Sample records for zircon oxygen isotope

  1. Isotopic Composition of Oxygen in Lunar Zircons

    NASA Technical Reports Server (NTRS)

    Nemchin, A. A.; Whitehouse, M. J.; Pidgeon, R. T.; Meyer, C.

    2005-01-01

    The recent discovery of heavy oxygen in zircons from the Jack Hills conglomerates Wilde et al. and Mojzsis et al. was interpreted as an indication of presence of liquid water on the surface of Early Earth. The distribution of ages of Jack Hills zircons and lunar zircons appears to be very similar and therefore analysis of oxygen in the lunar grains may provide a reference frame for further study of the early history of the Earth as well as give additional information regarding processes that operated on the Moon. In the present study we have analysed the oxygen isotopic composition of zircon grains from three lunar samples using the Swedish Museum of Natural History CAMECA 1270 ion microprobe. The samples were selected as likely tests for variations in lunar oxygen isotopic composition. Additional information is included in the original extended abstract.

  2. Long-Term (4 mo) Oxygen Isotope Exchange Experiment between Zircon and Hydrothermal Fluid

    NASA Astrophysics Data System (ADS)

    Bindeman, I. N.; Schmitt, A. K.; Lundstrom, C.; Golledge, S.

    2013-12-01

    Knowing oxygen diffusivity in zircon has several critical applications: 1) establishing zircon stability and solubility in hot silica-saturated hydrothermal solutions; 2) deriving metamorphic and magmatic heating timescales from intra-crystal oxygen isotopic gradients; 3) assessing the survivability of oxygen isotopic signatures in Hadean zircons. We report results of a microanalytical investigation of an isotope exchange experiment using a cold-seal pressure apparatus at 850°C and 500 MPa over 4 months duration. Natural zircon, quartz and rutile were sealed with a silica-rich solution doped with 18-O, D, 7-Li and 10-B in a gold capsule. The diffusion length-scales were examined by depth profiling using time-of-flight (TOF) and high-sensitivity dynamic secondary ionization mass spectrometry (SIMS). Starting materials had distinct and homogeneous δ18O: zircon from Mesa Falls tuff of Yellowstone (+3.6‰), rutile from Karelia (-29‰), Bishop Tuff Quartz (+8.4‰), and δ18O doped water (+400‰). Starting material zircon showed invariant 18O/16O during depth profiling. After the 4 month experiment, rutile crystal surfaces displayed etching (100's of nm), while zircon exteriors lacked visible change. Quartz was completely dissolved and reprecipitated in a minor residue. Rutile developed ~2 μm long Fickian diffusion profiles largely consistent with the wet diffusion coefficients for rutile previously reported [1]. Surface U-Pb dating of zircon detected no significant Pb loss from the outermost ~300 nm of the crystal face and returned identical core-face ages. We performed δ18O depth profiling of zircon in two directions. First, forward profiles (crystal rim inwards) by dynamic SIMS (no surface treatment besides Au-coating; Cs+ beam of 20 kV impact energy) showed initially high and decreasing 18O/16O over ~130 nm; TOF-SIMS forward profiles using a 2 kV Cs+ sputter beam and 25 kV Bi3+ primary ions on uncoated zircon surfaces (cleaned for 2 min with HF) yielded

  3. Oxygen isotopic composition and U-Pb discordance in zircon

    USGS Publications Warehouse

    Booth, A.L.; Kolodny, Y.; Chamberlain, C.P.; McWilliams, M.; Schmitt, A.K.; Wooden, J.

    2005-01-01

    We have investigated U-Pb discordance and oxygen isotopic composition of zircon using high-spatial resolution ??18O measurement by ion microprobe. ??18O in both concordant and discordant zircon grains provides an indication of the relationship between fluid interaction and discordance. Our results suggest that three characteristics of zircon are interrelated: (1) U-Pb systematics and concomitant age discordance, (2) ??18O and the water-rock interactions implied therein, and (3) zircon texture, as revealed by cathodoluminescence and BSE imaging. A key observation is that U-Pb-disturbed zircons are often also variably depleted in 18O, but the relationship between discordance and ??18O is not systematic. ??18O values of discordant zircons are generally lighter but irregular in their distribution. Textural differences between zircon grains can be correlated with both U-Pb discordance and ??18O. Discordant grains exhibit either a recrystallized, fractured, or strongly zoned CL texture, and are characteristic of 18O depletion. We interpret this to be a result of metamictization, leading to destruction of the zircon lattice and an increased susceptibility to lead loss. Conversely, grains that are concordant have less-expressed zoning and a smoother CL texture and are enriched in 18O. From this it is apparent that various stages of water-rock interaction, as evidenced by systematic variations in ??18O, leave their imprint on both the texture and U-Pb systematics of zircon. Copyright ?? 2005 Elsevier Ltd.

  4. Latest Pleistocene crustal cannibalization at Baekdusan (Changbaishan) as traced by oxygen isotopes of zircon from the Millennium Eruption

    NASA Astrophysics Data System (ADS)

    Cheong, Albert Chang-sik; Sohn, Young Kwan; Jeong, Youn-Joong; Jo, Hui Je; Park, Kye-Hun; Lee, Youn Soo; Li, Xian-Hua

    2017-07-01

    The silicic volcanism of Baekdusan (Changbaishan), which is on the border between North Korea and China, was initiated in the Late Pleistocene and culminated in the 10th century with a powerful (volcanic explosivity index = 7) commendite-trachyte eruption commonly referred to as the "Millennium Eruption." This study presents oxygen isotope data of zircon in trachydacitic pumices ejected during the Millennium Eruption, together with whole-rock geochemical and Sr-Nd-Pb isotopic data that manifest once again the A-type and EM1 affinities of the Millennium Eruption magma. The zircon crystals, dated by previous studies at ca. 12-9 ka, show a moderate inter-grain variation in δ18O from 3.69‰ to 5.03‰. These values are consistently lower than the normal mantle range, and interpreted to have resulted from the digestion of meteoric-hydrothermally altered intracaldera rocks in the shallow magma chamber beneath Baekdusan just prior to the crystallization of the zircons, rather than from derivation from low-δ18O sources deep in the mantle. The whole-rock geochemical/isotopic considerations suggest that the magma mainly self-cannibalized the earlier erupted volcanic carapace around the magma chamber. This study highlights the usefulness of zircon oxygen isotopes for characterizing past volcanic activity that has now been commonly eroded away and implies that the generation of Yellowstone-type low-δ18O magma is not a rare phenomenon in large-volume silicic eruptions.

  5. Zircon oxygen isotopes reveal Ivrea-Verbano Zone source characteristics of the Sesia Valley Caldera

    NASA Astrophysics Data System (ADS)

    Economos, R. C.; Quick, J. E.; Sinigoi, S.; de Silva, S. L.

    2013-12-01

    The Sesia Valley, in the Italian Alpine foothills, contains >14 km diameter caldera adjacent to and structurally shallower than the famous Ivrea-Verbano Zone deep crustal section. The caldera and its associated eruptive sequence presents opportunity to explore volcanic magmatism in light of exposed and well characterized source candidates, namely lower crustal gabbros and the mid-crustal metasedimentary Kinzigite formation. Original geochemical characteristics of volcanic units have been obscured by the effects of subsequent hydrothermal alteration. The resistance of the mineral zircon to fluid alteration makes it a prime candidate for the preservation and exploration of these geochemical signals, such as O isotopes. Lower crustal gabbros in the Ivrea-Verbano Zone have broadly monotonic whole-rock δ18O values between +8 and +9‰VSMOW (Sinigoi et al., 1994). Kinzigites preserve a much higher and more heterogeneous δ18O values, typically ranging from +10‰ up to +15‰ (Baker, 1990). Zircons from the caldera-forming rhyolitic eruption units and a pre-caldera rhyodacitic unit were analyzed by ion microprobe at UCLA for in-situ oxygen isotope ratios. External reproducibility of within-mount standard R33 grains range from 0.27 to 0.36‰. Rhyolites from the caldera-forming eruption yield a range of δ18O(zircon) values from 6.3‰ to 8.3‰. This range displays rough correlation with CL activity - CL active grains have lower δ18O(zircon) values while CL dark grains have higher δ18O(zircon) values. This variation may correlate with U contents, which are notoriously low in zircons from Ivrea-Verbano Zone gabbros. We argue that the range in O isotope values suggests zircons are a good fit for magmas influenced by gabbro and Kinzigite sources. However, these zircons do not appear to be inherited directly from either the gabbro or Kinzigite sources as their O isotope signatures are typically intermediate between the two. The pre-caldera rhyodacite sample displays a

  6. Oxygen diffusion in zircon

    NASA Astrophysics Data System (ADS)

    Watson, E. B.; Cherniak, D. J.

    1997-05-01

    Oxygen diffusion in natural, non-metamict zircon was characterized under both dry and water-present conditions at temperatures ranging from 765°C to 1500°C. Dry experiments were performed at atmospheric pressure by encapsulating polished zircon samples with a fine powder of 18O-enriched quartz and annealing the sealed capsules in air. Hydrothermal runs were conducted in cold-seal pressure vessels (7-70 MPa) or a piston cylinder apparatus (400-1000 MPa) on zircon samples encapsulated with both 18O-enriched quartz and 18O water. Diffusive-uptake profiles of 18O were measured in all samples with a particle accelerator, using the 18O(p, α) 15N reaction. For dry experimental conditions at 1100-1500°C, the resulting oxygen diffusivities (24 in all) are well described by: D dry (m 2/s) = 1.33 × 10 -4exp(-53920/T) There is no suggestion of diffusive anisotropy. Under wet conditions at 925°C, oxygen diffusion shows little or no dependence upon P H 2O in the range 7-1000 MPa, and is insensitive to total pressure as well. The results of 27 wet experiments at 767-1160°C and 7-1000 MPa can be described a single Arrhenius relationship: D wet (m 2/s) = 5.5 × 10 -12exp(-25280/T) The insensitivity of oxygen diffusion to P H 2O means that applications to geologic problems can be pursued knowing only whether the system of interest was 'wet' (i.e., P H 2O > 7MPa ) or 'dry'. Under dry conditions (presumably rare in the crust), zircons are extremely retentive of their oxygen isotopic signatures, to the extent that δ 18O would be perturbed at the center of a 200 μm zircon only during an extraordinarily hot and protracted event (e.g., 65 Ma at 900°C). Under wet conditions, δ 18O may or may not be retained in the central regions of individual crystals, cores or overgrowth rims, depending upon the specific thermal history of the system.

  7. Heavy Isotope Composition of Oxygen in Zircon from Soil Sample 14163: Lunar Perspective of an Early Ocean on the Earth

    NASA Technical Reports Server (NTRS)

    Nemchin, A. A.; Whitehouse, M. J.; Pidgeon, R. T.; Meyer, C.

    2006-01-01

    Thirty oxygen analyses of a large (sub-millimetre) zircon grain from the lunar soil sample 14163 have been determined using CAMECA 1270 ion microprobe. The sample 14163 was returned form the Fra Mauro region by Apollo 14 mission. Zircon grain of 0.6-0.8 mm in size extracted from the sample was imaged using CL detector fitted to the Philips Electron Microscope in order to reveal internal structure. Oxygen isotopes have been analysed during two sessions. The first set of data was collected using the original mount where the grain was set in the resin attached to the glass slide. This resulted in the two complications: (i) standard zircon has to be analysed from the separate mount and (ii) the lunar zircon grain was rased in the holder compared to the standard. In order to investigate, if the elevated oxygen compositions observed during this session could have resulted from this difference in geometric configuration during the standard and sample analyses, the lunar zircon was extracted from the original mount, remounted with the standard chip in the new resin disk and reanalysed during the second session. All analyses made during the first session show delta O-18 values heavier than 6.0%. The second set of data has a wider spread of delta O-18 values with some values as low as 5.6%. Nevertheless, a half of observed delta O-18 values in this set is also higher than 6.0%. Slightly lighter oxygen compositions observed during the second session indicate possible dependence of measured delta O-18 values on the geometry of analysed samples. Presence of zircons with similar heavy oxygen isotope compositions on the Moon, which neither had liquid water or felic crust similar to that on the Earth nor ever developed regime similar to plate tectonics, suggests that other mechanisms can be responsible for elevated delta O-18 values in zircons. This implies that there is no support for the presence of an ocean on the surface of the early Earth and as the ocean appears to be an

  8. Post-caldera volcanism: In situ measurement of U-Pb age and oxygen isotope ratio in Pleistocene zircons from Yellowstone caldera

    USGS Publications Warehouse

    Bindeman, I.N.; Valley, J.W.; Wooden, J.L.; Persing, H.M.

    2001-01-01

    The Yellowstone Plateau volcanic field, the site of some of the largest known silicic volcanic eruptions, is the present location of NE-migrating hotspot volcanic activity. Most volcanic rocks in the Yellowstone caldera (0.6 Ma), which formed in response to the climactic eruption of 1000 km3 of Lava Creek Tuff (LCT), have unusually low oxygen isotope ratios. Ion microprobe analysis of both U-Pb age and ??18O in zircons from these low-??18O lavas reveals evidence of complex inheritance and remelting. A majority of analyzed zircons from low-??18O lavas erupted inside the Yellowstone caldera have cores that range in age from 2.4 to 0.7 Ma, significantly older than their eruption ages (0.5-0.4 Ma). These ages and the high-??18O cores indicate that these lavas are largely derived from nearly total remelting of normal-??18O Huckleberry Ridge Tuff (HRT) and other pre-LCT volcanic rocks. A post-HRT low-??18O lava shows similar inheritance of HRT-age zircons. The recycling of volcanic rocks by shallow remelting can change the water content and eruptive potential of magma. This newly proposed mechanism of intracaldera volcanism is best studied by combining in situ analysis of oxygen and U-Pb isotope ratios of individual crystals. ?? 2001 Elsevier Science B.V. All rights reserved.

  9. The effect of weathering on U-Th-Pb and oxygen isotope systems of ancient zircons from the Jack Hills, Western Australia

    NASA Astrophysics Data System (ADS)

    Pidgeon, R. T.; Nemchin, A. A.; Whitehouse, M. J.

    2017-01-01

    We report the result of a SIMS U-Th-Pb and O-OH study of 44 ancient zircons from the Jack Hills in Western Australia with ages ranging from 4.3 Ga to 3.3 Ga. We have investigated the behaviour of oxygen isotopes and water in the grains by determining δ18O and OH values at a number of locations on the polished surfaces of each grain. We have divided the zircons into five groups on the basis of their U-Th-Pb and OH-oxygen isotopic behaviour. The first group has concordant U-Th-Pb ages, minimal common Pb, δ18O values consistent with zircons derived from mantle source rocks and no detectable OH content. U-Th-Pb systems in zircons from Groups 2, 3 and 4 vary from concordant to extremely discordant where influenced by cracks. Discordia intercepts with concordia at approximately zero Ma age are interpreted as disturbance of the zircon U-Th-Pb systems by weathering solutions during the extensive, deep weathering that has affected the Archean Yilgarn Craton of Western Australia since at least the Permian. Weathering solutions entering cracks have resulted in an influx of Th and U. δ18O values of Group 2 grains fall approximately within the "mantle" range and OH is within background levels or slightly elevated. δ18O values of Group 3 grains are characterised by an initial trend of decreasing δ18O with increasing OH content. With further increase in OH this trend reverses and δ18O becomes heavier with increasing OH. Group 4 grains have a distinct trend of increasing δ18O with increasing OH. These trends are explained in terms of the reaction of percolating water with the metamict zircon structure and appear to be independent of analytical overlap with cracks. Group five zircons are characterised by U-Pb systems that appear to consist of more than one age but show only minor U-Pb discordance. Nevertheless trends in δ18O versus OH in this group of grains resemble trends seen in the other groups. The observed trends of δ18O with OH in the Jack Hills zircons are similar

  10. Stability of Zircon and its Isotopic Ratios in High-Temperature Fluids: Long-Term (4 months) Isotope Exchange Experiment at 850 °C and 50 MPa

    NASA Astrophysics Data System (ADS)

    Bindeman, Ilya N.; Schmitt, Axel K.; Lundstrom, Craig C.; Hervig, Richard L.

    2018-05-01

    Stability of zircon in hydrothermal fluids and vanishingly slow rates of diffusion identify zircon as a reliable recorder of its formation conditions in recent and ancient rocks. Debate, however, persists on how rapidly oxygen and key trace elements (e.g., Li, B, Pb) diffuse when zircon is exposed to hot aqueous fluids. Here, we report results of a nano- to micrometer-scale investigation of isotopic exchange using natural zircon from Mesa Falls Tuff (Yellowstone) treated with quartz-saturated, isotopically (18O, D, 7Li, and 11B) labeled water with a nominal δ18O value of +450‰ over 4 months at 850°C and 50 MPa. Frontside (crystal rim inwards) δ18O depth profiling of zircon by magnetic sector SIMS shows initially high but decreasing 18O/16O over a 130 nm non-Fickian profile, with a decay length comparable to the signal from surficial Au coating deposited onto zircon. In contrast, backside (crystal interior outwards) depth profiling on a 2-3 µm thick wafer cut and thinned from treated zircon by focused ion beam (FIB) milling lacks any significant increase in 18O/16O during penetration of the original surface layer. Near-surface time-of-flight (TOF-SIMS) frontside profiles of uncoated zircon from 4-month and 1-day-long experiments as well as untreated zircons display similar enrichments of 18O over a distance of 20 nm. All frontside 18O profiles are here interpreted as transient surface signals from nm-thick surface enrichment or contamination unrelated to diffusion. Likewise, frontside depth profiling of H, Li, and B isotopes are similar for long- and short-duration experiments. Additionally, surface U-Pb dating of zircon from the 4-month experiment returned U-Pb ages by depth profiling with 1 µm penetration that were identical to untreated samples. Frontside and backside depth-profiling thus demonstrate that diffusive 18O enrichment in the presence of H2O is much slower than predicted from experiments in Watson and Cherniak (1997). Instead, intracrystalline

  11. Do Hf isotopes in magmatic zircons represent those of their host rocks?

    NASA Astrophysics Data System (ADS)

    Wang, Di; Wang, Xiao-Lei; Cai, Yue; Goldstein, Steven L.; Yang, Tao

    2018-04-01

    Lu-Hf isotopic system in zircon is a powerful and widely used geochemical tracer in studying petrogenesis of magmatic rocks and crustal evolution, assuming that zircon Hf isotopes can represent initial Hf isotopes of their parental whole rock. However, this assumption may not always be valid. Disequilibrium partial melting of continental crust would preferentially melt out non-zircon minerals with high time-integrated Lu/Hf ratios and generate partial melts with Hf isotope compositions that are more radiogenic than those of its magma source. Dissolution experiments (with hotplate, bomb and sintering procedures) of zircon-bearing samples demonstrate this disequilibrium effect where partial dissolution yielded variable and more radiogenic Hf isotope compositions than fully dissolved samples. A case study from the Neoproterozoic Jiuling batholith in southern China shows that about half of the investigated samples show decoupled Hf isotopes between zircons and the bulk rocks. This decoupling could reflect complex and prolonged magmatic processes, such as crustal assimilation, magma mixing, and disequilibrium melting, which are consistent with the wide temperature spectrum from ∼630 °C to ∼900 °C by Ti-in-zircon thermometer. We suggest that magmatic zircons may only record the Hf isotopic composition of their surrounding melt during crystallization and it is uncertain whether their Hf isotopic compositions can represent the primary Hf isotopic compositions of the bulk magmas. In this regard, using zircon Hf isotopic compositions to trace crustal evolution may be biased since most of these could be originally from disequilibrium partial melts.

  12. Zircon (Hf, O isotopes) as melt indicator: Melt infiltration and abundant new zircon growth within melt rich layers of granulite-facies lenses versus solid-state recrystallization in hosting amphibolite-facies gneisses (central Erzgebirge, Bohemian Massif)

    NASA Astrophysics Data System (ADS)

    Tichomirowa, Marion; Whitehouse, Martin; Gerdes, Axel; Schulz, Bernhard

    2018-03-01

    In the central Erzgebirge within the Bohemian Massif, lenses of high pressure and ultrahigh pressure felsic granulites occur within meta-sedimentary and meta-igneous amphibolite-facies felsic rocks. In the felsic granulite, melt rich parts and restite form alternating layers, and were identified by petrology and bulk rock geochemistry. Mineral assemblages representing the peak P-T conditions were best preserved in melanocratic restite layers. In contrast, in the melt rich leucocratic layers, garnet and related HP minerals as kyanite are almost completely resorbed. Both layers display differences in accessory minerals: melanosomes have frequent and large monazite and Fe-Ti-minerals but lack xenotime and apatite; leucosomes have abundant apatite and xenotime while monazite is rare. Here we present a detailed petrographic study of zircon grains (abundance, size, morphology, inclusions) in granulite-facies and amphibolite-facies felsic gneisses, along with their oxygen and hafnium isotope compositions. Our data complement earlier Usbnd Pb ages and trace element data (REE, Y, Hf, U) on zircons from the same rocks (Tichomirowa et al., 2005). Our results show that the degree of melting determines the behaviour of zircon in different layers of the granulites and associated amphibolite-facies rocks. In restite layers of the granulite lenses, small, inherited, and resorbed zircon grains are preserved and new zircon formation is very limited. In contrast, new zircons abundantly grew in the melt rich leucocratic layers. In these layers, the new zircons (Usbnd Pb age, trace elements, Hf, O isotopes) best preserve the information on peak metamorphic conditions due to intense corrosion of other metamorphic minerals. The new zircons often contain inherited cores. Compared to cores, the new zircons and rims show similar or slightly lower Hf isotope values, slightly higher Hf model ages, and decreased oxygen isotope ratios. The isotope compositions (Hf, O) of new zircons indicate

  13. Zircon U-Pb ages and Hf isotopic compositions indicate multiple sources for Grenvillian detrital zircon deposited in western Laurentia

    NASA Astrophysics Data System (ADS)

    Howard, Amanda L.; Farmer, G. Lang; Amato, Jeffrey M.; Fedo, Christopher M.

    2015-12-01

    Combined U-Pb ages and Hf isotopic data from 1.0 Ga to 1.3 Ga (Grenvillian) detrital zircon in Neoproterozoic and Cambrian siliciclastic sedimentary rocks in southwest North America, and from igneous zircon in potential Mesoproterozoic source rocks, are used to better assess the provenance of detrital zircon potentially transported across Laurentia in major river systems originating in the Grenville orogenic highlands. High-precision hafnium isotopic analyses of individual ∼1.1 Ga detrital zircon from Neoproterozoic siliciclastic sedimentary rocks in Sonora, northern Mexico, reveal that these zircons have low εHf (0) (-22 to -26) and were most likely derived from ∼1.1 Ga granitic rocks embedded in local Mojave Province Paleoproterozoic crust. In contrast, Grenvillian detrital zircons in Cambrian sedimentary rocks in Sonora, the Great Basin, and the Mojave Desert, have generally higher εHf (0) (-15 to -21) as demonstrated both by high precision solution-based, and by lower precision laser ablation, ICPMS data and were likely derived from more distal sources further to the east/southeast in Laurentia. Comparison to new and existing zircon U-Pb geochronology and Hf isotopic data from Grenvillian crystalline rocks from the Appalachian Mountains, central and west Texas, and from Paleoproterozoic terranes throughout southwest North America reveals that zircon in Cambrian sandstones need not entirely represent detritus transported across the continent from Grenville province rocks in the vicinity of the present-day southern Appalachian Mountains. Instead, these zircons could have been derived from more proximal, high εHf (0), ∼1.1 Ga, crystalline rocks such as those exposed today in the Llano Uplift in central Texas and in the Franklin Mountains of west Texas. Regardless of the exact source(s) of the Grenvillian detrital zircon, new and existing whole-rock Nd isotopic data from Neoproterozoic to Cambrian siliciclastic sedimentary rocks in the Mojave Desert

  14. Li isotopes in archean zircons

    NASA Astrophysics Data System (ADS)

    Bouvier, A.; Ushikubo, T.; Kita, N.; Cavosie, A. J.; Kozdon, R.; Valley, J. W.

