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Geological Society of America Special Papers

The geochronology revolution
James M. Mattinson Geological Society of America Special Papers 2013;500; 303-320 doi:10.1130/2013.2500(09)

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2013 Geological Society of America

The Geological Society of America Special Paper 500 2013

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CELEBRATING ADVANCES IN GEOSCIENCE

The geochronology revolution

James M. Mattinson* Department of Earth Science, University of California, Santa Barbara, California 93106-9630, USA

ABSTRACT 1896 marked the beginning of a decade that spawned both modern physics and the science of geochronology based on radioactive decay. The decade started with the discovery of radioactivity by Henri Becquerel in 1896, and ended with the formal publication of ages for natural mineral samples by Ernest Rutherford in 1906. The next fty years witnessed the discovery of isotopes and nuclear ssion; the development of the mass spectrograph and the mass spectrometer; application of the isotope dilution method to dating trace, accessory, and major minerals in typical crustal rocks; and publication of the ca. 4.55 Ga age for the Earth. Yet, after all this, geochronology was still viewed with suspicion by some geologists. In the past fty years, with additional major advances in instrumentation, technique, and interpretation, geochronology is fully integrated into almost all elds of geology. The three major dating methods from the 1950s and 1960s, U-Pb, K-Ar, and Rb-Sr, have been rened repeatedly. In particular, U-Pb and Ar-Ar, a modern variant of K-Ar, are now capable of <0.1% precisions, with spectacular results in recent studies of crucial problems such as the exact timing and duration of mass extinctions. Many new methods are now available to attack problems ranging from rates of metamorphic mineral growth to rates of uplift and erosion, to the time of surface exposure of geomorphic surfaces. It is a good time to be a geochronologist, or to collaborate with one or more. The future looks very bright.

INTRODUCTION Fifty years ago, at the time of the previous GSA commemorative book volume celebrating the 75th anniversary of The Geological Society of America, geochronology and other quantitative methods were not always welcomed with open arms by the geological community. Writing in that 75th anniversary volume, J. Hoover Mackin began his contribution as follows: Most of us are concerned, and some of us have strong feelings, pro or con, about what has been happening to geology in the past 25 years: greatly increased use of nongeologic techniques in the solution of

geologic problems, such as dating by radioisotope methods. At meetings of our societies, when older brethren gather together in hotel rooms after technical sessions, the discussion usually comes around to these changes. There are apt to be sad postmortems for certain departments, once powerful, which are now, owing to the retirement or ight of their older stalwarts, largely staffed by dial twisters and number jugglers (Mackin,1963, p. 135). Mackin (1963) wisely went on to caution the old-timers against blindly resisting all quantitative methods, and the young dial twisters and number jugglers against ignoring sound classical geological reasoning in interpreting their numerical data. Now, in

*mattinson@geol.ucsb.edu Mattinson, J.M., 2013, The geochronology revolution, in Bickford, M.E., ed., The Web of Geological Sciences: Advances, Impacts, and Interactions: Geological Society of America Special Paper 500, p. 303320, doi:10.1130/2013.2500(09). For permission to copy, contact editing@geosociety.org. 2013 The Geological Society of America. All rights reserved.

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Mattinson published the results in 1906. In 1907, with the encouragement of Rutherford, Boltwood published the rst dates based on the decay of uranium to lead. Thus, only about a decade after the discovery of radioactivity, the results of Rutherford and Boltwood demonstrated that Paleozoic and Precambrian geological materials ranged from hundreds of millions to billions of years old. However, at this stage there was little interest in the geologic context of the samples dated. Enter Arthur Holmes. Holmes was a student in physics in 1907 at the Royal College of Science, London, but switched his emphasis to geology in his third year. He was able to combine his interests in radioactivity and geology working with professor Robert Strutt, who had narrowly lost out to Rutherford in the race to publish the rst He/U dates. Strutts detailed studies had shown that helium leaked out of rocks and minerals quite readily, and he suggested that Holmes focus on the potentially more reliable Pb/U system. By 1911 Holmes had developed improved methods for Pb/U dating that he applied to a range of minerals from samples with well-dened stratigraphic ages. Within two years of this initial success, Holmes (1913) published a 196-page monograph, The Age of the Earth, in which he laid out the principles of radiometric dating, and presented a geologic time scale for the Pleistocene to the Precambrian, based on all He/U and Pb/U dates available at the time. We can view this as the beginning of modern geochronology in the sense of rigorous integration of dating and geology. Holmes devoted the rest of his long career to geochronology in general, and the problem of determining the age of the Earth in particular. At about the same time that Holmes was beginning his career in geochronology, Rutherford discovered the atomic nucleus with his famous experiments in which he bombarded thin metal foils with collimated beams of alpha particles. About two years later, J.J. Thomson, Rutherfords professor, used a primitive ancestor of todays sophisticated mass spectrometers to make the rst direct observation of isotopes: He discovered that neon had two forms with different masses, about mass 20 and mass 22, respectively. Almost simultaneously, the American chemist T.W. Richards made highly precise measurements of the atomic weights of Pb, analyzing Pb from Pb-ore minerals as well as Pb from U-ore minerals. He proved that Pb produced by the decay of U in U-ore minerals had a signicantly lower atomic weight than the ordinary Pb from Pb-ore minerals, a clear indication that Pb also consisted of different isotopes, depending on the origin of the Pb. These insights into the nature of matter would be central to further developments in geochronology, but only after signicant improvements in instrumentation. Early Isotopic Research Francis Aston (1919) improved on Thomsons primitive instrument. Astons mass spectrograph recorded the mass spectra of various elements on photographic plates, and allowed semiquantitative determinations of the ratios between different isotopes (Fig. 1). Aston initially conrmed Thomsons results on neon, then began working his way through the periodic

the modern era of geology, it is hard to imagine research in petrology, tectonics, stratigraphy, paleobiology, and indeed, the geologic time scale itself, that is not robustly based on geochronology. In this chapter, after a brief review of the early roots of geochronology, I will discuss some of the spectacular advances in techniques and instrumentation of the past 50 years that have led to the present state-of-the-art of geochronology, and its integration into almost all elds of geology. BRIEF HISTORY OF DEVELOPMENT OF GEOCHRONOLOGY: 18961963 This account of the early years of discovery and research into radioactivity and its application to geochronology is drawn from original papers where specically referenced, and more broadly from Harper (1973a compilation of benchmark papers in geochronology from 1906 to 1971), Faure (1977 this early edition contains a much richer discussion of the history of isotope geology than does the latest edition), Quinn (1995), Lewis (2000), Davis et al. (2003), Parrish and Noble (2003), and Mattinson (2013). Discovery Modern geochronology traces its roots to Henri Becquerel, a French physicist. In some ways, Becquerel was an unlikely and perhaps accidental hero (Badash, 1996). Following in his fathers footsteps, Becquerel had conducted research in phosphorescence, the property of some materials, including some uranium compounds, to emit light after exposure to sunlight or ultraviolet light. However, by 1895, the 43-year-old Becquerel evidently had been inactive in research for about ve years. The discovery in late 1895 by Wilhelm Roentgen of X rays emitted from a cathode-ray apparatus spurred Becquerel back into action. Becquerel began experiments with some of his phosphorescent uranium samples to determine if they might emit not just visible light after exposure to sunlight, but also invisible penetrating rays similar to Roentgens X-rays. By early 1896 Becquerel found that phosphorescent compounds of uranium indeed emitted penetrating radiation, but he also found, perhaps by accident, that exposure to sunlight was not required. The radiation, later called radioactivity by Marie and Pierre Curie, was a property of the material itself. Becquerel had discovered radioactivity. Within a few years of Becquerels discovery, Marie Curie had discovered two new elements, polonium and radium, both radioactive daughter products of uranium, and Ernest Rutherford and Frederick Soddy established the nature and mathematical principles of radioactive decay. Rutherford and Soddy further suggested that helium might be one of the stable daughter products of U decay. Rutherford realized that the ratio He/U could be used to date U-bearing minerals and, based on a suggestion by Bertrand Boltwood, predicted that Pb/U might prove even more useful. Rutherford presented the rst dates based on the radioactive decay of uranium to helium in a 1904 lecture, and formally

