A Century of U-Pb Geochronology

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Geological Society of America Bulletin

A century of U-Pb geochronology: The long quest towards concordance
F. Corfu Geological Society of America Bulletin 2013;125, no. 1-2;33-47 doi: 10.1130/B30698.1
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A century of U-Pb geochronology: The long quest towards concordance

F. Corfu
Department of Geosciences, University of Oslo, Postbox 1047, Blindern, N-0316 Oslo, Norway
ABSTRACT The U-Pb system is a prime geochronometer, mainly due to its occurrence as a pair of isotopically distinct but chemically identical decay systems with 235U decaying to 207Pb and 238 U to 206Pb, respectively. In addition, U has suitable half-lives and is hosted in some very convenient minerals, such as the widespread and robust mineral zircon. These twin decay systems, running at different speeds, allow an immediate verication of the validity of their ages, which must be concordant to be considered valid, although under favorable circumstances, discordant data can be extrapolated to the correct age. In detail, the degree of discordance can vary greatly, and discordance can have many different causes. The progress in developments of the U-Pb method is both a history of technical discoveries and advances, as well as a history of a long struggle toward concordance, toward an understanding of the causes of discordance, and toward ways to eliminate it. Despite the enormous progress achieved in this eld, the problems of U-Pb discordance have not yet been completely resolved and will be one of the main hurdles to overcome in the future. This paper reviews some of the main stages in the evolution of the method, focusing especially on the style, causes, and implications of U-Pb discordance in modern geochronology. Only one answer is the right one, and only that one is good enough. T.E. Krogh INTRODUCTION The development of U-Pb geochronology is rooted in the early days of discovery of radioactivity and the radioactive decay of U with emission of alpha and beta particles and a gradual accumulation of radiogenic Pb. A description of the most fundamental discoveries and of the progressive development of mass spectrometry is given in some detail in earlier reviews,
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CELEBRATING ADVANCES IN GEOSCIENCE
Invited Review
such as that by Davis et al. (2003), and will not be repeated here. Research on this subject during the rst 50 yr of the twentieth century prepared the ground for the emergence of U-Pb geochronology as a robust dating technique. The rst wave of applications in the 1950s developed basic techniques, undertook the rst geological case studies, and discovered the reality of U-Pb discordance. The second and subsequent waves searched for ways to accommodate U-Pb discordance and explored various strategies to eliminate it. Now, 60 yr later, we see two contrasting trends, two philosophies: one that continues the battle to eliminate discordance, but also a second one that bypasses the problem and solves the Gordian knot by essentially eliminating the concept, declaring U-Pb systems concordant by denition (see section Administrative Concordancy). This paper follows these historical developments. A brief description of the U-Pb method and specic technical aspects is given in an Appendix in the GSA Data Repository.1 More detailed descriptions of various aspects of the analytical technique and error analysis can be found in Parrish and Noble (2003), Bowring and Schmitz (2003), and Condon and Bowring (2012). EVOLUTION OF THE TECHNIQUE The PioneersRealization of U-Pb Discordance Following the discovery of radioactivity, and after several decades dedicated to research into fundamental aspects of radioactive systems, a critical advance was the development of mass spectrometry. The rst measurements of Pb isotopic compositions by Nier (1939) were an important analytical step in geochronology, which up to then had been based on bulk chemical ratios. In a review of the methods current by ca. 1950, and of the data obtained by then,
GSA Data Repository item 2013061, Brief description of the U-Pb method and specic technical aspects, is available at http://www.geosociety.org/pubs/ft2013 .htm or by request to editing@geosociety.org.
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Kulp et al. (1954) pointed out that analyses tended to give discrepant ages for 206Pb/ 238U, 207 Pb/ 235U, and 207Pb/ 206Pb. They discussed the various factors affecting the analyses, considering especially loss of Rn, and concluded that 207 Pb/ 235U was the most reliable, and 207Pb/ 206Pb was the least reliable age. Ahrens (1955a) used data for monazite from Rhodesia (Zimbabwe) reported by Holmes (1954) to show that the divergence between 206Pb/ 238U and 207Pb/ 235U and 207Pb/ 206Pb changed in systematic ways, and demonstrated graphically the convergence along curved trajectories toward a common age. Discordant data from Manitoba and Madagascar could in part be explained by the same scheme, and he interpreted the pattern as being due principally to Pb loss, also establishing that 207Pb/ 206Pb ages were those closest to the real age, the opposite of the conclusion of Kulp et al. (1954). In a subsequent paper, Ahrens (1955b) presented a semilogarithmic plot of t (time) 207Pb/ 235U versus log t 206Pb/ 238U, showing that the Rhodesian data tted a straight line, and, using preliminary versions of concordia diagrams, he discussed the causes of discordance. The modern version of the concordia diagram, together with a detailed mathematical treatment of the effects of loss and gain of Pb and U, was then provided by Wetherill (1956a, 1956b). His formalism became the basis for the subsequent treatment of discordant data (e.g., Russell and Ahrens, 1957; Wetherill, 1963). A different type of concordia diagram was later introduced by Tera and Wasserburg (1972) (see Appendix in the GSA Data Repository [see footnote 1]). Isotope DilutionThermal Ionization Mass Spectrometry (ID-TIMS) The application by Tilton et al. (1955) of isotope dilution techniques2 to the determination of U, Pb, and Th in minerals was the
2 Abbreviations used in this paper: ID-TIMSisotope dilutionthermal ionization mass spectrometry; SIMSsecondary ionization mass spectrometry; (LA-)ICP-MS(laser ablation) inductively coupled plasmamass spectrometry.
E-mail: fernando.corfu@geo.uio.no
GSA Bulletin; January/February 2013; v. 125; no. 1/2; p. 3347; doi: 10.1130/B30698.1; 6 gures; Data Repository item 2013061.
For permission to copy, contact editing@geosociety.org 2013 Geological Society of America
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 Corfu fundamental technical innovation that opened the doors to work with zircon. In the following half century, this mineral became the dominant geochronometer. Tilton and coworkers tested the method using a sample from a granitic rock from the Grenville Province. Zircon gave U-Pb and 207Pb/ 206Pb ages that were considered equal within the limits of uncertainty. The analysis of coarse titanite also yielded the same 207 Pb/ 206Pb age as the zircon. The procedure adopted in that study was extremely complex and time consuming, seen from our presentday perspective, but it represented a great step forward, permitting analysis of gram quantities of minerals, when much larger quantities had previously been necessary. Besides zircon, Tilton and Grnenfelder (1968) also examined the behavior of titanite (sphene) in different settings, observing a much lower susceptibility to partial Pb loss, although it was more easily reset (or newly formed) during high-temperature events. Modeling Phase With improvements in technique and increased production of data, attention was focused on the general problems of discordance of U-Pb systems in nature. There was a gradually growing consensus that the dominant cause of discordance was loss of Pb, and different attempts were made to rationalize the effect and extract reliable ages. Wetherill (1956b) had provided the basic graphic and mathematical tools for dealing with discordant data. Subsequently, several models were elaborated that linked discordance to various diffusion mechanisms, either simple volume diffusion, diffusion linked to gradual metamictization of the host, or diffusion linked to episodic activation (Nicolaysen, 1957; Tilton, 1960; Wasserburg, 1963; Wetherill, 1963). Pidgeon et al. (1966) conducted a series of experiments using portions of a large metamict zircon immersed in hot NaCl solutions and observed considerable leaching of Pb and a reduction of the Pb-U ratio. Grnenfelder et al. (1964) showed that some of the discordance reected mixing with old Pb components. Subsequently, a more sophisticated multistage Pb loss model was added to the toolbox (Allgre et al., 1974). Along a different track, Goldich and Mudrey (1972) had discussed a model of Pb loss by dilatancy with loss of water from microcapillaries in zircon during uplift. This mechanism is touched on also by a concept more recently discussed by Kramers et al. (2009), who