore a correction table is used to correct samples after 1890.

In the 1950′s another human intervention caused trouble for carbon dating: nuclear bomb testing induced a lot of radiation, which nearly doubled the atmospheric 14C content. Since then, the amount is fast decreasing, as the oceans replace it with “normal” 14C levels. The half life time of the excess 14C caused by this refresh rate is about 5 years.

This adds to the evidence that fossil fuel burning is the main cause of the increase of CO2 in the atmosphere…

4

  1. Trends in oxygen use.

To burn fossil fuels, you need oxygen. As for every type of fuel the ratio of oxygen use to fuel use is known, it is possible to calculate the total amount of oxygen which is used by fossil fuel burning. At the other hand, the real amount of oxygen which is used can be measured in the atmosphere. This is quite a challenging problem, as the change in atmospheric O2 from year to year is quite low, compared to the total amount of O2 (a few ppmv in over 200,000 ppmv). Moreover, as good as for CO2 as for oxygen, there is the seasonal to year-by-year influence of vegetation growth and decay. Only since the 1990′s, oxygen measurements with sufficient resolution are available. These revealed that there was less oxygen used than was calculated from fossil fuel use. This points to vegetation growth as source of extra O2, thus vegetation is a sink of CO2, at least since 1990.

This effectively excludes vegetation as the main cause of the recent increase.

The combination of O2 and d13C measurements allowed Battle e.a. to calculate how much CO2 was absorbed by vegetation and how much by the oceans (see the references above). The trends of O2 and CO2 in the period 1990-2000 can be combined in this nice diagram:


O2-CO2 trends 1990-2000, figure from the IPCC TAR

http://www.grida.no/climate/IPCC_tar/wg1/pdf/TAR-03.PDF


This doesn’t directly prove that all the CO2 increase in the atmosphere is from fossil fuel burning, but as both the oceans and vegetation are not the cause, and even show a net uptake, and other sources are much slower and/or smaller (rock weathering, volcanic outgassing,…),
there is only one fast possible source: fossil fuel burning.

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230 thoughts on “Engelbeen on why he thinks the CO2 increase is man made (part 3)

  1. The article states “The decrease of d13C in the atmosphere cannot be caused by some extra outgassing from the oceans, as that would INcrease the d13C ratios of the atmosphere … This effectively excludes the oceans as the main cause of the increase. ”

    I am just wondering whether there is any possibility of greater absorption of d12C in the oceans which might affect the balance? (This is not my area of expertise – so I am simply expressing curiosity here.)

  2. I agree that the increase in CO2 in the atmosphere is probably our fault, but this article’s logic isn’t entirely convincing.

    “The increase in CO2 in the atmosphere wasn’t caused by oceans or vegetation, so it must’ve been caused by human emissions.”

    Isn’t this much the same as the warmists when they say “we don’t know what else could have caused the rise in temperatures since 1975, therefore it must have been human-emitted CO2″?

    The argument from ignorance is only evidence of our ignorance.

  3. You have to set up your categories to match your measurements. Both the burning of ancient plants (i.e. fossil fuels) and the decay of modern plants (i.e. deforestation, harvesting crops, etc.) preferentially release C12. Hence all your measurements can show is that the increase in CO2 is associated with the dissolution of plants both ancient and modern. The O2 measurements show that living plants are a net sink of CO2, but say nothing about the behavior of recently dead plants. Hence your discussion is about the dissolution of ancient and modern dead plants as a source of CO2 versus living plants as a sink of CO2. These are the correct categories for your discussion.

  4. Dear Ferdinand,

    There is nothing to be learned beside the point that when you burn fossil fuel you create CO2. Also that you can track this CO2 due to it’s special Isotope-ratio(s) does not help you with the critical question: While anthropogenic CO2 is produced and also found in the atmosphere and the oceans, it however does not tell you anything about the reason of the increased atmospheric concentration.
    What natural CO2-level we would have in the atmosphere assuming the recent temperature increase but without burning any fossil fuel?

  5. ((What we can see, is that the d13C levels as well as in the atmosphere as in the upper oceans start to decrease from 1850 on, that is at the start of the industrial revolution. ))
    1850- the start of the industrial revolution, eh??
    Rubbish. Then again the worlds only 10,000 years old, isn’t it??
    You had tens of millions of people burning peat, charcoal, coal etc but there was NO CO2 influence until some dastardly bastard started a boiler and burnt wood.
    Start again FE this one is a shocker.
    regards

  6. And what effect does this increasing level of carbon dioxide in the atmosphere have on the climate?
    If any? Please cite peer reviewed papers, again, if any.

  7. The proof that CO2 increases are not man-made are glaringly obvious.

    It is claimed that the annual increase in CO2 is 2 ppm. Humans emit annually approximately 4.1 ppm. Through various mental gymnastics and distortions of reality it has been claimed that 50% of our CO2 emissions remain in the atmosphere.

    The only way that humans could possibly be responsible for the claimed 2 ppm annual rise in CO2 would be if no other organism or process on Earth contributed any CO2 whatsoever.

    If you believe that then there is no hope for you and no point discussing anything with you beyond, have you eaten and do you need the toilet!

  8. So what has happened over the last tens of thousands of years since man discovered how to make fire. Every house would have had at least one fire for cooking/heating. If you were lucky enough to be the Lord of the Manor, you would have had many fires in your house. What about large fires in nature? Here in Australia, France and the US wildfires are endemic.

  9. Aren’t there naturally burning peat and coal fires that have been around for thousands of years?

    Burning Mountain in New South Wales is estimated at about 6000 years old, I think.

  10. I am no scientist and have always been puzzled as to why the Industrial Revolution is used as the starting point for the addition of man-made CO2 to the atmosphere when countless generations of humans burnt wood, coal, manufactured carbon, animals and animal products,etc and in huge quantities for a given population. When the first Europeans in recently recorded history arrived in various parts of the New World, most remarked on the clarity of the light and the incredible visibility in fine weather, all due to a lack of various solids expelled into the atmosphere by burning various carboniferous substances. European pre-Industrial Revolution landscape painting depicts smoke in the atmosphere very clearly; surprisingly, this was not recognised for what it was when the paintings were executed, but was categorised by the intellectual elite (who knew about such things) as ‘aerial perspective’ and saw it as useful for depicting distance.

  11. It might be interesting to see the time line axis of the CO2 isotope graph extended out 10,000 and 100,000 years. Are there other periods of variability in the CO2 isotope mix?
    Also, how would the graphs look if the axis were adjusted to show the range of the change more accurately?

  12. My understanding, small though it may be, is that this paper is substantially challenged by Chiefio’s musings on the subject (sorry, I can’t find my pointer to the article). There, the discussion of the carbon isotope ratio covers also the behavior of plankton in the oceans, net, net, the ratio is not maintained.

  13. Sigh! Why don’t you fossil fuel deniers try actually engaging F. E.’s dicsussion?

    And Ben, when you say,

    The argument from ignorance is only evidence of our ignorance.

    you’re missing the point. The TAR graph shows there is little or no lack of knowledge on what happens to the fossil fuel carbon burned. That graph from the TAR is the one which convinced me, once I understood it, that the extra atmospheric CO2 comes from fossil fuels. What the graph says is that if you compare where the O2 levels in the atmosphere should be just from burning fossil fuels and from allowing for ocean uptake and land uptake, the final figure in 2000 is right where it should be. (It would be nice to see an updated version of the graph). This means there is no ignorance, but that the expected balance is right where it should be.

    I.e. we know where the atmospheric CO2 came from.

    The problem is that people of a skeptical bent trying to attack these facts merely discredit the entire skeptical movement in the eyes of scientists who can follow the argument and can see it’s correct. This is why skeptics like “Fred” or I have to make these arguments now and again to show that most skeptics do indeed agree with the facts. Please engage on this thread, but first work on learning what is being said and why denying that the excessCO2 in the atmosphere is manmade is contraproductive to the skeptic cause.

  14. Ben M:

    I agree that the increase in CO2 in the atmosphere is probably our fault, but this article’s logic isn’t entirely convincing.

    “The increase in CO2 in the atmosphere wasn’t caused by oceans or vegetation, so it must’ve been caused by human emissions.”

    Isn’t this much the same as the warmists when they say “we don’t know what else could have caused the rise in temperatures since 1975, therefore it must have been human-emitted CO2″?

    No-one says “we don’t know what else could have caused” either of these things. We know that fossil fuels release CO2; we know that humans have burned more than enough to account for the observed rise. Therefore, humans have cause the rise. If there is another source equal to the human source, there must be a sink equal to that, and it remains true that if humans had not burned all that fossil fuel, CO2 would not have increased.

    Similarly, we know that CO2 and other greenhouse gases control the radiative balance of the atmosphere. We know that concentrations of greenhouse gases have gone up, and calculations show that the increase should cause a temperature rise comparable to that observed. If there is another unknown agent causing a temperature rise of that magnitude, there must also be some second unknown agent causing a cooling of equal magnitude, and it remains true that if greenhouse gas concentrations hadn’t risen, the temperature wouldn’t have risen.

    Not only would vast unknown sources and sinks of CO2 and vast unknown climate variables have to exist, they would have had to not exist at any time in the last several thousand years, only to come into play at the same time that humans started burning fossil fuels in quantities sufficient to alter atmospheric composition.

    Occam’s Razor is the scientific principle which we can make very good use of here.

  15. This is all very interesting, but so what?

    The level of CO2 in the atmosphere has been far higher than present, and things were copacetic then.

  16. didn’t I read something a few months ago about some algae that showed preference for a certain isotope of carbon, thus throwing out isotope measurement as an indication of man’s emissions?

  17. So in 1700, there were 3 molecules of CO2 per 10,000 of other molecules in the atmosphere, including hundreds of molecules of H2O. Now, there are 4 molecules of CO2 and hundreds of H2O molecules.

    However, the anthropogenic warming allegedly started only in 1975. So there were 33 molecules of CO2 and thousands of H2O molecules per 100,000 molecules in the atmosphere, which didn’t caused human-induced “global warming”. But after 1975, the 34th molecule of CO2 (per 100,000 other molecules including thousands of H2O molecules) suddenly started catastrophic warming?

    It is beating a dead horse. Until someone recognizes the warming effect of additional CO2 in polar regions, which have low humidity and therefore the “greenhouse effect” should be strengthened most, the discussion is equal to “how many angels have to push planets to fly on their orbits.”

    Antarctic: CO2 definitely cools it, and prove that not.

    Arctic: subtract the 30-year AMO cycle and solar activity and get NOTHING.

    By the way, where’ s the tropospheric hot spot, predicted by models?

  18. There is about twice as much inorganic carbon in the atmosphere as organic carbon (using the graphite standard for organic and PDB standard for organic). The concentrations in the atmosphere for both have been increasing at about the same rate. Fossil fuel burning does not contribute to the increase in the inorganic concentration. The equatorial oceans are the source. The increase in atmospheric inorganic carbon is the result of a decrease in the oceans’ source-rate/sink rate ratio which affects both organic and inorganic concentrations. http://www.kidswincom.net/climate.pdf

  19. Please correct. You link to a page, saying that it is “the web page of Anton Uriarte Cantolla”. And yes, the contents are his, but no, it is incorrect to call it THE web page of him. It is just one web page where he has uploaded some contents in the past. He is now a blogger too, and has been a blogger since 2006, and he blogs here. Unfortunately for most of you, his blog is in spanish.

  20. I see suspect statistical reasoning, one example is comparing minimums and maximums of data smoothed or sampled over different periods. By definition data smoothed over a longer period (either by processing or due to the sampling method) will have reduced minimums and maximums. Comparing plots of data smoothed to different periods must be done with due care that I don’t see evident here. Making any direct statement about current minimums or maximums based solely off such a comparison with older data smoothed to a longer period is unscientific and has no basis is statistics.

  21. Dave Dardinger says:
    September 16, 2010 at 5:37 am
    Sigh! Why don’t you fossil fuel deniers try actually engaging F. E.’s dicsussion?

    —————–

    Dave Dardinger,

    Premature statement there Dave, show more patience. We are not yet 2 hrs into the comment period.

    Critical reading and thinking are not so instantaneous.

    You will get your wish.

    John

  22. why isn’t the co2 distribution homogenized? (figure 1). and isn’t it possible to measure the life time of added co2 in the atmosphere by comparing concentrations at different latitudes? for what other reasons would it not be uniform?
    (not so much ‘does it homogenize?’, as ‘why wont it homogenize?’)

  23. I am left wondering who it is that says human beings are not adding CO2 to the atmosphere. That is true while at the same time adding more water vapor.

    CH4 + 2O2 => 2H2O + CO2

    More molecules of water are added to atmosphere by at least 2:1 and reducing O2. The real story then is that we will not be able to breath at some point in the distant future because we have burned up all the oxygen.

  24. Two thoughts come to mind. First is the fact that there are about 5 coal fires in the world that each emit as much CO2 as all the vehicles in the US annually. Second it the fact that in chemistry, there are no reactions that would distinguish between the isotopes of CO2 on a kenetic basis. There simply isn’t enough mass difference to impact their diffusion rates. In animals, molecules in cells are in dynamic equilibrium with the environment, so the animal reflects the isotopic ratio of the elements it is exposed to. C14 is incorporated essentially immediately into algae upon exposure to (14)CO2 (Lehninger, Biochemistry, 1970, p. 494. I haven’t heard about plant differentially absorbing (12)CO2 over (13)CO2 until this paper. Hard to believe based on chemical reaction rates. But if you really learned something in college, it is that you always need to learn more.

  25. Anyone who has participated in a controlled burn of a patch of prairie grass understands that pre-industrial humans facilitated enormous CO2 emissions. Here in the central USA where prairie savannah dominated the landscape, entire states where thought to have been routinely burned off (every 1 to 3 years) by Native Americans.

  26. I find this article quite convincing. The ocean outgassing explanation is fine on a millennial scale — e.g. Vostok’s time delays between temperature change and large CO2 changes — but since the bulk of the ocean’s CO2 content is in the deeper, colder ocean the time frame of ocean-driven changes would be on the order of overturning circulation, around a thousand years, plus or minus several centuries, with dribs and drabs from ENSO upwelling.

    So yes, burning fossil fuels has caused the rise in CO2. Yes, it has warmed since the Little Ice Age. But, as the Idsos show quite convincingly at CO2Science.org, both of these phenomena are Good Things.

    But whether there is a causal relationship between the CO2 and the temperature rise remains in serious question, since all the current evidence points to negative feedbacks so powerful that the actual radiative contribution of the CO2 increase over the last century may be anywhere from a third of a degree C to unmeasurably small.

  27. Enneagram says:
    September 16, 2010 at 5:29 am
    That map seems instead a map of distribution of cattle.
    —————————
    Lots of swimming cattle in west Atlantic ;-)

  28. According to the IPCC 21 % (minimum) is manmade. With a preindustrial value of – 7 per mill, value of -26 per mill for fossil fuel, the decrease should be about – 11 per mill and not values araound – 8 per mill. Therefore this signature can’t be anthropogenic.

  29. If the recent well established greening of the planet is factored in, how much CO2 would be released as it decays? I am inclined to believe that the greening of the planet is likely a cyclical phenomenon such that it will hit a peak and then diminish, regardless of what caused the peak (better irrigation, wetter warmer climate, etc). This means that towards the downside slope of the greening peak, decaying vegetation will emit quite a bit of CO2 as opposed to using it up, and will emit more and more as greater amounts decay.

  30. I have not been able to find an explanation of the following circumstances, and wonder whwther your investigations can offer anything:
    > Looking at Vostok CO2 data in the periods : Present to
    > 10,000 years ago, 130,000 years ago to 140,000 years ago, 230,000 years
    > ago to 240,000 years ago, 315,000 years ago to 325,000 years ago
    > (which I take to be equivalent periods in the last four climate
    > cycles) I note that in the current cycle atmospheric CO2
    > concentrations have been on a rising trend whilst temperatures were on
    > a generally falling trend, whilst in the earlier periods both CO2 and
    > temperatures were on a falling trend. Is there an accepted theory as
    > to why this should be so? In view of low human populations 10,000
    > years ago, it seems unlikely that anthropogenic factors can have
    > influenced the change in behaviour?

  31. An excellent paper.
    Makes a strong case that human activity, whether from deforestation/agriculture or fossil fuel burning, has had a substantial impact on the isotopic composition of atmospheric CO2.
    The connection to AGW from this is very shaky at best, but fortunately the author did not even try to raise that claim.
    His paper shows the scale of the human impact to be eye opening and does strongly indicate a much more serious effort to restore and protect the global biosphere, on whose health we all depend.

  32. just sent an email to the UK Department od Energy and Climate Change

    ——————————————-

    Ref: Is the DECC Global Warming Anomaly graph incorrect? An updated base line should be used.

    In the graph below, published on the DECC website.

    http://www.decc.gov.uk/assets/decc/statistics/climate_change/1_20100319151831_e_@@_surfacetemperaturesummary.pdf

    In this graph the temperature anomalies are calculated fom the 1961-1990 average. (the base line)

    By climate convention (and other data sets are now doing this) this base line is a moving one..

    This graph should now calculate this graph, from a 1971-2000 base line..

    Unless, this graph is brought uptodate and inline with climate science convention.
    There will remain a suspicion, that the old baseline is being used, to show BIGGER anomalies, as evidence of man made global warming..

    Or is it the case the anomalies are now smaller, if the correct base line is used?

    If you could send me a recalculated graph with the correct baseline, I would be very apreciative,
    (ie you will use the exact methods used to creat the graph, less I make any errors if I attempt it myself)
    so that I can be reassured that this suspicion is not the case.

    However the official DECC website should do this as well.

    -end email———

    Actually, if you actually look at the graphs, both uk and global anomalies are on a bit of a downslope anyway, since, ~ 1998..

    A few more years of that and the will HAVE to start to explain a cooling trend…

    Watch that graph

  33. Yes , it all aligns so smoothly. You have not even convinced me the so called carbon dating back to 60,000 years is accurate, and dont get me wrong Ive read the theory. You do spin your hypothesis well though. I find much of this evidence is based on unproven or even unprovable assumptions and I wonder what you are up to.

  34. Who cares? The argument is about whether increases in atmospheric CO2, beyond its current saturated levels, can cause CAGW – its that for which we await the proof.

  35. This is probably a dumb question, so please forgive my ignorance. It is that ignorance I seek to reduce.
    What we are discussing here is only the surplus or “excess” of a specific CO2 correct? And this excess CO2 is solely of the kind produced by fossil fuel combustion, right? Are we able to discern the difference between carbon from a forest fire as opposed to a fleet of oil tankers? Or carbon produced from an eruption opposed to oil sands production? Also, would wildfire suppression affect anything here? Indigenous lore has it that there used to be fires the size of California or larger that burned for months or years until the area was “settled” and fire suppression practiced.

    I just want to separate the “apples” from the “oranges”.

  36. Nice work. Hope to read what you think of UHI soon too. Seems to me concrete and steel and asphalt have a lot more to do with “man-made global warming” than CO2 AND there’s a lot of CO2 introduced into the atmosphere because of these three items. Looks like we’re slowly getting around to talking about the real problem; the BIG problem -UHI. Eventually, you can boil everything down to basics.

  37. Dave Dardinger says:
    September 16, 2010 at 5:37 am
    Sigh! Why don’t you fossil fuel deniers try actually engaging F. E.’s dicsussion?

    Among the many flaws in the essay, the assumption that anthropogenic sources are the only possible explanation for increased d13Carb increases is among the fatal flaws to the argument. It is well known among geologists that the bloom of calcerous marine marine plankton have been responsible for substantially positive excursions of d13C whenever nutrient levels and a warming environment have encouraged their growth and emissions.

  38. Hey Englebeen, where are the computations that show how much less CO2 the oceans release due to man’s CO2 release. You and the rest never talk about the partial pressure of gasses and how our raising it suppresses natural release.

    The CO2 level would have gone up anyway!!! You need to show us that it would not have been as high without man’s CO2 and you are not doing that!!!!

  39. INGSOC says:
    September 16, 2010 at 7:11 am
    And this excess CO2 is solely of the kind produced by fossil fuel combustion, right?

    No, because rising sea levels during the inter-glacial and increased marine nutrients from all causes increase planktonic bloom and emissions of d13C.

  40. Actually, as I understand it, isotopic carbon is preferentially sequestered with c13, mostly due to the reaction response rate, greater takeup energy requiring increased energy for release. How much of the ratio of such, at that point, would end up concentrated in lifeforms, thus preferentially ‘lightening’ the carbon in the cycle that is still ‘free’?

    I fear one cannot have things both ways. It is either preferentially held within biology, or it is not. It requires increased time for the photosynthetic reaction to occur within the plant utilizing carbon 13 heavy co2, as well as increased activation energy for breaking the bond once formed.

    A biological system may tend to release the energy that can be easily released preferentially. (hypothesis, testable). This would tend to sequester heavier carbon preferentially on death of the organism (hypothesis, testable). If so, would there not potentially be an experiment by which this could be determined, I.E. a closed system monitored for carbon 13 versus carbon 12 ratios in the atmosphere, checking for enrichment or depletion in-atmospheric carbon? Given the nature of the oxygen cycle, it would likely be effective to test it using photosynthetic algae.

    If, indeed, a large percentage of the carbon dioxide is immediately taken up, there should be a change over time in the ratio of carbon (13) dioxide to carbon (12) dioxide.

    Should the ratio remain stable, the experiment is falsified. If it is altered, the observation of ratios from coal and fossil fuels becomes meaningless in the debate, as it would be very difficult to maintain such a ratio if there is a preferential alteration.

    It would appear C4 fixation of carbon is even more preferential than c3, and is a biologically ‘recent’ adaptation.

    Anyone feel up to an experiment?

  41. Dave Dardinger, what is a ‘fossil fuel denier’? And you obviously don’t realise that many of us who hang out at Anthony’s like to kinda sneak up on a discussion while we make random points and ask random questions that occur to us from the posting.

    If you know anything about how people learn, typical male (which includes many females) learning behaviour is not linear but zaps about all over the topic (and often around, but not on it) and teases out all sorts of nuggets of information that are pushed and pulled as far as they will go until the subject is quite well explored and understood. The classic male learning style is about as orderly as a haystack built in a high wind, while classic female learning behaviour (and that includes many males) is linear, goal focussed and once the learner can pass the test or do the assignment at the end of the course the learning is very largely filed as ‘no longer neccessary on voyage’ and eventually drops from the memory completely. Male learners rarely forget any random fact that once excited their curiosity.
    I’m here to learn, to contribute stuff where it seems appropriate and to enjoy hanging out with interesting people. Why are you here?

  42. I see someone appears to be conducting an advertising campaign on the Fox News Channel to announce their ‘great plan’ to save the environment with an extensive power plant carbon dioxide extraction and sequestration process. Of course, the rate payers will realize it is their civic duty to fund this procedure.

  43. Isn’t this trying to prove that the majority of increased co2 is from man, not that man is the cause of the increase? Clearly if man is producing 4molecules per 1000 and the atmospere is increasing by 2 per 1000 there is something else going on there. In a stable system with feedbacks stating that most of the co2 in the atmospere is from man burning fossil fuels does not prove that if man had not burnt the fossil fuels the equilibrium would not have been made another way. i.e. if there is a feed back mechanism equalising the concentrations of co2 between the atmosphere and the ocean – or plants and atmosphere the presence of man made co2 restricts output from another source.

    That is not to say the concentration has not been increased by man, but in effect you would have to prove first that concentrations of co2 in the atmosphere would be different if man had not burnt the fuels. As soon as you are involved with feedbacks – which clearly you are because the concentration increase does not increase the amount produced by man – showing the cause of the co2 in the atmosphere does not prove that if man had not burnt the fuel the concentration would have been less.

    Put in simpler terms, if we had not burnt the carbon more co2 may have been gassed from the oceans to compensate, because the current temperature requires more co2 in the atmosphere.

  44. Coal is a fossil fuel – but oil and gas?

    Most of the mass of the planets in the solar system is comprised of hydrocarbons.

    The possible implication is that reserves of oil and gas on Earth are virtually inexhaustible. I read somewhere that the Russians formed this theory decades ago (under instructions from Stalin?) and this has been responsible for an outstanding policy of energy exploitation. There is a lot of information and comment on the internet.

    Comments, anybody?

  45. D. Patterson,

    “Among the many flaws in the essay, the assumption that anthropogenic sources are the only possible explanation for increased d13Carb increases is among the fatal flaws to the argument.”

    I think the article is saying that d13 is decreasing not increasing.

  46. Hi Ferdinand, thanks for a clearly written article which appears to use good logic as far as it goes. I have a couple of questions.

    1) You told us in an earlier installment that the ‘natural’ increase in co2 due to the earth being a degree warmer than it used to be would be around (IIRC) 20ppm (from oceanic de-gassing). But co2 has risen @110ppm from @280 to @390. If we are responsible for around half of that increase, 55ppm, and the expected natural increase due to oceanic de-gassing is 20ppm, what is responsible for the other @35ppm?

    2) If the answer to 1) is “we don’t know”, then how do we know that the mystery factor wouldn’t cause more than 35ppm extra if we weren’t pumping fossil fuel produced co2 into the atmosphere? i.e. if there is a non-linear process at work, how do we know it wouldn’t ‘take up the slack’ if we emitted less?

    Thanks and regards.

