Carbon-14
Carbon-14, C-14, C or radiocarbon, is a radioactive isotope of carbon with an atomic nucleus containing 6 protons and 8 neutrons. Its presence in organic matter is the basis of the radiocarbon dating method pioneered by Willard Libby and colleagues to date archaeological, geological and hydrogeological samples. Carbon-14 was discovered on February 27, 1940, by Martin Kamen and Sam Ruben at the University of California Radiation Laboratory in Berkeley, California. Its existence had been suggested by Franz Kurie in 1934.
There are three naturally occurring isotopes of carbon on Earth: carbon-12, which makes up 99% of all carbon on Earth; carbon-13, which makes up 1%; and carbon-14, which occurs in trace amounts, making up about 1.2 atoms per 10 atoms of carbon in the atmosphere. C and C are both stable; C is unstable, with half-life years, decaying into nitrogen-14 through beta decay. Pure carbon-14 would have a specific activity of 62.4 mCi/mmol, or 164.9 GBq/g. The primary natural source of carbon-14 on Earth is cosmic ray action on nitrogen in the atmosphere, and it is therefore a cosmogenic nuclide. Open-air nuclear testing between 1955 and 1980 contributed to this pool, however.
The different isotopes of carbon do not differ appreciably in their chemical properties. This resemblance is used in chemical and biological research, in a technique called carbon labeling: carbon-14 atoms can be used to replace nonradioactive carbon, in order to trace chemical and biochemical reactions involving carbon atoms from any given organic compound.
Radioactive decay and detection
Carbon-14 undergoes beta decay:By emitting an electron and an electron antineutrino, one of the neutrons in carbon-14 decays to a proton and the carbon-14 decays into the stable isotope nitrogen-14.
As usual with beta decay, almost all the decay energy is carried away by the beta particle and the neutrino. The emitted beta particles have a maximum energy of about 156 keV, while their weighted mean energy is 49 keV. These are relatively low energies; the maximum distance traveled is estimated to be 22 cm in air and 0.27 mm in body tissue. The fraction of the radiation transmitted through the dead skin layer is estimated to be 0.11. Small amounts of carbon-14 are not easily detected by typical Geiger–Müller detectors; it is estimated that G-M detectors will not normally detect contamination of less than about 100,000 decays per minute. Liquid scintillation counting is the preferred method although more recently, accelerator mass spectrometry has become the method of choice; it counts all the carbon-14 atoms in the sample and not just the few that happen to decay during the measurements; it can therefore be used with much smaller samples, and gives results much more quickly. The G-M counting efficiency is estimated to be 3%. The half-value layer in water is 0.05 mm.
Radiocarbon dating
Radiocarbon dating is a radiometric dating method that uses C to determine the age of carbonaceous materials up to about 60,000 years old. The technique was developed by Willard Libby and his colleagues in 1949 during his tenure as a professor at the University of Chicago. Libby estimated that the radioactivity of exchangeable C would be about 14 decays per minute per gram of carbon, and this is still used as the activity of the modern radiocarbon standard. In 1960, Libby was awarded the Nobel Prize in chemistry for this work.One of the frequent uses of the technique is to date organic remains from archaeological sites. Plants fix atmospheric carbon during photosynthesis, so the level of C in plants and animals when they die, roughly equals the level of C in the atmosphere at that time. However, it thereafter decreases exponentially, so the date of death or fixation can be estimated. The initial C level for the calculation can either be estimated, or else directly compared with known year-by-year data from tree-ring data up to 10,000 years ago, or else from cave deposits, back to about 45,000 years before present. A calculation or a direct comparison of carbon-14 levels in a sample, with tree ring or cave-deposit C levels of a known age, then gives the wood or animal sample age-since-formation. Radiocarbon is also used to detect disturbance in natural ecosystems; for example, in peatland landscapes, radiocarbon can indicate that carbon which was previously stored in organic soils is being released due to land clearance or climate change.
Cosmogenic nuclides are also used as proxy data to characterize cosmic particle and solar activity of the distant past.
Origin
Natural production in the atmosphere
Carbon-14 is produced in the upper troposphere and the stratosphere by thermal neutrons absorbed by nitrogen atoms. When cosmic rays enter the atmosphere, they undergo various transformations, including the production of neutrons. The resulting neutrons participate in the following n-p reaction :The highest rate of carbon-14 production takes place at altitudes of and at high geomagnetic latitudes.