proposed that radiogenic Pb forms in the tetravalent state, and hence remains immobile until it is exposed to uids that change its redox state and make it mobile. They further point out that the last -decay in the chain to 207Pb involves more energy and causes more damage than the corresponding last decay to 206Pb; hence, the former may be lost preferentially, perhaps causing the commonly observed nonzero lower-intercept ages of discordant arrays of Precambrian zircon populations. While intellectually stimulating, these models and discussions could not provide unique and fully reliable solutions, and the problems of discordant U-Pb data remained a challenge (e.g., Kouvo and Tilton, 1966; Steiger and Wasserburg, 1966, 1969). New Strategies to Understand and Work around Discordance The rebound from these rather discouraging early phases in the development of U-Pb can be credited largely to the work and imagination of Leon Silver, at Caltech in Pasadena. He realized that the weak point in the analytical procedure was the absence of a suitable approach in selecting samples from which data could be successfully systematized and interpreted (Silver, 1963a, 1963b, p. 281). He understood that zircon populations in rocks can be extremely variable in terms of composition, crystallinity, and other parameters. He experimented in separating fractions according to size and magnetic variability, and his measurements of the U-Pb ratios of the different fractions revealed extreme variation in the degree of discordance, which correlated with U content and degree of radioactivity. The U-Pb results dened collinear arrays for which intercepts could be interpreted in terms of primary crystallization and secondary Pb loss (Silver, 1963a, 1963b; Silver and Deutsch, 1963). The presence of uranothorite inclusions was also shown to have a strong inuence on the degree of discordance. His tests established that the earlier-discussed Rn loss effect had no great inuence on the discordance of zircon. He also showed that volume diffusion alone could not explain the pattern, and the loss of Pb required additional controls from the internal parts of the zircon. Silvers developments set up analytical approaches that were to become standard procedures in the following two decades. Given that discordance was next to unavoidable in most samples, the strategy became that of maximizing the spread in order to establish more robust discordia lines and increase the reliability of their intercept ages. A major hurdle, however, remained the immense analytical effort needed to produce individual analyses from zircon fractions of 100500 mg (Silver and Deutsch, 1963), which severely limited the utility of the method. Krogh Revolution 1: Simplifying the Method The change of focus by Tom Krogh, then at the Carnegie Institution of Washington, to U-Pb geochronology from his previous involvement with Rb-Sr dating (Kamo et al., 2011) represents the next major step in the evolution of the method, and the one that really enabled the more widespread application and testing of the principles and analytical approaches dened by Leon Silvers work. The main components of the new technique were: (1) the change from ux-based decomposition of zircon to hydrothermal dissolution in Teon bombs, (2) the chemical separation of U and Pb using ion-exchange resin, and (3) the use of an articial 205Pb isotope as a tracer (Krogh, 1973; Krogh and Davis, 1975a). All chemical steps in this procedure were carried out in simple laminar ow hoods. In addition, Cameron et al. (1969) had introduced the Si-gel loading technique, which greatly facilitated mass spectrometry due to enhanced ionization of Pb, and Mattinson (1972) had devised an efcient way to distill the reagents used in the analysis. The main advantages of these combined modications were the drastic reduction (by three orders of magnitude) of the background contamination, much simpler analytical protocols, much smaller sample sizes, and better reproducibility. The new technique was rapidly embraced by the growing U-Pb community, expanding its application to address the evolution of orogens and decipher the timing of granitic magmatism and metamorphism, but also focusing on specic mechanisms causing U-Pb discordance. Good examples of the former are the studies by Pidgeon and Aftalion (1978) on the granites and metamorphic basement of Scotland, Baadsgaard et al. (1976) on early Archean Amitsoq gneisses of West Greenland, Gulson and Krogh (1973) on the Bergell granite, and Van Schmus et al. (1987) on Paleoproterozoic Trans-Hudson orogen. Gebauer et al. (1981) showed that it was possible to nd zircon and monazite and date rocks of mac and ultramac composition. Cliff (1980) and Schrer (1980), in part combining the age of different minerals, established the evolution of nappe complexes. In a study of discordance, Grauert et al. (1974) found that a major mechanism affecting detrital zircon ages was gain of U during metamorphism. The reduction in sample size permitted by the new technical advances led to the rst single-grain zircon studies (e.g., Lancelot et al., 1976; Schrer and Allgre, 1982). Other studies tested techniques to expand the range of discordance in order to obtain
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Geological Society of America Bulletin, January/February 2013
Downloaded from gsabulletin.gsapubs.org on May 1, 2013 A century of U-Pb geochronology: The long quest towards concordance better-constrained intercept ages (Aleinikoff, 1983; Steiger et al., 1993). Although this urry of activities and new applications helped to solve many geological questions, many of the studies involving zircon had to rely on extrapolating the age from discordant arrays, which in complex cases had detrimental effects on the precision and accuracy of the ages. Krogh Revolution 2: Reducing Discordance Since model solutions to discordance did not work very well, and since extrapolating the ages from discordant arrays could be problematic in all those cases that had undergone a Pb evolution involving more than just two stages, Tom Krogh concluded that the only reliable strategy had to be that of nding, isolating, and analyzing concordant domains of zircon. The groundwork laid by Silver and coworkers, and also by others, in the 1960s had shown that discordance is generally not a uniform property of zircon, but is especially prominent in specic parts of the grains. By means of leaching and etching experiments, Krogh and Davis (1974, 1975b) discovered that some zircon crystals contain easily dissolvable altered domains (Figs. 1E and 1F). Alteration was caused by uids attacking the rims of zircon or penetrating along fractures and attacking metamict domains. The fractures formed as a result of tensions caused by volume expansion during metamictization. The penetrating uid removed radiogenic Pb while it introduced elements such as Ca and Fe. Because altered domains are easily soluble and could be separated from the unaltered zircon by partial dissolution, several workers experimented with partial dissolution techniques. The results, however, were not encouraging because the technique introduced secondary effects, fractionating U from Pb in the remaining parts of the zircons (e.g., Pidgeon and Hopgood, 1975; Todt and Bsch, 1981; Turek et al., 1982). Mattinson (1994) reviewed these experiments and concluded that the fractionation of U from Pb was likely related to the precipitation of uorides during dissolution. Mattinson continued to experiment with, and rene these techniques and eventually discovered how to master them a decade later (see later herein). Krogh (1982a) chose instead a different track. To avoid the side effects of the chemical attacks, he opted to remove the outside of the grains, or of fragments of grains, by spinning them around in a steel chamber with a jet of compressed air (air abrasion method). His tests showed that, in many cases, the technique could indeed strip most of the discordant zircon matter. In a parallel development, he also experimented with a high-gradient magnetic device that separated
Figure 1. Cathodoluminescence (AE) and backscattered electron (F) images illustrating typical features of zircon affected by secondary modications causing partial resetting and discordance of U-Pb systems. Scale bar indicates 100 m. (A) Zircon crystal with regular growth zoning, but locally fractured and externally resorbed and overgrown by new highly luminescent (and low U) rims during a metamorphic overprint (modied from Corfu, 2007). (B) Small core with regular growth zoning, surrounded by more complex regular and sector-zoned domain, itself rimmed by high-luminescence outer layer. The texture indicates overgrowth and new reworking of a magmatic zircon during two separate high-grade metamorphic events, resulting in partially reset and discordant data (modied from Corfu, 2007). (C) Zircon crystal with regular and sector zoning, and locally thin rims of low luminescence cut by brittle fractures; the thin rims represent a metamorphic overprint that caused strong Pb loss, whereas the fractures formed during later mylonitization without causing signicant Pb loss (Austrheim and Corfu, 2009). (D) large zircon crystal strained by mylonitization, which caused internal fracturing and local distortion of the lattice and fragmentation of the rims in addition to full recrystallization and/or new growth of external neoblastic zircon grains. The strain in this case caused severe resetting of the U-Pb system (from Roffeis et al., 2012). (E) Zircon affected by alteration expressed by the black, botryoidal trains of alteration advancing along cracks and interfaces and forcing their way into metamict domains (from Medenbach, 1976). Alteration causes chemical changes and produces severe Pb loss. (F) A similar case, with alteration attacking metamict zones in the zircons and penetrating along cracks perpendicular to the zoning (modied from Nasdala et al., 2010).
