Radiocarbon dating (also referred to as carbon dating or carbon-14 dating) is a method for determining the age of an object containing organic material by using the properties of radiocarbon, a radioactive isotope of carbon.
The method was developed in the late 1940s at the University of Chicago by Willard Libby, who received the Nobel Prize in Chemistry for his work in 1960. It is based on the fact that radiocarbon (14
C) is constantly being created in the atmosphere by the interaction of cosmic rays with atmospheric nitrogen. The resulting 14
C combines with atmospheric oxygen to form radioactive carbon dioxide, which is incorporated into plants by photosynthesis; animals then acquire 14
C by eating the plants. When the animal or plant dies, it stops exchanging carbon with its environment, and thereafter the amount of 14
C it contains begins to decrease as the 14
C undergoes radioactive decay. Measuring the amount of 14
C in a sample from a dead plant or animal, such as a piece of wood or a fragment of bone, provides information that can be used to calculate when the animal or plant died. The older a sample is, the less 14
C there is to be detected, and because the half-life of 14
C (the period of time after which half of a given sample will have decayed) is about 5,730 years, the oldest dates that can be reliably measured by this process date to approximately 50,000 years ago, although special preparation methods occasionally make accurate analysis of older samples possible.
Research has been ongoing since the 1960s to determine what the proportion of 14
C in the atmosphere has been over the past fifty thousand years. The resulting data, in the form of a calibration curve, is now used to convert a given measurement of radiocarbon in a sample into an estimate of the sample's calendar age. Other corrections must be made to account for the proportion of 14
C in different types of organisms (fractionation), and the varying levels of 14
C throughout the biosphere (reservoir effects). Additional complications come from the burning of fossil fuels such as coal and oil, and from the above-ground nuclear tests done in the 1950s and 1960s. Because the time it takes to convert biological materials to fossil fuels is substantially longer than the time it takes for its 14
C to decay below detectable levels, fossil fuels contain almost no 14
C. As a result, beginning in the late 19th century, there was a noticeable drop in the proportion of 14
C as the carbon dioxide generated from burning fossil fuels began to accumlate in the atmosphere. Conversely, nuclear testing increased the amount of 14
The method was developed in the late 1940s at the University of Chicago by Willard Libby, who received the Nobel Prize in Chemistry for his work in 1960. It is based on the fact that radiocarbon (14
C) is constantly being created in the atmosphere by the interaction of cosmic rays with atmospheric nitrogen. The resulting 14
C combines with atmospheric oxygen to form radioactive carbon dioxide, which is incorporated into plants by photosynthesis; animals then acquire 14
C by eating the plants. When the animal or plant dies, it stops exchanging carbon with its environment, and thereafter the amount of 14
C it contains begins to decrease as the 14
C undergoes radioactive decay. Measuring the amount of 14
C in a sample from a dead plant or animal, such as a piece of wood or a fragment of bone, provides information that can be used to calculate when the animal or plant died. The older a sample is, the less 14
C there is to be detected, and because the half-life of 14
C (the period of time after which half of a given sample will have decayed) is about 5,730 years, the oldest dates that can be reliably measured by this process date to approximately 50,000 years ago, although special preparation methods occasionally make accurate analysis of older samples possible.
Research has been ongoing since the 1960s to determine what the proportion of 14
C in the atmosphere has been over the past fifty thousand years. The resulting data, in the form of a calibration curve, is now used to convert a given measurement of radiocarbon in a sample into an estimate of the sample's calendar age. Other corrections must be made to account for the proportion of 14
C in different types of organisms (fractionation), and the varying levels of 14
C throughout the biosphere (reservoir effects). Additional complications come from the burning of fossil fuels such as coal and oil, and from the above-ground nuclear tests done in the 1950s and 1960s. Because the time it takes to convert biological materials to fossil fuels is substantially longer than the time it takes for its 14
C to decay below detectable levels, fossil fuels contain almost no 14
C. As a result, beginning in the late 19th century, there was a noticeable drop in the proportion of 14
C as the carbon dioxide generated from burning fossil fuels began to accumlate in the atmosphere. Conversely, nuclear testing increased the amount of 14
C in the atmosphere, which reached a maximum in about 1965 of almost double the amount present in the atmosphere prior to nuclear testing.
Measurement of radiocarbon was originally done by beta-counting devices, which counted the amount of beta radiation emitted by decaying 14
C atoms in a sample. More recently, accelerator mass spectrometry has become the method of choice; it counts all the 14
C 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 (as small as individual plant seeds), and gives results much more quickly. The development of radiocarbon dating has had a profound impact on archaeology. In addition to permitting more accurate dating within archaeological sites than previous methods, it allows comparison of dates of events across great distances. Histories of archaeology often refer to its impact as the "radiocarbon revolution". Radiocarbon dating has allowed key transitions in prehistory to be dated, such as the end of the last ice age, and the beginning of the Neolithic and Bronze Age in different regions.