    2009-12-01

    Li is a fluid mobile, moderately incompatible element with a large mass difference between its two stable isotopes. Different processes can fractionate 7Li/6Li (fluid-rock interaction, metamorphic reactions, and Li diffusion), leading to variation by over 50‰ of δ7Li for common crustal material. These large variations make δ7Li a potential tracer of continental weathering and of the fluids affecting magma sources. Here, we report δ7Li and trace elements in Archean igneous zircons from TTG and sanukitoid granitoids from the Superior Province (Canada) in order to characterize Li in Archean zircons from well-described samples. These data are compared to detrital zircons from the Jack Hills (Western Australia) for which parent rock-type is uncertain. This study aims to better understand Li substitution in zircon and to evaluate the utility of δ7Li and [Li] for Archean petrogenesis. Zircons (n=71) were analyzed for δ7Li and trace elements (Li, P, Ca, Ti, V, Fe, Y, REE, U, Th) using an IMS-1280 ion microprobe. Most of the zircons display typical igneous REE patterns and zoning by CL. [Li] averages 13.1 ± 9 for TTG, 25.7 ± 19 for Sanukitoid and 31.0 ± 14 ppm for Jack Hills zircons, which are distinct from mantle-related zircons (<0.1 ppm). Values of δ7Li average 1.0 ± 4.5‰ for TTGs, 6.3 ± 4.4‰ for sanukitoids and -2.6 ± 8.8‰ for Jack Hills samples. Trace elements were analyzed from single spots in order to evaluate coupled substitutions. Atomic ratios (3Li+Y+REE)/P average 2.6, showing that Li and trivalent atoms are not charge-balanced by P, and suggesting that Li does not replace Zr, according to the xenotime substitution. However, (Y+REE)/(Li+P) atomic ratios average 1.0 ± 0.6, supporting the hypothesis that Li is interstitial and partly compensates trivalent cations. Several observations in this study suggest that [Li] is primary in the studied zircons: i) if Li is interstitial, charge-balance and slow diffusion of REE would control Li mobility

  15. 1.8 billion years of fluid-crust interaction: A zircon oxygen isotope record for the lower crust, western Churchill Province, Canadian Shield

    NASA Astrophysics Data System (ADS)

    Petts, Duane C.; Moser, Desmond E.; Longstaffe, Frederick J.; Davis, William J.; Stern, Richard A.

    2014-04-01

    The western Churchill Province of the Canadian Shield experienced a prolonged and complex formation history (ca. 4.04 to 1.70 Ga), with evidence for multiple episodes of orogenesis and regional magmatic activity. Here we report on the oxygen isotopic compositions of garnet and zircon recovered from lower crustal xenoliths, which have U-Pb ages between ca. 3.5 and 1.7 Ga. Overall, zircon from four metabasite xenoliths from the Rankin Inlet sample suite have δ18O values ranging from + 5.5 to + 8.6‰. Zircon from three metatonalite/anorthosite xenoliths and five metabasite xenoliths from the Repulse Bay sample suite have δ18O values of + 5.6 to + 8.3‰. High δ18O values (> + 6.0‰) for the oldest igneous zircon cores (ca. 3.5 Ga and 3.0-2.6 Ga) indicate that their metatonalite/anorthosite protolith magmas were generated from, or had assimilated, supracrustal rocks that interacted previously with surface-derived fluids. Igneous zircon cores (ca. 2.9-2.6 Ga) from one metabasite xenolith have δ18O values of + 5.6 to + 6.4‰, which suggests a formation from a mantle-derived basaltic/gabbroic magma. Metamorphic zircon cores (ca. 2.0-1.9 Ga) from one metabasite xenolith commonly have δ18O values between + 6.0 and + 6.3‰, which is indicative of a basalt/gabbro protolith and localized reworking of the lower crust caused by regional-scale plate convergence. The wide range of δ18O values (+ 5.5 to + 8.3‰) for ca. 1.75-1.70 Ga metamorphic zircon rims (identified in all xenoliths) indicates regional transient heating and reworking of mantle- and supracrustal-derived crust, induced by magmatic underplating along the crust-mantle boundary.

  16. On the longevity of silicic magma based on multi-isotope investigation of zircons and modeling their survivals destinies

    NASA Astrophysics Data System (ADS)

    Bindeman, I. N.; Wotzlaw, J. F.; Melnik, O. E.

    2015-12-01

    Large volumes of crystal poor, near-liquidus rhyolites are erupted worldwide as tuffs and lavas in rift and hot spots more common previously on early earth, creating temporally very high magma production rates. In this contribution we combine results of IDTIMS dating of zircons with numerical modeling of zircon crystallization. New investigation of zircons in major Yellowstone tuffs: Huckleberry Ridge (Members A,B,C), Mesa Falls, and Lava Creek (A,B) tuffs was done by a combination of in situ measurements of oxygen isotopes followed by ID-TIMS U-Pb dating, Hf isotopes and trace elemental investigation of single crystals. We discover that nearly all zircons are of eruption age, but display significant isotope (O,Hf) diversity and often show decoupled O and Hf isotope systematics. This record rapid (~103yrs) double or triple remelting and sequestration from diverse Archean crust and hydrothermally altered shallow-crustal rocks from previous eruptive cycles, followed by effective mixing of co-existing magma reservoirs with diverse zircons prior to eruptions. Similar results characterize other studied Snake River Plain rhyolites in pre-Yellowstone Heise complex. These results collectively suggest that zircons crystallize after reheating above saturation rejuvenation in isotopically-diverse areas of the crust in the magma plumbing system. Modeling of zircon and quartz dissolution and crystallization trajectories outline conditions of survival (inheritance) vs complete dissolution on conductive timescales, and when combined with a phase diagram, magma T-t paths can be computed. Zircon rejuvenation requires hot, >770-800°C peak temperatures lasting 10-102yrs. We speculate that near liquidus hot and dry Yellowstone rhyolites are kept alive in a multi-batch state by a series of interconnected pods and sills that can rapidly get thermomechanically assembled into large, shallow and eruptable supervolcanoic magma bodies. We suggest that overpressure and roof dynamics and

  17. New Hf isotope data from the Jack Hills zircons: constraints on the Hadean crustal evolution

    NASA Astrophysics Data System (ADS)

    Amelin, Y.; Davis, D.; Lee, D.

    2004-05-01

    Here we present a follow-up of our study of the "older" population of detrital zircons from the Jack Hills metaconglomerate W-74 [1]. We report Lu-Hf data for zircon grains, which have been previously analyzed with a number of techniques: BSE and CL imaging, detailed U-Pb SHRIMP geochronology, trace element concentrations, and oxygen isotopic compositions. After completion of non-destructive SIMS analyses and imaging, the zircons were extracted from the mounts, dissolved and analyzed for U-Pb and Lu-Hf using isotope dilution. Twenty five grains were air abraded before digestion, and eight grains were digested without abrasion. Four grains were cut, and the fragments were analyzed for U-Pb and Lu-Hf separately. The 207Pb/206Pb ages determined by isotope dilution vary between 3788-4186 Ma; the maximum SHRIMP spot 207Pb/206Pb ages of the same grains are between 3871-4276 Ma. The spot 207Pb/206Pb ages averaged over each grain are close to the whole grain isotope dilution values. The U-Pb discordance depends mainly on whether the grains were abraded: the median discordance of 27 abraded grains and fragments is 2.7 (the range is -0.4 to 20.2), whereas the median discordance of 11 unabraded grains and fragments is 66.5 (the range is 20.5 to 83.5). The epsilon176Hf values, calculated using the whole grain TIMS 207Pb/206Pb ages and the 176Lu decay constant of 1.865*10-11, are between -1.4 and -10.6. Using maximum SHRIMP spot 207Pb/206Pb ages and the same decay constant yields the range of epsilon176Hf of 0.1 to -8.6. If the decay constant of 1.983*10-11 is used instead, then the range of epsilon176Hf becomes 4.7 to -5.0 using the whole grain ages, or 6.3 to -3.0 using the maximum SHRIMP spot ages. Grain fragment analyses show internal variations of initial 176Hf/177Hf in three grains out of five. This observation is consistent with multi-episodic zircon growth rather than with ancient Pb loss. In the presentation we shall discuss the prospect of reliable interpretation of

  18. Hf isotope compositions In detrital zircons as a new tool for provenance studies

    NASA Astrophysics Data System (ADS)

    Jacobsen, Y. J.; Münker, C.; Mezger, K.

    2003-04-01

    Identifying the provenance of continental sediments is a major issue in palaeo-tectonic studies, providing important information for paleogeographic reconstructions. Isotope studies, e.g. those of whole rock Sm-Nd or detrital zircon U-Pb dating, have widely been used for this purpose. Here we assess the potential of combined Lu-Hf data and U-Pb ages determined on the same single detrital zircons as a new tool for provenance studies. Due to the low Lu/Hf ratios in zircons the Hf isotope composition of a zircon changes insignificantly after its crystallization. Thus each particular grain preserves information on the Hf-siotpe composition of its source and the age of this source. Provided that both the U-Pb and Lu-Hf isotope systems have not been disturbed, this information can be used to constrain the sources of each individual zircon. In order to demonstrate the capability of Hf isotope studies on detrital zircons for provenance studies, we obtained combined U-Pb ages and Lu-Hf isotope data for zircons from the Cambrian Junction Formation in New Zealand. The Junction Formation was deposited on the (present) SE margin of Gondwana near the Australian continent and consists of turbidites, siltstones and conglomerates [1]. Typical continent derived Paleozoic sediments in SE Gondwana generally show characteristic age maxima at 500-600 Ma, 1000-1200 Ma (Grenvillian) and additional older peaks (early Proterozoic to Archean) [2]. We focused on two groups of detrital zircons with Grenvillian and Proterozoic to Late Archean ages. The initial ɛHf values for these zircons range from 0.7 to -15.5 for the Grenvillian and from -5.2 to -14.1 for the Proterozoic/Archean zircons. Corresponding two stage Hf model ages range from ca. 1500 to 2500 Ma for the Grenvillian and from ca. 3200 to 3600 Ma for the Proterozoic/Archean zircons. Furthermore it can be shown that the Grenvillian zircons must have been derived from recycled Grenvillian provinces. Comparison of these Hf model ages

  19. What Hf isotopes in zircon tell us about crust-mantle evolution

    NASA Astrophysics Data System (ADS)

    Iizuka, Tsuyoshi; Yamaguchi, Takao; Itano, Keita; Hibiya, Yuki; Suzuki, Kazue

    2017-03-01

    The 176Lu-176Hf radioactive decay system has been widely used to study planetary crust-mantle differentiation. Of considerable utility in this regard is zircon, a resistant mineral that can be precisely dated by the U-Pb chronometer and record its initial Hf isotope composition due to having low Lu/Hf. Here we review zircon U-Pb age and Hf isotopic data mainly obtained over the last two decades and discuss their contributions to our current understanding of crust-mantle evolution, with emphasis on the Lu-Hf isotope composition of the bulk silicate Earth (BSE), early differentiation of the silicate Earth, and the evolution of the continental crust over geologic history. Meteorite zircon encapsulates the most primitive Hf isotope composition of our solar system, which was used to identify chondritic meteorites best representative of the BSE (176Hf/177Hf = 0.282793 ± 0.000011; 176Lu/177Hf = 0.0338 ± 0.0001). Hadean-Eoarchean detrital zircons yield highly unradiogenic Hf isotope compositions relative to the BSE, providing evidence for the development of a geochemically enriched silicate reservoir as early as 4.5 Ga. By combining the Hf and O isotope systematics, we propose that the early enriched silicate reservoir has resided at depth within the Earth rather than near the surface and may represent a fractionated residuum of a magma ocean underlying the proto-crust, like urKREEP beneath the anorthositic crust on the Moon. Detrital zircons from world major rivers potentially provide the most robust Hf isotope record of the preserved granitoid crust on a continental scale, whereas mafic rocks with various emplacement ages offer an opportunity to trace the Hf isotope evolution of juvenile continental crust (from εHf[4.5 Ga] = 0 to εHf[present] = + 13). The river zircon data as compared to the juvenile crust composition highlight that the supercontinent cycle has controlled the evolution of the continental crust by regulating the rates of crustal generation and intra

  20. Zircon geochronology and Hf-O isotope geochemistry from granites in the Iapetus Suture Zone in Ireland and the Isle of Man

    NASA Astrophysics Data System (ADS)

    Fritschle, Tobias; Daly, J. Stephen; Whitehouse, Martin J.; McConnell, Brian; Buhre, Stephan

    2014-05-01

    Late Caledonian syn- to post-orogenic granites located in the Iapetus Suture Zone (ISZ) in Ireland and Britain have been related to A-type subduction and possible slab breakoff [1] following the Laurentia-Avalonian collision. Lack of reliable age data (especially in Ireland) has inhibited petrogenetic investigations of these rocks. Hence, ion microprobe U-Pb and oxygen isotope analyses as well as LA-MC-ICPMS Lu-Hf isotopic measurements on zircons from Irish and Isle of Man granites have been undertaken to provide better constraints on this enigmatic episode of the Caledonian Orogeny. Four stages of Late Caledonian granitic magmatism (c. 435, 417, 410 and 394 Ma) are indicated by U-Pb dating of oscillatory-zoned magmatic zircons. The Crossdoney, Kentstown, Drogheda and Ballynamuddagh granites together with a rhyolite from Glenamaddy have yielded U-Pb concordia ages, interpreted as intrusion-ages, between 419.9 ± 4.3 Ma (Glenamaddy) and 415.8 ± 2.0 Ma (Crossdoney) with a weighted average of 417.5 ± 0.9 Ma (MSWD = 1.3). The Glenamaddy Granite - which intruded the Glenamaddy Rhyolite - yielded an age of 410 ± 2.1 Ma. In addition, the Rockabill Granite yielded a younger age of 393.9 ± 1.9 Ma, whereas the Carnsore Granite yielded an older age of 434.6 ± 1.9 Ma. Inherited zircons (487 to 453 Ma) occur in several of the granites, and are interpreted to have been derived from Ordovician arc magmatic rocks accreted within the ISZ. A younger group of c. 440 Ma inherited zircons occurs in the c. 417 Ma Crossdoney and Ballynamuddagh granites. These grains could be related to continued or renewed Silurian arc magmatism. Hf-O isotopic measurements on the dated zircon grains range between -2 and +7 ɛHfi units and 5.5 to 8.5 o δ18O. These are interpreted to indicate the contribution of juvenile mantle melts - possibly derived from the Ordovician arc - to some of the granites. Significant heterogeneities in zircon oxygen isotopes in at least four of the granites further

  1. Origins and evolution of rhyolitic magmas in the central Snake River Plain: insights from coupled high-precision geochronology, oxygen isotope, and hafnium isotope analyses of zircon

    NASA Astrophysics Data System (ADS)

    Colón, Dylan P.; Bindeman, Ilya N.; Wotzlaw, Jörn-Frederik; Christiansen, Eric H.; Stern, Richard A.

    2018-02-01

    We present new high-precision CA-ID-TIMS and in situ U-Pb ages together with Hf and O isotopic analyses (analyses performed all on the same grains) from four tuffs from the 15-10 Ma Bruneau-Jarbidge center of the Snake River Plain and from three rhyolitic units from the Kimberly borehole in the neighboring 10-6 Ma Twin Falls volcanic center. We find significant intrasample diversity in zircon ages (ranges of up to 3 Myr) and in δ18O (ranges of up to 6‰) and ɛHf (ranges of up to 24 ɛ units) values. Zircon rims are also more homogeneous than the associated cores, and we show that zircon rim growth occurs faster than the resolution of in situ dating techniques. CA-ID-TIMS dating of a subset of zircon grains from the Twin Falls samples reveals complex crystallization histories spanning 104-106 years prior to some eruptions, suggesting that magma genesis was characterized by the cyclic remelting of buried volcanic rocks and intrusions associated with previous magmatic episodes. Age-dependent trends in zircon isotopic compositions show that rhyolite production in the Yellowstone hotspot track is driven by the mixing of mantle-derived melts (normal δ18O and ɛHf) and a combination of Precambrian basement rock (normal δ18O and ɛHf down to - 60) and shallow Mesozoic and Cenozoic age rocks, some of which are hydrothermally altered (to low δ18O values) by earlier stages of Snake River Plain magmatism. These crustal melts hybridize with juvenile basalts and rhyolites to produce the erupted rhyolites. We also observe that the Precambrian basement rock is only an important component in the erupted magmas in the first eruption at each caldera center, suggesting that the accumulation of new intrusions quickly builds an upper crustal intrusive body which is isolated from the Precambrian basement and evolves towards more isotopically juvenile and lower-δ18O compositions over time.

  2. Re-evaluation of the origin and evolution of > 4.2 Ga zircons from the Jack Hills metasedimentary rocks

    NASA Astrophysics Data System (ADS)

    Nemchin, A. A.; Pidgeon, R. T.; Whitehouse, M. J.

    2006-04-01

    New data are presented on internal structures, U-Pb systematics and oxygen isotope compositions of eight detrital zircons with ages greater than 4.2 Ga, from the Jack Hills metasedimentary belt, Australia. Cathodoluminescence imaging, ion-microprobe U-Pb and oxygen isotope results show evidence for an extensive period of complex zircon growth, secondary reaction and U-Pb isotopic disturbance from 4.36 to 3.90 Ga. In addition many of the zircons have discordant U-Pb systems and excess common Pb indicating a superimposed, relatively recent, reaction between radiation damaged zircon and low temperature fluids. The significance of oxygen isotope compositions for zircons with complex internal structures and U-Pb systems is complicated by uncertainty in the origin of the grains and the unknown effect of later reactions. However, a minority of grains with sharp oscillatory zoning, uniform and concordant U-Pb systems, igneous Th-U ratios and low common Pb contents, are interpreted as undisturbed primary magmatic zircons. The oldest identified, oscillatory zoned, magmatic grain, with an age 4363 ± 20 Ma, is one of a few reported magmatic grains with this age, which is interpreted as the oldest reliable age for Hadean magmatic zircons. Mantle δ18O values are reported for these zircons. Younger oscillatory zoned zircon, including oscillatory zoned cores in complex grains, have δ18O values lower than 6.5‰, which are within the range of ion microprobe analysed δ18O values for zircons in high temperature equilibrium with the normal mantle rocks of 5.3 ± 0.6‰ (2 standard deviations). These values are also within the range of δ18O values found in lunar zircons. The absence of heavy oxygen in the grains that can be interpreted as primary magmatic zircons and the complex history over the period from 4.36 to 3.9 Ga, seen in all other Jack Hills zircons and reflected in the internal structures and U-Pb isotopic systems, questions the model for the early Earth involving long

  3. Magmatic oxygen fugacity estimated using zircon-melt partitioning of cerium

    NASA Astrophysics Data System (ADS)

    Smythe, Duane J.; Brenan, James M.

    2016-11-01

    Using a newly-calibrated relation for cerium redox equilibria in silicate melts (Smythe and Brenan, 2015), and an internally-consistent model for zircon-melt partitioning of Ce, we provide a method to estimate the prevailing redox conditions during crystallization of zircon-saturated magmas. With this approach, oxygen fugacities were calculated for samples from the Bishop tuff (USA), Toba tuff (Indonesia) and the Nain plutonic suite (Canada), which typically agree with independent estimates within one log unit or better. With the success of reproducing the fO2 of well-constrained igneous systems, we have applied our Ce-in-zircon oxygen barometer to estimating the redox state of Earth's earliest magmas. Using the composition of the Jack Hills Hadean zircons, combined with estimates of their parental magma composition, we determined the fO2 during zircon crystallization to be between FMQ -1.0 to +2.5 (where FMQ is the fayalite-magnetite-quartz buffer). Of the parental magmas considered, Archean tonalite-trondhjemite-granodiorite (TTG) compositions yield zircon-melt partitioning most similar to well-constrained modern suites (e.g., Sano et al., 2002). Although broadly consistent with previous redox estimates from the Jack Hills zircons, our results provide a more precise determination of fO2, narrowing the range for Hadean parental magmas by more than 8 orders of magnitude. Results suggest that relatively oxidized magmatic source regions, similar in oxidation state to that of 3.5 Ga komatiite suites, existed by ∼4.4 Ga.

  4. Magmatic and Crustal Differentiation History of Granitic Rocks from Hf-O Isotopes in Zircon

    NASA Astrophysics Data System (ADS)

    Kemp, , A. I. S.; Hawkesworth, , C. J.; Foster, , G. L.; Paterson, , B. A.; Woodhead, , J. D.; Hergt, , J. M.; Gray, , C. M.; Whitehouse, M. J.

    2007-02-01

    Granitic plutonism is the principal agent of crustal differentiation, but linking granite emplacement to crust formation requires knowledge of the magmatic evolution, which is notoriously difficult to reconstruct from bulk rock compositions. We unlocked the plutonic archive through hafnium (Hf) and oxygen (O) isotope analysis of zoned zircon crystals from the classic hornblende-bearing (I-type) granites of eastern Australia. This granite type forms by the reworking of sedimentary materials by mantle-like magmas instead of by remelting ancient metamorphosed igneous rocks as widely believed. I-type magmatism thus drives the coupled growth and differentiation of continental crust.

  5. U-Pb ages and Hf isotope compositions of zircons in plutonic rocks from the central Famatinian arc, Argentina

    NASA Astrophysics Data System (ADS)

    Otamendi, Juan E.; Ducea, Mihai N.; Cristofolini, Eber A.; Tibaldi, Alina M.; Camilletti, Giuliano C.; Bergantz, George W.

    2017-07-01

    The Famatinian arc formed around the South Iapetus rim during the Ordovician, when oceanic lithosphere subducted beneath the West Gondwana margin. We present combined in situ U-Th-Pb and Lu-Hf isotope analyses for zircon to gain insights into the origin and evolution of Famatinian magmatism. Zircon crystals sampled from four intermediate and silicic plutonic rocks confirm previous observations showing that voluminous magmatism took place during a relatively short pulse between the Early and Middle Ordovician (472-465 Ma). The entire zircon population for the four plutonic rocks yields coherent εHf negative values and spreads over several ranges of initial εHf(t) units (-0.3 to -8.0). The range of εHf units in detrital zircons of Famatinian metasedimentary rocks reflects a prolonged history of the cratonic sources during the Proterozoic to the earliest Phanerozoic. Typical tonalites and granodiorites that contain zircons with evolved Hf isotopic compositions formed upon incorporating (meta)sedimentary materials into calc-alkaline metaluminous magmas. The evolved Hf isotope ratios of zircons in the subduction related plutonic rocks strongly reflect the Hf isotopic character of the metasedimentary contaminant, even though the linked differentiation and growth of the Famatinian arc crust was driven by ascending and evolving mantle magmas. Geochronology and Hf isotope systematics in plutonic zircons allow us understanding the petrogenesis of igneous series and the provenance of magma sources. However, these data could be inadequate for computing model ages and supporting models of crustal evolution.

  6. An ion microprobe study of individual zircon phenocrysts from voluminous post-caldera rhyolites of the Yellowstone caldera

    NASA Astrophysics Data System (ADS)

    Watts, K. E.; Bindeman, I. N.; Schmitt, A. K.