The geochronology revolution table. In 1927 he analyzed ordinary Pb from Pb ore, and in 1929 he analyzed uranogenic Pb produced by the radioactive decay of uranium in uranium ore. The latter produced a stunning result. As expected, most of the Pb in the U ore was the 206Pb isotope, produced by the decay of 238U. However, the uranium ore also contained a signicant amount of 207Pb, much more than could be explained by contamination by ordinary Pb. It was clear that the excess 207Pb must have been generated by the decay of a previously unknown isotope of U, i.e., 235U. Several years later, after the different half-lives for 238U and 235U were approximately known, the 207Pb/206Pb ratio of uranogenic Pb could be used to determine an age based only on the Pb isotopic composition of a sample, independent of the concentrations of U and Pb. These discoveries greatly enhanced the power of the U-Pb dating system. Still further instrumental improvements replaced the photographic plates of Astons mass spectrograph with collection and electronic amplication of the small electrical currents produced by the separate ion beams of each isotope. The resulting mass spectrometer allowed much more precise and accurate isotope ratio measurements than the more primitive mass spectrograph, and analysis of samples a thousand times smaller. The brilliant Alfred Nier further improved mass spectrometer design (Fig. 2), and made several crucial analytical and conceptual contributions to the applications of radiogenic Pb and ordinary or common Pb to geochronology in general, and to determination of the age of the Earth in particular. The Development of the Isotope Dilution Method At about the same time that Nier was reporting his new isotopic results for Pb from Pb ores, another revolution was about

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to begin in nuclear physics. Again, the Curie laboratory played a leading role. Marie Curies daughter, Irene Joliot-Curie, and her husband, Frederic Joliot-Curie, bombarded a stable element with alpha particles, transforming it into a new radioactive element. This marked the rst laboratory transformation of one element into another. Over the next several years numerous labs conducted similar experiments on a variety of elements. In every case, the newly created radioactive isotopes were always within a few atomic mass units (amu) of the target element. In 1938, Irene Joliot-Curie and a visitor to her lab, Pavel Savitch, published results of experiments in which they bombarded U with neutrons. Their chemical analyses of the irradiation products of the experiment strongly suggested the presence of the rare earth element lanthanum. But because lanthanum is ~100 amu lighter than uranium, Joliot-Curie and Savitch were doubtful about the identication. In fact, their identication was correct. Joliot-Curie and Savitch had actually induced the nuclear ssion of 235U but failed to recognize it. The German team of Otto Hahn and Fritz Strassmann, who also had doubted the original result, duplicated the Joliot-Curie and Savitch neutron irradiation of U. They conducted exquisitely detailed chemical

Figure 1. One of F.W. Astons mass spectrographs. (A) is the cathode ray tube that produced high-energy electrons. The electrons were collimated in the (B) section of the instrument, and ionized the sample, which was introduced in gaseous form in the (C) section of the instrument. (D) marks the curved section of the ight tube that was positioned during operation between the poles of a large electromagnet. Just to the left of (E) the separated ion beams impinged on a photographic plate for detection and semiquantitative isotope ratio measurement. Courtesy of Cambridge Physics Outreach.

Figure 2. A.O. Nier, ca. 1940, with one of his early mass spectrometers, a 180-degree instrument; most of the curved tube would be between the poles of a large magnet. Ions were produced by electron bombardment in the mass spectrometer source, held in Niers right hand, and were measured in the collector section of the instrument, held in Niers left hand. This is apparently the instrument used by Nier for his superb measurements of the isotopic composition of uranium, radiogenic lead, and common lead in the late 1930s (University of Minnesota, courtesy of AIP Emilio Segre Visual Archives).

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Mattinson tope dilution were applied to the Rb-Sr and K-Ar parent-daughter systems. Rb and K were discovered to be weakly radioactive by 1906, but could only be exploited for geochronology by about the 1950s when instrumentation and methods had sufciently improved. Also developed in the early 1950s was the carbon-14 dating method. State-of-the-Art by 1963 By 1963, the big three of geochronology, U-Th-Pb, Rb-Sr, and K-Ar, were well established. Complexities in the U-Pb system caused by loss of radiogenic Pb by either episodic or continuous diffusion mechanisms (Wetherill, 1956, and Tilton, 1960, respectively) were reasonably well understood, and could be seen through by using the Wetherill (1956) concordia diagram (Fig. 3). Silver and Deutsch (1963) convincingly correlated the degree of Pb loss in zircon to the amount of radiation damage related to sample age and U + Th concentrations, an insight that would provide the basis for future generations of sample selection and sample pre-treatment strategies. Nicolaysen (1961) devised the isochron method for interpreting Rb-Sr age data (Fig. 4). The basic isochron method would later be applied to a wide variety of other isotopic parent-daughter systems. Evernden et al. (1960) presented experimental data on the diffusion of Ar in several minerals, and Hart (1964) provided further insights into closure temperature for both the K-Ar and Rb-Sr dating systems. Other systems, such as ssion track dating and U-series disequilibrium dating, were in their infancy.

analyses of the irradiated products and provided convincing evidence that barium, also ~100 amu lighter than uranium, was, along with several other elements, present after the neutron irradiation. By providing denitive proof that the atom had been split, Hahn and Strassmann received credit for the discovery of atomic ssion. Further research on ssion, the onset of World War II, and the Manhattan Project, led to the atomic bomb. But the pathway to the bomb required developing techniques to separate the ssionable 235U isotope from the much more abundant nonssionable 238U isotope. After the war, some scientists realized that the isotope separation techniques could be used to produce puried isotopes of many elements that could then be used as tracers for accurate measurements of very small amounts of material. This became known as the isotope dilution method. One such scientist was Harrison Brown at the University of Chicago. Brown was interested in applying new methods, such as low-level radiation counting, neutron activation, and isotope dilutionmass spectrometry, to measurement of trace elements in meteorites. Browns group included graduate students Clair (Pat) Patterson and George Tilton, along with mass-spectrometer and isotope-dilution expert M.G. Inghram. Isotope dilution analysis of U using highly puried 235U as a tracer or spike was an immediate success. However, the Pb isotopic work on meteorites went more slowly, owing to low Pb levels in most meteorite samples and high levels of Pb contamination in the environment, so the team turned its attention to minerals in terrestrial crustal rocks. The mass spectrometry methods they developed reduced the amount of Pb needed for analysis by a factor of ~1,000 compared with Niers earlier work. This, along with reductions in Pb contamination, allowed ages to be determined on reasonable amounts of common U and/or Th-bearing trace minerals, such as zircon, in ordinary crustal rocksthe foundation of modern U-Pb geochronology. After some delay owing to top secret classication of the very existence of puried 235U, the nal results (Tilton et al., 1955) presented Pb, U, and Th data for all the minerals in a ca. 1 Ga granite. The work, published in the GSA Bulletin, reported the highly radiogenic nature of Pb in zircon, and published the rst isotope dilution ages for zircon. Ironically, the title of the paper: Isotopic composition and distribution of lead, uranium, and thorium in a Precambrian granite, does not include the word zircon. Thus, some discussions of the history of U-Pb zircon dating have overlooked this seminal contribution. Tilton et al. (1955) also reported the moderately radiogenic nature of Pb in sphene (titanite), apatite, and magnetite, and the presence of non-radiogenic (common) Pb in feldspar. Patterson continued with the meteorite work, improved clean lab techniques still further, and determined a ca. 4.55 Ga age for meteorites and the Earth (Patterson et al., 1955; Patterson, 1956), quite compatible with modern measurements. At about the same time that Browns group developed the next generation of U-Th-Pb geochronology, similar techniques using advanced chemical separation, mass spectrometry, and iso-

Figure 3. Example of a concordia diagram plotted with synthetic data, showing different fractions of a 2 Ga zircon sample that have lost varying amounts of Pb during a 200 Ma disturbance. Even in the absence of the concordant 2 Ga point, the remaining data would still project to the 2 Ga upper intercept on concordia, giving the original age. MSWDmean square of weighted deviates.