  47. erik sloneker says:
    September 16, 2010 at 6:52 am
    Anyone who has participated in a controlled burn of a patch of prairie grass understands that pre-industrial humans facilitated enormous CO2 emissions. Here in the central USA where prairie savannah dominated the landscape, entire states where thought to have been routinely burned off (every 1 to 3 years) by Native Americans.
    —————————–
    And 1-3 years later the grassland has regrown, reaccumulating carbon as organic matter. Therefore there is no long-term net production of CO2 from this system. In contrast not many coal horizons replenish in 1-3 years.

  48. Roger. If methane is a “fossil fuel” and Saturn’s moon Titan is a big ball of methane it must mean one of two things.

    Since the scientific concensus claims hydrocarbons are based on organic matter, and who can argue against scientific concensus, Titan was obviously a life bearing moon.

  49. nevket240 says:
    September 16, 2010 at 4:38 am
    ((What we can see, is that the d13C levels as well as in the atmosphere as in the upper oceans start to decrease from 1850 on, that is at the start of the industrial revolution. ))
    1850- the start of the industrial revolution, eh??
    Rubbish. Then again the worlds only 10,000 years old, isn’t it??
    You had tens of millions of people burning peat, charcoal, coal etc but there was NO CO2 influence until some dastardly bastard started a boiler and burnt wood.
    Start again FE this one is a shocker.
    regards

    The thought that occurred to me was that 1850 is also close to the end of the LIA, when temperatures commenced warming anyway.

  50. “I am left wondering who it is that says human beings are not adding CO2 to the atmosphere. That is true while at the same time adding more water vapor.

    CH4 + 2O2 => 2H2O + CO2

    More molecules of water are added to atmosphere by at least 2:1 and reducing O2. The real story then is that we will not be able to breath at some point in the distant future because we have burned up all the oxygen.”

    Your equation was great, and then your conclusion became incredibly silly. At higher CO2 concentrations, all photosynthetic organisms photosynthesize at a higher rate, converting more CO2 BACK to O2. You have to include this equation as well.

    Your conclusion assumes that there are no other chemical reactions going on than the one you listed, and that O2 is the “limiting reagent” for the equation you listed. Let me assure you that there are BIG reactions going on all of the time which counterbalance the reaction that you showed, and as such, it is HIGHLY unlikely that O2 is the limiting reagent.

    Something truly bizzare would have to happen for the world to run out of Oxygen any time in the next few billion years.

  51. I think the article above is persuasive that much of the CO2 increase is from biologic sources, not mineral sources or outgassing from a warming ocean. However, the quick jump to man is at “fault” (as someone above used the word), is a little too quick. Man’s contribution is small compared with other biologic sources (decay of plants, peat, soil, maybe even oil seeps, etc.) The non-human biologic sources may accelerate when the Earth is warmed for other reasons. I have not see that this is excluded or quantified.

    Is the total biomass of bacteria, fungi, insects, etc., not likely to increase as the climate warms?

  52. When CO2 charged blood (venous blood) retention in the brain , brain begins to manufacture the most fantastic theories about CO2. Be very careful GWRS. as this condition leads to Auto-immune Illnesses.

  53. Why is there no thought given to the possibility that human addition of C02 to atmosphere just slows the outgassing from the oceans. The system is seeking equilibrium, human are just beating the ocean to the punch. The increase in atmospheric concentration would happen anyway.

  54. Marco – you are quite correct, how could I doubt the “scientific consensus”?

    I really should get back to the day job (space science) and search for the trillions of farting cows on Titan.

  55. This analysis is deeply flawed – there is not one mention of methane. One commenter touched upon it indirectly by mentioning that the analysis fails to consider bacteria. Methane is produced by bacteria, bacteria have twice the preference for carbon 12 as do plants (see the diagram in the OP showing methane at -50 compared to organic sources at -24, and methane released in the atmosphere degrades in less than a decade into CO2 and water vapor. As well, “fossil” methane exists in huge quantities as methane hydrate in both permafrost and in sea floor sediments both of which release the gas when warming occurs.

    Methane concentration in the atmosphere more than doubled (715ppb in 1890 to 1732ppb in 1990) since the beginning of the industrial revolution. Interestingly the growth in atmospheric concentration has slowed significantly in the past decade.

    Good article: “The Other Greenhouse Gas”

    http://www.scienceline.org/2007/03/env_knight_ipcccows/

    At any rate there’s an elephant in the room named “Methane” that can handily explain the decline in atmospheric C13. Why is there mention of it in the OP?

    Engelbeen on manmade CO2: FAIL

  56. This post raises an interesting question. If human use of fossil fuels results in decreasing the d13C ratio and thus increasing both the amount and percentage of 12C available in the atmosphere what affect does this have on plants which prefer 12C? It would seem to me it could only result in faster plant growth. Anybody out there know how low d13C ratios affect plants?

  57. I don’t disagree with the conclusions of the author, but he seems to be ignoring basic differential equations. Pick a point in the past – let’s say 200 years ago. Before that point almost no fossil fuels were burned (coal had been used for some time before that, but no extensive industrialization had yet taken place). So all of the sources were effectively neutral: oceans were d13+ and plants were d13-. But on the whole the ocean absorbed as much as it emitted and the plants absorbed as much as they emitted. Now add a strong d13- component to the mix: fossil fuel burning. And fossil fuel burning has no effective negative component: no strong d13- absorber to natch it. So, the ocean absorbs CO2, for instance, but it’s absorbing CO2 that has been enriched by fossil fuel emissions. Since the ocean has NO strong bias, the FRACTION of CO2 in the atmosphere that originated with fossil fuel burning (as opposed to all other sources) HAS to go up and the d13- effect HAS to be observed. But that statement does not lead one to the conclusion that all or some of the CO2 concentration delta is because of fossil fuel burning. Only that because of the isotopic differene we can tell that fossil fuels have been emitted into the atmosphere. This argument on it’s own only supports that observation.

    Even is CO2 concentrations were DECREASING the isotope ratio would be impacted by fossil fuels – and more strongly to boot. So, no, I’d argue this measurement alone doesn’t get one all the way to blaming fossil fuels for the increase in CO2 concentration.

    Any time that there is a net atmosphereic shift to/from vegitation and to/from ocean there is going to be a shift in isotope ratios in the atmospheres. That’s also completely true and completely independent of whether or not you even start thinking about fossil fuels. Since we know that gas solubility in water varies with temperature and that plant growth rates vary with temperature, precipitation, and land usage, isn’t a single measurement of an isotope shift in the atmosphere a little bit light data to jump straight to fossil fuels?

    I know that it’s a tough problem (from the standpoint of available data), but until we have good science that identifies of all the CO2 sinks and all of the CO2 sources as well as a good estimate of all their rates this is going to remain an open question.

    But thanks to the author for contributing to the discussion.

  58. RW says:

    “We know that fossil fuels release CO2; we know that humans have burned more than enough to account for the observed rise. Therefore, humans have cause the rise.”

    You need a course in logic, son. “Therefore…” may or may not be true, but it does not logically follow in your statement.

    Instead of playing a logic-challenged game, explain your belief of why a rise in a harmless trace gas is a problem that will plead to climate catastrophe, rather than being the beneficial effect of the rise in T since the LIA.

    If possible, try to keep the arm-waving to a minimum. And try to use Occam’s Razor as it was intended: there is no good reason [other than feeding at the public trough] to add an extraneous variable like CO2 to the long-accepted theory of natural climate variability — which has never been falsified despite the $billions in public funds being fruitlessly wasted trying to disprove it.

  59. “””” This adds to the evidence that fossil fuel burning is the main cause of the increase of CO2 in the atmosphere… “”””

    Well Englebeen; thanks very much for a very well detailed presentation of the whole Carbon Isotope question. It is certainly the most readable and informative presentation of that subject I have ever seen; so I am going to print it out and add itto my collection of Climate related papers.

    However with regard to the heading I pasted from your paper. It’s nt the first time I have seen that stated. Everybody pushing the man-made GW story says that; so I guess it must be true.

    Well no it doesn’t. What you have presented does not make that case. What it does establish, is that it is quite apparent that somewhere along the line of the recent history of Atmospheric CO2 and its changes, a NEW SOURCE of carbon started to be incorporated into the total carbon cycle (short term) as a result of human burning of fossil fuels. It DOES NOT prove that that particular source of new carbon is responsible for the increased amount of CO2 in the atmosphere.

    Now let me make myself clear on this point. I am NOT arguing that CO2 is NO going up in the atmosphere; I am not arguing that human activities are NOT the cause of (at least some of) that increased CO2 in the atmosphere. I’m simply saying that our burning of fossil fuels is certainly releasing to the atmosphere a new source of carbon that exhibits a difefrent signature; but the isotope argument doesn’t prove that all of the increase consists of fossil fuel carbon.

    We could illustrate the point by saying; suppose that we discovered in America a humungous expanse of new petroleum; that just came gushing out of every well we put down there and gave us a dirt cheap local source of super high quality petroleum that we exploited to the maximum. But this source of petroleum is weird; it contains a sizeable percentage of Argon; for unknown reasons; and so much Argon that we don’t know what to do with it; so we just let it vent off as we let the oil gush out.

    We can expect that if we had been collecting data on Argon in the atmosphere all these years; that we would start to see an upturn in the amount of Argon in the atmosphere as we extracted more of this weird oil and vented the Argon.

    Somebody who observed this data and knew of this particular deposit; could reasonably conjecture that we must be tapping that pool of weird oil.

    Same thing with the CO2 isotope story. Yes it demonstrates that carbon from fossil fuel sources is entering the environment as a result of our use of fossil fuel deposits. It does not prove that that is the cause of the increase in atmopsheric CO2 (although that very well might be true).

    Many years ago, I was involved in the deposition of epitaxial Gallium Arsenide Phosphide, onto Gallium Arsenide wafers to make LEDs. We made our own Epitaxial Reactors, and I personally designed and built a part of the reactor that handled and controlled the gas mixtures.

    We would start the process, by injecting into the reactor (after a purging cycle) a stream of Hydrogen that contained a low percentage of Arsine (AsH3). This gas would percolate through a fine long capillary that was wound up inside a three litre bottle that filled with the gas, and then exited out the other end of the bottle to the reactor to grow a layer of pure GaAs on the wafers. After establishing a steady growth and growing a base layer of GaAs, the gas flow of the Arsine mixture was dropped about about 40% ans simultaneously a new source of Hydrogen replaced the missing gas; and the new source contained Phosphine (PH3) , so the total hydrogen flow rate into the capillary remained unchanged; but now the composition changed from only an Arsine additive to a 60/40 mix of AsH3/PH3; and the change was instantaneous. This mixture was injected into the capillary and thence into the three litre bottle which was already full of Hydrogen plus a 100% content of Arsine. So the reactor continued to grow a 100% gallium Arsenide epi layer; but as the new mixture was added into the three litres of hydrogen mixture, the percentage of Arsine slowly dropped, while the percentage of Phosphine slowly increased; all automatically controlled by simple gas mixing laws; with no process controlelrs needed. The changing gas mixture now started to deposit a changing composition epi layer slowly grading from 100% gaAs to a GaAs0.6P0.4 mixed crystal that made the then highest efficiency Red LEDs. The smooth grading process followed the normal exponential time constant curve dictated by the volume of the bottle and the lenght and diameter of the capillary , along with the total flow rate.

    Actually, it was a bit more complicated than that, since we put three such capillary/bottles in series to give a synchronous three pole low pass filter, that changed the grading profile to a near Gaussian transition.

    The final gas composition mixture entering the reactor to grow the material could have been monitored; and simply revealed how the composition slowly changed merely as a result of an instantaneous step change in starting conditions launched by doign the Arsine Phosphine switch.

    Same thin is happening with the earth atmosphere; the fossil fuel content of the atmospheric carbon continues to increase; because we have continuously been using a new source of energy that contains that carbon and releasing its end product (CO2 ) to the atmosphere. The fact that the total CO2 is going up, is a quite separate issue fromt eh fact that we burn fossil fuels.
    And I repeat; Iam NOT claiming that humans are not the source of the increase in CO2; I don’t know what is; It is interesting that it is just 800 years since the mediaeval warm period when the earth Temperatures were hotter than now; and 800 years seems to be the propagation delay enshrined in the paleo records of Temperature rise followed by CO2 rise 800 years later .(and fall too).

    And again; thanks for the very detailed exposition; which I must digest in more detail.

  60. Andres Valencia says:
    September 16, 2010 at 8:27 am
    Thanks for the link. It surprised me that the USA has the greatest number of installed WINDMILLS: 33,000 . A lot of windmills to tear down by Don Anthony Quixote of Watts!!

  61. HelmutU says:
    September 16, 2010 at 6:58 am :

    That the IPCC minimum contribution of anthopogenic CO2 is 21%, and that the signature should, by this calculation, be -11%, but is actually -8%, up from -7% (my computer doesn’t appear to have a mill sign). It is this conclusion I was looking for with all the graphs and discussion of mechanisms. I didn’t see it.

    The recyling of fossil fuel CO2 is certainly a concern. The half-life of CO2 is a big deal. The removal process is proportional in some fashion to the total concentration, so we will continue to see a signature after introduction into the atmosphere. Another factor with a large uncertainty.
    The fine points of the math are beyond not just me, but many others. Could we see someone working out:
    a) the current, cumulative contribution of CO2 from fossil fuels post 1850 and 1945 (the start of so much was being dumped in the air) based on the isotopic data,
    b) the incremental increase year-to year as a proportion of 2 ppm, from this isotopic data, and
    c) the proportion of CO2 from fossil fuels incrementally added AFTER taking into consideration the half-life of CO2 and the changed proportion of fossil fuel CO2 in the previous year’s atmosphere?

    I hate to ask questions in this forum for lack of response. Complaints or accolades dominate the bogosphere as dialogue does not go well. But to advance, critical review must be matched with critical response.

  62. Mr Engelbeen – an excellent article, well put together.

    However, what it does not actually do is show unequivocally that the extra percentage of CO2 we observe in the atmosphere today, compared with historical times, is there purely because of human burning of fossil fuels.

    There is no doubt that human burning of fossil fuels has dumped a vast quantity of CO2 into the atmosphere and into the oceans. And the changes in isotope ratios found in the atmosphere and the oceans bear testimony to that.

    However, consider an alternative hypothesis: that the amount of CO2 in the atmosphere is actually controlled by the exchange of CO2 between the oceans and the atmosphere, with the oceans acting as a vast reservoir of CO2. Envisage that in this hypothesis, the percentage of CO2 in the atmosphere is controlled by factors affecting the oceans, for example the temperature of the oceans – so that merely adding CO2 to the atmosphere by burning simply results in absorption by the oceans.

    In this hypothesis, the recent rise in CO2 in the atmosphere is dictated by the oceans – for example, as the oceans warm there is outgassing of CO2 which causes the amount of CO2 in the atmosphere to rise.

    With constant interchange of CO2 between the oceans and the atmosphere, the isotope concentration values described would be consistent with this hypothesis, just as well as with the hypothesis that the CO2 concentration has rise purely because of human emissions of CO2.

  63. I see one commenter mentioned CH4 (methane) before I did by showing its degradation equation: CH4 + (2)O2 -> (2)H2O + CO2.

    One might begin objecting to CH4 as the C13 dilutant by saying that CH4 concentration in the atmosphere is hundreds of times less than CO2. While that’s true one must take into account that CO2 doesn’t degrade in ten years like methane does. Therefore all the methane released into the atmosphere since the beginning of the industrial revolution has long since degraded into water vapor and CO2. The remaining ~1800 parts per billion in the atmosphere today is what was emitted in only the last 10 years! Once you factor that into the equation along with CH4′s being twice the C13 dilutant as manmade (fossil) CO2 one finds that methane is a very significant source of low-C13 CO2. It also consumes oxygen when it degrades and so works to ever so slightly lower atmospheric O2.

    I’m not sure if the vastly increased emission of methane which precisely mimics the burning of fossil fuel is an equal contributor to the so-called manmade CO2 signature in the atmosphere but it is certainly significant enough that any analysis like the OP which ignores it is fundamentally flawed.

  64. The NASA map certainly puts the Kibosh on the notion that CO2 in the atmospehre is well mixed; and that appears to be a starting assumption in climate models. It clearly isn’t even approximately well mixed. To me; well mixed would eman that no matter where or when I took a sample of the atmosphere and analysed it, I would get the same composition on a molecular species (and isotopic) basis; at least within limits of differences that are of no consequence to any climate argument; and of course excluding taking a sample up somebody’s tailpipe or chimney.

    One thing does puzzle me. The oceans and the atmosphere are presumably somewhat near equilibrium in the Henry’s Law sense as to the segregation of CO2 between atmosphere and ocean. And we are told that the carbon in deep water storage, is not getting out into the atmosphere. So why is it that the CO2 isotopic composition of the near surface ocean water, and the near surface atmosphere don’t match. Is somebody claiming (proof please) that the Henry’s Law Segregation at the interface is highly isotope dependent. I haven’t heard that claim made before. Why isn’t the ocean exchanging exactly the same isotopic CO2 with the atmospehre whether releasing or taking up ?

  65. While I do understand the hypothesis that is being presented, there still remains the issue of “understanding” of isotopes specifically, carbon.

    C-12 -> Stable
    C-13 -> Stable
    C-14 -> beta decay + N14
    N-14 + n -> C-14 + H-1
    B-13 -> C-13 + beta decay

    So, the first thing that comes to mind is the source of C-13 is B-13 with an electron ejection (decay is tens of millisecs).

    Next question is how did Boron get into the atmosphere? Oceanic Boric Acid?

    http://www.google.com/url?sa=t&source=web&cd=1&sqi=2&ved=0CBIQFjAA&url=http%3A%2F%2Fwww3.interscience.wiley.com%2Fjournal%2F123311171%2Farticletext%3FDOI%3D10.1111%252Fj.2153-3490.1959.tb00039.x&ei=QTaSTJz4G43QsAPqveDkCQ&usg=AFQjCNG_Ew6QdUBveKDaZRERT8k6SbsSfQ

    Perhaps…

    Another question is how much of the past carbon is converted to C-14? How much B-13?

    http://cdiac.esd.ornl.gov/trends/co2/well-gr.html

    Of COURSE man made (nuke testing), but not fossil fuel related. Unfortunately, lots of variables.

    Based on available data and information, I could not even measure the “natural effect” vs “fossil fuel effect”. 100% Uncertain Unknowns.

    A good presentation of the measurement hypothesis can be found here:

    http://www.google.com/url?sa=t&source=web&cd=20&ved=0CEYQFjAJOAo&url=http%3A%2F%2Fwww.geo.cornell.edu%2Feas%2Feducation%2Fcourse%2Fdescr%2FEAS302%2F06Lectures%2F302_06Lecture33.pdf&ei=4UKSTP2MG5S6sQPKzbXBCg&usg=AFQjCNFkClELnSw4fTSpsPwkZHu7O1yctg

    The error bars are helpful in my conclusion that isotope ratios are cool, but work in progress.

  66. D. Patterson says:
    September 16, 2010 at 7:15 am
    Among the many flaws in the essay, the assumption that anthropogenic sources are the only possible explanation for increased d13Carb increases is among the fatal flaws to the argument. It is well known among geologists that the bloom of calcerous marine marine plankton have been responsible for substantially positive excursions of d13C whenever nutrient levels and a warming environment have encouraged their growth and emissions.
    ==================================================
    Same thing on land D.
    Fertilizer and soil bacteria

    Not even mentioning farming practices, fertilizer and bacteria, made me turn off to this “study”. Makes my opinion of it “total hogwash”

  67. Mike Edwards says:
    September 16, 2010 at 9:08 am

    There is no doubt that human burning of fossil fuels has dumped a vast quantity of CO2 into the atmosphere and into the oceans. And the changes in isotope ratios found in the atmosphere and the oceans bear testimony to that.

    No, it does not bear testimony to that as methane degradation causes exactly the same changes in isotope ratios and appears to be sufficient unto itself to explain it.

    Dig it: the industrial revolution began coincident with the end of the Little Ice Age circa 1800. The earth began warming at that time quite naturally unless one can somehow blame the LIA on human activity. A warming earth would naturally release methane from thawing permafrost and with a significant lag time also from the ocean floor. Combine that natural increase in methane emission with the explosive growth in the cattle industry (both beef and milk production) and you have a timeframe that matches the growth in manmade CO2 emission and where the isotope signature is the same for both CO2 contributors.

  68. Smokey, of course it follows. You think concentrations would have shot up anyway, if humans had never burned any fossil fuels? How would they have done that?

    There has never been a “theory of natural climate variability”. Physics tells us that greenhouse gases play a key role in determining atmospheric temperatures. CO2 is and has always been a greenhouse gas, and if its concentration varies, atmospheric temperatures vary. Fourier and Tyndall discovered this back in the 1800s. How come you’re still ignorant of it?

    CO2 is indeed a trace gas. It currently accounts for 0.039% of the atmosphere. Let’s assume you weigh 80kg. Eat 50 μg of Polonium-210 and it will kill you. That’s 0.0000000625% of your mass. So, what’s the relevance of anything being “trace”?

  69. Interesting piece of science. I’ve been following this and related topics for about 2 years and have not seen the corresponding calculation check. That is to estimate the tons per year of CO2 being produced in various human endeavors, and compare to the total mass of atmosphere. It should be possible to get within a factor of two. In the US, the Energy Information Administration (EIA) keeps track of fuel use, and we know that a typical 1000 MWe power plant emits about 20,000 tons/day CO2. I can do this estimate unless somebody here points out why it would be useless.

    Also – “Marko says: September 16, 2010 at 8:00 am
    Roger. If methane is a “fossil fuel” and Saturn’s moon Titan is a big ball of methane it must mean one of two things. Since the scientific concensus claims hydrocarbons are based on organic matter, and who can argue against scientific concensus, Titan was obviously a life bearing moon.”

    I have heard astronomer Sir Fred Hoyle argue this is exactly how methane formed on the other planets and moons.

  70. Nylo says: “…Anton Uriarte Cantolla…is now a blogger too, and has been a blogger since 2006, and he blogs here. Unfortunately for most of you, his blog is in spanish.”

    No problemo. Go to http://babelfish.yahoo.com/ then insert http://antonuriarte.blogspot.com/ in the “translate a webpage” window, select Spanish-to-English, and hit Translate. Vwallah! You can follow most of the text quite easily.

  71. Vince Causey says:
    September 16, 2010 at 7:48 am
    D. Patterson,
    [....]
    I think the article is saying that d13 is decreasing not increasing.

    Yes, and the rate of sea level rise potentially affecting the d13C levels has been declining. To put it briefly, there are a plethora of confounding factors whose existence has been denied in favor of assuming anthropogenic sources of combustion emissions. Contrary to the article, excursions of isotopic balances have long predated the Industrial Age, and science has barely even begun to acquire the data necessary to untangle the results, much less the causes and effects.

    O-C Strat, Oxygen-Carbon Isotope Stratigraphy
    The carbon isotope composition of marine limestone fluctuates on a shorter time scale than 87Sr/86Sr ratios (see SrStrat) and the pattern of fluctuation tends to be confined to individual basins. Such relatively short term excursions in marine carbonate d13C values may reflect changes in organic productivity and burial rates of organic carbon. e.g. in the Jurassic and Cretaceous positive d13C “anomalies” may correspond with higher levels of carbon storage in organic-rich mudstone and rising sea levels, while negative d13C excursions may correspond with lower sea levels and/or sub-aerial exposure of shelf areas. This secular variation has been used to correlate limestone strata on a local scale where the original marine carbonate d13C signature has been preserved (e.g. Vahrenkamp 1996).

    http://www.isotopic.co.uk/carbonstrat.html

    One of the potential anthropogenic effects is the exposure of more mudflats and soils by the human efforts to eradicate mosquitos and malaria by draining vast areas of swamp.

  72. There is valid disagreement on how much the rapid increase in atmophereic C02 is affecting the earth’s climate. However, anyone who has looked at the issue carefully and still does not understand that most of the rapid increase in CO2 is due to human burning of fossil fuels has serious problems unstanding rather simple science.[how so? b.mod]

    Reply: This was an inappropriate comment for a moderator to make ~ ctm

  73. George E. Smith:

    “The NASA map certainly puts the Kibosh on the notion that CO2 in the atmospehre is well mixed; and that appears to be a starting assumption in climate models.”

    It’s not a starting assumption in climate models.

    “It clearly isn’t even approximately well mixed. To me; well mixed would eman that no matter where or when I took a sample of the atmosphere and analysed it, I would get the same composition on a molecular species (and isotopic) basis; at least within limits of differences that are of no consequence to any climate argument;”

    And that is precisely what we see in the map. The colour scale ranges from about 365 to 385ppm – a global variation of no more than 3% either side of the mean. This is of no consequence to any climate argument.

  74. [blockquote]George E. Smith says:
    September 16, 2010 at 9:22 am
    [....] Why isn’t the ocean exchanging exactly the same isotopic CO2 with the atmospehre whether releasing or taking up ? [/blockquote]

    Variations in biological activity at various depths and in different basins of the hydrosphere for one example.

  75. I have a bath with a running tap and an open plug hole. There’s one guy controlling the tap, according to unknown rules that depend amongst other things on the water level, and another guy adjusting the flow out through the plug hole, similarly.

    We pour a few cubic centimetres of ink into the bath, and the water turns blue.

    The water level also rises. Has the colour change proved that the rise in level is caused by the addition of the ink, and not the two guys controlling tap and plug? If the water level had fallen but the water still turned blue, what would you have deduced?

    Personally, I am of the opinion that the source of the CO2 is indeed mankind – but I don’t believe this argument proves it. All it shows is that an increasing proportion of the CO2 in the air is fossil-sourced (scarcely surprising), but doesn’t say anything about the cause of the change in overall level. Still, it’s excellent to see the argument/evidence set out and debated. If only the IPCC did the same.