    2010-12-01

    Following the formation of the Yellowstone caldera from the 640 ka supereruption of the Lava Creek Tuff (LCT), a voluminous episode of post-caldera volcanism filled the caldera with >600 km3 of low-δ18O rhyolite. Such low-δ18O signatures require remelting of 100s of km3 of hydrothermally altered (18O-depleted) rock in the shallow crust. We present a high resolution oxygen isotope and geochronology (U-Th and U-Pb) study of individual zircon crystals from seven of these voluminous post-caldera rhyolites in order to elucidate their genesis. Oxygen isotope and geochronology analyses of zircon were performed with an ion microprobe that enabled us to doubly fingerprint 25-30 µm diameter spots. Host groundmass glasses and coexisting quartz were analyzed in bulk for oxygen isotopes by laser fluorination. We find that zircons from the youngest (200-80 ka) post-caldera rhyolites have oxygen isotopic compositions that are in equilibrium with low-δ18O host groundmass glasses and quartz and are unzoned in oxygen and U-Th age. This finding is in contrast to prior work on older (500-250 ka) post-caldera rhyolites, which exhibit isotopic disequilibria and age zoning, including the presence of clearly inherited zircon cores. Average U-Th crystallization ages and δ18O zircon values for Pitchstone Plateau flow (81±7 ka, 2.8±0.2‰), West Yellowstone flow (118±8 ka, 2.8±0.1‰), Elephant Back flow (175±22 ka, 2.7±0.2‰) and Tuff of Bluff Point (176±20 ka, 2.7±0.1‰) are overlapping or nearly overlapping in age and identical in oxygen isotope composition within uncertainty (2 SE). New U-Pb geochronology and oxygen isotope data for the North Biscuit Basin flow establish that it has an age (188±33 ka) and δ18O signature (2.8±0.2‰) that is distinctive of the youngest post-caldera rhyolites. Conversely, the South Biscuit Basin flow has a heterogeneous zircon population with ages that range from 550-250 ka. In this unit, older and larger (200-400 µm) zircons have more

  7. Oxygen isotopes reveal crustal contamination and a large, still partially molten magma chamber in Chaîne des Puys (French Massif Central)

    NASA Astrophysics Data System (ADS)

    France, Lydéric; Demacon, Mickael; Gurenko, Andrey A.; Briot, Danielle

    2016-09-01

    The two main magmatic properties associated with explosive eruptions are high viscosity of silica-rich magmas and/or high volatile contents. Magmatic processes responsible for the genesis of such magmas are differentiation through crystallization, and crustal contamination (or assimilation) as this process has the potential to enhance crystallization and add volatiles to the initial budget. In the Chaîne des Puy series (French Massif Central), silica- and H2O-rich magmas were only emitted during the most recent eruptions (ca. 6-15 ka). Here, we use in situ measurements of oxygen isotopes in zircons from two of the main trachytic eruptions from the Chaîne des Puys to track the crustal contamination component in a sequence that was previously presented as an archetypal fractional crystallization series. Zircons from Sarcoui volcano and Puy de Dôme display homogeneous oxygen isotope compositions with δ18O = 5.6 ± 0.25‰ and 5.6 ± 0.3‰, respectively, and have therefore crystallized from homogeneous melts with δ18Omelt = 7.1 ± 0.3‰. Compared to mantle derived melts resulting from pure fractional crystallization (δ18Odif.mant. = 6.4 ± 0.4‰), those δ18Omelt values are enriched in 18O and support a significant role of crustal contamination in the genesis of silica-rich melts in the Chaîne des Puys. Assimilation-fractional-crystallization models highlight that the degree of contamination was probably restricted to 5.5-9.5% with Rcrystallization/Rassimilation varying between 8 and 14. The very strong intra-site homogeneity of the isotopic data highlights that magmas were well homogenized before eruption, and consequently that crustal contamination was not the trigger of silica-rich eruptions in the Chaîne des Puys. The exceptionally strong inter-site homogeneity of the isotopic data brings to light that Sarcoui volcano and Puy de Dôme were fed by a single large magma chamber. Our results, together with recent thermo-kinetic models and an experimental

  8. Correlated microanalysis of zircon: Trace element, δ 18O, and U-Th-Pb isotopic constraints on the igneous origin of complex >3900 Ma detrital grains

    NASA Astrophysics Data System (ADS)

    Cavosie, Aaron J.; Valley, John W.; Wilde, Simon A.; E. I. M. F.

    2006-11-01

    The origins of >3900 Ma detrital zircons from Western Australia are controversial, in part due to their complexity and long geologic histories. Conflicting interpretations for the genesis of these zircons propose magmatic, hydrothermal, or metamorphic origins. To test the hypothesis that these zircons preserve magmatic compositions, trace elements [rare earth elements (REE), Y, P, Th, U] were analyzed by ion microprobe from a suite of >3900 Ma zircons from Jack Hills, Western Australia, and include some of the oldest detrital zircons known (4400-4300 Ma). The same ˜20 μm domains previously characterized for U/Pb age, oxygen isotope composition (δ 18O), and cathodoluminescence (CL) zoning were specifically targeted for analysis. The zircons are classified into two types based on the light-REE (LREE) composition of the domain analyzed. Zircons with Type 1 domains form the largest group (37 of 42), consisting of grains that preserve evolved REE compositions typical of igneous zircon from crustal rocks. Grains with Type 1 domains display a wide range of CL zoning patterns, yield nearly concordant U/Pb ages from 4400 to 3900 Ma, and preserve a narrow range of δ 18O values from 4.7‰ to 7.3‰ that overlap or are slightly elevated relative to mantle oxygen isotope composition. Type 1 domains are interpreted to preserve magmatic compositions. Type 2 domains occur in six zircons that contain spots with enriched light-REE (LREE) compositions, here defined as having chondrite normalized values of La N > 1 and Pr N > 10. A subset of analyses in Type 2 domains appear to result from incorporation of sub-surface mineral inclusions in the analysis volume, as evidenced by positively correlated secondary ion beam intensities for LREE, P, and Y, which are anti-correlated to Si, although not all Type 2 analyses show these features. The LREE enrichment also occurs in areas with discordant U/Pb ages and/or high Th/U ratios, and is apparently associated with past or present

  9. Contrasting Cu-Au and Sn-W Granite Metallogeny through the Zircon Geochemical and Isotopic Record

    NASA Astrophysics Data System (ADS)

    Gardiner, Nicholas; Hawkesworth, Chris; Robb, Laurence; Whitehouse, Martin; Roberts, Nick; Kirkland, Chris

    2017-04-01

    Magmatic genesis and evolution - mediated by geodynamic setting - exert a primary control on the propensity of granites to be metal fertile. A revolution in our understanding of these petrogenetic processes has been made through a range of mineral-based tools, most notably the common accessory mineral zircon. There is consequently considerable interest in whether the geochemical and isotopic compositions of zircon can be applied to metallogenic problems. The paired magmatic belts of Myanmar have broadly contrasting metallogenic affinities (Sn-W versus Cu-Au), and are interpreted to have formed on the accretionary margin of the subducting Neo-Tethys Ocean. They therefore present the opportunity to geochemically compare and contrast the zircon compositions in two end-member types of granite-hosted mineral deposits generated in collisional settings. We present an integrated zircon isotope (U-Pb, Lu-Hf, O) and trace element dataset that fingerprint: (a) source; (b) redox conditions; and (c) degree of fractionation. These variables all impact on magma fertility, and our key question to address is whether they can be reliably traced and calibrated within the Myanmar zircon record. Granitoid-hosted zircons from the I-type copper arc have juvenile ɛHf (+7 to +12) and mantle-like δ18O (5.3 ‰), whereas zircons from the S-type tin belt have low ɛHf (-7 to -13) and heavier δ18O (6.2-7.7 ‰). Plotting Hf versus U/Yb reaffirms that the tin belt magmas contain greater crustal contributions than the copper arc rocks. Links between whole rock Rb/Sr and zircon Eu/Eu* highlights that the latter can be used to monitor magma fractionation in systems that crystallize plagioclase (low Sr/Y). Ce/Ce* and Eu/Eu* in zircon are thus sensitive to redox and fractionation respectively, and can be used to evaluate the sensitivity of zircons to the metallogenic affinity of their host rocks. Tin contents that exceed the solubility limit are required in order to make a magmatic

  10. Using Oxygen Isotopes of Zircon to Evaluate Magmatic Evolution and Crustal Contamination in the Halifax Pluton, Nova Scotia

    NASA Astrophysics Data System (ADS)

    Murray, K. E.; Lackey, J.; Valley, J. W.; Nowak, R.

    2007-12-01

    Oxygen isotope analysis of zircon (Zrc) is well suited for parsing out the magmatic history in granitoids. The Halifax pluton is the largest pluton (1060 km2) in the peraluminous South Mountain batholith. The Halifax pluton is mapped as a concentrically zoned body, with outer units comprising granodiorite, monzogranite and a mafic porphyry; these units are locally rich in metasedimentary xenoliths and magmatic enclaves. The exterior units surround a more felsic core of leucogranite [1]. Previous oxygen isotope studies of the pluton report high whole rock δ18O values that range from 10.7-11.7‰ [2], and indicate a significant supracrustal component in the source of the pluton. We report the first δ18O(Zrc) values from the Peggy's Cove monzogranite and an associated mafic porphyry. Samples were collected across 30 km of discontinuous exposures of the monzogranite. Values of δ18O(Zrc) vary from 7.71-8.26‰ (average = 8.15±±0.32‰(2 S.D.); n = 10). Small but systematic E-W regional variation in δ18O(Zrc) values suggests heterogeneous magmatic contamination within the monzogranite. Meter-scale magmatic enclaves, observed in close association with pods of diverse xenoliths and smaller enclaves at the western Cranberry Head locality, are slightly enriched in δ18O relative to the host monzogranite. These data combined support a model of magma mingling and heterogeneous mixing at the rim of the pluton, with contamination by high-δ18O rocks. Additional high-δ18O(Zrc) data from granodiorites on the northern margin of the Halifax pluton concur with these observations [3]. Typically, closed magmatic systems show increasing δ18O with SiO2 because more felsic magmas have a greater percentage of high-δ18O minerals such as quartz and feldspar. Thus, the Halifax pluton appears to exhibit an enrichment trend opposite of what would be expected of a closed evolving system. Emplacement mechanisms for the Halifax pluton proposed by previous workers suggest that the outer

  11. Zircon U-Pb, O, and Hf isotopic constraints on Mesozoic magmatism in the Cyclades, Aegean Sea, Greece

    NASA Astrophysics Data System (ADS)

    Fu, Bin; Bröcker, Michael; Ireland, Trevor; Holden, Peter; Kinsley, Leslie P. J.

    2015-01-01

    Compared to the well-documented Cenozoic magmatic and metamorphic rocks of the Cyclades, Aegean Sea, Greece, the geodynamic context of older meta-igneous rocks occurring in the marble-schist sequences and mélanges of the Cycladic Blueschist Unit is as yet not fully understood. Here, we report O-Hf isotopic compositions of zircons ranging in age from ca. 320 Ma to ca. 80 Ma from metamorphic rocks exposed on the islands of Andros, Ios, Sifnos, and Syros with special emphasis on Triassic source rocks. Ion microprobe (SHRIMP II) single spot oxygen isotope analysis of pre-Cretaceous zircons from various felsic gneisses and meta-gabbros representing both the marble-schist sequences and the mélanges of the study area yielded a large range in δ18O values, varying from 2.7 ‰ to 10.1 ‰ VSMOW, with one outlier at -0.4 %. Initial ɛHf values (-12.5 to +15.7) suggest diverse sources for melts formed between Late Carboniferous to Late Cretaceous time that record derivation from mantle and reworked older continental crust. In particular, variable δ18O and ɛHf( t) values for Triassic igneous zircons suggest that magmatism of this age is more likely rift- than subduction-related. The significant crustal component in 160 Ma meta-gabbros from Andros implies that some Jurassic gabbroic rocks of the Hellenides are not part of SSZ-type (supra-subduction zone) ophiolites that are common elsewhere along the margin of the Pelagonian zone.

  12. Zircon Hf-O isotopic constraints on the origin of Late Mesozoic felsic volcanic rocks from the Great Xing'an Range, NE China

    NASA Astrophysics Data System (ADS)

    Gong, Mingyue; Tian, Wei; Fu, Bin; Wang, Shuangyue; Dong, Jinlong

    2018-05-01

    The voluminous Late Mesozoic magmatism was related to extensive re-melting of juvenile materials that were added to the Central East Asia continent in Phanerozoic time. The most favoured magma generation mechanism of Late Mesozoic magmas is partial melting of underplated lower crust that had radiogenic Hf-Nd isotopic characteristics, but this mechanism faces difficulties when interpreting other isotopic data. The tectonic environment controlling the generation of the Late Mesozoic felsic magmas is also in dispute. In this study, we obtained new U-Pb ages, and geochemical and isotopic data of representative Jurassic (154.4 ± 1.5 Ma) and Cretaceous (140.2 ± 1.5 Ma) felsic volcanic samples. The Jurassic sample has inherited zircon cores of Permian age, with depleted mantle-like εHf(t) of +7.4 - +8.5, which is in contrast with those of the magmatic zircons (εHf(t) = +2.4 ± 0.7). Whereas the inherited cores and the magmatic zircons have identical mantle-like δ18O composition ranges (4.25-5.29‰ and 4.69-5.54‰, respectively). These Hf-O isotopic characteristics suggest a mixed source of enriched mantle materials rather than ancient crustal components and a depleted mantle source represented by the inherited Permian zircon core. This mechanism is manifested by the eruption of Jurassic alkaline basalts originated from an enriched mantle source. The Cretaceous sample has high εHf(t) of +7.0 - +10.5, suggesting re-melting of a mafic magma derived from a depleted mantle-source. However, the sub-mantle zircon δ18O values (3.70-4.58‰) suggest the depleted mantle-derived mafic source rocks had experienced high temperature hydrothermal alteration at upper crustal level. Therefore, the Cretaceous felsic magma, if not all, could be generated by re-melting of down-dropped supracrustal volcanic rocks that experienced high temperature oxygen isotope alteration. The two processes, enriched mantle-contribution and supracrustal juvenile material re-melting, are new

  13. Creation of a continent recorded in zircon zoning

    USGS Publications Warehouse

    Moser, D.E.; Bowman, J.R.; Wooden, J.; Valley, J.W.; Mazdab, F.; Kita, N.

    2008-01-01

    We have discovered a robust microcrystalline record of the early genesis of North American lithosphere preserved in the U-Pb age and oxygen isotope zoning of zircons from a lower crustal paragneiss in the Neoarchean Superior province. Detrital igneous zircon cores with ??18O values of 5.1???-7.1??? record creation of primitive to increasingly evolved crust from 2.85 ?? 0.02 Ga to 2.67 ?? 0.02 Ga. Sharp chemical unconformity between cores and higher ??18O (8.4???-10.4???) metamorphic overgrowths as old as 2.66 ?? 0.01 Ga dictates a rapid sequence of arc unroofing, burial of detrital zircons in hydrosphere-altered sediment, and transport to lower crust late in upper plate assembly. The period to 2.58 ?? 0.01 Ga included ???80 m.y. of high-temperature (???700-650 ??C), nearly continuous overgrowth events reflecting stages in maturation of the subjacent mantle root. Huronian continental rifting is recorded by the youngest zircon tip growth at 2512 ?? 8 Ma (??? 600 ??C) signaling magma intraplating and the onset of rigid plate behavior. This >150 m.y. microscopic isotope record in single crystals demonstrates the sluggish volume diffusion of U, Pb, and O in zircon throughout protracted regional metamorphism, and the consequent advances now possible in reconstructing planetary dynamics with zircon zoning. ?? 2008 The Geological Society of America.

  14. Origin of zircon-bearing mantle eclogites entrained in the V. Grib kimberlite (Arkhangelsk region, NW Russia): Evidence from mineral geochemistry and the U-Pb and Lu-Hf isotope compositions of zircon

    NASA Astrophysics Data System (ADS)

    Shchukina, Elena V.; Agashev, Alexey M.; Zedgenizov, Dmitry A.

    2018-05-01

    The concentrations of major and trace elements in minerals, reconstructed whole-rock compositions of zircon-bearing equigranular eclogites from the V. Grib kimberlite pipe located within the Arkhangelsk Diamondiferous Province (North-Western Russia), and results of the U-Pb and Lu-Hf isotope analyses of zircon grains from eclogites and granulite xenoliths are reported. These data suggest that the equigranular eclogites could represent the fragments of mid-ocean-ridge basalt that were metamorphosed during Paleoproterozoic subduction at 1.7-1.9 Ga. The Hf isotope compositions of the eclogitic zircon display uniformity and indicate corresponding Hf-depleted mantle model ages of 2.2-2.3 Ga. The formation of zircon in eclogites could have resulted from interactions with metasomatic/subduction-related fluids just prior to, but associated with, Paleoproterozoic eclogite formation. A link between eclogitic zircon formation and continental lower-crustal rocks can be excluded based on differences in the Hf isotope compositions of eclogitic and granulitic zircon grains. The U-Pb upper intercept age of granulitic zircon of 2716 ± 61 Ma provides a new minimum age constraint for zircon crystallisation and granulite formation. The U-Pb ages obtained from granulitic zircon show two stages of Pb loss at 2.2-2.6 Ga and 1.7-2.0 Ga. The late Paleoproterozoic stage of Pb loss recorded in granulitic zircon is due to the intensive reworking of basement crustal rocks, which was caused by a tectonic process/subduction event associated with equigranular eclogite formation. Our data, along with evidence previously obtained from the V. Grib pipe coarse-granular eclogites, show at least two main subduction events in the lithospheric mantle of the Arkhangelsk region: the Archean (2.8 Ga) and Paleoproterozoic (1.7-1.9 Ga) subductions, which correspond to major magmatic and metamorphic events in the Baltic Shield.

  15. The first Lu-Hf zircon isotope data for gabbro-diorite-tonalite associations of the Urals

    NASA Astrophysics Data System (ADS)

    Ronkin, Yu. L.; Smirnov, V. N.; Ivanov, K. S.; Gerdes, A.

    2017-01-01

    The Lu-Hf isotope systematics of zircon from the gabbro-plagiogranite association (gabbro, diorite, tonalite, and plagiogranite), which is one of the most typical associations of igneous rocks in the Urals, was studied for the first time. The isotope study yielded a unified age limit of 433 Ma, which corresponds to the time of formation of this rock association. The younger "rejuvenated" ages characterize superimposed thermal impact events, induced by the volcanic arc activity, as well as collisional and postcollisional processes. Here, the initial 176Hf/177Hf( t) ratio in the studied zircon from gabbro and plagiogranite corresponds in fact to a highly LILE-depleted (DM) mantle.

  16. Petrogenesis of Mesozoic granites in the Xitian, South China: Evidence from whole-rock geochemistry and zircon isotopes

    NASA Astrophysics Data System (ADS)

    Liu, Q.; Sun, J.; He, M.; Hou, Q.; Niu, R.

    2017-12-01

    Mesozoic granitoids are widespread in southeastern China, which accompanied with lots of world-famous polymetallic deposits. The mineralization is believed to be related to the Mesozoic granitic magmatism. However, the petrogenesis of these granites and their relation to the mineralization are still debated. As a typical granitic pluton, Xitian granites from the eastern Hunan Province are formed during this period and associated with tungsten-tin deposit. Whole-rock geochemical, SIMS zircon geochronology and oxygen isotopes, as well as LA-ICPMS zircon Lu-Hf isotopic analyses, were carried out on a suite of rocks from Xitian granitic pluton to constrain their magmatic sources and petrogenesis. Xitian granitic pluton is mainly composed of biotite adamellite, biotite granite, fine-grained granite. SIMS and LA-ICPMS U-Pb dating of zircons indicate that there are two episodes of these rocks, i.e., Late Triassic granites (227-233Ma) and Late Jurassic granites (150-154Ma). The Xitian granites are silica-rich, potassic and weakly peraluminous. Petrographic and geochemical features show that they are highly fractionated I-type granites. The combined elemental and isotopic results indicated that the Late Triassic granite in Xitian area experienced a process of crystal fractionation of crustal-derived magmas coupled with strong assimilation of the surrounding rocks. The occurrence of Jurassic granitoids in Xitian area is attributed to ascending of mantle-derived magmas, which provide heat for partial melting of crustal materials. The Late Jurassic granite may be derived from juvenile crust or partial melting of ancient crustal rocks, whereas high degrees of crystal fractionation further enriched tungsten-tin in the evolved granitic rocks. This work was financially supported by the Research Cooperation between Institute and University of Chinese Academy of Sciences grant (Y552012Y00), Public Welfare Project of the Ministry of land and Resources of China (201211024

  17. Zircon U-Pb age and Hf-O isotopes of felsic rocks from the Atlantis Bank, Southwest Indian Ridge

    NASA Astrophysics Data System (ADS)

    Liu, C. Z.; Zhang, W. Q.

    2017-12-01

    Hole U1473A was drilled to 790 meters below seafloor on the Atlantis Bank, an oceanic core complex in the Southwest Indian Ridge, where the upper crust has been removed by detachment faulting. The recovered core consists dominantly of olivine gabbro, with subordinate gabbro, gabbro with varying Fe-Ti oxide concentrations. Felsic veins intermittently occur throughout the whole core section. Zircons separated from twenty-four felsic samples have been conducted for U-Pb dating and O isotope analyses on the Cameca 1280 and Lu-Hf isotopes by laser ablation coupled with a MC-ICPMS. The zircons have highly variable contents of U (12-2078 ppm) and Th (5-801 ppm), yielding Th/U ratios of 0.33-0.81. They are typical oceanic zircons as defined by the trace element discrimination plots of Grimes et al. (2015). The weighted mean 206Pb/238U ages of the analyzed zircons vary from 11.29 to 12.57 Ma. Age differences between felsic veins throughout the whole core are not resolved within analytical uncertainty of the SIMS measurements. All felsic samples have similar zircon Hf isotope compositions, with initial 176Hf/177Hf ratios of 0.283126-0.283197 and ɛHf values of 12.76-15.27. Zircons from all felsic samples but one have mantle-like δ18O values of 5.14-5.50‰. Zircons from one sample show partial resorption or total recrystallization; in comparison, they have lower δ18O values of 4.81±0.21‰. Such characteristics provide clear evidence for hydrothermal alteration after magmatic intrusion.

  18. Triple oxygen isotope composition of photosynthetic oxygen

    NASA Astrophysics Data System (ADS)

    van der Meer, Anne; Kaiser, Jan

    2013-04-01

    The measurement of biological production rates is essential for our understanding how marine ecosystems are sustained and how much CO2 is taken up through aquatic photosynthesis. Traditional techniques to measure marine production are laborious and subject to systematic errors. A biogeochemical approach based on triple oxygen isotope measurements in dissolved oxygen (O2) has been developed over the last few years, which allows the derivation of gross productivity integrated over the depth of the mixed layer and the time-scale of O2 gas exchange (Luz and Barkan, 2000). This approach exploits the relative 17O/16O and 18O/16O isotope ratio differences of dissolved O2 compared to atmospheric O2 to work out the rate of biological production. Two parameters are key for this calculation: the isotopic composition of dissolved O2 in equilibrium with air and the isotopic composition of photosynthetic oxygen. Recently, a controversy has emerged in the literature over these parameters (Kaiser, 2011) and one of the goals of this research is to provide additional data to resolve this controversy. In order to obtain more information on the isotopic signature of biological oxygen, laboratory experiments have been conducted to determine the isotopic composition of oxygen produced by different phytoplankton cultures.