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 Corfu zircon based on faint paramagnetic properties, thereby eliminating the zircons that had undergone even very small amounts of alteration, gaining Fe and losing Pb (Krogh, 1982b). In general, to achieve the best results, these methods had to be combined with careful inspection and selection of the grains under a binocular microscope, and in specic cases with imaging (cf. Corfu et al., 2003). The efciency of these treatments was further greatly improved by the growing ability to measure smaller and smaller samples due to progressive renements of the Krogh (1973) technique by miniaturizing dissolution bombs and columns, reducing the blank, which by the end of the 1980s in some laboratories had started to creep below 1 picogram Pb, and taking advantage of improved mass spectrometers. High-Resolution ID-TIMS Geochronology The array of technical improvements, and the development of abrasion, with its much improved control on discordance, made it possible to address a variety of geological problems at a level of detail that would not have been possible before. As exemplary applications in that period, one can mention the systematic determination of the chronostratigraphy of Archean and Proterozoic greenstone belts, the dating of ophiolite complexes, the resolution of the emplacement sequence of multistage granitoid complexes and polymetamorphic evolution of lower-crustal terrains, the dating of mac dike swarms, and constraining the age of ore deposits and of major meteorite impacts (e.g., Krogh et al., 1987; Dunning and Pedersen, 1988; Davidson and van Breemen, 1988; Davis et al., 1989; Barth et al., 1989; Davis and Smith, 1991; Hansmann and Oberli, 1991; Corfu and Davis, 1992; Parrish, 1995; Kamo et al., 1996a, 1996b). The new analytical approaches contributed at two distinct levels: on the one hand, by providing accurate ages that permitted correlation of geological elements across belts, across continents, and between continents and, on the other hand, by providing the detailed age resolution necessary to address the speed and kinematics of rock-forming and rock-deforming processes. Besides the ubiquitous zircon, a variety of other minerals could be routinely analyzed, among them, especially titanite and monazite, but also the less common baddeleyite, xenotime, allanite, rutile, and perovskite, or the common but less suitable apatite. More specic dating applications are those dealing with the formation of very young rocks, such as the progressive deposition of opal in veins at Yucca Mountain studied by Neymark et al. (2000). Kober Technique: Zircon Evaporation An interesting alternative for dating zircon was developed by Berndt Kober in Heidelberg. It involved mounting a zircon directly on a Relament and then, after inserting it into a mass spectrometer, subjecting it to rounds of progressive heating, which released Pb, and depositing it on a facing cold lament, from where it could subsequently be ionized and measured (Kober, 1986, 1987). This procedure allowed, in principle, the extraction and purging of disturbed Pb from discordant domains before reaching the more rmly held undisturbed Pb. In the ideal case, the extraction procedure would provide a number of sequential steps, allowing verication of whether the composition remained constant, suggesting a closed system, or changed progressively, suggesting that Pb was disturbed because of loss or mixing with older components. An additional benet of the technique was the fact that it only required a thermal ionization mass spectrometer without facilities for low-blank chemical dissolution and separation. The technique was used successfully in a number of studies (e.g., Krner et al., 1991; Jaeckel et al., 1997). Its main drawback, however, is the fact that it provides only Pb-Pb but no U-Pb information, and hence no direct way to verify the degree of discordance. The measurement procedure is also relatively time consuming. These disadvantages have limited the number of applications of this technique. Recently, a modied version has been proposed that promises to provide a better control of the isotopic fractionation and thus contribute to high-age-resolution geochronology (Davis, 2008). The Ion Probe: The Early Challenges and Progress Around 1980, ID-TIMS was joined by secondary ion mass spectrometry (SIMS). Following early steps in Cambridge and Chicago, the main contribution for U-Pb dating was the development of the sensitive high-resolution ion microprobe (SHRIMP) at the Australian National University (ANU) in Canberra by Bill Compston and his group (Williams, 1998). The original attempts to use regular ion probes for U-Pb dating (e.g., Hinton and Long, 1979) encountered difculties because of problems correcting for molecular interferences on the desired Pb isotope masses. The SHRIMP main solution was to build a large ion microprobe that was capable of achieving high mass resolution without having to compromise the sensitivity. The SHRIMP instrument attracted a large interest from the community, mainly because of the high spatial resolution, which permitted the analysis of discrete domains of polished sections through grains, with the further advantages of a high analytical speed and the preservation of most of the analyzed objects. When compared to ID-TIMS, the main disadvantage of the ion probe was a considerable decrease in precision, and hence loss of temporal resolution. This stemmed mainly from the much smaller amount of material available for measurement. Another critical step was the determination of the U-Pb ratios, which in SIMS must be calibrated against the corresponding ratios of an external standard, in contrast to ID-TIMS, where the ratios are obtained by mixing a tracer of known composition with the sample. Because the sputtering of U and Pb is controlled to some degree by the composition and/or structure of the sample (McLaren et al., 1994), discrepancies can arise between sample and standard when they have quite distinct basic properties. The anomalous behavior is evident in some zircons very rich in U, such as the cases reported by Harrison et al. (1987) and Wiedenbeck (1995). This potential problem is now largely recognized in the SIMS community, and modern analytical protocols are generally concerned with proper matching of the reference zircons. Ion probe dating has been applied to the entire range of terrestrial geological problems, but especially to the study of multistage crustal growth and metamorphism, the genesis of granites, and the sources of xenocrystic and detrital zircons (e.g., Williams, 1998, 2001; Williams et al., 1984; Kinny and Dawson, 1992; Nutman et al., 1996). One of the most celebrated studies was the discovery of 4-b.y.-old zircon grains in conglomerates at Mount Narryer and Jack Hills in Western Australia (Froude et al., 1983), which spawned many other studies on these rare and very critical earliest witnesses of Earth evolution (e.g., Compston and Pidgeon, 1986; Wilde et al., 2001). Special applications of the SIMS technique were also those focused on the rare zircons in meteorites and in rocks brought back from the moon by the Apollo missions (Ireland and Wlotzka, 1992; Nemchin et al., 2008, 2009). LA-ICP-MS Technique: Problems and Solutions The latest addition to the arsenal of U-Pb dating methods is the laser ablationinductively coupled plasmamass spectrometry (LA-ICP-MS) technique. The rst experiments with U-Pb dating by LA-ICP-MS were done in the early 1990s (Fryer et al., 1993), and from there the technique rapidly improved. In less than a decade, many laboratories worldwide had adopted it, contributing to many improve-