  76. The post doesn’t mention precipitation. Doesn’t rain remove CO² from the atmosphere? Is one form of CO² scrubbed preferentially over another? It wouldn’t take much of a difference to throw all the calculations off, would it?

  77. Doug Proctor says:
    September 16, 2010 at 9:04 am
    HelmutU says:
    September 16, 2010 at 6:58 am :
    [....]
    The recyling of fossil fuel CO2 is certainly a concern.

    Is the “recyling of fossil fuel CO2…certainly a concern,” or is the deprivation of CO2 merely a means for meddling humans to unwittingly commit mass suicide as a consequence of CO2 concentrations falling too low to support photosynthesis by the Plant Kingdom?

  78. George E. Smith said on Engelbeen on why he thinks the CO2 increase is man made (part 3)
    September 16, 2010 at 9:22 am
    There will be some fractionation each time CO2 is emitted from or absorbed by water because of the 45/44 molecular weights ratio. This fractionation process can explain the seasonal cycle just as well or better than seasonal growth cycle of plants. http://www.kidswincom.net/climate.pdf

  79. I was outraged to read Ben’s comment that man is “at fault.”
    Englebeen has done a nice job of showing that isotope evidence matches the known fact that humans accelerated burning of “fossil fuels” since around 1850 or thereabouts. He has also quite clearly shown that about half that CO2 has caused a fluorishing of plants.

    Where do you get “fault?” I say we are heroes!!

    There is no need for another score of posters to whine that maybe the CO2 increase is not anthropogenic.

    Your tailpipe feeds the hungry.

  80. BillD says:
    September 16, 2010 at 10:27 am
    There is valid disagreement on how much the rapid increase in atmophereic C02 is affecting the earth’s climate. However, anyone who has looked at the issue carefully and still does not understand that most of the rapid increase in CO2 is due to human burning of fossil fuels has serious problems unstanding rather simple science.[how so? b.mod]

    No Bill. The argument made is a logical fallacy called an argument from ignorance. The carbon isotope ratios are analyzed, the sources of different istopes are analyzed, known natural sources are ruled out, and then the question is asked: If not fossil fuel then what else could it be?

    The what else is methane which in less than 10 years degrades into water vapor and CO2 and most importantly for this discussion it causes the same isotope signature that burning of fossil causes. Some or even most of the 150% rise in atmospheric methane since the industrial revolution could be man-made. It’s estimated that the cattle industry contributes 16% of total annual emission. Anaerobic decomposition in landfills and other waste disposal generates methane. Methane is present in large quantities along with fossil fuel deposits. Methane vented from active coal mines contributes an estimated 10%. It is also released from oil wells and natural gas wells. As well it is released by thawing permafrost and warming ocean bottoms.

    I was quite surprised to find that although the OP included a drawing showing methane as being twice as effective in abililty to alter carbon isotope ratios yet it was not even mentioned in the analysis – like the proverbial elephant in the room.

    While there is no doubt in my mind that fossil fuel burning contributes to some fraction of the observed isotope ratios it’s pretty clear that methane does the same thing and in fact could be the dominant factor in changing carbon isotope ratio. Yet methane wasn’t even mentioned in the analysis!

    Perhaps you or someone else can explain why the analysis failed to see the elephant sitting in the corner of the room.

  81. Let’s assume for a second that there are no equilibrium processes which would have CO2 at current levels, even if humans didn’t exist.

    Humans do produce some amount of CO2, and added to the net CO2 from all other processes, the total is higher than it would have been, meaning that humans have produced the incremental CO2.

    So now, granted all this, what is your point?!

  82. I could be all wet here. So take this with a grain of salt. I had a hard time finding the answer. I found one source that talk about it. Humans respire 13CO2. Has anyone calculated the increase in this isotope as a function of the increasing animal population? With the greening of the planet, other animals that respire this isotope would also be more abundant given a more abundant food supply.

    Could this be at least a part of the extra 13CO2 in the atmosphere?

  83. ” Pamela Gray says: September 16, 2010 at 11:29 am
    I could be all wet here. So take this with a grain of salt. I had a hard time finding the answer. I found one source that talk about it. Humans respire 13CO2. Has anyone calculated the increase in this isotope as a function of the increasing animal population?”

    Pamela: The carbon isotope ratio that you respire is identical to the isotope ratio of the carbon in the food you eat. The human body is a chemical reactor, not a nuclear reactor. Both 13C and 12C are stable, but 14C is radioactive and Beta decays with a 5730 year half life, too slow to change the isotopic ratio inside your body. When you die, the 14C decays and the ratio can tell us when you died, up to about 60,000 years, or 10 half-lives.

  84. The ratio of 12 to 13 is -.5%.

    reference http://iopscience.iop.org/1063-7818/32/11/A08

    World population between 1850 and 2011 has increased by 6 to 7 billion people.

    reference http://geography.about.com/od/obtainpopulationdata/a/worldpopulation.htm

    We breath out between 252 Kg/yr and 525Kg/yr. We make our own so there is not a balance between what we take in as food and what we breath out. This number has not considered the increase in all animal populations as a result of the greening of the planet.

    reference http://wiki.answers.com/Q/How_much_CO2_is_exhaled_by_the_average_human_each_year

  85. So if we are breathing out more 13CO2 along with more 12CO2 due to population growth, and the greening of the planet prefers 12CO2, human population growth could be causing at least some of the extra 13CO2 in the atmosphere.

    Wonder what restrictions and taxes will be placed on that issue.

  86. I would like to ask one question – if all geologic carbon – coal, oil, carbonate etc., were in the atmosphere, what would the percentage of CO2 be?
    Sorry, I meant I would like to ask two questions – how much hotter would it be then?

  87. 899 says:
    September 16, 2010 at 6:00 am
    This is all very interesting, but so what?

    The level of CO2 in the atmosphere has been far higher than present, and things were copacetic then.
    ____________

    If you believe what GCM’s say about the 40% increase in CO2 since the 1700′s, then the “so what” becomes the significant changes that are climate is undergoing and will be undergoing. If you don’t believe what the GCM’s are saying, then who cares if the CO2 levels are higher than they’ve been for hundreds of thousands of years.

    Only an extreme minority currently would ever seriously no doubt that human activity has caused the 40% increase in CO2 since the 1700′s. So while this is an interesting, and mostly accurate post, it is hardly earth-shattering or particularily interesting. The core issue really is how sensitive is the climate system to this anthropogenic based increase in CO2. And of course the next step that some are working on already is some sort of geoengineering efforts to reduce the CO2 levels or mitigate their effects.

  88. Chris Knight,

    Look up the theories on the Earth’s atmosphere during the Hadean era. They’re based on the idea that most of the Earth’s carbonate resources were in the atmosphere.

  89. http://ethomas.web.wesleyan.edu/ees123/clathrate.htm

    Unique features of clathrates as part of the carbon cycle

    Methane hydrates are part of the carbon cycle with unique features: they serve as a possible large source of isotopically extremely light carbon, but NOT as a sink. The carbon in methane hydrate was originally stored in the sediments (lithosphere, out of contact with the ocean and atmosphere) as organic carbon. Thus only carbon with the isotopic signature of organic carbon is taken out of the ocean-atmosphere reservoir – influencing the carbon isotopic value of the remainder in the well-known way (ratio of organic carbon to carbonate of sediments). Within the lithosphere, isotopically light carbon is strongly enriched in the methane in gas hydrates by bacterial action. The isotopically heavier remainder is isotopically not much heavier than ‘normal’ carbonate, and ends up in carbonate in the lithosphere. As long as both the methane hydrates and the remainder remain in the sediments there is no effect on the exospheric carbon reservoirs, but when the methane hydrates dissociate, material strongly depleted in the heavy isotopes escapes from the lithosphere into the ocean-atmospheric reservoir – making that reservoir lighter. The effect on the large sediment reservoir is not noticeable.

    This means that the carbon that is stored in the methane hydrates was taken from the ocean-atmosphere system as carbon with an average isotopic composition of about -25‰, but the carbon returning to the ocean atmosphere system through the methane hydrate loop is isotopically ~ -60‰. Overall decreasing methane hydrate reservoirs (e.g., as a result of fluctuating sea levels during glacial -interglacial alternation) thus lead to a secular trend towards a lighter carbon isotopic signature of the ocean-atmosphere reservoir.

  90. Dan, your reply is too simplistic. Our isotopic ratio of what we breath out may or may not be based on what we breath in or eat. There are many variables to take into account related to exhaled composition and ratios of CO2.

  91. RW,

    “And that is precisely what we see in the map. The colour scale ranges from about 365 to 385ppm – a global variation of no more than 3% either side of the mean. This is of no consequence to any climate argument.”

    No consequence? Let’s look at the increase in radiative forcing that would occur by going from 365 to 385 ppm. Using the IPCC as source, dF = 5.85Ln (C1/C0).

    Calculating the respective dF for 385 and 365 ppm and deriving the ratio, we get
    Ln(385/280) / Ln(365/280)
    = (Ln385- Ln365) / (Ln365 – Ln280)
    =0.318/0.264
    =1.2

    In other words, that teensy weensy 3% translates to a forcing increase of 20% more as we go from 365 to 385ppm. It sometimes pays to do some basic checking before shooting from the hip.

  92. R. Gates says:
    September 16, 2010 at 12:08 pm

    Only an extreme minority currently would ever seriously no doubt that human activity has caused the 40% increase in CO2 since the 1700′s. So while this is an interesting, and mostly accurate post

    Yeah, “Only an extreme minority currently would ever seriously no doubt that” the Emperor is wearing no clothes.

    Our conclusion: People are not responsible for the documented rise of carbon in the atmosphere.
    Not only do the numbers fail to match, the numbers can’t be made to match.

    Alan Siddons and Joe D’Aleo. Carbon Dioxide: The Houdini of Gases. September 05, 2007. http://www.ilovemycarbondioxide.com/pdf/Carbon_Dioxide_The_Houdini_of_Gases.pdf

  93. Responding to BillD, Dave Springer says:

    “The argument made is a logical fallacy called an argument from ignorance.”

    If it were not for the alarmists’ argument ad ignorantium, the scare ‘em crowd wouldn’t have much left to say. The argument from ignorance concludes with the belief that a harmless and beneficial trace gas is the main driver of climate change “because we can’t think of any other reason.” The alarmist crowd is terrified to death of the Scientific Method, preferring ad-hom arguments and illogical, one-sided propaganda like Al Gore’s AIT.

    RW tries to re-frame the argument, avoiding the question by substituting a false strawman: “There has never been a ‘theory of natural climate variability’.”

    Ignorance is no excuse. Dr Roy Spencer has been quoted here before: “No one has falsified the hypothesis that the observed temperatures changes are a consequence of natural variability.”

    So who should we listen to? An internationally esteemed climatologist, and to planet Earth – which has not boiled over as demanded by grant-sniffing climate modelers?

    Or to… “RW”?

  94. In the 400 years before, there is only a small variation, probably caused by the temperature drop in the Little Ice Age.
    There was no such change in CO2 during the Spoerer minimum, so either it was not colder then or the drop has little to do with temperature.

  95. RW says:
    September 16, 2010 at 10:29 am
    [....]And that is precisely what we see in the map. The colour scale ranges from about 365 to 385ppm – a global variation of no more than 3% either side of the mean. This is of no consequence to any climate argument.

    The IPCC and other Alarmists claim anthropogenic fossil fuel combustion is responsible for about 4 to 5 gigatons of carbon dioxide per year of which only 1.5 gigatons remains unsequestered by the environment that sequesters the other 110 gigatons of natural carbon dioxide emissions. So, if you believe that a 3% variance in the global carbon dioxide concentrations is too insignificant to take notice, why should you believe an approximate 1.5% to 3% increase of anthropogenic carbon dioxide, according to the IPCC bookkeeping, is supposeed to be Alarming?

  96. I have never doubted that the increase in CO_2 levels was real, and that the burning of fossil fuels has contributed significantly to it. It is also clear to me that the Earth has warmed over the last quarter of the 20th century, although the extent of the warming is uncertain since the data has been manipulated in an untrustworthy way. I am doubtful that increased CO_2 is entirely responsible for the observed warming – in fact most of it seems to me to be cyclical and natural. The models are not worth spit and I believe the sensitivity of the climate to increased CO_2 has been considerably overtstated. I am extremely skeptical that the observed warming and higher CO_2 levels are likely to be harmful.

    The point is that people are skeptical about different aspects of the AGW story. Since this is one aspect of the story about which I am not skeptical, it is interesting to watch the responses of those who are.

  97. From the paper referenced by Engelbeen above: “But in contrast with what happens during photosynthesis, in the process of calcite precipitation into shells of marine organisms there is no isotopic discrimination with respect to the ratio 13C/12C of marine waters.”

    Yes, photosynthesis does discriminate 13C and 12C, which is the basis for this thread. But just as marine animal shell production does no isotopic discrimination, I found no reference to animal (or human-only) isotopic discrimination in oxidative metabolic processes. I would be interested in seeing such a discussion.

  98. Trend without end, Amen.
    All trends lead to Warming.
    A trend for all seasons.
    In Trends we Trust.
    This Trend ain’t big enough for both of us.
    ——————-
    Don’t trend on me.
    Take this trend and shove it, I ain’t going there no more.
    Trender Bender: When hysteria meet the brick wall of reality.
    Take the last Trend to Warmsville, and I’ll meet you at the Glacier.
    Four score and 7 Trends ago.

  99. Jaraj V said, “It is beating a dead horse. Until someone recognizes the warming effect of additional CO2 in polar regions, which have low humidity and therefore the “greenhouse effect” should be strengthened most, the discussion is equal to “how many angels have to push planets to fly on their orbits.” ”

    Let’s not forget that this warming in the Arctic would be rather weak. Who cares if it’s -31.0 rather than -31.1 deg C? It’s not going to change the climate that anyone would notice.

    The Arctic ice melting depends largely on warm air from the South and not solar energy during the summer. The low angle, reflection, and travel distance through the atmosphere attenuate solar input to less than 3% of direct overhead sunlight. This energy, hitting water, would heat it ever so little and this energy would be lost to evaporative cooling almost immediately. Hitting ice, lot’s of reflection, little effect. Then, there is the occasional influx of warm water into the Arctic basin, very effectively melting the ice from below.

    I wonder, so what if we increase CO2? It does not warm the climate in any way that makes detectable changes and it helps the plants, the marine life, the corals (acidification, if any at all, is trumped by adaptation and tolerance), and our food supply. There’s no down side here.

  100. Congrats Ferdinand.

    I’ve enjoyed every one of your patient logical explanations.

    I’m still waiting for someone to offer any evidence that burning fossil fuels will cause
    a net decrease in C02.

  101. #
    #
    wsbriggs says:
    September 16, 2010 at 5:28 am

    My understanding, small though it may be, is that this paper is substantially challenged by Chiefio’s musings on the subject (sorry, I can’t find my pointer to the article). There, the discussion of the carbon isotope ratio covers also the behavior of plankton in the oceans, net, net, the ratio is not maintained.
    _________________________________________________________
    I have that pointer bookmarked
    The Trouble With C12 C13 Ratios:

    http://chiefio.wordpress.com/2009/02/25/the-trouble-with-c12-c13-ratios/

  102. F.E.

    Thank you for your comment inducing Part 3. You obviously spent a significant amount of time on it. You do know how to stimulate discussion.

    I have no position on whether man has caused the industrial age increase in atmospheric CO2. This is because I am waiting for sufficient or even partial significant evidence of it.

    I do not see any significant evidence in your Part 3 with respect to whether man has caused the industrial age increase in atmospheric CO2.

    You said in the final paragraph of Part 3,

    This doesn’t directly prove that all the CO2 increase in the atmosphere is from fossil fuel burning, but as both the oceans and vegetation are not the cause, and even show a net uptake, and other sources are much slower and/or smaller (rock weathering, volcanic outgassing,…), there is only one fast possible source: fossil fuel burning.

    Another thing it does not prove (directly or indirectly) is that industrial era atmospheric CO2 conc net increases must be caused (in whole or in part) by our fossil fuel CO2 emissions; in spite of no one denying that man put increased amounts of CO2 yearly into the atmosphere from fossil fuel emissions during the whole industrial age. In other words, as Paul Birch more simply said in a comment to your Part 1 on August 5, 2010 at 12:06 pm ;

    “We simply do not know how much CO2 there would have been in the atmosphere at this time in the absence of anthropogenic emission. CO2 levels might have risen at the same rate, or stayed constant, or even gone down. They might even have risen faster!”

    I sincerely hope there will be a Part 4 where you provide evidence showing proof that the industrial era CO2 atmospheric conc increase has been caused by man’s undeniable increases in yearly CO2 emissions from burning fossil fuels.

    I also note that your part Part 1 & Part 2 contained similar issues as this Part 3. For reference those posts were:

    Part 1 – Why you think the CO2 increase is man-made based on interpretation of Ice Core CO2 Proxies

    Part 2 – Why the CO2 increase is man-made based on simplistic CO2 atmospheric mass balance equation

    F.E., in closure, thank you again, these past posts are interesting but I think most of us would rather like to see evidence showing proof of how CO2 increases in the atmosphere cause warming or other effects. We are looking forward to that.

    John

  103. Smokey:

    “natural variablity” is not a theory. It is the absence of a theory. It is a statement that says “things change” which is pretty much a meaningless statement unless you put numbers on it. Things fall to earth is not a theory, although it is true. you seem to think that “natural variability” is somehow the logical opposite of AGW. Its not.

    1. GHGs warm the planet AND the data show unexplained variability

    when you can demonstrate that the above is false or that either side implies the negation of the other side, then you have something. Simply, it does not follow from the fact that GHGs warm the planet, that there will be no unexplained variability in the data. And neither does it follow from the observation of unexplained variability in the data that GHGs do not warm the planet. neither of these follow because both sides of the conjunction happen to be true.

  104. “”” Fred H. Haynie says:
    September 16, 2010 at 10:51 am
    George E. Smith said on Engelbeen on why he thinks the CO2 increase is man made (part 3)
    September 16, 2010 at 9:22 am
    There will be some fractionation each time CO2 is emitted from or absorbed by water because of the 45/44 molecular weights ratio. This fractionation process can explain the seasonal cycle just as well or better than seasonal growth cycle of plants. http://www.kidswincom.net/climate.pdf “””

    Well I suppose it is reasonable for those processes to vary with molecular weight.

    So just what are the water/atmosphere ratios (equilibrium) for the following species:-
    16O12C16O, 16O13C16O, 16O12C18O,16O13C18O, 18O12C18O, 18O13C18O Just the values at some nominal normal Temperature would be useful; but graphs versus Temperature would be more helpful.

    Also what are the take up ratios for each of those species in the growing plants .

    I’m sure they are all different; but are they all properly accounted for in the models. And given that the CO2 abundance can vary by 3% over the globe; how to they collect that data for each of the weather measuring stations so they can correlate their Temperature anomalies with their local CO2 abundance to get a global summary.

    That was the point of my observation that atmospheric CO2 is not well mixed. Too bad there isn’t a similar color map showing the global amount of seasonal variation in the atmospheric CO2. It may be 6 ppm p-p for ML, but it is 18 ppm p-p for pretty much all of the arctic oceanic region. and at the south pole it is more like -1 ppm p-p; being out of phase with the northern cyclic variations.

    That data suggests a lot of rapid transfer between the oceans and the atmosphere, since in the Arctic, that 18 ppm drop happens in just 5 months; so that is hardly time for any deep ocean biologic processes to affect what is most likely a simple segregation coefficient at the water/air interface..

    And if the13C/12C take up at the ocean surface is a drmatic as RW suggests, isn’t that interchange causing its own shift in the atmospheric CO2 isotopic ratios.

  105. [Just for Pamela: Did you have a great day?]

    The CO2 atmospheric concentration plot seems to correlate most with an active ocean rather than industrial areas. For example, most of Europe shows low CO2 and so does eastern North America. The west coast of North America has very active sea life due to upwelling of deep ocean water there (cold). The Gulf Stream appears to have very high CO2 levels, as does the Mediterranean (both warm). The Western Pacific also has higher CO2 levels according to the map, and so does the eastern Indian ocean.

    It isn’t at all clear that humans are responsible. The map does point to the oceans as being the prime source of CO2.

    Interestingly, there are many areas with low CO2 concentrations. The tropical regions of South America, Africa, and Borneo. Equatorial waters seem to be sinks.

    If you wanted to blame industrialization for CO2, why does Japan have such a low concentration? Why does the industrial area around Hong Kong have a lower CO2 concentration than California? Why does India seem to be more of a sink than a source despite having a population of about 1 billion people?

    It appears far more likely that methane is the source of CO2, via methanotrophic bacteria. They are found in all waters, and are associated with methane vents such as the California coast from Santa Monica to Oregon, the mid-Atlantic ridge, and the Black Sea. See http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2446507/.

    Mud volcanoes in the Mediterranean Sea produce very methane-rich sediments that are strongly depleted in 13C. See http://aem.asm.org/cgi/content/full/66/3/1126.

    The Caspian Sea and the Sea of Okhotsk are also major sources of methane. These are both high CO2 features on the CO2 map. See http://books.google.com/books?id=r_2Ia8wOBlgC&pg=PA138&lpg=PA138&dq=methane+caspian+sea&source=bl&ots=0p6fuf40C8&sig=GnKSIBCGk8hIiqDPRgcqjE3ZJMQ&hl=en&ei=T4WSTIOLG42CsQPts5zACg&sa=X&oi=book_result&ct=result&resnum=6&ved=0CCYQ6AEwBQ#v=onepage&q=methane%20caspian%20sea&f=false.

    If we could see the same map of methane distribution in the atmosphere, we would have our answer. It turns out we can. See http://photojournal.jpl.nasa.gov/browse/PIA09941.jpg.

    But what does that image show? At first it appears that the test failed. But if you notice, the methane has highest concentrations surrounding the areas we noticed had high CO2 concentrations. Could it be that we are simply seeing depletion of methane by conversion to CO2? And there are other sources of methane, like Antarctica, where the CO2 conversion apparently doesn’t take place. How many methanotrophs would we expect to find in Antarctica?

    It seems we keep over-estimating the impact of people. 7 billion people can’t do all that much compared to bacteria.

  106. PeterB in Indianapolis says:
    September 16, 2010 at 8:02 am

    ….Your conclusion assumes that there are no other chemical reactions going on than the one you listed, and that O2 is the “limiting reagent” for the equation you listed. Let me assure you that there are BIG reactions going on all of the time which counterbalance the reaction that you showed, and as such, it is HIGHLY unlikely that O2 is the limiting reagent.

    Something truly bizzare would have to happen for the world to run out of Oxygen any time in the next few billion years.
    __________________________________________________
    Some bizzare thing like idiotic humans managing to sequester CO2 and dropping the atmospheric level below 180PPM – ALL plants would then die.

    What I found truly amazing was this plant/CO2 study:

    Plant photosynthetic activity can reduce the Co2 within the plant canopy to between 200 and 250 ppm… I observed a 50 ppm drop in within a tomato plant canopy just a few minutes after direct sunlight at dawn entered a green house (Harper et al 1979) … photosynthesis can be halted when CO2 concentration approaches 200 ppm… (Morgan 2003) Carbon dioxide is heavier than air and does not easily mix into the greenhouse atmosphere by diffusion… Source

    Think about it a plant can drop the CO2 in its vicinity by 50ppm in minutes!

    Another key piece of evidence that we’re living on a planet with CO2 levels currently at the very bottom of the normal range is the whole new group of plants that evolved several million years ago to cope withthe low levels of CO2. They developed a new method of photosynthesis called C4 which permits greater water efficiency and the ability to photosynthesise in higher temperatures at greatly reduced CO2 levels.
    An even better adaption called CAM evolved in plants like cacti.

    At 200 pm CO2 trees starve http://biblioteca.universia.net/ficha.do?id=912067
    (Since I last looked this reference has been removed from the internet. It does not correlate well with the Ice core data.)

    However stomata data by Wagner, Aaby and Visscher prove that the ice core data is seriously in error. The ice core data can be corrected using J.J.Drake’s correlation, the profile does not change but the ppm values do so the analysis is still valid.

    http://www.bio.uu.nl/~palaeo/people/Rike/index.html

    Actual Paper.

    http://www.pnas.org/content/99/19/12011.full.pdf

    The whole “official” CO2 historic measurement is called into question by this paper. It looks at the dogma and politics behind the 70 years of CO2 measurement as well as the science. It is a very interesting read. http://www.co2web.info/ESEF3VO2.pdf

    More Info:
    Plant Stomata react more accurately to CO2 concentration, as has been determined in experiments. (More CO2 means fewer stomata, as plants exchange CO2 more efficiently) Historical collections of leaves can be used to determine past CO2 levels. In most cases, researchers are bound by the modern paradigm, and get confused by the low stomata counts of the past. Stomata cannot measure very high CO2, but only indicate high C)2. Higher CO2 levels over 325ppm are underestimated. When reading stomata research, you need to filter out the ruling paradigm when the problematical ice-core data is used to calibrate the stomata, when it should be the reverse.
    Rapid atmospheric changes are well known from past reconstructions:
    See http://www.ncbi.nlm.nih.gov/pmc/articles/PMC129389/pdf/pq1902012011.pdf
    & http://www.geocraft.com/WVFossils/Reference_Docs/Late_Holocene_CO2_3000-4300_BP_Jessen_etal_2005.pdf

    Changes of close to 100ppm in a century are quite common.