In 1939, Martin Kamen and Samuel Ruben of the Radiation Laboratory at Berkeley began experiments to determine if any of the elements common in organic matter had isotopes with half-lives long enough to be of value in biomedical research. They synthesized 14
C using the laboratory's cyclotron accelerator and soon discovered that the atom's half-life was far longer than had been previously thought.[1] This was followed by a prediction by Serge A. Korff, then employed at the Franklin Institute in Philadelphia, that the interaction of thermal neutrons with 14
N in the upper atmosphere would create 14
C.[note 1][3][4] It had previously been thought that 14
C would be more likely to be created by deuterons interacting with 13
C.[1] At some time during World War II, Willard Libby, who was then at Berkeley, learned of Korff's research and conceived the idea that it might be possible to use radiocarbon for dating.[3][4]
In 1945, Libby moved to the University of Chicago where he began his work on radiocarbon dating. He published a paper in 1946 in which he proposed that the carbon in living matter might include 14
C as well as non-radioactive carbon.[5][6] Libby and several collaborators proceeded to experiment with methane collected from sewage works in Baltimore, and after isotopically enriching their samples they were able to demonstrate that they contained 14
C. By contrast, methane created from petroleum showed no radiocarbon activity because of its age. The results were summarized in a paper in Science in 1947, in which the authors commented that their results implied it would be possible to date materials containing carbon of organic origin.[5][7]
Libby and James Arnold proceeded to test the radiocarbon dating theory by analyzing samples with known ages. For example, two samples taken from the tombs of two Egyptian kings, Zoser and Sneferu, independently dated to 2625 BC plus or minus 75 years, were dated by radiocarbon measurement to an average of 2800 BC plus or minus 250 years. These results were published in Science in December 1949.[8][9][note 2] Within 11 years of their announcement, more than 20 radiocarbon dating laboratories had been set up worldwide.[11] In 1960, Libby was awarded the Nobel Prize in Chemistry for this work.[5]
In nature, carbon exists as two stable, nonradioactive isotopes: carbon-12 (12
C), and carbon-13 (13
C), and a radioactive isotope, carbon-14 (14
C), also known as "radiocarbon". The half-life of 14
C (the time it takes for half of a given amount of 14
C to decay) is about 5,730 years, so its concentration in the atmosphere might be expected to decrease over thousands of years, but 14
University of Chicago where he began his work on radiocarbon dating. He published a paper in 1946 in which he proposed that the carbon in living matter might include 14
C as well as non-radioactive carbon.[5][6] Libby and several collaborators proceeded to experiment with methane collected from sewage works in Baltimore, and after isotopically enriching their samples they were able to demonstrate that they contained 14
C. By contrast, methane created from petroleum showed no radiocarbon activity because of its age. The results were summarized in a paper in Science in 1947, in which the authors commented that their results implied it would be possible to date materials containing carbon of organic origin.[5][7]
Libby and James Arnold proceeded to test the radiocarbon dating theory by analyzing samples with known ages. For example, two samples taken from the tombs of two Egyptian kings, Zoser and Sneferu, independently dated to 2625 BC plus or minus 75 years, were dated by radiocarbon measurement to an average of 2800 BC plus or minus 250 years. These results were published in Science in December 1949.[8][9][note 2] Within 11 years of their announcement, more than 20 radiocarbon dating laboratories had been set up worldwide.[11] In 1960, Libby was awarded the Nobel Prize in Chemistry for this work.[5]
In nature, carbon exists as two stable, nonradioactive isotopes: carbon-12 (12
C), and carbon-13 (13
C), and a radioactive isotope, carbon-14 (14
C), also known as "radiocarbon". The half-life of 14
C (the time it takes for half of a given amount of 14
C to decay) is about 5,730 years, so its concentration in the atmosphere might be expected to decrease over thousands of years, but 14
C is constantly being produced in the lower stratosphere and upper troposphere, primarily by galactic cosmic rays, and to a lesser degree by solar cosmic rays.[5][12] These cosmic rays generate neutrons as they travel through the atmosphere which can strike nitrogen-14 (14
N) atoms and turn them into 14
C.[5] The following nuclear reaction is the main pathway by which 14
C is created:
Once produced, the 14
C quickly combines with the oxygen in the atmosphere to form first carbon monoxide (CO),[14] and ultimately carbon dioxide (CO
2).[15]
Carbon dioxide produced in this way diffuses in the atmosphere, is dissolved in the ocean, and is taken up by plants via photosynthesis. Animals eat the plants, and ultimately the radiocarbon is distributed throughout the biosphere. The ratio of 14
C to 12
C is approximately 1.25 parts of 14
C to 1012 parts of 12
C.[16] In addition, about 1% of the carbon atoms are of the stable isotope 13
C.[5]
The equation for the radioactive decay of 14
C is:[17]
By emitting a beta particle (an electron, e−) and an electron antineutrino (
ν
e), one of the neutrons in the 14
C nucleus changes to a proton and the 14
C nucleus reverts to the stable (non-radioactive) isotope 14
N.[18]
During its life, a plant or animal is in equilibrium with its surroundings by exchanging carbon either with the atmosphere or through its diet. It will, therefore, have the same proportion of 14
C as the atmosphere, or in the case of marine animals or plants, with the ocean. Once it dies, it ceases to acquire 14
C, but the 14
C within its biological material at that time will continue to decay, and so the ratio of 14
C to 12
C in its remains will gradually decrease. Because 14
C as the atmosphere, or in the case of marine animals or plants, with the ocean. Once it dies, it ceases to acquire 14
C, but the 14
C within its biological material at that time will continue to decay, and so the ratio of 14
C to 12
C in its remains will gradually decrease. Because 14
C decays at a known rate, the proportion of radiocarbon can be used to determine how long it has been since a given sample stopped exchanging carbon – the older the sample, the less 14
C will be left.[16]
The equation governing the decay of a radioactive isotope is:[5]
where N0 is the number of atoms of the isotope in the original sample (at time t = 0, when the organism from which the sample was taken died), and N is the number of atoms left after time t.[5] λ is a constant that depends on the particular isotope; for a given isotope it is equal to the reciprocal of the mean-life – i.e. the average or expected time a given atom will survive before undergoing radioactive decay.[5] The mean-life, denoted by τ, of 14
C is 8,267 years,[note 4] so the equation above can be rewritten as:[20]
The half-life of a radioactive isotope (usually denoted by t1/2) is a more familiar concept than the mean-life, so although the equations above are expressed in terms of the mean-life, it is more usual to quote the value of 14
C's half-life than its mean-life. The currently accepted value for the half-life of 14
C is 5,730 ± 40 years.[5] This means that after 5,730 years, only half of the initial 14
C's half-life than its mean-life. The currently accepted value for the half-life of 14
C is 5,730 ± 40 years.[5] This means that after 5,730 years, only half of the initial 14
C will remain; a quarter will remain after 11,460 years; an eighth after 17,190 years; and so on.