The geochronology revolution THE NEXT FIFTY YEARS: THE EXPLOSION IN GEOCHRONOLOGY The fty years between 1963 and the present have seen, quite literally, an explosion in the amount of geochronological research, the diversity of methods, the quality of the analyses, and the sophistication of data interpretation. Major driving forces have included development of new instrumentation, analytical techniques, data analysis techniques, and, especially in the last decade, laboratory collaboration at national and international levels. This section provides a few highlights of this tremendous geochronology revolution. Instrumentation Conventional Mass Spectrometers In the early 1960s, most mass spectrometers were modestly updated versions of the Nier-type design (e.g., Inghram and Hayden, 1954; Shields, 1962), and many instruments in academic labs were custom-built, using off-the-shelf electronics and the skills of local machine shops and glassblowers. In these mass spectrometers, highly puried samples of the elements of interest were loaded into the instrument, either dried onto a lament and ionized by thermal ionization or introduced as a gas and ionized by electron bombardment. Signals were recorded on, and laboriously read from, paper charts. Calculations were made on large mechanical calculating machines. By the mid- to late-1960s, development of mini-computers allowed some level of computer control of mass spectrometer operation, plus digital

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collection and reduction of data, with major increases in precision and accuracy (e.g., Wasserburg, et al., 1969). The growing demands of the nuclear industry for large numbers of mass spectrometers to monitor enrichment levels of 235U throughout the nuclear fuel production cycle led to increased commercial production of high-quality mass spectrometers, thus providing greater access to high-quality instruments for academic labs. Highly linear ion-counting systems such as the Daly detector also became available in the 1960s, allowing accurate measurements on still smaller samples. Solid-state electronics gradually replaced vacuum tubes, and by the early 1980s a new generation of multi-collector mass spectrometers with modern electronics, high levels of computer control, computer designed ion optics, and modern vacuum systems emerged. These remarkable instruments continue to be improved, and to provide astonishing levels of precision and accuracy, beyond the wildest imagination of the likes of Aston and Nier, the pioneers to whom we owe such a great debt. Secondary Ion Mass Spectrometers In the early 1980s, a revolutionary new approach to zircon U-Pb dating emerged: secondary ion mass spectrometry or SIMS (Fig. 5). This approach is exemplied by the sensitive high-resolution ion microprobe or SHRIMP; e.g., Compston et al. (1982, 1984); and see Ireland and Williams (2003) for an excellent summary. The use of an ion microprobe for U-Pb dating had been demonstrated earlier by Andersen and Hinthorne (1972), but the standard ion microprobe used in that study lacked the resolution for effective zircon dating. Compston successfully overcame these limitations, and the instrument has been widely adopted around the world. The SHRIMP and competing CAMECA instruments typically use a beam of oxygen ions to sputter spots typically ~550 m diameter and a few micrometers deep on the polished surfaces of thin sections or grain mounts. During the sputtering process, a fraction of the sputtered atoms are ionized and introduced into the mass spectrometer section of the instrument, permitting measurement of the relative intensities of isotopes of Pb, U, Th, and other elements. The intensities are normalized to results for zircon standards that have been accurately dated by isotope dilutionthermal ionization mass spectrometry or ID-TIMS methods. Owing to the very small amount of sample actually analyzed, the need for standardization, small amounts of instrumental drift with time, and slight variations in results related to matrix effects, SIMS zircon 206Pb/238U dates have uncertainties in the 1%2% 2-sigma range (e.g., Nemchin et al., 2013). This is signicantly greater than the 0.1% for recent high-quality ID-TIMS ages (e.g., Schoene et al., 2010). However, the lower accuracy and precision of SIMS dating is offset by the ability to image, then date different domains within individual zircon grains. This high spatial resolution can resolve age complexities related to older inherited cores, multi-generational younger overgrowths-replacements-alterations, etc. (Fig. 6). Many U-Pb geochronology labs now complement the superb precision and

Figure 4. Example of a Rb-Sr isochron diagram re-plotted using data from a lunar meteorite from Rankenburg et al. (2007). The error ellipses shown larger than actual size for visibility. The age is calculated from the slope of the isochron. The Y-intercept gives the initial ratio of 87Rr/86Sr at the time the lunar source rock was formed.

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Figure 5. A recent example of the SHRIMP SIMS instrument. Samples are bombarded with ions in the right-hand section of the instrument and after a lengthy passage, rst through an electrostatic sector, then a magnetic sector, arrive at the left-hand side of the instrument to be counted. Source: Geoscience Australia.

accuracy of the ID-TIMS method with the high-resolution capabilities of SIMS analysis for the best possible results. With SIMS dating, the ability to analyze grains directly eliminates the arduous, time-consuming low-blank dissolution chemical separation procedures required prior to ID-TIMS analysis. In addition, the actual data measurements using SIMS are faster than for ID-TIMS. This rapid analysis capability opens up new possibilities for projects that would be impractical with IDTIMS. A spectacular example is the mass spectrometric mining

of Hadean zircons from the Narryer Gneiss Complex in Western Australia (e.g., Holden et al., 2009). The host rock for the ancient zircon, a conglomerate deposited at ca. 3 Ga, contains zircons of a wide range of ages, and only a very small percentage of the zircon grains are greater than 4 Ga. These oldest zircon grains are a precious archive of geochemical information about the Earths earliest igneous processes, and the evolution of the Earths early mantle. Holden et al. (2009) used SHRIMP instruments set up for automatic operation to eventually screen some 100,000 zircon grains. As individual zircon grains with greater than 4 Ga ages were identied, they were used for a wide array of petrologic and isotopic studies (e.g., Hopkins et al., 2010, and references therein). This work also highlights another advantage of SIMS analysisonly a minute amount of material is consumed in a typical SIMS analysisthe technique is essentially nondestructive. The identied ancient zircon grains were available for a wide array of additional analyses. Inductively Coupled PlasmaMass Spectrometers At about the same time as the emergence of the SHRIMP in the early 1980s, another new instrument, the inductively coupled plasma mass spectrometer, or ICP-MS, was developed. The

Figure 6. 24 m diameter laser ablation spots on a zircon grain dated by LA-ICPMS. Cathodoluminescence (CL) imaging prior to analysis reveals protolith zircon with classical igneous oscillatory zoning that has been partially overgrown and replaced by younger zircon associated with migmatization. For this gure, the grain mount was re-imaged by CL after LA-ICPMS analysis. Zircon analyzed by SIMS would appear about identical, except that the analysis pits would be shallower (photo by the author).

