Greenland Ice CO2 – Chemical Reactions or Natural Variability?

Guest Post By: Renee Hannon

Introduction
This post examines whether CO2 measurements in Greenland ice cores demonstrate natural variability as an alternative hypothesis to in-situ chemical reactions. Twenty years ago, scientists theorized Greenland ice core CO2 data were unreliable because CO2 trapped in air bubbles had potentially been altered by in-situ chemical reactions. This theory was put forward to explain why Greenland CO2 data showed higher variability and higher concentrations when compared with Antarctic ice core CO2 measurements located in the opposite polar region about 11,000 miles away. The theory of chemical alteration has gone unchallenged during the last twenty years. Since then, CO2 data from Greenland ice cores was dismissed and only CO2 data from Antarctic ice cores is currently used as the “gold standard” database. As a result, Greenland CO2 datasets are not used in climate science studies to understand Northern and Southern hemispheres interactions and the sensitivity of greenhouse gases under various climatic conditions.

Greenland Ice CO2 Chemical Reaction Theory
From earlier studies it was apparent that CO2 concentrations of trapped air in bubbles from Greenland ice core data were different than CO2 concentrations from Antarctic ice cores (Anklin, 1995, Stauffer, 1985). CO2 concentrations in Greenland ice cores are generally 20 ppm higher and show higher standard deviations (6-10 ppm versus 2-3 ppm) than in Antarctic ice cores during the recent Holocene interglacial period. Greenland CO2 concentrations from ice cores (GRIP, NGRIP, DYE3) agree well with each other and all show similar disagreements from Antarctica. See my previous post for a more thorough discussion of Greenland CO2 over the past 50,000 years here.

Detailed laboratory measurements to understand CO2 differences between the poles were performed on annual layers of Greenland ice cores, using the Antarctic Byrd ice core as the baseline (Tschumi, 2000). The focus of these studies was to determine potential chemical reactions that may cause variable and surplus CO2 measurements in the Greenland ice cores. CO2 was analyzed with an infrared laser absorption spectrometer. Some results of the study are shown in Figure 1.

Greenland CO2 “surplus” in the study is defined where CO2 in the GRIP ice samples are higher than CO2 in the Antarctic Byrd ice core. In addition to being high, CO2 surplus in the samples show short-term variations from 15-25 ppm within annual layers younger than 2700 years BP. In older sections of the Greenland ice core, larger CO2 variability ranging from 40-80 ppm were measured.

Figure 1. Greenland CO2 and H2O2 measurements on GRIP ice cores. Data from Tschumi, 2000. Years are Before Present (BP) from 1950. Horizontal red dashed line is Antarctic Byrd CO2 values for the approximate same timeframe.

Tschumi concludes that a “generally positive” correlation exists between CO2 surplus and carbonates or the Ca+ proxy used to explain high CO2 in Greenland ice cores. Correlation coefficients ranged from 0.24 to 0.55. Therefore, production of CO2 from an acid-carbonate reaction is reasonable when CO2 peak values correlate with a maximum of the carbonate. More interestingly, there is a strong negative correlation between CO2 peak values and hydrogen peroxide (H2O2) with correlation coefficients from -0.65 to -0.93. This strong negative correlation led Tschumi to introduce another reaction; the oxidation of organic compounds to produce enriched CO2 values in Greenland samples.

In Greenland ice cores which experience high snow accumulation, annual timing of different species is highly resolved, clearly detected at all depths and used for annual layer counting (Rasmussen, 2006). Tschumi acknowledges that acidity, carbonates and calcium show short-term annual variations in ice samples. However, he states that oxidants like HCHO (formaldehyde) and H2O2 were believed to show no seasonal variations below the firn-ice transition, although his data shows strong annual variations. Annual amplitude can be dampened by diffusion, especially for gases. Studies show that most of the smoothing of H2O2 occurs in the top 10 meters of the ice sheet and there is no significant reduction in the H2O2 amplitude after 25 years (Anklin, 1997). Fuhrer, 1993 and Rasmussen, 2006, both show short-term annual variations of calcium and H2O2 at depths of 1400 m in the Summit GRIP and NGRIP ice cores. Rasmussen also shows that calcium has fewer peaks and lower resolution than H2O2 in ice cores, similar to what is seen in Tschumi’s data.

Lastly, Tschumi and Anklin make no mention of atmospheric annual CO2 variability at Mauna Loa, Hawaii and Point Barrow, Alaska, versus the lack of annual variability at the South Pole. This difference persists even though the Hawaiian and Alaskan observatories have been measuring atmospheric CO2 since 1958 and 1975, respectively. Their omission of annual CO2 variability as a plausible explanation for ice cores from Greenland showing variable CO2 measurements is puzzling.

Present day Arctic CO2 shows More Variability than Antarctic
Investigating present day atmospheric CO2 concentrations in the Arctic compared to the Antarctic provides a reasonable analog. Figure 2 shows the past few years of CO2 measurements for Barrow and South Pole (SPO) observatory stations for comparison.

Presently in the Arctic, as shown by Barrow data, short-term annual CO2 amplitude cycles range by almost 20 ppm. CO2 rises during the winter months after terrestrial respiration and falls during the summer during photosynthesis showing strong evidence of a natural biospheric signal (Haverd, 2020). These same annual trends occur in many Northern Hemisphere observatories such as Barrow BRW, Summit SUM, Finland PAL, Norway ZEP and Russia TIK (NOAA, 2020). Additionally, CO2 annual amplitudes in the northern latitudes have increased by 35% over the past 50 years (Graven, 2013). For example, CO2 amplitudes have increased from 14 ppm in 1970 to almost 20 ppm in 2020. Changes in CO2 uptake and release is evidence that the Northern Hemisphere terrestrial component is progressively taking up more carbon during spring and summer as CO2 levels increase (Haverd, 2020).

Figure 2. Left graph shows Barrow CO2 values in blue and South Pole SPO CO2 values in gray over two years. Upper right plot shows Short-Wavelength InfraRed (SWIR) CO2 column-averaged mixing ratio data projected on a global map for April and lower right plot for August 2018.

In contrast, a very weak fluctuation of opposite polarity is seen in South Pole (SPO) CO2 measurements shown by the gray dark line in Figure 2. This same weak amplitude occurs in Antarctic Syowa Station SYO, Halley Station HBA, Palmer Station PSA, Drake Passage DRP, and Ushuaia, Argentina USH observatories. The CO2 short-term annual amplitudes in the Southern Hemisphere are barely noticeable and only fluctuate by 1-2 ppm per yearly cycle over the past 50 years. It seems reasonable that the Antarctic, which is surrounded by oceans, would see minimal terrestrial influence on annual CO2 variability.

The Mauna Loa MLO observatory has annual cycles that are in-between Barrow and South Pole with CO2 amplitudes varying 5-6 ppm per year. The amplitude at MLO has only increased by 15% over the past 50 years, while the amplitude at Barrow has increased by twice that much. There is no distinguishable amplitude change over time south of 35 deg N (Graven, 2013).

The global maps in Figure 2 are from GOSAT, a satellite designed specifically for monitoring greenhouse gases from space. The maps show monthly overviews of the global distribution of CO2 and demonstrate the seasonal oscillation which is restricted to the northern latitudes. During the summer months, CO2 is lower in the Arctic and high latitudes compared to the tropics as shown by the August SWIR CO2 global concentrations. During the winter dormant period, CO2 increases by almost 20 ppm across most of the high latitudes dominated by land masses with maximums in the spring as shown by the April SWIR CO2 global map.

Greenland Ice CO2 Variability Compares well with Present-day Arctic Cycles
Short-term CO2 variability in Greenland ice cores matches reasonably well to present day atmospheric CO2 annual cycles seen in the Arctic observatories. Figure 3 compares an annual CO2 cycle at the Barrow observatory to CO2 variations in the Greenland ice cores. The duration and variability, or amplitude, are similar. The amplitude is about 15 ppm for the 1100-year BP sample and up to 25 ppm for the older 2700-year BP sample. The Barrow observatory currently shows amplitude in the 18-20 ppm range presently and as low as 14 ppm during 1970.

Figure 3. GRIP ice core CO2 cycles compared to Barrow CO2 cycles for approximately 2 annual layers. Ages are in years BP from 1950.

Anklin, 1995 asserts that Greenland ice sections show short term CO2 variations on the order of 10-20 ppm in annual layers which cannot represent atmospheric variation. However, as discussed, Arctic observatories clearly measure summer and winter CO2 fluctuations of that magnitude over the past 50 years (Graven, 2013).

In contrast, CO2 in Antarctic ice cores only show variations of 1-2 ppm annually (Anklin, 1995). This is expected because southern latitude observatories show that CO2 has a very weak, if any, annual amplitude variation due to the lack of extensive terrestrial regions. Additionally, annual layers in Antarctic ice cores are barely distinguishable, if at all, due to less annual precipitation and more closely packed layers (Rasmussen, 2006). Therefore, CO2 should show more variability in Greenland ice cores than Antarctic ice cores as observed in present-day CO2 observatories.

