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(This is a sample cover image for this issue. The actual cover is not yet available at this time.) This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues. Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. In most cases authors are permitted to post their version of the article (e.g. in Word or Tex form) to their personal website or institutional repository. Authors requiring further information regarding Elsevier’s archiving and manuscript policies are encouraged to visit: http://www.elsevier.com/copyright Author's personal copy Lithos 160-161 (2013) 268–282 Contents lists available at SciVerse ScienceDirect Lithos journal homepage: www.elsevier.com/locate/lithos Is Myanmar jadeitite of Jurassic age? A result from incompletely recrystallized inherited zircon Tzen-Fu Yui a,⁎, Mayuko Fukoyama a, b, Yoshiyuki Iizuka a, Chao-Ming Wu c, Tsai-Way Wu d, J.G. Liou e, Marty Grove e a Institute of Earth Sciences, Academia Sinica, Taipei, 11529, Taiwan, ROC Graduate School of Engineering and Resource Science, Akita University, Japan Department of Applied Arts, Fu-jen Catholic University, Hsinchuang, Taiwan, ROC d Department of Earth Sciences, University of Western Ontario, London, Ontario, Canada e Department of Geological and Environmental Sciences, Stanford University, Stanford, CA 94305, USA b c a r t i c l e i n f o Article history: Received 3 September 2012 Accepted 19 December 2012 Available online 27 December 2012 Keywords: Myanmar jadeitite Zircon SHRIMP U–Pb dating a b s t r a c t Zircons from two Myanmar jadeitite samples were separated for texture, mineral inclusion, U–Pb dating and trace element composition analyses. Three types of zircons, with respect to U–Pb isotope system, were recognized. Type I zircons are inherited ones, yielding an igneous protolith age of 160 ± 1 Ma; Type II zircons are metasomatic/hydrothermal ones, giving a (minimum) jadeitite formation age of 77 ± 3 Ma; and Type III zircons are incompletely recrystallized ones, with non-coherent and geologically meaningless ages from 153 to 105 Ma. These Myanmar jadeitites would therefore have formed through whole-sale metasomatic replacement processes. Compared with Type I zircons, Type II zircons show typical metasomatic/hydrothermal geochemical signatures, with low Th/U ratio (b 0.1), small Ce anomaly (Ce/Ce*=b 5) and low ΣREE content (40–115 ppm). Type III zircons, however, commonly have the above geochemical signatures straddle in between Type I and Type II zircons. It is shown that the resetting rates of various trace element compositions and U–Pb isotope system of inherited zircons are not coupled “in phase” in response to zircon recrystallization during jadeitite formation. The observed abnormally low Th/U ratio and small Ce anomaly of some Type I zircons, as well as the lack of negative Eu anomaly of all Type I zircons, should be suspected to be of secondary origin. In extreme cases, incompletely recrystallized zircons may show typical metasomatic/hydrothermal geochemical signatures, but leave U–Pb isotope system partially reset or even largely unchanged. Such zircons easily lead to incorrect age interpretation, and hence erroneous geological implication. The Myanmar jadeitites, based on the present study, might have formed during the Late Cretaceous subduction before the beginning of India–Asia continental collision at Paleocene. Previously proposed Late Jurassic ages for Myanmar jadeitites are suggested as results rooted on data retrieved from incompletely recrystallized inherited zircons. © 2012 Elsevier B.V. All rights reserved. 1. Introduction Jadeitite is an uncommon rock type often associated with eclogite and blueschist in high-pressure metamorphic belts around the world. It is a fluid–rock interaction product enclosed within serpentinite formed under subduction environments (e.g., Harlow and Sorensen, 2005; Harlow et al., 2007). The formation mechanism(s) of jadeitites would thus reveal important clues on element migration/cycling during subduction and the age of jadeitite, theoretically, would provide useful time constraints for regional tectonics (see Tsujimori ⁎ Corresponding author at: Institute of Earth Sciences, Academia Sinica, Taipei, 11529, Taiwan, ROC. Tel.: +886 2 27839910x621; fax: +886 2 27839871. E-mail address: tfyui@earth.sinica.edu.tw (T.-F. Yui). 0024-4937/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.lithos.2012.12.011 and Harlow, 2012 and the references therein; Flores et al., 2012; Yui et al., 2012). There are two possible formation mechanisms for jadeitite, which, accordingly, can be divided into two types. The “vein precipitation type” or the “P-type” jadeitite is formed through direct precipitation from a Na–Al–Si-rich aqueous fluid infiltrating through serpentinites and the “metasomatic replacement type” or the “R-type” jadeitite is formed through whole-sale metasomatic replacement of (igneous) tectonic blocks within serpentinites (Tsujimori and Harlow, 2012; Yui et al., 2010). Zircons in jadeitite may therefore be either recrystallized/newly-formed contemporaneous with jadeite formation, or inherited from protoliths. As a result, U–Pb dating of such zircons would theoretically yield the jadeitite age or the protolith igneous age, respectively. However, since both types of jadeitite may share similar characteristics, it may not be easy to confidently categorize a specific Author's personal copy T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 jadeitite sample in question. Furthermore, the lack of clear-cut criteria to discriminate igneous zircons from hydrothermal/metamorphic ones has also been noted recently (e.g., Bulle et al., 2010; Harley et al., 2007), not to mention the potential problems with respect to incomplete recrystallization of inherited zircons during jadeitite formation. Controversial suggestions on the geological meaning of the U–Pb dating results of zircons from a specific jadeitite occurrence (i.e., protolith igneous age or metasomatic/hydrothermal jadeitite age) have therefore been proposed even with the information on internal textures, mineral/fluid inclusions, Th/U ratio, trace-element characteristics, and O-isotope composition of zircons (Bröcker and Keasling, 2006; Bulle et al., 2010; Fu et al., 2010, 2012; Tsujimori et al., 2005). The Jade Mine Tract in northern Myanmar, located at the northern extremity of the Sagaing fault in the Hpakan area of the Kachin State, is the most famous jadeitite resource in Asia. Recent U–Pb zircon dating studies suggested that these jadeitites might have formed during 269 the Late Jurassic time (Qiu et al., 2009; Shi et al., 2008). In this study, SHRIMP U–Pb dating results on zircons with complicated internal textures from two Myanmar jadeitite samples are presented. The data clearly demonstrate that any interpretation on jadeitite U–Pb zircon ages must be regarded with caution. 