The geochronology revolution ICP-MS typically uses a plasma of Ar ions that can efciently ionize most elements in the periodic table. The ions are then introduced into a high-resolution mass spectrometer for isotopic analysis. Work by Gray and Date (e.g., Date and Gray, 1981; Gray and Date, 1983) was seminal in the development of the plasma source and its combination with a high-resolution mass spectrometer. Initially, all samples were fed into the plasma in solution with use of spikes or standard solutions to measure trace element concentrations and correct for instrumental drift, mass bias, and fractionation. Within a few years, however, lasers were being used to ablate material from solid samples and feed the material into the plasma using a carrier gas, again, thanks to the pioneering efforts of Gray (e.g., Gray, 1985). This became known as laser ablationinductively coupled plasma mass spectrometry, or LA-ICPMS. By the early to mid-1990s, the laser ablation technique was applied to U-Pb dating of zircon (e.g., Feng et al., 1993; Fryer et al., 1993). Kosler and Sylvester (2003) provide an excellent summary of the development of LA-ICPMS zircon dating. Another major step forward was the coupling of the ICP source with a high-resolution multi-collector mass spectrometer, allowing high-accuracy isotopic measurements of elements of interest in geochronology and radiogenic isotope tracer studies (Walder et al., 1993). As in the case of the SIMS, unknown samples are interspersed with zircon standards of known age. In recent years, LA-ICPMS U-Pb dating has made rapid advances spurred by improvements in lasers and ICPMS instruments, including simultaneous multi-collection with several ion counters, signicant decreases in spot size, depth, and amount of sample consumed. These improvements have allowed development of more powerful techniques such as depth proling with single pulse laser ablation analysis (e.g., Cottle et al., 2009). In terms of precision and accuracy, the LA-ICPMS U-Pb zircon dating technique is now comparable to the SIMS zircon dating technique. A signicant advantage of LA-ICPMS is that individual spot analyses require even less time than individual spot analyses for SIMS. High throughput is an important factor in studies requiring analysis of large numbers of zircon grains, e.g., studies of detrital zircon grains; see Gehrels (2000) and Fedo et al. (2003). As in the case of SIMS, U-Pb dating by LA-ICPMS has been extended to several other minerals. At this stage, it is necessary to include an important caveat, at the suggestion of a perceptive reviewer. The enormous volume of SIMS and especially LA-ICPMS U-Pb dating made possible by rapid analyses has a down side. To quote the reviewer, More and more papers of poor quality data and even poorer interpretations that have considerable disregard for the known complexity of zircon are being published with an emphasis on volume of data. The result is a dumbing down of the discipline and more and more difcult distinction to be made by geologists between highly reliable work and that of sometimes unreliable interpretations made using uncritical inspection of data and analytical quality. This issue will be increasingly important in the eld of micro-beam geochronology in future years. The good

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news is that many labs are paying close attention to data quality and interpretation, and to developing improved techniques. Tandem-Accelerator Mass Spectrometer Also in the early 1980s, the tandem-accelerator mass spectrometer was designed, with major advantages for C-14 and cosmogenic nuclide studies (e.g., Purser et al., 1982). Earlier analyses relied on counting the radioactive decay of 14C and other short-lived isotopes of interest. To use 14C with a half-life of 5730 a as an example, only ca. 4 107 of the total 14C atoms in a sample will decay and be counted in an entire day, assuming 100% counting efciency. The tandem-accelerator mass spectrometer measures the 14C atoms present in the sample directly, rather than having to wait for them to decay. The new instrument has allowed sample size reduction from thousands of milligrams to <1 mg, and dating of older samples in which the 14C is almost totally decayed away. The instrument has also been applied to other dating systems with great success, e.g., cosmic ray exposure ages used to determine geomorphic denudation rates. Improved Techniques K-Ar to 40Ar-39Ar Method The K-Ar dating system was the rst of the big three to experience a major innovation in technique. The K-Ar method, based on the decay of 40K, the minor radioactive isotope of K, requires physically splitting a rock or mineral sample into two aliquots prior to analysis. One aliquot is used for analysis of the daughter isotope, 40Ar, an inert gas, typically by isotope dilution mass spectrometry after extracting the Ar by fusing the sample in a vacuum. The other aliquot is used for the analysis of K, using one of several possible techniques, most often by ame photometry. Overall, conventional K-Ar dating tends to be somewhat limited in precision and accuracy by possible heterogeneity between the two aliquots, by the imprecision of the methods used for K determination, by difculty in assessing whether or not some Ar has escaped from the dated sample during its lifetime, and whether or not any excess 40Ar is present (McDougall and Harrison, 1988). Development of the 40Ar-39Ar technique was a huge step forward (Merrihue and Turner, 1966). An excellent detailed reference on the theory of the method and its application to a wide range of terrestrial and lunar samples is McDougall and Harrison (1988). In the 40Ar-39Ar, or Ar-Ar method, the unknown samples to be dated, along with interspersed welldated standards, are irradiated with neutrons in a nuclear reactor. During the irradiation, a small fraction of the major non-radioactive isotope of potassium (39K) is converted to 39Ar via a neutron in, proton out reaction. 39Ar is extremely rare in nature, owing to its short half-life of 269 years, and thus it serves as an ideal proxy for the amount of K in the sample. With both the daughter and the proxy of the parent now in the form of Ar gas, the parent/daughter ratio can be precisely measured by mass spectrometry after extraction from the sample

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Mattinson was the measurement of new decay constants for 238U and 235U by Jaffey et al. (1971). These constants are about an order of magnitude more precise than those previously used, greatly reducing a major source of uncertainty in calculated U-Pb ages. These developments opened the way for a generational improvement in the zircon method by Tom Krogh of the Carnegie Institution Geophysical Lab. Krogh (1973) developed a new, low-contamination method for digesting zircon using hydrouoric acid in a Teon container inside a stainless steel pressure vessel. The chemical resistance of the Teon and strength of the steel jacket allowed

by heating. usually with a laser or a furnace based on electrical resistance or radio frequency induction. With the Ar-Ar method, the need to split the sample and the imprecision of the old, separate K measurements are eliminated, and precision of the calculated age is dependent primarily on the mass spectrometry plus the quality of the ages for the standards. Also thanks to the elimination of sample splitting, very small samples, including single grains, can be analyzed. There is still the issue of 40Ar loss, as discussed above for K-Ar, e.g., during slow cooling, reheating, or alteration. However, since the daughter isotope and the proxy for the parent isotope are both in the form of Ar gas, a spectrum of ages can be obtained by incrementally heating the sample (Fig. 7). Thus, the Ar is released in a series of separately analyzed steps at progressively higher temperatures, rather than in one bulk step. The series of steps might yield a complex progression of ages, or a well-dened plateau of equivalent ages, permitting more rigorous age interpretations. Laser heating of samples has been used successfully for analysis of small single grains, in situ dating in polished rock slabs, and studies of diffusion of Ar in sections of large mineral grains. As with other geochronology methods, improvements in instrumentation and techniques opened the way for more and more precise measurements on smaller and smaller samples. Precisions of the best Ar-Ar dates improved to 0.1% or better, comparable to precisions for the best 206Pb/238U zircon dates. However, in cases where both high-quality Ar-Ar and 206Pb/238U zircon ages were available from identical samples with simple rapid cooling histories, the Ar-Ar ages were commonly ~1% younger. This discrepancy has been resolved only in the past decade or so by a major cooperative effort by geochronologists. U-Pb Zircon Method U-Pb dating by ID-TIMS. The U-Pb zircon dating method experienced major innovations just a few years after the development of the Ar-Ar technique. In the case of U-Pb, several factors, some independent, and some inter-related, combined to drive a major advance. For most of the 1960s, zircon analysis techniques still followed the pioneering methods of Tilton et al. (1955): Zircon samples were fused in a borate-based ux in platinum crucibles; Pb and U were separated by liquid-liquid extraction using large amounts of reagents; and Pb was typically loaded as a sulde for mass spectrometry. As a result, even with extreme care in handling and purication of reagents, the Pb blankthe amount of Pb contamination introduced during a typical zircon analysiswas quite large. This, along with the Pb sulde loading method, limited precise age determinations to zircon samples that contained at least 1020 g of radiogenic Pb. The rst advance was the availability of clean, chemically resistant Teon for laboratory use. A second advance was a new method of loading Pb for mass spectrometry. Cameron et al. (1969) used a mixture of silica gel and phosphoric acid to load Pb on rhenium laments, producing yet another factor of 1,000 decrease in the amount of Pb needed for mass spectrometric analysis, while improving precision and accuracy. A third advance

Figure 7. Examples of Ar-Ar step-heating release diagrams replotted using data from Lunar samples from Turner (1971). The upper diagram, representing data for lunar rock 12013, yields a broad age plateau, suggesting minimal post-crystallization disturbance of the isotopic system. The lower diagram, representing data for lunar rock 10068, shows the effect of major Ar loss in the two lowest temperature release steps, shown as open rectangles, and a plateau for the four higher temperature release steps, shown as shaded rectangles.