Arctic H2O2 Variations are Anticorrelated with CO2
Hydrogen peroxide is recognized as an atmospheric oxidant and was extensively studied in the 1980s for its role in acid rain (Sakugawa, et. al, 1990). H2O2 is associated with water vapor content in the air and solar radiation. Its formation, decomposition, and deposition processes are not clearly understood. Studies do confirm that atmospheric H2O2 concentrations show distinct seasonal variations of higher concentrations in the summer and lower in the winter.

Hydrogen peroxide is also present in high concentrations in both Arctic and Antarctic polar snow and high snow accumulation ice cores (Sigg, 1988 and Beer, 1991). Like atmospheric variability, hydrogen peroxide shows a strong seasonality with high concentrations in summer snow layers and low values in winter snow shown in Figure 4.

Figure 4. The annual variation of H202 compared to δ18O and CO2. H202 data from Beer, 1990. The δ18O value is used as a proxy for the temperature.

Interestingly, present day atmospheric CO2 in the Arctic shows a strong anticorrelation to hydrogen peroxide as shown in Figure 4b. As H2O2 rapidly increases in summer, CO2 rapidly decreases due to terrestrial photosynthesis as described earlier. During the winter, CO2 is at its high while H2O2 is low.

Tschumi also noted that many Greenland ice core samples demonstrate remarkable anticorrelations between CO2 and hydrogen peroxide shown in Figure 1. Tschumi assumed the reduction of the oxidant H2O2 was a chemical reaction with an organic compound to create surplus CO2 in the ice core sample. Recall, Tschumi’s research was premised upon finding a chemical reaction to explain the variability and “surplus” CO2 in the Greenland ice cores.

Both atmospheric hydrogen peroxide and CO2 demonstrate large annual variations in the Arctic today. Additionally, a strong anticorrelation between CO2 and hydrogen peroxide is observed both present day as well as in ice cores. A much simpler explanation of the ice core anticorrelation between these two gases is natural annual variability rather than a chemical reaction.

Holocene Greenland Ice CO2 Variability
Ranges and standard deviations for CO2 variations in Greenland ice cores in addition to present day observatories are shown in the table below. The data are separated into three groups. Group 1 are annual observatory ranges from Barrow, Mauna Loa, and South Pole highlighted in blue for present day comparison. Group 2 are Greenland ice core data between 850 to 2700 years highlighted in green. Greenland ice samples between 7000 to 8300 years are Group 3, highlighted in orange.

Recent observatory data shows significant latitudinal differences between annual CO2 amplitudes and standard deviations. The Barrow Arctic observatory shows high annual amplitude variations with standard deviations of 5-6 ppm. South Pole CO2 data shows very small annual amplitude variations of 1-2 ppm with a small standard deviation and Mauna Loa is in between.

In ice cores, Anklin states standard deviations of CO2 range from 6 to 10 ppm for Greenland ice which is much higher than standard deviations of CO2 in Antarctic ice cores of 2 to 3 ppm. The CO2 deviations in Barrow and the South Pole observatories are like the deviations Anklin observes between Greenland and Antarctic ice core data. In summary, the Greenland ice core CO2 ranges and standard deviations for years younger than 2700 years agree well with Barrow observatory data.

Table 1: CO2 ranges and standard deviations from observation stations and Greenland ice core data.

Figure 5. CO2 data from Greenland ice cores from NOAA 2020 Barrow observatory, GRIP Anklin 1995, Tschumi 2000, and Dye 3 Neftel 1985. Ranges in blue and means in red. Potential outliers in gray. Only Barrow CO2 ranges are shown for present day. Before present is < 1950.

The graph in Figure 5 shows the ranges of Greenland ice core CO2 concentrations and the means over the past 8500 years for the detailed annual layer samples. Data from an annual cycle in 1975 and 2000 AD are included from the Barrow observatory station for comparison. Again, amplitudes or ranges during the past 2700 years are comparable to present day except for one data point around 850 years that is an outlier. Greenland CO2 calculated means during this time are from 280 to 300 ppm which are only slightly higher than Antarctic ice CO2 means of 277 to 282 ppm, respectively. The Greenland means compared to Antarctic means are close to the present-day interhemispheric CO2 gradient of 2-5 ppm. Clearly, Greenland CO2 data appears viable and simply demonstrates CO2 is variable in the Arctic as seen in present annual atmospheric conditions.

If any data is suspect, it would be the older Greenland CO2 data from 6500-8700 years which is highly variable showing ranges of 40-90 ppm. These CO2 data are sampled during the Arctic climate optimum where arctic temperatures were approximately 2 to 4 degrees C warmer than today. During this time, it is speculated there was no permanent sea ice in the Arctic and Arctic biomes were shifted northward, where Arctic tundra was replaced with cool conifer forests. Large amounts of open water during the summer and presence of temperate and significant boreal regions may have led to large increases in CO2 annual fluctuations in northern latitudes. These highly variable CO2 data may represent very different climate conditions than we are experiencing present day and provide valuable information on past CO2 fluctuations.

Natural Variability of Greenland Ice CO2 is a Viable Explanation
Atmospheric CO2 annual variability that are unique to northern latitudes can explain why Greenland CO2 measurements in ice cores behave differently than in Antarctic ice cores. The Arctic and Antarctic polar regions have different natural biospheres. These polar regions exhibit different short-term behavior of atmospheric CO2; large annual 20 ppm fluctuations in the Arctic from terrestrial influence and minor 1-2 ppm fluctuations in Antarctic. Additionally, the Arctic has higher snow accumulation rates than the Antarctic allowing for preservation of thicker annual ice layers.

A case for Greenland CO2 data being just as accurate as the Antarctic ice core CO2 has been offered. This explanation uses modern analog data from observatories rather than the 20-year old theory of in-situ chemical reactions. A theory requiring a complex process of in-situ chemical reactions to explain Greenland CO2 variability seems unnecessary. Incorporating Greenland ice core CO2 data would significantly alter scientific studies that utilize only the lazy Antarctic CO2 profile to make interpretations concerning Global climate change. If Greenland ice core CO2 data is even qualitatively correct, then it needs to be re-examined and incorporated into polar and interhemispheric greenhouse gas interpretations. Dismissing an entire polar region dataset because it doesn’t match Antarctic ice cores and explaining away the Greenland data with complex chemical reactions ignores data from modern observatories.

Acknowledgements: Special thanks to Donald Ince and Andy May for reviewing and editing this article.

References Cited
Anklin, M., J.M. Barnola, J. Schwander, B. Stauffer, and D. Raynaud, Processes affecting the CO2 concentration measured in Greenland ice, Tellus, Ser. B, 47, 461-470, 1995.

Anklin, M., and R. Bales, Recent increase in H2O2 concentration at Summit, Greenland, Journal of Geophysical Research, vol. 201, No. D15, pg 19099-19104, 1997.

Beer, J., et. al, Seasonal Variations in the Concentrations of Be, Cl, NO3, SO4, H202, Pb, H, Mineral Dust, and 180 in Greenland Snow. Atmospheric Environment Vol. 25A, No. 5/6 pp. 899-904, 1991. Paywalled.

Fuhrer, K., A. Neftel, M. Anklin and V. Maggi, Continuous Measurements of Hydrogen Perioxide, Folmaldehyde, Calcium and Ammonium Concentrations along the new GRIP ice core from Summit, Central Greenland, Atmospheric Environment Vol. 27A, No. 12 pp. 1873-1880, 1993.

GOSAT Data Products. http://data2.gosat.nies.go.jp/

Graven, H., R. Keeling, S. Piper, P. Patra, B. Stephens, S. Wofsy, L. Welp, C. Sweeney, Enhanced Seasonal Exchange of CO2 by Northern Ecosystems since 1960, Science, Vol. 341, Issue 6150, pp. 1085-1089, 2013. DOI: 10.1126/science.1239207

Haverd, V., B. Smith, J. Canadell, M. Cuntz, S. Mikaloff-Fletcher, G. Farquhar, W. Woodgate, P. Briggs, C. Trudinger, Higher than expected CO2 fertilization inferred from leaf to global observations, Global Change Biology, 2020. https://doi.org/10.1111/gcb.14950.

NOAA ESRL Global Monitoring Division – Global Greenhouse Gas Reference Network., 2020.

Rasmusen, S., K. Andersen, A. Svenson, J. et.al, A new Greenland ice core chronology for the last glacial termination, Journal of Geophyscial Research: Atmospheres/Volume 111, Issue D6, 2006. https://doi.org/10.1029/2005JD006079

Sigg, A. and Neftel, A, Seasonal Variations in Hydrogen peroxide in polar ice cores, Annals of Glaciology 10, 1988.

Stauffer, B, Neftel, A, Oeschger, H, Schwander, J 1985 CO2 concentration in air extracted from Greenland ice samples. In Langway, C C Jr, Oeschger, H, Dansgaard, W (eds) Greenland ice core: geophysics, geochemistry and the environment. Washington, DC, American Geophysical Union (Geophysical Monograph 33). Paywalled.