2. Geological background Geologically, Myanmar (Burma) can be divided into the Western province and the Eastern province, separated by the Sagaing fault (Fig. 1). The Western province is also named as the Burma microplate, whereas the Eastern province is part of the Shan-Thai block. The east dipping Andaman subduction zone that continues onshore along the western margin of the Western province (the Burma microplate) marks the presently active boundary with Indian plate to the west. The Sukhotai-Lao fold belt and the Nan-Uttaradit suture denote the Fig. 1. Geologic overview of the Myanmar area (modified after Searle et al., 2007). Samples in the present study are from the Hpakan area of the Jade Mines belt. STD: South Tibet Detachment. Author's personal copy 270 T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 Early or Late Triassic suturing between the Shan-Thai block and the Indo-China block to the east (see Metcalfe, 2000; Mitchell, 1977; Mitchell et al., 2007; Searle et al., 2007; and the references therein). The Indo-Burman Ranges of the western Burma microplate are composed mainly of Upper Cretaceous–Paleogene marine sedimentary rocks unconformably overlying Upper Triassic flysch-type sediments and associated Jurassic ophiolitic rocks, thought to be the southern continuation of the Indus-Yarlung Zangbo suture zone (Mitchell, 1993). To the east of the Indo-Burman Ranges, there are a series of mid-Cretaceous to Miocene sedimentary basins (Chindwin, Minbu and Pathein basins). Along with the basins, a belt of calc-alkaline Late Cretaceous plutons and Cenozoic volcanoes signifies the long-lived Andaman subduction system (Mitchell, 1993). The Eastern province of Myanmar is composed of the Paleozoic Mogok metamorphic belt (MMB in Fig. 1) to the west and the Upper Carboniferous–Lower Permian Mergui Group metasediments (not shown in Fig. 1) to the east (Mitchell, 1992, 1993). Subduction-related Jurassic–Miocene granites intruded the Mogok metamorphics (Barley et al., 2003). The age of metamorphism, however, has been discussed controversially. Mitchell et al. (2007) proposed two possibilities; either (1) there are three stages of metamorphism during Early Permian, Early Jurassic and Early Tertiary time, respectively, or (2) there are two stages of metamorphism during late Cretaceous and Early Tertiary time, respectively. On the other hand, Searle et al. (2007) suggested that metamorphism occurred during Jurassic–Early Cretaceous, Paleocene– Early Eocene and Late Eocene-Oligocene time. The N–S trending Sagaing fault is a 1200 km long dextral fault. The distance of the right-lateral displacement has been estimated from less than 100–150 km (Bertrand and Rangin, 2003) to ~ 450 km (Mitchell, 1993) or even more. In the south, the fault connects to the Andaman back-arc spreading centre, and in the north, it splays into three prominent metamorphic belts within the Western province (Fig. 1). These three metamorphic belts, from west to east, are the Jade Mines belt (JM in Fig. 1), the Katha-Gangaw ranges (KGR in Fig. 1) and the Tagaung-Myitkyina belt (TMB in Fig. 1). The Jade Mines belt has been subjected to high-pressure metamorphism, whereas low- to medium-pressure/high-temperature metamorphic rocks prevail in the Katha-Gangaw ranges and the Tagaung-Myitkyina belt (Mitchell, 1993). In the Jade Mines belt, various kinds of jadeitites, in association with eclogite, amphibolite, blueschist and chromitite, occur as boulders in drainages, or as tectonic blocks/veins within serpentinite(-peridotite) mélange (Chhibber, 1934; Goffé et al., 2002; Shi et al., 2001). Metasomatic amphiboles are commonly present in between jadeitite and hosting serpentinized peridotite. These amphiboles are sodic to sodic-calcic in nature, including eckermannite, magnesiokatophorite, nyböite, glaucophane, richterite and winchite (Shi et al., 2003). Late stage albite veins cross-cutting jadeitites are not uncommon. The P–T conditions for jadeitite formation have been estimated at 1.0– 1.5 GPa/300–500 °C (Mével and Kiénast, 1986), >1.4 GPa/400–450 °C (Goffé et al., 2002), >1.0 GPa/250–370 °C (Shi et al., 2003) or ~1.5 GPa/ ~380 °C (Oberhänsli et al., 2007). Based on U–Pb dating of zircons from jadeitites, Shi et al. (2008) and Qiu et al. (2009) suggested that Myanmar jadeitite would have formed during the Late Jurassic time, i.e., 147±3 and 158±2 Ma, respectively. However, Goffé et al. (2002) reported 39Ar/40Ar ages on phengites in eclogites, blueschists, jadeitites and amphibolites from the Jade Mines belt. The results yielded much younger ages, including an ~80 Ma for eclogite-facies metamorphism and an~30 Ma for blueschist-facies overprinting. zircon and catapleiite ((Na2,Ca)ZrSi3O9 · 2H2O) (Supplementary Table S1). Due to the high content of amphiboles, the rock could also be named as jadeite-amphibole rock. Jadeite is mostly sub- to anhedral in form, replaced by retrograde prismatic to fibrous Na-amphiboles (Fig. 2a). Catapleiite is Ca-rich and is present along rims of some zircon grains as a retrograde phase (see Figs. 2c–d and 3a–b). Sample BUR Z2 mainly consists of jadeite (~ 85 vol.%), omphacite (Ae5Jd49Quad46, ~14 vol.%) and minor amounts of zircon. There are two types of jadeite, reflecting different growth stages. Jd-I (Jd99Quad1, ~15 vol.%) is high in Jd component and low in modal abundance, whereas Jd-II (Jd89Quad11, ~70 vol.%) is slightly lower in Jd component but high in modal amount (Supplementary Table S1). Textural relation shows that Jd-I is replaced by Jd-II, which, in turn, is replaced by omphacite (Fig. 2b). Residual Jd-I is generally anhedral and small in grain size, mostly less than 0.2–0.5 mm. It is surrounded by subhedral prisms of Jd-II with a grain size of 0.5 × 1–1 × 2.5 mm. Omphacite, replacing Jd-II, also has a large grain size (0.5–2 mm). Both samples (BUR Z1 and BUR Z2) mainly show a granoblastic texture. Slightly preferred orientation of minerals is observed only in small domains. 3. Sample description 5.1. Mineral inclusion and internal texture of zircon Two jadeitite samples from the Hpakan area of the Jade Mines belt, provided by a local miner, were chosen in the present study. Both samples are white in color. Sample BUR Z1 is coarse grained (0.5–1.5 mm). It contains mainly jadeite (Ae1Jd96Quad3, ~65 vol.%) and Na-amphiboles (eckermannite±glaucophane, ~34 vol.%), with minor amounts of Zircons from jadeitite sample BUR Z1 are sub- to anhedral and 150 × 250–200 × 350 μm in size. Some grains are slightly fractured. A few zircons exhibit a reaction rim with jadeite/Na-amphiboles and/or later infiltrated fluid, forming catapleiite (Figs. 2c–d and 3a–b). Mineral inclusions are common in zircon, including feldspars 4. Analytical methods Zircons, concentrated by standard heavy mineral separation processes and hand picking for final purity, were mounted in an epoxy disc with a 25-mm diameter and a 4-mm thickness. All grains were imaged with transmitted light and reflected light under a petrographic microscope. Cathodoluminescence (CL) and back-scattered electron images were taken with a JEOL 5600 SEM to identify internal texture, inclusions and physical defects. Zircon U–Th–Pb dating analyses and trace element (Y, Hf and REEs) determinations were conducted on the SHRIMP-RG (reverse geometry) ion microprobe co-operated by U.S. Geological Survey and Stanford University in the SUMAC facility at Stanford University. The primary ion beam size is about 25 μm. Analytical and data reduction procedures followed those given by Williams (1998). For age standardization, concentrations of uranium from standard zircon CZ3 (550 ppm U) were used. U–Pb ratios were determined through replicate analyses of standard zircons R33 (419 Ma) (Black et al., 2004). Detailed procedures were described by Yui et al. (2010). Precisions for REE determinations were estimated in the range of ±5% for HREE, ±10–15% for MREE, and up to ±40% for La (all values at 2σ). A LABRAM HR confocal micro-Raman spectrometer equipped with a Ar + laser with 514.5 nm excitation, housed in the Institute of Earth Sciences, Academia Sinica, was employed to identify inclusion phases in zircons. The laser beam size was about 2–5 μm and the laser power on the sample surface was about 15 mW. Qualitative chemical analyses for identification of mineral inclusions were also carried out, when inclusions are exposed on the zircon polished surface, with a JEOL SEM JSM-6360LV coupled with an energy dispersive X-ray (EDX) spectrometer housed in the Institute of Earth Sciences, Academia Sinica. Chemical analysis for jadeitite was carried out at the Department of Earth Sciences, University of Western Ontario. Major-element analyses were done by X-ray fluorescence spectrometry with the precision for all major-element determinations better than ±5%. Trace element analyses including REEs were carried out by the Fusion-ICP-MS method using a Perkin Elmer Sciex ELAN 6000 ICP-MS. The precisions are about ±15–20% for Th and U, and better than ±10% for others. 