  107. Speaking of Volcanoes:

    The true extent to which the ocean bed is dotted with volcanoes has been revealed by researchers who have counted 201,055 underwater cones. This is over 10 times more than have been found before.
    The team estimates that in total there could be about 3 million submarine volcanoes, 39,000 of which rise more than 1000 metres over the sea bed. http://www.newscientist.com/article/dn12218

    Volcano Outgasing of CO2.
    “The primary source of carbon/CO2 is outgassing from the Earth’s interior at midocean ridges, hotspot volcanoes, and subduction-related volcanic arcs. “http://www.columbia.edu/~vjd1/carbon.htm

  108. Steven mosher says:

    ” ‘natural variablity’ is not a theory.”

    I prefer Dr Spencer’s climate null hypothesis:

    No one has falsified the hypothesis that the observed temperature changes are a consequence of natural variability.

  109. Steven mosher says:
    September 16, 2010 at 2:05 pm
    Smokey:

    “natural variablity” is not a theory. It is the absence of a theory. It is a statement that says “things change” which is pretty much a meaningless statement unless you put numbers on it. Things fall to earth is not a theory, although it is true. you seem to think that “natural variability” is somehow the logical opposite of AGW. Its not.

    You are sailing very close to argumentum ad ignorantium, i.e.

    “We won’t accept natural variability as an argument because:
    it is not difficult to find some aspect of natural chaotic non-equilibrium emergent pattern variability that is not fully understood and mathematically described to the finest detail.”

    Follow this logic and you will find we know nothing at all about anything.

    Natural variability is a perfectly valid null hypothesis.

    A null hypothesis is a valid way to approach any scientific question.

    The CAGW hypothesis cannot survive the scientific process any more than anaerobic bacteria can survive in the presence of oxygen.

  110. Steven mosher says to Smokey on:
    September 16, 2010 at 2:05 pm

    1. GHGs warm the planet AND the data show unexplained variability

    when you can demonstrate that the above is false or that either side implies the negation of the other side, then you have something.

    —————————-

    Steven Mosher,

    I think your statement is not quite right. It appears to be that you are claiming that GHGs (all of them) combined with all other known and unknown processes involved in the earth system warm the planet. I do not think this has ever been demonstrated scientifically. By themselves in a simplified (non-realistic) scenarios without the total earth system processes included there have been discussions about possibility of GHGs warming the planet, maybe that is what you are thinking . . . . but they are just discussions. Your claim is often assumed / postulated /implied / believed . . . . . all those yes but demonstrated scientifically . . . no. If you can show it scientifically or cite papers that show it then please do so for everyone’s benefit. Then we will provide falsifications. Until then there is nothing for us to falsify.

    By just looking at the climate data (temps) there is nothing in it that proves GHGs warm the planet. It needs a theory to be developed and be stated as a hypothesis and be tested against the climate data.

    As for natural variability, prior to man’s hypothesized influence , the climate sure did vary widely. The data shows that. No need for a theory and hypothesis to see that climate varied significantly before man’s influence . . . just look at the data. It had to be natural, no man influence. A hypothesis is only needed if you wish to understand why it varied and what natural variability consists of by mechanisms.

    John

  111. Bob Shapiro says: “Let’s assume for a second that there are no equilibrium processes which would have CO2 at current levels, even if humans didn’t exist.”

    Let’s not. You’re begging the question.

    “Humans do produce some amount of CO2, and added to the net CO2 from all other processes, the total is higher than it would have been, meaning that humans have produced the incremental CO2. So now, granted all this, what is your point?!”

    The incremental CO2 may be negligible.

  112. Steven mosher says:
    September 16, 2010 at 1:38 pm
    I’m still waiting for someone to offer any evidence that burning fossil fuels will cause
    a net decrease in C02.

    Why would anyone in their right mind WANT to “cause a net decrease in CO2″?

  113. Steven mosher says:
    September 16, 2010 at 1:38 pm
    Congrats Ferdinand.

    I’ve enjoyed every one of your patient logical explanations.

    I’m still waiting for someone to offer any evidence that burning fossil fuels will cause
    a net decrease in C02.

    Why would anyone in their right mind WANT to “cause a net decrease in CO2″ and risk the extinction of photosynthetic plant life?

    Increased plant growth encourages a greater mass of plant life to grow in previously marginal terrestrial and marine environments. The increased mass of plant life consumes more CO2. The increased rate of CO2 consumption maintains the CO2 concentrations at whatever minimum level the Plant Kingdom can no longer diminish. In the event of a sudden change of climate from a warmer inter-glacial period to a colder ice age, the disruption of the carbon cycle for plant life could result in =<~180ppm levels too low for photosynthesis and too fast for adaptation to avoid extinction.

    Burning fossil fuels may or may not result in lower CO2 concentrations in the atmosphere, but it is not inconceivable for fossil fuels to stimulate enough new plant growth to generally maintain concentrations or lower them in some other circumstances.

  114. 3.0 Abusing Doctor Suess: Pulling the Cat out of the Hat

    So far, the evidence presents the rather tantalizing implication that volcanogenic CO2 emission is a significant if not dominant contributor to atmospheric CO2 levels. The next logical step for those trying to prove that the CO2 rise is anthropogenic is to find a signature to fingerprint anthropogenic CO2 as separate from all other sources of CO2. The research of one Harmon Craig, first submitted for publication on ISO:1953-Apr-20, found that 13C & 14C are enriched in carbonates. Harmon Craig discusses the carbon dating errors that can be introduced by natural isotopic fractionation, along with other processes (Craig, 1954). While Rankama (1954), suggests that 13C depletion is characteristic of biogenic sources, Craig (1954) goes so far as to suggest the use of 13C as a tracer for 14C. This becomes the subject of research by Hans E. Suess into the contamination of 14C dates by variations in normal atmospheric 14C, which quantified the effect of processes discussed by Craig (1954). Part of Suess’ explanation of his own results was seized upon as a way to fingerprint fossil fuel CO2 because fossil fuels, being too old to contain measurable amounts of this cosmogenic isotope, will deplete atmospheric concentrations of 14C when burned. In Cleveland & Morris (2006, p. 427) Hans Suess and the Suess Effect, used to account for contamination of radiocarbon dates by various phenomena, are given the following entries:

    Suess, Hans 1909-1993, U.S Chemist who developed an improved method of carbon-14 dating and used it to document that the burning of fossil fuels had a profound influence on the earth’s stocks and flows of carbon. (Fossil fuels are so ancient that they contain no C-14.)

    ………

    Source : http://carbon-budget.geologist-1011.net/

    REPLY: SNIPPED MAJORITY OF CONTENT – please don’t repost entire website stories here. That’s what links are for – Anthony

  115. Methane forcing is about 20% of all GHG forcings. It has increased from about 700 to 1800 parts per billion in the last century or 4 times faster than CO2. Interestingly it decays into CO2 after ten years. So that means it has added CO2 to the atmosphere over the past century about 18000 parts per billion or 18 parts per million. This then accounts for over 20% of the increase in CO2 since pre-industrial times (87ppm).

    You can check the numbers above here:

    http://en.wikipedia.org/wiki/Greenhouse_gas#Greenhouse_gas_emissions

    If CO2 from degradation of methane was exactly as light in heavy carbon isotopes as carbon from coal and oil then it would account for 20% of the isotope “signature” i.e. the slightly declining heavy carbon isotopes over the past century as graphed in the OP.

    But wait, I also provided links in previous comments establishing the fact that CH4 is twice as light in heavy carbon isotopes as fossil fuel carbon. So it has twice the diluting effect or about 40% of the so-called fossil fuel isotope signature.

    This of course raises the question of how much methane is anthropogenic and/or what the heck is driving its rapid increase in the past century. If the increase is either anthropogenic and/or a natural source that can be reduced then, given its residence time in the atmosphere is only 10 years, it appears to be much lower hanging fruit if one’s interest is truly in reducing the ostensibly growing and eventually catastrophic greenhouse effect. If we could bring methane emissions back to pre-industrial level it would reduce anthropogenic global warming by more than ten percent in ten years. There is no way to get such a fast reduction in greenhouse warming by actions taken to reduce CO2 emissions.

  116. R. Gates says: “…Only an extreme minority currently would ever seriously no doubt that human activity has caused the 40% increase in CO2 since the 1700′s.”

    Yes, R, we know you think science is about taking a vote.

    “So while this is an interesting, and mostly accurate post, it is hardly earth-shattering or particularily interesting.”

    Uh, so it’s interesting but not particularily [sic] interesting. Right.

    “The core issue really is how sensitive is the climate system to this anthropogenic based increase in CO2. And of course the next step that some are working on already is some sort of geoengineering efforts to reduce the CO2 levels or mitigate their effects.”

    And those efforts, being based on ‘consensus’ drivel instead of science, will fail.

  117. Scarlet Pumpernickel says:
    September 16, 2010 at 4:09 pm

    Incorrect, you cannot distinguish carbon with the ratio from what comes out of volcanoes.

    http://carbon-budget.geologist-1011.net/

    Yes but is there any reason to believe that volcanic activity increased at the same time the industrial revolution began? If not then it’s a constant factor that can be ignored unlike, say, planetary albedo which is modeled as a constant but is actually known to be a significant variable with very poor understanding of what causes the variation.

  118. D. Patterson:

    “Burning fossil fuels may or may not result in lower CO2 concentrations in the atmosphere, but it is not inconceivable for fossil fuels to stimulate enough new plant growth to generally maintain concentrations or lower them in some other circumstances.”

    You missed the point. Absent any evidence that burning Fossil fuels causes a net decrease, absent ANY argument, I think the reasonable alternative is the obvious.
    It causes a net increase. Now that obvious conclusion also happens to be supported by a wealth of evidence which our kind author has assembled over three posts. There is no evidence of a net decrease from burning FF, there is substantial ( but never conclusive) evidence that it causes a net increase. The possibility that you might doubt it, does not amount to an argument. So, I am waiting for someone to argue that it causes a decrease, and back that argument up.

  119. Nick Stokes says:

    quote
    This is an excellent article, which sets out the facts systematically, and makes it easy to understand. Congratulations, Ferdinand.
    unquote

    Nick, forget the money from sweet Solitaire (I assume you are paid by that pert Poictesme* of an old man’s dreams, because I can imagine no other reason for your blindness) and look at the second graph above.

    Ferdinand says that it’s obvious that the change began in 1850. Que? Look carefully. When does the ratio begin to change? Come on, look. Does it really only begin to go down in 1850? If you believe that you need a) an eye test and b) a brain transplant. This is science as delusion, when even a graph which refutes the hypothesis is offered as proof of it.

    From the main post:
    quote
    What we can see, is that the d13C levels as well as in the atmosphere as in the upper oceans start to decrease from 1850 on, that is at the start of the industrial revolution.
    unquote

    Ferdinand, that is utter tosh. Look at the graph. When does the ratio of 13C/12C start to decrease? Look, please trust your eyes. No, there is no sudden change in 1850. It starts to go down in 1700 (ish). OK, the fall increases in 1850, but it doesn’t start then. Why, my dear chap, does it fall from 1700 to 1850? If you’d like an explanation I’ll do it tomorrow (a hard folkie night tonight with added whisky, but look up diatoms, and silica as a critical resource for these pretty members of the plankton population) and in the meantime please look at that graph and ask yourself how you have got to a state where you can choose 1850 as a significant date.

    Interesting that you have made the same error here as you did with the CO2 mass balance — you are confusing an increase in production with a reduction in sink.

    JF
    *pronounced ‘pwah-temm’, an earthly paradise, an unattainable summit of earthly desire. Aka ‘a yummy mummy’. [waves]

  120. Charles S. Opalek, PE says:
    September 16, 2010 at 4:07 pm

    Man contributes 3.27% of the CO2, Nature 96.73%. What’s the problem?

    The problem is nature is evidently only sequestering 98.5% the total emissions each year and the remainder is accumulating as a rising atmospheric CO2 concentration. One of the least contestable facts in this matter is that atmospheric CO2 levels have began rising faster and faster since the beginning of the industrial revolution where human activity emits twice the amount it takes to account for the rise.

    That in itself is very interesting as it raises the question of what’s happening in nature that is sequestering half of human emissions. Someone else mentioned in this thread, and I’ve brought up the point myself in other threads, that the ocean determines the equilibrium point of atmospheric CO2 and that if human contribution is absent the ocean would have outgassed more of its vast store (many times greater than the atmosphere) of CO2 and the current level would still be 380ppm and rising. The most likely suspect for a change in oceanic equilibrium point is that the Little Ice Age ended about the same time the industrial revolution started and the ocean’s delayed response to the end of several centuries of ice-age cold is raising the partial pressure equlibrium point of the ocean/atmosphere interface. This greater equilibrium point could be satisfied by either human contribution directly to the atmosphere or in the absence of human emission the ocean would have released the same amount.

  121. I’m not saying that the ocean determines the partial pressure equilibrium point of atmospheric CO2 but it very well could and that must be falsified in some manner before we can know that any reduction in human emissions will actually reduce CO2 partial pressure. For all we know we could reduce anthropogenic emissions and the ocean, still seeking the same equilibrium point, would just replace the human emission with oceanic emission.

  122. Vince Causey – you are using an equation that gives the globally averaged forcing from a change in the global average CO2 concentration. Regional variations can’t, I don’t think, be evaluated in the same way.

    Smokey: calculations by many groups of scientists have shown that natural variations cannot be the cause of the current warming. Roy Spencer must, I think, have his own idiosyncratic definition of “falsified”.

  123. ATTN: Pamela Grey

    The short answer is no. In a chemical reaction, molecules containing C-13 react slightly slower than molecules containing C-12. This is called the kinetic isotope effect and is temperature dependent. However, the difference in reaction rates depends on the formula weight of the molecules in some reaction. Carbon dioxide containing C-12 has a formula weight of 44 vs 45 for molecules containing C-13 which would react about 2% slower and have a slightly lower rate of diffusion into plant leaves for example.

    BTW, the concentration of CO2 in a local sample of air is reported for purified dry air which does not occur in the earth’s atmosphere and is comprised of nitrogen, oxygen and the inert gases, which are the fixed gases, and CO2. Climates models are fatally flawed because (1) these use the wrong metric for CO2 and (2) there is no uniform distribution of the masses of various constituents of the atmosphere in space and time as shown by daily weather maps. High pressure cells have more mass than do low pressure cells. More importantly there is no uniform distribution of water as vapor and clouds

  124. So explain it to me again. The ratio between lighter and heavier CO2 is getting smaller. And the overall CO2 amount in the air is increasing. So we are putting more of the lighter isotope CO2 into the air because of fossil fuel, animal life, and decaying vegetation emits this isotope thus decreasing the ratio of lighter to heavier CO2. If what we breath out has 4 times more CO2 than what we breath in, with an average -0.5 ratio in human breath, with population growth of 6 billion since the start of the industrial age, and growing exponentially, wouldn’t that affect the ratio as well? If you say plants are using it, fine, but we still keep pumping out more CO2 than we breath in. And we are doing it in exponentially greater amounts.

    So who has the calculation? I’ve included a graph and reference to population growth. It has quite a hockey stick shape to it. Looks a lot like the growth in CO2. I wonder where the population explosion is taking place? In countries with a car in every driveway? Hardly.

    http://www.theoildrum.com/story/2005/12/18/1387/0641

    I am not stuck on this but I fail to see the closed system here regarding human breath if what we are talking about is the increasing measurement of CO2 in the air and asking where the CO2 increase is coming from. It has to be readily available and robust to downturns in fossil fuel burning.

    It just seems to me that the population boom might match CO2 growth much better than standard of living growth for those countries involved in the explosion (which by definition includes having energy to make your new cars and gadgets go).

  125. At one time, I was intrigued with the idea that the modern CO2 increase might be a result rather than a cause of the modern temperature increase, however the extreme sensitivity required to make this work when average global temperatures have only changed 0.6 to 0.7 degrees C on a base level of 14 degrees C since 1880 (I suspect many people probably believe this must have been at least a 3 degree C change to justify all the hype and alarm) means that the CO2 concentration temperature coefficient must be on the order of 170 ppm per deg C. At that rate, a 2.3 degree C average temperature drop would remove all the CO2 from the atmosphere. It seems quite unlikely that the CO2 concentration temperature sensitivity could be anywhere near this high.

    The only other possible natural (or semi-natural if caused by the massive addition of dish-washing detergent to the ocean or deforestation policies on land) would be a large increase in the proportion of CO2 producing bio-forms (animals) as opposed to CO2 consuming bio-forms, (plants) perhaps as a global oceanic bloom of micro-organisms that exhale CO2.

    As I understand the author’s article, he is saying that there is a distinction between inorganic and organic CO2 sources and the modern CO2 increases appear to have the signature of organic CO2. In my opinion that does not appear to rule the possibility of modern organic CO2 production-consumption imbalance making a major contribution to our observed CO2 increase. To exclude this possibility, one would have to show that the relative natural organic CO2 production and consumption rates have not changed in recent times.

  126. Dave Springer says:
    September 16, 2010 at 4:55 pm

    How can you argue that nature sucks up 98.5% of total emissions but only 50% of anthropogenic emissions? An increase in the natural source-rate/sink-rate ratio can just as easily explain the the rate of accumulation. The rate of accumulation has been relatively constant for around thirty years while the rate of anthropogenic emissions has been increasing. It would take only 1.5% change in the natural ratio to decrease the accumulation rate to zero or double it. A natural “dynamic equilbrium” is one of the bad assumptions made by climate modelers that leads to the 98.5% figure that we know varies seasonally by well more than 1.5%.

  127. RW says:

    “Smokey: calculations by many groups of scientists have shown that natural variations cannot be the cause of the current warming. Roy Spencer must, I think, have his own idiosyncratic definition of “falsified”.”

    There is nothing unusual about the current rise in temperatures. They have been exceeded many times during the Holocene, although much colder temperatures are the norm.

    And of course, Dr Roy Spencer wins the credibility contest against “RW”. No one has falsified the hypothesis that the observed temperature changes are the result of the same natural variability that has occurred repeatedly in the pre-SUV era..

  128. Sorry, Pamela, but I think you seriously mis-understand some of the science here.

    Pamela Gray says:
    September 16, 2010 at 5:37 pm

    If what we breath out has 4 times more CO2 than what we breath in, with an average -0.5 ratio in human breath, with population growth of 6 billion since the start of the industrial age, and growing exponentially, wouldn’t that affect the ratio as well?

    and

    The ratio of 12 to 13 is -.5%.

    reference http://iopscience.iop.org/1063-7818/32/11/A08

    The paper speaks of “respiratory tests and preparations enriched with the stable 13C isotope” so this is a situation where they are intentionally changing the C13 ratios to study what happens. And the “-0.5%” is actually “~0.5%: and that is the “accuracy of carbon isotope ratio measurements in CO2 of exhaled air performed with the TDL”. So after they intentionally enhance the C13 ratio, they can measure the ratio in the exhaled air to within 0.5%.

  129. Pamela:
    Please let me try to explain from a completely different direction. Inspired air contains about 0.3 mmHg partial pressure CO2. Exhaled air is about 32 mmHg, so you breathe out air that has about 100 times as much CO2 as you inhale.

    But this is not as relevant as the fact that you produce and exhale about .97 kg/day CO2, and it all comes from burning food, either plant or animal matter. That’s 354 kg/year CO2 per person. Fecal production is much smaller at about 0.18 kg/day. Therefore, the atmospheric CO2 you generate from burning food is almost completely returned to the atmosphere rather than stored in your body or dumped into the sewage system. So it doesn’t matter if humans can or do separate 12C from 13C, there would be little net effect on the atmosphere.

  130. R. Gates says:
    September 16, 2010 at 12:08 pm
    If you believe what GCM’s say about the 40% increase in CO2 since the 1700′s, then the “so what” becomes the significant changes that are climate is undergoing and will be undergoing. If you don’t believe what the GCM’s are saying, then who cares if the CO2 levels are higher than they’ve been for hundreds of thousands of years.

    Only an extreme minority currently would ever seriously no doubt that human activity has caused the 40% increase in CO2 since the 1700′s. So while this is an interesting, and mostly accurate post, it is hardly earth-shattering or particularily interesting. The core issue really is how sensitive is the climate system to this anthropogenic based increase in CO2. And of course the next step that some are working on already is some sort of geoengineering efforts to reduce the CO2 levels or mitigate their effects.

    Well, golly gee by willikers, Mr. Gates!
    .
    Will you now commence to run around with your underwear over your head, screaming and screeching at the top of your lungs about how all that thar CO2 is a-going to kill us dead?
    .
    The way I see things is thusly: MORE CO2 is beneficial to man than LESS CO2, by dint of the fact that PLANTS NEED that gas to survive.
    .
    More plants = MORE food = HAPPY MAMMALS, avians and other creatures.
    .
    GOT A PROBLEM WITH THAT SITUATION, Mr. Gates?
    .
    Or are you one of them thar people-haters who want to conduct a Pol Pot-style GENOCIDE?
    .
    You’ll be telling us all about that, won’t you?
    .
    Real soon now?

  131. Anthony, I am getting tired. I have been reading these CO2 exegeses too many times. Not your fault. Post certainly gets lots of hits (apparently) and comments. And not my business, but I would greatly appreciate if some of the regulars who seem to have important and valid arguments could act as “peer reviewers” to a poster like Englebeen so that he could present his material and add his answers to the questions or points of other scientists. I feel like the wheels are spinning; too many of the same excellent comments over and over again, but little scientific rigor in getting them together. At the same time I greatly appreciate (almost) all comments and thank those who have the time and energy to continue to post. At this point I think I have “had it” with CO2. Let it continue to grow in the environment and maybe we might remain a little warmer and somewhat more prosperous (or less poor, lots of plants, not as much dependence on rainfall, more efficient energy resources, and maybe we can hold the next glaciation at bay for a longer time).

  132. Still don’t get it. Atmospheric % of CO2 is not anywhere near the % of CO2 in our exhaled breath. Let’s just stick to measuring two vials of air: ambient, and our exhaled breath. If it is a closed balanced system, the two should have equal concentrations. Yes?

    There is evidence of a balanced system with vegetation. There is a seasonal variation in atmospheric % of CO2 that balances itself out by growth and decay of vegetation. This can be measured. We can even account for the greening of the planet. More CO2 is taken up, and the same amount is emitted upon decay. Why does this not apply to the animal kingdom? In the case of humans, we just keep populating the Earth more and more. It is not balanced. It would be like having an endless season of vegetative growth (or the reverse: decay) that never quits.

    The population curve is interesting. If one were to assume that every person in the hockey stick “working” end is also now driving a car and heating their home with whatever fuel they prefer, it would make sense that a higher standard of living is at fault. But the population growth is NOT in countries with higher standards of living. What else is there about this mass of poorer throngs of humanity that could be emitting more CO2?

  133. From wikipedia so take with a grain of salt.

    http://en.wikipedia.org/wiki/Breathing

    “The air we inhale is roughly 78% by volume nitrogen, 21% oxygen, 0.96% argon and 0.04% carbon dioxide, helium, water, and other gases. In addition to air, underwater divers often breathe oxygen-rich or helium-rich gas mixes. Oxygen and analgesic gases are sometimes given to patients under medical care. The atmosphere in space suits is pure oxygen. Also our reliance on this relatively small amount of oxygen can cause over activity or euphoria in pure or oxygen rich environments.

    The permanent gases in gas we exhale are roughly 4% to 5% more carbon dioxide and 4% to 5% less oxygen than was inhaled. Additionally vapors and trace gases are present: 5% water vapor, several parts per million (ppm) of hydrogen and carbon monoxide, 1 part per million (ppm) of ammonia and less than 1 ppm of acetone, methanol, ethanol (unless ethanol has been ingested, in which case much higher concentrations would occur in the breath, cf. Breathalyzer) and other volatile organic compounds. The exact amount of exhaled oxygen and carbon dioxide varies according to the fitness, energy expenditure and diet of that particular person.”

    This change in (there is an increase as well as a change in isotope ratio compared to the air we take in) CO2 is an immediate source of additional CO2, and especially when plants are dormant. You are trying to tell me that this additional and immediate source of CO2 cannot contribute ANYTHING to the measured increasing CO2 at our monitoring stations? Plants take it up immediately? Even in the winter? I still don’t get it. And to reiterate, I’m not talking about any other measurement than the daily, weekly, monthly, and yearly amount of CO2 being measured in the atmosphere. I’m not talking about a model that says this is a closed, balanced system between eating veggies and exhaling.

  134. By the way, I’m not on a kick against having babies. Have however many you want. I’m just trying to explore all the possible sources of this increasing CO2, and that population curve is a very nice fit with the CO2 curve.

  135. This is a great article.
    What he points out that many source of CO2 that many skeptics have cited are in fact invalid. So yes there is a large source of CO2 undetermined. Given that humans have been generating CO2 in an exponential amount since the 1800′s, this does seem like an obvious choice. Yet many say SHOW ME THE MONEY. I say ok, fine, show me your theory about what ELSE is causing CO2 increase, if not humans?

  136. What I am trying to find is a rather regular (almost mathematically regular) source of increasing CO2 that would lead to the stair stepping CO2 graph. Population increase is now so large that it is developing an exponential (almost mathematically regular) shape. Since population increase and CO2 increase do not match energy consumption increase over the same period (and I wish I had a good graph of energy consumption over this time period), especially in China and India, I just have to wonder if the immediate increase is from breathing out. If someone can find a graph of world energy consumption over the last 2000 years (and of course this has to be modeled), please post. I could be barking up the wrong tree ring here. Remember that back in the day, open fires, inside or outside, were very inefficient ways of keeping a house warm or cooking a meal, so EVERY household burned lots and lots of energy on a daily basis. Energy use now is WAY more efficient than it used to be. This could be why the graphs I have seen so far are really messy and don’t agree with each other at all.