Sakugawa, H., Kaplan, I., Tsai, W., and Cohen, Y. Atmospheric hydrogen peroxide, Environ. Sci. Technol., 1990, 24, 10, 1452-1462.

Tschumi, J. and B.Stauffer, Reconstructing of the past atmospheric CO2 concentrations based on ice-core analyses: open questions due to in situ production of CO2 in the ice. Cambridge University Press: 2000.

92 thoughts on “Greenland Ice CO2 – Chemical Reactions or Natural Variability?

  1. The northern hemisphere is 61% water and 39% land, the southern hemisphere is 81% water and 19% land, Having twice as much land in the northern hemisphere will substantially alter CO2 production profiles and monthly spread. You would not expect to see the same results in both.

    • To add to the above: the Antarctic has more high pressure than the Arctic. In the warmer Arctic low pressure areas play a larger role. The warmer the surface (Holocene Optimum) the less sea ice is present in the Arctic and by a much higher evaporation even more low pressure areas (with their ascending local surface air) are formed. The less sea ice there is, the more the regional Arctic circumstances will be reflected in the snow flakes to be formed.

      The Antarctic however creates its own stable climate. The stable vast quantity of ice and snow over the Antarctic (plus the large surface of winter sea ice around the Antarctic) creates a vast and stable high pressure area over the Antarctic. The high pressure results in constantly descending stratospheric (!) air. This over the central Antarctic descending air reflects the CO2 content of the stratosphere. Stratospheric air may be supposed to have a ‘more global’ fingerprint. Later at lower latitudes this over the surface flowing stratospheric air will ascend again and will form snow flakes at the higher elevations. Some of that newly formed upper air returns to the Antarctic, bringing snow over there. The air content of the snow flakes will have a more stratospheric (= more global) fingerprint.

      Over the Arctic the in the low pressure areas rising local air reflects the more varying Arctic circumstances. And the less sea ice there is in the Arctic the more low pressure areas will be formed and the higher the share of the local fingerprint will be. Under relatively ‘warm’ Arctic circumstances the share of descending stratospheric air will be lower – and hence the share of the global fingerprint.

      • I agree with the jist of this reply. The Antarctic is more isolated from air and water circulations because of the circumpolar water currents in the Southern Ocean, which tend to also steer wind currents and patterns which inhibit mixing over the Antarctic continent. Ergo, there is much less seasonal and annual variation from the biggest sources and sinks, bio growth and decomposition, ocean uptake and release, etc.

      • Wim,
        Yes, the Antarctic is the “underlying Global trend” and your explanation of a semi-permanent high pressure zone over Antarctic affecting the stratosphere is a nice theory (or hypothesis). In contrast, the Arctic is the short term deviation or moving low pressure zone that gets the alarmists all excited. I’m wet and cold in Alaska this summer, but red salmon fishing is steady.

    • Some percent more energy from the Sun during the SH-summers compared to the NH-summers (closer to the Sun) combined with more sea surface in the south gives more sea surface outgassing of CO2 in the SH summer periode. Less NH CO2-consumption by plants at the same time is the combined reason for the yearly variability of CO2. And as the Earth heats (for many reasons), CO2 accumulation i atmosphere rises – as usual, even during corona lock-down – now five months – remarkable!

  2. Translation of what I read” “If we manipulate the raw data enough it will tell us exactly what we want.”

    Ice core’s are simply not suitable as proxy vessels for a gas that can be generated, chemically altered, escape, and otherwise change.

    Climate infatuated people will continue to “discover” whatever it is they want from sheer scientific bias no matter what the issues are. All it takes is faith that the truth is already known and all that has to be done is support it.

    Just look at the Mauna Loa CO2 data and spot the huge dip in the increase of atmospheric CO2 during the lock down of Western economies – oh wait, there isn’t any. Not until someone goes and “fixes” the data anyway.

  3. The northern hemisphere has a vastly larger area of rich topsoil.

    Upland topsoil is enriched by upwelling natural gas which is
    consumed by aerobic microbes, oxidized, and the CO2 passes
    into the atmosphere.

    The difference between spring and late summer CO2 reading is
    caused by frozen or at least cold spring soil retarding the upwelling
    of natural gas being reflected in the much lower amount of gas
    being oxidized.

    August temperatures warms or thaws the ground, speeding the
    upwelling of the natural gas, with a much greater volume
    available to be oxidized.

    A soil organic carbon map should be thought of as a guide
    to the amount of natural gas, in the presence of adequate
    moisture, available to enrich the soil, and the microbes
    oxidizing it produce the differential between northern and
    southern hemisphere readings.

    • The only problem with this theory is that the so called up welling natural gas does not and never has existed.

      • Again, in decent upland soil, soil not in a flood plain, dig a hole about 2.5 feet in diameter through the
        topsoil, past all evident roots and worm castings. Take the salad bowl, invert it. Drill a hole in the now top,
        and install a brass gas line fitting for a 1/4″ copper tube. Solder the fitting in, place the inverted bowl
        in the bottom of the hole, and refill the hole, consolidating the soil as it is refilled.

        Cut the copper tube off several inches above the topsoil and install a closed gas valve.

        Allow enough time to elapse to allow the bowl to capture the upwelling gas. According to
        soil maps of your area, showing very rich topsoil, 24 hours should be enough time.

        I did my first such test in Kansas where the black topsoil was ~ 1 meter thick. 24 hours gave me a very
        high reading of a combustible gas, over 250PPM.

        The soil scientists have said that the reason that the soil was so deep in the Midwest was that tall grass roots reached to the bottom of the soil. They confused cause with effect. The tall grass with the deep roots was the
        dominate foliage because over time, the grass with the deepest roots survived the wild fires and droughts
        to become the dominate foliage.

        When you know real cause of these effects, you can see many conclusions are incorrect. My friend Andy May,
        a petroleum physicist, no longer speaks to me because I told him that the rock which they call “source rock”
        is a layer which captured the upwelling hydrocarbons over time as the layers solidified. In the Baaken,
        you see many such layers, and still some of the smaller molecules make it to the surface, enriching the soil above.

        It is difficult for people to shift their paradigm. The Russians and Dr, Thomas Gold were correct. There is
        a never ending supply of hydrocarbons.

        Think of the earth as a large petroleum distillery. The heat, pressure, and minerals and metals determine
        whether the molecules remain simple or form much larger molecules.

        I am going long on this email, but I would like to give you the reference which started my effort to prove
        Dr. Gold was correct. This link is to a program which Dr. William Woods did for BBC which I first
        saw in 2007. The important section starts at 43min. into the program. When Dr. Woods said that the soil
        grows back, I knew that a tremendous amount of energy is required to make the soil “grow back”, I knew that nothing that humans did 500 years ago caused the soil to “Grow back”.
        terra preta – Bing video

        terra preta – Bing video

        My opinion is that the gas was natural gas, not just methane, but at the time, a meter which could
        differentiate the sub constituents would have cost over $14,000. This is a hobby for me in my retirement
        so I could not justify that expense.

        I just got a current quote from Sensit for their ethane detectors, ($9K to 10k dollars).

        I know that you always have a CO2 meter, so if you could find the time to do the first experiment,
        you will understand that the carbon balance used by the USEPA is incorrect.

        The hydrocarbons which they have found in topsoil are not absorbed from the atmosphere. When CH4
        hits the atmosphere, it rises. This is the reason that all of the natural gas listed as absorbed by upland
        is wrong.

        Look again at the photo I gave you last year after with the above in mind.

        I missed the last Heartland Climate meeting because I was having my rt hip replaced. Yesterday, I was
        able to spin the cranks on my trainer for 10 minutes.

        This is important for all humanity. No end to hydrocarbons,

        Thanks,
        Jerry

        Again, in decent upland soil, soil not in a flood plain, dig a hole about 2.5 feet in diameter through the
        topsoil, past all evident roots and worm castings. Take the salad bowl, invert it. Drill a hole in the now top,
        and install a brass gas line fitting for a 1/4″ copper tube. Solder the fitting in, place the inverted bowl
        in the bottom of the hole, and refill the hole, consolidating the soil as it is refilled.

        Cut the copper tube off several inches above the topsoil and install a closed gas valve.

        Allow enough time to elapse to allow the bowl to capture the upwelling gas. According to
        soil maps of your area, showing very rich topsoil, 24 hours should be enough time.

        I did my first such test in Kansas where the black topsoil was ~ 1 meter thick. 24 hours gave me a very
        high reading of a combustible gas, over 250PPM.

        The soil scientists have said that the reason that the soil was so deep in the Midwest was that tall grass roots reached to the bottom of the soil. They confused cause with effect. The tall grass with the deep roots was the
        dominate foliage because over time, the grass with the deepest roots survived the wild fires and droughts
        to become the dominate foliage.

        When you know real cause of these effects, you can see many conclusions are incorrect. My friend Andy May,
        a petroleum physicist, no longer speaks to me because I told him that the rock which they call “source rock”
        is a layer which captured the upwelling hydrocarbons over time as the layers solidified. In the Baaken,
        you see many such layers, and still some of the smaller molecules make it to the surface, enriching the soil above.