The above calculations make several assumptions, such as that the level of 14
C in the atmosphere has remained constant over time.[5] In fact, the level of 14
C in the atmosphere has varied significantly and as a result, the values provided by the equation above have to be corrected by using data from other sources.[21] This is done by calibration curves (discussed below), which convert a measurement of 14
C in a sample into an estimated calendar age. The calculations involve several steps and include an intermediate value called the "radiocarbon age", which is the age in "radiocarbon years" of the sample: an age quoted in radiocarbon years means that no calibration curve has been used − the calculations for radiocarbon years assume that the atmospheric 14
C/12
C ratio has not changed over time.[22][23]
Calculating radiocarbon ages also requires the value of the half-life for 14
C. In Libby's 1949 paper he used a value of 5720 ± 47 years, based on research by Engelkemeir et al.[24] This was remarkably close to the modern value, but shortly afterwards the accepted value was revised to 5568 ± 30 years,[25] and this value was in use for more than a decade. It was revised again in the early 1960s to 5,730 ± 40 years,[26][27] which meant that many calculated dates in papers published prior to this were incorrect (the error in the half-life is about 3%).[note 5] For consistency with these early papers, it was agreed at the 1962 Radiocarbon Conference in Cambridge (UK) to use the "Libby half-life" of 5568 years. Radiocarbon ages are still calculated using this half-life, and are known as "Conventional Radiocarbon Age". Since the calibration curve (IntCal) also reports past atmospheric 14
C concentration using this conventional age, any conventional ages calibrated against the IntCal curve will produce a correct calibrated age. When a date is quoted, the reader should be aware that if it is an uncalibrated date (a term used for dates given in radiocarbon years) it may differ substantially from the best estimate of the actual calendar date, both because it uses the wrong value for the half-life of 14
C, and because no correction (calibration) has been applied for the historical variation of 14
C in the atmosphere over time.[22][23][29][note 6]
Carbon is distributed throughout the atmosphere, the biosphere, and the oceans; these are referred to collectively as the carbon exchange reservoir,[32] and each component is also referred to individually as a carbon exchange reservoir. The different elements of the carbon exchange reservoir vary in how much carbon they store, and in how long it takes for the 14
C generated by cosmic rays to fully mix with them. This affects the ratio of 14
C to 12
C in the different reservoirs, and hence the radiocarbon ages of samples that originated in each reservoir.[5] The atmosphere, which is where 14
C is generated, contains about 1.9% of the total carbon in the reservoirs, and the 14
C it contains mixes in less than seven years.[33] The ratio of 14
C to 12
C in the atmosphere is taken as the baseline for the other reservoirs: if another reservoir has a lower ratio of 14
C to 12
C, it indicates that the carbon is older and hence that either some of the 14
C has decayed, or the reservoir is receiving carbon that is not at the atmospheric baseline.[21] The ocean surface is an example: it contains 2.4% of the carbon in the exchange reservoir, but there is only about 95% as much 14
C as would be expected if the ratio were the same as in the atmosphere.[5] The time it takes for carbon from the atmosphere to mix with the surface ocean is only a few years,[34] but the surface waters also receive water from the deep ocean, which has more than 90% of the carbon in the reservoir.[21] Water in the deep ocean takes about 1,000 years to circulate back through surface waters, and so the surface waters contain a combination of older water, with depleted 14
C, and water recently at the surface, with 14
C in equilibrium with the atmosphere.[21]
Creatures living at the ocean surface have the same 14
C ratios as the water they live in, and as a result of the reduced 14
C/12
C ratio, the radiocarbon age of marine life is typically about 400 years.[35][36] Organisms on land are in closer equilibrium with the atmosphere and have the same 14
C/Creatures living at the ocean surface have the same 14
C ratios as the water they live in, and as a result of the reduced 14
C/12
C ratio, the radiocarbon age of marine life is typically about 400 years.[35][36] Organisms on land are in closer equilibrium with the atmosphere and have the same 14
C/12
C ratio as the atmosphere.[5][note 8] These organisms contain about 1.3% of the carbon in the reservoir; sea organisms have a mass of less than 1% of those on land and are not shown in the diagram. Accumulated dead organic matter, of both plants and animals, exceeds the mass of the biosphere by a factor of nearly 3, and since this matter is no longer exchanging carbon with its environment, it has a 14
C/12
C ratio lower than that of the biosphere.[5]
The variation in the 14
C/12
C ratio in different parts of the carbon exchange reservoir means that a straightforward calculation of the age of a sample based on the amount of 14
C it contains will often give an incorrect result. There are several other possible sources of error that need to be considered. The errors are of four general types:
Coal and oil began to be burned in large quantities during the 19th century. Both are sufficiently old that they contain little or no detectable 14
C and, as a result, the CO
2 released substantially diluted the atmospheric 14
C/12
C ratio. Dating an object from the early 20th century hence gives an apparent date older than the true date. For the same reason, 14
C concentrations in the neighbourhood of large cities are lower than the atmospheric average. This fossil fuel effect (also known as the Suess effect, after Hans Suess, who first reported it in 1955) would only amount to a reduction of 0.2% in 14
C activity if the additional carbon from fossil fuels were distributed throughout the carbon exchange reservoir, but because of the long delay in mixing with the deep ocean, the actual effect is a 3% reduction.[38][42]
A much larger effect comes from above-ground nuclear testing, which released large numbers of neutrons into the atmosphere, resulting in the creation of 14 Coal and oil began to be burned in large quantities during the 19th century. Both are sufficiently old that they contain little or no detectable 14 A much larger effect comes from above-ground nuclear testing, which released large numbers of neutrons into the atmosphere, resulting in the creation of 14 Photosynthesis is the primary process by which carbon moves from the atmosphere into living things. In photosynthetic pathways 12 To determine the degree of fractionation that takes place in a given plant, the amounts of both 12 where the ‰ sign indicates parts per thousand.[44] Because the PDB standard contains an unusually high proportion of 13 For marine organisms, the details of the photosynthesis reactions are less well understood, and the δ13C values for marine photosynthetic organisms are dependent on temperature. At higher temperatures, CO
C and, as a result, the CO
2 released substantially diluted the atmospheric 14
C/12
C ratio. Dating an object from the early 20th century hence gives an apparent date older than the true date. For the same reason, 14
C concentrations in the neighbourhood of large cities are lower than the atmospheric average. This fossil fuel effect (also known as the Suess effect, after Hans Suess, who first reported it in 1955) would only amount to a reduction of 0.2% in 14
C activity if the additional carbon from fossil fuels were distributed throughout the carbon exchange reservoir, but because of the long delay in mixing with the deep ocean, the actual effect is a 3% reduction.[38][42]
C. From about 1950 until 1963, when atmospheric nuclear testing was banned, it is estimated that several tonnes of 14
C were created. If all this extra 14
C had immediately been spread across the entire carbon exchange reservoir, it would have led to an increase in the 14
C/12
C ratio of only a few per cent, but the immediate effect was to almost double the amount of 14
C in the atmosphere, with the peak level occurring in 1964 for the northern hemisphere, and in 1966 for the southern hemisphere. The level has since dropped, as this bomb pulse or "bomb carbon" (as it is sometimes called) percolates into the rest of the reservoir.[38][42][43][37]
C is absorbed slightly more easily than 13
C, which in turn is more easily absorbed than 14
C. The differential uptake of the three carbon isotopes leads to 13
C/12
C and 14
C/12
C ratios in plants that differ from the ratios in the atmosphere. This effect is known as isotopic fractionation.[44][45]
12
C and 13
C isotopes are measured, and the resulting 13
C/12
C ratio is then compared to a standard ratio known as PDB.[note 9] The 13
C/12
C ratio is used instead of 14
C/12
C because the former is much easier to measure, and the latter can be easily derived: the depletion of 13
C relative to 12
C is proportional to the difference in the atomic masses of the two isotopes, so the depletion for 14
C is twice the depletion of 13
C.[21] The fractionation of 13
C, known as δ13C, is calculated as follows:[44]
C,[note 10] most measured δ13C values are negative.