The geochronology revolution digestion of zircon at high temperatures and pressures in small volumes of hydrouoric acid with very low Pb blanks. Krogh also developed small-scale ion exchange techniques to separate Pb and U from the other components of zircon. At the same time, Mattinson (1972), then a post-doc in Kroghs lab, designed a simple, all-Teon sub-boiling still that produced very high-purity hydrouoric and other acids, further reducing Pb blanks. All of these developments opened the path for precise and accurate U-Pb dating of very small zircon samples, including single grains and fragments of grains. Krogh was responsible for, or an inspiration for, many other signicant advances, such as synthesis of 205Pb for isotope dilution analysis of Pb (Krogh and Davis, 1975; Parrish and Krogh, 1987), which allowed full analysis of Pb from zircon in a single mass spectrometer run. Previously, zircon was divided into two aliquotsone for measuring concentration, and one for measuring Pb isotopic composition. As in the case of Ar-Ar dating, the 205 Pb tracer eliminated possible errors associated with sample splitting and opened the way for analyzing much smaller samples. The distribution to the U-Pb geochronology community of 205Pb made by Parrish and Krogh (1987) was immediately followed by a marked improvement in the quality of ID-TIMS work worldwide. Krogh (1982) also developed an air abrasion technique for the selective removal of the outer layers of zircon grains. In many igneous rocks in particular, the outer, late crystallized zones of zircon grains are higher in U and Th than are the inner zones. The higher U and Th concentrations generate higher degrees of radiation damage, rendering the outer zones more susceptible

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to Pb loss, as shown originally by Silver and Deutsch (1963). Kroghs air abrasion method was the rst simple and reliable method for selectively removing the outer zones prior to analysis (Fig. 8). Air abrasion remained the pre-treatment method of choice for over 20 years, until a new technique, CA-TIMS or chemical abrasion (Mattinson, 2000a, 2003, 2005), began to be widely adopted. The CA-TIMS technique uses a high-temperature annealing step prior to partial dissolution in hydrouoric acid. The annealing step eliminates undesirable leaching effects that hampered earlier attempts to use partial dissolution as a pretreatment for zircons. CA-TIMS not only effectively removes outer high U + Th radiation-damaged layers, but is also effective at penetrating zircon grains along fractures and other defects to mine out interior high U + Th zones. This selective removal of highly-radiation-damaged zircon zones in many cases results in a residue of minimally damaged, perfectly concordant closed system zircon (Fig. 9). In recent years, the silica gel method for running Pb has been further improved (Gerstenberger and Haase, 1997), allowing precise measurements of still smaller Pb samples. Also in recent

Figure 8. Concordia diagram re-plotted from data for low uranium zircon fractions from Krogh (1982). The open ellipses are from slightly discordant non-treated zircon fractions. The shaded ellipse is from a strongly air-abraded zircon fraction. Removal of the outer, higher-U zones of the zircon grains by the air abrasion removes almost all of the parts of the zircon grains that have lost Pb, yielding an almost completely concordant result for the abraded zircon fraction.

Figure 9. A CA-TIMS multi-step release diagram modied from Mattinson (2005, g. 7). Diagram A is analogous to an Ar-Ar stepheating release diagram, showing major Pb loss for the rst two relatively low-temperature steps, very minor Pb loss for the third step, and a plateau for the remaining ten steps. These latter steps are all perfectly concordant, based on the full isotopic data (not shown here). Diagram B reveals that the early steps are the highest in U, whereas the concordant plateau steps have U concentrations less than a tenth that of the rst, highly discordant step. The progressive decrease in U concentrations from the early steps to the later steps demonstrates the highly selective nature of the CA-TIMS dissolution process.

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Mattinson of the 87Rb decay constant have been published. Most recently, Rotenberg et al. (2012) presented results of a ~30-year laboratory accumulation experiment, measuring the amount of radiogenic 87 Sr formed from a large batch of highly puried RbClO4 over that time span. The result of 1.3968 + 0.0027/0.0018 1011 a1 is the most precise measurement to date, with precisions comparable to those for the U decay constants. The new result also is quite consistent, within errors, with six of the seven other studies completed between 1982 and 2011 (Rotenberg et al., 2012, g. 4). It will be interesting to see if, over the next several years, Rb-Sr geochronology regains its place as one of the premier geochronology systems, thanks to better understanding of the behavior of Rb and Sr in rocks and minerals, and to the latest decay constant results. New Dating Systems Since 1963, many new decay systems have been developed for geochronology. In many cases these new systems have become viable, thanks to new generations of instrumentation, such as multi-collector TIMS instruments, and multi-collector ICP instruments. One way to track the growth is by surveying the contents of widely used textbooks and monographs that focus on isotope geology in general, and geochronology in particular. For example, papers in the classic Geochronology of Rock Systems (Kulp, 1961) are entirely devoted to Rb-Sr, K-Ar, and U-Pb, with brief mention of C-14 and development of other chronometers (Kulp, 1961, p. 165). The small book Ages of Rocks, Planets, and Stars (Faul, 1966) also concentrates on C-14, Rb-Sr, K-Ar, and U-Pb, but includes brief discussions of U-series disequilibrium, ssion track, and the now little used U-Th-He dating method. The rst edition of Faures widely used text (Faure, 1977) adds coverage of the then-well-established Ar-Ar method, and includes full chapters on ssion track dating and other forms of radiation damage, U-series disequilibrium dating, and C-14 dating. A single chapter (Faure, 1977, p. 183196) describes the Re-Os, Lu-Hf, and K-Ca systems as most promising but notes that these decay systems have found only limited applications for age determinations of rocks and minerals. Further, Faure (1977) suggests that the Sm-Nd and La-Ce + Ba systems may be of some interest, with recent work on Sm-Nd having yielded promising results. Jger and Hunziker (1979) cover Rb-Sr, K-Ar, Ar-Ar, U-Pb, and ssion track dating, with brief mention of C-14, U-series disequilibrium, and Sm-Nd. In Faures second edition (Faure, 1986), Sm-Nd, Lu-Hf, Re-Os, and K-Ca systems ll six chapters, totaling 80 pages, and are joined by another full chapter on dating with cosmogenic nuclides. More recent volumes, such as Dickin (2005), Faure and Mensing (2005), and Allgre (2008), include full coverage of still more systems, including La-Ce, La-Ba, the renaissance of U-Th-He dating, and the use of extinct nuclides for understanding very early solar-system history. All told, depending on how one counts, close to 40 different dating methods are now available, spanning age ranges from months to billions of years.

years, the constants used in calculation of U-Pb ages have been ne-tuned. The decay constant of 235U, relative to the decay constant of 238U, has been re-determined (Mattinson, 2000b, 2010; Schoene et al., 2006). The result is about an order of magnitude more precise than the relative value of Jaffey et al. (1971). The 235U/238U ratio of natural uranium in zircon and other minerals used for U-Pb geochronology of common igneous and metamorphic rocks has also been re-determined with much greater accuracy and precision (Hiess et al., 2012). The two improved constants combine to greatly increase the accuracy of 207Pb/206Pb ages, relative to 206Pb/238U ages, permitting better evaluation of apparent concordancy versus apparent slight discordancy for U-Pb ages, thus allowing more accurate age interpretations. U-Pb dating by SIMS and LA-ICPMS. As mentioned in the section on instrumentation earlier, micro-beam methods for dating zircons, then other minerals, emerged in the early 1980s and early 1990s using SIMS and LA-ICPMS, respectively. These are discussed in more detail in a later section. Rb-Sr The third big three technique of the 1950s and 1960s, Rb-Sr, also beneted from improved instrumentation and techniques, but it has been slow to reach the level of the Ar-Ar and U-Pb systems. Difculty in accurately determining the 87Rb decay constant has long limited the overall accuracy of Rb-Sr geochronology. For example, starting in the mid- to late 1950s, two quite disparate decay constants for 87Rb were used in different labs. One decay constant, 1.39 1011 a1, was based on using concordant U-Pb dates on uraninite and monazite in pegmatites to calculate the 87Rb decay constant from 87Sr/87Rb ratios in coexisting micas in the pegmatites (Aldrich et al.,1956). Note: Adjustment of this constant using the newer Jaffey et al. (1971) U decay constants would give a decay constant of ~1.41 1011 a1. The other decay constant in use, based on liquid scintillation counting of the beta emissions from natural Rb (Flynn and Glendenin, 1959), was 1.47 1011 a1, more than 4% higher than the 1.39 value, casting considerable doubt on the accuracy of R-Sr dates using either decay constant. Also damaging for Rb-Sr geochronology: The Rb-Sr whole-rock method was widely used as a dating tool for igneous crystallization during the 1960s and 1970s, but lost credibility in the 1980s as evidence of whole-rock open-system behavior mounted (Dickin, 2005, p. 51). Improvement, at least in terms of decay constant accuracy, was gradual. By 1977, the publication date of recommendations on adoption of a standard set of decay constants by the International Subcommission on Geochronology (Steiger and Jger, 1977), several additional studies had been completed on the 87Rb decay constant, but there was still considerable scatter. Steiger and Jger (1977, p. 360361) noted that the new value for the 87Rb decay constant should lie between 1.41 and 1.43 1011/yr, recommended that a value of 1.42 1011/yr be accepted for provisional use, but warned that the problem of the 87Rb decay constant was not denitely solved. In the years following the 1977 Steiger and Jger report, several more measurements