  137. Ferdinand,

    1. The carbon deposits to call “fossil fuels” are not derived from recycled biomass or fossils – unless the laws of thermodynamics have changed.

    2. The Carbon isotope ratios cannot discern biogenic from non biogenic sources, especially when an archaen diamond has “observation by Giardini & Melton6 that such cannot be considered a reliable criterion for ascertaining the origin of petroleum. Giardini & Melton took a primoridial natural diamond of 8.65 carats and measured the carbon isotope ratio of the CO2 entrapped in its inclusions. The results were an isotope ratio of –35.2% on the standard PeeDee scale. Previously the carbon isotope ratios more negative than – 18.0% had been assigned a biological origin. The diamond tested by Giardini & Melton was measured to be of an age of crystallization of at least 3.1 x 10^9 years, well before any record of biological life on Earth. The observation by Giardini & Melton destroyed any claimed validity of the carbon isotope ratio as a determinant of the origin of petroleum, – and probably of any other carbon compound.”

    There is an outstanding prize of US$10,000 for anyone who can demonstrate empirically and experimentally that petroleum can spontaneously form from subjecting biomass to the pressures and temperatures typical for the bottom of sedimentary basins.

    However, experimental evidence of the spontaneous production of hydrocarbons from a mixture of CaCO3, FeO and H20 has been published and replicated. The fossil fuelers, however, continue their assertions by resort to rhetoric or applying the logical fallacy of arguing the consequent.

    QED.

  138. Smokey

    “There is nothing unusual about the current rise in temperatures. They have been exceeded many times during the Holocene, although much colder temperatures are the norm.”

    there is nothing “unusual” about the fall in temps after a volcanp. nevertheless we can explain that variation by understanding the physics. The increase in temps may well be within the entire envelop of past changes. That says Nothing about the cause of the current rise and nothing about the rate of increase. But for the addition of C02 since say 1850 it would be cooler than it is now.

    Think of it this way. You watch a car decelerate from 60 miles per hour to 0.
    and another. and another. and still more. and you conclude from this that it is natural for a car to decelerate to 0. Now did they decelerate because

    1. the driver took the pedal off the gas
    2. the car ran out of gas
    3. it hit the wall
    4. the driver hit the brakes.

    On your view of things they all did the same thing so there is nothing unusual about a car slowing. the case for AGW is not made on the usualness or unusualness of the magnitude of the rise. It made from observing that physics predicts that if you put more C02 in the atmosphere temperatures will go up. Similarly, I could predict that if you apply the brakes the car will slow down. Its not a counter argument for you to point out that other things can slow a car down, or that some cars in the past slowed down because they hit walls or ran out of gas, or ran out if gas while the brakes were being applied. GHGs warm the planet. More GHGs make matters worse. are their other factors? of course. Do GHGs DOMINATE the change? that is the real question.

  139. Jean Parisot says:
    September 16, 2010 at 7:17 pm
    How is the uneven distribution of atmospheric CO2 factored into various IPCC models?

    It isn’t. The models assume that the atmospheric gases are “well-mixed” and that distribution of mass is uniform, but they do take into account that the density of the
    atmosphere decreases with altitude

    As I mentioned above, high pressure cells have more mass than low pressure cells.
    Water vapor lowers the density of air and there is no uniforn distribution of it in the lower atmosphere, i.e. below 30,000 ft.

    The water droplets of clouds contain atmospheric gases including CO2 and the clouds can transport these gases to various locations. The amount of CO2 held in clouds would be difficult to estimate but it is not zero. Rain can “wash” CO2 out of the atmosphere.

  140. Ferdinand,
    Thanks for the article, however Dave Springer’s methane arguments are valid and need to be considered further. Regrettably fossil fuels are not the only potential reservoir of light carbon that can exchange with atmospheric CO2. Your arguments are sound and there probably is a component of fossil light-carbon in the lowering of the delta C13 ratios of atmospheric CO2, it is just that without knowing the methane contribution you can not prove your case.

  141. John Whitman:

    “Steven Mosher,

    “I think your statement is not quite right. It appears to be that you are claiming that GHGs (all of them) combined with all other known and unknown processes involved in the earth system warm the planet. I do not think this has ever been demonstrated scientifically. By themselves in a simplified (non-realistic) scenarios without the total earth system processes included there have been discussions about possibility of GHGs warming the planet, maybe that is what you are thinking . . . . but they are just discussions. Your claim is often assumed / postulated /implied / believed . . . . . all those yes but demonstrated scientifically . . . no. If you can show it scientifically or cite papers that show it then please do so for everyone’s benefit. Then we will provide falsifications. Until then there is nothing for us to falsify.”

    1. we know from physics that GHGs warm the planet.
    2. There is no physical theory to even suggest that they cool the planet
    3. The question is, how much
    A. so small as to be non measureable
    B. large enough to be measurable
    Further, like many people you utterly misunderstand the the notion of “falsification.” no theory is falsified. Theories have to be “falsifiable.” That speaks only to this: they have to make statements that can be measured against observations. So simply the theory that holds that increasing GHGs will warm the planet is confirmed ( never proven) by our observations. Since 1850 ghgs have increased, so has the temperature. Further, if we try to predict the course of temperature from 1850 to today and hypothecate no forcing from C02 our predictions go horribly wrong. (see ch09 ar4) Absent any evidence or theory that GHGs cool the planet, and in light of theory and evidence that consistently claims they will, the balance of the evidence warrants the rational belief that they do. Theory predicts they will. they have.

    “By just looking at the climate data (temps) there is nothing in it that proves GHGs warm the planet. It needs a theory to be developed and be stated as a hypothesis and be tested against the climate data.”

    The theory that GHGs (like water vapor) warm the planet is well established and well developed. It’s been stated as a hypothesis for over a hundred years. the data confirms the theory. no theory is EVER proven. ever. We only have degrees of certitude. Is it logically possible that GHGs could not cause warming? sure. Is there any theory that suggest this? no. if there WAS, then that theory would be at odds with the last 160 years of data.

    “As for natural variability, prior to man’s hypothesized influence , the climate sure did vary widely. The data shows that. No need for a theory and hypothesis to see that climate varied significantly before man’s influence . . . just look at the data. It had to be natural, no man influence. A hypothesis is only needed if you wish to understand why it varied and what natural variability consists of by mechanisms.”

    i’m far more skeptical of data before 1900 than any of the so called skeptics here. nevertheless, as you point out, merely pointing to variability is no theory. For the incurious, I suppose one could observe that people get old and die. its natural. for the scientist, for the curious, its human nature to wonder why and to try to explain it. So, merely pointing at variability and grunting “nature” is not very interesting in my book but it seems to be enough for some folks. go figure.

    John

  142. Thanks all for the lot of comments!

    As I am travelling now with limited Internet access, my reactions on the main points will be for tonight…

    Ferdinand

  143. intrepid_wanders says:

    While I do understand the hypothesis that is being presented, there still remains the issue of “understanding” of isotopes specifically, carbon.

    C-12 -> Stable
    C-13 -> Stable
    C-14 -> beta decay + N14
    N-14 + n -> C-14 + H-1
    B-13 -> C-13 + beta decay

    So, the first thing that comes to mind is the source of C-13 is B-13 with an electron ejection (decay is tens of millisecs).

    You’d also need something producing the boron 13 to decay to carbon 13. This production of carbon 13 would appear to be more likely to happen in stars than on the surface of Earth.

    Conversion of nitrogen to carbon happens in the upper atmosphere, which is mostly nitrogen anyway. However carbon 14 has been found in fossil fuels. Coal is mostly carbon, oil is mostly carbon and hydrogen. So it appears that other nuclear reactions an create this isotope of carbon. If this is neutron capture such coal or oil may well contain more heavy carbon (and hydrogen) isotopes. But that not exposed to a source of neutrons would contain carbon from the original organic sources. These sources likely to be random and variable anyway.

  144. Harvey says:

    quote
    I say ok, fine, show me your theory about what ELSE is causing CO2 increase, if not humans?
    unquote

    Reduced pull-down into deep ocean rather than increased output by humans. Pulldown mechanism tending towards heavier isotopes as diatoms and C4 phytoplankton take more of the load. You can find a recent report of phytoplankton population decline by Googling “Global phytoplankton decline over the past century
    Daniel G. Boyce1, Marlon R. Lewis2 & Boris Worm1″ and a general search will show you the carbon metabolic response of starved phytoplankton. The effects of human-induced dust increases can be found by searching for “Increasing eolian dust deposition in the western United States linked to human activity”, and further searches on the limitation of diatom populations by silica availability is easily done. From this information you may easily show that a) starved phytoplankton will pull down relatively more 13C and 14C b) diatom populations will increase relative to the calcareous phytos in an ocean which is being fed with more silica c) diatoms pull down more heavy isotopes of carbon compared to well-fed calcareous phytos.

    Or:

    Minute warming of deep ocean methane deposits by currents responding to the MWP. Increased metabolic activity by methanophages in response, emitting light isotope CO2. See graphs of warming followed by CO2 increase in many articles about historical CO2 levels, with the lag being hundreds of years.

    Or:

    Methane deposits in polar regions responding to reduced acid rain levels as pollution controls reduce sulphate emissions. More light signal methane emitted and metabolised by bacteria.

    Or:

    Oil and surfactant pollution of ocean surface means fewer breaking waves, less efficient entrainment of CO2 by bubbles and reduced dissolving of CO2. (Note that matches of ocean and atmosphere CO2 levels have been done in shallow water where mixing by wave action is assured.)

    Or:

    something we haven’t thought about.

    Steven Mosher: you pride yourself on your rigorous take on the science, excoriating (rightly in my view but what do I know?) those who try to reject basic scientific facts like the greenhouse effect. Can I ask you to do something for me? Examine the graph above, (Fig 4, the sponge isotope data) and simply post here the dates at which you see the light isotope signal beginning. Three dates, of course, Jamaica, Pedro Bank and atmospheric.

    Do any of your dates match Ferdinand’s assertion that :

    quote
    What we can see, is that the d13C levels as well as in the atmosphere as in the upper oceans ***start to decrease*** from 1850 on, that is at the start of the industrial revolution. In the 400 years before, there is only a small variation, probably caused by the temperature drop in the Little Ice Age.
    unquote

    TIA

    JF
    *** my emphasis

  145. Our input of CO2 from burning fossil fuels is 3% of the total annual input. the rest is from natural sources. ( these figures are from the US Dept of Energy who I assume have done their homework). So there is no way that all the current increase are our fault. We must also look at the residence time of CO2 in the atmosphere and if we believe the IPCC this is 200 years. If we believe current research it is 3-5 years possibly less. Ice core research also shows that temperature increase is followed by a parallel increase in atmospheric CO2 600 to 1000 years later. So today’s modest increase is caused by the Medieval Warm period not use of coal.
    All this isotope research is based on several assumptions. One I find strange is the carbonate content at 1% in the graphic above. Considering that limastone is the ost prolific of sedimentary rocks and aged back to pre-cambrian times I think that this assumption is very wrong.

  146. Ben M says
    —————-
    Isn’t this much the same as the warmists when they say “we don’t know what else could have caused the rise in temperatures since 1975, therefore it must have been human-emitted CO2″?

    The argument from ignorance is only evidence of our ignorance.
    —————-
    Ben it’s just an simple accounting problem.
    If the book-keeper finds a big hole in the balance sheet you go looking for the embezzler.

    You don’t expect that the money just evaporated into thin air.

  147. mkelly says:
    September 16, 2010 at 6:43 am
    More molecules of water are added to atmosphere by at least 2:1 and reducing O2.

    So if you are looking to prove AGW it would be sensible to monitor and track the levels of oxygen, carbon dioxide and water vapour in the atmosphere… simples… atmospheric changes would reflect the chemistry of burning fossils… simples… but no… the AGW argument seems to rest upon dubious measurements and proxies of unknown validity… I just don’t get it… more to the point: I just don’t buy it… and if the AGW theory was right then the real story would be about declining oxygen levels… so again I just don’t get it and I just won’t but it.

    The oceans are massive temperature sensitive depositories of CO2… they absorb CO2 when they cool… and outgas CO2 when they warm… if the earth is warming then we should expect atmospheric CO2 levels to rise… and looking at the official data this is exactly what is happening… no surprise.. no problem.. and even if you think it is a problem (which is very unfortunately for you) it is a problem you can’t resolve because mankind is just too insignificant… as King Canute proved many centuries ago – man can’t command the tide. Now I have a lot of respect for King Canute… he didn’t use the tides – not a proxy for tides… he used actual observations – he didn’t fiddle with the high and low water mark readings… if only the AGWers had the same integrity as King Canute.

    The more AGW tracts I read the more convinced I am that we are dealing with missionaries from the Victoria age… in those days white men wearing dog collars would sail away to some far flung continent and start talking to the indigenous heathens… there they would try to terrorise the uneducated locals with stories of a fiery hell and eternal damnation… and if they still didn’t convert then they would buy off the chief with some western trinkets.

    In this day and age the AGW missionaries believe in their moral and intellectual superiority… they cloak themselves in the white coat of the scientist… and then they set sail to talk to the sheeple… again they try to terrorise the sheeple with their stories of how the earth is being turned into a fiery hell… and again if that doesn’t convert the indigenous heathens they start buying off leaders with money so the leaders can buy more western trinkets.

  148. Steven mosher says:
    September 16, 2010 at 10:40 pm

    1. we know from physics that GHGs warm the planet.

    —————–

    Steven Mosher,

    Thank you for your thoughtful reply.

    We are not discussing this topic on a shared set of fundamental ideas. Namely, we do not share the same set of fundamental ideas on what is the basis of human knowledge and therefore scientific knowledge. That is common among individuals. I think discussion of those fundamental ideas, which we do not share, will take us far off topic on this post.

    We agree to disagree. Nature will decide for us.

    John

  149. Ferdinand,

    If it is possible to measure the changes in the amount of CO2 in the atmosphere to better than 0.1 ppm, why is it not possible to do the same for O2?

  150. Roll up! Roll up!
    Lets plays Pin the Tail on the Mauna Loa Donkey

    Background
    ========
    1) Study the global CO2 level map produced by NASA – shown at the top of this page.
    2) Study the latest CO2 readings from Mauna Loa – see http://en.wikipedia.org/wiki/File:Mauna_Loa_Carbon_Dioxide-en.svg

    Technique
    ========
    Locate Mauna Loa on the CO2 map by matching up the CO2 levels.

    Winning The Game
    ==============
    Winning the game requires you to have correctly identified the geographic location of Mauna Loa on the CO2 map.

    WARNING
    ========
    Do not use a pin to locate Mauna Loa on your computer screen… a clean finger is recommended.

    LEGAL
    =====
    The organisers of this competition reserve the right to alter the data and the map of the globe at any time.

  151. Louis Hissink,

    “However, experimental evidence of the spontaneous production of hydrocarbons from a mixture of CaCO3, FeO and H20 has been published and replicated.”

    While the abiogenic hypothesis is an intriguing one, and chemically plausible, opponents do have one serious criticism. That is, at the high temperatures associated with this inorganic reaction, the hydrocarbons rapidly breakdown. If true, I would say this is a serious problem.

  152. Tips on how to win Pin the Tail on the Mauna Loa Donkey
    1) Remember the NASA map is for July 2003
    2) Remember the NASA map is for the atmosphere at an altitude of 8 kilometres
    3) Remember the Mauna Loa observatory is at an altitude of 3397 metres
    4) Remember that CO2 levels change with altitude – see http://www.biomind.de/realCO2/realCO2-1.htm

  153. Steven mosher,

    “Similarly, I could predict that if you apply the brakes the car will slow down. Its not a counter argument for you to point out that other things can slow a car down, or that some cars in the past slowed down because they hit walls or ran out of gas, or ran out if gas while the brakes were being applied. GHGs warm the planet.”

    Clever, but false analogy. We know that the car will slow down and stop if you apply the brakes. We don’t know that adding more CO2 will warm the planet at all because we don’t know the sign and magnitude of the feedbacks.

    Pursuing your car analogy, we should envisage a car where the hydraulic cable feeding the brakes have holes, and the brake is connected to the throttle by some complex serious of interconnections, the aggregate result of which is unknown, and the driver is sitting on a chair affixed to the roof of the car and attempting to press the brake peddle with the handle of a broom (the last part thanks to Mr Bean).

    That is the true CO2 analogy.

  154. nvw says:
    September 16, 2010 at 10:23 pm

    Ferdinand,
    Thanks for the article, however Dave Springer’s methane arguments are valid and need to be considered further. Regrettably fossil fuels are not the only potential reservoir of light carbon that can exchange with atmospheric CO2. Your arguments are sound and there probably is a component of fossil light-carbon in the lowering of the delta C13 ratios of atmospheric CO2, it is just that without knowing the methane contribution you can not prove your case.

    Thanks for noticing. It can be very frustrating when you know you have a valid point and no one takes note of it. Englebeen clearly needs to address it but he can dodge it, purposely or otherwise without appearing dishonest, when it is buried amongst a large number of unrelated comments begging a response.

  155. Dave Springer says:
    September 17, 2010 at 5:56 am
    when you know you have a valid … but he can dodge it….

    Without a doubt anything can be dodged in the land of smoke and mirrors.

  156. @nvw

    P.S. One can never prove an argument from ignorance. That doesn’t make them invalid scientific hypotheses however. Karl Popper explained how to make an argument from ignorance a valid scientific hypothesis with his well known example of white swans. Popper formed the hypothesis that “all swans are white”. At the time a colored swan had never been observed. He pointed out that it would be impossible to prove that are no colored swans in nature because there was no known scientific principle that forbids a colored swan and no matter how thorough the search for a colored swan the possibility would always remain that somewhere a colored swan was overlooked. He then went on to describe falsification. The hypothesis that no colored swans exist in nature could be disproven by the discovery of a single colored swan. Thus the hypothesis was legitimate and following from that any similar argument from ignorance in science is legitimate so long as it can, at least in principle, be disproven.

    Englebeen made a legitimate colored swan argument. He hypothesized that nothing exists in nature that can duplicate the fossil fuel light carbon isotope signature. I disproved his hypothesis by showing that methane can produce the same signature. Methane, in this case, is equivalent to finding a colored swan.

    Just for a historical note of reference the Australian Black Swan was discovered subsequent to Popper’s example of falsification.

    More on Popper and falsification here:

    http://en.wikipedia.org/wiki/Falsifiability#Two_types_of_statements:_observational_and_categorical

  157. Folks, I think we are looking for a steady pump, not the up and down nature of ocean sinks, or even seasonal vegetation. What entity, what ecosystem, what area on this planet is steadily increasing in regular amounts day in and day out, and increasing each time at a fairly regular rate? Looking at graphs of things that increase, there is a near perfect match between CO2 and human population growth. So looking at human behavior is a reasonable place to look for a steadily increasing pump. The only thing I have found so far that is steadily increasing and that matches CO2 and is strong enough to overcome being washed out by rain or decreased by cold, or fluctuated by energy use, in other words is immediately replaced by more CO2, is exhaling CO2 out in a steadily growing population. What organism (or organisms) in the animal kingdom is undergoing a steadily increasing population that matches the CO2 graph?

  158. Steven mosher says: September 16, 2010 at 10:09 pm
    1. GHGs warm the planet.
    2. More GHGs make matters worse.

    I can agree with #1, but more at ‘insulate’ than ‘warm’. I assume by ‘worse’ in #2, you mean more warming. One would have to assume the system is not self-limiting, which is at best a guess.

  159. When researching info for commenting on F.E.’s post, I ran across something that I had not seen before regarding the source of earth’s 13C and 12C.

    In the following four reference links we can find that the solar wind is a source for 13C and 12C on earth. I take them as evidence that it arrives depleted in 13C when compare to earth’s isotopic standard pre-industrial ratio of 1 (13C) to 90 (12C). The ratio range of 13C and 12C from the solar wind look to be about the same ratio range as the 12C and 13C that F.E. says are from fossil fuel CO2 emissions.

    Solar winds varying with Solar Cycles cause variation in deposition rates of 13C and 12C into the earth system. Those solar wind depositions on earth are in the same range of ratios of 13C and 12C as the range of ratios found in release of carbon by fossil fuel emissions.

    http://solar-center.stanford.edu/FAQ/Qsolwindcomp.html

    http://www.springerlink.com/content/4436600382381753/

    http://www.als.lbl.gov/als/science/sci_archive/83spacedust.html

    http://www.icsu-scope.org/downloadpubs/scope13/chapter02.html#fig2.1

    I hope those links came out OK. : )

    John

  160. Steven mosher, I’ve read your book. You need to read Dr. Spencers book.

    Get involved in the world of Cybernetics. You will learn something that most should be taught in college, instead of all that green crap.

  161. CO2 increases go up and down with sea temperature. For example In 2008 during the deep La Nina, in those months, the rise in CO2 was negligable. This is explained by the IPCC as the biosphere consuming more CO2 during La Nina cycles, because of the favourable weather that ensues. I question this particularly as this also occured after Pinatubo erruption. Erruptions cause a dimming and are quite different from the ENSO cycle. Well it now looks like we’ll be entering a minimum, maybe something approaching the Maunder minimum, as the sea surface temperatures plunge and the CO2 increase too ( as they have done in every other La Nina cycle), let us ponder for a moment whether the following scientific statement, really is as “fantastic” as everyone says it is:

    http://www.biomind.de/realCO2/statements.htm

    What fascinates me is that this statement was made in 2007, well before it was clear that the sun had gone quiet and there wasn’t a hint of a record breaking La Nina back then.

  162. Moderator,

    My post from about 1 hour ago probably went to the spam netherlands because it had 4 links in it.

    Can you retrieve it from the nehter gods?

    John

    [Done.]

  163. It seems like hardly a week goes by, without someone reporting the discovery of some new source of atmospheric CO2 or methane. Whether it is desert soils or whatever there just are so many diverse ways CO2 moves around in the environment. And of course one of those ways is our burning of fossil fuels; what about all the forests we burn too or that burn themselves; do they not also have a plant (fossil fuel) signature too ?

    In any case; I’m simply not convinced that anybody has done anything like a credible accounting of all the carbon in the environment and the physics/chemistry of every exchange mechanism (with the atmosphere).

    So yes I am not naive enough to believe that man’s burning of fossil fuels and forests is not adding some carbon to the atmosphere; but I haven’t seen any solid accounting, that would convince me that all of the increase is fossil fuel related; or forest burning related; I simply don’t believe we know.

    But I do not believe that Ferdinand’s exposition here (which I think is very good and worthwhile) estabishes anything more than the obvious fact that fossil or other biological carbon is being released in the atmosphere as a result of human activites; and that isotopic signatures indicate that; but we already know we are doing that anyway. Most people from Africa have black skin; so what we already know that; we don’t have to do any DNA tests to demonstrate the obvious. same with atmospheric fossil CO2.

    Africans do well pretty much anywhere they go in the world. Fossil CO2 works pretty much the same as any other CO2 in the atmosphere. Get used to it; there will be a lot bigger fraction of fossil CO2 in the atmospehre as we keep on burning it; and that will happen whether the total CO2 goes up or down or sideways; and if we start burning some of that Argon rich fossil fuel, then the Atmopsheric Argon will go up too.

    Remember you read it first here on WUWT.

  164. John Marshall says:
    September 17, 2010 at 1:44 am
    Our input of CO2 from burning fossil fuels is 3% of the total annual input. the rest is from natural sources. ( these figures are from the US Dept of Energy who I assume have done their homework). So there is no way that all the current increase are our fault.

    Except of course that those natural sources are accompanied by natural sinks that absorb 101.5% of those sources.

    [REPLY - Yes, almost half of human CO2 output currently accumulates in the atmospheric sink. The result is c. 0.4% annual increase in CO2 in the atmosphere. ~ Evan]

  165. Steven mosher says:
    September 16, 2010 at 10:40 pm [ ... ]

    Speaking for myself, I have never claimed that GHGs [by which everyone really means CO2, because taxing methane would be much more difficult], cool the planet. That appears to be somewhat of a red herring argument.

    The important questions are: Is the effect of elevated CO2 overcome by other feedbacks? Is the warming effect of CO2 at all significant, or even empirically measurable? Or, is it so small [a sensitivity of <1°C] that it can be completely disregarded as inconsequential?

    In other words, will more CO2 cause runaway global warming and climate catastrophe? Or is the effect of human-emitted CO2 so tiny that it is unmeasurable? The latter is, after all, the current state of the science. Since the actual temperature effect of human-emitted CO2 is unmeasurable, then everything claimed about rising CO2 is speculation.

    The answer to those questions should determine our response. Too many people, however, assume the effect will be catastrophic — against all empirical evidence to the contrary. They stop at their conjecture, without following the scientific method through to its conclusion.

    As I’ve shown in dozens of charts posted, the putative effect of CO2 is indistinguishable from natural climate variability. The rise in temperature over the past century or so is coincidental with the rise in CO2. There is a better correlation with solar irradiance [or with U.S. postal rates, for that matter]. There is no cause-and-effect shown between rising CO2 and rising temperature; the correlation is always the reverse: rising temperature causes rising CO2 levels.