2 has poor solubility in water, which means there is less CO
2 available for the photosynthetic reactions. Under these conditions, fractionation is reduced, and at temperatures above 14 °C the δ13C values are correspondingly higher, while at lower temperatures, CO
2 becomes more soluble and hence more available to marine organisms.δ
2 has poor solubility in water, which means there is less CO
2 available for the photosynthetic reactions. Under these conditions, fractionation is reduced, and at temperatures above 14 °C the δ13C values are correspondingly higher, while at lower temperatures, CO
2 becomes more soluble and hence more available to marine organisms.[45] The δ13C value for animals depends on their diet. An animal that eats food with high δ13C values will have a higher δ13C than one that eats food with lower δ13C values.[44] The animal's own biochemical processes can also impact the results: for example, both bone minerals and bone collagen typically have a higher concentration of 13
C than is found in the animal's diet, though for different biochemical reasons. The enrichment of bone 13
C also implies that excreted material is depleted in 13
C relative to the diet.[48]
Since 13
C makes up about 1% of the carbon in a sample, the 13
C/12
C ratio can be accurately measured by mass spectrometry.[21] Typical values of δ13C have been found by experiment for many plants, as well as for different parts of animals such as bone collagen, but when dating a given sample it is better to determine the δ13C value for that sample directly than to rely on the published values.[44]
The carbon exchange between atmospheric CO
2 and carbonate at the ocean surface is also subject to fractionation, with 14
C in the atmosphere more likely than 12
C to dissolve in the ocean. The result is an overall
Since 13
C makes up about 1% of the carbon in a sample, the 13
C/12
C ratio can be accurately measured by mass spectrometry.[21] Typical values of δ13C have been found by experiment for many plants, as well as for different parts of animals such as bone collagen, but when dating a given sample it is better to determine the δ13C value for that sample directly than to rely on the published values.[44]
The carbon exchange between atmospheric CO
2 and carbonate at the ocean surface is also subject to fractionation, with 14
C in the atmosphere more likely than 12
C to dissolve in the ocean. The result is an overall increase in the 14
C/12
C ratio in the ocean of 1.5%, relative to the 14
C/12
C ratio in the atmosphere. This increase in 14
C concentration almost exactly cancels out the decrease caused by the upwelling of water (containing old, and hence 14
C depleted, carbon) from the deep ocean, so that direct measurements of 14
C radiation are similar to measurements for the rest of the biosphere. Correcting for isotopic fractionation, as is done for all radiocarbon dates to allow comparison between results from different parts of the biosphere, gives an apparent age of about 400 years for ocean surface water.[21][36]
Libby's original exchange reservoir hypothesis assumed that the 14
C/12
C ratio in the exchange reservoir is constant all over the world,[49] but it has since been discovered that there are several causes of variation in the ratio across the reservoir.[35]
The The marine effect: The CO
2 in the atmosphere transfers to the ocean by dissolving in the surface water as carbonate and bicarbonate ions; at the same time the carbonate ions in the water are returning to the air as CO
2.[49] This exchange process brings14
C from the atmosphere into the surface waters of the ocean, but the 14
C thus introduced takes a long time to percolate through the entire volume of the ocean. The deepest parts of the ocean mix very slowly with the surface waters, and the mixing is uneven. The main mechanism that brings deep water to the surface is upwelling, which is more common in regions closer to the equator. Upwelling is also influenced by factors such as the topography of the local ocean bottom and coastlines, the climate, and wind patterns. Overall, the mixing of deep and surface waters takes far longer than the mixing of atmospheric CO
2 with the surface waters, and as a result water from some deep ocean areas has an apparent radiocarbon age of several thousand years. Upwelling mixes this "old" water with the surface water, giving the surface water an apparent age of about several hundred years (after correcting for fractionation).[35] This effect is not uniform – the average effect is about 400 years, but there are local deviations of several hundred years for areas that are geographically close to each other.[35][36] These deviations can be accounted for in calibration, and users of software such as CALIB can provide as an input the appropriate correction for the location of their samples.[15] The effect also applies to marine organisms such as shells, and marine mammals such as whales and seals, which have radiocarbon ages that appear to be hundreds of years old.[35]
The northern and southern hemispheres have atmospheric circulation systems that are sufficiently independent of each other that there is a noticeable time lag in mixing between the two. The atmospheric 14
C/12
C ratio is lower in the southern hemisphere, with an apparent additional age of about 40 years for radiocarbon results from the south as compared to the north.[note 11] This is because the greater surface area of ocean in the southern hemisphere means that there is more carbon exchanged between the ocean and the atmosphere than in the north. Since the surface ocean is depleted in 14
C because of the marine effect, 14
C is removed from the southern atmosphere more quickly than in the north.[35][50] The effect is strengthened by strong upwelling around Antarctica.[12]
If the ca
If the carbon in freshwater is partly acquired from aged carbon, such as rocks, then the result will be a reduction in the 14
C/12
C ratio in the water. For example, rivers that pass over limestone, which is mostly composed of calcium carbonate, will acquire carbonate ions. Similarly, groundwater can contain carbon derived from the rocks through which it has passed. These rocks are usually so old that they no longer contain any measurable 14
C, so this carbon lowers the 14
C/12
C ratio of the water it enters, which can lead to apparent ages of thousands of years for both the affected water and the plants and freshwater organisms that live in it.[21] This is known as the hard water effect because it is often associated with calcium ions, which are characteristic of hard water; other sources of carbon such as humus can produce similar results, and can also reduce the apparent age if they are of more recent origin than the sample.[35] The effect varies greatly and there is no general offset that can be applied; additional research is usually needed to determine the size of the offset, for example by comparing the radiocarbon age of deposited freshwater shells with associated organic material.[51]