5. Results Author's personal copy T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 271 Fig. 2. (a) Optical micrograph of sample BUR Z1, showing jadeite (Jd) replaced by Na-amphibole (Na-Am), and (b) backscattered electron image of sample BUR Z2 showing different stages of jadeite and late-stage omphacite (omp). Backscattered electron images of zircons showing some composite mineral inclusion in (c) zircon grain 13 and (d) 23 from sample BUR Z1 and (e) zircon grain 4 from sample BUR Z2; as well as zircon fracturing in (f) grain 7 from sample BUR Z2. See text for details. Small white speckles on zircon polished surface in c-f are relicts of gold coating after SHRIMP analysis. (K-feldspar and albite), chlorite, jadeite, Na-amphiboles and catapleiite, on the basis of Raman and EDX spectra (Figs. 2c–d, 3a, c and e). Among them, K-feldspar, albite and chlorite were only observed as inclusions in zircon but are not present in jadeitite matrix. Many jadeite, Naamphibole and catapleiite inclusions, not restricted to zircon rims and being irregular/angular in form, are mostly related/connected to fractures, although isolated ones on zircon polished surface are also present (Figs. 2c–d, 3c and e). So are some chlorite inclusions. A few inclusions contain composite minerals, in which catapleiite replaces chlorite, jadeite and/or Na-amphiboles (Figs. 2c–d, 3a and e), and jadeite replaces chlorite (not shown). Fluid inclusions were not observed. Zircon grains/domains without mineral inclusions or with feldspars and chlorite inclusions generally exhibit oscillatory zoning pattern under cathodoluminescence (CL) (Fig. 3b and d). These zircons usually display medium to dark, and occasionally light, CL. On the other hand, zircon grains/domains, which are fractured or contain jadeite, Na-amphibole, and occasionally chlorite inclusions, mostly show a heterogeneous patchy/cauliflower-like texture (Fig. 3d and f). Note that catapleiite inclusions are present in both kinds of zircon grains/domains, although they are less common and smaller in size in zircon grains/domains with oscillatory zoning. Zircons from jadeitite sample BUR Z2 are sub- to anhedral and 100 × 200–500 × 700 μm in size. Some zircon grains are highly fractured. Jadeite veins invade into zircon crystals along such fractures and contain broken zircon chips (Figs. 2f, 4a and e). Irregular/angular-form jadeite and omphacite inclusions, some of which can often be traced to fractures, are common in some zircon grains/domains (Figs. 2e–f, 4a and e). Chlorite inclusions are also present (Fig. 4c), although rare. In a few cases, jadeite replaces chlorite in composite inclusion pockets (Fig. 2e). Fluid inclusions were not observed. Zircon grains/domains without prominent fractures and mineral inclusions usually exhibit oscillatory zoning pattern under cathodoluminescence (CL) (Fig. 4d and f). Sector zoning is also observed in a few cases. By contrast, zircon Author's personal copy 272 T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 Fig. 3. Representative backscattered electron images and CL images of zircon grains 2 (a and b), 10 (c and d) and 15 (e and f) from sample BUR Z1. Zircons are slightly fractured, containing inclusions of albite (Ab), K-feldspar (Kfs), chlorite (Chl), jadeite (Jd), Na-amphibole (Na-Am) and catapleiite (Cat). Raman and EDX spectra of some inclusions are also given. Note that some inclusions contain composite minerals. Zircon grains/domains with oscillatory zonings under CL (Type I) yield old U–Pb ages, whereas zircon grains/domains with a heterogeneous patchy/cauliflower-like texture under CL (Type II) yield younger U–Pb ages. Zircon Type I or II is labeled next to the SHRIMP analyzing spot. grains/domains, with fractures or jadeite/omphacite inclusions, often show a heterogeneous patchy/cauliflower-like texture (Fig. 4b and f). 5.2. U–Pb age determination of zircon Nineteen SHRIMP-RG dating analyses were carried out on fifteen zircon grains from sample BUR Z1 (Table 1). One analysis shows a high U content of 2562 ppm and yields the oldest age of 166 Ma. It has been reported that zircons with U content in excess of ~2500 ppm usually show a progressive increase in apparent radiogenic 206Pb/238U ratios (and therefore apparent ages) with increasing U content due to U-dependent changes in sputtering and secondary ionization efficiency during SHRIMP analysis (Butera et al., 2001; White and Ireland, 2012). This analysis is therefore excluded from age calculation. The other fifteen analyses from zircon domains with oscillatory zonings yield an age of 160±1 Ma (MSWD=3.0) (Fig. 5a). Th/U ratios for these zircon analyses are higher than 0.1 (Table 1). The remaining three analyses, all from heterogeneous patchy domains, give an age of 77±3 Ma (MSWD=1.8) with Th/U ratios lower than 0.1 (Fig. 5a, Table 1). Zircons yielding old ages with oscillatory zonings are categorized as Type I and zircons giving young ages with a heterogeneous patchy texture, Type II. Sixteen SHRIMP-RG dating analyses were carried out on twelve zircon grains from sample BUR Z2 (Table 1). Eight analyses from zircon domains with oscillatory zonings yield an age of 159 ± 1 Ma (MSWD = 2.1) (Fig. 5b) and have Th/U ratios ranging from 0.04 to 0.26 (Table 1). The age is comparable to those of Type I zircons from sample BUR Z1. These zircon grains/domains are thus also categorized as Type I. The other eight analyses from heterogeneous patchy domains are mostly discordant and do not yield a coherent age. These ages scatter from 153 to 105 Ma (Fig. 5b), older than that of Type II zircons from sample BUR Z1. The corresponding Th/U ratios range from 0.07 to 0.29 (Table 1). These zircons are categorized as Type III. Author's personal copy T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 273 Fig. 4. Representative backscattered electron images and CL images of zircon grains 7 (a and b), 9 (c and d) and 10 (e and f) from sample BUR Z2. Raman and EDX spectra of some inclusions are also given. Zircon grains/domains without prominent fractures (Type I) generally do not contain jadeite inclusions, show oscillatory zonings, and give old U–Pb ages. On the other hand, highly fractured zircon gains/domains (Tpye III) contain jadeite inclusions, show a heterogeneous patchy/cauliflower-like texture and yield younger U–Pb ages. Zircon Type I or III is labeled next to the SHRIMP analyzing spot. 5.3. Trace element composition of zircon The chondrite-normalized REE patterns of Type I zircons from sample BUR Z1 show characteristic positive Ce anomalies (Ce/Ce* = 12–1260) and enriched HREE, but no Eu anomalies (Table 2, Fig. 6a). On the other hand, Type II zircons show a small positive Ce anomaly (Ce/Ce*= 2–3), slightly enriched LREE, and a small but distinct positive Eu anomaly (Eu/Eu* = 2.0–3.8) (Table 2, Fig. 6a). Total REE content of Type I zircons (i.e., 530–1170 ppm) is much higher than that of Type II zircons (i.e., 40–115 ppm) (Table 2). The chondrite-normalized REE patterns of Type I zircons from sample BUR Z2 are similar to those of Type I zircons from sample BUR Z1, including characteristic positive Ce anomalies (Ce/Ce* = 9–161), enriched HREE, and no Eu anomalies (Table 2, Fig. 6b). Type III zircons in this sample, however, show comparable but less distinct features as Type II zircons in sample BUR Z1. For example, Type III zircons also Author's personal copy 274 T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 Table 1 SHRIMP-RG U–Th–Pb analytical data of zircon. Type BUR Z1 1-1 2-2 3-1 3-2 4-1 5-1 5-2 6-1 7-1 8-1 8-2 9-1 10-1 10-2 11-1 12-1 13-1 14-1 15-1 BUR Z2 1-1 1-2 2-1 3-1 3-2 4-1 5-1 5-2 6-1 7-1 8-1 9-1 10-1 10-2 11-1 16-1 U Th (ppm) (ppm) I I I I I I I I I I I I I II I I II I II 294 1685 2562 212 295 1841 501 326 449 332 1448 1829 166 220 407 297 68 329 650 44 654 1001 25 40 627 70 39 67 42 371 704 17 10 57 39 1 41 39 III I I I III I III III I III I I I III III III 156 1878 466 113 122 145 68 546 660 199 1323 116 312 329 477 264 15 445 47 5 17 15 5 157 42 37 350 5 23 46 72 31 1. Radiogenic 206Pb. 2. Common Pb component (%) of total 206 Th/U 206 Pb*1 206 Pbc2 Total 238 U/206Pb (ppm) (%) 0.15 0.39 0.39 0.12 0.14 0.34 0.14 0.12 0.15 0.13 0.26 0.38 0.10 0.05 0.14 0.13 0.01 0.12 0.06 6.3 36.8 57.4 4.7 6.2 39.6 10.8 7.2 9.7 7.3 31.3 40.1 3.6 2.2 8.6 6.5 0.7 7.0 6.8 – 0.05 0.02 0.56 – 0.12 – 0.17 – – 0.04 0.14 0.36 – – 0.40 – 0.32 – 40.05 39.38 38.36 39.11 40.97 39.96 40.01 39.06 39.77 39.26 39.81 39.18 39.59 