        It is difficult for people to shift their paradigm. The Russians and Dr, Thomas Gold were correct. There is
        a never ending supply of hydrocarbons.

        Think of the earth as a large petroleum distillery. The heat, pressure, and minerals and metals determine
        whether the molecules remain simple or form much larger molecules.

        I am going long on this email, but I would like to give you the reference which started my effort to prove
        Dr. Gold was correct. This link is to a program which Dr. William Woods did for BBC which I first
        saw in 2007. The important section starts at 43min. into the program. When Dr. Woods said that the soil
        grows back, I knew that a tremendous amount of energy is required to make the soil “grow back”, I knew that nothing that humans did 500 years ago caused the soil to “Grow back”.
        terra preta – Bing video

        terra preta – Bing video

        My opinion is that the gas was natural gas, not just methane, but at the time, a meter which could
        differentiate the sub constituents would have cost over $14,000. This is a hobby for me in my retirement
        so I could not justify that expense.

        I just got a current quote from Sensit for their ethane detectors, ($9K to 10k dollars).

        I know that you always have a CO2 meter, so if you could find the time to do the first experiment,
        you will understand that the carbon balance used by the USEPA is incorrect.

        The hydrocarbons which they have found in topsoil are not absorbed from the atmosphere. When CH4
        hits the atmosphere, it rises. This is the reason that all of the natural gas listed as absorbed by upland
        is wrong.

        Look again at the photo I gave you last year after with the above in mind.

        I missed the last Heartland Climate meeting because I was having my rt hip replaced. Yesterday, I was
        able to spin the cranks on my trainer for 10 minutes.

        This is important for all humanity. No end to hydrocarbons,

        Thanks,
        Jerry

        Simple test for CO2 output from soil.

        For sign of microbes consuming hydrocarbons, find a spot of decent topsoil, remove the surface foliage in an area about 18″ in diameter, maintaining a flat surface. Take a 12″ stainless steel salad bowl, run a bead of adhesive around the rim. Invert it on a sheet of vinyl plastic large enough to leave a 3″ skirt past the perimeter of the inverted bowl. Once the glue is dry, take a sharp knife and trim out the plastic inside the bowl, leaving the bowl open. Invert the bowl with the skirt, place your CO2 meter on continuous read under the bowl, making sure that the skirt is flat. Place a 10lb weight on the inverted salad bowl, and sand on the skirt, to prevent the wind sucking the CO2 out of the bowl.
        Having noted the ambient CO2 reading, ambient temperature, wind speed, and approximate moisture level, allow CO2 to accumulate for 12 hours.

        On my property in East Tennessee the last time I did the test, with ambient ~60 degrees F, less than 3 mph wind, and very damp soil, my ambient reading was 403PPM CO2. After 12 hours under the bowl, the CO2 reading was 960PPM CO2.

        For a test to prove to yourself that the microbes are consuming natural gas, that test
        will be described below.

      • MarkW, Of course there are many sources of natural gas in the ground and under the sea floor. There are also sources of oil, that is how the LaBrea tar pits in Los Angeles and similar oils seeps in Kansas and Oklahoma got there. As Jerry says, microbes evolved millions of years ago to eat both natural gas and crude oil, see this quote,

        “The microbes did a spectacular job of eating a lot of the natural gas,” says biogeochemist Chris Reddy of the Woods Hole Oceanographic Institution. The relatively small hydrocarbon molecules in natural gas are the easiest for microorganisms to eat. “The rate and capacity is a mind-boggling testament to microbes,” he adds.”
        https://www.scientificamerican.com/article/how-microbes-helped-clean-bp-s-oil-spill/

    • Hi Jerry, I’m happy to talk to you and I agree that the soil generates Methane, Ethane, C3 and C4 worldwide, except maybe in deserts. And it generates quite a lot of it in some areas, like Kansas, Oklahoma and Texas. Also some conventionally generated hydrocarbons are always being generated in organic rich rocks (coal and source rocks) and some escapes to the upper layers of the soil and out into the atmosphere. This is very true in Kansas with shallow mature source rocks, also true in Oklahoma, California, Kazakhstan, Venezuela and many other areas. These areas have heavy hydrocarbons on the surface, those with many more than 5 Carbons.

      • Hi Andy,

        My above was a too hasty attempt at cut and paste.

        I have been studding hydrocarbons in a casual way since my general
        science teacher, in 1958, told us that all the outer planets of the solar
        system had hydrocarbons in their atmosphere.

        At the time, I thought methane was an artifact of biological life. The next
        event in my quest for truth was the analysis of a meteorite reported in the
        news. ‘The analysis included a large percentage of hydrocarbons.

        My favorite uncle was a drilling superintendent for a large exploration
        company. He was a pioneer and early expert of slant drilling. He supervised
        many of the sites in LA from which many holes were drilled from a façade
        which looked like a multi story building. He supervised many offshore rigs.

        When I discussed my theory that hydrocarbons were a natural chemical
        process and not fossils, he said that the people in his business were aware
        that there was too much oil at great depth to be fossils. He had many
        contacts with the Russian hydrocarbon industry.

        During the first “energy crisis” the API, at one point, feared that a substitute
        for hydrocarbons might be found when were being told that there was only
        a 25 year supply remaining. The API published a paper which said that
        there was as much hydrocarbon under the surface of the earth as water
        in the oceans. Unfortunately, I lost my copy of this paper in a divorce, and
        for obvious reasons, searches yield no results.

        The reports that I read do say that Mars does have Methane in its atmosphere,
        and there is natural gas rising in the deserts, but as I have stated many times
        hydrocarbons rise all around the earth, but are not evenly distributed. If
        there is an igneous or metamorphic layer near the surface, the natural gas
        is mostly or completely blocked, and the topsoil, as around Atlanta is red clay.
        https://www.bing.com/search?q=does+mars+have+methane+in+its+atmosphere&cvid=3ed68957652b49a8ad87c7d765bf5d07&FORM=ANAB01&PC=HCTS

        In the presence of adequate moisture, the upwelling natural gas is oxidized by
        aerobic microbes, enriching the soil and expelling CO2 into the atmosphere.

        The depth of topsoil depends on the amount of upwelling natural gas,
        adequate moisture, and the ability of oxygen to penetrate, to feed
        the aerobic microbes. Top soil in areas of the Ukraine is up to two meters
        thick.

        Thomas Gold’s friends produced methane on a diamond anvil after his death.

        One of the illogical arguments against abiotic hydrocarbons produced
        at great depth is the perceived lack of carbon.

        The earth continuously reprocesses carbon by subduction of limestone
        at the edge of continental plates. About 25years ago Chemistry in Britain
        published an article on producing hydrocarbons on the bench.

        I no longer have access to The Royal Society, so I cannot retrieve that
        article.

        I know that you are friends with Willie Soon. Would you ask him if he
        believes that chemistry and physics is the same in the rest of the
        universe as it is on earth? It is my belief that it is.

        The great Horse Head Nebulae photographed by Hubble was analyzed
        as a high percentage Hydrocarbons. Every exoplanet’s atmosphere
        which has been analyzed is said to contain hydrocarbons.

        Logic tells me that hydrocarbons in the Horse Head Nebulae are
        not biotic. To think that they are on earth defies logic.

        It is also worth noting that The USGS has a series of papers known
        as Paper 1570 which is actually a series of papers which is very
        hard to find in regular searches. It is actually about 900 pages
        of studies about abiotic hydrocarbons produced under the surface
        of the earth, but as far as I can tell (I have not read all of it), they
        do not understand the relationship of the deep earth production
        of hydrocarbons and the way which they continuously reach the
        surface, as I have proved.

        http://dggs.alaska.gov/webpubs/usgs/p/text/p1570.pdf

        As David Middleton calls me, The Abiotic Hydrocarbon Guy
        I consider it an honour.

  4. I know that the standard explanation is that the Taiga, the “massive circumpolar boreal forest” forms the biological sink for carbon dioxide. However, when in 2008 I first saw posted graphs showing this northern hemisphere CO2 summer draw-down signal, I was intrigued. There are two hats I can wear, geoscience (professional) and bioscience (amateur) and I viewed this atmospheric response from my geoscience experience and not the standard bioscience perspective. After all, thinking outside the box is what scientists are suppose to do 

    In 2009 I decided to study this issue so I looked at CO2 data for high and low latitudes from both hemispheres, continental and oceanic locations, & high and low elevations. From inspection it is clear that there is a global pattern to these data. Consider the CO2 variation as a signal, its greatest amplitude and sharpest onset is at the highest Arctic latitudes (e.g. Barrow, Alaska), the signal propagates south through the atmosphere; Mauna Loa, Hawaii is later in time and smaller in amplitude than at Barrow, and it then reverses phase into the Southern Hemisphere, down to the South Pole which has the smallest amplitude excursion of all.