Volcanic eruptions eject large amounts of carbon into the air. The carbon is of geological origin and has no detectable Volcanic eruptions eject large amounts of carbon into the air. The carbon is of geological origin and has no detectable 14
C, so the 14
C/12
C ratio in the vicinity of the volcano is depressed relative to surrounding areas. Dormant volcanoes can also emit aged carbon. Plants that photosynthesize this carbon also have lower 14
C/12
C ratios: for example, plants in the neighbourhood of the Furnas caldera in the Azores were found to have apparent ages that ranged from 250 years to 3320 years.[52]
Any addition of carbon to a sample of a different age will cause the measured date to be inaccurate. Contamination with modern carbon causes a sample to appear to be younger than it really is: the effect is greater for older samples. If a sample that is 17,000 years old is contaminated so that 1% of the sample is modern carbon, it will appear to be 600 years younger; for a sample that is 34,000 years old, the same amount of contamination would cause an error of 4,000 years. Contamination with old carbon, with no remaining 14
C, causes an error in the other direction independent of age – a sample contaminated with 1% old carbon will appear to be about 80 years older than it truly is, regardless of the date of the sample.[53]
Particularly for older samples, it may be useful to enrich the amount of 14
C in the sample before testing. This can be done with a thermal diffusion column. The process takes about a month and requires a sample about ten times as large as would be needed otherwise, but it allows more precise measurement of the 14
C/12
C ratio in old material and extends the maximum age that can be reliably reported.[57]
Once contamination has been removed, samples must be converted to a form suitable for the measuring technology to be used.[58] Where gas is required, CO
2 is widely used.[58][59] For samples to be used in liquid scintillation counters, the carbon must be in liquid form; the sample is typically converted to benzene. For accelerator mass spectrometry, solid graphite targets are the most common, although gaseous CO
2 can also be used.[58][60]
The quantity of material needed for testing depends on the sample type and the technology being used. There are two types of testing technology: detectors that record radioactivity, known as beta counters, and accelerator mass spectrometers. For beta counters, a sample weighing at least 10 grams (0.35 ounces) is typically required.[58] Accelerator mass spectrometry is much more sensitive, and samples containing as little as 0.5 milligrams of carbon can be used.[61]
For decades after Libby performed the first radiocarbon dating experiments, the only way to measure the 14 Once contamination has been removed, samples must be converted to a form suitable for the measuring technology to be used.[58] Where gas is required, CO The quantity of material needed for testing depends on the sample type and the technology being used. There are two types of testing technology: detectors that record radioactivity, known as beta counters, and accelerator mass spectrometers. For beta counters, a sample weighing at least 10 grams (0.35 ounces) is typically required.[58] Accelerator mass spectrometry is much more sensitive, and samples containing as little as 0.5 milligrams of carbon can be used.[61]
For decades after Libby performed the first radiocarbon dating experiments, the only way to measure the 14 Libby's first detector was a Geiger counter of his own design. He converted the carbon in his sample to lamp black (soot) and coated the inner surface of a cylinder with it. This cylinder was inserted into the counter in such a way that the counting wire was inside the sample cylinder, in order that there should be no material between the sample and the wire.[58] Any interposing material would have interfered with the detection of radioactivity, since the beta particles emitted by decaying 14 Libby's method was soon superseded by gas proporti Libby's first detector was a Geiger counter of his own design. He converted the carbon in his sample to lamp black (soot) and coated the inner surface of a cylinder with it. This cylinder was inserted into the counter in such a way that the counting wire was inside the sample cylinder, in order that there should be no material between the sample and the wire.[58] Any interposing material would have interfered with the detection of radioactivity, since the beta particles emitted by decaying 14 Libby's method was soon superseded by gas proportional counters, which were less affected by bomb carbon (the additional proportional counters The other common technology used for measuring 14 For both the gas proportional counter and liquid scintillation counter, what is measured is the number of beta particles detected in a given time period. Since the mass of the sample is known, this can be converted to a standard measure of activity in units of either counts per minute per gram of carbon (cpm/g C), or becquerels per kg (Bq/kg C, in SI units). Each measuring device is also used to measure the activity of a blank sample – a sample prepared from carbon old enough to have no activity. This provides a value for the background radiation, which must be subtracted from the measured activity of the sample being dated to get the activity attributable solely to that sample's 14 AMS counts the atoms of 14 The calculations to be performed on the measurements taken depend on the technology used, since beta counters measure the sample's radioactivity whereas AMS determines the ratio of the three different carbon isotopes in the sample.[72]
To determine the age of a sample whose activity has been measured by beta counting, the ratio of its activity to the activity of the standard must be found. To determine this, a blank sample (of old, or dead, carbon) is measured, and a sample of known activity is measured. The additional samples allow errors such as background radiation and systematic errors in the laboratory setup to be detected and corrected for.[68] The most common standard sample materia The calculations to be performed on the measurements taken depend on the technology used, since beta counters measure the sample's radioactivity whereas AMS determines the ratio of the three different carbon isotopes in the sample.[72]
To determine the age of a sample whose activity has been measured by beta counting, the ratio of its activity to the activity of the standard must be found. To determine this, a blank sample (of old, or dead, carbon) is measured, and a sample of known activity is measured. The additional samples allow errors such as background radiation and systematic errors in the laboratory setup to be detected and corrected for.[68] The most common standard sample material is oxalic acid, such as the HOxII standard, 1,000 lb of which was prepared by the National Institute of Standards and Technology (NIST) in 1977 from French beet harvests.[73][74]