    If CO2 was in fact a strong driver of temperature, the planet would have warmed much more than it has [only a fraction of a degree, after an almost 40% increase in CO2. And a large part of that warming had nothing whatever to do with atmospheric CO2 concentration].

    The real world evidence points to the fact that any effect from CO2 is minuscule at best, and that the rise in CO2 is the result of warmer temperatures, not vice-versa. The current warming — even in the extraordinarily unlikely event that it was due 100% to CO2 and nothing else — is insignificant, and is well within past temperature parameters.

    The only verified real world effect of more CO2 is increased agricultural productivity. Those who try and make the case that CO2 is a problem have not been able to falsify the null hypothesis as stated by Dr Spencer:

    No one has falsified the hypothesis that the observed temperature changes are a consequence of natural variability.

  166. ” Pamela Gray says: September 16, 2010 at 8:49 pm
    From wikipedia so take with a grain of salt.

    [snip] The Wikipedia stuff is close enough to accurate. I spent more than a decade designing breathing apparatus for divers, submarines, and spacecraft.

    “You are trying to tell me that this additional and immediate source of CO2 cannot contribute ANYTHING to the measured increasing CO2 at our monitoring stations?”

    No. I am saying that in the span of 100s of years, the human population, as animal matter, has negligible effect. The total mass of plant material in the biosphere is far greater than animal mass. If a tree dies, it usually falls over, and bacteria and insect animals consume the cellulose and sugars made from CO2 and H2O by photosynthesis. The animals respire and return the CO2 and H2O to the atmosphere. On a scale of 100 million years, (call it the Devonian-Permian period) some of the plants died, got covered by dirt (I am greatly simplifying here) and became coal. Total CO2 in the atmosphere was therefore reduced as the coal mass was taken from the atmosphere by the now-dead plants. CO2 dropped from 3000 ppm to 400 ppm during that time. Now mankind is digging up some of the coal and increasing CO2, which was sequestered by the dead plants.

    “Plants take it up immediately? Even in the winter? I still don’t get it. And to reiterate, I’m not talking about any other measurement than the daily, weekly, monthly, and yearly amount of CO2 being measured in the atmosphere. ”

    At that scale, I think it most analogous to see it as a few animals (humans if you will) eating a tiny fraction of the world’s plant mass (trees are heavy) and turning that mass into CO2 and H2O a few years earlier than the bacteria that would have later eaten the plant material and done the CO2 generation. Human respiration is just traded at the expense of insects doing the same thing to the same plants.

    “I’m not talking about a model that says this is a closed, balanced system between eating veggies and exhaling.”

    In which case I haven’t a clue what you ARE talking about.

    Mod: feel free to give Pamela my email address so we can take this offline.
    Dan

  167. Sorry all for the late reply,

    I was away for a trip to Brittany, just back now. My article was published a little early, so it will take some time to answer the most relevant questions.

    About humans using wood, peat and other natural products from photosynthesis for steam and steel production and other industrial uses in the early days of the (pre) industrial period, and organics from plants and animals for cooking, food and breathing the CO2 out again: these show practically the same isotopic “fingerprint” as fossil fuels. The difference is that all the CO2 was incorporated in the organics not too long ago, some months (for food) to a few hundred years ago (for peat and wood), including the incorporation of preferentially 12C in the organics, leaving more 13CO2 in the atmosphere. When used for food or production, the same amount is ultimately returning to the atmosphere, giving back approximately the same isotopic composition as before. Thus using recent organics doesn’t change the total amount of CO2 in the atmosphere, neither the isotopic composition of carbon in the atmosphere.

    Of course, this is not absolute, as some increasing amount of (12C depleted) carbon derivatives are stored in food/feed and body fat of animals and humans. I haven’t calculated these amounts, but I don’t think these are such enormous quantities, compared to the quantities of fossil fuel used for power and heating.

    Even if it were enormous quantities, that is not relevant, as the oxygen use shows that there is more plant growth than that there is plant organics destruction: the latter includes all oxygen use from plant decay via soil microbes, methane seeping away from melting permafrost or sea bottom hydrates, burning coal heaps, huge forest fires, etc…

    Except for methane (will be for next message), there is little difference between the isotopic composition of recent or fossil organics, but even if there was: the fact that there is more CO2 built in in recent organics than is produced by all other known (and unknown) natural processes together, only increases the 13C/12C ratio, while we measure a decrease. Thus with other words, recent vegetation is a net sink for CO2, not a source.

  168. Good article Ferdinand.

    My how they scream, if you told most rational people that atmospheric CO2 has been steadily rising since about the time of the industrial revolution, there had been no known major non anthropogenic impacting the CO2 cycle, and that the rate of that rise was at about half the rate you’d expect given the amount of CO2 released through the burning of fossil fuels, rational people would instinctively use Occam’s razor and conclude that the most likely explanation for the rise was that about half of the fossil fuel released CO2 was being removed by the oceans and biosphere.

    It’s the ideological need of your detractors on this thread for there to be another explanation that drives them, it’s that desperate need for an alternative, any alternative, that turns them from being skeptics into something else.

  169. Dave Springer says:
    September 17, 2010 at 6:17 am
    “I disproved his hypothesis by showing that methane can produce the same signature.”

    You are correct, methane, in the form of natural gas, is indeed a fossil fuel.

  170. @Engelbeen

    “The difference is that all the CO2 was incorporated in the organics not too long ago, some months (for food) to a few hundred years ago (for peat and wood), including the incorporation of preferentially 12C in the organics, leaving more 13CO2 in the atmosphere.

    o Plants incorporate exactly the same isotope ratio that is produced when they burn so I don’t understand why you claimed it leaves more C13 in the atmosphere.

    o I would have mentioned biomass combustion like slash & burn agriculture, wood for paper, construction, and heating but thought it was a quibble. But since you go there I’ll point out that we’re looking at what man did in the past 150 years and he certainly cleared a lot of old growth forest without replacing it. For much of it there hasn’t been enough time to replace it even if he replanted a tree for every one he took out. It’s probably only a few percent of the isotope signature but it could be more. On the other hand it’s still an anthropogenic contribution of CO2 so I decided to let it slide unless and until it became an issue.

    Even if it were enormous quantities, that is not relevant, as the oxygen use shows that there is more plant growth than that there is plant organics destruction: the latter includes all oxygen use from plant decay via soil microbes, methane seeping away from melting permafrost or sea bottom hydrates, burning coal heaps, huge forest fires, etc…

    Atmospheric oxygen provides no clues. The oxygen cycle from all processes is too small a fraction to measure accurately. 99.5% of the reservior is in the lithosphere, it took photosynthesis billions of years to build up the 0.5% in the atmosphere, and the portion in the biosphere is the rounding error (0.01%) in the two reservoirs. Any signal is buried so deep in the noise you’ll never pull it out even if you had reliable data going back to the beginning of the industrial revolution. In fact you have questionable data going back 10 years.

    Moreover, where you reference Battle:

    “The combination of O2 and d13C measurements allowed Battle e.a. to calculate how much CO2 was absorbed by vegetation and how much by the oceans (see the references above).”

    Methane degradatino to CO2 screws this all up. I clearly showed that 20% of the CO2 increase in the atmosphere since the beginning of the industrial revolution comes by way of accumulated natural methane degradation. Moreover, natural gas (fossil methane) is a signicant fraction of our fossil fuel consumption and has been used for a very long time to say nothing of how much was discarded as a nuisance when it came up out of all the holes we poked in the ground looking for oil. Due to methane being twice as light in heavy carbon isotopes as other fuels, and it consumes oxygen when burned or let to naturally degrade (10 years resident in the atmosphere before it oxydizes). Thereby it effects the oxygen cycle just as much as it effects the isotope signature which is demonstrably a large fraction that might be anywhere from 20% of the signature to over 50%.

  171. Dave Springer says:
    September 16, 2010 at 4:17 pm

    Methane forcing is about 20% of all GHG forcings. It has increased from about 700 to 1800 parts per billion in the last century or 4 times faster than CO2. Interestingly it decays into CO2 after ten years. So that means it has added CO2 to the atmosphere over the past century about 18000 parts per billion or 18 parts per million. This then accounts for over 20% of the increase in CO2 since pre-industrial times (87ppm).

    Assuming the initial CH4 levels were stable ie. there was a natural and balanced methane cycle, I think you need to work on the net increase of atmospheric methane, 1100 ppb. You also need to calculate the CO2 contribution from the increased CH4 from the average value of the increased CH4 over the period, not the latest value, ie 550 ppb. so, with the CH4 resident time of 10 years, we get a 5500 ppb or 5.5 ppm increase in CO2 . But then we need to take into account that we’ve lost half the CH4 derived CO2 to sinks, so the atmospheric CO2 increase from atmospheric CH4 comes to about 2.75 ppm.

  172. “The decrease of d13C in the atmosphere cannot be caused by some extra outgassing from the oceans, as that would INcrease the d13C ratios of the atmosphere (even including the fractionation at the ocean-air border), while we see a DEcrease both in the oceans and the atmosphere. This effectively excludes the oceans as the main cause of the increase.”

    There are a number of reasons why this statement is not true.

    1) The atmospheric isotopic CO2 lags deeper ocean surface water carbon isotopes (also shown in figure 4) Indicating that the atmosphere is responding to a isotopic ocean change that occurred before.

    2) The ratio of isotopic carbon can not change the same from the atmosphere to the ocean. The same concentrations that change the ratio in the atmosphere must be much larger for the same ocean change because of the different states of matter.

    3) Volcanoes contribute to the change in isotopic carbon ratio and although may not have that large an effect in the atmosphere directly, likely have a much bigger influence under the ocean. (partly due to 4)

    4) Plate tectonics and ocean circulation have a large influence on the movement of carbon from the bottom of the ocean to the surface. These events are seismic cyclic waves over long periods so the carbon ratio can change over many years. (depending where the activity is can cause stable periods too)

    5) Individual El Nino’s contribute towards the increase in atmopsheric CO2 by about 3-4 ppmv, so that means 3-4 ppmv (like human fossil fuels) also lost in sinks given a total of 7-8ppmv.

    6) The oceans have warmed nearly 1c in the past 50 years so at least 8-16 ppmv is outgassed. With number 5 this easily contributes to half of the CO2 emissions during this time.

    While more scientific evidence is needed these do show how this ratio can change and 1) + 2) provides at least some of this evidence.

  173. For anyone interested Battle’s modus operandi regarding the oxygen cycle can be viewed here:

    http://citeseerx.ist.psu.edu/viewdoc/download?doi=10.1.1.129.4517&rep=rep1&type=pdf

    GLOBAL BIOGEOCHEMICAL CYCLES, VOL. 20, GB1010, doi:10.1029/2005GB002534, 2006

    Atmospheric potential oxygen: New
    observations and their implications for some
    atmospheric and oceanic models

    snippage in quotes

    “The APO data set described above is unprecedented
    in its temporal and spatial coverage. Nonetheless, it remains
    sparse in both senses.”

    Sparse data. Check.

    “2.4. Rejected Data
    [27] Criteria for rejecting individual samples or replicate
    pairs/triplets are discussed by Keeling et al. [1998] and
    Bender et al. [2005]. In addition, we choose to omit four
    more subsets of the data from further consideration.”

    Cherry picking. Check.

    “3.1. Detrending and Creation of a Climatology
    [36] Determining the climatological gradient of APO
    using both the PU and SIO data sets presents two
    complications. First, APO exhibits a secular decrease,
    due to the net effects of oceanic and fossil fuel uptake
    and release of O2 and CO2. In order to reduce the 7-year
    time series into a single climatological year, we need to
    remove this trend. Second, the SIO and PU data sets of
    O2/N2 are each referenced to an arbitrary standard that is
    unique to the home laboratory [Keeling et al., 1998;
    Bender et al., 1996].”

    Adjust (pencil whip) the data. Check.

    “3.2. Annual Mean Values From Interpolation
    [38] As discussed above, the data set has limited spatial
    coverage and substantial temporal unevenness. One way to
    construct north-south gradients in the face of these limitations
    is to treat the coordinate grid as two-dimensional
    (sin(latitude) and time) and interpolate to regularly spaced
    values on this grid.”

    Fill in the gaps in coverage by using the closest measurement. Check.

    “3.3. Annual Mean Values From Seasonal Cycles
    [42] We also consider an alternative approach to constructing
    north-south gradients from sparse data. We divide
    the shipboard data into 8 groups: 30, 20, 10 N and S, 0–
    9N, and 0–9S. For each group we calculate a seasonal
    cycle with a constant offset. These offsets are the annual
    mean values for each interval.”

    Replace pesky unknown variables with constants. Check.

    “5. Modeling
    [48] In order to begin understanding the processes that
    lead to the patterns of APO that we observe, we have
    employed an updated version of the modeling approach of
    Gruber ’01.”

    Build a computer model and monkey around with it until generates some of the pencil whipped data set. Check.

    “[65] There are at least two possible causes for the datamodel
    discrepancy in the size of the bulge. First, the
    modeled transport in the atmosphere may be too vigorous,
    either poleward or vertically. If so, the calculated peak will
    be attenuated. Second, as discussed by Gruber ’01, the
    regions for which the air-sea O2 fluxes are determined are
    probably too coarse to allow the atmospheric transport
    model to capture the detailed structure of O2 in the immediate
    vicinity of the equator.”

    Wave hands around offering possible explanations for why the model output doesn’t match reality. Check.

    “[86] We look forward to continued improvement in data
    coverage and quality, both temporally and spatially. With
    longer records, we will have the opportunity to determine
    the factors that control interannual variations in the APO
    gradients we have characterized. Better spatial coverage,
    particularly beyond the Pacific basin, will improve our
    ability to test zonal transport and vertical mixing over
    continents in atmospheric transport models and make our
    test of air-sea flux fields far more stringent. Finally, reduction
    in site-to-site biases through improved and automated
    collection equipment will strengthen all of the analyses
    presented here.”

    Wrap up by asking for more funding. Checkarooni.

    Welcome to climate [post-normal] science – the biggest house of cards ever constructed.

  174. Andrew W says:
    September 17, 2010 at 2:26 pm

    “Assuming the initial CH4 levels were stable ie. there was a natural and balanced methane cycle, I think you need to work on the net increase of atmospheric methane, 1100 ppb. You also need to calculate the CO2 contribution from the increased CH4 from the average value of the increased CH4 over the period, not the latest value, ie 550 ppb. so, with the CH4 resident time of 10 years, we get a 5500 ppb or 5.5 ppm increase in CO2 . But then we need to take into account that we’ve lost half the CH4 derived CO2 to sinks, so the atmospheric CO2 increase from atmospheric CH4 comes to about 2.75 ppm.”

    Everything you said applies to CO2 emission from fossil fuels. The sinks don’t discriminate by source. If you reduce the demonstrable 18ppm contribution from methane degradation down to 3ppm then you also reduce the fossil fuel contribution from 70ppm to 12ppm (roughly). You can’t have your cake and eat it too.

  175. Several objected to the “elephant in the room” problem: the oxydation of natural methane to CO2 which has a much lower 13C/12C ratio than CO2 coming from oil or coal.

    But there is a problem with this elephant:
    More than half of the body parts of the elephant are human manifactured.

    Methane is easely measured in ice cores and follows the temperature proxy even better than CO2. The previous interglacial, the Eemian was some 2°C warmer than the current warm period, the Holocene. That also included that Nordic areas were much warmer than today, with forests reaching the Arctic Ocean.

    Anyway, all possible natural sources of methane were at work at higher temperatures than today. The maximum CH4 level during the warmest period was some 700 ppbv. Of course, the resolution was quite coarse: 600 years average. See:

    http://www.ferdinand-engelbeen.be/klimaat/eemian.html

    Today, we measure some 1600-1900 ppbv. As good as for the CO2 record, the CH4 record shows a typical “hockeystick”, be it starting a little earlier, around 1750 (or even before). Maybe caused by intensivation of agriculture and feedstock expansion. See:

    In this case, the resolution of the the DSS ice core record is some 21 years, and for the other two ice cores it is 8 years.

    The interesting point is that the pre-1750 period shows only 600-700 ppbv of methane, similar levels as in the Eemian, but with a much better resolution. The 1,000 years Law Dome DSS core CH4 measurements were recently expanded to 2,000 years ((MacFarling Meure et al. 2006), see:
    ftp://ftp.ncdc.noaa.gov/pub/data/paleo/icecore/antarctica/law/law2006.txt
    also available as Excel file:
    ftp://ftp.ncdc.noaa.gov/pub/data/paleo/icecore/antarctica/law/law2006.xls
    The same result: 600-700 ppbv methane…

    Thus it seems that the excess over 600-700 ppbv is all human made, mostly in the most recent period. Any influence on d13C levels, beyond the variablility of the natural influx of methane (+/- 40 ppbv around the average CH4 level in the past) is thus also human-made.

  176. It’s the ideological need of your detractors on this thread for there to be another explanation that drives them, it’s that desperate need for an alternative, any alternative, that turns them from being skeptics into something else.

    In truth there are deniers. There are also skeptics. And the difficult thing is that it is hard to draw a line and separate the two. It is wrong for the AGW crowd to label and dismiss skeptics as deniers. But it is equally wrong to pretend that those who really are deniers are skeptics.

    Before anyone in the AGW camp gets too carried away with this comment, let me say they have a similar problem over there with climate zealots. There are scientists over in that camp applying rational processes and keeping truly open minds. But there are also far too many zealots whose minds are closed and who are simply looking for evidence to support a predetermined conclusion. And it is again hard to draw a line between the two.

  177. Dave Springer says:
    September 16, 2010 at 4:17 pm

    Methane forcing is about 20% of all GHG forcings. It has increased from about 700 to 1800 parts per billion in the last century or 4 times faster than CO2. Interestingly it decays into CO2 after ten years. So that means it has added CO2 to the atmosphere over the past century about 18000 parts per billion or 18 parts per million. This then accounts for over 20% of the increase in CO2 since pre-industrial times (87ppm).

    There is some error in reasoning here: input is not accumulation! In the same 100 years, the total input of CO2 from fossil fuel burning was some 150 ppmv, that didn’t give more than the same 87 ppmv increase of CO2 in the atmosphere… That is not including land use changes, which indeed also add (an uncertain) amount of CO2 to the atmosphere.

    Further, one need to make a differentiation between the natural CH4 supply and the human-made excess in CH4.
    In pre-industrial times there was some kind of equilibrium between methane production, the CO2 cycle and the isotopic levels, all three influenced by temperature as main driver of the changes. When the temperature was maintained over a longer period (either glacial or interglacial), CO2 levels, methane levels and isotope ratio’s all show more or less stable figures, with only small excursions around those levels. That means that the constant supply of methane and its degradation to CO2 and the influence of the isotopic changes because of methane degradation was compensated somewhere in the whole carbon cycle. And that the supply of methane to maintain the 600-700 ppbv methane level in the atmosphere had no influence on either total CO2 level or isotopic level.

    In current times, all three variables show changes far beyond what temperature influences showed in the past. Will see what I can make of it tomorrow for the 13C/12C ratio’s, it’s getting late here…

    Your idea to tackle methane first was proposed by James Hansen not so long ago, indeed as that is easier to do than for CO2. One of the reasons that methane increase is leveling off may be that rice cultivating is more and more using “dry” methods, where less water is used for shorter periods…

  178. @andrew

    I didn’t calculate the methane contribution by current level. I added the pre-industrial level (700ppb) to the modern level (1900ppb) and divided by two to get a rough average of annual emission during the past century. I was conserative if anything because the 700ppb figure is from 1850 not 1900 as was presumably considerably higher than 700ppb 50 years after the start of the industrial revolution.

    But now that you mention it here’s an interesting tidbit for you to consider that I was heretofore unaware of (from wikipedia):

    Atmospheric methane
    Methane concentrations graph.
    Main article: Methane

    Early in the Earth’s history—about 3.5 billion years ago—there was 1,000 times as much methane in the atmosphere as there is now. The earliest methane was released into the atmosphere by volcanic activity. During this time, Earth’s earliest life appeared. These first, ancient bacteria added to the methane concentration by converting hydrogen and carbon dioxide into methane and water. Oxygen did not become a major part of the atmosphere until photosynthetic organisms evolved later in Earth’s history. With no oxygen, methane stayed in the atmosphere longer and at higher concentrations than it does today.

    The most powerful (mole for mole) greenhouse gas, 50 times as potent as CO2, was once 1000 times greater concentration in the atmosphere, which according to CAGW gospel should make the earth’s surface hot enough to melt lead, yet the temperature remained conducive to life and in fact was substantially similar to global average temperature today. WATT is up with that? I mean I knew life goes on, flourishes actually, with CO2 concentration 20 times greater in the past but I didn’t know that methane had been 1000 times greater.

    I consider evidence from the geologic column that the earth’s surface temperature has never exceeded about 6C-8C warmer than today when CO2 and methane concentrations were 20 times and 1000 times higher than today something that must be explained.

    The only constant in this equation is a liquid ocean with an atmospheric pressure which sets its surface boiling point at 100C. The only reasonable explanation for CO2 and methane not mattering much (if any) in the past is that they really don’t matter much because there’s a thermostat associated with the water cycle. As forcings go up (no matter the source forcings are forcings) it increases the speed of the water cycle and as forcings go down it decreases the speed of the water cycle. A faster water cycle means a faster evaporation/condensation cycle. This cycle is a heat pump which can move vast amounts of energy in latent heat from surface to thousands of feet higher and when it condenses it forms a cloud during the day (which is when clouds usually form) it also radically reduces surface forcing underneath it by reflecting most of the sunshine right back out into space before it reaches the surface.

    I remain open to better explanations that fit the indisputable evidence from the geologic column.

    most reasonable explanation I know is appears that the water cycle serves as a variable negative feedback. When surface temp rises or falls by changes in forcings the water cycle speeds up and slows down respectively. If the feedback is negative (which it could be through cloud cover albedo forcings and evaporation/ condensation heat pump working faster) and then no other greenhouse gases matter any at all except perhaps to keep the planet from becoming a big snowball which they appear to do with only limited success lately. Forcings are forcings no matter the source.

  179. @Engelbeen

    “Several objected to the “elephant in the room” problem: the oxydation of natural methane to CO2 which has a much lower 13C/12C ratio than CO2 coming from oil or coal.”

    “But there is a problem with this elephant:
    More than half of the body parts of the elephant are human manifactured.”

    I never claimed that the methane rise of 150% since 1850 was not anthropogenic in part or in whole. In fact I noted the correlation between the methane rise and the beginning of the industrial revolution and noted some known sources like blow-off from oil wells that’s neither burned nor captured and used as natural gas and of course an estimated 16% is from the modern cattle industry which kicked into high gear concommitant with the beginning of the industrial revolution.

    I also noted that it appeared that if one’s interest was truly in limiting the greenhouse effect then methane is by far the first GHG you want to target. At least with coal, oil, and natural gas we get substantial value out of its combustion. We aren’t gettting jack diddly squat in comparison from methane emissions.

    This is simply illustrative of the fact that AGW has a designated bogeyman – fossil fuel combustion – and the designation is a political/ideological decision. In any sane scientific or engineering analysis limiting methane emission is where to get the most return for the least disruption. The fact of the matter is that disruption of the status quo (plus never ending funding for more research) is exactly what motivates the whole AGW charade. You can’t modify and control civilization by controlling methane emissions but you can with CO2 – it’s the designated scapegoat.

  180. @Engelbeen

    “There is some error in reasoning here: input is not accumulation!”

    In this case it is. Methane is generated at the surface but it decomposes into CO2 in the stratosphere. How do those particular CO2 molecules deposited directly into the stratosphere make it back down to the surface to be sucked up by a CO2 sink? Conversely CO2 generated by fossil fuels are generated primarily on the surface in close proximity to CO2 sinks.

  181. @Engelbeen

    Ah, I knew I read it somewhere:

    http://geosci.uchicago.edu/~archer/reprints/archer.2008.tail_implications.pdf

    “The rate of natural CO2 uptake in any given year is not determined by the CO2 emissions in that particular year, but rather by the excess of CO2 in the atmosphere that has accumulated over the past century.”

    I’m not sure I agree with that but it disputes your position that accumulation doesn’t count. What I am sure of is that CO2 in the stratosphere has a rather long lifetime due to very limited mixing with the troposphere and the bottom of the troposphere is where all the CO2 sinks exist. CO2 from fossil fuel combustion is almost literally done right on top of carbon sinks (like the nearest green thing or body of water) but CO2 from methane degradation in the stratosphere takes at least decades to reach a carbon sink.

  182. In this case it is. Methane is generated at the surface but it decomposes into CO2 in the stratosphere. How do those particular CO2 molecules deposited directly into the stratosphere make it back down to the surface to be sucked up by a CO2 sink?

    Obviously it never does, it just stays up there forever and ever, after all, it took, oh, a whole ten years or so for the CH4 to get to the stratosphere in the first place.

  183. My understanding is that proposals for one of the major changes in atmospheric carbon dioxide highlight Mother Nature’s invention of the tree maybe 380 million years ago. Trees are capable of turning over all sorts of soils and breaking rock with their roots. The thought is that the rate of soil and rock weathering, the sequestering of carbon dioxide into carbonates by interaction of atmospheric carbon dioxide with water and soil, increased five-fold due to the increased reaction area created by the turning action of tree roots, eventually dropping the world into a major ice age. ( A seemingly humorous extension of the model is that temperatures went back up when insects came along to eat the trees!) This sequestration process has been in operation since the world began and it is estimated that the amount of carbonates sequestered by this process as well as life processes is now thought to be close to 100 million gigatons, swamping the ocean sink by a factor of 2500:1. Carbonate sequested for millions or billions of years would have no carbon 14 whatsoever. My short investigation ( I am no expert) indicates that much less than a gigaton of carbon dioxide is thought to be released each year by dissolution of this carbonate, especially through volcanic action. Does this low projected value make sense? It seems to me that 1gt noise on 100,000,000gt is a mighty small number.