85.21 40.58 39.07 85.65 40.14 82.40 1.0 0.4 0.4 1.2 1.0 0.4 0.8 1.0 0.8 1.0 0.5 0.4 1.4 1.6 0.9 1.0 2.9 1.0 0.9 0.10 0.24 0.10 0.04 0.14 0.10 0.07 0.29 0.06 0.19 0.26 0.04 0.07 0.14 0.15 0.12 3.1 40.4 9.9 2.4 2.1 3.0 1.3 11.2 14.4 2.8 28.8 2.5 6.7 6.4 9.2 5.5 1.14 0.06 – 0.95 9.51 0.41 0.93 0.10 – 0.86 0.17 – 0.18 5.64 0.24 0.65 43.39 39.91 40.61 40.48 51.02 40.93 44.69 41.81 39.50 60.43 39.48 39.90 40.13 44.53 44.37 41.51 1.4 0.4 0.8 1.7 1.7 1.5 2.2 0.7 0.7 1.4 0.5 1.6 1.0 1.1 0.8 1.1 Pb, determined by 207 Total 207 1σ (%) Pb/206Pb 206 Pb/238U age 1σ (%) (Ma) 1σ (Ma) 0.0482 0.0488 0.0496 0.0541 0.0524 0.0486 0.0511 0.0501 0.0522 0.0488 0.0499 0.0504 0.0527 0.0474 0.0505 0.0517 0.0373 0.0511 0.0481 3.5 1.5 1.2 3.9 3.4 1.5 2.6 3.2 2.7 3.2 2.2 1.4 4.5 6.0 2.9 3.4 12.1 3.2 3.4 159.2 161.7 165.8 161.8 154.8 159.5 158.8 162.8 159.5 162.3 159.8 162.3 160.1 75.2 156.7 162.5 75.8 158.3 77.7 1.7 0.7 0.6 2.0 1.6 0.7 1.3 1.6 1.4 1.6 0.8 0.7 2.2 1.2 1.4 1.7 2.3 1.6 0.7 0.0517 0.0499 0.0476 0.0550 0.0990 0.0546 0.0529 0.0505 0.0519 0.0553 0.0518 0.0513 0.0538 0.0750 0.0479 0.0510 4.7 1.4 2.9 5.3 4.4 4.6 9.1 2.5 2.2 4.8 1.6 5.4 3.2 2.7 2.7 3.6 146.4 159.4 157.1 156.2 117.4 154.6 141.9 152.1 160.7 104.9 160.8 159.1 157.8 138.6 143.9 153.1 2.1 0.7 1.3 2.6 2.1 2.3 3.2 1.1 1.1 1.5 0.8 2.6 1.6 1.6 1.1 1.7 Pb correction (Williams, 1998). exhibit small positive Ce anomalies (Ce/Ce* = 4–14), slightly enriched LREE, and small positive Eu anomalies (Eu/Eu*=1–1.8) (Table 2, Fig. 6c), but these features mostly overlap with those of Type I zircons in sample BUR Z2. Total REE content of Type III zircons (i.e., 53– 1064 ppm) largely overlaps with that of Type I zircons (i.e., 248– 1143 ppm) (Table 2). 5.4. Chemical characteristics of jadeitite Both jadeitite samples are high in Al and Na, and low in K (Table 3). Sample BUR Z1 is higher in Mg and LOI, whereas sample BUR Z2 is slightly higher in Ca, reflecting their different mineral constituents. The two samples also show different REE characteristics. Sample BUR Z1 is higher in LREE and MREE content, whereas sample BUR Z2 is higher in HREE (Fig. 7a). The latter sample has a relatively flat or concave REE pattern ((La/Lu)N = 1.1) with a small positive Eu anomaly (Eu/Eu* = 1.3), similar to those Myanmar jadeitites reported by Shi et al. (2008). On the other hand, the former sample has an enriched LREE and flat HREE pattern ((La/Lu)N = 19.5) without Eu anomaly, similar to Tone (Japan) jadeitite reported by Yui et al. (2012). In the primitive mantle (Sun and McDonough, 1989) normalized spidergram, these two jadeitites are notably enriched in Zr and Hf, but depleted in Ti, Ta and Nb (Fig. 7b). The enrichment of Zr and Hf relative to other elements in the spidergram seems to be a common feature for all jadeitites that have been studied (Fig. 7b). 6. Discussion 6.1. Geological meaning of zircon U–Pb dates Type I zircons from sample BUR Z1 show oscillatory zoning under CL, contain K-feldspar and albite inclusions that are not present in jadeitite matrix, exhibit high Th/U ratio in the range of 0.10–0.39 (Table 1), and have large Ce anomaly (Ce/Ce* = 12–1260) and high ΣREE content (530–1170 ppm) with HREE enrichment (Figs. 8 and 9). All these features are similar to those of inherited igneous zircons in Tone jadeitites from Kyushu (Japan) described by Mori et al. (2011) and Yui et al. (2012). The geochemical signatures of these zircons are also comparable with those of igneous zircons from oceanic crust characterized by Th/U > 0.1, Ce anomaly > 10, and ΣREE content > 500 ppm (Grimes et al., 2009). However, it is noted that Type I zircons in this sample contain inclusions of chlorite and catapleiite too. Catapleiite is a reaction product between zircon and jadeite/Na-amphibole and/or between zircon and an infiltrated fluid phase subsequent to jadeiteamphibole formation. It should be a post-zircon phase. Catapleiite “inclusions” in Type I zircons therefore would be best interpreted as “pseudo-inclusions” noted by Zhang et al. (2009) and Bulle et al. (2010) that later interaction with rock matrix/infiltrated fluid may cause the formation of metamorphic/hydrothermal “young” minerals in “old (igneous)” zircon domains. In this respect, chlorite inclusions could also be regarded as a hydration product of mafic igneous minerals. The dating result 160 ± 1 Ma of Type I zircons from sample BUR Z1 is Author's personal copy T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 Fig. 5. Tera-Wasserburg concordia diagram showing zircon ages from (a) sample BUR Z1 and (b) BUR Z2. therefore interpreted as the igneous age of jadeitite protolith. It is worth to point out that oscillatory zoning itself is not a conclusive signature that such Type I zircons should be of igneous origin. Metasomatic/ hydrothermal zircons from Guatemala jadeitite studied by Yui et al. (2010) yielded a jadeitite formation age younger than that of regional eclogite-facies metamorphism. These metasomatic/hydrothermal zircons were also shown to display oscillatory zoning. However, they exhibit distinct metasomatic/hydrothermal geochemical signatures as Type II zircons in this study discussed below. Type II zircons in sample BUR Z1, compared with Type I zircons, exhibit a heterogeneous patchy texture under CL, show lower Th/U ratios (b0.1), have smaller Ce anomaly (Ce/Ce* = 2–3) and lower abundance of ΣREE content (40–115 ppm). These geochemical features are similar to those of metasomatic/hydrothermal zircons in jadeitites from north of Motagua fault, Guatemala (Yui et al., 2010) and Tone, Kyushu, Japan (Mori et al., 2011; Yui et al., 2012) (Figs. 8 and 9). The small but distinct positive Eu anomaly of Type II zircons is surely related to the decomposition of protolithic feldspars. The frequent occurrence of jadeite/Na-amphiboles/catapleiite inclusions in Type II zircons of this specific sample indicates that these Type II zircons would be genetically related to the formation of these phases as a result of fluid infiltration. The common irregular/angular form with microfractures from acute angles of catapleiite (composite) inclusions (Fig. 2c–d) demonstrates that such inclusions should be related to zircon fracturing. Similar features were also observed for most, if not all, jadeite and Na-amphibole inclusions (Figs. 2c–d and 275 3e). Coupled with the heterogeneous patchy texture under CL, these Type II zircons should be a result of recrystallization of Type I inherited zircons due to fluid infiltration along fractures (Corfu et al., 2003). Their age, 77 ± 3 Ma, would therefore designate the formation time of jadeite, Na-amphibole and/or catapleiite. In studying the Na-amphiboles associated with Myanmar jadeitites, Shi et al. (2003) concluded that Na-amphiboles might have formed simultaneously with and slightly later than jadeite. Unfortunately, it is difficult to determine the time gap between the formation of jadeite/Na-amphibole and the formation of catapleiite, except that catapleiite must have formed later. Nonetheless, Type II zircon grain 15 is less affected by catapleiite formation (Fig. 3e–f) but still yields a similar young age as other Type II zircons. Moreover, catapleiite pseudo-inclusions were also observed in some Type I zircons, but did not cause significant zircon recrystallization. These observations would indicate that the fluid responsible for the formation of jadeite/Na-amphibole may have played a determinant role in forming Type II zircons. The U–Pb age of Type II zircons, 77 ± 3 Ma, is therefore interpreted as the (minimum) formation age of jadeitite. By contrast, Type I zircons in sample BUR Z2 are not as distinct in their geochemical signatures, which straddle both igneous and metasomatic/hydrothermal values shown by zircons in sample BUR Z1 (Figs. 8a and 9). For example, some Type I zircons exhibit low Th/U ratios (b0.1) and small Ce anomalies (Ce/Ce* = ~ 9), different from the geochemical characteristics of igneous zircons. However, these zircons occasionally contain chlorite pseudo-inclusions. They show oscillatory/sector zoning and yield an age of 159 ± 1 Ma, comparable to those of Type I zircons from sample