The results from AMS testing are in the form of ratios of 12 Both beta counting and AMS results have to be corrected for fractionation. This is necessary because different materials of the same age, which because of fractionation have naturally different 14 Once the corrected 14 The calculation uses 8,033, the mean-life derived from Libby's half-life of 5,568 years, not 8,267, the mean-life derived from the more accurate modern value of 5,730 years. Libby's value for the half-life is used to maintain consistency with early radiocarbon testing results; calibration curves include a correction for this, so the accuracy of final reported calendar ages is assured.[75]
The reliability of the results can be improved by lengthening the testing time. For example, if counting beta decays for 250 minutes is enough to give an error of ± 80 years, with 68% confidence, then doubling the counting time to 500 minutes will allow a sample with only half as much 14 Radiocarbon dating is The reliability of the results can be improved by lengthening the testing time. For example, if counting beta decays for 250 minutes is enough to give an error of ± 80 years, with 68% confidence, then doubling the counting time to 500 minutes will allow a sample with only half as much 14 Radiocarbon dating is generally limited to dating samples no more than 50,000 years old, as samples older than that have insufficient 14 Radiocarbon dates are generally presented with a range of one standard deviation (usually represented by the Greek letter sigma as 1σ) on either side of the mean. However, a date range of 1σ represents only a 68% confidence level, so the true age of the object being measured may lie outside the range of dates quoted. This was demonstrated in 1970 by an experiment run by the British Museum radiocarbon laboratory, in which weekly measurements were taken on the same sample for six months. The results varied widely (though consistently with a normal distribution of errors in the measurements), and included multiple date ranges (of 1σ confidence) that did not overlap with each other. The measurements included one with a range from about 4250 to about 4390 years ago, and another with a range from about 4520 to about 4690.[77]
Errors in procedure can also lead to errors in the results. If 1% of the benzene in a modern reference sample accidentally evaporates, scintillation counting will give a radiocarbon age that is too young by about 80 years.[78]
The calculations given above produce dates in radiocarbon years: i.e. dates that represent the age the sample would be if the 14 To produce a curve that can be used to relate calendar years to radiocarbon years, a sequence of securely dated samples is needed which can be tested to determine their radiocarbon age. The study of tree rings led to the first such sequence: individual pieces of wood show characteristic sequences of rings that vary in thickness because of environmental factors such as the amount of rainfall in a given year. These factors affect all trees in an area, so examining tree-ring sequences from old wood allows the identification of overlapping sequences. In this way, an uninterrupted sequence of tree rings can be extended far into the past. The first such published sequence, based on bristlecone pine tree rings, was created by Wesley Ferguson.[40] Hans Suess used this data to publish the first calibration curve for radiocarbon dating in 1967.[38][39][80] The curve showed two types of variation from the straig To produce a curve that can be used to relate calendar years to radiocarbon years, a sequence of securely dated samples is needed which can be tested to determine their radiocarbon age. The study of tree rings led to the first such sequence: individual pieces of wood show characteristic sequences of rings that vary in thickness because of environmental factors such as the amount of rainfall in a given year. These factors affect all trees in an area, so examining tree-ring sequences from old wood allows the identification of overlapping sequences. In this way, an uninterrupted sequence of tree rings can be extended far into the past. The first such published sequence, based on bristlecone pine tree rings, was created by Wesley Ferguson.[40] Hans Suess used this data to publish the first calibration curve for radiocarbon dating in 1967.[38][39][80] The curve showed two types of variation from the straight line: a long term fluctuation with a period of about 9,000 years, and a shorter-term variation, often referred to as "wiggles", with a period of decades. Suess said he drew the line showing the wiggles by "cosmic schwung", by which he meant that the variations were caused by extraterrestrial forces. It was unclear for some time whether the wiggles were real or not, but they are now well-established.[38][39][81] These short term fluctuations in the calibration curve are now known as de Vries effects, after Hessel de Vries.[82]
A calibration curve is used by taking the radiocarbon date reported by a laboratory and reading across from that date on the vertical axis of the graph. The point where this horizontal line intersects the curve will give the calendar age of the sample on the horizontal axis. This is the reverse of the way the curve is constructed: a point on the graph is derived from a sample of known age, such as a tree ring; when it is tested, the resulting radiocarbon age gives a data point for the graph.[41]
Over the next thirty years many calibration curves were published using a variety of methods and statistical approaches.[41] These were superseded by the IntCal series of curves, beginning with IntCal98, published in 1998, and updated in 2004, 2009, 2013, and 2020.[83] The improvements to these curves are based on new data gathered from tree rings, varves, coral, plant macrofossils, speleothems, and foraminifera. The IntCal20 data includes separate curves for the northern and southern hemispheres, as they differ systematically because of the hemisphere effect. The southern curve (SHCAL20) is based on independent data where possible and derived from the northern curve by adding the average offset for the southern hemisphere where no direct data was available. There is also a separate marine calibration curve, MARINE20.[29][84][85][86] For a set of samples forming a sequence with a known separation in time, these samples form a subset of the calibration curve. The sequence can be compared to the calibration curve and the best match to the sequence established. This "wiggle-matching" technique can lead to more precise dating than is possible with individual radiocarbon dates.[87] Wiggle-matching can be used in places where there is a plateau on the calibration curve, and hence can provide a much more accurate date than the intercept or probability methods are able to produce.[88] The technique is not restricted to tree rings; for example, a stratified tephra sequence in New Zealand, believed to predate human colonization of the islands, has been dated to 1314 AD ± 12 years by wiggle-matching.[89] The wiggles also mean that reading a date from a calibration curve can give more than one answer: this occurs when the curve wiggles up and down enough that the radiocarbon age intercepts the curve in more than one place, which may lead to a radiocarbon result being reported as two separate age ranges, corresponding to the two parts of the curve that the radiocarbon age intercepted.[41]