The geochronology revolution It is beyond the scope of this broad survey to provide detailed discussions of all of these newer methods, so a few brief examples must sufce. Systems such as Sm-Nd and Lu-Hf have proven invaluable for dating high-grade garnet-bearing metamorphic rocks, and even the time span of metamorphic garnet growth. Re-Os has been used for direct dating of ore minerals, basalts, and organic-rich shales. The renaissance of U-Th-He dating is of particular interest inasmuch as the very rst radiometric dates by Rutherford were based on the decay of U and its numerous intermediate daughter isotopes to helium. As discussed earlier, Strutt soon demonstrated that helium was readily lost from highly radioactive minerals, and dating based on helium accumulation in U Th-rich minerals fell into disrepute for nearly twenty years (Harper, 1973, p. 14). U-Th-He dating enjoyed a short-lived revival from ca. 1929 to the mid-1930s. Helium dates for a suite of stratigraphically well-constrained mostly basaltic rocks appeared to agree closely with existing U-Th-Pb dates. Holmes actually published an updated version of his geologic time scale based on a combination of the new helium dates plus existing U-Th-Pb dates. Shortly thereafter, the calibration of an instrument used in the helium dating was found to be in error by more than a factor of two (Harper, 1973, p. 6970). After this debacle, the U-Th-He dating method attracted only minor further interest until its potential for low-temperature thermochronology was realized (e.g., Zeitler et al., 1987; Wolf et al., 1996; Reiners and Farley, 1999). Ironically, the methods greatest weakness, the relatively low temperatures at which helium diffuses out of minerals, is the primary reason for its reincarnation as an important low-temperature thermochronometer. K-Ar, then Ar-Ar dating of perthitic alkali feldspars, has a history similar in some respects to that of the U-Th-He dating method (see McDougall and Harrison, 1988, for more detailed discussion). Dating of perthitic alkali felspar from metamorphic rocks and slowly cooled igneous rocks usually yielded ages that were too low compared with ages for other minerals. The mineral was deemed unsuitable, and largely abandoned for dating work. Later, investigations using detailed Ar-Ar age spectra revealed that perthitic alkali feldspar commonly contained a record of cooling between ~250 and 150 C, and could be an important thermochronometer for this temperature range. In summary, the modern geochronologist has available a wide array of dating methods with which to approach geologic problems ranging from the earliest history of the solar system to rates of topsoil loss from erosion. Data Analysis In the 1950s and 1960s, data analysis was primitive at best. Uncertainties for individual analyses were commonly based on some general idea about overall reproducibility of mass spectrometer runs plus, in some cases, a provision for the typically large decay constant uncertainties. Data were plotted by hand on large sheets of graph paper. Isochrons and discordia lines through arrays of data points were tted by eye, using a long ruler, with

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an overall age uncertainty deduced from how much the position of the ruler could be varied while still overlapping most of the data points. These primitive methods would soon be supplanted by more rigorous data analysis. York (1968) developed the equations for tting a straight line to data points with correlated errors, typical of most geochronological data. Brooks et al. (1972) expanded on Yorks work, specically for evaluation of Rb-Sr data. Ludwig (1980) and Davis (1982) focused on uncertainties in U-Pb data. Subsequently, Ludwig (e.g., 1988, 1998a, 1998b, 2000, etc.) published a remarkable series of contributions to calculation, plotting, and interpretation of U-Pb data, plus data from many other decay systems used in geochronology. Sample Size ReductionSpatial Resolution One consistent trend in geochronology has been the constant push to obtain precise and accurate ages on ever-smaller samples. A major driving force behind this trend, especially in the case of U-Pb zircon dating, has been increasing recognition of the complexity of geochronological samples. Zircon populations in many igneous rocks consist entirely of grains formed during magmatic crystallization. However, in some igneous rocks, zircon grain populations might comprise primary igneous zircon crystallized from the magma, older inherited zircon grains or cores from older rocks in the magmas source area, older zircon grains entrained during the magmas passage through the crust, younger zircon overgrowths or replacements added during subsequent metamorphism. Data from a large multigrain sample of such a complex population can be challenging to interpret. Zircon from a volcanic ash fallow would be subject to the same possible complexities, with the added problem of possible entrainment of xenocrystic zircon during eruption and ow over the Earths surface. Ar-Ar analyses of volcanic minerals such as sanidine in ash fallsows are also susceptible to entrainment of xenocrystic sanidine. For these reasons, analysis of individual grains is a powerful tool, allowing outliers to be excluded from the main igneous population of grains. In addition, for the zircon method, grains can be studied in detail using various imaging techniques plus micro-beam dating techniques either to directly date the appropriate parts of individual grains or to assist in grain selection and/or interpretation of single grain analyses. Recently, additional ways of evaluating spot or single grain analyses have been added to the geochronologists arsenal of tools. One particularly powerful tool is analysis of trace elements, particularly the rare earth elements (REE) on the same volume of zircon used for U-Pb geochronology: single grains, Schoene et al. (2010); and SIMS, e.g., Mazdab and Wooden (2006), Mattinson et al. (2006, 2009), Grimes et al. (2007), and McClelland et al. (2009). Incorporation of REE in zircon during crystallization reects not only the composition of the bulk rock system from which the zircon is forming, and the partition coefcients for the various REE in zircon, but also the nature of other minerals that form before or during zircon crystallization and compete with zircon for the available REE. Thus, REE patterns can help place the measured