BUR Z1. They are therefore also regarded to be inherited from an igneous protolith, at least with respect to the U–Pb isotope system. Pooled together, the 23 Type I zircon data from both BUR Z1 and BUR Z2 samples lead to an igneous protolith age of 160 ± 1 Ma (MSWD = 2.8) for the Myanmar jadeitite. Type III zircons in sample BUR Z2 are mostly fractured, contain jadeite/omphacite inclusions, and show a heterogeneous patchy texture under CL, indicating that they would have been subjected to deformation and recrystallization during jadeite/omphacite formation. Many jadeite/omphacite inclusions have irregular/angular form with microfractures (Figs. 2e–f, 4a and e), demonstrating that they could be pseudo-inclusions. The geochemical characteristics of these zircons, however, are not as distinct as those of Type II zircons and can not be clearly distinguished from Type I zircons (Figs. 8 and 9). The resulting ages are discordant and non-coherent. Apparent ages of 8 analyses scatter from 153 to 105 Ma. This age range may indicate a protracted jadeite formation period. Alternatively, the age range is a result of incomplete resetting of U and Pb isotope compositions during zircon recrystallization. In view of the non-distinct geochemical signatures of these Type III zircons compared with those of Type II zircons in sample BUR Z1, as well as that most jadeite/omphacite inclusions in Type III zircons might be pseudo-inclusions, the latter interpretation is more likely. In summary, zircons from both jadeitite samples BUR Z1 and BUR Z2 would be inherited igneous ones, which may probably explain the large grain size of some zircons up to 500–700 μm. These zircons were affected by different degrees of fracturing and recrystallization during the subsequent metasomatic/hydrothermal event forming jadeitite. The jadeitites studied would then belong to the metasomatic replacement (R-) type (Tsujimori and Harlow, 2012; Yui et al., 2010). Type I zircons contain albite, K-feldspar and chlorite inclusions that were not observed in jadeitite matrix. While chlorite is regarded as a hydration product of igneous mafic minerals and albite might also be a result of Na-metasomatism of igneous plagioclase, K-feldspar would be an igneous mineral. Together with the large grain size of zircons, the observations would indicate that the protolith of these jadeitites might be felsic igneous intrusions. K-feldspar of igneous origin was also reported as inclusions in inherited zircons from Tone (Japan) jadeitite, of which the possible protolith was proposed to be oceanic Author's personal copy 276 T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 Table 2 Trace element concentration (ppm) of zircon determined by SHRIMP-RG. BUR Z1 1-1 2-2 3-1 3-2 4-1 5-1 5-2 6-1 7-1 8-1 8-2 9-1 10-1 10-2 11-1 12-1 13-1 14-1 15-1 BUR Z2 1-1 1-2 2-1 3-1 3-2 4-1 5-1 5-2 6-1 7-1 8-1 9-1 10-1 10-2 11-1 16-1 Type La Ce Nd Sm Eu Gd Dy Er Yb Y Hf Ce/Ce*1 Eu/Eu*1 (Sm/La)N1 (Yb/Gd)N1 I I I I I I I I I I I I I II I I II I II 0.0081 0.0049 0.013 0.0084 0.13 0.072 0.39 0.0012 0.022 0.0046 0.0013 0.18 0.0047 0.28 0.060 0.024 0.022 0.0035 3.5 8.0 22.6 33.7 3.8 4.2 28.9 13.7 5.6 9.5 6.4 26.4 25.2 2.9 0.81 8.2 5.5 0.14 6.3 5.2 0.19 0.61 1.5 0.13 0.22 0.78 1.1 0.24 0.31 0.20 0.62 1.1 0.14 0.052 0.26 0.46 0.024 0.17 0.28 0.80 2.2 3.9 0.71 0.60 2.5 1.6 0.95 1.5 0.99 2.4 2.8 0.61 0.0090 1.3 1.4 0.0031 0.91 0.03 0.96 2.1 3.9 0.94 0.83 2.3 2.0 1.3 2.1 1.1 2.5 3.1 0.69 0.030 1.4 1.6 0.013 1.1 0.11 12 22 34 11 10 25 25 16 27 16 29 30 9.1 0.21 20 18 0.12 16 0.25 68 86 107 68 62 106 131 99 139 98 132 108 57 2.5 120 92 3.0 95 2.0 137 135 155 164 145 173 255 237 305 229 233 168 136 14 268 208 23 219 7.7 313 262 306 423 357 336 545 571 682 544 455 322 356 60 614 494 88 521 24 842 910 1096 977 871 1161 1627 1416 1904 1376 1518 1157 806 87 1645 1249 139 1307 51 16583 15287 15021 12685 12767 15884 13083 12777 12953 13648 15337 13927 12705 12495 13169 12824 11296 13970 15528 167 446 266 87 13 88 12 395 86 193 1260 37 96 2 40 43 3 237 2 0.93 0.91 1.0 1.0 1.0 0.88 0.95 1.1 0.99 0.88 0.90 1.0 0.91 2.1 0.84 0.97 2.0 0.87 3.8 153 685 474 131 7.2 53 6.5 1253 104 330 2792 24 199 0.050 34 91 0.22 404 0.013 30 15 11 48 42 16 26 43 30 42 19 13 48 343 36 33 922 38 118 III I I I III I III III I III I I I III III III 0.19 0.13 0.0083 0.041 0.091 0.033 0.23 0.18 0.0047 0.20 0.35 0.017 0.06 0.50 0.24 1.1 2.7 12.6 5.3 1.0 1.2 2.4 2.3 6.9 5.1 1.9 12.3 0.94 2.6 6.7 6.0 11.5 0.33 0.74 0.24 0.11 0.32 0.26 0.49 0.48 0.17 0.40 1.0 0.075 0.31 0.92 0.59 2.3 0.49 2.7 1.9 0.46 0.28 0.65 0.20 1.3 0.69 0.44 2.6 0.42 0.94 1.3 2.3 1.8 0.73 3.3 2.8 0.47 0.37 0.99 0.25 1.7 0.83 0.48 2.7 0.51 1.3 1.9 3.0 2.3 8.3 30 36 5.6 3.6 12 0.93 20 10 3.2 26 6.2 16 20 37 24 38 84 165 31 19 67 5 75 42 14 79 33 70 84 147 130 85 109 318 63 46 143 11 123 70 37 107 68 135 163 279 291 200 175 615 147 87 296 33 208 136 79 183 163 272 307 494 600 496 706 1827 368 246 816 64 781 441 192 723 404 806 964 1660 1658 11108 11436 9489 12713 4589 10302 9278 7966 14043 8839 11283 13281 10931 7208 6144 9870 6 26 100 9 4 18 14 4 161 4 12 17 12 5 9 4 1.1 1.1 1.0 0.90 1.1 1.1 1.0 1.8 1.0 1.2 1.0 1.0 1.0 1.2 1.0 1.1 4.0 33 364 17 4.8 30 12 1.3 231 3.4 12 39 23 3.9 15 2.6 29 7.0 21 32 29 30 12 43 16 30 8.7 32 21 19 16 30 1/3 2/3 × NdN , and the subscript “N” indicates normalization to chondrite values of Sun and McDonough (1989). 1. Ce/Ce* = CeN/(LaN × PrN)1/2, Eu/Eu* = EuN/(SmN × GdN)1/2, PrN = LaN plagiogranite or subduction-zone adakitic granite (Yui et al., 2012). The same protolith suggestion can be applied to Myanmar jadeitite. 6.2. Geochemical dilemma due to incomplete zircon recrystallization Typical inherited igneous zircons and completely recrystallized metasomatic/hydrothermal zircons in jadeitite can be clearly distinguished from each other not only by their U–Pb ages, but also by the type of mineral inclusions and geochemical signatures, as exemplified by Type I and Type II zircons from sample BUR Z1 in the present study (Fig. 9), as well as by those zircons from Tone (Japan) and Guatemala jadeitites reported previously (Mori et al., 2011; Yui et al., 2010, 2012) (Fig. 8). Metasomatic/hydrothermal zircons are shown to be characteristically low in Th/U ratio, Ce anomaly, and ΣREE content. Complications in geochemical distinctions, however, may arise if zircons are not completely recrystallized. Despite the patchy texture under CL and the presence of jadeite/ omphacite inclusions, incompletely recrystallized zircons, such as Type III zircons in sample BUR Z2 in the present study, yield non-coherent ages. It is noted that some such incompletely recrystallized Type III zircons, although exhibiting metasomatic/hydrothermal-like low Th/U ratios or small positive Ce anomalies, have high ΣREE content (Table 4). It is further noted that the resetting of various trace element contents and U–Pb isotope systems during zircon recrystallization may not be coupled “in phase”. The resetting of Ce concentration seems to proceed faster than that of Th/U ratio or U–Pb isotope system for most Type III zircons during jadeitite formation (Fig. 9). As an example, Type III zircon grains/domains 5-2 and 16-1 in sample BUR Z2 show patchy texture under CL, have low Ce anomaly (Ce/Ce*=~4), but yet give 206Pb/238U apparent ages at 153–152 Ma, only slightly younger than those of inherited igneous zircons. However, these zircons exhibit Th/U ratios higher than 0.1 (see Tables 1 and 2). Such inconsistent geochemical characteristics of zircons would imply incomplete zircon recrystallization and be a warning not to take apparent ages of such zircons as the time of jadeitite formation. This suggestion may also be applied to Type II zircons from Osayama jadeitite (Fu et al., 2010), which were suggested to be of metasomatic/hydrothermal origin but have Th/U ratios larger than 0.1 (see Fig. 8c). In this respect, some Type I zircons in sample BUR Z2 have low Th/U ratios or small Ce anomalies (Table 4). These uncommon geochemical signatures for igneous zircon should be suspected to be of secondary origin. Furthermore, inherited zircons in the present study, as well as those in Tone (Japan) jadeitite (Mori et al., 2011; Yui et al., 2012), do not show prominent negative Eu anomaly (Fig. 6). It is well documented that prominent negative Eu anomaly is a common feature for igneous zircons, except for zircons from carbonatite, kimberlite, and some syenites (Belousova et al., 2002; Hoskin and Schaltegger, 2003). Zircons from oceanic crust usually have negative Eu anomaly (Eu/Eu*= b0.6) (Grimes et al., 2009), too. Whether the lack of negative Eu anomaly is an indigenous signature of inherited igneous zircons in jadeitite would be an interesting issue to explore. All these observations indicate that resetting of U–Pb isotope system seems to commonly take place at a slower pace than alteration of trace element compositions during zircon recrystallization upon jadeitite formation. The factors causing this decoupling of recrystallization rate of chemical/isotope systems in zircon would include P–T conditions, zircon fracturing, fluid/rock ratio, ionic radii, and redox-pH conditions. For example, it is well known that the larger Th 4+ would be Author's personal copy T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 277 lattice (Hoskin and Schaltegger, 2003). Besides, the original compositions may also play a role during such kinetic non-equilibrium recrystallizations. However, how these factors work together and what the resulting integrated effect on recrystallization rate would be for those elements concerned during zircon recrystallization have not yet been fully studied. The consequences for such zircon incomplete recrystallization could be easily recognized as shown in the present case, but could also lead to serious problems in age interpretation. Extreme cases could be envisioned that incompletely recrystallized zircons may have their geochemical signatures altered but still keep U–Pb age dates largely unchanged or only slightly modified. This would easily lead to an incorrect age/geological interpretation as shown below. 6.3. Jurassic subduction for the Jade Mines belt? Fig. 6. Chondrite (Sun and McDonough, 1989) normalized REE patterns of (a) Type I and Type II zircons from sample BUR Z1, (b) Type I zircons from sample BUR Z2 and (c) Type III zircons from Bur Z2. Pr content of zircons was not analyzed and its chondrite normalized 1/3 2/3 ×NdN . Note that Type II zircons have lower ΣREE value was calculated by PrN =LaN abundances and show smaller positive Ce anomalies than Type I zircons from sample BUR Z1. They also show small but distinct positive Eu anomalies. Such differences are not clearly distinguished between Type I and Type III zircons from sample BUR Z2. preferentially expelled from zircon lattice relative to the smaller U 4+ during recrystallization (Hoskin and Schaltegger, 2003). Besides, Ce 4+ may be reduced to Ce 3+ during jadeitite formation (Yui et al., 2010). The latter has a larger ionic radius less compatible with zircon The Myanmar jadeitites have been previously dated by Shi et al. (2008) and Qiu et al. (2009) based on zircon U–Pb SHRIMP/laser-ICPMS techniques, respectively. Shi et al. (2008) reported an inherited igneous (oceanic crust)/hydrothermal age at 163± 3 Ma by 18 analyses on Group I zircons, a jadeitite formation age at 147 ± 3 Ma by 10 analyses on Group II zircons and an unknown thermal event at 122 ± 5 Ma by one single analysis on Group III zircon. On the other hand, Qiu et al. (2009) suggested a slightly older jadeitite formation age of 158±2 Ma by 75 U–Pb dates on hydrothermal/metasomatic zircons. However, Qiu et al. (2009) proposed that their result is actually indistinguishable from that given by Shi et al. (2008) if the igneous/hydrothermal and jadeitite ages from the latter were pooled together, which would lead to an age of 157 ± 4 Ma. Both studies therefore suggested that Myanmar jadeitites should have formed during the Late Jurassic (i.e., 158–147 Ma) subduction between the Indian plate and the Burma microplate. Shi et al. (2008) related this subduction with some Mesozoic subduction-related calc-alkaline magmatism at 170–120 Ma along the Mogok belt (Barley et al., 2003). An Andean type continental margin along the southern border of Asian plate since at least Early Jurassic was also proposed based on temporal correlation of these igneous activities with those in the Karakoram and Hindu Kush areas (Searle et al., 2007). However, Mitchell et al. (2012) preferred to relate the intrusives along the Mogok belt to the subduction–collision with the Shan-Thai block, rather than to the subduction of the Indian plate. Qiu et al. (2009) also denied the connection between the inferred Jurassic subduction and the Mogok belt, but suggested a genetic relation with the Katha-Gangaw ranges (Fig. 1). It is noted that eclogite was recently reported west of the Katha-Gangaw ranges (Enami et al., 2012), although the details, including the time of high-pressure metamorphism, are not yet clear. These different opinions clearly indicate inadequate geological constraints of the area. The ages and the characteristics of the Myanmar jadeitite zircons studied by Shi et al. (2008) and Qiu et al. (2009) are compiled in Table 3 Major and trace element concentrations of Myanmar jadeitites. Major element (%) SiO2 TiO2 Al2O3 Fe2O31 MnO MgO CaO K2O Na2O P2O5 L.O.I. Total BUR Z1 BUR Z2 58.40 57.98 0.01 0.02 19.53 22.44 1.53 1.04 0.02 0.02 4.96 1.72 0.30 2.19 0.05 0.05 13.84 13.23 0.01 0.02 1.34 0.65 99.99 99.36 Trace element (ppm) La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Bur Z1 Bur Z2 5.46 0.80 13.20 1.30 1.47 0.16 5.77 0.60 0.96 0.13 0.23 0.06 0.54 0.15 0.05 0.03 0.19 0.24 0.03 0.06 0.09 0.25 0.02 0.06 0.14 0.39 0.03 0.08 Trace element (ppm) Hf Ta Nb Zr Y Th U Sr Rb Ba Ni Co Cr Eu/Eu*2 Bur Z1 Bur Z2 5.0 16.9 b0.01 b0.01 b0.2 b0.2 169 744 2 2 2.5 0.2 0.11 0.30 31 64 2.0 b0.2 b10 11 65 161 18 5 90 10 1.0 1.3 1. Total Fe as Fe2O3. 2. Eu/Eu* = EuN/(SmN × GdN)1/2, and the subscript “N” indicates normalization to chondrite values of Sun and McDonough (1989). Author's personal copy 278 T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 Fig. 7. (a) Chondrite normalized REE pattern and (b) Primitive Mantle normalized spidergram of Myanmar jadeitites in this study. Also shown are respective fields of Myanmar jadeitites reported by Shi et al. (2008), Itoigawa-Ohmi omphacites in jadeitite reported by Morishita et al. (2007), and Guatemala jadeitites reported by Simons et al. (2010) and Yui et al. (2010). Patterns for one Tone (Japan) jadeitite (Yui et al., 2012) and one Monviso jadeitite (Compagnoni et al., 2012) are also included for comparison. Table 4, together with those of zircons from this work. Although the ages, the geochemical features and the textures of zircons they studied are similar with each other and are largely comparable to those of zircons in the present study, particularly resembling those of zircons from sample BUR Z2, the related interpretations differ. For example, inherited igneous zircons were suggested to be present in jadeitites studied by Shi et al. (2008) and the present work, but all zircons studied were considered to be of metasomatic/hydrothermal origin by Qiu et al. (2009). Both Shi et al. (2008) and Qiu et al. (2009) proposed a Late Jurassic time for the formation of Myanmar jadeitite, the present study, however, indicates a lower limiting jadeitite age of 77 Ma. 6.3.1. Evaluation of protolith age Shi et al. (2008) characterized their Group I zircons by showing oscillatory zoning and the presence of a Na-free/Mg-rich inclusion phase. The Na-free/Mg-rich phase is similar to chlorite included within zircons in the present study. While chlorite is interpreted as a pseudoinclusion phase resulting from hydration reaction of igneous mafic minerals through fractures, other phases of possible igneous constituents, such as feldspars (especially K-feldspar), are also identified as inclusions in Type I zircons in the present study. The two ages derived from these zircons, i.e., 163 ± 3 Ma (Shi et al., 2008) and 160 ± 1 Ma (this study), are consistent with each other within analytical uncertainty and would unambiguously signify the age of igneous protolith of