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 A century of U-Pb geochronology: The long quest towards concordance ments and renements. The method is attractive mainly because of the high throughput capability, which makes it ideal for the study of large populations, such as in detrital zircon studies. The precision tends to be comparable to that achieved by SIMS, but the latter has the advantage of consuming much less of the target (spots of 25 m 3 m for SIMS vs. 30 m 30 m for LA-ICP-MS, but these volumes can vary considerably depending on the task envisaged and the operator choices). The main initial challenges for LA-ICP-MS were achieving control of the analytical fractionation between U and Pb, and correcting for common Pb, due to the presence of mercury in the argon gas used to produce the plasma that causes an isobaric interference by 204Hg on 204Pb. Different groups have adopted different strategies for coping with these problems (Koler et al., 2002; Horn et al., 2000; Jackson et al., 2004; Gehrels et al., 2008; Cottle et al., 2009). The LA-ICP method is now widely used to address many different geological problems, although the limited precision makes it most attractive for the study of detrital zircon populations (e.g., Koler et al., 2002; Gerdes and Zeh, 2006). Chemical U + ThTotal Pb Dating Chemical dating is based on the determination of the ratio between the total amount of radiogenic Pb and U + Th. This method had represented one of the initial steps into U-Pb dating in the early decades of the twentieth century, but after the advent of efcient isotopic measurement techniques around 19401950, chemical dating had all but fallen into disuse. Thanks to the technical progress of modern electron microprobes, and the consequent increase in sensitivity, the method has now undergone a considerable revival (Suzuki and Adachi, 1991; Montel et al., 1996; Crowley and Ghent, 1999; Goncalves et al., 2005; Jercinovic and Williams, 2005). The two basic requirements of the method are (1) closed-system behavior, i.e., the system has not lost or gained U, Th, or Pb since its formation, and (2) absence of initial Pb. Because it is not based on the measurement of isotopes, the chemical method cannot take advantage of the information from the two separate decay chains of 235U to 207Pb and 238 U to 206Pb, with chemically identical pairs of parent and daughter isotopes but different decay speeds, which act as independent chronometers and enable us to evaluate whether or not the system has remained closed. The main area of application of chemical dating has been monazite, largely thanks to its very high levels of U and especially Th, and hence Pb, which facilitate the measurement. In addition, monazite is much less prone to Pb loss than zircon, and hence more likely to be concordant or nearly so (Parrish, 1990). The main advantage of chemical dating over other methods is the ability to analyze very small areas of minerals (5 m or less), helping to connect the obtained age to the structural and petrologic context. Mattinson: Development of Chemical Abrasion As mentioned earlier herein, the early attempts to remove discordant domains from zircon by means of leaching or partial dissolution were not very successful, mainly because the process introduced some articial fractionation of U from Pb, presumably due to the precipitation of uorides during dissolution. Jim Mattinson in Santa Barbara understood this (Mattinson, 1994) but continued nonetheless to experiment with partial dissolution until he eventually succeeded, developing a new reliable technique. The critical element in chemical abrasion is the fact that crystalline zircon with a low dose of radioactivity-induced defects can be thermally annealed (at temperatures of 800 1000 C), recovering the original zircon lattice, in a period of time over which it is insufcient to repair the damage of much more strongly metamict domains (Mattinson, 2005, 2011). Subsequent exposure to hydrouoric acid dissolves the metamict domains much more easily than the annealed crystalline zircon components, thus making it possible to isolate the latter. Annealing is important, not only because it protects the crystalline parts from easy dissolution, but especially because it immobilizes the Pb and U in the crystalline parts, preventing the smallscale leaching that was an important cause of U-Pb fractionation in the original experiments. A more subtle effect of the original partial dissolution experiments was the preferential leaching from crystalline zircon of young Pb (Corfu, 2000), separating it from the earlier-produced Pb, which may have been frozen-in during earlier geological annealing events (Davis and Krogh, 2000). The effect could also be caused by the fact that the 238U chain has one more alpha emission than the 235U chain, potentially making 206Pb more leachable than 207Pb (but, as mentioned already, the opposite effect has been suggested by Kramers et al. [2009] in consideration of the more energetic last decay in the 235U compared to the 238U chain). In the decade since its development, chemical abrasion has taken a rm place in the toolbox of most ID-TIMS laboratories and has undoubtedly contributed to improve the quality of many geochronological studies (e.g., Schaltegger et al., 2008; Schoene et al., 2010a, 2010b), which also benet from improved emitters (Gerstenberger and Haase, 1997). As pointed out by Mattinson (2011), the method only works if the zircon grains include some domains that have remained closed systems throughout their history; it cannot restore a lost age. In my experience, it is generally difcult to apply the method to U-rich and metamict grains because they dissolve too easily, even in cases where the grains, though rich in U, are free of alteration and yield concordant data when treated with air abrasion (e.g., Svensen et al., 2012). Pb-Pb Dating The Pb-Pb method is a special branch of U-Pb geochronology, but it has been used mostly to pursue a different type of problem, namely, employing the Pb composition of U-poor or U-free minerals and rocks to study the genesis of rocks rather than to date them. Occasionally, however, the two tracks overlap and complement each other. One of the most prominent applications of Pb isotopic analysis to dating was that of Patterson (1956), who determined the rst (essentially) correct age of 4.55 Ga for meteorites and, by extension, the planet Earth. Subsequent work, combined with U-Pb and other isotopic systems, and with progressive improvements of the techniques, has greatly rened the scale of details of the chronology of the early solar system (e.g., Tilton, 1973; Tatsumoto et al., 1973; Tera and Wasserburg, 1975; Allgre et al., 1995; Amelin et al., 2002, 2009). Terrestrial applications of Pb-Pb techniques have been less notable from the perspective of precise dating, focusing mainly on genetic questions. An interesting line of experiments exploring geochronological applications involved differential leaching and dissolution of silicates. These experiments yielded important insights into the distribution of U and Th inside specic minerals and into their control on Pb evolution and closed-system behavior of potential chronometers (e.g., Frei and Kamber, 1995; Frei et al., 1997). The main handicap of the method has been the necessity to rely solely on the Pb composition, without assistance from U-Pb, thus limiting the ability to evaluate the state of concordance of the analyses. Another interesting application of the Pb-Pb method is the dating of ancient limestones (Moorbath et al., 1987; Jahn and Cuvellier, 1994; Bau et al., 1999). THE ROAD TOWARD CONCORDANCE: A UTOPIAN GOAL? As reviewed earlier herein, after the discovery of radioactivity a century ago, progress in U-Pb geochronology has been enormous, with
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 Corfu the development of different methods that have been tested and rened, some dropped and picked up again and further expanded. At present, U-Pb dating is the method of choice in many studies of magmatic systems, metamorphism, and provenance. Thousands of studies have examined the behavior of the decay system, the behavior of U-Pb in different minerals, and the response in different geological settings. The preoccupation with discordance, which laid a cloud of skepticism over the initial enthusiasm, has been largely dispersed by the subsequent developments. Today, we have reasonably good control of the behavior of U-Pb systems. Yet, do we really understand discordance; do we really know how to navigate around it? Concordant U-Pb ages are qualitatively, analyses in which the 206Pb/238U, 207Pb/235U, and 207 Pb/206Pb ages are equal within analytical error, or, visually, U/Pb and Pb/Pb ages whose corresponding isotope ratios have a 95% condence error ellipse that (to a greater or lesser degree) overlaps the concordia curve (Ludwig, 1998, p. 665; Fig. 2A). Although the basic denition of concordance is clear-cut, as soon as the analytical error is considered, the term becomes somewhat fuzzy, occasionally progressing into extreme fogginess. Near-Concordance In modern high-precision ID-TIMS studies, it is common to observe that high-quality, highly reproducible sets of U-Pb analyses do not plot exactly on the concordia curve but variously to the right of it (Fig. 2B; e.g., Kamo et al., 1996a; Schmitz and Bowring, 2001; Parrish and Noble, 2003; Schoene et al., 2006). An important reason for this behavior is the apparently slightly incorrect U decay constant (Jaffey et al., 1971) as discussed by Schoene et al. (2006). Correcting such data with a revised decay constant for 235 U, as proposed by Mattinson (2010), can often shift the concordia curve to match the data much more closely. However, even the use of the better matching decay constant does not always succeed in bringing data sets into concordance. Another factor that can affect the degree of discordance is the U isotopic composition. Early studies had shown that 238U/235U in zircon was homogeneous within 0.5% (Doe and Newell, 1965), and in the following half a century all laboratories used the value of 238U/235U = 137.88 recommended by Steiger and Jger (1977). However, more detailed modern investigations show that the ratio is likely too high, and measurements of various reference materials give values that are up to 0.08% lower (Condon et al., 2010; Hiess et al., 2012). The effect of such a change on the calculated ages is relatively minor