    What follows is a description of my simple scoping study to establish if there is a correlatable relationship between the atmospheric CO2 summer minima at Barrow, Alaska and the extent of the Arctic Ocean open water (ice free) area.

    Establishing the open water area of the Arctic Ocean is relatively straight forward using published sea ice data, if we accept the idea of a progressive northward zonal melt of sea ice as the boreal summer advances. My assumption that the southerly located frozen waters of the Sea of Okhotsk, Bering Sea, Hudson Bay & Baltic Seas all melt before the Arctic Ocean ice does, is of course a simplification prone to error, but one that could be corrected by using a detailed latitudinal melt history database.

    In order to determine the strength of the CO2 summer draw-down signal for Barrow we must establish the notional carbon dioxide concentration that would exist if the summer sink was inactive. The CO2 data base for Barrow extends from 1974 to 2006, by using an appropriately designed filter it is possible to preserve only the winter data and discard all the summer values. By this means the preserved winter data can be curve fitted and the equation of this curve used to establish (despite the rising annual trend) the hypothetical inactive sink summer CO2 concentration at Barrow for all of the 33 years in the record. A cross-correlation of the strength of the CO2 draw-down signal at Barrow versus the Arctic Ocean open water extent for July thru November, fitted with a simple linear trend curve, has an R squared value of 0.664.

    The amplitude of the annual Antarctic CO2 signal is small compared to the Barrow data. The South Pole CO2 record is for a high elevation continental location, when compared with the time series data for Syowa, a low elevation coastal Antarctic station, both of these CO2 data sets are coincident in amplitude and phase. The simple sinusoidal form of these data matches the phase of the annual variation in areal extent of the Southern Ocean sea ice. This phase locked match with the surrounding Southern Ocean sea ice area suggests a local geochemical cause for the austral summer CO2 draw-down, rather than a distant land-based biochemical cause for this signal.

    Questions & Comments
    1. Why, if the Arctic Ocean is the predominant cause of the Barrow CO2 signal, is the Southern Ocean signal so weak in Antarctica?
    The Arctic Ocean is a geographical feature with a defined southern coastline, whereas the Southern Ocean is unbounded in its northern latitude. The Arctic is a “ponded ocean” and occurs at higher latitude and has lower surface water salinity than the open Southern Ocean does. The key question therefore is “Does surface water salinity affect the rate of CO2 uptake by cold ocean waters?”

    2. Is it possible to determine the total mass of CO2 removed from the Arctic atmosphere by the boreal summer draw-down?
    A comparison of the Barrow sea level data with the high altitude Greenland Summit data suggests that the summer CO2 draw-down affects the full vertical extent of the Arctic atmosphere.

    The R squared correlation coefficient of 0.664, noted above, gives support to the idea that the ice free Arctic Ocean sea water acts as a CO2 sink during the northern hemisphere summer, in addition to the currently recognised land based Taiga biological sinks.

    • Phillip
      1… The Arctic Ocean has very little direct impact on the Barrow signal. The Barrow signal should be considered in combination with the annual atmospheric circulation patterns.

      2…. No. Refer to 1.

      • Martin

        The problem I have with the conventional explanation is that the amplitude of the signal increase with latitude. The question – Why does the Barrow signal have the greatest amplitude? can be answered by proximity to the source of the signal draw-down. In the case of Barrow that is the open waters in summer of the Arctic Ocean and not the Taiga. A correlation coefficient of 0.644 cannot be dismissed with an unsupported categorical no. I brought data and ideas to the table, you brought intransigence.

        • Hi Phillip
          Look at the atmospheric flow towards these high NH stations during the rise and fall phases. Also consider the height of the tropopause, the rise and fall.
          All surface sample station values are the result of what is carried to them not the immediate area around them.
          Greg from climategrog produced a chart using and overlaying Barrow CO2 and Arctic sea ice area, the fit was perfect over many years. It is the wind that controls both. Look at the annual precision of all mid to high NH CO2 profiles.

          On Judith Currie’s site in the comments section I have produced exacting evidence for both Arctic and Antarctic sea ice area movements that exactly coincide with hurricane formation and acceleration.

          “Atmospheric entanglement” …. No-one knows how to study it, but it is a treasure trove of understanding and provides profound clarity. The vast majority of articles on wuwt, climate etc are of single subject, such as the head post.
          Regards
          Martin

          • Thanks for the reminder Martin. I think this is what you are referring to:

            https://climategrog.wordpress.com/co2_nh_ice_area_2001/

            It was Alert, Canada I used actually but in essence you are correct. Looking at the way the inter-annual variations in the depths of the troughs seems to indicate a direct relationship, rather than just a general correlation of two independent annual cycles which convenient scaling.

          • Greg,
            Congratulations, that is really neat work.

            I interpret your graph in the following way:
            The process we observe is the action of a mechanical valve that throttles an active gas draw-down system.
            Note in particular the asymmetry of the process (slow onset versus rapid collapse).
            1. The build-up of ice in the fall slowly shuts down the gas dissolution into the Arctic waters as the ice extent grows.
            2. During the winter, with the ocean ice carapace complete, the atmospheric gas concentration rises.
            3. In the spring the ice cracks and the open water polynya allow rapid gas draw down into the suddenly opened waters.

            Add to this the biological component of the story (the delta C13 objection). In the spring the high light levels set the phytoplankton going before the ice has cracked. On carapace failure and ice melting the surface low saline ocean water rapidly takes up the excess CO2 from the atmosphere and delivers it to the biological system.
            In summary- Summer light equals biology. Winter dark equals mechanics.
            Please publish your work.

          • Phillip
            The natural atmospheric actions cause a mechanical reaction at regular and various times. The signature is seen, recorded in its effect from pole to pole. I have studied every year in detail for the satellite era. Stay away from mean or average data, the signatures can only be seen in the raw individual data. For every action there is a reaction, air is a fluid with long ranging energy transfer.
            The O’Connell’s tried to explain it in their radiosonde study. In my opinion they tarnished their great work with a poor description of atmospheric energy transfer.
            Go to the Chartic.com site and look at the undulating maximum Arctic and Antarctic sea ice extent over the peak three months. It is the wind. Then look at Barrow and Alert and other high latitude CO2 values, same trend, scolluped.
            The science is not settled, they don’t even know enough to comprehend that they don’t know enough.
            With regards
            Martin

          • Greg,
            Interesting plot of CO2 and sea ice extent at Alert, Canada. A couple of questions/thoughts. First, I didn’t realize there was much debate on the CO2 seasonal cycles being influenced by the terrestrial versus ocean. I was under the impression that the delta C13 was well understood. Thanks Fred for your explanation below. Is there another isotope such as delta C14 that might help distinguish between ocean versus terrestrial influences on the seasonal CO2 fluctuations.

            Secondly, how fast does gas diffuse into water. Isn’t that a slower process than terrestrial photosynthesis and respiration. Correlation isn’t necessarily causation.

          • “First, I didn’t realize there was much debate on the CO2 seasonal cycles being influenced by the terrestrial versus ocean.”
            Renee,
            I assume that you mean terrestrial biology versus ocean physics?

            The whole history of climate science shows that it is a political movement rather than a scientific endeavour. In the early days it was clear to me as an environmental scientist that the proponents of the dangerous carbon dioxide emissions theory had no geological knowledge or expertise.
            For example, it was assumed that the combustion of fossil fuels was the only source of anthropogenic CO2. The failure to realise that limestone is a chemical feed for the iron smelting process and also for the production of cement, and that both of these chemical processes release mineral rock sourced CO2 into the atmosphere was a glaring error in their story.
            The next error was the assumption that the only mechanism that removes CO2 from the atmosphere and sequesters carbon is biological. Biology creates reduced carbon compounds, sugars, cellulose etc. However, the sequestration of oxidised carbon in the form of mineral carbonates was at first ignored and then on correction also assumed to be a purely biological process. The inorganic precipitation of mineral carbonates from seawater in the form of oolites and mineral cements, a significant geological process, was ignored.
            Then we have the joke issue of ocean acidification, this in a buffered solution of calcium and magnesium metal ions? You get the picture, geochemical ignorance writ large.
            So, when Greg and Fred present evidence of marine processes as part of the story their analysis needs to be assessed in the light of science and not that of the agenda of a poisonous political cabal.

  5. Apples and Ocelots, there is no confidence that Antarctic cores aren’t losing most of their CO2 due to atmospheric electrostatics, there’s no melt there just compression where-as Greenland constantly has melts as well as compression.

    It is impossible to compare the two, not even Mann could fabricate a relation.

    • Prjindigo,
      Antarctic ice core gas data are routinely used as proxies for past CO2 concentrations via Scripps and NOAA and as an analog to present day global CO2 concentrations. CO2 tends to be synchronous with Antarctic temperatures as it was measured in Antarctic cores which provides confidence in its preservation in ice cores. However, Antarctic ice core CO2 is out of phase with Arctic temperatures suggesting minimal relationship with Arctic climatic conditions.
      https://imgur.com/a/bJfBZ3z

      It is difficult to compare the Present day elevated CO2 records to the past since CO2 data from the Northern Hemisphere during the Holocene has been discredited. The scant Greenland CO2 data that is available shows CO2 is more variable than Antarctic CO2 and as high as 400+ ppm in the Holocene. Despite being routinely used in climate research, Antarctic CO2 is probably not representative of global and/or Arctic CO2 trends. So, don’t ignore the high resolution CO2 series in the Arctic and use the most mundane suppressed Antarctic CO2 data as a past indicator. But I guess scientists could ignore both of them as you suggest.