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Mattinson dine analysis to fundamental problems in stratigraphy and biogeology. To quote Bowring and Schmitz (2003, p. 305): What are the durations of mass extinctions? How long does ecological recovery take following a major extinction? Do evolutionary radiations correlate with changes in chemistry and temperature of the ocean-atmosphere system and global climate? With modern instrumentation and techniques, both the zircon U-Pb and the Ar-Ar methods seemed ideally suited to answer these questions. A number of groups attacked a particularly attractive target the timing and duration of the mass extinction at the PermianTriassic (P-T) boundary, the greatest extinction event in the stratigraphic record. Several marine sections in south China expose the Permo-Triassic boundary, including the type section at Meishan. The sedimentary beds are intercalated with numerous thin volcanic ash beds that contain zircon and sanidine, seemingly ideal for dating by the latest high-precision U-Pb and Ar-Ar techniques, respectively. However, the high-precision data sets yielded slightly different ages for the Permo-Triassic boundary, outside of the stated uncertainties, not only for U-Pb versus Ar-Ar results but also for U-Pb results from different laboratories. At this point, it would have been unsurprising if a bunker mentality prevailed. Instead an international group formed the EARTHTIME Initiative, a community effort primarily involving U-Pb geochronologists and Ar-Ar geochronologists, to resolve the issue of disparity of ages between different labs and different techniques. This will be discussed in more detail in the section below on Collaboration and Inter-calibration. For now, the important point is that the controversy drove home the necessity of: (1) analyzing zircon grains individually, rather than analyzing multi-grain samples; (2) inter-calibrating isotope dilution tracers used in U-Pb labs; (3) dealing with Pb loss in zircon grains by replacing air abrasion with CA-TIMS; and (4) reevaluating the accuracy of the decay constants, age standards, and analytical protocols used in Ar-Ar labs. See Schmitz and Kuiper (2013) for an excellent summary of these general issues, as well as the saga of dating the P-T boundary specically. At the present time, these issues have been mostly resolved, and the high precision of modern U-Pb and Ar-Ar methods has been matched by high accuracy (Fig. 11). Micro-beam Analysis Micro-beam analysis, predominantly using SIMS and LAICPMS techniques, has become an increasingly vital part of modern geochronology. Zircon, with a combination of relatively high concentrations of U and Th, and virtually no initial Pb, is particularly well suited for this approach, although several other minerals are also attractive targets. As discussed earlier, the major advantage of micro-beam techniques is high spatial resolutionthe ability to date small spots in the range of several microns to a few tens of microns in diameter on polished sections of individual mineral grains. Typically, placement of spots is guided by ne-scale imaging techniques such as cathodoluminescence, or CL, and backscattered electrons, or BSE (e.g., Hanchar and Miller, 1993; Corfu et al., 2003; Ireland and Williams, 2003; and see Fig. 6).

age of zircon in petrologic context. For example, garnet and zircon both strongly favor incorporation of the heavy rare earth elements (HREE). In the absence of garnet, say, in typical igneous rocks, zircon shows strong HREE enrichments. However, in garnet-bearing high-pressure and ultra-high-pressure (UHP) metamorphic rocks, the garnet competes strongly for the HREE, and zircon growing under these conditions is characterized by relatively at HREE patterns (e.g., Rubatto, 2002; and see Fig. 10). Micro-inclusions in zircon can also provide important petrologic context. For example, Katayama et al. (2001) demonstrated that cores of zircon that crystallized during UHP metamorphism of the Kokchetav massif in northern Kazakhstan contained microinclusions of diamond, coesite, and jadite. In contrast, the outer rims of the zircons lacked these UHP inclusions, and evidently crystallized during later, retrograde metamorphism. Other dating problems, such as direct dating of garnet to determining the time span of metamorphic garnet growth, are less amenable to dating of tiny individual crystals or micro-beam techniques. However, these problems can be approached through physical sampling techniques such as micro-milling core and rim samples of sectioned garnet grains, or by taking advantage of the natural zoning of appropriate elements within individual garnet grains. Some examples will be discussed below. Single Grain Analyses: Zircon U-Pb, and Ar-Ar One of the most fruitful areas of geochronological research in the last 1520 years has been the application of highprecision methods such as U-Pb zircon analysis and Ar-Ar sani-

Figure 10. Simultaneous U-Pb age (ages not shown) and REE concentration measurements on zircon from a UHP eclogite using the SHRIMP reveals older, pre-metamorphic protolith zircon cores with typical igneous REE patterns, with strongly enriched HREE and negative Eu anomalies. The cores are rimmed by younger UHP zircon, whose at HREE patterns and lack of negative Eu anomalies indicate crystallization in competition for HREE from metamorphic garnet, and the absence of plagioclase in the eclogitic host rock, respectively, both indicative of high-pressure metamorphic crystallization. Modied from Mattinson et al. (2007).

The geochronology revolution These imaging techniques are sensitive to variations in trace element chemistry and degree of crystallinity, revealing internal zoning, inherited cores, and different types of overgrowths and alterations. This, along with in situ trace-element studies as discussed above, provides petrologic context for ages determined from individual spot ages (e.g., Fig. 10). As discussed earlier, the precision of ages determined by SIMS and LA-ICPMS techniques is limited by a number of factors, typically to 1%2% 2-sigma (e.g., Nemchin et al., 2013). This renders micro-beam techniques, by themselves, less viable for geochronologic problems that require <0.1% age uncertainties, such as high-precision geologic time-scale work. In such cases, micro-beam methods can be used to screen samples that

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will be analyzed by single-grain ID-TIMS techniques. It is even possible for individual grains, or more correctly, half-grains, that have been characterized by micro-beam techniques to be plucked out of their epoxy mounts and re-dated by the higher precision, higher accuracy ID-TIMS method. Before leaving the topic of micro-beam analysis, it is important to note that the electron microprobe has been applied with considerable success to monazite U-Th-Pb geochronology. Unlike SIMS and LA-ICPMS methods, electron microprobe geochronology is a non-isotopic technique, based on measuring the elemental amounts of U, Th, and Pb in samples. However, the ability to make these measurements on the micron scale permits in situ investigation of the chronology of complex metamorphism and deformation fabrics (e.g., see Williams and Jercinovic, 2002, for an excellent summary). Micro-Milling For some mineral dating techniques, such as Sm-Nd dating of garnet, the concentrations of the parent and daughter isotopes are too low, and the radiogenic enrichments of the daughter isotope are too low to permit dating by micro-beam techniques. Interesting problems, such as the growth rate of metamorphic garnet, must be approached in other ways. One successful approach has been to apply micro-milling techniques. Micromilling allows selective sampling of different parts of single grains, typically in thin sections, thick sections, or polished slabs. Material milled from the core region of the grain, and from the rim of the grain, is collected and analyzed separately, revealing the time span of metamorphic growth (e.g., Ducea et al., 2003; Dragovic et al., 2012). Mineral Zoning An alternative method for dating the time span of garnet crystallization combines the Lu-Hf and Sm-Nd dating techniques in garnets (Fig. 12; and see Lapen et al., 2003; Kylander-Clark et al., 2007; Kohn, 2009; and Smit et al., 2010). This method takes advantage of the tendency of garnet to preferentially concentrate the HREE. Lu, the heaviest REE, is so strongly partitioned into garnet during the early stages of garnet growth, i.e., into the early-formed cores of garnet grains, that much less Lu is available for incorporation into the rims of the garnet grains. Thus, dating whole garnet grains by the Lu-Hf method yields ages that are strongly biased toward early garnet growth. In contrast, Sm and Nd, both lighter REE, and very close together in the REE spectrum, are more evenly distributed throughout garnet cores and rims, yielding a ca. mean age of garnet growth. With some modeling of the actual distributions of Lu, Hf, Sm, and Nd within a particular garnet, ages for both the early garnet formation (core) and the late garnet formation (rim) can be deduced. Collaboration and Inter-Calibration Until about a decade ago, most U-Pb geochronology labs operated quite independently, other than a few efforts to distribute

Figure 11. Dating the Permo-Triassic (P-T) boundary over the past ~22 years. Dates from seven studies are plotted with 2-sigma error bars (the original Ar-Ar results were quoted with 1-sigma errors): Solid circles are dates based on U-Pb zircon analyses; open circles are dates based on Ar-Ar sanidine analyses. A plots results from SHRIMP analyses of 34 zircon grains by Claou-Long et al. (1991). B plots an Ar-Ar sanidine analysis by Renne et al. (1995). C plots ID-TIMS U-Pb air-abraded zircon analyses by Bowring et al. (1998). Zircon and sanidine for these rst three studies were separated from the boundary clay layer just below the P-T boundary. D plots IDTIMS U-Pb air abraded and leached data from Mundil et al. (2001) for a layer just 8 cm above the P-T boundary. Zircon data from the boundary clay itself that are complex and, as indicated by the shaded bar above the error bar, suggest a possible older age (see Schmitz and Kuiper, 2013) for a more detailed discussion. E is Mundil et al. (2004), applying the CA-TIMS method, modied for single grain zircon analysis. Meanwhile, Renne and others had been working on rening the decay constants for 40K. Applying the new constants to the results of Renne et al. (1995) increased the earlier date by ~1% (Renne et al., 2010). This new result is shown as F. Finally, G plots an exceptionally detailed CA-TIMS U-Pb zircon study by Shen et al. (2011), demonstrating that the extinction peak occurred just before 252.28 0.08 million years ago. (Shen et al., 2011, p. 1367). This gure is adapted from Schmitz and Kuiper (2013).