Myanmar jadeitites. East of the Indo-Burma Range, there are two, eastern and western, belts of dismembered ophiolites signifying the ancient plate boundary (Fig. 1) (Acharyya, 2007; Chhibber, 1934). Serpentinites (±peridotites), hosting the Myanmar jadeitite and HP rocks in the Jade Mines belt, are considered to be part of these belts. The on-land emplacements of these ophiolitic rocks were suggested to have taken place during Early Cretaceous to mid-Eocene (Acharyya, 2007; Mitchell, 1993). A K–Ar age of 158 ±20 Ma from hornblende-bearing pegmatite associated with harzburgites in the southern part of the western ophiolite belt (United Nations, 1978) demonstrates that parts of these ophiolites are relicts of Jurassic oceanic crust. The age of the inferred igneous protolith of jadeitites, i.e., 163 ± 3 Ma (Shi et al., 2008) or 160 ± 1 Ma (this study), agrees with this K–Ar date and is more precisely constrained. The jadeitite, as well as other high-pressure rocks in the Jade Mines belt, would therefore be genetically related to Jurassic igneous activities in oceanic environment(s), which could well be correlated with some ophiolites of Jurassic ages along the Indus-Yarlung Zangbo suture (see Hébert et al., 2012; and the references therein), as proposed by Mitchell (1993). Author's personal copy T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 279 Fig. 9. (a) Th/U-age and (b) Ce/Ce*-age plots of zircons in the present study. I, II and III means Type I (igneous), Type II (metasomatic/hydrothermal) and Type III (incompletely recrystallized) zircons, respectively. Compositional and age ranges for zircons from Myanmar jadeitites reported by Shi et al. (2008) and Qiu et al. (2009) are also shown for comparison. Note that most Type III zircons show small Ce/Ce* ratios. See text for details. Fig. 8. Ce/Ce*–Th/U plot for zircons from (a) Myanmar, (b) Tone (Japan), and (c) Osayama (Japan) and Guatemala jadeitites. For Tone jadeitite, Type II zircon of Mori et al. (2011) is equivalent to Type II plus Type III zircon in this study, whereas Type I+II zircon of Yui et al. (2012) is equivalent to Type III zircon in this study. For others, I, II and III means Type I (igneous), Type II (metasomatic/hydrothermal) and Type III (incompletely recrystallized) zircons, respectively. 6.3.2. Evaluation of jadeitite age Both Group II zircons studied by Shi et al. (2008) and all zircons studied by Qiu et al. (2009) are characterized by the lack of oscillatory zoning and the presence of jadeite or omphacite inclusions. These authors suggested that such zircons would be of metasomatic/hydrothermal origin, yielding the jadeitite formation age of 147 ± 3 Ma (Shi et al., 2008) or 158 ± 2 Ma (Qiu et al., 2009). Since the inclusion textures were not presented, it is also possible that these jadeite/omphacite inclusions in zircons in these two studies are actually pseudo-inclusions. As a matter of fact, Shi et al. (2008) mentioned that zircon grains they studied are fractured in different extent. The geochemical features of these zircons presented by Shi et al. (2008) and Qiu et al. (2009) are not as distinct as those metasomatic/ hydrothermal signatures shown by Type II zircons in the present study (see Table 4). In fact, their various compositional ranges are more comparable to Type III zircons in this study (Fig. 9). The latter contain jadeite/omphacite pseudo-inclusions and are interpreted to be incompletely recrystallized. It is noted that about half of the analyzed “metasomatic/hydrothermal” zircons presented by Shi et al. (2008) and Qiu et al. (2009) have at least one geochemical signature being non-dintinct (Table 4). Despite that these zircons yield respective coherent ages in these two studies (Fig. 10a), the dates should be regarded as incompletely reset ones, analogous to Type III zircons in this study, and should not bear any geological meaning. By contrast, the rest of the zircons in these two studies do show typical metasomatic/ hydrothermal geochemical signatures. However, ages from these apparently completely recrystallized zircons are similar to, or even slightly older than, those of incompletely recrystallized zircons in these two studies, respectively, and the resulting ages also differ between the two studies (Fig. 10). These features are more consistent with an interpretation that all such “metasomatic/hydrothermal” zircons studied by Shi et al. (2008) and Qiu et al. (2009) might be incompletely reset with respect to U and Pb isotope systems. The fact that the degree of age discordance between 206Pb– 238U and 208Pb– 232Th systems for zircons studied by Qiu et al. (2009) is skewed to negative values with decreasing Th/U ratios or Th content (Fig. 11), although may be an analytical artifact due to low Th concentrations, can be interpreted as a corollary of incomplete resetting. The age coherence, as well as the apparent ages of these zircons being similar to the inherited igneous zircon age, certainly implies very low degrees of recrystallization in terms of U–Pb system. This may also explain why the “metasomatic/ hydrothermal” zircons studied by Shi et al. (2008) and Qiu et al. (2009) are mostly feature-less under CL or show less prominent patchy texture compared with Type II and III zircons observed here. Different extent of zircon recrystallization could theoretically result from different fluid/rock ratios, different degrees of zircon fracturing, and/or different redox-pH conditions. In view of these assessments, the claimed “metasomatic/hydrothermal” zircons in Shi et al. (2008) and Qiu et al. (2009) should be better regarded as incompletely recrystallized inherited zircons. Only Type II zircons in the present study can be reasonably considered, in all aspects, as being completely recrystallized during jadeitite formation. Only one single analysis of Group III zircon was given by Shi et al. (2008), which yielded an age of 122 ± 5 Ma. The zircon has a low Th/ U ratio (i.e., 0.07). No other chemical compositions are available for evaluating the extent of zircon recrystallization. Since the age is older than the Type II zircons and falls into the age range of Type III zircons in the present study, this Group III zircon is also suggested to be incompletely recrystallized. On the bases of 39Ar/ 40Ar phengite dating for HP rocks, Goffé et al. (2002) postulated that eclogite facies metamorphism of the Jade Author's personal copy 280 T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 Table 4 Characteristics of zircons from Myanmar jadeitite. BUR Z1 (this study) Inherited igneous zircon (Type I) Metasomatic/hydrothermal zircon (Type II) BUR Z2 (this study) Inherited igneous zircon (Type I) Incompletely recrystallized zircon (Type III) Shi et al. (2008) inherited igneous/hydrothermal zircon (Group I) Metasomatic/hydrothermal zircon (Group II) Unknown thermal event zircon (Group III) Qiu et al. (2009) metasomatic/hydrothermal zircon Age (Ma) Th/U Ce anomaly/Eu anomaly ΣREE (ppm) CL images Inclusions 160 ± 1 (n = 15) 0.10–0.39 (n = 15) 12–1260/~1.0 (n = 15) 530–1170 Oscillatory zoning 77 ± 3 (n = 3) 0.01–0.06 (n = 3) 2–3/2.0–3.8 (n = 3) 40–115 Patchy structure Albite, K-feldspar, chlorite, catapleiite Jadeite, Na-amphibole, chlorite, catapleiite 159 ± 1 (n = 8) 153–105 (n = 8) 0.04–0.26 (n = 8) 0.07–0.29 (n = 8) 9–161/~ 1.0 (n = 8) 4–14/1.0–1.8 (n = 8) 248–1143 53–1064 Oscillatory zoning Patchy structure Chlorite Jadeite, omphacite, chlorite 163 ± 3 (n = 18) 0.05–0.31 (n = 18) – – Oscillatory zoning 147 ± 3 (n = 10) 0.07–0.18 (n = 10) – – No zoning, bright L Na-free/Mg-rich phase (chlorite?) Jadeite 122 ± 5 (n = 1) 0.07 (n = 1) – – No zoning, bright L – 157 ± 4 (n = 75) 0.04–0.19 (n = 16) 1–4/0.8–1.9 (n = 16) 52–286 Irregular or slightly patchy structure Jadeite, omphacite Mines belt took place at around 80 Ma. The (minimum) age of jadeitite formation, 77 ± 3 Ma, suggested in this study, is in accord with this time frame and implies a Late Cretaceous subduction event. This age is older than the age of Himalayan ultrahigh-pressure gneisses, 53–46 Ma (e.g., Kaneko et al., 2003; Leech et al., 2005). The latter signifies the minimum age of continental collision at the western syntaxis of Himalaya. It can therefore be concluded that jadeitites and associated high-pressure rocks from the Jade Mines belt in northern Myanmar should be products during Late-Cretaceous, but not Jurassic, subduction before India-Asia continental collision. 