206Pb/238U
A-III
age 1 age 2
concordant
A-II
discordia line two-stage evolution projected from the origin of the concordia curve (= 0 Ma) projected from an ancient lower intercept age
discordant
A-I
reversely discordant
B
discordant
concordant
207Pb/235U
Figure 2. Concordia diagram with data points (ellipses representing analytical uncertainty) illustrating some terms and concepts discussed in the text. (A-I) Concordant versus discordant analyses. (A-II) Discordia line dened by a suite of discordant, and one concordant analyses, where the intercepts reect two distinct events that affected the population. (A-III) Interpretation of nearly concordant data assuming ancient partial resetting (age 1 by projection from the time of the early disturbance) or modern Pb loss (age 2 by projection from the origin). (B) Typical example of high-precision isotope dilutionthermal ionization mass spectrometry (ID-TIMS) data (from Schoene et al., 2006) plotting in a cluster to the right of the concordia curve (calculated with the decay constants of Jaffey et al., 1971).
for relatively young minerals (causing an effect of 1 m.y.), but it becomes a more important element in meteorite studies, especially because some of the earliest solar system materials show larger deviations of up to 0.4% in the 238U/235U ratio, attributed to the decay of 247Cm, and resulting in changes of the calculated 207Pb/206Pb ratios of up to 5 m.y. (Brennecka et al., 2010). A second set of causes that has been widely discussed, and convincingly proven in some cases, is related to initial disequilibrium in the decay chains from U to Pb. Incorporation of excess 230Th at the time of formation of a mineral results in excess 206Pb with data that plot reversely discordant (Figs. 2A-I). This behavior is very evident in young monazites (Schrer, 1984; Parrish, 1990) because of the strong geochemical afnity for Th in monazite (and allanite). If the Th/U ratio of the magma is known or can be approximated, the effect can be corrected.
The alternative is to use the 207Pb/235U age alone, which is not affected by 230Th excess. For zircon, the behavior is generally the reverse, because the mineral forms mostly with a decit of 230 Th, which then translates into a decit of 206Pb (but there are exceptions, such as high Th/U zircon in carbonatites; Amelin and Zaitsev, 2002). The effect from 230Th decit is rather minor; for example, in the 28 Ma Fish Canyon tuff zircons investigated by Schmitz and Bowring (2001), the correction causes a shift of ~0.08 m.y. A related phenomenon is the excess of 231Pa, which produces an excess of 207Pb (Fig. 2A-I). The phenomenon has been demonstrated convincingly in two cases (Parrish and Noble, 2003; Anczkiewicz et al., 2001) where the effect is very strong, but it has been discussed as a possible cause in many other cases where the discordance toward too high 207Pb/235U ratios for uniform 206Pb/238U is distinct, but not extreme.
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 A century of U-Pb geochronology: The long quest towards concordance Among the most interesting observations are those of Kamo et al. (1989, 2003), Schmitz and Bowring (2001), Amelin and Zaitsev (2002), and Dunning and Hodych (1990). Crowley et al. (2007) documented an effect corresponding to ~50 k.y. for the 0.8 Ma Bishop Tuff zircon. A distinct deviation of 207Pb/235U in baddeleyite has also been interpreted, however, in terms of loss of 222Rn rather than 231Pa excess (Heaman and LeCheminant, 2001). In its oxidized form, Pa+5 is predicted to be more enriched with respect to U (Barth et al., 1989). Direct measurements of 231 Pa in Holocene zircon crystals suggest, however, that the effect on the ages should be very small (Schmitt, 2007). In practice, subtle disequilibrium effects can be difcult to distinguish from effects caused by other factors, such as small amounts of inheritance of xenocrystic material, Pb loss, incorrect common Pb corrections, or simply analytical biases from improper blank corrections, fractionation, and instrumental nonlinearities. Hard-Wired Discordance More severely discordant data will generally have been produced by either Pb loss or mixing. Solid state diffusion of Pb from zircon is extremely slow and unlikely to be effective at normal crustal temperatures (Mezger and Krogstad, 1997; Cherniak and Watson, 2001); hence, loss of Pb must be accomplished either by extraction of Pb from altered domains by uids (Figs. 1E and 1F; Krogh and Davis, 1974, 1975b) or by expulsion and/or intracrystalline redistribution of Pb from the lattice during deformation and recrystallization (Figs. 1A1D; e.g., Pidgeon et al., 1998; Connelly, 2001; McFarlane et al., 2005; Reddy et al., 2006). The former mechanism generally implies the parallel existence of concordant and discordant domains, making it possible to isolate the concordant parts by some of the techniques mentioned previously herein, and obtain concordant ages. By contrast, Pb loss by recrystallization and/or redistribution often means that there may not be any parts of a mineral left with preserved close-system relationships and thus that are capable of providing concordant ages. These cases are typical of high-grade metamorphic terrains, or sites affected by meteorite impact, causing shock metamorphism where zircons or other minerals have been very strongly reworked so that only discordant data can be extracted (Fig. 2A-II; e.g., Corfu et al., 1994; Connelly, 2001; Moser et al., 2011). The same phenomenon can in part also be seen in xenocrystic zircon populations where targeted analyses only provide partially reset discordant ages (e.g., Cornell et al., 2000), or in titanite (Tucker et al., 1987, 1990; Krogh, 1994) and in rutile (Blackburn et al., 2011). The results of such thorough partial resetting by recrystallization, commonly paired with local new growth, are linear arrays of data points between the time of crystallization and that of secondary reworking and/or local new growth (e.g., Krogh et al., 1993; Moser et al., 2009). Reverse Discordance Reversely discordant data, i.e., data with too high 206Pb/238U and/or too low 207Pb/235U ages plotting above the concordia curve in Wetherill diagrams (Fig. 2A-I), can be the results of several processes that remove U or introduce unsupported radiogenic Pb. The phenomenon is not uncommon in minerals such as monazite or allanite, which are prone to alteration and chemical mobility (Poitrasson et al., 1996). In addition, such minerals incorporate high amounts of Th, including 230Th, and hence will normally build up excess 206Pb, resulting in reversely discordant data, as discussed before (Schrer, 1984). In zircon, reverse discordance is more rarely observed, most likely because U is anchored much more strongly in the crystal lattice than Pb. Reverse discordance can be produced articially by SIMS in U-rich zircon in which the sputtering behavior is different from that of the reference zircon (e.g., McLaren et al., 1994; Wiedenbeck, 1995). Natural reverse discordance has, however, been observed in some particular cases, such as in an Early Archean gneiss from Antarctica where reversely discordant analyses plot along a paleodiscordia array, showing that the discordance is not an analytical artifact but is due to ancient redistribution of U and Pb (Williams et al., 1984). A similar case has also been described by McFarlane et al. (2005), and another is shown in Figure 3. Zircons from a gabbro from the island of Senja in northern Norway plot both normally as well as reversely discordant but dene a well-constrained discordia line for which the lower intercept corresponds to the time of the Caledonian orogeny, which affected the region, hence demonstrating that a gain of radiogenic Pb in parts of some zircon grains during metamorphism was the likely cause. Romer (2003) discussed potential mechanisms capable of creating reversely discordant data, focusing in particular on the role of alpha recoil in creating small-scale heterogeneities in zircon or other minerals (see also Mattinson et al., 1996), heterogeneities which eventually can result in reversely discordant data due to paleo-annealing events, or laboratory leaching processes, or differential sputtering during SIMS analyses.
206Pb/238U
1850 1830 1810 1790 1770