  19. Tectono-magmatic evolution of the Chihuahua-Sinaloa border region in northern Mexico: Insights from zircon-apatite U-Pb geochronology, zircon Hf isotope composition and geochemistry of granodiorite intrusions

    NASA Astrophysics Data System (ADS)

    Mahar, Munazzam Ali; Goodell, Philip C.; Feinstein, Michael Nicholas

    2016-11-01

    We present the whole-rock geochemistry, LA-ICP-MS zircon-apatite U-Pb ages and zircon Hf isotope composition of the granodioritic plutons at the southwestern boundary of Chihuahua with the states of Sinaloa and Sonora. These granodiorites are exposed in the north and south of the Rio El Fuerte in southwest Chihuahua and northern Sinaloa. The magmatism spans over a time period of 37 Ma from 90 to 53 Ma. Zircons are exclusively magmatic with strong oscillatory zoning. No inheritance of any age has been observed. Our new U-Pb dating ( 250 analyses) does not support the involvement of older basement lithologies in the generation of the granitic magmas. The U-Pb apatite ages from granodiorites in southwest Chihuahua vary from 52 to 70 Ma. These apatite ages are 1 to 20 Ma younger than the corresponding zircon U-Pb crystallization ages, suggesting variable cooling rates from very fast to 15 °C/Ma ( 800 °C to 500 °C) and shallow to moderate emplacement depths. In contrast, U-Pb apatite ages from the Sinaloa batholith are restricted from 64 to 61 Ma and are indistinguishable from the zircon U-Pb ages range from 67 to 60 Ma within the error, indicating rapid cooling and very shallow emplacement. However, one sample from El Realito showed a larger difference of 20 Ma in zircon-apatite age pair: zircon 80 ± 0.8 Ma and apatite 60.6 ± 4 Ma, suggesting a slower cooling rate of 15 °C/Ma. The weighted mean initial εHf (t) isotope composition (2σ) of granodiorites varies from + 1.8 to + 5.2. The radiogenic Hf isotope composition coupled with previous Sr-Nd isotope data demonstrates a significant shift from multiple crustal sources in the Sonoran batholithic belt to the predominant contribution of the mantle-derived magmas in the southwest Chihuahua and northern Sinaloa. Based on U-Pb ages, the absence of inheritance, typical high Th/U ratio and radiogenic Hf isotope composition, we suggest that the Late Cretaceous-Paleogene magmatic rocks in this region are not derived from

  20. Contrasting sources of Late Paleozoic rhyolite magma in the Polish Lowlands: evidence from U-Pb ages and Hf and O isotope composition in zircon

    NASA Astrophysics Data System (ADS)

    Słodczyk, Elżbieta; Pietranik, Anna; Glynn, Sarah; Wiedenbeck, Michael; Breitkreuz, Christoph; Dhuime, Bruno

    2018-02-01

    The Polish Lowlands, located southwest of the Teisseyre-Tornquist Zone, within Trans-European Suture Zone, were affected by bimodal, but dominantly rhyolitic, magmatism during the Late Paleozoic. Thanks to the inherited zircon they contain, these rhyolitic rocks provide a direct source of information about the pre-Permian rocks underlying the Polish Lowland. This paper presents zircon U-Pb geochronology and Hf and O isotopic results from five drill core samples representing four rhyolites and one granite. Based on the ratio of inherited vs. autocrystic zircon, the rhyolites can be divided into two groups: northern rhyolites, where autocrystic zircon is more abundant and southern rhyolites, where inherited zircon dominates. We suggest that the magma sources and the processes responsible for generating high silica magmas differ between the northern and southern rhyolites. Isotopically distinct sources were available during formation of northern rhyolites, as the Hf and O isotopes in magmatic zircon differ between the two analysed localities of northern rhyolites. A mixing between magmas formed from Baltica-derived mudstone-siltstone sediments and Avalonian basement or mantle can explain the diversity between the zircon compositions from the northern localities Daszewo and Wysoka Kamieńska. Conversely, the southern rhyolites from our two localities contain zircon with similar compositions, and these units can be further correlated with results from the North East German Basin, suggesting uniform source rocks over this larger region. Based on the ages of inherited zircon and the isotopic composition of magmatic ones, we suggest that the dominant source of the southern rhyolites is Variscan foreland sediments mixed with Baltica/Avalonia-derived sediments.

  1. GHR1 - A new Eocene natural reference material for U-Pb and Hf isotopic measurements in zircon

    NASA Astrophysics Data System (ADS)

    Ibanez-Mejia, M.; Eddy, M. P.

    2017-12-01

    We present chemical abrasion-isotope dilution-thermal ionization (CA-ID-TIMS) U-Pb zircon geochronology and solution multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) Hf isotopic data from a proposed natural zircon reference material for use during in situ analyses of U-Pb and Hf isotopic ratios. The sample, GHR1, was collected from the rapakivi intrusive phase of the Eocene Golden Horn batholith in Washington, USA. Zircons separated from this sample range up to 250-300 μm in length and have moderate aspect ratios. A weighted mean of 15 Th-corrected 206Pb/238U zircon dates from GHR1 produced at the Massachusetts Institute of Technology is 48.132 ± 0.023 Ma (2σ analytical and tracer uncertainties only, MSWD=1.70) confirming that there is little or no inter-crystal age heterogeneity at the scale of a few 10 kyr. Solution MC-ICP-MS measurements of chemically purified aliquots give a 176Hf/177Hf weighted mean of 0.283050 ± 17 (2σ, n=10), corresponding to a ɛHf0 of ca. +9.3. The 2σ variability of these measurements is comparable to our reproducibility of the JMC-475 Hf isotopic standard 0.282160 ± 14 (n= 13), suggesting that GHR1 zircons are homogenous with respect to 176Hf/177Hf. In situ 206Pb/238U dates from collaborating secondary ion mass spectrometry (SIMS), sensitive high-resolution ion microprobe (SHRIMP), and laser ablation ICP-MS (LA-ICP-MS) laboratories are in excellent agreement with the CA-ID-TIMS date and illustrate the reproducibility and potential value of this reference zircon. The mean values of 176Hf/177Hf measurements from two LA-ICP-MS laboratories are in agreement with the solution MC-ICP-MS value, but show slightly greater dispersion and higher (Lu+Yb)/Hf values. We attribute this discrepancy to apatite inclusions that are high in REE and may lead to greater isobaric interferences on 176Hf. These inclusions and potential isobaric interferences from REE were removed during the chemical abrasion step prior to bulk

  2. Magma mixing and the generation of isotopically juvenile silicic magma at Yellowstone caldera inferred from coupling 238U–230Th ages with trace elements and Hf and O isotopes in zircon and Pb isotopes in sanidine

    USGS Publications Warehouse

    Stelten, Mark E.; Cooper, Kari M.; Vazquez, Jorge A.; Reid, Mary R.; Barfod, Gry H.; Wimpenny, Josh; Yin, Qing-Zhu

    2013-01-01

    The nature of compositional heterogeneity within large silicic magma bodies has important implications for how silicic reservoirs are assembled and evolve through time. We examine compositional heterogeneity in the youngest (~170 to 70 ka) post-caldera volcanism at Yellowstone caldera, the Central Plateau Member (CPM) rhyolites, as a case study. We compare 238U–230Th age, trace-element, and Hf isotopic data from zircons, and major-element, Ba, and Pb isotopic data from sanidines hosted in two CPM rhyolites (Hayden Valley and Solfatara Plateau flows) and one extracaldera rhyolite (Gibbon River flow), all of which erupted near the caldera margin ca. 100 ka. The Hayden Valley flow hosts two zircon populations and one sanidine population that are consistent with residence in the CPM reservoir. The Gibbon River flow hosts one zircon population that is compositionally distinct from Hayden Valley flow zircons. The Solfatara Plateau flow contains multiple sanidine populations and all three zircon populations found in the Hayden Valley and Gibbon River flows, demonstrating that the Solfatara Plateau flow formed by mixing extracaldera magma with the margin of the CPM reservoir. This process highlights the dynamic nature of magmatic interactions at the margins of large silicic reservoirs. More generally, Hf isotopic data from the CPM zircons provide the first direct evidence for isotopically juvenile magmas contributing mass to the youngest post-caldera magmatic system and demonstrate that the sources contributing magma to the CPM reservoir were heterogeneous in 176Hf/177Hf at ca. 100 ka. Thus, the limited compositional variability of CPM glasses reflects homogenization occurring within the CPM reservoir, not a homogeneous source.

  3. Applying the Ce-in-zircon oxygen geobarometer to diverse silicic magmatic systems

    NASA Astrophysics Data System (ADS)

    Claiborne, L. L.; Miller, C. F.

    2012-12-01

    Zircon provides information on age, temperature, and composition of the magma from which it grew. In systems such as Mount St. Helens, where zircon is not coeval with the rest of the crystal cargo, it provides the only accessible record of the extended history of the magmatic system, including cycles of intrusion, crystallization and rejuvenation beneath an active volcano (Claiborne et al., 2010). The rare earth elements, which are present in measureable quantities in zircon, provide information about the composition of the magma from which zircon grew. Unique among the generally trivalent rare earth elements, cerium can exist as either trivalent or tetravalent, depending on the oxidation state of the magma. The tetravalent ion is highly compatible in zircon, in the site that usually hosts tetravalent zirconium, and so the amount of Cerium in zircon relative (relative to what would be expected of trivalent Ce) depends the oxidation state of the magma from which it grew. Trail et al. (2011) proposed a calibration based on experimental data that uses the Ce anomaly in zircon as a direct proxy for magma oxidation (fugacity), describing the relationship between Ce in zircon and magma oxygen fugacity as ln(Ce/Ce*)D = (0.1156±0.0050)xln(fO2)+(13860±708)/T-(6.125±0.484). For systems like Mount St. Helens, where the major minerals record only events in the hundreds to thousands of years leading to eruption, (including the Fe-Ti oxides traditionally relied upon for records of oxidation state of the magmas), this presents a novel approach for understanding more extended histories of oxidation of magmas in the tens and hundreds of thousands of years of magmatism at a volcanic center. This calibration also promises to help us better constrain conditions of crystallization in intrusive portions of volcanic systems, as well as plutonic bodes. We apply this new oxygen geobarometer to natural volcanic and plutonic zircons from a variety of tectonic settings, and compare to

  4. Zircon trace element and isotopic (Sr, Nd, Hf, Pb) effects of assimilation-fractional crystallization of pegmatite magma: A case study of the Guangshigou biotite pegmatites from the North Qinling Orogen, central China

    NASA Astrophysics Data System (ADS)

    Yuan, Feng; Liu, Jia-Jun; Carranza, Emmanuel John M.; Zhang, Shuai; Zhai, De-Gao; Liu, Gang; Wang, Gong-Wen; Zhang, Hong-Yuan; Sha, Ya-Zhou; Yang, Shang-Song

    2018-03-01

    Evidence for open-system magmatic processes related to wallrock assimilation accompanied by fractional crystallization (AFC) is present in the Guangshigou biotite pegmatites, North Qinling Orogen. The biotite pegmatite-gneiss contacts generally coincide with the greatest enrichment of U and Th. Zircon Usbnd Pb dating constrains the crystallization ages of the biotite pegmatite (rim zone-415 ± 2.6 Ma; internal zone-413.5 ± 2.5 Ma), in line with a pyrite Pbsbnd Pb isochron age (413 ± 22 Ma). Metamict areas in zircon show generally elevated concentrations of trace elements and expulsion of radioactive Pb. Internal zone samples, representing uncontaminated magma, have negative to positive zircon ( 413 Ma) εHf(t) (- 1.53 - + 3.24), low εNd(t) values (- 2.4), and old Hf and Nd model ages (tDM2 = 1.5-1.19 Ga, T2DM = 1.35 Ga, respectively), indicating a dominantly recycled Mesoproterozoic lower crustal material with involvement of some juvenile materials in the source region. The magmatic oxygen fugacity (fO2) and crystallization temperatures ranges from - 24.81 to - 13.34 of log fO2 and 570 °C to 793 °C, respectively. Compared to the internal zone, pegmatite rim samples display a variable and lower εNd(t) values (- 3.9 to - 2.8) and T2DM (1.47-1.37 Ga), but similar Hf isotopic compositions, favouring a three-component isotopic mixing model (recycled Mesoproterozoic lower crust materials, juvenile materials, and host gneiss). Pronounced variations of Ti, Y, U, Th, Hf, and REE concentrations in zircon from grain to grain in individual samples and from area to area within individual grains suggest a fluctuating crystallization environment in hybridized magma from which the rim-hosted zircons crystallized. Variable and high radiogenic Pb ratios of pyrites forming in the hybridized magma were inherited from the matrix. Zircons from both zones exhibit similar Hf isotope patterns, indicating the rim-hosted zircons crystallized during the early stage of hybridization of

  5. Zircon U-Pb geochronology and Sr-Nd-Pb-Hf isotopic constraints on the timing and origin of Mesozoic granitoids hosting the Mo deposits in northern Xilamulun district, NE China

    NASA Astrophysics Data System (ADS)

    Shu, Qihai; Lai, Yong; Zhou, Yitao; Xu, Jiajia; Wu, Huaying

    2015-12-01

    Located in the east section of the Central Asian orogen in northeastern China, the Xilamulun district comprises several newly discovered molybdenum deposits, primarily of porphyry type and Mesozoic ages. This district is divided by the Xilamulun fault into the southern and the northern parts. In this paper, we present new zircon U-Pb dating, trace elements and Hf isotope, and/or whole rock Sr-Nd-Pb isotopic results for the host granitoids from three Mo deposits (Yangchang, Haisugou and Shabutai) in northern Xilamulun. Our aim is to constrain the age and petrogenesis of these intrusions and their implications for Mo mineralization. Zircon U-Pb LA-ICP-MS dating shows that the monzogranites from the Shabutai and Yangchang deposits formed at 138.4 ± 1.5 and 137.4 ± 2.1 Ma, respectively, which is identical to the molybdenite Re-Os ages and coeval well with the other Mo deposits in this region, thereby indicating an Early Cretaceous magmatism and Mo mineralization event. Zircon Ce/Nd ratios from the mineralized intrusions are significantly higher than the barren granites, implying that the mineralization-related magmas are characterized by higher oxygen fugacity. These mineralized intrusions share similar zircon in-situ Hf and whole rock Sr-Nd isotopic compositions, with slightly negative to positive εHf(t) ranging from - 0.8 to + 10.0, restricted εNd(t) values from - 3.7 to + 1.6 but a little variable (87Sr/86Sr)i ratios between 0.7021 and 0.7074, indicative of formation from primary magmas generated from a dominantly juvenile lower crust source derived from depleted mantle, despite diverse consequent processes (e.g., magma mixing, fractional crystallization and crustal contamination) during their evolution. The Pb isotopes (whole rock) also show a narrow range of initial compositions, with (206Pb/204Pb)i = 18.03-18.88, (207Pb/204Pb)i = 15.48-15.58 and (208Pb/204Pb)i = 37.72-38.28, in agreement with Sr-Nd-Hf isotopes reflecting the dominance of a mantle component

  6. High Precision Isotope Analyses Using Multi-Collector SIMS: Applications to Earth and Planetary Science.

    NASA Astrophysics Data System (ADS)

    Kita, N. T.; Ushikubo, T.; Valley, J. W.

    2008-05-01

    The CAMECA IMS-1280 large radius, multicollector ion microprobe at the Wisc-SIMS National Facility is capable of high accuracy and precision for in situ analysis of isotope ratios. With improved hardware stability and software capability, high precision isotope analyses are routinely performed, typically 5 min per spot. We have developed analytical protocols for stable isotope analyses of oxygen, carbon, Mg, Si and Sulfur using multi-collector Faraday Cups (MCFC) and achieved precision of 0.1-0.2 ‰ (1SD) from a typically 10μm spot analyses. A number of isotopically homogeneous mineral standards have been prepared and calibrated in order to certify the accuracy of analyses in the same level. When spatial resolution is critical, spot size is reduced down to sub- μm for δ 18O to obtain better than 0.5‰ (1SD) precision by using electron multiplier (EM) on multi-collection system. Multi-collection EM analysis is also applied at 10 ppm level to Li isotope ratios in zircon with precision better than 2‰ (1SD). A few applications will be presented. (1) Oxygen three isotope analyses of chondrules in ordinary chondrites revealed both mass dependent and mass independent oxygen isotope fractionations among chondrules as well as within individual chondrules. The results give constraints on the process of chondrule formation and origin of isotope reservoirs in the early solar system. (2) High precision 26Al-26Mg (half life of 0.73 Ma) chronology is applied to zoned melilite and anorthite from Ca, Al-rich inclusions (CAI) in Leoville meteorite, and a well-defined internal isochron is obtained. The results indicate the Al- Mg system was remained closed within 40ky of the crystallization of melilite and anorthite in this CAI. (3) Sub- μm spot analyses of δ18O in isotopically zoned zircon from high-grade metamorphism reveals a diffusion profile of ~6‰ over 2μm, indicating slow diffusion of oxygen in zircon. This result also implies that old Archean detrital zircons (> 4

  7. Small Volume Isotopic Analysis of Zircon Using LA-MC-ICP-MS U-Pb and Lu-Hf and Sub-ng Amounts of Hf in Solution

    NASA Astrophysics Data System (ADS)

    Bauer, A.; Horstwood, M. S.

    2016-12-01

    Crust-mantle evolution studies are greatly informed by zircon U-Pb and Lu-Hf isotopic datasets and the ease with which these data can now be acquired has seen their application become commonplace. In order to deconvolute geochemical change and interpret geologic variation in complexly zoned zircons, this information is most ideally obtained on the smallest volume of zircon by successive SIMS U-Pb and LA-MC-ICP-MS Lu-Hf isotopic analyses. However, due to variations in zircon growth zone geometry at depth, the Lu-Hf analysis may not relate to the lower volume U-Pb analysis, potentially causing inaccuracy of the resultant age-corrected Hf isotope signature. Laser ablation split-stream methods are applied to be certain that U-Pb and Lu-Hf data represent the same volume of zircon, however, the sampling volume remains relatively large at 40x30µm1. Coupled ID-TIMS U-Pb and solution MC-ICP-MS Lu-Hf work traditionally utilize whole-zircon dissolution ( 10-50ng Hf), which has the potential to homogenize different zones of geologic significance within an analysis. Conversely, modern ID-TIMS U-Pb methods utilize microsampling of zircon grains, often providing < 5ng Hf, thereby challenging conventional Lu-Hf acquisition protocols to achieve the required precision. In order to obtain usable precision on minimal zircon volumes, we developed laser ablation methods using successive 25um spot U-Pb and Lu-Hf ablation pits with a combined depth of 18um, and low-volume solution introduction methods without Hf-REE separation utilizing Hf amounts as low as 0.4ng, while retaining an uncertainty level of ca. 1 ɛHf for both methods. We investigated methods of Yb interference correction and the potential for matrix effects, with a particular focus on the accurate quantification of 176Lu/177Hf. These improvements reduce the minimum amount of material required for U-Pb and Hf isotopic analysis of zircon by about an order of magnitude. 1Ibanez-Mejia et al (2015). PreRes, 267, 285-310.

  8. Isotope U-Pb age on single zircon and REE distribution in rocks and zircon from paleoproterozoic Kandalaksha-Kolvitsa complex Baltic shield

    NASA Astrophysics Data System (ADS)

    Steshenko, Ekaterina; Bayanova, Tamara; Drogobuzhskaya, Svetlana; Lyalina, Ludmila; Serov, Pavel; Chashchin, Viktor; Elizarov, Dmitriy

    2017-04-01

    Kandalaksha-Kolvitsa paleoproterozoic complex located in the N-E part of Baltic shield and consists of three zones. Marginal zone (mesocratic metanorite) lies at the base of the massif. Main zone is composed of leucocratic metagabbro. The upper zone is alteration of mataanorthosite and leucocratic metagabbro. All rocks were subjected to granulate and anorthositic metamorphism. Age of magmatic crystallization of the massif was determined for the first time, using the U-Pb isotope method for single zircon grains. Three fractions of single zircons from anorthosite of the Kandalaksha massif gave precise U-Pb age of 2435.5 ± 4.8 Ma. For the first time REE concentration (WR) was determined using a quadrupole mass spectrometer (Agilent 7500 ce ICP-MS) in the main varieties of rocks of the Kandalaksha-Kolvitsa paleoproterozoic complex. Anorthosite and leucocratic metagabbros (main zone) are characterized by a flat spectrum distribution of HREE, which were normalized by [1]. The REE pattern is characterized by significant positive anomalies of Eu ((Eu / Eu *)n = 3.72-3.91) in anorthosite and leucogabbros and 7.26 - in ortoamfibolitah. General content of individual elements that are common for this type of rocks: Cen = 5.82-8.54, Ybn = 1.54-1.58, which indicates that the process of crystallization of the rock occurred with predominant accumulation of plagioclase. According to geochemical and Nd-Sr isotopic data (ISr=0.702 - 0.706, ɛNd(T) = +1 - (-3)) Kandalaksha Kolvitsa complex, appear to have a general plume source with Paleoproterozoic layered intrusions of the Baltic Shield [2] Distribution of REE (ELAN-9000 ICP-MS) in zircon have a typical magmatic species: a positive Ce, negative Eu anomaly and HREE flat spectrum. Titanium content in zircons were measured for the calculation of their crystallization temperature with 8350C. These data are evidence of magmatic origin of zircon [3]. The scientific researches are supported by RFBR (projects № 15-35-20501, № 16

  9. Device and method for separating oxygen isotopes

    DOEpatents

    Rockwood, Stephen D.; Sander, Robert K.

    1984-01-01

    A device and method for separating oxygen isotopes with an ArF laser which produces coherent radiation at approximately 193 nm. The output of the ArF laser is filtered in natural air and applied to an irradiation cell where it preferentially photodissociates molecules of oxygen gas containing .sup.17 O or .sup.18 O oxygen nuclides. A scavenger such as O.sub.2, CO or ethylene is used to collect the preferentially dissociated oxygen atoms and recycled to produce isotopically enriched molecular oxygen gas. Other embodiments utilize an ArF laser which is narrowly tuned with a prism or diffraction grating to preferentially photodissociate desired isotopes. Similarly, desired mixtures of isotopic gas can be used as a filter to photodissociate enriched preselected isotopes of oxygen.

  10. Recovering the primary geochemistry of Jack Hills zircons through quantitative estimates of chemical alteration

    NASA Astrophysics Data System (ADS)

    Bell, Elizabeth A.; Boehnke, Patrick; Harrison, T. Mark

    2016-10-01

    Despite the robust nature of zircon in most crustal and surface environments, chemical alteration, especially associated with radiation damaged regions, can affect its geochemistry. This consideration is especially important when drawing inferences from the detrital record where the original rock context is missing. Typically, alteration is qualitatively diagnosed through inspection of zircon REE patterns and the style of zoning shown by cathodoluminescence imaging, since fluid-mediated alteration often causes a flat, high LREE pattern. Due to the much lower abundance of LREE in zircon relative both to other crustal materials and to the other REE, disturbance to the LREE pattern is the most likely first sign of disruption to zircon trace element contents. Using a database of 378 (148 new) trace element and 801 (201 new) oxygen isotope measurements on zircons from Jack Hills, Western Australia, we propose a quantitative framework for assessing chemical contamination and exchange with fluids in this population. The Light Rare Earth Element Index is scaled on the relative abundance of light to middle REE, or LREE-I = (Dy/Nd) + (Dy/Sm). LREE-I values vary systematically with other known contaminants (e.g., Fe, P) more faithfully than other suggested proxies for zircon alteration (Sm/La, various absolute concentrations of LREEs) and can be used to distinguish primary compositions when textural evidence for alteration is ambiguous. We find that zircon oxygen isotopes do not vary systematically with placement on or off cracks or with degree of LREE-related chemical alteration, suggesting an essentially primary signature. By omitting zircons affected by LREE-related alteration or contamination by mineral inclusions, we present the best estimate for the primary igneous geochemistry of the Jack Hills zircons. This approach increases the available dataset by allowing for discrimination of on-crack analyses (and analyses with ambiguous or no information on spot placement or

  11. Major zircon megacryst suites of the Indo-Pacific lithospheric margin (ZIP) and their petrogenetic and regional implications

    NASA Astrophysics Data System (ADS)

    Sutherland, Lin; Graham, Ian; Yaxley, Gregory; Armstrong, Richard; Giuliani, Gaston; Hoskin, Paul; Nechaev, Victor; Woodhead, Jon

    2016-04-01

    Zircon megacrysts (± gem corundum) appear in basalt fields of Indo-Pacific origin over a 12,000 km zone (ZIP) along West Pacific continental margins. Age-dating, trace element, oxygen and hafnium isotope studies on representative zircons (East Australia-Asia) indicate diverse magmatic sources. The U-Pb (249 to 1 Ma) and zircon fission track (ZFT) ages (65 to 1 Ma) suggest thermal annealing during later basalt transport, with < 1 to 203 Ma gaps between the U-Pb and ZFT ages. Magmatic growth zonation and Zr/Hf ratios (0.01-0.02) suggest alkaline magmatic sources, while Ti—in—zircon thermometry suggests that most zircons crystallized within ranges between 550 and 830 °C. Chondrite-normalised multi-element plots show variable enrichment patterns, mostly without marked Eu depletion, indicating little plagioclase fractionation in source melts. Key elements and ratios matched against zircons from magmatic rocks suggest a range of ultramafic to felsic source melts. Zircon O-isotope ratios (δ18O in the range 4 to 11‰) and initial Hf isotope ratios (ɛHf in the range +2 to +14) encompass ranges for both mantle and crustal melts. Calculated Depleted Mantle (TDM 0.03-0.56 Ga) and Crustal Residence (0.20-1.02 Ga) model ages suggest several mantle events, continental break-ups (Rodinia and Gondwana) and convergent margin collisions left imprints in the zircon source melts. East Australian ZIP sites reflect prolonged intraplate magmatism (~85 Ma), often during times of fast-migrating lithosphere. In contrast, East Asian-Russian ZIP sites reflect later basaltic magmatism (<40 Ma), often linked to episodes of back-arc rifting and spreading, slow-migrating lithosphere and slab subduction.