The rate of C production can be modeled, yielding values of 16,400 or 18,800 atoms of per second per square meter of Earth's surface, which agrees with the global carbon budget that can be used to backtrack, but attempts to measure the production time directly in situ were not very successful. Production rates vary because of changes to the cosmic ray flux caused by the heliospheric modulation, and, of great significance, due to variations in the Earth's magnetic field. Changes in the carbon cycle however can make such effects difficult to isolate and quantify.
Occasional spikes may occur, known as Miyake events; for example, there is evidence for an unusually high production rate in AD 774–775, caused by an extreme
solar energetic particle event, the strongest such event to have occurred within the last ten millennia.
Another "extraordinarily large" C increase has been associated with a 5480 BC event, which is unlikely to be a solar energetic particle event.
The largest known Miyake event took place ca. 12350 BCE.
Carbon-14 may also be produced by lightning but in amounts negligible, globally, compared to cosmic ray production. Local effects of cloud-ground discharge through sample residues are unclear, but possibly significant.
Other carbon-14 sources
Carbon-14 can also be produced by other neutron reactions, including in particular CC and OC with thermal neutrons, and NC and OC with fast neutrons. The most notable routes for C production by thermal neutron irradiation of targets are summarized in the table.Another source of carbon-14 is cluster decay branches from traces of naturally occurring isotopes of radium, though this decay mode has a branching ratio on the order of relative to alpha decay, so radiogenic carbon-14 is extremely rare.
| Parent isotope | Natural abundance, % | Cross section for thermal neutron capture, b | Reaction |
| N | 99.634 | 1.81 | NC |
| C | 1.103 | 0.0009 | CC |
| O | 0.0383 | 0.235 | OC |
Formation during nuclear tests
The above-ground nuclear tests that occurred in several countries in 1955-1980 dramatically increased the amount of C in the atmosphere and subsequently the biosphere; after the tests ended, the atmospheric concentration of the isotope began to decrease, as radioactive CO was fixed into plant and animal tissue, and dissolved in the oceans.One side-effect of the change in atmospheric C is that this has enabled some options for determining the birth year of an individual, in particular, the amount of C in tooth enamel, or the carbon-14 concentration in the lens of the eye.
In 2019, Scientific American reported that carbon-14 from nuclear testing has been found in animals from one of the most inaccessible regions on Earth, the Mariana Trench in the Pacific Ocean.
The concentration of C in atmospheric CO, reported as the C/C ratio with respect to a standard, has declined to levels similar to those prior to the above-ground nuclear tests of the 1950s and 1960s. Though the extra C generated by those nuclear tests has not disappeared from the atmosphere, oceans and biosphere, it is diluted due to the Suess effect.
Emissions from nuclear power plants
Carbon-14 is produced in coolant at boiling water reactors and pressurized water reactors. It is typically released into the air in the form of carbon dioxide at BWRs, and methane at PWRs. Best practice for nuclear power plant operator management of carbon-14 includes releasing it at night, when plants are not photosynthesizing. Carbon-14 is also generated inside nuclear fuels, and if the spent fuel is sent to nuclear reprocessing then the C is released, for example as CO during PUREX.Occurrence
Dispersion in the environment
After production in the upper atmosphere, the carbon-14 reacts rapidly to form mostly CO, which subsequently oxidizes at a slower rate to form, radioactive carbon dioxide. The gas mixes rapidly and becomes evenly distributed throughout the atmosphere. Carbon dioxide also dissolves in water and thus permeates the oceans, but at a slower rate. The atmospheric half-life for removal of has been estimated at roughly 12 to 16 years in the Northern Hemisphere. The transfer between the ocean shallow layer and the large reservoir of bicarbonates in the ocean depths occurs at a limited rate.In 2009 the activity of was 238 Bq per kg carbon of fresh terrestrial biomatter, close to the values before atmospheric nuclear testing.
Total inventory
The inventory of carbon-14 in Earth's biosphere is about 300 megacuries, of which most is in the oceans.The following inventory of carbon-14 has been given:
- Global inventory: ~8500 PBq
- * Atmosphere: 140 PBq
- * Terrestrial materials: the balance
- From nuclear testing : 220 PBq