Intercepts at 42420 & 1802.3 0.7 Ma MSWD = 0.30
0.33
1750
0.31
207Pb/235U
4.7 5.1
Figure 3. Example of reverse discordance most likely caused by U loss or Pb gain during a metamorphic overprint, as suggested by the high degree of collinearity of the data and the lower-intercept age of 424 20 Ma, which corresponds to the Caledonian orogeny affecting this region. The zircon population is from a Paleoproterozoic gabbro (Hamn gabbro) on the island of Senja, northern Norway (Corfu, 2005, personal observation). MSWDmean square of weighted deviates.
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 Corfu SOME MODERN DILEMMAS Role of Xenocrysts, Antecrysts, and Pb Loss in High-Resolution Geochronology High-precision U-Pb geochronology has now advanced to a stage where it is possible to study in detail the chronology of magmatism and emplacement processes of complex multistage plutons, dening rates and speed of magma emplacement, the time of residence in crustal magma chambers, and the speed of cooling, and calibrating accurately the time scale (e.g., Bowring and Schmitz, 2003; Matzel et al., 2006). Disequilibrium dating by SIMS of zircon in recent magmatic systems also provides fundamental new insights into the evolution of magma chambers (e.g., Reid et al., 1997; Schmitt, 2006). Some magmatic systems develop very fast; for example, in the Bishop Tuff, zircons are shown to have crystallized within 5 k.y. at 767.1 0.9 ka (Crowley et al., 2007). More commonly, however, studies of plutonic or volcanic rocks reveal more complicated patterns with individual zircon grains dening ages spread over longer periods of up to 1 m.y. or more, and thought to reect growth during early as well as late stages of the magma evolution, mixing, and crystallization (e.g., Mundil et al., 2001; Miller et al., 2007; Schaltegger et al., 2008; Lima et al., 2012). The main difculty in interpreting such U-Pb data is in identifying correctly the reasons for the specic distribution of discrete data patterns. In favorable cases, a sample contains a uniform zircon population, which yields a reproducible cluster of data with just subordinate outliers, and hence the age can be reasonably based on the coherent group. In felsic magmas that evolve over a period of time, it is generally the youngest data points that are considered to represent the most likely age of emplacement, whereas the older ones are taken to represent antecryst or xenocrysts formed before nal consolidation (Miller et al., 2007). The determination of the trace-element composition of the dated zircon grains yields additional information that can help to discriminate the genesis of grains with different ages, evaluating whether they may have been linked by fractionation, or, alternatively, mixing processes (Schoene et al., 2010b). One critical question affecting modern studies done with chemical abrasion ID-TIMS is whether Pb loss effects can be completely eliminated by the chemical abrasion procedure. Some examples show that this assumption is not always valid (Schoene et al., 2010a). A similar uncertainty, but in the opposite direction, is introduced by the difculty of evaluating whether some slightly too old grains might indicate the presence of antecrysts or traces of xenocrystic material. Finally, the not always easily controllable role of disequilibrium in 230Th, 231Pa, and 222 Rn, discussed previously, can further complicate the interpretation of high-resolution data. Ultimately, the overriding criterion for the validity of an interpretation is the mutual coherence of the data, their consistency with the various properties of the analyzed zircons, the consistency with coexisting minerals, and the consistency within the geological framework (e.g., Schmitz and Bowring, 2001; Ramezani et al., 2007; Shen et al., 2011). Modern versus Ancient Pb Loss A somewhat related dilemma, which becomes more acute in interpreting Paleozoic and older U-Pb data sets, concerns the interpretation of data that are nearly, but not fully, concordant (Fig. 2A-III). One common solution is to extrapolate to the concordia curve by projecting the data from a lower-intercept age of 0 Ma, which is equivalent to using the 207Pb/206Pb age of the near-concordant cluster and assuming a modern disturbance (age 2 in Fig. 2A-III). The alternative possibility is that the slight discordance is due to ancient Pb loss: In such cases, the ages can be extrapolated by projecting a line through the data from lower-intercept ages corresponding to the time of the supposed event (age 1 in Fig. 2A-III). The second choice is generally made based on the evidence from independent geological factors, paired with the trends of the data and the behavior dictated by comparable data patterns in related units. In some cases, the choice is strongly supported by the combined available evidence, whereas in other cases, it is very much open to debate and often decided on the basis of the interpreters bias. An interesting example of this dilemma was reported by Stern et al. (2009), where air-abraded zircon yielded a main group of 0.9% discordant data with a 207Pb/206Pb age of 3465.4 0.6 Ma, but two chemically abraded zircon grains yielded data points closer to concordia and with a slightly higher 207Pb/206Pb age of 3467.1 0.6 Ma, which overlapped the upper-intercept age of a line through all the analyses of abraded zircons, including a few as much as 3% discordant. The question as to whether discordant data should be interpreted in terms of modern or ancient disturbances can also have a large impact on the use of Hf isotopic compositions in zircon. Recent advances in the analysis of Hf isotopic compositions using multicollector ICP-MS techniques have greatly improved the opportunities to study crustal growth processes, especially those concerning the earliest evolution of Earth. These studies employ zircon, which can be dated by U-Pb and contains much Hf (1%) and little Lu, therefore facilitating the determination of initial Hf isotopic compositions. One approach is to dissolve the zircon and separate U, Pb, and Hf before the measurement (e.g., Amelin et al., 1999, 2011). The alternative is to analyze parts of the minerals with LA-ICP-MS or using combinations of ion probe and ICP-MS (e.g., Harrison et al., 2005). One of the most recent techniques developed is based on the determination, by LA-ICP-MS, of the Hf isotopic composition concurrently with the 207Pb/206Pb ratio in the same targeted zircon domain. The technique has the advantage of linking the Hf composition to the age of the same specic parts of multistage zircon and thus makes it possible to evaluate mixing relationships and the composition of end members (Kemp et al., 2009). The use of 207Pb/206Pb ages, however, can be problematic if the data are discordant, and the discordance is related to ancient disturbances rather than modern Pb loss. Whereas new growth of zircon involves the buildup of layers with lower 207Pb/206Pb but distinct, generally higher, 176 Hf/177Hf, ancient Pb loss from zircon will reduce the 207Pb/206Pb ratio without affecting the Hf composition (Corfu and Noble, 1992; Kemp et al., 2010). The Hf isotopic data are commonly discussed in frames of reference dened by the chondritic evolution, whereby 176Hf/177Hf ratios are transformed into deviations from the chondritic value at their specic age. Because of the dependence of Hf on the age, calculations with ages that are too low or too high will result in erroneous Hf values. This relationship can be illustrated using an example from Kemp et al. (2010), who reported ages and Hf compositions of Archean detrital zircons from the Jack Hills conglomerates in Western Australia. The study utilized zircon initially dated in multiple spots with the ion probe, yielding precious information into the U-Pb behavior of each grain. Subsequent analyses were carried out with LA-ICP-MS by measuring Hf and Pb concurrently on the same zircon spots. Two examples are discussed here. Grain jh177 was analyzed in three spots with the ion probe, yielding the three U-Pb data points shown in Figure 4A. The three analyses are concordant within error, but their 207Pb/206Pb ages show a distinct dispersion between 3901 Ma and 4029 Ma, indicative of an ancient disturbance. The subsequent LA-ICP-MS analyses, done in the same spots, yielded a similar spread in 207Pb/206Pb age from 3941 to 4067 Ma. Without further information, it is not possible to construct an accurate projection to the real age. For the sake of discussion, discordia lines are projected through the three analyses from arbitrary lower-intercept ages of 2000 Ma and 3000
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 A century of U-Pb geochronology: The long quest towards concordance
0.9
error ellipses are 68.3% conf
206 Pb/ 238
jh17-7.1+2+3
projected from 3000 Ma 4055 130 Ma
MSWD = 0.17
Hf
4100
jh17-7.1+2+3
calculated with concurrent 207Pb/206Pb age
B
CHUR
approximate 2 uncertainty
+ calculated for 4055 Ma