  184. Dave Springer says:
    September 17, 2010 at 6:56 pm

    “There is some error in reasoning here: input is not accumulation!”

    In this case it is. Methane is generated at the surface but it decomposes into CO2 in the stratosphere. How do those particular CO2 molecules deposited directly into the stratosphere make it back down to the surface to be sucked up by a CO2 sink? Conversely CO2 generated by fossil fuels are generated primarily on the surface in close proximity to CO2 sinks.

    I don’t see the problem: while CO2 from methane is mainly formed at the troposphere-stratosphere border from oxydation by hydroxyl radicals and ozone (both formed by UV radiation), there still is an exchange of air between the stratosphere and troposphere: up in the tropics and down near the poles, including stirring up wherever there are tropical storms. See (already from 1995):

    http://www.ems.psu.edu/~brune/m465/strattropdynholton.pdf

    That there is atmospheric mixing between the two layers is also visible in the opposite way: ground level based seasonal exchanges can be measured even in the lower stratosphere with some year delay:

    Lower stratosphere CO2 levels measured during regular (commercial) flights Scandinavia – Boston.

    And stratospheric CO2 levels simply follow the near ground CO2 level increase, again with a delay.

    About the influence of the extra methane induced CO2 on isotopic changes:

    If we may use the 10 years half life of the extra human induced methane CO2, that means that of the current 11oo ppbv extra CH4, some 0.11 ppmv CO2 is formed per year at -40 per mil d13C. Humans currently emit 4 ppmv CO2 per year at -24 per mil average. Thus the release of human CH4 is currently responsible for 2.7% of the CO2 increase per year, but some 5% of the d13C decrease. This ratio was somewhat higher in the early days of the (pre)industrial revolution, but both increased near in parallel.

    As the oxygen derived sink rates still have large margins of error (+/- 50% for biogenic uptake and +/- 30% for ocean uptake), the influence of human methane releases is largely within the error margins.

    Anyway, as the increase of methane levels is quite surely human induced (as good as land use changes), I don’t see a problem for the original point, that oxygen levels and changes in isotopic levels exclude the oceans ánd vegetation as main sources for the increase of CO2 in the atmosphere.

    Dave Springer says:
    September 17, 2010 at 8:49 pm

    I’m not sure I agree with that but it disputes your position that accumulation doesn’t count.

    I never said or implied that accumulation doesn’t count, to the contrary. Indeed accumulation is all what counts. The accumulated emissions and the accumulation in the atmosphere show a near perfect match over the past 100+ years:

    As there is not much difference in CO2 levels between the different atmospheric layers, the exchange of CO2 from different sources between the air layers is much faster than you expect, from months to a few years (about one year for the lower stratosphere to 5 years for the mid-stratosphere). See:

    http://onlinelibrary.wiley.com/doi/10.1111/j.2153-3490.1973.tb00615.x/pdf

    and

    http://www.nature.com/nature/journal/v316/n6030/abs/316708a0.html

  185. matthu says:
    September 16, 2010 at 4:17 am

    I am just wondering whether there is any possibility of greater absorption of d12C in the oceans which might affect the balance? (This is not my area of expertise – so I am simply expressing curiosity here.)

    Indeed there is a two-way fractionation of carbon isotopes between water and air at the water-air border. In both cases, the lighter isotope migrates faster than the heavier ones. The fractionation gives a depletion of -10 per mil for the ocean-air transfer and -2 per mil for the air-ocean transfer. Thus a complete cycle decreases the isotopic level of the atmosphere with about -8 per mil compared to the oceans. See:

    http://dge.stanford.edu/SCOPE/SCOPE_16/SCOPE_16_1.5.05_Siegenthaler_249-257.pdf

    For deep ocean upwelling (0 to +1 per mil) that means some -8 to -7 per mil in the atmosphere, while biolife in the upper oceans increase the d13C value to +1 to +5 per mil, thus upper ocean-air exchanges over the seasons give -7 to -3 per mil d13C levels in the atmosphere.

    That made that the pre-industrial atmosphere in average was at about -6.4 per mil. As we are currently at -8 per mil, any extra upwelling of the deep oceans or increase in temperature of the ocean surface would increase the per mil of the atmosphere…

  186. FYI all

    Detailed breakdown of anthropogenic methane emissions by source and country plus 20 year forward projections:

    http://www.epa.gov/methane/excel/methane_baselines.xls

    Abatement technologies, costs, and other characteristics by source and country:

    http://www.epa.gov/methane/excel/techtbls.xls

    Too bad the biggest producers of methane are countries that aren’t going to sign up for abatement. The US is already doing a lot of methane abatement unilaterally and voluntarily.

    As an experiment a global cap & trade on methane emissions makes some sense because it might be possible to measure the result in global temperature anomaly. CO2 has such a long residence time in the atmosphere if we were to curtail emissions in any reasonable quantity it would be 100 years (if at all) before we could tell if it helped or not whereas with methane abatement we might be able see a result in 20 years or less.

    In any case if the serious desire is to actually reduce greenhouse gas effect rather than a serious desire to control the world through controlling energy production and consumption then the only thing that makes sense is methane abatement as that is easily the most cost effective and quick way to reduce it.

    The problem appears to be that the ideological interests in controlling energy production and use vastly outweigh the genuine interest in mitigating global warming so CO2 remains the focal point where the CAGW cabal applies the pressure.

    What a revolting situation. Money and power, as usual, are the determining factors while the objective science and engineering which should be the determining factors are left by the wayside.

  187. HelmutU says:
    September 16, 2010 at 6:58 am

    According to the IPCC 21 % (minimum) is manmade. With a preindustrial value of – 7 per mill, value of -26 per mill for fossil fuel, the decrease should be about – 11 per mill and not values araound – 8 per mill. Therefore this signature can’t be anthropogenic.

    You forget that every year some 20% of all CO2 in the atmosphere is exchanged with CO2 from other reservoirs. The exchange with vegetation doesn’t make much difference for the isotope changes, as much of what returns from vegetation decay has the same composition as what was incorporated in the previous season. Only the difference between uptake and release of CO2 from vegetation (currently more uptake than release) adds to the increase of 13C over 12C. The ocean surface doesn’t make much difference too, as there is only a very limited increase of CO2 in the upper oceans, which also increases the d13C level in the atmosphere.

    The main source which may dilute the d13C decrease from fossil fuel burning are the deep oceans, as the upwelling around the equator brings fresh CO2 from the deep (at 0 to -1 per mil d13C) to the surface, while at the other end, the sinks at the poles simply use the available CO2 from the atmosphere. In both cases with some discrimination of the isotopes.

    It is possible to have an impression of the amounts of CO2 circulating from the deep oceans which can cause the observed decrease of d13C:

    As the only sure source of the d13C decrease is fossil fuel burning, the difference between what is the theoretical full decrease and what is observed may be either from exchanges (without any or much change in total mass) or by addition of extra (13C rich) CO2 or a mix of both. The latter two possibilities are prohibited by the mass balance:
    The addition of 8 GtC/year CO2 from fossil fuel use, if diluted to obtain the observed d13C range, would need 40 GtC additional CO2 from the (deep) oceans, thus an increase of in total 48 GtC (or anyway some in addition to the 8 GtC), while the real increase is 4 GtC…

  188. @Engelbeen

    You are quite wrong about how quickly troposphere and stratosphere mix. Experimental results show the mean lifetime of stratospheric methane to be between (roughly) 70 and 110 years.

    From the Journal of Geophysical Research (Atmospheres)

    [my emphasis]

    http://europa.agu.org/?view=article&uri=/journals/jd/97JD02215.xml

    Evaluation of source gas lifetimes from stratospheric observations

    C. M. Volk, J. W. Elkins, D. W. Fahey, G. S. Dutton, J. M. Gilligan,
    M. Loewenstein, J. R. Podolske, K. R. Chan, M. R. Gunson,

    Simultaneous in situ measurements of the long‐lived trace species N2O, CH4, 12, CFC‐113, CFC‐11, CCl4, CH3CCl3, H‐1211, and SF6 were made in the lower stratosphere and upper troposphere on board the NASA ER‐2 high‐altitude aircraft during the 1994 campaign Airborne Southern Hemisphere Ozone Experiment/ Measurements for Assessing the Effects of Stratospheric Aircraft. The observed extratropical tracer abundances exhibit compact mutual correlations that show little interhemispheric difference or seasonal variability except at higher altitudes in southern hemisphere spring. The environmental impact of the measured source gases depends, among other factors, on the rate at which they release ozone‐depleting chemicals in the stratosphere, that is, on their stratospheric lifetimes. We calculate the mean age of the air from the SF6 measurements and show how stratospheric lifetimes of the other species may be derived semiempirically from their observed gradients with respect to mean age at the extratropical tropopause. We also derive independent stratospheric lifetimes using the CFC‐11 lifetime and the slopes of the tracer’s correlations with CFC‐11. In both cases, we correct for the influence of tropospheric growth on stratospheric tracer gradients using the observed mean age of the air, time series of observed tropospheric abundances, and model‐derived estimates of the width of the stratospheric age spectrum. Lifetime results from the two methods are consistent with each other. Our best estimates for stratospheric lifetimes are 122 ± 24 years for N2O, 93 ± 18 years for CH4, 87 ± 17 years for CFC‐12, 100 ± 32 years for CFC‐113, 32 ± 6 years for CCl4, 34 ± 7 years for CH3CCl3, and 24 ± 6 years for H‐1211. Most of these estimates are significantly smaller than currently recommended lifetimes, which are based largely on photochemical model calculations. Because the derived stratospheric lifetimes are identical to atmospheric lifetimes for most of the species considered, the shorter lifetimes would imply a faster recovery of the ozone layer following the phaseout of industrial halocarbons than currently predicted.

  189. quote from the original article:

    What we can see, is that the d13C levels as well as in the atmosphere as in the upper oceans start to decrease from 1850 on, that is at the start of the industrial revolution.

    unquote
    This relates to the (combined) graphs showing delta 13C falling, Shallow Bank, Jamaica etc.

    Ferdinand (and Mosher) seems too engaged elsewhere to address my question above: eyeball the graphs, when does the delta 13C begin to fall. Is it in 1850? Is that what the graphs say? Maybe that nice Tamino could use one of his complicated ways of working out flex points and settle the matter.

    Does anyone want to defend the statement that the delta13C begins to fall in 1850 at the start of the Industrial Revolution? Or do people agree with me that the graphs show delta13C falling well before that date? Which makes me wonder what Ferdinand thinks caused the fall before anthropogenic CO2 production really took off.

    Ferdinand?
    Mosher?
    Anyone?

    JF

  190. Larry says:
    September 16, 2010 at 7:45 am

    Isn’t this trying to prove that the majority of increased co2 is from man, not that man is the cause of the increase? Clearly if man is producing 4molecules per 1000 and the atmospere is increasing by 2 per 1000 there is something else going on there.

    [snip]

    That is not to say the concentration has not been increased by man, but in effect you would have to prove first that concentrations of co2 in the atmosphere would be different if man had not burnt the fuels. As soon as you are involved with feedbacks – which clearly you are because the concentration increase does not increase the amount produced by man – showing the cause of the co2 in the atmosphere does not prove that if man had not burnt the fuel the concentration would have been less.

    Put in simpler terms, if we had not burnt the carbon more co2 may have been gassed from the oceans to compensate, because the current temperature requires more co2 in the atmosphere.

    The ice cores show convincingly that the “natural” equilibrium was influenced by temperature changes at about 8 ppmv/°C during the past 800,000 years. That makes that the equilibrium CO2 level at current temperatures was around 290 ppmv. We are currently at 390 ppmv and we see that nature absorbes 2 ppmv CO2/year at current CO2 levels. That proves that we are currently above the natural equilibrium of the CO2 cycle.

    Indeed the higher level of CO2 suppresses the oceanic outgassing near the equator and increases the uptake of CO2 near the poles (and by vegetation), near perfectly in ratio to the total increase. That doesn’t prove that without human emissions there wouldn’t be any increase of CO2 in the atmosphere, but according to 800,000 years of history, that is not very likely.

  191. Dave Springer says:
    September 18, 2010 at 6:13 am
    @Engelbeen

    You are quite wrong about how quickly troposphere and stratosphere mix. Experimental results show the mean lifetime of stratospheric methane to be between (roughly) 70 and 110 years.

    Must be different for different layers in the stratosphere, as ozone normally destroys CH4. And ozone is quite rapidely distributed between the equator and the poles. But I did find some more comment on CH4 from the IPCC TAR at:

    http://www.ipcc.ch/ipccreports/tar/wg1/134.htm

    Where it is said that less than 10% of the CH4 reaches the stratosphere and indeed has a half life time there of over 100 years. But over 90% has a half life time of less than 10 years in the troposphere.

    Anyway, the long lifetime of CH4 in the stratosphere has little relevancy for the isotope ratio’s or total CO2 mass, but may have more relevancy for GHG effect, as its oxydation increases the water level in an atmospheric layer which is normally very dry, see:

    http://mls.jpl.nasa.gov/joe/Randel_1998.pdf

    http://www.ipcc.ch/ipccreports/tar/wg1/134.htm

  192. Julian Flood says:

    Yes, you are indeed correct that delta 13c starts to decline well before 1850 on figure 4. In fact the decline starts around 1600 and part of this explanation Iv’e touched on my last post on 17th, at 2.33pm. Clearly this explanation on the orginal post about delta 13c is dubious at best and likely a natural occurance with no evidence against it shown on here. The change of ppmv in the atmosphere where the significant delta 13c changed was very likely too small to have this much effect. Scientific evidence shows the ocean changed first and the atmosphere responded.

  193. Gail Combs says:
    September 16, 2010 at 1:41 pm

    wsbriggs says:
    September 16, 2010 at 5:28 am

    My understanding, small though it may be, is that this paper is substantially challenged by Chiefio’s musings on the subject (sorry, I can’t find my pointer to the article). There, the discussion of the carbon isotope ratio covers also the behavior of plankton in the oceans, net, net, the ratio is not maintained.
    _________________________________________________________
    I have that pointer bookmarked
    The Trouble With C12 C13 Ratios:

    http://chiefio.wordpress.com/2009/02/25/the-trouble-with-c12-c13-ratios/

    That paper is quite interesting, and it would be relevant if vegetation was not taking more CO2 away than it gives back (as the oxygen balance shows). In that case it would be impossible to make a differentiation between fossil fuel burning and rotting or burning vegetation (except for 14C/12C ratio changes). In the current case, the uptake of CO2 by land vegetation exceeds the destruction of the same in any way (burning, decay by bacteria, feed and food). That makes that vegetation increases the 13C/12C ratio for the part which makes the difference between CO2 uptake and decay and therefore the difference in d13C discrimination between the different plant species is not very relevant. Whatever the discrimation ratio, plants don’t contribute to the increase in the atmosphere, neither to the d13C decrease, they show the opposite behaviour for the past about 20 years, thanks to the “greening earth”.

  194. Matt G says:
    September 17, 2010 at 2:33 pm

    1) The atmospheric isotopic CO2 lags deeper ocean surface water carbon isotopes (also shown in figure 4) Indicating that the atmosphere is responding to a isotopic ocean change that occurred before.

    The deep oceans show a d13C level of zero to +1 per mil. At upwelling places the extra nutritients induce abundant biolife near the surface, which increases the d13C level to +1 to +5 per mil. Any CO2 released from the oceans would increase the d13C levels of the atmosphere, while we see a decrease. The upper ocean d13C levels respond to the decrease in the atmosphere. So it is just the opposite of what you say.

    2) The ratio of isotopic carbon can not change the same from the atmosphere to the ocean. The same concentrations that change the ratio in the atmosphere must be much larger for the same ocean change because of the different states of matter.

    The upper level of the oceans needs far less CO2 than the atmosphere for changes: the atmosphere contains about 800 GtC as CO2, the upper part of the oceans (the “mixed layer”) contains about 1000 GtC. An increase of 30% CO2 in the atmosphere results in only 3% increase of CO2/bi/carbonate in the ocean surface at equilibrium, due to the change in pH which opposes the uptake.
    Deep ocean exchanges with the atmosphere are limited and result in about 1.5 GtC more uptake than release.

    3) Volcanoes contribute to the change in isotopic carbon ratio and although may not have that large an effect in the atmosphere directly, likely have a much bigger influence under the ocean. (partly due to 4)

    Again, please inform you about the isotopic composition of volcanic CO2 from eruptions and vents: most of the volcanic CO2 has a high (around zero) d13C level, compared to atmospheric CO2. Any such releases would increase the d13C level of the atmospheric carbon, while we see a decrease. Many volcanoes in a subduction zone release CO2 from decomposing calcite deposits at the sea bottom. These have a near zero d13C level.

    4) Plate tectonics and ocean circulation have a large influence on the movement of carbon from the bottom of the ocean to the surface. These events are seismic cyclic waves over long periods so the carbon ratio can change over many years. (depending where the activity is can cause stable periods too)

    Over geological relevant times, that is true. But for the past near million years, that doesn’t play any measurable role.

    5) Individual El Nino’s contribute towards the increase in atmospheric CO2 by about 3-4 ppmv, so that means 3-4 ppmv (like human fossil fuels) also lost in sinks given a total of 7-8ppmv.

    Individual La Niña periods contribute to a (relative) decrease in atmospheric CO2 increase rate by about the same amount: ENSO influences to both sides and only influences the variability around the trend, not the trend itself. The trend is clearly caused by the emissions, as all the other natural causes together form a sink which only absorbs halve of the quantity that the emissions give.

    6) The oceans have warmed nearly 1c in the past 50 years so at least 8-16 ppmv is outgassed. With number 5 this easily contributes to half of the CO2 emissions during this time.

    By far not: the total increase since the start of the industrial revolution is about 100 ppmv, while humans emitted near 200 ppmv.

    While more scientific evidence is needed these do show how this ratio can change and 1) + 2) provides at least some of this evidence.

    1) and 2) provide the evidence that the oceans can’t be the source of the increase…

  195. Matt G says:
    September 18, 2010 at 7:44 am
    & Julian Flood says:

    Yes, you are indeed correct that delta 13c starts to decline well before 1850 on figure 4.

    Well, may be right, but up to about 1850 you are looking at the natural variability of d13C levels (+/- 0.1 per mil), only beyond that date, the “fossil” signal becomes large enough to be seen beyond the natural “noise”.

    Methane levels even increased from 600 to 700 ppbv in the period of 6000 years ago to 1850 (after that sky rocketing to 1800 ppbv). Some see that as a proof that agriculture (rice) had already such an influence on methane levels…

  196. So We’re back to the majority of the Methane being destroyed in the troposphere within 10 years and the CO2 from its decomposition not, as Dave Springer thought, being suspended indefinitely in the stratosphere.

  197. tallbloke says:
    September 16, 2010 at 7:49 am

    Hi Ferdinand, thanks for a clearly written article which appears to use good logic as far as it goes. I have a couple of questions.

    1) You told us in an earlier installment that the ‘natural’ increase in co2 due to the earth being a degree warmer than it used to be would be around (IIRC) 20ppm (from oceanic de-gassing). But co2 has risen @110ppm from @280 to @390. If we are responsible for around half of that increase, 55ppm, and the expected natural increase due to oceanic de-gassing is 20ppm, what is responsible for the other @35ppm?

    Humans have added near 200 ppmv in the past 160 years, thus halve that would be 100 ppmv increase. Thus humans are responsible for (almost) all of the increase…

    2) If the answer to 1) is “we don’t know”, then how do we know that the mystery factor wouldn’t cause more than 35ppm extra if we weren’t pumping fossil fuel produced co2 into the atmosphere? i.e. if there is a non-linear process at work, how do we know it wouldn’t ‘take up the slack’ if we emitted less?

    We do know the cause(s) of the increase, but what will happen if we stop all emissions today is more controversial: some claim a 5 years half life time (but that is based on the refresh rate of 150/800 GtC per year, nothing to do with a decay rate), others about 40 years (seems more plausible) and the IPCC claims different half life times between slightly over a year and many hundreds of years. All three claim that there will be a drop if we stop all emissions today. The near 40 years half life time is based on the current CO2 levels and the current sink rate of about 45% of the emissions, which is quite constant over the past 100+ years, thanks to the slightly exponential increase rate of the emissions…

  198. Merrick says:
    September 16, 2010 at 8:47 am

    Even is CO2 concentrations were DECREASING the isotope ratio would be impacted by fossil fuels – and more strongly to boot. So, no, I’d argue this measurement alone doesn’t get one all the way to blaming fossil fuels for the increase in CO2 concentration.
    and
    Since we know that gas solubility in water varies with temperature and that plant growth rates vary with temperature, precipitation, and land usage, isn’t a single measurement of an isotope shift in the atmosphere a little bit light data to jump straight to fossil fuels?

    You are right, isotopic changes on their own don’t prove that fossil fuel burning is the cause of the recent increase of CO2 in the atmosphere. But the combination of factors do: the mass balance (covered in part 1), combined with the oxygen balance and the isotopic changes does the job:

    - the isotopic changes do exclude the oceans as main source of the increase.
    - the mass balance excludes the oceans as part of the increase.
    - the oxygen balance excludes vegetation as the source of the increase.
    - the burning of fossil fuels fits all observations, none are contradicted.
    - all alternative explanations must fit all observations, all of the alternative explanations I have heard of do contradict one or more observations.

  199. Doug Proctor says:
    September 16, 2010 at 9:04 am
    HelmutU says:
    September 16, 2010 at 6:58 am :

    That the IPCC minimum contribution of anthopogenic CO2 is 21%, and that the signature should, by this calculation, be -11%, but is actually -8%, up from -7% (my computer doesn’t appear to have a mill sign). It is this conclusion I was looking for with all the graphs and discussion of mechanisms. I didn’t see it.

    The recyling of fossil fuel CO2 is certainly a concern. The half-life of CO2 is a big deal. The removal process is proportional in some fashion to the total concentration, so we will continue to see a signature after introduction into the atmosphere. Another factor with a large uncertainty.
    The fine points of the math are beyond not just me, but many others. Could we see someone working out:
    a) the current, cumulative contribution of CO2 from fossil fuels post 1850 and 1945 (the start of so much was being dumped in the air) based on the isotopic data,
    b) the incremental increase year-to year as a proportion of 2 ppm, from this isotopic data, and
    c) the proportion of CO2 from fossil fuels incrementally added AFTER taking into consideration the half-life of CO2 and the changed proportion of fossil fuel CO2 in the previous year’s atmosphere?

    No worry, I have worked it out, assuming a quite realistic half life time of 38 years for an excess amount of CO2 in the atmosphere (based on the current 4 GtC sink rate per year for an excess 100 GtC, see the basic calculation at http://www.john-daly.com/carbon.htm ) and a refresh rate of 150/800 GtC/year.

    The decay rate with a 38 years half life influences the total amount (whatever the type or origin) of CO2 residing in the atmosphere, while the refresh rate influences the isotopic composition (or what rests of the CO2 of fossil origin in the atmosphere). Deep ocean – atmosphere exchanges estimated at 40 GtC/year (based on the resulting isotope changes). For the past 160 years of emissions that gives following plot:

    Where tCA is the total amount of CO2 in the atmosphere, calculated and observed and FA% the fraction of “fossil” CO2 in the atmosphere in percent and FL% the fraction of fossil CO2 in the ocean mixed layer.

    With the same assumptions, one can compare what the d13C levels should do by adding the emissions and what they really have done over the past 160 years:

    Again A is atmospheric and L is mixed ocean layer.
    This is not a perfect match, but not far away either, it needs some incorporation of what vegetation probably did do (not included yet) with the d13C ratio’s.

  200. Thankyou for the reply.

    *Ferdinand Engelbeen says:

    1) The atmospheric isotopic CO2 lags deeper ocean surface water carbon isotopes (also shown in figure 4) Indicating that the atmosphere is responding to a isotopic ocean change that occurred before.
    *The deep oceans show a d13C level of zero to +1 per mil. At upwelling places the extra nutritients induce abundant biolife near the surface, which increases the d13C level to +1 to +5 per mil. Any CO2 released from the oceans would increase the d13C levels of the atmosphere, while we see a decrease. The upper ocean d13C levels respond to the decrease in the atmosphere. So it is just the opposite of what you say.

    Sorry for misunderstanding you, by deeper ocean surface water I mean at depths like <50m, 125m , 300m etc. I would have mentioned the deep ocean only in this context. This shows the atmosphere is lagged and responding to these depths, not the depths responding to the atmosphere.

    2) The ratio of isotopic carbon can not change the same from the atmosphere to the ocean. The same concentrations that change the ratio in the atmosphere must be much larger for the same ocean change because of the different states of matter.
    *The upper level of the oceans needs far less CO2 than the atmosphere for changes: the atmosphere contains about 800 GtC as CO2, the upper part of the oceans (the “mixed layer”) contains about 1000 GtC. An increase of 30% CO2 in the atmosphere results in only 3% increase of CO2/bi/carbonate in the ocean surface at equilibrium, due to the change in pH which opposes the uptake.
    Deep ocean exchanges with the atmosphere are limited and result in about 1.5 GtC more uptake than release.