Bayesian statistical techniques can be applied when there are several radiocarbon dates to be calibrated. For example, if a series of radiocarbon dates is taken from different levels in a stratigraphic sequence, Bayesian analysis can be used to evaluate dates which are outliers and can calculate improved probability distributions, based on the prior information that the sequence should be ordered in time.[87] When Bayesian analysis was introduced, its use was limited by the need to use mainframe computers to perform the calculations, but the technique has since been implemented on programs available for personal computers, such as OxCal.[90]
Soon after the publication of Libby's 1949 paper in Science, universities around the world began establishing radiocarbon-dating laboratories, and by the end of the 1950s there were more than 20 active 14 The development of radiocarbon dating has had a profound impac Soon after the publication of Libby's 1949 paper in Science, universities around the world began establishing radiocarbon-dating laboratories, and by the end of the 1950s there were more than 20 active 14 The development of radiocarbon dating has had a profound impact on archaeology – often described as the "radiocarbon revolution".[107] In the words of anthropologist R. E. Taylor, "[107] In the words of anthropologist R. E. Taylor, "14 The dating framework provided by radiocarbon led to a change in the prevailing view of how innovations spread through prehistoric Europe. Researchers had previously thought that many ideas spread by diffusion through the continent, or by invasions of peoples bringing new cultural ideas with them. As radiocarbon dates began to prove these ideas wrong in many instances, it became apparent that these innovations must sometimes have arisen locally. This has been described as a "second radiocarbon revolution", and with regard to British prehistory, archaeologist Richard Atkinson has characterized the impact of radiocarbon dating as "radical ... therapy" for the "progressive disease of invasionism". More broadly, the success of radiocarbon dating stimulated interest in analytical and statistical approaches to archaeological data.[108] Taylor has also described the impact of AMS, and the ability to obtain accurate measurements from very small samples, as ushering in a third radiocarbon revolution.[109]
Occasionally, radiocarbon dating techniques date an object of popular interest, for example, the Shroud of Turin, a piece of linen cloth thought by some to bear an image of Jesus Christ after his crucifixion. Three separate laboratories dated samples of linen from the Shroud in 1988; the results pointed to 14th-century origins, raising doubts about the shroud's authenticity as an alleged 1st-century relic.[17]
Researchers have studied other radioactive isotopes created by cosmic rays to determine if they could also be used to assist in dating objects of archaeological interest; such isotopes include 3
2 is widely used.[58][59] For samples to be used in liquid scintillation counters, the carbon must be in liquid form; the sample is typically converted to benzene. For accelerator mass spectrometry, solid graphite targets are the most common, although gaseous CO
2 can also be used.[58][60]
C in a sample was to detect the radioactive decay of individual carbon atoms.[58] In this approach, what is measured is the activity, in number of decay events per unit mass per time period, of the sample.[59] This method is also known as "beta counting", because it is the beta particles emitted by the decaying 14
C atoms that are detected.[62] In the late 1970s an alternative approach became available: directly counting the number of 14
C and 12
C atoms in a given sample, via accelerator mass spectrometry, usually referred to as AMS.[58] AMS counts the 14
C/12
C ratio directly, instead of the activity of the sample, but measurements of activity and 14
C/12
C ratio can be converted into each other exactly.[59] For some time, beta counting methods were more accurate than AMS, but AMS is now more accurate and has become the method of choice for radiocarbon measurements.[63][64] In addition to improved accuracy, AMS has two further significant advantages over beta counting: it can perform accurate testing on samples much too small for beta counting, and it is much faster – an accuracy of 1% can be achieved in minutes with AMS, which is far quicker than would be achievable with the older technology.[65]
Beta counting
C are so weak that half are stopped by a 0.01 mm thickness of aluminium.[59]
C are so weak that half are stopped by a 0.01 mm thickness of aluminium.[59]
C created by nuclear weapons testing). These counters record bursts of ionization caused by the beta particles emitted by the decaying 14
C atoms; the bursts are proportional to the energy of the particle, so other sources of ionization, such as background radiation, can be identified and ignored. The counters are surrounded by lead or steel shielding, to eliminate background radiation and to reduce the incidence of cosmic rays. In addition, anticoincidence detectors are used; these record events outside the counter and any event recorded simultaneously both inside and outside the counter is regarded as an extraneous event and ignored.[59]
C activity is liquid scintillation counting, which was invented in 1950, but which had to wait until the early 1960s, when efficient methods of benzene synthesis were developed, to become competitive with gas counting; after 1970 liquid counters became the more common technology choice for newly constructed dating laboratories. The counters work by detecting flashes of light caused by the beta particles emitted by 14
C as they interact with a fluorescing agent added to the benzene. Like gas counters, liquid scintillation counters require shielding and anticoincidence counters.[66][67]
C. In addition, a sample with a standard activity is measured, to provide a baseline for comparison.[68]
C and 12
C in a given sample, determining the 14
C/12
C ratio directly. The sample, often in the form of graphite, is made to emit C− ions (carbon atoms with a single negative charge), which are injected into an accelerator. The ions are accelerated and passed through a stripper, which removes several electrons so that the ions emerge with a positive charge. The ions, which may have from 1 to 4 positive charges (C+ to C4+), depending on the accelerator design, are then passed through a magnet that curves their path; the heavier ions are curved less than the lighter ones, so the different isotopes emerge as separate streams of ions. A particle detector then records the number of ions detected in the 14
C stream, but since the volume of 12
C (and 13
C, needed for calibration) is too great for individual ion detection, counts are determined by measuring the electric current created in a Faraday cup.[69] The large positive charge induced by the stripper forces molecules such as 13