all Hf data calculated with concurrent 207Pb/206Pb ages
DM
3900

0.8
MSWD = 2.0
MC C UC
+ +
3700 jh17-26.1+2 3500

0.7
projected from 2000 Ma 8 4280 77 Ma

MSWD =1.3
jh17-26.1+2
calculated with concurrent 207Pb/206Pb age
3300
30 40
207 Pb/ 235 U

MSWD = 3.1
50
60
12
calculated for 4280 Ma
3700
3900
4100 age [Ma]
4300
4500
Figure 4. (A) Concordia diagram showing U-Pb spot analyses by secondary ionization mass spectrometry (SIMS) on two zircon grains jh177 and jh1726 from a Jack Hills detrital zircon population (Kemp et al., 2010). (B) Plot of Hf vs. age for the data obtained by laser ablationinductively coupled plasmamass spectrometry (LA-ICP-MS) from the same zircon grains as in A, calculated and plotted using both the concurrent 207Pb/ 206Pb ages (the procedure followed by Kemp et al., 2010) and the inferred upper-intercept age of the discordant arrays. Use of the 207Pb/ 206Pb ages of discordant analyses introduces an articial spread in Hf and a signicant bias toward more negative values. The eld delimited by the stippled line encompasses all the Hf values calculated using the concurrent 207Pb/ 206Pb ages in Kemp et al. (2010). Abbreviations: DMdepleted mantle, CHURchondritic uniform reservoir; MCmac crust; UCCupper continental crust; MSWDmean square of weighted deviates.
Ma, yielding upper-intercept ages of 3994 Ma and 4055 Ma, respectively, where the probability of t improves for the older lower-intercept age. The merits of this projection are also supported by the fact that the upper-intercept age best matches the oldest reported 207Pb/206Pb. In Kemp et al. (2010), the Hf data were calculated using the concurrent 207Pb/206Pb ages, yielding distinct Hf values of 7.7 to 3 (Fig. 4B). By contrast, calculation of Hf using the extrapolated upper-intercept age of 4055 Ma yields values of 4.6 to 5.5, which overlap each other within error. The second example, grain jh1726, is more extreme. Here, the ion probe data yielded two discordant data points with slightly divergent 207Pb/206Pb ages of 4054 Ma and 4031 Ma (Fig. 4A), whereas the 207Pb/206Pb ages obtained concurrently with the Hf composition by LAICP-MS gave 4015 Ma and 3841 Ma. Hence, there is again evidence for nonzero Pb loss. In this case, making an extrapolation to concordia is much more uncertain. Use of a lower-intercept age of 3000 Ma leads to an impossibly old age, whereas a lower-intercept age of 2000 Ma yields an upper-intercept age of 4280 Ma. The Hf calculated using the concurrent 207Pb/206Pb ages shows a large variation between 6.2 and 9.9, whereas the extrapolated age of 4280 Ma
produces Hf values that are identical within error (Fig. 4B). The lower-intercept age of 2000 Ma is used here only to demonstrate the general concept. The fact that the resulting Hf values are identical is simply due to the fact that the measured 176Hf/177Hf values are also essentially identical. In absolute terms, however, the Hf values calculated with an inferred primary (= concordant age) are dramatically different (giving slightly positive values) from those calculated using the discordant 207Pb/206Pb ages. It is not the purpose of this section to advocate specic ages and argue in favor or against specic Hf values for the ancient Jack Hills zircons, but the examples stress the importance of a proper consideration of the reality, and the causes and the effects of U-Pb discordance on the results and their interpretations. In the chosen examples, it is clear that the dispersion of the calculated Hf data is both articially enlarged and biased toward too negative values. These cases are representative of the approach followed in a number of studies focused on early crustal evolution, as well as studies that use Hf isotopes in zircon to deal with the younger history of Earth. Evidently simply ignoring discordance distorts the reality, because, as the present examples show, discordance matters.
Subconcordant Data and the Handicap of Low Precision The hard-wired discordance discussed in the previous section can produce linear arrays of data points, which, when the difference between the two intercept ages is small enough, become subparallel to the concordia curve and, dependent on the magnitude of the uncertainty, indistinguishable from it (e.g., Corfu et al., 1994; Corfu, 2007). Resolving whether a set of data denes a subconcordant linear array representing a single disturbed, or two mixed, generations, or whether it represents a random distribution of dates, each representing the concordant age of a particular grain, is largely a function of the analytical uncertainty. Such a case is demonstrated by the example in Figure 5 using data reported by Moser et al. (2009). The more precise ID-TIMS data are discordant but plot on a discordia line (Fig. 5A), whereas the less precise SIMS data all overlap the concordia curve within error (Fig. 5B). In this particular case, the two sets of data complement each other very well, and once integrated with the textural information of the zircon grains, and the geological context, they back up a coherent interpretation of two specic events. However,
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 Corfu taken alone without the supplementary information, the SIMS data could also be explained in terms of multiple growth periods, or multiple sources if this were a detrital zircon population. In fact, the pattern mimics that seen in many modern studies of complex high-grade terrains, or of detrital zircon populations done by SIMS or LA-ICP-MS, where the data are considered concordant as long as they are not more than several percent discordant (often a 5% or 10% cutoff limit is used). For Precambrian zircons, the 207Pb/206Pb ages will generally be used and interpreted by means of probability density diagrams. Such an articial example, constructed using the data from Moser et al. (2009), is shown in Figure 5C. The statistical treatment extracts the two main age peaks corresponding to the initial crystallization at 2670 Ma and secondary overprint in response to the Vredefort impact at 2023 Ma. However, there are also several other peaks of variable magnitude, which in this case are known to be geologically meaningless. However, in a modern detrital zircon study, such a pattern would normally be interpreted as indicating real ages, and the possibility that individual subconcordant data may be recording partial resetting or mixing is rarely, if ever, considered. This may not be a very important factor in sedimentary rocks produced from relatively simple sources, such as an island arc, but it is likely to have serious repercussions on the apparent age distribution produced in zircon derived from more complex high-grade terranes. Administrative Concordancy Some contamination by common Pb (and U) is essentially unavoidable in all dating techniques. Some common geochronometers such as titanite and apatite, and to some degree also monazite, incorporate some initial Pb. Zircon is generally virtually free of initial common Pb, except crystals with rare compositions, or those that are altered or contain inclusions of Pb-bearing minerals. The ID-TIMS method introduces Pb and U contamination during the dissolution, the chemical separation, and the loading on a lament in preparation for the mass spectrometry. In SIMS and LA-ICP-MS measurements, contaminant Pb (and U) can be introduced mainly during the mounting and polishing process. Practitioners of all three methods are concerned with keeping the common Pb levels as low as possible, and have devised specic techniques to achieve this goal. Nevertheless, it is likely that some contamination will affect every analysis. In good ID-TIMS laboratories, the Pb blank reaches levels as low as 0.2 pg, i.e., a few femtograms 204Pb, a level still easily detected in a thermal ionization mass spectrometer. Hence,
2670 Ma
0.50 2600
A ID-TIMS data
0.46
2400
206Pb/238U
0.42 2200 2600
2023 Ma
0.38 2000 2400
0.34
Vredefort 7 crater 2200 rebound