  6. Excellent article.

    A note:
    Ice cores assume precipitation CONSTANTLY accumulates as ice. That being the case, we come to a strange conclusion: There was no polar ice at all a ~million years ago – because there is no ice core record before that.

    Someone, please explain the ramifications of this. Thanks.

    • Let’s start by immediately dispelling the myth that the oldest polar ice is only about 1 million years old, using a an announcement from three years ago:
      “Scientists announced today that a core drilled in Antarctica has yielded 2.7-million-year-old ice, an astonishing find 1.7 million years older than the previous record-holder.” Ref: https://www.sciencemag.org/news/2017/08/record-shattering-27-million-year-old-ice-core-reveals-start-ice-ages.

      This dating has not been discredited, with additional reporting of some very interesting data obtained from this old ice, as recently at October 30, 2019: “Today, more than 2 years after presenting the discovery of the world’s oldest ice core, scientists have published an analysis of the 2.7-million-year-old sample. One surprising finding: Air bubbles from 1.5 million years ago—from a time before the planet’s ice age cycles suddenly doubled in length—contain lower than expected levels of carbon dioxide (CO2), a possible clue to the shift in the ice age cycle.” Ref:
      https://www.sciencemag.org/news/2019/10/world-s-oldest-ice-core-could-solve-mystery-flipped-ice-age-cycles

      As to why there is no ice that dates back to, say, 10 million years ago, I suspect that geothermal energy in the rock underlying both the Greenland ice sheet and the Antarctic polar cap progressively melts the ice that at this rock/ice interface and the liquid water slowly drains away at the edges of the ice sheets, with the ice overburden pressure slowly but continuously forcing younger ice down to this interface.

      In any event, there is no possibility of finding any ice older than about 30 millions years because this around the time Earth exited the last of the completely ice-free global climate periods known as “greenhouse” or “hothouse” Earth conditions.

      • The article says …

        “To reach further back in time, a team of scientists targeted so-called “blue ice” near Antarctica’s surface in the Allan Hills. Here, ancient ice flows have exhumed the oldest ice from the deep. Old ice layers are driven up from below, while wind strips away snow and younger ice.”

        So this profile is completely different from before. And we know the age of the top ice how exactly? Assumption = Conclusion?

        “I suspect that geothermal energy in the rock underlying both the Greenland ice sheet and the Antarctic polar cap progressively melts the ice that at this rock/ice interface”

        Could random periods of geothermal warming completely wipe away our aging ability?

        Let’s say there was a big melt 1200 to 1100 years ago. There is no ice accumulation, and an actual melt. Dating is now all wrong.

        Maybe we have 100 million years of ice, but we think its 1 million because all the melts are missing from history. Something to think about.

        • Zoe Phin asked: “So this profile is completely different from before. And we know the age of the top ice how exactly? Assumption = Conclusion?”

          Zoe, if you would have bothered to read . . . perhaps more importantly, understand what you read . . . you would have understood this statement in the second linked article: “. . . and Michael Bender, a geochemist at Princeton University, developed a way to date chunks of ice directly from trace amounts of argon and potassium gases they contain.”

          Zoe also asked: “Could random periods of geothermal warming completely wipe away our aging ability? Let’s say there was a big melt 1200 to 1100 years ago. There is no ice accumulation, and an actual melt. Dating is now all wrong.”

          Paleoclimatology science would clearly reveal if all the ice on Greenland or the Antarctic continent had melted within the last 20 million years or so. There was most certainly no “big melt” 1200 to 1100 years ago . . . that is well within the period of recorded human history. And finally, dating by C14 radioisotope analysis is good to about 50,000 years ago, and other radioisotopes and radioisotope ratios can provide fairly accurate dating much further back in time. “For example, the age of the Amitsoq gneisses from western Greenland was determined to be 3.60 ± 0.05 Ga (billion years ago) using uranium–lead dating and 3.56 ± 0.10 Ga (billion years ago) using lead–lead dating, results that are consistent with each other.” — source: https://en.wikipedia.org/wiki/Radiometric_dating. And in case you need to know, historical temperature exposures (your “random periods of geothermal warming”) have no impact on the accuracy of radioisotope dating.

        • “date chunks of ice directly from trace amounts of argon and potassium gases they contain.”

          Funny how that is not done for every layer of typical ice cores – just this top blue ice.

          And of course radiometric dating makes an absurd assumption about supernova sprinkling Earth one time, and one time only. Even though these isotopes can also be generated by strong lightning.

          • Sorry, Zoe, it’s no longer worth my time replying to sophomoric misunderstandings of basic science.

            I tried.

          • Funny, Gordon.
            I’m more than familiar with your “basic science”, but I’m also smart enough to question whether it’s just sticky dogma.

  7. Renee
    Nice article, thank you.
    The problem that you are facing is that there has been no comprehensive credible explanation of the annual CO2 cycle based on the global sample stations. Firstly they are surface stations with Mauna Loa being one of the highest altitude. Trying to draw a conclusion from the near surface layer, without any discussion or consideration to annual atmospheric circulation patterns is impossible.

    The reality is that the entire vertical column up to and beyond the 100km level must be considered. Isn’t there a problem with increased drag on satellites due to increased CO2? Look at the 50ppm variation annually at 90 to 100km.

    The level of CO2 at Barrow increases by 15ppm in autumn and only 5ppm over the three months of winter when human and biosphere are at the highest outputs. Some years the chart is near flat over that winter period. Why = atmospheric flow variation from the landmass.
    Regards

    • Martin,
      It is interesting that CO2 levels are consistent between Mauna Loa at 3,400 meter and Cape Kumukahi at only 7 meter height also on Hawaii. For land stations, latitude is more important, height provides some delay and averaging of seasonal amplitudes.

      The level of CO2 in the Arctic increases by 15 ppm in autumn as trees begin respiration and drop their foliage. The biosphere is dormant over the winter period and no longer photosynthesizing CO2. https://science.sciencemag.org/content/341/6150/1085.full

      • Renee
        Much of the air reaching the Mauna Loa station has its origin at the ocean surface and reaches the station by orographic uplift. However, these data are usually deleted based on the assumption that it has been depleted of CO2 from vegetation on the flanks of the mountain. So, what the Keeling Curve is really measuring is the CO2-maximum (excluding the volcanic emissions) as though vegetation isn’t a part of the Carbon Cycle and therefore air parcels downwind of the volcano — moving eastward — supposedly always have the higher CO2 concentrations. It seems to me that the data processing, while smoothing the data, biases it upwards from the true representative concentrations, and may be hiding some information.

        Barrow doesn’t have these issues, but I have reservations about human influence because of the proximity to the airport and village.

        • Clyde,
          Thanks for the comments on the Mauna Loa station. The CO2 annual amplitude swings are only a third of Barrow suggestive of a more oceanic influence and less terrestrial. Perhaps in the early 1990s so much attention was focused on Mauna Loa CO2 readings, that large CO2 fluctuations in the Arctic were not widely accepted to explain the CO2 variance in the Greenland ice cores.

          Compared to Barrow, other Arctic observatories also demonstrate similar annual CO2 fluctuations. These include Summit SUM, Finland PAL, Norway ZEP and Russia TIK.
          https://imgur.com/a/BhFTwRi

  8. Renee
    The annual variation in high northern hemisphere CO2 values has and will always occur. The Antarctica record as discussed, has and always will be one of minor variation. The historic record that you have provided should be included in the total discussion.

    The problem is not that the historic Greenland data is questionable, it is the so called scientific mind that opposes its inclusion is questionable. This is why the scientific discussion does not progress or develop on this and many more climate related matters.
    Five years I have watched the CO2 discussion, it’s like ground hog day.
    Regards
    Martin

  9. Did I miss measurements of oxygen isotopes in the trapped H2O2? Is there not potentail for a story there?
    Geoff S

      • Hi Renee,
        The information content of oxygen isotopes is not a topic I have thought through. Can you think of any reasons that might make research useless? Geoff S

        • Geoff,
          I think there’s a great research project on H2O2, H2O2 isotopes, why there is a strong anti-correlation between CO2 and H2O2, and the relationship to temperature and/or oxygen isotopes of precipitation.

          Are you thinking of putting together a proposal?

  10. So-called “polar amplification” had to be rebranded Arctic amplification because Antarctic is far more stable.

    Maybe the reason Greenland CO2 is more variable because the climate is more variable. Naturally.

    • Greg,
      Arctic amplification it is indeed. Greenland CO2 variability appears to be more related to the Arctic climate and past temperatures. Just like Antarctic ice core CO2 is fairly stable and tends to be more synchronized with stable Antarctic temperatures.

