For decades after Libby performed the first radiocarbon dating experiments, the only way to measure the in a sample was to detect the radioactive decay of individual carbon atoms. In the late 1970s an alternative approach became available: directly counting the number of and atoms in a given sample, via accelerator mass spectrometry, usually referred to as AMS. 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.
Beta counting 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. 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 . In addition, a sample with a standard activity is measured, to provide a baseline for comparison.
Accelerator mass spectrometry AMS counts the atoms of and in a given sample, determining the / 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 stream, but since the volume of (and , needed for calibration) is too great for individual ion detection, counts are determined by measuring the electric current created in a
Faraday cup. The large positive charge induced by the stripper forces molecules such as , which has a weight close enough to to interfere with the measurements, to dissociate, so they are not detected. Most AMS machines also measure the sample's , for use in calculating the sample's radiocarbon age. 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 and .
Calculations 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. The results from AMS testing are in the form of ratios of , , and , which are used to calculate Fm, the "fraction modern". This is defined as the ratio between the / ratio in the sample and the / ratio in modern carbon, which is in turn defined as the / ratio that would have been measured in 1950 had there been no fossil fuel effect. :\text{Age} = - \ln (\text{Fm})\cdot 8033\text{ years} The calculation uses 8,033 years, the mean-life derived from Libby's half-life of 5,568 years, not 8,267 years, 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 not affected. Radiocarbon dating is generally limited to dating samples no more than 50,000 years old, as samples older than that have insufficient 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. 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.
Calibration The calculations given above produce dates in radiocarbon years: i.e. dates that represent the age the sample would be if the / ratio had been constant historically. 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. 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. These short term fluctuations in the calibration curve are now known as de Vries effects, after
Hessel de Vries. 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. The improvements to these curves are based on new data gathered from tree rings,
varves,
coral, plant
macrofossils,
speleothems, and
foraminifera. There are separate curves for the northern hemisphere (IntCal20) and southern hemisphere (SHCal20), as they differ systematically because of the hemisphere effect. The continuous sequence of tree-ring dates for the northern hemisphere goes back to 13,910 BP as of 2020, and this provides close to annual dating for IntCal20 much of the period, reduced where there are calibration plateaus, and increased when short term C spikes due to
Miyake events provide additional correlation. Radiocarbon dating earlier than the continuous tree ring sequence relies on correlation with more approximate records. 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. 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. 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. 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. 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.
Reporting dates Several formats for citing radiocarbon results have been used since the first samples were dated. As of 2019, the standard format required by the journal
Radiocarbon is as follows. Uncalibrated dates should be reported as ": {{var|{}^14C year}} ± BP", where: • identifies the laboratory that tested the sample, and the sample ID • {{var|{}^14C year}} is the laboratory's determination of the age of the sample, in radiocarbon years • is the laboratory's estimate of the error in the age, at 1σ confidence. • 'BP' stands for "
before present", referring to a reference date of 1950, so that "500 BP" means the year AD 1450. For example, the uncalibrated date "UtC-2020: 3510 ± 60 BP" indicates that the sample was tested by the Utrecht van der Graaff Laboratorium ("UtC"), where it has a sample number of "2020", and that the uncalibrated age is 3510 years before present, ± 60 years. Related forms are sometimes used: for example, "2.3 ka BP" means 2,300 radiocarbon years before present (i.e. 350 BC), and " yr BP" might be used to distinguish the uncalibrated date from a date derived from another dating method such as
thermoluminescence.
Radiocarbon gives two options for reporting calibrated dates. A common format is "cal ", where: • is the range of dates corresponding to the given confidence level • indicates the confidence level for the given date range. For example, "cal 1220–1281 AD (1σ)" means a calibrated date for which the true date lies between AD 1220 and AD 1281, with a confidence level of '1 sigma', or
approximately 68%. Calibrated dates can also be expressed as "BP" instead of using "BC" and "AD". The curve used to calibrate the results should be the latest available IntCal curve. Calibrated dates should also identify any programs, such as OxCal, used to perform the calibration. ==Use in archaeology==