6.3.3. Implications for other jadeitite occurrences In the Cycladic blueschist belt, jadeitites are present as minor blocks within eclogite- to epidote blueschist-facies mélange sequences on the islands of Tinos and Syros, Greece. Zircons from these jadeitites and associated mélange blocks of eclogite, omphacitite, glaucophanite and Fig. 10. Histogram of “metasomatic/hydrothermal” zircon ages with (a) non-typical and (b) typical metasomatic/hydrothermal geochemical characteristics from Shi et al. (2008) and Qiu et al. (2009). The ages of these two zircon categories are similar in these two studies, respectively. The resulting ages, however, differ between the two studies. See text for details. chlorite-actinolite rock have been dated previously, yielding U–Pb ages of ca. 80 Ma (Bröcker and Keasling, 2006). These ages are older than the Eocene HP metamorphic ages (ca. 53–40 Ma) of the Cycladic blueschist belt (e.g., Bröcker and Enders, 2001; Tomaschek et al., 2003; and the references therein). Despite of the characteristic metasomatic mineral inclusions (such as omphacite, epidote, glaucophane, and actinolite etc.), zircons from these rocks generally show oscillatory/ sector zoning, have high Th/U ratios and exhibit igneous-like O-isotope compositions (Bröcker and Keasling, 2006; Fu et al., 2010, 2012). Most mineral inclusions in these zircons were also suggested to be pseudo-inclusions (Bulle et al., 2010). Zircons are therefore most probably inherited. Consequently, the zircon U–Pb dates should designate Fig. 11. (a) Degree of age discordance — Th/U and (b) U (Th) — Th/U plots for zircons from Myanmar jadeitites reported by Qiu et al. (2009). Degree of age discordance is defined as 100×((206Pb/238U)age/(208Pb/232Th)age−1). The degree of age discordance is skewed to negative values with decreasing Th content. The relation may indicate incomplete resetting of U–Th–Pb isotope system as a result of preferential expelling of Th during zircon recrystallization. Author's personal copy T.-F. Yui et al. / Lithos 160-161 (2013) 268–282 the time of their protolith igneous activities, but not the age of jadeitite formation or HP metamorphism (Bröcker and Keasling, 2006; Fu et al., 2010, 2012). Recently, there have been several reports dealing with SHRIMP U–Pb dating on zircons from various jadeitite occurrences, including Voikar-Syninsky, Polar Urals, Russia (Meng et al., 2011), Sierra del Convento, Cuba (Cárdenas-Párraga et al., 2012), Rio San Juan Complex, Dominican Republic (Schertl et al., 2012) and Kanto Mountains, Japan (Fukuyama et al., 2013). Most zircons in these jadeitites show oscillatory zoning under CL. They were claimed to contain jadeite/ omphacite or fluid inclusions and therefore to be of metasomatic/ hydrothermal origin. However, geochemical characteristics of these zircons are largely non-typical (e.g., Th/U > 0.1) compared with Type II metasomatic/hydrothermal zircons in this study. Some of the age results were also shown to be not in accord with regional geological information (Tsujimori and Harlow, 2012). Zircons from these jadeitite occurrences therefore may also be inherited ones. Further evaluation/ examination is obviously required. Incomplete recrystallization of inherited zircons may not be uncommon during jadeitite formation through whole-sale metasomatic replacement processes, probably due to the low temperature conditions (~100–450 °C) (Harlow, 1994; Shigeno et al., 2005). 281 chondrite (Shi et al., 2008). In this regard, dehydrated fluid from subducted sediments may have contributed to the LREE enrichment in the infiltrated fluid during the formation of Na-amphiboles. The observed different chemistries, and consequently mineral constituents, between the two jadeitite samples in this study may therefore be related to their spatial positions with respect to hosting serpentinite. In the absence of field occurrence information of the samples studied, this proposition may be a speculation. However, a comparable case was presented by Compagnoni et al. (2012), who reported a rock sample with quartz-jadeite rock at the core and jadeitite at the rim from serpentinite debris of the Monviso massif, western Alps. The rim jadeitite was shown to be distinctly higher in Mg, Ca, Ni, Cr and Co than quartz-jadeite rock. The feature is presumably related to the infiltrated serpentinization fluid during jadeitite formation. Acknowledgements Helpful comments/suggestions from H.-P. Schertl and an anonymous reviewer are highly appreciated. We would like to thank J.L. Wooden for his help and suggestions during our SHRIMP work. This study was financially supported by the National Science Council, Taiwan. 7. Concluding remarks The Myanmar jadeitite samples in the present work, as well as those studied by Shi et al. (2008) and Qiu et al. (2009), should be categorized as “metasomatic replacement type” or “R type” following the above discussion. Three types of zircons, in terms of U–Pb isotope system, were recognized in this study. Type I zircons are inherited ones, yielding an igneous protolith age of 160 ± 1 Ma; Type II zircons are metasomatic/hydrothermal ones, giving a (minimum) jadeitite formation age of 77 ± 3 Ma; and Type III zircons are incompletely recrystallized ones, with non-coherent and geologically meaningless ages from 153 to 105 Ma. This study also shows that completely recrystallized zircons during jadeitite formation, such as Type II zircons, would exhibit typical metasomatic/hydrothermal geochemical characteristics and record U–Pb age of jadeitite formation. However, the resetting rates of various trace element compositions and U–Pb isotope system during zircon recrystallization are not coupled “in phase”. Incompletely recrystallized zircons may partially retain igneous geochemical signatures, and in the worst case, such zircons may show typical metasomatic/hydrothermal geochemical signatures but give a coherent apparent age irrelevant to jadeitite formation. A thumb rule based on geochemical criteria for evaluating U–Pb SHRIMP dating on metasomatic recrystallized zircons from jadeitite, or other metasomatic products, can thus be derived. With typical metasomatic/hydrothermal geochemical signatures, zircons may or may not be completely recrystallized with respect to U–Pb isotope system. On the other hand, if zircons show non-typical metasomatic/ hydrothermal geochemical signatures, they are most probably incompletely recrystallized. Their U–Pb ages must be subjected to rigorous examinations before conclusions. Lastly, a few words regarding jadeitite chemistry seem warranted. Given the presence of inherited zircons with the same age, both samples studied most likely have resulted from whole-sale metasomatic replacement of a common protolith. Despite the distinctly high Al and Na contents in both samples, sample BUR Z1 is higher in Mg and LREE than sample BUR Z2 (Table 3). The latter sample is chemically similar to those jadeitites studied by Shi et al. (2008) (Fig. 7). The chemical differences are probably due to additional metasomatic reactions forming Na-amphiboles in sample BUR Z1. Shi et al. (2003) noted that metasomatic Na-amphiboles commonly developed in between jadeitite and hosting serpentinized peridotite in the Jade Mines belt. While nearby serpentinite may be the source for Mg, it has a flat REE pattern with REE abundances less than 10 times of Appendix A. Supplementary data Supplementary data to this article can be found online at http:// dx.doi.org/10.1016/j.lithos.2012.12.011. References Acharyya, S.K., 2007. Collisional emplacement history of the Naga-Andaman ophiolites and the position of the eastern Indian suture. Journal of Asian Earth Sciences 29, 229–242. Barley, M.E., Pickard, A.L., Khin, Z., Rak, P., Doyle, M.G., 2003. 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