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… 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). 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. 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 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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