      During past abrupt events such as the D-O events, Arctic temperature fluctuations were much more pronounced than Antarctic. And so were Greenland CO2 excursions.
      https://imgur.com/a/fm5Zb1H

      • The Arctic is the weak pole, the Antarctic is a magnitude more resilient. Both are heavily influenced by the volume of tropical / low latitude convection. There is a clear Ying yang relationship.

  11. “CO2 surplus in the samples show short-term variations from 15-25 ppm within annual layers younger than 2700 years BP.” That’s comparable with the diurnal variation, at least here at 19°S. The OCO2 results for 2014-5 show the substantial annual CO2 flux in the NH, not so much in the SH. Very little evidence of the bad people spewing CO2 into the atmosphere, which presumably explains why no more results published after that.
    It’s called the Carbon Cycle.

    • Hans,
      I didn’t see any discussion of sulfate emissions in your link. Perhaps in an earlier post by Ferdinand discusses the different chemistry between Greenland and Antarctic ice cores. I would very much appreciate Ferdinand’s opinion and feedback.

      Yes, Greenland ice cores do have higher levels of sulfate and calcium than Antarctic ice cores. The higher levels of calcium (carbonate) in Greenland ice were the main reason for the theory of higher CO2 readings due to a carbonate-acidity chemical reaction.

        • Zoe,
          Ferdinand in his link above makes some excellent points.

          Measurements of air in the firn confirm the link of ice core air with the atmosphere. There is a significant overlap of results from three independent ice cores and the modern atmospheric record. This and other results confirm the CO2 mixing ratio of the ice air is representative of the atmosphere. http://www.acoustics.washington.edu/fis437/resources/Week%2010/Etheridge%20et%20al.%201996.pdf

          I do agree with Jaworowski on the editing and rejection of CO2 and methane ice gas samples. There are a large amount of rejected samples in Antarctic ice cores. Some are valid due to obvious contamination or cracks. Most disregarded ice gas samples are because they fall outside a deviation from a spline fit. And of course, I disagree with the fact that entire Greenland ice core CO2 data is rejected.
          https://imgur.com/a/fbX8IjM
          https://epic.awi.de/id/eprint/45035/1/koehler2017essd.pdf

          • “There is a significant overlap of results from three independent ice cores and the modern atmospheric record.”

            Jaworowski shows more than 3 studies. He also highlights differences between wet and dry methods of extraction.

            Can you be sure these 3 studies are not collusion or ideollgical agreement between 3 reasearch teams and their highly edited datasets?

            “Measurements of air in the firn confirm the link of ice core air with the atmosphere.”

            I’m sure that is mostly true for the top of the ice.

          • Zoe,
            Jaworowski has so many claims, hard to know where to start. Here’s a reference addressing the wet and dry extraction methods.
            T. GüllükF. SlemrB. Stauffer, “Simultaneous measurements of CO2, CH4, and N2O in air extracted by sublimation from Antarctica ice cores: Confirmation of the data obtained using other extraction techniques”, Journal of Geophysical Research: Atmospheres (1984–2012)l Volume 103, Issue D13, pages 15971–15978, 20 July 1998

          • Thank You, Renee.

            The word “wet” appears one time and is not referring to a method.

            This paper compares a sublimation method to the dry method. They are in agreement – but this doesn’t change the fact that both underestimate CO2 compared to the wet method.

            Am I wrong?

      • Negative Renee. Limitations of the ice core record were disputed, but never refuted.

        As is typical of reconstructions (‘artificial atmospheric data’), what ice core records do or don’t represent can never be established, owing to major uncertainties that cannot be quantified. Those uncertainties yield an endless game of tail chasing: One reconstruction differs from another – not necessarily because of differences in the atmosphere but because of different yet largely undocumented factors that have influenced the extracted ice and how that artificial data is then interpreted. Stereotypical is the arbitrary fudge in the age of air that was invoked to force agreement/overlap with actual measurements of atmospheric CO2.

        Establishing how much CO2 was actually in the atmosphere can be achieved only with ‘real atmospheric data’.

  12. The big sink in the North for CO2 is the open cold water of the of the Arctic ocean. The area that is open changes drastically each year (check sea ice concentration north of 70 degrees). When the ice freezes in winter, the CO2 being delivered from the tropics, builds up. When the ice melts in summer, all that buildup is absorbed by the cold water as well as being consumed by phytoplankton blooms. I get an r^2 of 0.994 with a multi-linear regression on sea ice concentration and estimated natural emissions.

    • Fred,
      “I get an r^2 of 0.994 with a multi-linear regression on sea ice concentration and estimated natural emissions.”
      Nice work.
      That’s a slam dunk number.
      Please publish.

    • Fred and Phillip,
      In Barrow, large differences in carbon dioxide on a seasonal basis, is perfectly anticorrelated with the δ13C of carbon dioxide indicating it is controlled almost entirely by the terrestrial biosphere. When plants take up carbon dioxide, they prefer 12C over 13C. This leaves more 13C in the atmosphere, which increases the δ13C of the atmosphere. Oceanic exchange would affect total carbon dioxide but not δ13C and therefore appears to play little to no role in determining overall CO2 levels at Barrow (after NOAA.gov).
      https://imgur.com/a/hqrvOsS

      • Renee,
        The reason you find a correlation between ppm CO2 and C13/C12 ratio is by definition it is an indexed fraction of the ppm fraction. The total is the amount of organic depleted fraction plus the inorganic fraction. The value is indexed to actual ratio by assigning a value of zero (0) to the inorganic fraction Ppm can be express as amount in kg/m^2 at one atmosphere by multiplying by 44/28.8/1000000*10.197*1013. The total amount (T) equals the organic amount (O) plus the inorganic amount (I). Knowing this we can calculate the amounts of the organic fraction and inorganic fraction.
        The relationship is T*m= O*o+I*i at any one point in time. The value for m is the measured atmospheric indexed value. The values for i is zero and the value for o can change with time. The value for O also changes with time.
        Scripps columns 9 and 10 show how these changes occur seasonally and from year to year. The year to year rate of change is not affected by latitude (the column 10 curves for all nine sites are not statistically different). Based on that data I calculate a value around -13 for o that has not changed significantly and the amount of O has steadily increased over the last 40 years.

        Another factor to consider is there is a whole lot more seasonally dependent biological activity in the Arctic ocean than there is in northern forest.

      • Renee,
        You said, “Oceanic exchange would affect total carbon dioxide but not δ13C and therefore appears to play little to no role in determining overall CO2 levels at Barrow (after NOAA.gov).” If I understand what you are saying, then I think it is wrong. Phase changes in water will tend to concentrate the lighter carbon isotopes in the atmosphere. That is, any sublimation of ice will lose C12 in greater proportion to C13, enriching the atmosphere in C12. If all the ice doesn’t sublimate, but ends up melting, then the C13 enriched ice will increase the relative concentration of C13 in the ocean. Similarly, any water vapor evaporating from the liquid water (such as by energy added by wind) will preferentially remove the lighter C12, thus increasing the proportion of C12 in the atmosphere.

        • Clyde
          And then there is the issue of the precipitation of carbonate ions from solution into mineral calcite.
          Remind me again.
          How do we measure the amount of C13 in the ocean water?

  13. The Arctic is the weak pole, the Antarctic is a magnitude more resilient. Both are heavily influenced by the annual volume of tropical / low latitude convection. There is a clear Ying yang relationship.

  14. Stopped reading after the half dozeteenth instance of “theory” and “theorised” where “hypothesis” and “hypothesised” should have been used.

    • jollygreen,
      “In scientific reasoning, a hypothesis is an assumption made before any research has been completed for the sake of testing. A theory on the other hand is a principle set to explain phenomena already supported by data. Theories will pull together experimental results to provide explanations.“ Merriam-Webster.com

      Since the CO2 experimental data have already been measured and collected by Tschumi and others, then theory is the proper term for explanation of the results. Thanks for pointing out, I accidentally used hypothesis in the first sentence which should have been theory.

  15. I am sorry but I’ll have to go with the consensus on this one. A lot of the figures and discussion relate to seasonal variations in CO2 and with the higher levels of CO2 in Arctic measurements and all of that misses the problem. The problem was if the large changes in CO2 levels detected in Greenland cores over decades, centuries and millennia truly represent changes in atmospheric CO2 or not.

    CO2 is a global gas, like CH4, and in both cases if over the last decade their concentration went up significantly, every record should show it. There is no way that over a period of a decade or more CO2 can go up consistently in a part of the world and not in another.

    In 1972, after analyzing the isotopic composition of ice cores from Camp Century in Greenland, Willi Dansgaard reported that the last glacial period showed over 20 abrupt interstadials marked by very intense warming (Johnsen et al. 1972). The discovery was met with indifference by a scientific community still struggling to identify Milankovitch cycles in the data. Willi had showed his discovery at a meeting in 1971 and all he got was a big yawn from the audience. That’s how the discovery of the more abrupt climate changes in the planet was received by the scientific community.