CH, which has a weight close enough to 14
C to interfere with the measurements, to dissociate, so they are not detected.[70] Most AMS machines also measure the sample's δ13C, for use in calculating the sample's radiocarbon age.[71] The use of AMS, as opposed to simpler forms of mass spectrometry, is necessary because of the need to distinguish the carbon isotopes from other atoms or molecules that are very close in mass, such as 14
N and 13
CH.[58] As with beta counting, both blank samples and standard samples are used.[69] Two different kinds of blank may be measured: a sample of dead carbon that has undergone no chemical processing, to detect any machine background, and a sample known as a process blank made from dead carbon that is processed into target material in exactly the same way as the sample which is being dated. Any 14
C signal from the machine background blank is likely to be caused either by beams of ions that have not followed the expected path inside the detector or by carbon hydrides such as 12
CH
2 or 13
CH. A 14
C signal from the process blank measures the amount of contamination introduced during the preparation of the sample. These measurements are used in the subsequent calculation of the age of the sample.[72]
Calculations
C, 13
C, and 14
C, which are used to calculate Fm, the "fraction modern". This is defined as the ratio between the 14
C/12
C ratio in the sample and the 14
C/12
C ratio in modern carbon, which is in turn defined as the 14
C/12
C ratio that would have been measured in 1950 had there been no fossil fuel effect.[72]
C/12
C ratios, will appear to be of different ages because the 14
C/12
C ratio is taken as the indicator of age. To avoid this, all radiocarbon measurements are converted to the measurement that would have been seen had the sample been made of wood, which has a known δ13
C value of −25‰.[22]
C/12
C ratio is known, a "radiocarbon age" is calculated using:[75]
Errors and reliability
C to be measured with the same error term of 80 years.[76]
C to be measured with the same error term of 80 years.[76]
C to be measurable. Older dates have been obtained by using special sample preparation techniques, large samples, and very long measurement times. These techniques can allow measurement of dates up to 60,000 and in some cases up to 75,000 years before the present.[63]
C/12
C ratio had been constant historically.[79] Although Libby had pointed out as early as 1955 the possibility that this assumption was incorrect, it was not until discrepancies began to accumulate between measured ages and known historical dates for artefacts that it became clear that a correction would need to be applied to radiocarbon ages to obtain calendar dates.[80]
Reporting dates
scrolls were discovered in caves near the Dead Sea that proved to contain writing in Hebrew and Aramaic, most of which are thought to have been produced by the Essenes, a small Jewish sect. These scrolls are of great significance in the study of Biblical texts because many of them contain the earliest known version of books of the Hebrew bible.[104] A sample of the linen wrapping from one of these scrolls, the Great Isaiah Scroll, was included in a 1955 analysis by Libby, with an estimated age of 1,917 ± 200 years.[104][105] Based on an analysis of the writing style, palaeographic estimates were made of the age of 21 of the scrolls, and samples from most of these, along with other scrolls which had not been palaeographically dated, were tested by two AMS laboratories in the 1990s. The results ranged in age from the early 4th century BC to the mid 4th century AD. In all but two cases the scrolls were determined to be within 100 years of the palaeographically determined age. The Isaiah scroll was included in the testing and was found to have two possible date ranges at a 2σ confidence level, because of the shape of the calibration curve at that point: there is a 15% chance that it dates from 355 to 295 BC, and an 84% chance that it dates from 210 to 45 BC. Subsequently, these dates were criticized on the grounds that before the scrolls were tested, they had been treated with modern castor oil in order to make the writing easier to read; it was argued that failure to remove the castor oil sufficiently would have caused the dates to be too young. Multiple papers have been published both supporting and opposing the criticism.[104]
Impact
C research laboratories. It quickly became apparent that the principles of radiocarbon dating were valid, despite certain discrepancies, the causes of which then remained unknown.[106]
C research laboratories. It quickly became apparent that the principles of radiocarbon dating were valid, despite certain discrepancies, the causes of which then remained unknown.[106]
C data made a world prehistory possible by contributing a time scale that transcends local, regional and continental boundaries". It provides more accurate dating within sites than previous methods, which usually derived either from stratigraphy or from typologies (e.g. of stone tools or pottery); it also allows comparison and synchronization of events across great distances. The advent of radiocarbon dating may even have led to better field methods in archaeology since better data recording leads to a firmer association of objects with the samples to be tested. These improved field methods were sometimes motivated by attempts to prove that a 14
C date was incorrect. Taylor also suggests that the availability of definite date information freed archaeologists from the need to focus so much of their energy on determining the dates of their finds, and led to an expansion of the questions archaeologists were willing to research. For example, from the 1970s questions about the evolution of human behaviour were much more frequently seen in archaeology.[108]
He, 10
Be, 21
Ne, 26
Al, and 36
Cl. With the development of AMS in the 1980s it became possible to measure these isotopes precisely enough for them to be the basis of useful dating techniques, which have been primarily applied to dating rocks.[110] Naturally occurring radioactive isotopes can also form the basis of dating methods, as with potassium–argon dating, argon–argon dating, and uranium series dating.[111] Other dating techniques of interest to archaeologists include thermoluminescence, optically stimulated luminescence, electron spin resonance, and fission track dating, as well as techniques that depend on annual bands or layers, such as dendrochronology, tephrochronology, and varve chronology.[112]
This article was submitted to WikiJournal of Science for external academic peer review in 2017 (reviewer reports). The updated content was reintegrated into the Wikipedia page under a CC-BY-SA-3.0 license (2018). The version of record as reviewed is: Mike Christie; et al. (1 June 2018), Henry Hoff; W. Brian Whalley (eds.), "Radiocarbon dating" (PDF), WikiJournal of Science, 1 (1): 6, doi:10.15347/WJS/2018.006, ISSN 2470-6345, Wikidata Q55120317