    2) still looks correct and even given an example for this. The upper ocean needs far more CO2 than the atmophere for the same percentage change. This example is already in this text and contradicts what is mentioned at the beginning. In liquid water your example shows the same volume results in a 3% versus 30% change in the atmosphere. The same concentrations that change the ratio in the atmosphere must be much larger for the same ocean change because of different states of matter is exactly just this.

    3) Volcanoes contribute to the change in isotopic carbon ratio and although may not have that large an effect in the atmosphere directly, likely have a much bigger influence under the ocean. (partly due to 4)
    *Again, please inform you about the isotopic composition of volcanic CO2 from eruptions and vents: most of the volcanic CO2 has a high (around zero) d13C level, compared to atmospheric CO2. Any such releases would increase the d13C level of the atmospheric carbon, while we see a decrease. Many volcanoes in a subduction zone release CO2 from decomposing calcite deposits at the sea bottom. These have a near zero d13C level.

    Yes, direct volcanoes (ie on land) to the atmsophere don't show high d13C levels, but some do. Whereas there are many more under the ocean covering 70+ percent of the planet surface. The reason why these can have much larger influence is because these eruptions can disturb oil and coal deposits on the ocean bed, naturally changing the d13C, not just calcite deposits. Therefore the reason why d13C levels vary on different volcanoes. These levels were varing and declining before the industrial revolution so nature does influence them.

    4) Plate tectonics and ocean circulation have a large influence on the movement of carbon from the bottom of the ocean to the surface. These events are seismic cyclic waves over long periods so the carbon ratio can change over many years. (depending where the activity is can cause stable periods too)
    *Over geological relevant times, that is true. But for the past near million years, that doesn’t play any measurable role.

    What evidence shows that natural events over millions of years aren't starting over recent centuries? Especially when only have data back to the 14th century in this example and being less accurate then recent decades. Hence, the need for further scientific evidence/discoveries.

    5) Individual El Nino’s contribute towards the increase in atmospheric CO2 by about 3-4 ppmv, so that means 3-4 ppmv (like human fossil fuels) also lost in sinks given a total of 7-8ppmv.
    *Individual La Niña periods contribute to a (relative) decrease in atmospheric CO2 increase rate by about the same amount: ENSO influences to both sides and only influences the variability around the trend, not the trend itself. The trend is clearly caused by the emissions, as all the other natural causes together form a sink which only absorbs halve of the quantity that the emissions give.

    The ENSO does influence both sides, but over recent decades this has become mainly postive. More stronger El Nino's than weaker La Ninas and this balance changes the output to increasing CO2 in the atmosphere. Once in the atmosphere the CO2 still has to be removed and there is not one rule for this CO2 and different one for human fossil based. La Nina's can't remove the CO2 as quick as El Ninos add it because the values are equal to human fossil based. If it can't remove all human CO2 it also can't remove all CO2 from El Nino.

    6) The oceans have warmed nearly 1c in the past 50 years so at least 8-16 ppmv is outgassed. With number 5 this easily contributes to half of the CO2 emissions during this time.
    *By far not: the total increase since the start of the industrial revolution is about 100 ppmv, while humans emitted near 200 ppmv.

    El Nino's have added over this period more than the 100 ppmv since the industrial revolution, but of course a good proportion of this has gone back in sinks. That is simply not true 40-50% of this is by far off . Just used the known approx value of increase since then and doubled it because not sure where half of the human emissions has gone. This ignores outgassing of rising ocean temperatures over the period with near 1c rise in just the past 50 years. My second responce to ENSO suports that CO2 can build up from these because the La Ninas have been fewer plus weaker and because of this can't sink all of the CO2 outgassed from El Ninos. The El Nino's cause further warming of other areas of the ocean further increasing CO2 levels.

    While more scientific evidence is needed these do show how this ratio can change and 1) + 2) provides at least some of this evidence.
    *1) and 2) provide the evidence that the oceans can’t be the source of the increase…

    1) and 2) have been misunderstood and show the opposite view still.

  201. re; methane

    It appears the science isn’t quite as settled as one might imagine.

    Near as I can tell the oxidization the atmosphere is the primary sink and is driven by UVB. Where that happens and at what half-life appears to depend on a lot on where it was emitted. Nearer the equator is a high source of emissions both natural (wetlands) and manmade (rice farming). This is largely swept up into the stratosphere by strong convection cells with stratospheric tops. From there it is transported poleward where it sinks. The poles are very intense in UVB (ozone holes) and UVB is stronger in the stratosphere. Given the higher UVB environment on this route it appears to have a lifetime of about 5-7 years in this route. Emissions away from the equator, which are just as large from both natural (wetlands) and manmade (mining & agriculture) sources, mix horizontally in the troposphere very well but tend not to be driven up through the tropopause at near the rate happening around the equator. Presumably these have a longer half-life as they spend longer mixing horizontally in a lower UVB environment. The stratosphere isn’t as dry as it would be without manmade methane. The 5ppm water vapor content of the stratosphere is believed to be mostly due to CH4 + 2 O2 -> CO2 + 2 H2O.

    A huge enigma exists in that for 10 years from 1998-2007 methane content in the atmosphere stopped rising. Methane has increased about 150% on what appears to be a smooth curve that correlates well with rising anthropogenic production. However there’s yet another confounding factor which is methane clathrates (methane trapped in permafrost and ocean sediments – a staggering amount of it and where rising temperature must release some portion of it. Another confounding factor is the Little Ice Age which ended right about when the industrial revolution began. A transition from a cooler earth that persisted for several centuries to the first two centuries of a warmer earth has to be taken into account. The transition would necessary entail release of methane from methane ice and increased generation from more wetland activity. On the other hand the warmer earth would presumably have a higher methane transport rate through the atmosphere.

    In any event it’s becoming clear that methane plays a GHG role half that of CO2. Moreover whereas anthropogenic activity adds just a few percent to the total carbon cycle it more than doubles the natural methane cycle. And since methane has a much shorter half-life in the atmosphere if we were to focus on limiting methane instead of CO2 we’d get a much bigger bang for our buck and we’d see presumably measurable results in the next decade. And if we didn’t like the result we could undo it just as quickly.

    In the meantime we should probably relax (relax not eliminate) the rules on SO2 emissions (everyone remembers or knows about acid rain, right?) as studies show anthropogenic sources can have a marked cooling effect. SO2 has a rather short half-life as well so it’s much more amenable to experiments that may be undone. Selectively removing or throttling industrial SO2 smokestack scrubbers to get a higher global emission rate without concentration in any smaller area sufficient to make acid rain a problem seems like a cheap way to get a measure of global cooling. We can also selectively change the mix of low of high sulfur diesel to get an increased but well distributed atmospheric SO2 rise.

    The thing of it is that methane and SO2 mediation doesn’t appeal to politicians because it is cheaper and easier and doesn’t have huge tax & control opportunities like CO2 has. As well, it doesn’t appeal to Malthusian ideologists either because there isn’t much change in civilization that goes along with it. So we find ourselves stuck trying to regulate CO2 emission which is politically impossible globally and regionally only by nations willing to give up economic competitiveness for what will amount to nothing more than a futile gesture.

    Nearer the equator it is largly swept up into the stratosphere from convection and getting past the tropopause with the aid of high topped convective cells (thunderstorms, hurricanes

  202. Matt G says:
    September 18, 2010 at 12:39 pm

    1) Sorry for misunderstanding you, by deeper ocean surface water I mean at depths like <50m, 125m , 300m etc. I would have mentioned the deep ocean only in this context. This shows the atmosphere is lagged and responding to these depths, not the depths responding to the atmosphere.

    The mixed layer of the oceans in average is some 200 m and in general follows the atmosphere with a some lag (about 1.5 years). In the case of d13C changes, the mixed layer follows the changes in the atmosphere not the reverse. That can be read in the (free preprint) work of Böhm e.a. at:

    http://www.boehmf.de/Boehm_et_al_g_cubed_preprint.pdf

    From that source (also visible in the last graph of the preprint):
    The marine d13C decrease from preindustrial times to the 1960s was about 80% of the atmospheric change. The marine d13C decrease from the 1960s to the 1980s, however, was only half the atmospheric change.
    After 1990, the rate of decrease in the sponges reaches that in the atmosphere, still not leading the dance…

    2) still looks correct and even given an example for this. The upper ocean needs far more CO2 than the atmophere for the same percentage change. This example is already in this text and contradicts what is mentioned at the beginning. In liquid water your example shows the same volume results in a 3% versus 30% change in the atmosphere. The same concentrations that change the ratio in the atmosphere must be much larger for the same ocean change because of different states of matter is exactly just this.

    My interpretation of your text was that the oceans needed more CO2 to reach an equilibrium with changes in the atmosphere, but you are right that for the same % change, the oceans need far more CO2. But that is not relevant, as the oceans mixed layer is in (pCO2) equilibrium with the atmosphere with only 10% of the change in the atmosphere… Thus any change in the mixed layer will have little effect on the atmosphere, while the reverse is easier to obtain.

    3) Yes, direct volcanoes (ie on land) to the atmsophere don’t show high d13C levels, but some do. Whereas there are many more under the ocean covering 70+ percent of the planet surface. The reason why these can have much larger influence is because these eruptions can disturb oil and coal deposits on the ocean bed, naturally changing the d13C, not just calcite deposits. Therefore the reason why d13C levels vary on different volcanoes. These levels were varing and declining before the industrial revolution so nature does influence them.

    The historical variability in atmospheric d13C can be found in ice cores, which show that for the past 11,000 years there is not much change: about 0.3 per mil, see:

    http://www.nature.com/nature/journal/v461/n7263/full/nature08393.html

    The changes in deep ocean d13C needs enormous quantities of carbon with a different isotopic composition, as the quantity of carbon already dissolved in the deep oceans is enormous. As there is little difference in d13C level between the current deep ocean and the calcite deposits of even 3 million years ago at about the start of the recurrent ice ages, all tectonic activity from then until now hasn’t changed the d13C level of the deep oceans that much. See:

    http://ethomas.web.wesleyan.edu/ees123/caiso.htm

    4) What evidence shows that natural events over millions of years aren’t starting over recent centuries?

    See 3) and why should natural events follow the human emissions in such an exact rate? See: http://www.ferdinand-engelbeen.be/klimaat/klim_img/acc_co2_1900_2004.jpg

    5) The ENSO does influence both sides, but over recent decades this has become mainly postive. More stronger El Nino’s than weaker La Ninas and this balance changes the output to increasing CO2 in the atmosphere. Once in the atmosphere the CO2 still has to be removed and there is not one rule for this CO2 and different one for human fossil based. La Nina’s can’t remove the CO2 as quick as El Ninos add it because the values are equal to human fossil based. If it can’t remove all human CO2 it also can’t remove all CO2 from El Nino.

    If you have read part one, about the mass balance: at least over the past 50 years, nature is a net sink for CO2. That means whatever the El Niño’s added, more was removed by the combination of vegetation and oceanic uptake. Further, human emissions were continuous, El Niño’s temporarely and mostly followed by cooler oceans…
    Based on the CO2/temperature ratio of the past, the increase in SST of about 0.6°C since about 1960 would have increased the CO2 level with about 5 ppmv, while the observed increase in that period is 60 ppmv. The real short-term influence of temperature on CO2 fluctuations around the trend is about 4 ppmv/°C, including the 1998 El Niño warming and the 1992 Pinatubo cooling…

    6) El Nino’s have added over this period more than the 100 ppmv since the industrial revolution, but of course a good proportion of this has gone back in sinks. That is simply not true 40-50% of this is by far off . Just used the known approx value of increase since then and doubled it because not sure where half of the human emissions has gone. This ignores outgassing of rising ocean temperatures over the period with near 1c rise in just the past 50 years. My second responce to ENSO suports that CO2 can build up from these because the La Ninas have been fewer plus weaker and because of this can’t sink all of the CO2 outgassed from El Ninos. The El Nino’s cause further warming of other areas of the ocean further increasing CO2 levels.

    The El Niño’s may have added to the temperature rise, but here you are double counting: during an El Niño, the temperature increase removes 4 ppmv/°C CO2 less than the trend (which is 55% of the emissions). If the temperature drops again after the El Niño peak, back to the same temperature as before, then the sink rate goes back to “normal”. If a La Niña follows and temperature drops further, then the removal rate increases with some 4 ppmv/°C. That all is temporarely. Thus an El Niño doesn’t influence CO2 levels more than what the temperature temporarely dictates. Only a permanent increase or decrease in temperature gives a permanent increase or decrease in “equilibrium” CO2 levels. Simply compare the contribution of human emissions (currently 8 GtC/year) with the natural variability (+/- 2 GtC/year) in sink rate (currently about 4 GtC/year):

    Where 1 ppmv = 2.1 GtC

    1) and 2) have been misunderstood and show the opposite view still.

    I don’t think so…

  203. George E. Smith says:
    September 16, 2010 at 9:22 am

    The NASA map certainly puts the Kibosh on the notion that CO2 in the atmospehre is well mixed; and that appears to be a starting assumption in climate models. It clearly isn’t even approximately well mixed. To me; well mixed would eman that no matter where or when I took a sample of the atmosphere and analysed it, I would get the same composition on a molecular species (and isotopic) basis; at least within limits of differences that are of no consequence to any climate argument; and of course excluding taking a sample up somebody’s tailpipe or chimney.

    You would be right if there were no variable sources and sinks at work. As about 20% of all CO2 is going back and forth between the atmosphere and other reservoirs over the seasons, then it is no wonder that there are differences in CO2 levels between altitudes and latitudes over a year, even for a well mixed gas. The above AIRS satellite data are the average only for one month mid-summer. A similar plot for mid-winter would show the opposite picture with lower levels in the NH than in the SH. Yearly averages are far more even over the globe (in over 95% of the atmosphere), with a slight lag of the SH (which points to the main source of extra CO2 in the NH). See:

    And as the AIRS plot shows: a variability of +/- 10 ppmv on a scale of near 400 ppmv is hardly a proof of bad mixing, see the raw data and “cleaned” daily averages of two stations (NH and SH near the equator) for the year 2008 at full scale:

    One thing does puzzle me. The oceans and the atmosphere are presumably somewhat near equilibrium in the Henry’s Law sense as to the segregation of CO2 between atmosphere and ocean. And we are told that the carbon in deep water storage, is not getting out into the atmosphere. So why is it that the CO2 isotopic composition of the near surface ocean water, and the near surface atmosphere don’t match. Is somebody claiming (proof please) that the Henry’s Law Segregation at the interface is highly isotope dependent. I haven’t heard that claim made before. Why isn’t the ocean exchanging exactly the same isotopic CO2 with the atmospehre whether releasing or taking up ?

    The physical explanation is a matter of difference in mass, therefore velocity and speed of transfer between air and water (and reverse) at the air-water border layer. See:

    http://dge.stanford.edu/SCOPE/SCOPE_16/SCOPE_16_1.5.05_Siegenthaler_249-257.pdf

    Besides that, there is some exchange of CO2 between the deep oceans and the atmosphere via the THC sink in the NE Atlantic and the upwelling in the mid-Pacific (and other sink/source places), but these are indeed quite limited in capacity.

  204. @Engelbeen

    The abstract from the link you gave about ocean/atmosphere CO2 exchange doesn’t help your case.

    “Isotopic fractionation factors for the CO2 transfer between atmosphere and ocean are calculated, taking into account equilibrium and kinetic fractionation. Diffusion of CO2 into the water, which is rate limiting for mean oceanic conditions, fractionates the carbon isotopes only little. I3C/I2C fractionations are found to be -1.8 to – 2.3%0 for atmosphere-to-ocean transfer, and -9.7 to -10.2%0 for ocean-to-atmosphere transfer.
    A different case is absorption by alkaline solutions which is controlled simultaneously by CO2 diffusion and the reaction between CO2and OH-. The reaction rate exhibits a fractionation for I3C/I2C of about -27%0.”

    Unless I’m reading that wrong the ocean fractionates very little when it absorbs CO2 but emits CO2 that is 5x as light. Something in the ocean is sinking carbon 13 and thus making the atmosphere lighter.

    Has anyone investigated or factored-in how high nutrient content in runoff due to human activity might be effecting the unbalanced isotope exchange?

    I appreciate your responsiveness, by the way. I know it takes a lot of time and patience. Just for the record I’m pretty convinced that human activity is responsible for rising atmospheric CO2 but I don’t necessarily agree that fossil fuel combustion is the major contributor. I also don’t agree that it can be proven as the science behind it is soft and not amenable to experimentation with controlled variables so what we end up with are correlations conflated with causation, questionable proxy data, all leading to accounts of what’s happening that are more narrative than conclusive.

    As well I don’t think there’s anything that can be done on a global basis to limit anthropogenic CO2 production to any extent that will make a meaningful difference – human civilization simply depends too much on its meager (3%) contribution to the CO2 cycle and no nation that isn’t willing to give up its economic growth potential is going to volunteer to throw itself under the bus to make a futile gesture unless its government has gone completely daft.

  205. Dave Springer says:
    September 20, 2010 at 9:22 am

    Unless I’m reading that wrong the ocean fractionates very little when it absorbs CO2 but emits CO2 that is 5x as light. Something in the ocean is sinking carbon 13 and thus making the atmosphere lighter.

    It is a physical process, the difference in mass and therefore (migration and evaporation) speed which makes that there is fractionation, as good as is the case for “heavy” water (D2O) and heavy oxygen (18O) water. The reverse process seems less selective.

    The net difference is -8 per mil between ocean water and atmosphere for a full cycle, but more with extra degassing and less with extra absorption. Depending of the source, the deep ocean upwelling would give a net atmospheric d13C level of -7 to -8 per mil, while surface water would give -4 to -7 per mil, due to the higher d13C levels in the surface caused by biolife. The net result in the pre-industrial past of all such movements was around -6.4 +/-0.1 per mil in the atmosphere.

    Currently we are at -8 per mil. Thus one-way deep ocean upwelling would decrease the d13C level of the atmosphere (a two way source and sink would be near break-even), but as deep ocean upwelling also is an extra source of nutritients, that increases biolife in the upper oceans and thus 12C removal. The net result of this all would be a d13C increase in the atmosphere, while a decrease is observed…

    Further, the oceans are currently a net sink for CO2, which also should increase the d13C level of the atmosphere, while we measure a decrease…

    That makes that the oceans can’t be the cause of the CO2 increase in the atmosphere, neither of the d13C decline.

    And if you combine all facts, the case of the human contribution (fossil fuel combustion, methane emissions, land use changes) is quite solid, as that fits all observations…

  206. Steven mosher says:
    September 16, 2010 at 4:33 pm
    D. Patterson:

    “Burning fossil fuels may or may not result in lower CO2 concentrations in the atmosphere, but it is not inconceivable for fossil fuels to stimulate enough new plant growth to generally maintain concentrations or lower them in some other circumstances.”

    You missed the point. Absent any evidence that burning Fossil fuels causes a net decrease, absent ANY argument, I think the reasonable alternative is the obvious.

    It causes a net increase. Now that obvious conclusion also happens to be supported by a wealth of evidence which our kind author has assembled over three posts. There is no evidence of a net decrease from burning FF, there is substantial ( but never conclusive) evidence that it causes a net increase. The possibility that you might doubt it, does not amount to an argument. So, I am waiting for someone to argue that it causes a decrease, and back that argument up.

    I understood your point quite clearly. You are plainly suggesting the uncontroversial fact that the burning of fossil fuels obviously emits carbon dioxide as a product of the combustion process and must therefore cause a net increase in atmospheric concentrations of carbon dioxide. Such an argument is invalid, because it wrongly assumes the addition of of carbon dioxide to the atmosphere can only and must only result in continuing net increases of carbon dioxide concentrations in the atmosphere. The real world evidence demonstrates such an assumption is not true and is, in fact, contrary to experience.

    The biosphere is responsible for taking Earth’s earlier atmosphere that was more than a hundred times more massive than today and composed of nearly all carbon dioxide, removed nearly all of that carbon dioxide from the atmosphere, and deposited the carbon dioxide in the lithosphere, hydrosphere, and biosphere. The only reason there is any more than a trace amount of carbon dioxide in the atmosphere today is the continued geological emissions and the inability of the biosphere to reduce the carbon dioxide beyond equilibrium levels without suffering extinction upon the cessation of photosynthesis. In other words, the biosphere has demonstrated an unquestionable capacity to reduce mega-atmospheric concentrations of carbon dioxide to the minimum equilibrium levels achievable by the biosphere over a sufficient time period.

    The only questions we need to have answered about the carbon dioxide added to the atmosphere by the burning of fossil fuels is just how long of a time period the biosphere will require to reduce the additions to the equilibrium levels and what those equilibrium levels are in a particular time period and circumstance. Until and unless the biosphere becomes extinct or virtually extinct due to <180ppm levels of carbon dioxide and or ice age events, the biosphere will always remove added carbon dioxide from fossil fuels or any other source until the atmospheric concentrations reach the equilibrium levels. So, it is not a question of if there is an ultimate net decrease after burning fossil fuels, but it is a question of how soon or when the net decrease to equilibrium levels occurs.

    Given the biosphere's past achievement of reducing more than 100 present Earth atmospheres with something like 988,000 parts per million of carbon dioxide to only 280-390 parts per million in an atmosphere with less than 100th the mass, someone is going to have a lot of mighty mighty fancy explaining to do as to why the biosphere can no longer capable of handling one or a few percentage points of anthropogenic carbon dioxide emissions to the latest trace ~280-390 parts per million or less. Furthermore…

    What are the past equilibrium levels?

    Are the anthropogenic sources of carbon dioxide: 1. net additions in the short term, 2. net decreases in the short term, or 3. no significant changes in the short term?

    What constitutes a significant change in carbon dioxide levels when past equilibrium levels of carbon dioxide were 1,000ppm, 2,500ppm, and greater to more than 7,000ppm?

  207. D. Patterson says:
    September 21, 2010 at 2:42 am

    Furthermore…

    What are the past equilibrium levels?

    Are the anthropogenic sources of carbon dioxide: 1. net additions in the short term, 2. net decreases in the short term, or 3. no significant changes in the short term?

    What constitutes a significant change in carbon dioxide levels when past equilibrium levels of carbon dioxide were 1,000ppm, 2,500ppm, and greater to more than 7,000ppm?

    Most of these amounts of the (far) past are buried in relative stable carbonate and/or fossil fuel layers. For the current geological distribution of the continents, the 180-300 ppmv CO2 levels found in ice cores may be the most relevant levels, as these show a remarkable linear ratio between CO2 levels (lagging) and temperature of about 8 ppmv/°C, sustained over 800,000 years.

    Based on that ratio, the current temperature would give some 290 ppmv for CO2, which did go up together with the emissions since the start of the industrial revolution till nowadays 390 ppmv. The decay rate of this excess CO2 may be around 40 years, see: http://www.john-daly.com/carbon.htm

  208. Spector says:
    September 22, 2010 at 2:41 am

    I note there has been a report of a massive decline in phytoplankton over the last 100 years as the oceans appear to be becoming more transparent. If true, could this also be a cause of more CO2 in the atmosphere?

    http://dalnews.dal.ca/2010/07/28/photoplank.html

    http://wattsupwiththat.com/2010/07/30/now-its-phytoplankton-panic/

    Plankton indeed is a part of the carbon cycle which removes CO2 from the atmosphere by depositing calcite (shells) and organic carbon out of the upper ocean mixed layer into the deep oceans. That would influence the sink rate of the oceans and thus indirectly increase the increase rate in the atmosphere. But the increase rate in the atmosphere shows a more steady state in recent years.

  209. Ferdinand Engelbeen says:
    September 21, 2010 at 7:17 am
    [....]
    Most of these amounts of the (far) past are buried in relative stable carbonate and/or fossil fuel layers. For the current geological distribution of the continents, the 180-300 ppmv CO2 levels found in ice cores may be the most relevant levels, as these show a remarkable linear ratio between CO2 levels (lagging) and temperature of about 8 ppmv/°C, sustained over 800,000 years.

    The biosphere is still removing carbon dioxide from the atmosphere and depositing it in the biosphere, hydrosphere, and lithosphere. The fundamental mechanisms which functioned to do so in what you want to distance as the “far” past is still at work and relevant today.

    There is strong evidence to regard the ice core data you cite as authoritative for carbon dioxide levels as suspect due to errors in assumptions, errors in collection, and errors in interpretation. In any case, the currently extraordinarily low levels of atmospheric carbon dioxide have little to do with the current or past geographic locations of the contnental plates. The continental plates have been in generally similar locations for the past 100 million years. You havee to go back to a time before the arrival of the first trees and the first colonization of the formerly barren continents to find them clustered from the Antarctic Circle to positions straddling the equator. So, giving the continental locations as an excuse for the lower carbon dioxide levels is a false and misleading argument.

    As for a linear relationship for atmospheric levels of carbon dioxide, it must be remembered the apparent linearity is a statistical illusion obtained by smoothing the data. Carbon dioxide and oxygen levels fluctuated between a series of overlapping cycles ranging from 11 years to multiple centuries. using only the smoothed data series hides the non-linear aspects and behavior of a dataset with perhaps a linear trend.

    Based on that ratio, the current temperature would give some 290 ppmv for CO2, which did go up together with the emissions since the start of the industrial revolution till nowadays 390 ppmv. The decay rate of this excess CO2 may be around 40 years, see: http://www.john-daly.com/carbon.htm

    There is no evidence whatsoever that 390ppm of atmospheric carbon dioxide is “excess.” On the contrary, geological and paleontological evidence tends to indicate 390ppm can be fairly described as something like 800ppm to perhaps 1800ppm below normal levels, even for an ice age.

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