    12 years later, in 1984, Hans Oeschger reported that the abrupt temperature changes discovered by Dansgaard were associated with large changes in CO2. His article was Stauffer et al., 1984. Atmospheric CO2 Concentration During the Last Glaciation. published in the Annals of Glaciology. Just look at figure 2 of that paper (notice that the X axis is in core meters and represents 10,000 years).

    That got the attention of everybody, to the point that when talking about the abrupt climatic changes discovered by Dansgaard, everybody added the name Oeschger to them. These were the early days of the global warming frenzy, so everybody wanted the association of big changes in temperature and big changes in CO2 to be real. Willi had no choice but to share the merit of his discovery with the latecomer to the party Hans, but he did it graciously as he was a true gentleman.

    However there was a big problem for the temperature-CO2 association. The Antarctic cores did not show the changes in CO2. It is inconceivable that CO2 could go up by 60 ppm in the Arctic for a period of 1000 years and it didn’t change in Antarctica. More research showed that CH4 was behaving as a global gas and it was going up simultaneously in Greenland and Antarctica at the abrupt climatic changes of the Last Glacial Period, so much that it has been used to synchronize the Antarctic cores to the better dated Greenland ones.

    That Greenland CO2 records had been chemically altered by a process linked to the changing climate conditions was the only plausible explanation to the conundrum. The alternatives are that CO2 behaves nonphysically in the atmosphere at certain times or that the Antarctic records have a problem registering changes in CO2 over periods of millennia, but we know Antarctic records had no problem registering the CO2 changes associated to Heinrich events.

    So answering the question at the heading of your article, Greenland Ice CO2 – Chemical Reactions or Natural Variability? We have to answer that both, and the chemical reactions make the Greenland records unreliable for past changes in CO2 and that is why nobody uses them anymore. I don’t either. The consensus is not always wrong.

    • Javier,
      Thanks for your comments and interesting history of Dansgaard and Oeschger. This post is focused on short-term atmospheric CO2 variations between the Northern and Southern latitudes as as alternative theory to explain the Greenland ice CO2 higher standard deviations compared to Antarctic ice cores. During the last 2700 years Greenland’s ice CO2 standard deviations are surprising similar to present day. Also during this time, Greenland ice CO2 does not demonstrate large changes from the Antarctic ice CO2. In fact, the mean of the Greenland CO2 data is within the present day inter-hemispheric gradient of 2-5 ppm. So perhaps it is useable data and not chemically altered.

      I agree CH4 is a well mixed global gas and should be used to synchronize Greenland and Antarctic cores. CO2, of course, behaves differently than CH4. CH4 shows seasonal swings in both the Arctic and Antarctic, whereas CO2 has large seasonal fluctuations in the Arctic and practically none in the Antarctic. The inter-hemispheric CO2 gradient has been increasing since the 1970s. The inter-hemispheric gradient between Mauna Loa and South Pole has increased from 2 to 4 ppm in just 30 years. Francey, 2019, figure 9. https://acp.copernicus.org/articles/19/14741/2019/. And is an even larger increase between Barrow and South Pole.

      I agree the 50-100 ppm CO2 differences seen in the Early Holocene and during the D-O events are not easily explained. However, temperature behavior between the Arctic and Antarctic was significantly different during D-O events and even during the Arctic climate optimum. There is a temperature-CO2 association in the Antarctic ice data shown by my graph in the comments above. Why would a temperature-CO2 association not exist for the Arctic? Perhaps the true global CO2 answer lies somewhere in between.

      Some data is higher quality than others and deserves more weight. Then there’s data that doesn’t conform to consensus or prevailing theory that is disposed of in various ways. In this case, all of Greenland ice CO2 data isn’t used even though, as I’ve shown, seasonal variability can explain why it is different than the Antarctic monotone measurements.

  16. There is no way that over a period of a decade or more CO2 can go up consistently in a part of the world and not in another.

    Yes it can and it does. The southern ocean is a bigger CO2 sink vs the NH due to significant latitudinal temperature profile differences relative to the outgassing temperature threshold of 25.6C.

    r(138) = .67, p is < .00001, significant at p < .01 for 30S-45S SST and Law Dome CO2, plot#3:

    https://i.postimg.cc/gc8xBKPH/CO2-Outgassing.jpg

    Renee posted a link during her last blog post [thanks],

    “Recent hemispheric asymmetry in global ocean warming induced by climate change and internal variability” which featured the following image to which I overlaid a few items of interest:

    https://i.postimg.cc/SNxfLNTc/Rathore-etal-Fig-1-Asymmetrical-OHC-vs-SORCE-TSI-overlay.jpg

    • I made a small mistake in the first link that was corrected below: the degrees of freedom is 115, not 138, but the result remains p is < .00001, significant at p < .01.

      Thanks Renee for another thought-provoking article.

  17. I guess I didn’t explain myself properly. CO2 concentration can and does change at different rate over Greenland and Antarctica but that cannot lead to the huge disparity seen in records over D-O events. At D-O interstadials the Greenland records shows an abrupt increase of ~60 ppm that is then maintained for 1000 years or more, while the Antarctic records show no increase at all.

    This is an image of what happened in Antarctica from a paper by Ahn & Brook 2014:
    https://www.researchgate.net/publication/261997407/figure/fig1/AS:267743668731924@1440846473176/Time-evolution-of-CO2-and-Antarctic-isotope-temperature-during-Greenlandic-stadials-a.png

    It can be compared to the figure 2 from the Stauffer article linked above.

    CO2 is a gas that diffuses in air with a diffusion coefficient of 16 mm^2/s. There is absolutely no way a 60 ppm sudden increase in the difference between the poles could be maintained for 1000 years. Our emissions are concentrated mainly in the Northern Hemisphere yet the increase shows in the Antarctic records and we are only talking about 70 years. That is why no serious scientist that has looked into this problem has publicly maintained that the Greenland records are fine and can be trusted, and that is why no scientist has used them since the problem was discovered.

    I haven’t looked into the nature of the problem that produced the false elevated records at the time of the D-O events because I don’t care much about it, but for the D-O events those molecules have been there for 30-75,000 years. Is it possible that for the past 3000 years the record reflects properly the atmospheric CO2? Sure, but since we know there is a problem you would have to demonstrate first that the problem over that time period is negligible and that is not an easy task.

    • Javier,
      I understand the dilemma of 50 to 100 ppm CO2 differences between the polar regions. I have plotted up most of the Greenland CO2 data and compared it to Antarctic data, https://imgur.com/a/svxbn48 and zoom in here https://imgur.com/a/fm5Zb1H.

      The Greenland CO2 has a strong CO2-temperature relationship. Greenland ice cores have higher snow accumulation, less gas diffusion and retain higher frequency events. Antarctic ice cores, especially Dome C, have very low snow accumulation and extensive gas diffusion. Notice during many of the D-O events where Greenland gas increases significantly, Antarctic CO2 is only making a minor excursion. The CO2 in Antarctic sees the event but appears to be suppressed, gas diffusion? Greenland CO2 even sees the 8.2 kyr cooling, and Antarctic CO2 does not. Is the Greenland CO2 data conveniently chemically altered at 8.2 kyr? Which value is correct? Prevailing literature assumes Antarctic is correct. I’m not convinced.

      We can agree to disagree on this one.

      • Yes, I have no problem agreeing to disagree 🙂 I am no expert on the matter and just find the evidence quite convincing. Thus I am not trying to convince anybody, just playing devil’s advocate.

        The Greenland CO2 has a strong CO2-temperature relationship.

        That actually makes me suspicious 🙂 Few strong CO2-temp relationships in the paleorecord resist a close scrutiny. Also temperature (or more properly enthalpy), unlike CO2, shows very little diffusion and mostly relies on active transport by the oceans and the atmosphere. So even if CO2 is produced by an Arctic increase in temperature it would diffuse over the entire planet unlike the heat that can remain regional. The gas diffusion problem in Antarctic cores would have to be CO2-specific since CH4 doesn’t show any problem.

        In any case it is an interesting discussion, thanks.

          • Thanks for the reference. To me this would suggest that what affects Greenland CO2 records also affects Antarctic records only to a much lesser degree. Of course I am always open to a re-evaluation of the evidence. What is clear to me from my own analysis is that CO2 proxies, not only ice cores, but even more Boron, paleosols, stomata, and phytoplancton, are problematic, and thus we don’t have an adequate knowledge of CO2 levels in the past as to draw conclusions regarding its role in climate change.

          • Actually I believe CO2 in ice cores are direct measurements and not proxies, unlike temperatures which are proxies from oxygen isotopes.

          • They are a direct measurement of CO2 “inside the ice core at the present time”, which is a proxy for atmospheric CO2 outside the ice in the past.

            Proxies are always affected by factors that we know about and can compensate, factors that we know about but can’t compensate and therefore are assumed invariant over long periods of time or modeled, and factors that we don’t know about and we can’t even consider when calculating the error interval. Proxies are far from being the actual measurement and should always be considered tentative approximations.

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