0.38 2000
11
13
B SIMS data
7 9
207Pb/235U
0.34
11
13
Relative probability
C SIMS
207Pb/206Pb
- ages
2000
2200
207Pb/206Pb
2400
2600
- age [Ma]
Figure 5. Zircon U-Pb data from a mac xenolith from the Lace kimberlite in South Africa. The zircon formed magmatically at 2670 Ma and was strongly disturbed by the processes caused by deep crustal deformation and metamorphism after the Vredefort meteorite impact (Moser et al., 2009). (A) Isotope dilutionthermal ionization mass spectrometry (ID-TIMS) data plot along a discordia line. (B) Secondary ionization mass spectrometry (SIMS) data showing the same trend as the ID-TIMS data but at lower resolution. Spot analyses show that zircon lost Pb due to crystal-plastic deformation, although full resetting was achieved only in a few domains (Moser et al., 2009). (C) Relative probability plot of the SIMS 207Pb/ 206Pb ages extracting a number of peaks and subpeaks. The initial and the nal peaks correspond to the two real events, but the intermediate ones are spurious and geologically meaningless. The example shows that an awareness of discordance and precision are important for accurate interpretations.
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Downloaded from gsabulletin.gsapubs.org on May 1, 2013 A century of U-Pb geochronology: The long quest towards concordance ID-TIMS analyses always include the measurement of 204Pb, which is then used to correct for the nonradiogenic Pb. Questions affecting the precision are usually related to the proportion of blank versus initial Pb, and to how well one knows, or can estimate, their compositions and uncertainties. These factors propagate into the total uncertainty, and for very small samples they become its dominant element. In SIMS analyses, measuring the 204Pb peak can be difcult because of the very small signal produced during the analysis and because of overlaps with potential isobaric interferences. Thus, besides measuring 204Pb directly and correcting as in ID-TIMS, the so-called 207Pb and 208 Pb corrections are also used. The former assumes concordance and calculates the amount of common Pb needed to shift the measured 207 Pb/206Pb to the concordant equivalent. The latter assumes instead that Th, U, and Pb were not disturbed in the mineral and calculates the amount of common Pb from the difference between the measured and the expected 208Pb/206Pb. The 208Pb correction, however, has been shown to introduce signicant uncertainties in samples with normal to high Th/U (Williams, 1998). The disadvantage of the 207Pb method is that, for samples that are actually discordant, the dictated administrative concordance will result in an overcorrection and a biased age, and also implies a loss of information on the mutual isotopic relationships between grains, information which can be important for the interpretation. In LA-ICP-MS analyses, the main problem is caused by the interference on 204Pb by 204Hg introduced with the Ar gas. It is, in principle, possible to minimize the amount of Hg present and correct for it by measuring the abundance of 202Hg (Gerdes and Zeh, 2009), but most users consider that this correction introduces too much uncertainty, and choose instead to either make no correction at all, based on the assumption that zircon has no common Pb and that the blank is negligible, or they correct the common Pb with a model calculation that assumes a coherent behavior of Th/Pb and U/Pb and estimates the time of the isotopic disturbance (Andersen, 2002). Both approaches can have problematic implications for the accuracy of the data and the geological deductions. Discriminating Origins of Zircon (and Other Minerals) Based on Th/U Factors that are important for a proper interpretation of U-Pb data include the geological and mineralogical context of the studied minerals, the internal textures of the minerals, the age relationships between different components of a mineral and between different coexisting minerals, the type and spatial arrangement of inclusions, and the minerals chemical composition. An increasing number of studies have been devoted to the systematic assessment of the role of trace elements in zircon (Heaman et al., 1990; Belousova et al., 2002; Hoskin and Schaltegger, 2003), especially of the rare earth elements (REEs) (Rubatto, 2002; Whitehouse and Platt, 2003) and Ti (Watson and Harrison, 2005; Fu et al., 2008), the latter for geothermometry. An important branch also deals with stable isotopes in zircon (e.g., Valley et al., 2005; Whitehouse and Nemchin, 2008). One of the most commonly discussed geochemical discriminants of U-bearing minerals is the Th/U ratio, because it can be measured directly during isotopic analysis, or it can be estimated from 208Pb/206Pb. The ratio of Th/U is popular mainly because of the widespread perception that it can be used to distinguish magmatic from metamorphic zircon (or titanite) (Bingen et al., 2001; Rubatto, 2002; Kramers and Mouri, 2011). It is indeed correct that magmatic zircon and titanite quite commonly yield Th/U of 1.00.2, whereas metamorphic zircon in amphibolite- and eclogite-facies rocks tends to have ratios of 0.20.0. There are, however, many exceptions. For example, very low Th/U ratios are very common in magmatic zircons grown in highly evolved granites, aplites, pegmatites, and leucosomes in migmatites. One factor affecting the ratio is the scavenging of Th by other minerals, such as monazite or epidote (Bingen et al., 2001), but another important reason is the fact that Th/U tends to decrease progressively during the evolution of granitic systems (Fig. 6), and hence zircon in highly evolved rocks will simply inherit the low Th/U from the magma. Conversely, high Th/U ratios can be very prominent in metamorphic zircon and titanite of high-grade rocks (e.g., Moser and Heaman, 1997; Corfu et al., 1994). Hence, it is important to stress the fact that Th/U alone has a very limited diagnostic value (Whitehouse and Kamber, 2005; Harley et al., 2007) and should only be considered in combination with other lines of evidence. FINAL REMARKS Progress in the development of U-Pb dating techniques has been driven forward by the spirit of technical innovation, but at the same time, it has been moderated by some inherent limitations. Many imaginative approaches had to be developed to make the system work. The recognition of the causes of U-Pb discordance and establishment of techniques to deal with this problem have contributed to the emergence of U-Pb as a prime geochronological tool. Discordance, however, remains a general problem, the minimization of which still requires work and creative solutions, unless, out of convenience, the historical consciousness of discordance simply disappears from the collective awareness.
whole-rock values
Th
[ppm]
1 4:
100
main body Central Aaregranite Bergell Giuv
2:
Th /U
1: 1
marginal facies
Mont Blanc Vallorcine Grimsel
Figure 6. Whole-rock Th-U ratios in granitic systems from the central Alps show a very systematic behavior, with both a general increase in U and Th levels during evolution of the systems and a gradual decline in their Th/U ratio (from Rybach, 1973; Rybach and Labhart, 1973). The ratio is especially low in pegmatites and aplites.
aplite stocks
10
aplites
10
100
Th
3: 1
[ppm]
schist gneiss granite
10
pegmatite
+ + +
1 10
0.1
1: 1
1 6:
U [ppm] Th /U
U [ppm]
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Encouragements by Editor Brendan Murphy and constructive reviews by Don W. Davis and an anonymous reviewer are gratefully acknowledged.
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SCIENCE EDITOR: BRENDAN MURPHY MANUSCRIPT RECEIVED 21 MARCH 2012 REVISED MANUSCRIPT RECEIVED 7 JULY 2012 MANUSCRIPT ACCEPTED 11 JULY 2012
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A Century of U-Pb Geochronology

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A century of U-Pb geochronology: The long quest towards concordance

CELEBRATING ADVANCES IN GEOSCIENCE

For permission to copy, contact editing@geosociety.org 2013 Geological Society of America

Geological Society of America Bulletin, January/February 2013

Geological Society of America Bulletin, January/February 2013

Geological Society of America Bulletin, January/February 2013

Geological Society of America Bulletin, January/February 2013

Geological Society of America Bulletin, January/February 2013

1850 1830 1810 1790 1770

Geological Society of America Bulletin, January/February 2013

Geological Society of America Bulletin, January/February 2013

error ellipses are 68.3% conf

206 Pb/ 238

+ calculated for 4055 Ma

projected from 2000 Ma 3994 45 Ma

3700 jh17-26.1+2 3500

projected from 2000 Ma 8 4280 77 Ma

projected from 0 Ma 4050 9 Ma

calculated for 4280 Ma

4100 age [Ma]

Geological Society of America Bulletin, January/February 2013

0.42 2200 2600

Vredefort 7 crater 2200 rebound

Geological Society of America Bulletin, January/February 2013

Mont Blanc Vallorcine Grimsel

schist gneiss granite

Geological Society of America Bulletin, January/February 2013

Downloaded from gsabulletin.gsapubs.org on May 1, 2013 Corfu

Geological Society of America Bulletin, January/February 2013

Geological Society of America Bulletin, January/February 2013

Downloaded from gsabulletin.gsapubs.org on May 1, 2013 Corfu

Geological Society of America Bulletin, January/February 2013

Geological Society of America Bulletin, January/February 2013

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