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Mattinson slightly different ages, outside of experimental errors, for crucial geologic problems such as the exact timing of the Permo-Triassic boundarymass extinction, as discussed briey in the section above on single grain analyses: zircon U-Pb, and Ar-Ar. After some preliminary discussions, leading geochronologistsSam Bowring, Randy Parrish, and Paul Renneorganized the Earthtime Initiative for the purpose of bringing the international geochronology community together to resolve these problems. At an early stage, common samples for U-Pb zircon and Ar-Ar dating were distributed to numerous international labs. A signicant number of the labs completed analyses and reported their results blindwithout being aware of the results from any of the other labs. The results showed signicant scatter outside estimated analytical uncertainties for both the U-Pb zircon and the Ar-Ar experiment. For the U-Pb community, attention focused on possible errors in isotope tracer calibrations and possible varying degrees of minor Pb loss from the standard zircons. The rst of these issues was approached initially by distributing recently prepared calibration solutions from a few labs, and eventually by preparing and distributing two new U-Pb isotope tracer solutions to the international community. A major effort was put into highly accurate calibration of the U-Pb tracer solutions, with reevaluations of all possible sources of error, ranging from the exact level of purity of the widely used NBS/NIST Pb isotopic standards to the exact isotopic ratio of 238U/235U in a large collection of zircon and other minerals used for U-Pb geochronology. The second issue was approached initially by using the then-new CA-TIMS method to pre-treat one particular zircon standard prior to distribution, and later by preparing a set of standard synthetic U-Pb age solutions, eliminating the possibility of heterogeneities in zircon samples distributed to different labs. At this stage almost all U-Pb labs were able to obtain agreement at the <0.1% 2-sigma level. Moreover, re-analysis of single zircon grains from the Permo-Triassic boundary section using the CA-TIMS technique brought results for different U-Pb labs into excellent agreement, within very small analytical uncertainties (Fig. 11; cf. Mundil et al., 2004, and Shen et al., 2011). Ar-Ar tests proceeded from standard sample distribution, to standard samples irradiated together in the same reactor, and, in progress, use of a 40Ar/39Ar dating intercalibration pipette system (Turrin et al., 2010), which will travel from lab to lab to directly calibrate mass spectrometer performance. Meanwhile, the major source of discordance between U-Pb zircon ages and Ar-Ar ages has been identied as error in the 40K decay constants. Revised 40K decay constants, based on comparisons between U-Pb zircon versus Ar-Ar pairs from the same samples (e.g., Min et al., 2000; Renne et al., 2010) and independent inter-calibrations between Ar-Ar dates and astronomical dating (e.g., Kuiper et al., 2008; Rivera et al., 2011), now bring Ar-Ar ages for the PermoTriassic boundary into excellent agreement with the latest U-Pb zircon results (e.g., Fig. 11, and Schmitz and Kuiper, 2013). During the decade-long history of Earthtime, formal and informal contacts among international labs have greatly

Figure 12. Lu-Hf and Sm-Nd isochrons for garnet and other minerals from high-pressure to ultra-high-pressure (HP-UHP) rocks. Data replotted from sample MS09001 of Smit et al. (2010). Error ellipses have been greatly enlarged so that the data points are visible. The Lu-Hf isochron age is strongly biased toward the early stage of garnet growth, represented by the Lu-rich garnet cores. The Sm-Nd is biased toward the later stages of garnet growth.

samples for use as standards, e.g., Wiedenbeck et al. (1995), and the usual diffusion of knowledge that took place when a Ph.D. from one lab became a post-doc at another. That each laboratory had its own in-house U-Pb spike and calibration solutions was the rule rather than the exception. Ar-Ar labs were perhaps more closely linked, at least in terms of complete reliance on the availability of well-characterized and widely accepted age standards for every single Ar-Ar analysis, but not necessarily in other important ways. In retrospect, it should have come as no surprise that different labs, even those using the same method, obtained

The geochronology revolution increased, sharing tips on best practices, lessons learned the hard way, etc. Open collaboration and cooperation are now the rule rather than the exception. Over the past decade this level of communication, collaboration, and cooperation have been essential to the numerous advances associated with Earthtime. The entire international geochronological community will benet from continuing to use this model. SUMMARY AND CONCLUSIONS Fifty years ago, after a sometimes-difcult fty-year-long infancy and adolescence, geochronology reached young adulthood. Senior members of the geologic community did not always appreciate the brash newcomer. In some cases, the lab-oriented scientists were lacking in basic geological background, and made incorrect interpretations. In other cases the newcomers committed the cardinal sin of clearly demonstrating that a long-held conclusion was simply wronghow could rocks that looked Precambrian turn out to be Mesozoic? Over the last fty years, progress in geochronology has been spectacular as instrumentation, analytical techniques, and integration of geochronology with geologic-petrologic processes have made enormous leaps. For example, in the early part of the past fty years, geochronologists were quite satised with age uncertainties of a few percent. In the past decade, much smaller discrepancies between ages determined by different labs and/or by different techniques spurred a major effort to identify and correct the sources of errors that might be responsible, and to drive age uncertainties below the 0.1% level. As geochronology matured, it became more and more deeply integrated into nearly every eld of geology. Evidently, derogatory terms such as dial twisters and number jugglers fell out of favor as more geologists eagerly sought collaborations with geochronologists, and as most young geochronologists were educated in geology departments rather than in chemistry and physics departments. Of course, some of the increased acceptance of geochronology compared to the early days might be explained by the old saying that science makes progress one funeral at a time. Now, few would deny the phenomenal contributions of geochronology to our knowledge of the timing of important geological events and rates of geological processes, ranging from early solar system processes to an increasingly accurate and detailed understanding of Earth, Lunar, and even Martian evolution. As it happens, the advances in geochronology in the past several years, especially in the U-Pb and Ar-Ar dating methods, make this a particularly fortuitous time for a review of progress in geochronology. The ability to date geologic events with <0.1% age uncertainties opens the way for deciphering geologic history at a remarkable level of detail. Two recent examples of state-of-the-art zircon U-Pb geochronology can be found in Schoene et al. (2010) and Shen et al. (2011). In Schoene et al. (2010), high-precision U-Pb ages of zircon demonstrate that the Triassic-Jurassic boundary, the end-Triassic mass extinction, and the onset of Central Atlantic Magmatic Province terrestrial

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ood volcanism are all coeval within less than ca. 150 ka. Shen et al. (2011), using the same techniques, demonstrate that the Permo-Triassic mass extinction event had a maximum duration of 200 100 ka. Comparable work is under way in many labs to build up a detailed, very high quality chronology for the rest of the Phanerozoic time scale. Arthur Holmes died in 1965, just after the publication of the GSA 75th anniversary volume, with the dial twisters and number jugglers comment. Holmes undoubtedly would be pleased with the astonishing progress in geochronology, the acceptance and integration of geochronology into so many elds of geology, the dogged pursuit of a more and more accurate geological time scale, and especially with the outstanding young scientists who continue to advance the eld. The future looks particularly bright. ACKNOWLEDGMENTS I would like to dedicate this chapter to the late George R. Tilton, my Ph.D. co-advisor and later fellow professor at UCSB, and to the late Thomas E. Krogh, my post-doctoral advisor at the Geophysical Laboratory, Carnegie Institution of Washington. I regard them as the grandfather and father, respectively, of modern U-Pb zircon geochronology. Just as they stood on the shoulders of their predecessors, so we all stand on theirs. I am especially grateful for helpful reviews from Drs. Chris Mattinson, Randy Parrish, Paul Renne, and Scott Samson. Their thoughtful and constructive suggestions have signicantly improved this paper. REFERENCES CITED
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