  12. Assessing the isotopic evolution of S-type granites of the Carlos Chagas Batholith, SE Brazil: Clues from U-Pb, Hf isotopes, Ti geothermometry and trace element composition of zircon

    NASA Astrophysics Data System (ADS)

    Melo, Marilane G.; Lana, Cristiano; Stevens, Gary; Pedrosa-Soares, Antônio C.; Gerdes, Axel; Alkmin, Leonardo A.; Nalini, Hermínio A.; Alkmim, Fernando F.

    2017-07-01

    The Carlos Chagas batholith (CCB) is a very large ( 14,000 km2) S-type granitic body formed during the syn-collisional stage of the Araçuaí orogen (southeastern Brazil). Zircons extracted from the CCB record a wide range of U-Pb ages (from 825 to 490 Ma), indicating a complex history of inheritance, magmatic crystallization and partial melting during the evolution of the orogeny. Magmatic zircons (ca. 578-588 Ma) are marked by similar Hf isotope compositions and REE patterns to those of inherited cores (ca. 825-600 Ma), indicating that these aspects of the chemical signature of the magmatic zircons have likely been inherited from the source. The U-Pb ages and initial 176Hf/177Hf ratios from anatectic and metamorphic zircon domains are consistent with a two-stage metamorphic evolution marked by contrasting mechanisms of zircon growth and recrystallization during the orogeny. Ti-in-zircon thermometry is consistent with the findings of previous metamorphic work and indicates that the two metamorphic events in the batholith reached granulite facies conditions (> 800 °C) producing two generations of garnet via fluid-absent partial melting reactions. The oldest metamorphic episode (ca. 570-550 Ma) is recorded by development of thin anatectic overgrowths on older cores and by growth of new anatectic zircon crystals. Both domains have higher initial 176Hf/177Hf values compared to relict cores and display REE patterns typical of zircon that grew contemporaneously with peritectic garnet through biotite-absent fluid partial melting reactions. Hf isotopic and chemical evidences indicate that a second anatectic episode (ca. 535-500 Ma) is only recorded in parts from the CCB. In these rocks, the growth of new anatectic zircon and/or overgrowths is marked by high initial 176Hf/177Hf values and also by formation of second generation of garnet, as indicated by petrographic observations and REE patterns. In addition, some rocks contain zircon crystals formed by solid

  13. Detrital Zircon U-Pb and Hf-isotope Constrains on Basement Ages, Granitic Magmatism, and Sediment Provenance in the Malay Peninsula

    NASA Astrophysics Data System (ADS)

    Sevastjanova, Inga; Clements, Benjamin; Hall, Robert; Belousova, Elena; Pearson, Norman; Griffin, William

    2010-05-01

    The Malay Peninsula forms the western part of central Sundaland in SE Asia. Sundaland comprises Indochina, the Thai-Malay Peninsula, Sumatra, Java, Borneo, and the shallow shelf between these landmasses. It is a composite region of continental crustal fragments that are separated by sutures that represent remnant ocean basins and volcanic arcs. The Malay Peninsula includes two of these fragments - East Malaya and Sibumasu - separated by the Bentong-Raub Suture Zone. The latter is a Palaeo-Tethyan ocean remnant. Granitoids of the Malay Peninsula are the major sources of detrital zircon in Sundaland. East Malaya is intruded by Permian-Triassic Eastern Province granitoids interpreted as products of Palaeozoic subduction of oceanic crust beneath the East Malaya Volcanic Arc. Sibumasu is intruded by Triassic Main Range Province granitoids interpreted as syn- to post-collisional magmatism following suturing to East Malaya. Locally, there are minor Late Cretaceous plutons. Basements of Sibumasu and East Malaya are not exposed and their ages are poorly constrained. The exact timing of the collision between these fragments is also contentious. In order to resolve these uncertainties, 752 U-Pb analyses from 9 samples were carried out on detrital zircons from modern rivers draining the Malay Peninsula and, of these, 243 grains from 6 samples were selected for Hf-isotope analyses. U-Pb zircon ages show that small numbers of Neoarchean-Proterozoic grains are consistently present in all samples, but do not form prominent populations. Permian-Triassic populations are dominant. Only one sample contains a small Jurassic population probably sourced from the area of Thailand and most likely recycled from fluvial-alluvial Mesozoic 'red-beds'. Late Cretaceous populations are locally abundant. Hf-isotope crustal model ages suggest that basement beneath the Malay Peninsula is heterogeneous. Some basement may be Neoarchean but there is no evidence for basement older than 2.8 Ga beneath

  14. Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

    USGS Publications Warehouse

    Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

    2007-01-01

    Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

  15. Improved 206Pb/238U microprobe geochronology by the monitoring of a trace-element-related matrix effect; SHRIMP, ID-TIMS, ELA-ICP-MS and oxygen isotope documentation for a series of zircon standards

    USGS Publications Warehouse

    Black, L.P.; Kamo, S.L.; Allen, C.M.; Davis, D.W.; Aleinikoff, J.N.; Valley, J.W.; Mundil, R.; Campbell, I.H.; Korsch, R.J.; Williams, I.S.; Foudoulis, C.

    2004-01-01

    Precise isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) documentation is given for two new Palaeozoic zircon standards (TEMORA 2 and R33). These data, in combination with results for previously documented standards (AS3, SL13, QGNG and TEMORA 1), provide the basis for a detailed investigation of inconsistencies in 206Pb/238U ages measured by microprobe. Although these ages are normally consistent between any two standards, their relative age offsets are often different from those established by ID-TIMS. This is true for both sensitive high-resolution ion-microprobe (SHRIMP) and excimer laser ablation-inductively coupled plasma-mass spectrometry (ELA-ICP-MS) dating, although the age offsets are in the opposite sense for the two techniques. Various factors have been investigated for possible correlations with age bias, in an attempt to resolve why the accuracy of the method is worse than the indicated precision. Crystallographic orientation, position on the grain-mount and oxygen isotopic composition are unrelated to the bias. There are, however, striking correlations between the 206Pb/238U age offsets and P, Sm and, most particularly, Nd abundances in the zircons. Although these are not believed to be the primary cause of this apparent matrix effect, they indicate that ionisation of 206Pb/238U is influenced, at least in part, by a combination of trace elements. Nd is sufficiently representative of the controlling trace elements that it provides a quantitative means of correcting for the microprobe age bias. This approach has the potential to reduce age biases associated with different techniques, different instrumentation and different standards within and between laboratories. Crown Copyright ?? 2004 Published by Elsevier B.V. All rights reserved.

  16. Paleoproterozoic mojaveprovince in northwestern Mexico? Isotopic and U-Pb zircon geochronologic studies of precambrian and Cambrian crystalline and sedimentary rocks, Caborca, Sonora

    USGS Publications Warehouse

    Lang, Farmer G.; Bowring, S.A.; Matzel, J.; Maldonado, G.E.; Fedo, C.; Wooden, J.

    2005-01-01

    Whole-rock Nd isotopic data and U-Pb zircon geochronology from Precambrian crystalline rocks in the Caborca area, northern Sonora, reveal that these rocks are most likely a segment of the Paleoproterozoic Mojave province. Supporting this conclusion are the observations that paragneiss from the ??? 1.75 Ga Bamori Complex has a 2.4 Ga Nd model age and contains detrital zircons ranging in age from Paleo- proterozoic (1.75 Ga) to Archean (3.2 Ga). Paragneisses with similar age and isotopic characteristics occur in the Mojave province in southern California. In addition, "A-type" granite exposed at the southern end of Cerro Rajon has ca 2.0 Ga Nd model age and a U-Pb zircon age of 1.71 Ga, which are similar to those of Paleoproterozoic granites in the Mojave province. Unlike the U.S. Mojave province, the Caborcan crust contains ca. 1.1 Ga granite (Aibo Granite), which our new Nd isotopic data suggest is largely the product of anatexis of the local Precambrian basement. Detrital zircons from Neoproterozoic to early Cambrian miogeoclinal arenites at Caborca show dominant populations ca. 1.7 Ga, ca. 1.4 Ga, and ca. 1.1 Ga, with subordinate Early Cambrian and Archean zircons. These zircons were likely derived predominately from North American crust to the east and northeast, and not from the underlying Caborcan basement. The general age and isotopic similarities between Mojave province basement and overlying miogeoclinal sedimentary rocks in Sonora and southern California is necessary, but not sufficient, proof of the hypothesis that Sonoran crust is allochthonous and was transported to its current position during the Mesozoic along the proposed Mojave-Sonora megashear. One viable alternative model is that the Caborcan Precambrian crust is an isolated, autochthonous segment of Mojave province crust that shares a similar, but not identical, Proterozoic geological history with Mojave province crust found in the southwest United States ?? 2005 Geological Society of America.

  17. Oxygen isotope study of the Long Valley magma system, California: isotope thermometry and convection in large silicic magma bodies

    NASA Astrophysics Data System (ADS)

    Bindeman, Ilya; Valley, John

    2002-07-01

    Products of voluminous pyroclastic eruptions with eruptive draw-down of several kilometers provide a snap-shot view of batholith-scale magma chambers, and quench pre-eruptive isotopic fractionations (i.e., temperatures) between minerals. We report analyses of oxygen isotope ratio in individual quartz phenocrysts and concentrates of magnetite, pyroxene, and zircon from individual pumice clasts of ignimbrite and fall units of caldera-forming 0.76 Ma Bishop Tuff (BT), pre-caldera Glass Mountain (2.1-0.78 Ma), and post-caldera rhyolites (0.65-0.04 Ma) to characterize the long-lived, batholith-scale magma chamber beneath Long Valley Caldera in California. Values of δ18O show a subtle 1‰ decrease from the oldest Glass Mountain lavas to the youngest post-caldera rhyolites. Older Glass Mountain lavas exhibit larger ( 1‰) variability of δ18O(quartz). The youngest domes of Glass Mountain are similar to BT in δ18O(quartz) values and reflect convective homogenization during formation of BT magma chamber surrounded by extremely heterogeneous country rocks (ranging from 2 to +29‰). Oxygen isotope thermometry of BT confirms a temperature gradient between "Late" (815 °C) and "Early" (715 °C) BT. The δ18O(quartz) values of "Early" and "Late" BT are +8.33 and 8.21‰, consistent with a constant δ18O(melt)=7.8+/-0.1‰ and 100 °C temperature difference. Zircon-melt saturation equilibria gives a similar temperature range. Values of δ18O(quartz) for different stratigraphic units of BT, and in pumice clasts ranging in pre-eruptive depths from 6 to 11 km (based on melt inclusions), and document vertical and lateral homogeneity of δ18O(melt). Worldwide, five other large-volume rhyolites, Lava Creek, Lower Bandelier, Fish Canyon, Cerro Galan, and Toba, exhibit equal δ18O(melt) values of earlier and later erupted portions in each of the these climactic caldera-forming eruptions. We interpret the large-scale δ18O homogeneity of BT and other large magma chambers as evidence

  18. Evidence from detrital zircons for the existence of continental crust and oceans on the Earth 4.4 Gyr ago.

    PubMed

    Wilde, S A; Valley, J W; Peck, W H; Graham, C M

    2001-01-11

    No crustal rocks are known to have survived since the time of the intense meteor bombardment that affected Earth between its formation about 4,550 Myr ago and 4,030 Myr, the age of the oldest known components in the Acasta Gneiss of northwestern Canada. But evidence of an even older crust is provided by detrital zircons in metamorphosed sediments at Mt Narryer and Jack Hills in the Narryer Gneiss Terrane, Yilgarn Craton, Western Australia, where grains as old as approximately 4,276 Myr have been found. Here we report, based on a detailed micro-analytical study of Jack Hills zircons, the discovery of a detrital zircon with an age as old as 4,404+/-8 Myr--about 130 million years older than any previously identified on Earth. We found that the zircon is zoned with respect to rare earth elements and oxygen isotope ratios (delta18O values from 7.4 to 5.0%), indicating that it formed from an evolving magmatic source. The evolved chemistry, high delta18O value and micro-inclusions of SiO2 are consistent with growth from a granitic melt with a delta18O value from 8.5 to 9.5%. Magmatic oxygen isotope ratios in this range point toward the involvement of supracrustal material that has undergone low-temperature interaction with a liquid hydrosphere. This zircon thus represents the earliest evidence for continental crust and oceans on the Earth.

  19. New Insights Into the Genesis and Compositional Evolution of I-type Granitic magmas in the Lachlan Fold Belt (SE Australia) by in situ Hf Isotopic Analysis of Zircon

    NASA Astrophysics Data System (ADS)

    Kemp, T. I.; Hawkesworth, C. J.; Hergt, J. M.; Woodhead, J.

    2004-05-01

    Isotope studies have proved of enormous benefit in fingerprinting the source rocks of silicic magmas and tracing open system petrogenetic processes, such as crustal assimilation or magma mixing. Quantification of these processes, especially the role of mantle-derived magmas, is essential to formulating realistic models for the thermal regime and compositional evolution of the continental crust. However, this remains problematic, since whole-rock isotopic data registers the final state of the magmatic system but gives no information on the pathways by which this state was attained. For example, the eNd - initial 87Sr/86Sr isotopic array defined by the classic I- and S-type granites of the Lachlan Fold Belt has been variously interpreted to reflect (1) mixing between two end-member magmas, one depleted mantle-like, the other evolved and continental crust-like, (2) mixing between a juvenile magma and a magma sourced from mafic lower crust, accompanied by sediment assimilation, (3) derivation of the granites from mixed source rocks and (4) derivation from a sequence of protoliths of various ages and sedimentary maturity. The implications of these possibilities for crustal architecture, and whether granitic magmatism was associated with the recycling or growth of new continental crust are drastically different. One way to now resolve such ambiguities is by unravelling the isotopic information encoded in the fine-scale growth zoning of minerals such as zircon, which potentially tracks the processes operative during crystallisation. To this end we report the first laser-ablation ICP-MS study into the Hf isotope stratigraphy of zircons hosted by LFB I-type granites and their mafic enclaves. This is integrated with a prior U-Pb isotope study and trace element concentrations measured on the same zircons. Two suites were investigated, the Cobargo and Why Worry Suites of the Bega Batholith. Although the bulk rock isotopic variation within these suites is restricted, this study

  20. 40Ar/39Ar dating and zircon chronochemistry for the Izu-Bonin rear arc, IODP site U1437

    NASA Astrophysics Data System (ADS)

    Schmitt, A. K.; Konrad, K.; Andrews, G. D.; Horie, K.; Brown, S. R.; Koppers, A. A. P.; Busby, C.; Tamura, Y.

    2016-12-01

    The scientific objective of IODP Expedition 350 drilling at Site U1437 (31°47.390'N, 139°01.580'E) was to reveal the "missing half of the subduction factory": the rear arc of a long-lived intraoceanic subduction zone. Site U1437 lies in a 50 km long and 20 km wide volcano-bounded basin, 90 km west of the Izu arc front, and is the only IODP site drilled in the rear arc. The Izu rear arc is dominated by Miocene basaltic to dacitic seamount chains, which strike at a high angle to the arc front. Radiometric dating targeted a single igneous unit (1390 mbsf), and fine to coarse volcaniclastic units for which we present zircon and 40Ar/39Ar (hornblende, plagioclase, and groundmass) age determinations. All zircons analyzed as grain separates were screened for contamination from drill-mud (Andrews et al., 2016) by analyzing trace elements and, where material was available, O and Hf isotope compositions. Igneous Unit 1 is a rhyolite sheet and yielded concordant in-situ and crystal separate U-Pb zircon ages (13.7±0.3 Ma; MSWD = 1.3; n = 40 spots), whereas the 40Ar/39Ar hornblende plateau age (12.9±0.3; MSWD = 1.1; n = 9 steps) is slightly younger, possibly reflecting pre-eruptive zircon crystallization, or alteration of hornblende. U-Pb zircon and 40Ar/39Ar plateau ages from samples above igneous Unit 1 are concordant with biostratigraphic and paleomagnetic ages (available to 1300 mbsf), but plagioclase and groundmass samples below 1300 m become younger with depth, hinting at post-depositional alteration. A single zircon from 1600 mbsf yielded a U-Pb age of 15.4±1.8 Ma; its trace element composition resembles other igneous zircons from U1437, and is tentatively interpreted as a Middle Miocene age for the lowermost lithostratigraphic unit VII. Oxygen and Hf isotopic values of igneous zircon indicate mantle origins, with some influence of assimilation of hydrothermally altered oceanic crust evident in sub-mantle oxygen isotopic compositions. Lessons from site U1437 are

  1. From Crustal Anatexis to Pluton Emplacement: High-Precision Zircon Geochronology Reveals the Thermal History of the Larderello-Travale Geothermal System (Italy)

    NASA Astrophysics Data System (ADS)

    Farina, F.; Dini, A.; Ovtcharova, M.; Davies, J.; Bouvier, A. S.; Baumgartner, L. P.; Caricchi, L.; Schaltegger, U.

    2017-12-01

    Late Miocene to recent post-collisional extension in Tuscany (Italy) led to the emplacement of shallow-level granitic plutons and to the eruption of small rhyolitic bodies. The intrusion of peraluminous two-mica and tourmaline-bearing granites triggered the formation of the steam-dominated Larderello-Travale geothermal system. In this study, zircon crystals from granite samples obtained from drill holes at 3.0-4.5 km depth were investigated by combining in-situ oxygen isotopes analysis and high-precision CA-ID-TIMS U-Pb age determinations to gain insight into the nature of the magmatic heat source fuelling the geothermal field. Magmatic zircon crystals display δ18O values ranging from 8.6 to 13.5‰ and crystals from individual samples exhibit inter- and intra-grain oxygen isotope variability exceeding 3‰. The geochronological data indicates the existence of three magmatic pulses with ages between 3.637 ± 0.008 and 1.671 ± 0.004 Ma. More importantly, zircon crystals from individual samples exhibit an age spread as large as 200-400 ky. This age dispersion, which is more than one order of magnitude greater than the uncertainty on a single date, suggest that most of the zircon did not crystallize at the emplacement level, but within isolated and isotopically distinct magma batches before large-scale homogenization in a magmatic reservoir at depth. The rate of assembly and final volume of this reservoir is estimated using the distribution of precise U-Pb zircon dates following the approach of Caricchi et al. (2014). Thermal modelling indicates that the heat flow at the surface in the geothermal field cannot be sustained by the inferred reservoir or by heat advection from the mantle. Our data suggest the existence of a younger shallow-level intrusion, whose occurrence also accounts for the existence of confined magmatic fluids at the top of the Larderello-Travale intrusion. We conclude that a multi-disciplinary approach, integrating high-precision zircon dating, in

  2. Zircon U-Pb ages and Hf-O isotopic composition of migmatites from the Zanjan-Takab complex, NW Iran: Constraints on partial melting of metasediments

    NASA Astrophysics Data System (ADS)

    Moghadam, Hadi Shafaii; Li, Xian-Hua; Stern, Robert J.; Ghorbani, Ghasem; Bakhshizad, Farzaneh

    2016-01-01

    We study migmatites and other metamorphic rocks in the Zanjan-Takab region of NW Iran and use these results to report the first evidence of Oligocene core complex formation in Iran. Four samples of migmatites associated with paragneisses, including leucosomes and associated para-amphibolite melanosomes were selected for U-Pb dating and Hf-O isotopic analysis. Zircon cores - interpreted as originally detrital zircons - have variable ages that peak at ca. 100-110 Ma, but their sedimentation age - indicated by the youngest 206Pb/238U ages - is ca. 35-40 Ma. New zircons associated with incipient melting occur as overgrowths around zircon cores and/or as newly grown grains. Morphologies and internal structures suggest that rim growth and formation of new zircons were associated with partial melting. All four samples contain zircons with rims that yield 206Pb/238U ages of 28-25 Ma, indicating that partial melting occurred in Late Oligocene time. δ18O values for zircon rims vary between 8.2 and 12.3‰, significantly higher than expected for mantle inputs (δ18O 6‰) and consistent with equilibrium with surface materials. Zircon rims yield εHf(t) between 2.2 and 12.4 and two-stage Hf model ages of 448-562 Ma, indicating that the region is underlain by Cadomian-Caledonian crust. According to the Hf-O isotopic values, the main mechanism forming zircon rims was dissolution of pre-existing detrital zircons with reprecipitation of new zircon shortly thereafter. Oligocene ages indicate that partial melting accompanied core complex formation in the Zanjan-Takab region. Extension, melting, and core complex formation in south-central Iran are Eocene in age, but younger ages of Oligocene-Miocene in NW Iran and Turkey indicate that extension was distributed throughout the region during Cenozoic time.

  3. Zircon and baddeleyite from the economic ultramafic-mafic Noril'sk-1 intrusion (Russia): Hf-isotope constraints on source composition

    NASA Astrophysics Data System (ADS)

    Malitch, K. N.; Belousova, E. A.; Badanina, I. Yu.; Griffin, W. L.

    2012-04-01

    of the Noril'sk-1 intrusion, which served as the favorable factor for accumulation of ores of unique scales and concentrations, To test this hypothesis, in situ Hf-isotope data were collected on the dated spots within single zircon grains. The analysis used a New Wave LUV213 laser-ablation microprobe attached to a Nu plasma MC-ICP-MS at GEMOC (Griffin et al. 2002). Hf-isotope results grouped on the basis of lithology show notable differences. Zircons from the unmineralized 'layered rock sequence' (e.g., olivine-free gabbro, olivine-bearing gabbro and olivine gabbro) are characterized by the most 'radiogenic' initial 176Hf/177Hf and some of ɛHf values close to those of the Depleted Mantle. Irrespective of zircon population most radiogenic Hf-isotope compositions are typical for olivine-free gabbro (mean ɛHf 7.3 ± 1.1 for sample N1-4), olivine-bearing gabbro (9.2 ± 3.8, sample N1-5) and olivine gabbro (8.3 ± 2.0, sample N1-6). In contrast, zircons from the leucogabbro that encloses the low-sulphide horizon (N1-3), and plagiowehrlite (N1-7) and taxitic-textured rocks (N1-8 and N1-9) with disseminated sulphide ores have less radiogenic Hf-isotope values (e.g., mean ɛHf6.2 ± 1.4, 5.9 ± 2.3, 6.4 ± 1.2 and 4.9±1.4, respectively). The least radiogenic values (ɛHffrom -2.9 to +2.3, mean ɛHf = 0.1 ± 1.9) are recorded in gabbro-diorite from the upper part of intrusion. The baddeleyite from olivine-free gabbro has the narrowest range of ɛHf values (e.g. 6.8-8.4), with a mean of ɛHfof 7.6 ± 0.8, closely matching that of zircon (mean ɛHf= 7.3 ± 1.1). Zircons from the leucogabbro that hosts the low-sulphide horizon (N1-3), and ultramafic and taxitic-textured lithologies with disseminated sulphide ores (N1-7, N1-8 and N1-9) have less radiogenic ɛHf values than those in barren lithologies. The Hf-isotope data for zircons from ore-bearing rocks thus suggest that the Noril'sk magmas represent mixing between a juvenile source equivalent to the Depleted Mantle and a

  4. Hf isotope evidence for effective impact melt homogenisation at the Sudbury impact crater, Ontario, Canada

    NASA Astrophysics Data System (ADS)

    Kenny, Gavin G.; Petrus, Joseph A.; Whitehouse, Martin J.; Daly, J. Stephen; Kamber, Balz S.

    2017-10-01

    We report on the first zircon hafnium-oxygen isotope and trace element study of a transect through one of the largest terrestrial impact melt sheets. The differentiated melt sheet at the 1.85 Ga, originally ca. 200 km in diameter Sudbury impact crater, Ontario, Canada, yields a tight range of uniform zircon Hf isotope compositions (εHf(1850) of ca. -9 to -12). This is consistent with its well-established crustal origin and indicates differentiation from a single melt that was initially efficiently homogenised. We propose that the heterogeneity in other isotopic systems, such as Pb, in early-emplaced impact melt at Sudbury is associated with volatility-related depletion during the impact cratering process. This depletion leaves the isotopic systems of more volatile elements more susceptible to contamination during post-impact assimilation of country rock, whereas the systems of more refractory elements preserve initial homogeneities. Zircon oxygen isotope compositions in the melt sheet are also restricted in range relative to those in the impacted target rocks. However, they display a marked offset approximately one-third up the melt sheet stratigraphy that is interpreted to be a result of post-impact assimilation of 18O-enirched rocks into the base of the cooling impact melt. Given that impact cratering was a more dominant process in the early history of the inner Solar System than it is today, and the possibility that impact melt sheets were sources of ex situ Hadean zircon grains, these findings may have significance for the interpretation of the early zircon Hf record. We speculate that apparent εHf-time arrays observed in the oldest terrestrial and lunar zircon datasets may be related to impact melting homogenising previously more diverse crust. We also show that spatially restricted partial melting of rocks buried beneath the superheated impact melt at Sudbury provided a zircon crystallising environment distinct to the impact melt sheet itself.

  5. Meteorite zircon constraints on the bulk Lu-Hf isotope composition and early differentiation of the Earth.

    PubMed

    Iizuka, Tsuyoshi; Yamaguchi, Takao; Hibiya, Yuki; Amelin, Yuri

    2015-04-28

    Knowledge of planetary differentiation is crucial for understanding the chemical and thermal evolution of terrestrial planets. The (176)Lu-(176)Hf radioactive decay system has been widely used to constrain the timescales and mechanisms of silicate differentiation on Earth, but the data interpretation requires accurate estimation of Hf isotope evolution of the bulk Earth. Because both Lu and Hf are refractory lithophile elements, the isotope evolution can be potentially extrapolated from the present-day (176)Hf/(177)Hf and (176)Lu/(177)Hf in undifferentiated chondrite meteorites. However, these ratios in chondrites are highly variable due to the metamorphic redistribution of Lu and Hf, making it difficult to ascertain the correct reference values for the bulk Earth. In addition, it has been proposed that chondrites contain excess (176)Hf due to the accelerated decay of (176)Lu resulting from photoexcitation to a short-lived isomer. If so, the paradigm of a chondritic Earth would be invalid for the Lu-Hf system. Herein we report the first, to our knowledge, high-precision Lu-Hf isotope analysis of meteorite crystalline zircon, a mineral that is resistant to metamorphism and has low Lu/Hf. We use the meteorite zircon data to define the Solar System initial (176)Hf/(177)Hf (0.279781 ± 0.000018) and further to identify pristine chondrites that contain no excess (176)Hf and accurately represent the Lu-Hf system of the bulk Earth ((176)Hf/(177)Hf = 0.282793 ± 0.000011; (176)Lu/(177)Hf = 0.0338 ± 0.0001). Our results provide firm evidence that the most primitive Hf in terrestrial zircon reflects the development of a chemically enriched silicate reservoir on Earth as far back as 4.5 billion years ago.

  6. Meteorite zircon constraints on the bulk Lu−Hf isotope composition and early differentiation of the Earth

    PubMed Central

    Iizuka, Tsuyoshi; Yamaguchi, Takao; Hibiya, Yuki; Amelin, Yuri

    2015-01-01

    Knowledge of planetary differentiation is crucial for understanding the chemical and thermal evolution of terrestrial planets. The 176Lu−176Hf radioactive decay system has been widely used to constrain the timescales and mechanisms of silicate differentiation on Earth, but the data interpretation requires accurate estimation of Hf isotope evolution of the bulk Earth. Because both Lu and Hf are refractory lithophile elements, the isotope evolution can be potentially extrapolated from the present-day 176Hf/177Hf and 176Lu/177Hf in undifferentiated chondrite meteorites. However, these ratios in chondrites are highly variable due to the metamorphic redistribution of Lu and Hf, making it difficult to ascertain the correct reference values for the bulk Earth. In addition, it has been proposed that chondrites contain excess 176Hf due to the accelerated decay of 176Lu resulting from photoexcitation to a short-lived isomer. If so, the paradigm of a chondritic Earth would be invalid for the Lu−Hf system. Herein we report the first, to our knowledge, high-precision Lu−Hf isotope analysis of meteorite crystalline zircon, a mineral that is resistant to metamorphism and has low Lu/Hf. We use the meteorite zircon data to define the Solar System initial 176Hf/177Hf (0.279781 ± 0.000018) and further to identify pristine chondrites that contain no excess 176Hf and accurately represent the Lu−Hf system of the bulk Earth (176Hf/177Hf = 0.282793 ± 0.000011; 176Lu/177Hf = 0.0338 ± 0.0001). Our results provide firm evidence that the most primitive Hf in terrestrial zircon reflects the development of a chemically enriched silicate reservoir on Earth as far back as 4.5 billion years ago. PMID:25870298

  7. A hidden Late Cretaceous arc and subsequent magmatic events in the Caucasus-Iran-Anatolia (CIA) orogenic belt: Detrital zircon U-Pb and Hf isotopic constraints

    NASA Astrophysics Data System (ADS)

    Tien, C. Y.; Lin, Y. C.; Chu, M. F.; Chung, S. L.; Bi˙ngöl, A. F.

    2017-12-01

    The Caucasus-Iran-Anatolia (CIA) orogenic belt formed by "Turkic-type orogeny" consists mainly of subduction-accretion complexes following the collision between Eurasia and Arabia and the closure of Neotethy. This study reports U-Pb and Hf isotopic data of detrital zircon separates from five Eocene to mid-Miocene sandstone samples from Divrigi and Duranlar in the west to the Mus basin in the east, all locating in the northern part of the Bitlis-Zagros suture zone. The U-Pb age data suggest four main magmatic episodes: (1) 100-70 Ma, (2) 60-40 Ma, (3) 30 Ma, and (4) 15 Ma. The Late Cretaceous zircons recovered mainly from the Mus basin are marked by a significant Hf isotopic variation over time, with ɛHf(T) values dropping from +15 to -10. Zircons from the second and third episodes show spatial variations in isotopic compositions, with positive ɛHf(T) values (+10 to +5) in the Mus basin and heterogeneous ɛHf(T) values (+10 to -10) in the west. The fourth and youngest episode of zircons, mainly from Duranlar area, shows uniform ɛHf(T) values around +5. We attribute the Late Cretaceous episode of zircons to the broadly coeval Elazig arc magmatism that, according to our counterpart study, occurred as a short-lived, intra-oceanic arc system by subduction initiation after the formation of Neotethyan ophiolites in the region. Moreover, we argue that this Late Cretaceous arc system may have existed more widely within the southern branch of Neothethys than that suggested by present-day outcrops. The dramatic change in Hf isotopic composition from 100 to 70 Ma, also observed in the rock record by our counterpart study, may be interpreted as a result of subduction to accretion processes. The remaining three episodes of zircons are related to younger stages of magmatism within or around the suture zone that remains poorly studied. Our results indicate that detrital zircon is a useful tool to uncover "hidden" magmatic records in the CIA and other "Turkic-type" orogenic

  8. Uncoupled O and Hf isotopic systems in zircon from the contrasting granite suites of the New England Orogen, eastern Australia: Implications for studies of Phanerozoic magma genesis

    NASA Astrophysics Data System (ADS)

    Jeon, Heejin; Williams, Ian S.; Bennett, Vickie C.

    2014-12-01

    The Permo-Triassic granites of the New England Orogen, eastern Australia, were emplaced into a volcanic arc complex accreted to the eastern Gondwana margin in the Late Devonian or Early Carboniferous. Zircon U-Pb dating shows that the S-type Hillgrove (∼297 Ma) and Bundarra (∼287 Ma) Supersuites predated intrusion of the I-type Moonbi Supersuite (∼250 Ma) by up to 50 Ma. The high δ18Ozrn of the S-type granites (10.0-11.5‰), and range of U-Pb ages (∼370-300 Ma) and δ18Ozrn (∼5-10‰) of their inherited zircon cores, show that their source rocks were predominantly weathered Carboniferous volcaniclastics, the youngest deposited < 25 Ma before the granites were emplaced. In contrast, the lower δ18Ozrn (6.9-7.8‰) and lack of inheritance in the I-type granites is consistent with a zircon poor, more juvenile source, probably a mafic igneous underplate mixed with a small amount of volcanogenic and/or oceanic sediment. Despite the differences in source materials, the εHf(t) values of all granites, both S- and I-type, are similar (+5.0 ± 0.5 cf. +5.9 ± 0.5), consistent with both the mafic and sedimentary components in the granite sources being relatively young and similar in Hf isotopic composition at the time of granite genesis. In young, isotopically juvenile orogens, the O isotopic composition of well-dated igneous and inherited zircon can be a much more sensitive indicator of petrogenetic processes than the zircon Hf isotopic compositions alone.

  9. Paleoclimate Reconstruction at Lamanai, Belize Using Oxygen-Isotope Tropical Dendrochronology

    NASA Astrophysics Data System (ADS)

    Prentice, A.; Webb, E. A.; White, C. D.; Graham, E.

    2009-05-01

    Tropical dendrochronology can be complicated because many trees growing in these areas lack distinct visible annual rings. However, the oxygen-isotope composition of wood growing in tropical regions can provide a record of seasonal fluctuations in the amount of precipitation even when visible rings are absent. Variations in the oxygen-isotope compositions of cellulose as the trees grow can be related to the relative timing of wet and dry seasons and used to identify periods of drought. In this study, the oxygen-isotope composition was determined for cellulose extracted from living trees at the site of Lamanai, Belize to assess the variation in oxygen-isotope values that result from heterogeneity within individual tree rings and seasonal fluctuations in amount of precipitation. In temperate regions, the latewood rings that form during periods of reduced growth are traditionally selected for oxygen-isotope analysis of cellulose because their oxygen-isotope compositions are more directly influenced by climate and precipitation during the growing season. However, in tropical isotope dendrochronology, when visible rings are present, detailed sampling of both the light coloured earlywood and the denser latewood is required. At Lamanai, a seasonal signal was evident in the oxygen- isotope composition of the cellulose when tree rings were sectioned in very small increments (approximately every mm), sub-sampling both earlywood and latewood. However, the visible rings did not always correspond with minimum or maximum oxygen-isotope values. As a result, the amplitude of the oxygen-isotope signal obtained by considering only latewood samples is smaller than that obtained from fine-increment sampling. Hence, the oxygen-isotope values of latewood samples alone did not provide accurate data for climate reconstruction. Multiple series of latewood samples extracted from different cross-sections of the same tree did not consistently show the same trends in oxygen isotope values

  10. An Integrated Analytical Approach to Obtaining Reliable U-Pb and Hf Isotopic Data from Complex (>3.9 to 3.3 Ga) Zircon from the Acasta Gneiss Complex

    NASA Astrophysics Data System (ADS)

    Bauer, A.; Bowring, S. A.; Vervoort, J. D.; Fisher, C. M.

    2014-12-01

    The Acasta Gneiss Complex (AGC) of northwestern Canada preserves some of Earth's oldest granitic crust (>4.03 Ga) and thereby contains important insight into crust forming processes on the early Earth. In general, rocks of the AGC have undergone a complex history of metamorphism and deformation (Archean and Paleoproterozoic)1,2, and, as a consequence, the zircons retain a complex history including inheritance, magmatic and metamorphic overgrowths, recrystallization, and multi-stage Pb loss. Previously published Hf isotopic data on zircons show within sample variability in excess of analytical uncertainty2,3,4. In order to assess the meaning and significance of this apparent isotopic variability, we are using two different methods to obtain coupled U-Pb and Lu-Hf isotopic data in zircon from a suite of rocks ranging in age from ca. > 3.9 Ga to 3.3 Ga. To obtain these data from the same volume of zircon, our approach involves: 1) split stream LA-ICPMS for U-Pb and Lu-Hf; 2) mechanical isolation of zircon domains for chemical abrasion and ID-TIMS U-Pb analyses and solution ICPMS for Lu-Hf recovered from U-Pb ion exchange chromatography. The deconvolution of complex histories requires this integrated approach and permits us to take advantage of both high spatial resolution and highest precision measurements to ultimately decipher the age and isotopic composition of discrete domains of multi-phase zircon. We demonstrate our approach with both relatively simple and complex grain populations in an attempt to understand within and between grain heterogeneity. The samples with the simplest zircon systematics have increasingly negative ɛHf from oldest to youngest, consistent with involvement of 4.0 Ga or older crust in later generations; also, none of our samples have been derived solely from strongly depleted sources. The presence of intra-zircon variability within samples from the AGC reflects a complex history of magmatic additions requiring melting/assimilation of older

  11. Decoding a protracted zircon geochronological record in ultrahigh temperature granulite, and persistence of partial melting in the crust, Rogaland, Norway

    NASA Astrophysics Data System (ADS)

    Laurent, Antonin T.; Bingen, Bernard; Duchene, Stephanie; Whitehouse, Martin J.; Seydoux-Guillaume, Anne-magali; Bosse, Valerie

    2018-04-01

    This contribution evaluates the relation between protracted zircon geochronological signal and protracted crustal melting in the course of polyphase high to ultrahigh temperature (UHT; T > 900 °C) granulite facies metamorphism. New U-Pb, oxygen isotope, trace element, ion imaging and cathodoluminescence (CL) imaging data in zircon are reported from five samples from Rogaland, South Norway. The data reveal that the spread of apparent age captured by zircon, between 1040 and 930 Ma, results both from open-system growth and closed-system post-crystallization disturbance. Post-crystallization disturbance is evidenced by inverse age zoning induced by solid-state recrystallization of metamict cores that received an alpha dose above 35 × 1017 α g-1. Zircon neocrystallization is documented by CL-dark domains displaying O isotope open-system behaviour. In UHT samples, O isotopic ratios are homogenous (δ18O = 8.91 ± 0.08‰), pointing to high-temperature diffusion. Scanning ion imaging of these CL-dark domains did not reveal unsupported radiogenic Pb. The continuous geochronological signal retrieved from the CL-dark zircon in UHT samples is similar to that of monazite for the two recognized metamorphic phases (M1: 1040-990 Ma; M2: 940-930 Ma). A specific zircon-forming event is identified in the orthopyroxene and UHT zone with a probability peak at ca. 975 Ma, lasting until ca. 955 Ma. Coupling U-Pb geochronology and Ti-in-zircon thermometry provides firm evidence of protracted melting lasting up to 110 My (1040-930 Ma) in the UHT zone, 85 My (ca. 1040-955 Ma) in the orthopyroxene zone and some 40 My (ca. 1040-1000 Ma) in the regional basement. These results demonstrate the persistence of melt over long timescales in the crust, punctuated by two UHT incursions.

  12. Juvenile crust formation in the Zimbabwe Craton deduced from the O-Hf isotopic record of 3.8-3.1 Ga detrital zircons

    NASA Astrophysics Data System (ADS)

    Bolhar, Robert; Hofmann, Axel; Kemp, Anthony I. S.; Whitehouse, Martin J.; Wind, Sandra; Kamber, Balz S.

    2017-10-01

    Hafnium and oxygen isotopic compositions measured in-situ on U-Pb dated zircon from Archaean sedimentary successions belonging to the 2.9-2.8 Ga Belingwean/Bulawayan groups and previously undated Sebakwian Group are used to characterize the crustal evolution of the Zimbabwe Craton prior to 3.0 Ga. Microstructural and compositional criteria were used to minimize effects arising from Pb loss due to metamorphic overprinting and interaction with low-temperature fluids. 207Pb/206Pb age spectra (concordance >90%) reveal prominent peaks at 3.8, 3.6, 3.5, and 3.35 Ga, corresponding to documented geological events, both globally and within the Zimbabwe Craton. Zircon δ18O values from +4 to +10‰ point to both derivation from magmas in equilibrium with mantle oxygen and the incorporation of material that had previously interacted with water in near-surface environments. In εHf-time space, 3.8-3.6 Ga grains define an array consistent with reworking of a mafic reservoir (176Lu/177Hf ∼0.015) that separated from chondritic mantle at ∼3.9 Ga. Crustal domains formed after 3.6 Ga depict a more complex evolution, involving contribution from chondritic mantle sources and, to a lesser extent, reworking of pre-existing crust. Protracted remelting was not accompanied by significant mantle depletion prior to 3.35 Ga. This implies that early crust production in the Zimbabwe Craton did not cause complementary enriched and depleted reservoirs that were tapped by later magmas, possibly because the volume of crust extracted and stabilised was too small to influence (asthenospheric) mantle isotopic evolution. Growth of continental crust through pulsed emplacement of juvenile (chondritic mantle-derived) melts, into and onto the existing cratonic nucleus, however, involved formation of complementary depleted subcontinental lithospheric mantle since the early Archaean, indicative of strongly coupled evolutionary histories of both reservoirs, with limited evidence for recycling and lateral

  13. Low {delta}{sup 18}O magma, Isle of Skye, Scotland: Evidence from zircons

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gilliam, C.E.; Valley, J.W.

    1997-12-01

    Zircons in Tertiary granitic rocks from the Isle of Skye, Scotland were resistant to measurable oxygen isotope exchange during intense hydrothermal activity in the subvolcanic environment. Five granite bodies from the Western Red Hills complex were investigated; four have {sup 18}O (Zrc) = 4.1 {+-} 0.2{per_thousand} (VSMOW) while the fifth, which intruded before major cauldron subsidence, is 2{per_thousand} lower. Zircons from Lewisian gneiss are visually and isotopically distinct indicating that zircons in the granite are not xenocrysts from the Lewisian basement. Analysis of different magnetic and size fractions of zircon shows no significant correlation to {delta}{sup 18}O supporting the conclusionmore » that these values represent the true magmatic compositions and that the Western Red Hills granites intruded as low {delta}{sup 18}O magmas with a whole rock {delta}{sup 18}O {le} 6.0%. Quartz separates from four granites are close to the calculated magmatic values in {delta}{sup 18}O, but in the fifth, values are 5% lower indicating variable exchange of quartz with low {delta}{sup 18}O heated meteoric waters. These results might be explained by magmatic interaction with hydrothermally altered crust early in the evolution of the granites, before crystallization of zircon, followed by interaction with later hydrothermal fluids. Alternatively, independent evidence for low {delta}{sup 18}O mafic magmatism in NW Scotland suggests the presence of large quantities of low {delta}{sup 18}O subducted ocean crust in the subcontinental lithosphere that could contaminate or be the source of low {delta}{sup 18}O mantle-derived melts. 31 refs., 4 figs., 1 tab.« less

  14. Evidence of extinct 244Pu in ancient terrestrial zircons

    NASA Astrophysics Data System (ADS)

    Harrison, T. M.; Turner, G.; Holland, G.; Gilmour, J. D.; Mojzsis, S. J.

    2003-04-01

    could result from loss of Xe after 4.0 Ga or represent U-Pu fractionation. We are currently repeating the exercise with older zircons and intend to search for correlations with REE patterns, oxygen isotopes, and the degree of U-Pb concordance, and to investigate the thermal release characteristics of the xenon. In addition to constraining the terrestrial Pu/U ratio these investigations may allow us to characterise the geochemical behaviour of Pu as a constraint on the earliest crust forming processes.

  15. Oxygen isotope corrections for online δ34S analysis

    USGS Publications Warehouse

    Fry, B.; Silva, S.R.; Kendall, C.; Anderson, R.K.

    2002-01-01

    Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

  16. A latitudinal study of oxygen isotopes within horsehair

    NASA Astrophysics Data System (ADS)

    Thompson, E.; Bronk Ramsey, C.; McConnell, J. R.

    2016-12-01

    This study aims to explore the hypothesis that 'if oxygen isotope ratios deplete with decreasing temperature then a study of oxygen isotope ratios within horsehair from Oxfordshire to Iceland will show a latitudinal depletion gradient'. By looking at oxygen isotope values at different geographical positions, we can track the relationship with latitude and with different regional climate features. This will provide a firmer understanding of how to compare climate records from different locations. Additionally, a comparison of the horse breeds from this study to those analysed within previous studies will create an even better understanding of the intra-species variation within the δ18O values of horsehair. A total of 24 horses were sampled on the 7th March from Thordale Stud in Shetland, the Icelandic Food And Veterinary Authority in Iceland, the Exmoor Pony Centre in Exmoor and the Pigeon House Equestrian Centre in Oxfordshire. By starting the sampling process from the most recent growth at the follicle, the sampling date becomes a chronological marker, temporally fixing the first sample within a sequential set of data points extending for one year or longer, depending on the length of each individual hair. The samples were analysed for oxygen isotope values using an IRMS coupled within a Sercon HTEA. Preliminary results show a latitudinal gradient is evident on comparison between the locations, consistent with the findings of Darling and Talbot's study of fresh water isotopes in the British Isles (2003). These results support the hypothesis, showing that a study of oxygen isotope ratios within horse hair from Oxfordshire to Iceland showing a latitudinal depletion gradient, consistent with a depletion of oxygen isotope ratios due to decreasing temperatures. Darling, W. and Talbot, J. (2003). The O and H stable isotope composition of freshwaters in the British Isles. 1. Rainfall. Hydrol. Earth System Science, 7(2), pp.163-181.

  17. Is Myanmar jadeitite of Jurassic age? A result from incompletely recrystallized inherited zircon

    NASA Astrophysics Data System (ADS)

    Yui, Tzen-Fu; Fukoyama, Mayuko; Iizuka, Yoshiyuki; Wu, Chao-Ming; Wu, Tsai-Way; Liou, J. G.; Grove, Marty

    2013-02-01

    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 (< 0.1), small Ce anomaly (Ce/Ce* = < 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

  18. Using Triple Oxygen Isotope Analyses of Biogenic Carbonate to Reconstruct Early Triassic Ocean Oxygen Isotopic Values and Temperatures

    NASA Astrophysics Data System (ADS)

    Gibbons, J. A.; Sharp, Z. D.; Atudorei, V.

    2017-12-01

    The calcite-water triple oxygen isotope fractionation is used to determine isotopic equilibrium and ancient ocean oxygen isotopic values and temperatures. Unlike conventional δ18O analysis where the formation water's isotopic value is assumed, paired δ17O-δ18O measurements allow for the water's isotopic composition to be calculated because there is only one unique solution for equilibrium fractionation using Δ17O-δ18O values (where Δ17O=δ17O-0.528δ18O). To a first approximation, the calcite-water equilibrium fractionation factor, θ (where θ=ln17α/ln18α), varies with temperature by 0.00001/°. The calcite-water equilibrium fractionation line was determined at two temperatures, 30° and 0°, by using modern carbonate samples that formed in ocean water with a δ18O value of 0‰. The θ values for the 30° and 0° samples are 0.52515 and 0.52486, respectively. Oxygen values were measured using complete fluorination in nickel tubes with BrF5 as the reaction reagent. We calibrated all oxygen values to the SMOW-SLAP scale by measuring SMOW, SLAP, San Carlos olivine, NBS-18, NBS-19, and PDB. The triple oxygen isotope calcite-water equilibrium fractionation line was applied to well preserved Early Triassic ammonite shells from the Western United States. Based on paired δ17O-δ18O measurements, the samples did not form in equilibrium with an ice-free ocean with an oxygen isotopic value of -1‰ or the modern ocean value of 0‰. Assuming the calcite is still primary and formed in equilibrium with the ocean water, our data indicate that the δ18O value of the ocean in the early Triassic was 3-5‰ lower than modern. Samples from the Smithian thermal maximum formed in water 10° warmer than samples from after the thermal maximum. Paired δ17O-δ18O measurements of pristine ancient carbonates may provide a better understanding of past ocean conditions during climate change events.

  19. Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

    PubMed

    Yurimoto, H; Ito, M; Nagasawa, H

    1998-12-04

    A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope composition (approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

  20. Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

    PubMed

    Yurimoto; Ito; Nagasawa

    1998-12-04

    A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

  1. Evolution of the depleted mantle and growth of the continental crust: improving on the imperfect detrital zircon record

    NASA Astrophysics Data System (ADS)

    Vervoort, J. D.; Kemp, A. I. S.; Patchett, P. J.

    2012-04-01

    One of the basic tenets of terrestrial geochemistry is that the continental crust has been extracted from the mantle leaving the latter depleted in incompatible elements. Nd and Hf isotopes have long shown that this process has been an essential feature of the Earth throughout its history. There is wide agreement on the general nature of this process, but the details of the isotopic record—and their implications for the depletion of the mantle and the extraction of continental crust—remain debated. Recently, much attention has been given to detrital zircons in both modern and ancient sediments. An advantage of this approach is the integration of the crystallization history of the zircon from the U-Pb chronometer with its Hf isotopic composition, which can provide important information on whether the zircons have been derived from juvenile or reworked crust. One essential requirement in this approach, however, is to unambiguously determine the crystallization ages of the zircons. We suggest that this represents an important—but generally ignored—source of uncertainty in the Hf isotopic record from detrital zircons. The quality filter most often used to assess the integrity of zircon U-Pb systematics is concordance; if a zircon is concordant, it is assumed that the U-Pb age is accurate. A concordance filter is less effective in old zircons, however, because ancient Pb loss, viewed today, parallels concordia. Without the benefit from the geological context of the host rock to the zircons, it is impossible to unambiguously determine it true crystallization age. Ancient Pb loss in zircons produces an apparent age less than the true magmatic age. The initial Hf isotopic composition of these zircons, as a result, will be calculated at the wrong age and will be anomalously low (by ~2.2 epsilon Hf units per 0.1 Ga). Hf model ages, calculated from these parameters, will be artificially old and spurious. The combination of unradiogenic Hf and Hf model ages > U-Pb ages

  2. The oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Brown, B. Alex

    The properties of the oxygen isotopes provide diverse examples of progress made in experiments and theory. This chain of isotopes has been studied from beyond the proton drip line in 12O to beyond the neutron drip line in 25,26O. This short survey starts with the microscopic G matrix approach for 18O of Kuo and Brown in the 1960’s and shows how theory has evolved. The nuclear structure around the doubly-magic nucleus 24O is particularly simple in terms of the nuclear shell model. The nuclear structure around the doubly-magic nucleus 16O exhibits the coexistence of single-particle and collective structure.

  3. The oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Alex Brown, B.

    The properties of the oxygen isotopes provide diverse examples of progress made in experiments and theory. This chain of isotopes has been studied from beyond the proton drip line in 12O to beyond the neutron drip line in 25,26O. This short survey starts with the microscopic G matrix approach for 18O of Kuo and Brown in the 1960's and shows how theory has evolved. The nuclear structure around the doubly-magic nucleus 24O is particularly simple in terms of the nuclear shell model. The nuclear structure around the doubly-magic nucleus 16O exhibits the coexistence of single-particle and collective structure.

  4. Testing the reliability of information extracted from ancient zircon

    NASA Astrophysics Data System (ADS)

    Kielman, Ross; Whitehouse, Martin; Nemchin, Alexander

    2015-04-01

    Studies combining zircon U-Pb chronology, trace element distribution as well as O and Hf isotope systematics are a powerful way to gain understanding of the processes shaping Earth's evolution, especially in detrital populations where constraints from the original host are missing. Such studies of the Hadean detrital zircon population abundant in sedimentary rocks in Western Australia have involved analysis of an unusually large number of individual grains, but also highlighted potential problems with the approach, only apparent when multiple analyses are obtained from individual grains. A common feature of the Hadean as well as many early Archaean zircon populations is their apparent inhomogeneity, which reduces confidence in conclusions based on studies combining chemistry and isotopic characteristics of zircon. In order to test the reliability of information extracted from early Earth zircon, we report results from one of the first in-depth multi-method study of zircon from a relatively simple early Archean magmatic rock, used as an analogue to ancient detrital zircon. The approach involves making multiple SIMS analyses in individual grains in order to be comparable to the most advanced studies of detrital zircon populations. The investigated sample is a relatively undeformed, non-migmatitic ca. 3.8 Ga tonalite collected a few kms south of the Isua Greenstone Belt, southwest Greenland. Extracted zircon grains can be combined into three different groups based on the behavior of their U-Pb systems: (i) grains that show internally consistent and concordant ages and define an average age of 3805±15 Ma, taken to be the age of the rock, (ii) grains that are distributed close to the concordia line, but with significant variability between multiple analyses, suggesting an ancient Pb loss and (iii) grains that have multiple analyses distributed along a discordia pointing towards a zero intercept, indicating geologically recent Pb-loss. This overall behavior has

  5. Hydrogen diffusion in Zircon

    NASA Astrophysics Data System (ADS)

    Ingrin, Jannick; Zhang, Peipei

    2016-04-01

    Hydrogen mobility in gem quality zircon single crystals from Madagascar was investigated through H-D exchange experiments. Thin slices were annealed in a horizontal furnace flushed with a gas mixture of Ar/D2(10%) under ambient pressure between 900 ° C to 1150 ° C. FTIR analyses were performed on oriented slices before and after each annealing run. H diffusion along [100] and [010] follow the same diffusion law D = D0exp[-E /RT], with log D0 = 2.24 ± 1.57 (in m2/s) and E = 374 ± 39 kJ/mol. H diffusion along [001] follows a slightly more rapid diffusion law, with log D0 = 1.11 ± 0.22 (in m2/s) and E = 334 ± 49 kJ/mol. H diffusion in zircon has much higher activation energy and slower diffusivity than other NAMs below 1150 ° C even iron-poor garnets which are known to be among the slowest (Blanchard and Ingrin, 2004; Kurka et al. 2005). During H-D exchange zircon incorporates also deuterium. This hydration reaction involves uranium reduction as it is shown from the exchange of U5+ and U4+ characteristic bands in the near infrared region during annealing. It is the first time that a hydration reaction U5+ + OH- = U4+ + O2- + 1/2H2, is experimentally reported. The kinetics of deuterium incorporation is slightly slower than hydrogen diffusion, suggesting that the reaction is limited by hydrogen mobility. Hydrogen isotopic memory of zircon is higher than other NAMs. Zircons will be moderately retentive of H signatures at mid-crustal metamorphic temperatures. At 500 ° C, a zircon with a radius of 300 μm would retain its H isotopic signature over more than a million years. However, a zircon is unable to retain this information for geologically significant times under high-grade metamorphism unless the grain size is large enough. Refrences Blanchard, M. and Ingrin, J. (2004) Hydrogen diffusion in Dora Maira pyrope. Physics and Chemistry of Minerals, 31, 593-605. Kurka, A., Blanchard, M. and Ingrin, J. (2005) Kinetics of hydrogen extraction and deuteration in

  6. Isotopic-Geochemical Features of Zircon and Its Significance for Reconstructing the Geological History of Paleoarchean Granulites in the Ukrainian Shield

    NASA Astrophysics Data System (ADS)

    Lobach-Zhuchenko, S. B.; Kaulina, T. V.; Lokhov, K. I.; Egorova, Yu. S.; Skublov, S. G.; Galankina, O. L.; Antonov, A. V.

    2017-12-01

    This paper presents the results of a complex study (morphology of grains, internal texture in cathodoluminescence and backscattered electrons, microprobe analysis, Lu-Hf data) of five groups (generations) of zircon crystals differing in age and separated from the same granulite sample pertaining to the Bug River Complex of the Ukrainian Shield. The data show that the oldest zircon crystals of the first group (3.74 Ga in age) are xenogenic and initially crystallized from a granitic melt; zircon of the second group (3.66 Ga) formed from a mafic melt contaminated by felsic country rocks. The third group (3.59 Ga) is represented by zircons that formed about 100 Ma later than the second group under conditions of granulite-facies metamorphism and with the participation of fluid-saturated anatectic melt. Two Paleoproterozoic zircon groups ( 2.5 and 2.1 Ga) also formed under granulite-facies conditions; to a certain extent, their structure and composition were controlled by fluid. The geochemistry of all zircon generations provides evidence for their crystallization in the continental crust, but from the sources differing in the contribution of mantle-derived material and in oxygen fugacity.

  7. Interpreting U-Pb data from primary and secondary features in lunar zircon

    NASA Astrophysics Data System (ADS)

    Grange, M. L.; Pidgeon, R. T.; Nemchin, A. A.; Timms, N. E.; Meyer, C.

    2013-01-01

    In this paper, we describe primary and secondary microstructures and textural characteristics found in lunar zircon and discuss the relationships between these features and the zircon U-Pb isotopic systems and the significance of these features for understanding lunar processes. Lunar zircons can be classified according to: (i) textural relationships between zircon and surrounding minerals in the host breccias, (ii) the internal microstructures of the zircon grains as identified by optical microscopy, cathodoluminescence (CL) imaging and electron backscattered diffraction (EBSD) mapping and (iii) results of in situ ion microprobe analyses of the Th-U-Pb isotopic systems. Primary zircon can occur as part of a cogenetic mineral assemblage (lithic clast) or as an individual mineral clast and is unzoned, or has sector and/or oscillatory zoning. The age of primary zircon is obtained when multiple ion microprobe analyses across the polished surface of the grain give reproducible and essentially concordant data. A secondary set of microstructures, superimposed on primary zircon, include localised recrystallised domains, localised amorphous domains, crystal-plastic deformation, planar deformation features and fractures, and are associated with impact processes. The first two secondary microstructures often yield internally consistent and close to concordant U-Pb ages that we interpret as dating impact events. Others secondary microstructures such as planar deformation features, crystal-plastic deformation and micro-fractures can provide channels for Pb diffusion and result in partial resetting of the U-Pb isotopic systems.

  8. Ti-in-Zircon Thermometer: Preliminary Results

    NASA Astrophysics Data System (ADS)

    Fu, B.; Cavosie, A. J.; Clechenko, C. C.; Fournelle, J.; Kita, N. T.; Lackey, J.; Page, F.; Wilde, S. A.; Valley, J. W.

    2005-12-01

    , permissive of low rutile activity. Peraluminous granites have lower whole-rock TiO2 content (0.02-0.21 wt.%) than metaluminous granites (0.54-0.91 wt.%), and both have similar zircon saturation temperatures (710-780°C). The low Ti content and apparent temperature in zircons from anorthosite and metagabbro (magmatic T = ca. 1000-1100°C) and the homogeneity of igneous zircon cores vs. metamorphic rims in metagabbro suggest that Ti content was reset during granulite-facies metamorphism (750°C, 1.0 Ga), in contrast to the current estimate of extremely low diffusivity of Ti in zircon. The Ti contents of >3.9 Ga Jack Hills detrital zircons are consistent with previously published data that were used to constrain magmatic temperature and thus the composition of unknown host rocks (W&H, 2005, Science 308:841). However, these values overlap those from both felsic and mafic rocks, and the Ti data are not sufficient to independently identify parent melt chemistry unless post-crystallization changes can be ruled out. The best evidence of pre-4 Ga evolved crust is provided by previously reported oxygen isotope ratios and felsic mineral inclusions in zircon (see Cavosie et al., 2005, EPSL 235:663).

  9. Hadean Crustal Processes Revealed from Oxygen Isotopes and U-Th-Pb Depth Profiling of Pre-4.0 Ga Detrital Zircons from Western Australia

    NASA Technical Reports Server (NTRS)

    Trail, D.; Mojzsis, S. J.; Harrison, T. M.

    2005-01-01

    Because physical and chemical processes of the past are determined from analysis of a preserved geologic record, little is known about terrestrial crustal processes of the first 500 Ma during the so-called Hadean Eon. What is known from direct measurements has been derived almost exclusively from the study of greater than 4.0 Ga detrital zircons from the Jack Hills, Western Australia. The geochemistry of these zircons has direct application to understanding the origin and evolution of the rocks during the Hadean because: (i) U-Th-Pb age determinations by ion microprobe suggests the presence of crust as early as 4.37 Ga, or shortly after lunar formation; (ii) high-resolution U-Th-Pb zircon depth profiles reported here reveal several episodes of zircon growth in the Hadean previously unrecognized; (iii) core regions of pre-4.0 Ga zircons with igneous compositions are enriched in O-18 and contain metaluminous and peraluminous mineral inclusions, both features indicative of S-type grainitod protoliths. Study of these ancient zircons provides a unique window into the first half billion years that permits assessment of the potential of the Hadean Earth to host an emergent biosphere.

  10. Post‐mortem oxygen isotope exchange within cultured diatom silica

    PubMed Central

    Sloane, Hilary J.; Rickaby, Rosalind E.M.; Cox, Eileen J.; Leng, Melanie J.

    2017-01-01

    Rationale Potential post‐mortem alteration to the oxygen isotope composition of biogenic silica is critical to the validity of palaeoclimate reconstructions based on oxygen isotope ratios (δ18O values) from sedimentary silica. We calculate the degree of oxygen isotope alteration within freshly cultured diatom biogenic silica in response to heating and storing in the laboratory. Methods The experiments used freshly cultured diatom silica. Silica samples were either stored in water or dried at temperatures between 20 °C and 80 °C. The mass of affected oxygen and the associated silica‐water isotope fractionation during alteration were calculated by conducting parallel experiments using endmember waters with δ18O values of −6.3 to −5.9 ‰ and −36.3 to −35.0 ‰. Dehydroxylation and subsequent oxygen liberation were achieved by stepwise fluorination with BrF5. The 18O/16O ratios were measured using a ThermoFinnigan MAT 253 isotope ratio mass spectrometer. Results Significant alterations in silica δ18O values were observed, most notably an increase in the δ18O values following drying at 40–80 °C. Storage in water for 7 days between 20 and 80 °C also led to significant alteration in δ18O values. Mass balance calculations suggest that the amount of affected oxygen is positively correlated with temperature. The estimated oxygen isotope fractionation during alteration is an inverse function of temperature, consistent with the extrapolation of models for high‐temperature silica‐water oxygen isotope fractionation. Conclusions Routinely used preparatory methods may impart significant alterations to the δ18O values of biogenic silica, particularly when dealing with modern cultured or field‐collected material. The significance of such processes within natural aquatic environments is uncertain; however, there is potential that similar processes also affect sedimentary diatoms, with implications for the interpretation of biogenic silica‐hosted δ18O

  11. The oxygen isotope composition of Almahata Sitta

    NASA Astrophysics Data System (ADS)

    Rumble, Douglas; Zolensky, Michael E.; Friedrich, Jon M.; Jenniskens, Peter; Shaddad, Muawia H.

    2010-10-01

    Eleven fragments of the meteorite Almahata Sitta (AHS) have been analyzed for oxygen isotopes. The fragments were separately collected as individual stones from the meteorite's linear strewn field in the Nubian Desert. Each of the fragments represents a sample of a different and distinct portion of asteroid 2008 TC3. Ten of the fragments span the same range of values of δ18O, δ17O, and Δ17O, and follow the same trend along the carbonaceous chondrite anhydrous minerals (CCAM) line as monomict and polymict members of the ureilite family of meteorites. The oxygen isotope composition of fragment #25 is consistent with its resemblance petrographically to an H5 ordinary chondrite. Our results demonstrate that a single small asteroidal parent body, asteroid 2008 TC3, only 4 m in length, encompassed the entire range of variation in oxygen isotope compositions measured for monomict and polymict ureilites.

  12. Early Paleozoic tectonic reconstruction of Iran: Tales from detrital zircon geochronology

    NASA Astrophysics Data System (ADS)

    Moghadam, Hadi Shafaii; Li, Xian-Hua; Griffin, William L.; Stern, Robert J.; Thomsen, Tonny B.; Meinhold, Guido; Aharipour, Reza; O'Reilly, Suzanne Y.

    2017-01-01

    In this study we use detrital zircons to probe the Early Paleozoic history of NE Iran and evaluate the link between sediment sources and Gondwanan pre-Cadomian, Cadomian and younger events. U-Pb zircon ages and Hf isotopic compositions are reported for detrital zircons from Ordovician and Early Devonian sedimentary rocks from NE Iran. These clastic rocks are dominated by zircons with major age populations at 2.5 Ga, 0.8-0.6 Ga, 0.5 Ga and 0.5-0.4 Ga as well as a minor broad peak at 1.0 Ga. The source of 2.5 Ga detrital zircons is enigmatic; they may have been supplied from the Saharan Metacraton (or West African Craton) to the southwest or Afghanistan-Tarim to the east. The detrital zircons with age populations at 0.8-0.6 Ga probably originated from Cryogenian-Ediacaran juvenile igneous rocks of the Arabian-Nubian Shield; this inference is supported by their juvenile Hf isotopes, although some negative εHf (t) values suggest that other sources (such as the West African Craton) were also involved. The age peak at ca 0.5 Ga correlates with Cadomian magmatism reported from Iranian basement and elsewhere in north Gondwana. The variable εHf (t) values of Cadomian detrital zircons, resembling the εHf (t) values of zircons in magmatic Cadomian rocks from Iran and Taurides (Turkey), suggest an Andean-type margin and the involvement of reworked older crust in the generation of the magmatic rocks. The youngest age population at 0.5-0.4 Ga is interpreted to represent Gondwana rifting and the opening of Paleotethys, which probably started in Late Cambrian-Ordovician time. A combination of U-Pb dating and Hf-isotope data from Iran, Turkey and North Gondwana confirms that Iran and Turkey were parts of Gondwana at least until late Paleozoic time.

  13. Two types of gneisses associated with eclogite at Shuanghe in the Dabie terrane: carbon isotope, zircon U-Pb dating and oxygen isotope

    NASA Astrophysics Data System (ADS)

    Zheng, Yong-Fei; Gong, Bing; Zhao, Zi-Fu; Fu, Bin; Li, Yi-Liang

    2003-10-01

    There are two types of gneisses, biotite paragneiss and granitic orthogneiss, to be closely associated with UHP eclogite at Shuanghe in the Dabie terrane. Both concentration and isotope composition of bulk carbon in apatite and host gneisses were determined by the EA-MS online technique. Structural carbonate within the apatite was detected by the XRD and FTIR techniques. Significant 13C-depletion was observed in the apatite with δ13C values of -28.6‰ to -22.3‰ and the carbon concentrations of 0.70-4.98 wt.% CO 2 despite a large variation in δ18O from -4.3‰ to +10.6‰ for these gneisses. There is significant heterogeneity in both δ13C and δ18O within the gneisses on the scale of several tens meters, pointing to the presence of secondary processes after the UHP metamorphism. Considerable amounts of carbonate carbon occur in some of the gneisses that were also depleted in 13C primarily, but subjected to overprint of 13C-rich CO 2-bearing fluid after the UHP metamorphism. The 13C-depleted carbon in the gneisses is interpreted to be inherited from their precursors that suffered meteoric-hydrothermal alteration before plate subduction. Both low δ13C values and structural carbonate in the apatite suggest the presence of 13C-poor CO 2 in the UHP metamorphic fluid. The 13C-poor CO 2 is undoubtedly derived from oxidation of organic matter in the subsurface fluid during the prograde UHP metamorphism. Zircons from two samples of the granitic orthogneiss exhibit low δ18O values of -4.1‰ to -1.1‰, demonstrating that its protolith was significantly depleted in 18O prior to magma crystallization. U-Pb discordia datings for the 18O-depleted zircons yield Neoproterozoic ages of 724-768 Ma for the protolith of the granitic orthogneiss, consistent with protolith ages of most eclogites and orthogneisses from the other regions in the Dabie-Sulu orogen. Therefore, the meteoric-hydrothermal alteration is directly dated to occur at mid-Neoproterozoic, and may be correlated

  14. Oxygen isotope trajectories of crystallizing melts: Insights from modeling and the plutonic record

    NASA Astrophysics Data System (ADS)

    Bucholz, Claire E.; Jagoutz, Oliver; VanTongeren, Jill A.; Setera, Jacob; Wang, Zhengrong

    2017-06-01

    Elevated oxygen isotope values in igneous rocks are often used to fingerprint supracrustal alteration or assimilation of material that once resided near the surface of the earth. The δ18O value of a melt, however, can also increase through closed-system fractional crystallization. In order to quantify the change in melt δ18O due to crystallization, we develop a detailed closed-system fractional crystallization mass balance model and apply it to six experimentally- and naturally-determined liquid lines of descent (LLDs), which cover nearly complete crystallization intervals (melt fractions of 1 to <0.1). The studied LLDs vary from anhydrous tholeiitic basalts to hydrous high-K and calc-alkaline basalts and are characterized by distinct melt temperature-SiO2 trajectories, as well as, crystallizing phase relationships. Our model results demonstrate that melt fraction-temperature-SiO2 relationships of crystallizing melts, which are strongly a function of magmatic water content, will control the specific δ18O path of a crystallizing melt. Hydrous melts, typical of subduction zones, undergo larger increases in δ18O during early stages of crystallization due to their lower magmatic temperatures, greater initial increases in SiO2 content, and high temperature stability of low δ18O phases, such as oxides, amphibole, and anorthitic plagioclase (versus albite). Conversely, relatively dry, tholeiitic melts only experience significant increases in δ18O at degrees of crystallization greater than 80%. Total calculated increases in melt δ18O of 1.0-1.5‰ can be attributed to crystallization from ∼50 to 70 wt.% SiO2 for modeled closed-system crystallizing melt compositions. As an example application, we compare our closed system model results to oxygen isotope mineral data from two natural plutonic sequences, a relatively dry, tholeiitic sequence from the Upper and Upper Main Zones (UUMZ) of the Bushveld Complex (South Africa) and a high-K, hydrous sequence from the arc

  15. The Oxygen Isotopic Composition of the Sun

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.; Kallio, A.; Heber, V. S.; Jarzebinski, G.; Mao, P.; Coath, C.; Kunihiro, T.; Wiens, R. C.; Judith, A.; Burnett, D. S.

    2010-12-01

    An accurate and precise determination of the oxygen isotopic composition of the Sun is the highest priority scientific goal of the Genesis Mission [1] as such data would provide a baseline from which one could interpret the oxygen isotopic anomalies found at all spatial scales in inner solar system materials. We have measured oxygen isotope compositions of implanted solar wind in 40 spots along a radial traverse of the Genesis SiC target sample 60001 by depth profiling with the UCLA MegaSIMS [2]. Mass-dependent fractionation induced by the solar wind concentrator [3] ion optics was corrected by comparison of the concentrator 22Ne/20Ne with that measured in a bulk solar wind target (diamond-like carbon on Si, [4]). The solar wind captured at L1 has an isotopic composition of (δ18O, δ17O) ≈ (-99, -79)‰, a value which is far removed from the terrestrial mass fractionation line. Profiles from the central portion of the target, where solar concentrations are highest and background corrections minimal, yield a mean Δ17O = -28.3 ± 1.8 ‰ indicating that the Earth and other planetary materials from the inner solar system are highly depleted in 16O relative to the solar wind. A mass-dependent fractionation of ~ -20%/amu in the acceleration of solar wind is required if we hypothesize that the photospheric oxygen isotope value, which represents the bulk starting composition of the solar system, is on the 16O-mixing line characteristic of refractory phase in primitive meteorites [5]. With this assumption, our preferred value for the bulk solar oxygen isotope composition is δ18O ≈ δ17O ≈ -57‰. A mechanism is required to fractionate oxygen isotopes in a non-mass-dependent manner to deplete 16O by ~6 to 7% in the rocky materials of the solar nebula. As oxygen is the third most abundant element in the solar system, and the most abundant in the terrestrial planets, this mechanism must operate on a large scale. Isotope-selective photochemistry, for example as in

  16. Calcium and Oxygen Isotopic Composition of Calcium Carbonates

    NASA Astrophysics Data System (ADS)

    Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

    2016-04-01

    Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40

  17. Detrital Zircons Split Sibumasu in East Gondwana

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Chung, S. L.

    2017-12-01

    It is widely accepted that Sibumasu developed as a united terrane and originated from NW Australian margin in East Gondwana. Here we report new detrital zircon U-Pb-Hf isotopic data from Sumatra that, in combination with literature data, challenge and refute the above long-held view. In particular, the East and West Sumatra terranes share nearly identical Precambrian to Paleozoic detrital zircon age distributions and Hf isotopes, indicating a common provenance/origin for them. The Sumatra detrital zircons exhibit a prominent population of ca. 1170-1070 Ma, indistinguishable from those of the Lhasa and West Burma terranes, with detritus most probably sourcing from western Australia. By contrast, Sibuma (Sibumasu excluding Sumatra) detrital zircons display a prevailing population of ca. 980-935 Ma, strongly resembling those of the western Qiangtang terrane, with detrital materials most likely derived from Greater India and Himalayas. Such markedly distinct detrital zircon age profiles between Sumatra and Sibuma require disparate sources/origin for them, provoking disintegration of the widely-adopted, but outdated, term Sibumasu and thus inviting a new configuration of East Gondwana in the early Paleozoic, with Sumatra and West Burma lying outboard the Lhasa terrane in the NW Australian margin and Sibuma situated in the northern Greater Indian margin. More future investigations are needed to establish the precise rifting and drifting histories of Sumatra and Sibuma, as two separated terranes, during the breakup of Gondwana.

  18. Paragneiss zircon geochronology and trace element geochemistry, North Qaidam HP/UHP terrane, western China

    USGS Publications Warehouse

    Mattinson, C.G.; Wooden, J.L.; Zhang, J.X.; Bird, D.K.

    2009-01-01

    In the southeastern part of the North Qaidam terrane, near Dulan, paragneiss hosts minor peridotite and UHP eclogite. Zircon geochronology and trace element geochemistry of three paragneiss samples (located within a ???3 km transect) indicates that eclogite-facies metamorphism resulted in variable degrees of zircon growth and recrystallization in the three samples. Inherited zircon core age groups at 1.8 and 2.5 Ga suggest that the protoliths of these rocks may have received sediments from the Yangtze or North China cratons. Mineral inclusions, depletion in HREE, and absence of negative Eu anomalies indicate that zircon U-Pb ages of 431 ?? 5 Ma and 426 ?? 4 Ma reflect eclogite-facies zircon growth in two of the samples. Ti-in-zircon thermometry results are tightly grouped at ???660 and ???600 ??C, respectively. Inclusions of metamorphic minerals, scarcity of inherited cores, and lack of isotopic or trace element inheritance demonstrate that significant new metamorphic zircon growth must have occurred. In contrast, zircon in the third sample is dominated by inherited grains, and rims show isotopic and trace element inheritance, suggesting solid-state recrystallization of detrital zircon with only minor new growth. ?? 2009 Elsevier Ltd.

  19. Oxygen isotope fractionation between analcime and water - An experimental study

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

    The oxygen isotope fractionation between analcime and water is studied to test the feasibility of using zeolites as low-temperature thermometers. The fractionation of oxygen isotopes between natural analcime and water is determined at 300, 350, and 400 C, and at fluid pressures ranging from 1.5 to 5.0 kbar. Also, isotope ratios for the analcime framework, the channel water, and bulk water are obtained. The results suggest that the channel water is depleted in O-18 relative to bulk water by a constant value of about 5 percent, nearly independent of temperature. The analcime-water fractionation curve is presented, showing that the exchange has little effect on grain morphology and does not involve recrystallization. The exchange is faster than any other observed for a silicate. The exchange rates suggest that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. It is concluded that calibrated zeolites may be excellent low-temperature oxygen isotope geothermometers.

  20. A chronostratigraphic assessment of the Moenave Formation, USA using C-isotope chemostratigraphy and detrital zircon geochronology: Implications for the terrestrial end Triassic extinction

    NASA Astrophysics Data System (ADS)

    Suarez, Celina A.; Knobbe, Todd K.; Crowley, James L.; Kirkland, James I.; Milner, Andrew R. C.

    2017-10-01

    The Late Triassic is a period of abrupt climate change associated with a disruption to the global carbon cycle usually ascribed to the emplacement of the Central Atlantic Magmatic Province (CAMP). Geochronologic, paleontologic, and geochemical studies have shown that the CAMP was likely the major factor for the end-Triassic extinction (ETE), however, difficulties correlating and dating terrestrial strata has left the nature of the terrestrial extinction in question. The lacustrine Whitmore Point Member (WPM) of the Moenave Formation is ideal for investigating these details because it is reported to be Late Triassic to Early Jurassic. However, currently there are conflicting age constraints between biostratigraphy and magnetostratigraphy. In this study we attempt to elucidate the ETE by incorporating C-isotope chemostratigraphy and detrital zircon geochronology. Detrital zircon geochronology suggests the upper part of the Dinosaur Canyon Member (DCM) is younger (201.33 ± 0.07/0.12/0.25 Ma) than the ETE (201.564 Ma) suggesting the ETE is in the middle to lower DCM, in agreement with track biostratigraphy (first occurrence of Eubrontes, Anomoepus, and Batrachopus). Meanwhile a distinct negative carbon isotope (NCIE) excursion (-5.5‰) occurs at the base of the WPM at Potter Canyon, AZ with a more subtle NCIE at the base of the WPM at Black Canyon, UT (-2.0‰) that may correlate to the initial NCIE at the ETE. However, the WPM NCIE is correlated to the preservation of organic C (relative %C) suggesting it may be either related to local lake productivity and biases in organic matter preservation or may be a negative CIE in the Jurassic Hettangian stage. With the addition of the detrital zircon data, we suggest the M2r reversal at the base of the WPM is a reversal in the Hettangian (the H24r, H25r, or H26r) and the ETE is within the DCM. Additional C-isotope analysis of the DCM is necessary to determine if the initial NCIE that is the hallmark of the ETE occurs in

  1. Oxygen isotope geospeedometry by SIMS

    NASA Astrophysics Data System (ADS)

    Bonamici, C. E.; Valley, J. W.

    2013-12-01

    Geospeedometry, a discipline closely related and complimentary to thermochronology, exploits the phenomenon of diffusion in order to extract rate and duration information for segments of a rock's thermal history. Geospeedometry data, when anchored in absolute time by geochronologic data, allow for the construction of detailed temperature-time paths for specific terranes and geologic processes. We highlight the developing field of SIMS-based oxygen isotope geospeedometry with an application from granulites of the Adirondack Mountains (New York) and discuss potential future applications based on a recently updated and expanded modeling tool, the Fast Grain Boundary diffusion program (FGB; Eiler et al. 1994). Equilibrium oxygen isotope ratios in minerals are a function of temperature and bulk rock composition. In dynamic systems, intragrain oxygen isotope zoning can develop in response to geologic events that affect the thermal state of a rock and/or induce recrystallization, especially tectonic deformation and fluid infiltration. As an example, titanite grains from late-Grenville shear zones in the northwestern Adirondack Mountains exhibit a range of δ18O zoning patterns that record post-peak metamorphic cooling, episodic fluid infiltration, and deformation-facilitated recrystallization. Many titanite grains preserve smooth, core-to-rim decreasing, diffusional δ18O profiles, which are amenable to diffusion modeling. FGB models that best fit the measured δ18O profiles indicate cooling from ~700-500°C in just 2-5 m.y., a rapid thermal change signaling the final gravitational collapse of the late-Grenville orogen. Titanite can also be utilized as a U-Pb chronometer, and comparison of δ18O and U-Pb age zoning patterns within the Adirondack titanites pins the episode of rapid cooling inferred from the δ18O record to some time between 1054 and 1047 Ma. The expanded capabilities of FGB also allow for evaluation of a range of heating-cooling histories for the

  2. Using the magmatic record to constrain the growth of continental crust-The Eoarchean zircon Hf record of Greenland

    NASA Astrophysics Data System (ADS)

    Fisher, Christopher M.; Vervoort, Jeffrey D.

    2018-04-01

    Southern West Greenland contains some of the best-studied and best-preserved magmatic Eoarchean rocks on Earth, and these provide an excellent vantage point from which to view long-standing questions regarding the growth of the earliest continental crust. In order to address the questions surrounding early crustal growth and complementary mantle depletion, we present Laser Ablation Split Stream (LASS) analyses of the U-Pb and Hf isotope compositions of zircon from eleven samples of the least-altered meta-igneous rocks from the Itsaq (Amîtsoq) Gneisses of the Isukasia and Nuuk regions of southern West Greenland. This analytical technique allows a less ambiguous approach to determining the age and Hf isotope composition of complicated zircon. Results corroborate previous findings that Eoarchean zircon from the Itsaq Gneiss (∼3.85 Ga to ∼3.63 Ga) were derived from a broadly chondritic source. In contrast to the Sm-Nd whole rock isotope record for southern West Greenland, the zircon Lu-Hf isotope record provides no evidence for early mantle depletion, nor does it suggest the presence of crust older than ∼3.85 Ga in Greenland. Utilizing LASS U-Pb and Hf data from the Greenland zircons studied here, we demonstrate the importance of focusing on the magmatic (rather than detrital) zircon record to more confidently understand early crustal growth and mantle depletion. We compare the Greenland Hf isotope data with other Eoarchean magmatic complexes such as the Acasta Gneiss Complex, Nuvvuagittuq greenstone belt, and the gneissic complexes of southern Africa, and all lack zircons with suprachondritic Hf isotope compositions. In total, these data suggest only a very modest volume of crust was produced during (or survived from) the Hadean and earliest Eoarchean. There remains no record of planet-scale early Earth mantle depletion in the Hf isotope record prior to 3.8 Ga.

  3. SHRIMP-RG U-Pb isotopic systematics of zircon from the Angel Lake orthogneiss, East Humboldt Range, Nevada: Is this really archean crust?

    USGS Publications Warehouse

    Premo, Wayne R.; Castineiras, Pedro; Wooden, Joseph L.

    2008-01-01

    New SHRIMP-RG (sensitive high-resolution ion microprobe-reverse geometry) data confirm the existence of Archean components within zircon grains of a sample from the orthogneiss of Angel Lake, Nevada, United States, previously interpreted as a nappe of Archean crust. However, the combined evidence strongly suggests that this orthogneiss is a highly deformed, Late Cretaceous monzogranite derived from melting of a sedimentary source dominated by Archean detritus. Zircon grains from the same sample used previously for isotope dilution-thermal ionization mass spectrometry (ID-TIMS) isotopic work were analyzed using the SHRIMP-RG to better define the age and origin of the orthogneiss. Prior to analysis, imaging revealed a morphological variability and intragrain, polyphase nature of the zircon population. The SHRIMP-RG yielded 207Pb/206Pb ages between ca. 2430 and 2580 Ma (a best-fit mean 207Pb/206Pb age of 2531 ± 19 Ma; 95% confidence) from mostly rounded to subrounded zircons and zircon components (cores). In addition, several analyses from rounded to subrounded cores or grains yielded discordant 207Pb/206Pb ages between ca. 1460 and ca. 2170 Ma, consistent with known regional magmatic events. All cores of Proterozoic to latest Archean age were encased within clear, typically low Th/U (206Pb/238U ages between 72 and 91 Ma, consistent with magmatic ages from Lamoille Canyon to the south. An age of ca. 90 Ma is suggested, the younger 206Pb/238U ages resulting from Pb loss. The Cretaceous and Precambrian zircon components also have distinct trace element characteristics, indicating that these age groups are not related to the same igneous source. These results support recent geophysical interpretations and negate the contention that the Archean-Proterozoic boundary extends into the central Great Basin area. They further suggest that the world-class gold deposits along the Carlin Trend are not underlain by Archean cratonal crust, but rather by the Proterozoic Mojave

  4. Isotopic evidence for oxygenated Mesoarchaean shallow oceans

    NASA Astrophysics Data System (ADS)

    Eickmann, Benjamin; Hofmann, Axel; Wille, Martin; Bui, Thi Hao; Wing, Boswell A.; Schoenberg, Ronny

    2018-02-01

    Mass-independent fractionation of sulfur isotopes (MIF-S) in Archaean sediments results from photochemical processing of atmospheric sulfur species in an oxygen-depleted atmosphere. Geological preservation of MIF-S provides evidence for microbial sulfate reduction (MSR) in low-sulfate Paleoarchaean (3.8-3.2 billion years ago (Ga)) and Neoarchaean (2.8-2.5 Ga) oceans, but the significance of MSR in Mesoarchaean (3.2-2.8 Ga) oceans is less clear. Here we present multiple sulfur and iron isotope data of early diagenetic pyrites from 2.97-Gyr-old stromatolitic dolomites deposited in a tidal flat environment of the Nsuze Group, Pongola Supergroup, South Africa. We identified consistently negative Δ33S values in pyrite, which indicates photochemical reactions under anoxic atmospheric conditions, but large mass-dependent sulfur isotope fractionations of 30‰ in δ34S, identifying active MSR. Negative pyrite δ56Fe values (-1.31 to -0.88‰) record Fe oxidation in oxygen-bearing shallow oceans coupled with biogenic Fe reduction during diagenesis, consistent with the onset of local Fe cycling in oxygen oases 3.0 Ga. We therefore suggest the presence of oxygenated near-shore shallow-marine environments with ≥5 μM sulfate at this time, in spite of the clear presence of an overall reduced Mesoarchaean atmosphere.

  5. Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature

    NASA Astrophysics Data System (ADS)

    Hayles, J.; Shen, B.; Homann, M.; Yeung, L.

    2017-12-01

    One point of contention among geoscientists is whether the 18O/16O ratio of seawater is roughly constant, or if it varies considerably throughout geologic time. On one hand, the oxygen isotope composition of the ocean is thought to be well buffered by high- and low-temperature interactions between seawater and seafloor rocks. If these interactions do not vary on billion-year timescales, the oxygen-isotope compositions of marine sedimentary rocks mostly relate to changes in seawater temperature and global ice volume. On the other hand, long-term cooling of the planetary interior would alter these water-rock interactions leading to a secular change in the oxygen isotope composition of seawater. Models suggest that this secular change would enrich seawater with heavy oxygen isotopes over time. In this study, we present new, high precision, triple-oxygen-isotope (18O/16O, 17O/16O) analyses of marine chert samples from 3.45 Ga to 460Ma. The results of these analyses are paired with a new theoretical quartz-water equilibrium curve and a simplified seawater model to provide possible pairings of δ'18O and Δ'17O for the water which these samples could have formed in equilibrium with. Analysis of the new sample data, in addition to published chert triple oxygen isotope compositions, shows a general trend of older chert samples being progressively incompatible with waters possessing a modern-like seawater triple oxygen isotope composition. Implications on constraining the secular evolution of seawater δ18O and temperature will be discussed.

  6. Oxygen and carbon isotope disequilibria in Galapagos corals: isotopic thermometry and calcification physiology

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    McConnaughey, T.A.

    1986-01-01

    Biological carbonate skeletons are built largely from carbon dioxide, which reacts to form carbonate ion within thin extracellular solutions. The light isotopes of carbon and oxygen react faster than the heavy isotopes, depleting the resulting carbonate ions in /sup 13/C and /sup 18/O. Calcium carbonate precipitation occurs sufficiently fast that the skeleton remains out of isotopic equilibrium with surrounding fluids. This explanation for isotopic disequilibrium in biological carbonates was partially simulated in vitro, producing results similar to those seen in non-photosynthetic corals. Photosynthetic corals have higher /sup 13/C//sup 12/C ratios due to the preferential removal of /sup 12/C (as organicmore » carbon) from the reservoir of dissolved inorganic carbon. The oxygen isotopic variations in corals can be used to reconstruct past sea surface temperatures to an accuracy of about 0.5/sup 0/C. The carbon isotopic content of photosynthetic corals provides an indication of cloudiness. Using isotopic data from Galapagos corals, it was possible to construct proxy histories of the El Nino phenomenon. The physiology of skeletogenesis appears to be surprisingly similar in calcium carbonate, calcium phosphate, and silica precipitating systems.« less

  7. Normalization of oxygen and hydrogen isotope data

    USGS Publications Warehouse

    Coplen, T.B.

    1988-01-01

    To resolve confusion due to expression of isotopic data from different laboratories on non-corresponding scales, oxygen isotope analyses of all substances can be expressed relative to VSMOW or VPDB (Vienna Peedee belemnite) on scales normalized such that the ??18O of SLAP is -55.5% relative to VSMOW. H3+ contribution in hydrogen isotope ratio analysis can be easily determined using two gaseous reference samples that differ greatly in deuterium content. ?? 1988.

  8. Integrated in situ U-Pb Age and Hf-O Analyses of Zircon from the Northern Yangtze Block: New Insights into the Neoproterozoic Low-δ18O Magmas in the South China Block

    NASA Astrophysics Data System (ADS)

    Yang, Y. N.; Wang, X. C.; Li, Q. L.; Li, X. H.

    2015-12-01

    The oxygen isotopic composition of Neoproterozoic magmas from the northern Yangtze Block holds a key for the origin of large-scale 18O depletion in the HP and UHP metamorphic rocks in the Dabie-Sulu orogenic belt, northern margin of the South China Block. We report here the integrated in situ U-Pb dating and O-Hf isotope analyses of zircon grains from sedimentary and volcanic rocks of the late Neoproterozoic Suixian Group (SG) from the northern Yangtze Block. Detrital zircon grains display age peaks of 0.73-0.74 Ga, 0.79 Ga, and 2.0 Ga. Zircon U-Pb ages together with Hf-O isotopic composition indicate provenance of SG dominantly from proximal Neoproterozoic igneous rock and likely hidden Paleoproterozoic basement along the northern margin of the Yangtze Block. The zircon δ18O values from SG range from 10.5‰ to 1.3‰. Zircon grains with negative δ18O value, typical result of magma-ice interaction, were not identified in this study. The major phase of low-δ18O (< 4‰) magmas initiated at ca. 780 Ma, long before the first glaciation event (< 715 Ma) in the South China Block. Thus caution should be taken when using low-δ18O zircon grains to infer cold climate. Low-δ18O zircon grains have large ranges of ɛHf(t) values, varying from -15.5 to 10.7, concentrating on negative ɛHf(t). This strongly argues against the possibility that the low-δ18O magma was produced by partial melting of high-temperature hydrothermally altered oceanic crust because this model predicted MORB-like Hf isotopes for the resultant low-δ18O magmas. This study emphasizes that high-T water-rock interaction and continental rifting tectonic setting are essential to generate abundant low-δ18O magmas. The important application of our study is to confirm that most of negative-δ18O zircons identified in HP and UHP metamorphic rocks may not have been inherited from their Neoproterozoic protoliths.

  9. Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim

    NASA Technical Reports Server (NTRS)

    Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.

    2013-01-01

    Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

  10. Oxygen and iron isotope studies of magnetite produced by magnetotactic bacteria

    USGS Publications Warehouse

    Mandernack, K.W.; Bazylinski, D.A.; Shanks, Wayne C.; Bullen, T.D.

    1999-01-01

    A series of carefully controlled laboratory studies was carried out to investigate oxygen and iron isotope fractionation during the intracellular production of magnetite (Fe3O4) by two different species of magnetotactic bacteria at temperatures between 4??and 35??C under microaerobic and anaerobic conditions. No detectable fractionation of iron isotopes in the bacterial magnetites was observed. However, oxygen isotope measurements indicated a temperature-dependent fractionation for Fe3O4 and water that is consistent with that observed for Fe3O4 produced extracellularly by thermophilic Fe3+-reducing bacteria. These results contrast with established fractionation curves estimated from either high-temperature experiments or theoretical calculations. With the fractionation curve established in this report, oxygen-18 isotope values of bacterial Fe3O4 may be useful in paleoenvironmental studies for determining the oxygen-18 isotope values of formation waters and for inferring paleotemperatures.

  11. Mass-spectrometric mining of Hadean zircons by automated SHRIMP multi-collector and single-collector U/Pb zircon age dating: The first 100,000 grains

    NASA Astrophysics Data System (ADS)

    Holden, Peter; Lanc, Peter; Ireland, Trevor R.; Harrison, T. Mark; Foster, John J.; Bruce, Zane

    2009-09-01

    significant numbers of zircons for statistically limited studies including correlations between age and morphology, mineral-inclusion paragenesis, as well as isotopic studies including Hf and O isotopic compositions, Pu-Xe, and Sm-Nd isotopes.

  12. Oxygen Isotopic Analyses of Water Extracted from the Martian Meteorite NWA 7034

    NASA Astrophysics Data System (ADS)

    Nunn, M.; Agee, C. B.; Thiemens, M. H.

    2012-12-01

    Introduction: The NWA 7034 meteorite has been identified as Martian, but it is distinct from the Shergottite-Nakhlite-Chassignite (SNC) grouping of meteorites in its petrology (it is the only known Martian basaltic breccia) and bulk silicate oxygen isotopic composition (Δ17O = 0.56 ± 0.06 ‰, where Δ17O = δ17O - 0.528 x δ18O, compared to the average SNC Δ17O ≈ 0.3 ‰) [e.g., 1-2]. We report here measurements of the oxygen isotopic composition of water extracted from NWA 7034 by stepwise heating. Methods: A piece (~1.2g) of NWA 7034 was pumped to vacuum until outgassing had stopped before heating to 50, 150, 320, 500, and 1000°C. The sample was maintained at each temperature step for at least one hour while collecting evolved volatiles in a liquid nitrogen cold trap. Water was selectively converted to molecular oxygen, the oxygen isotopic composition of which was then measured on a double collecting isotope ratio mass spectrometer. Results: Our stepwise heating experiments indicate NWA 7034 contains 3330ppm water, and this water has an average oxygen isotopic composition of Δ17O = 0.330 ± 0.011‰. The oxygen isotopic composition of water in NWA 7034 is unlike that of the silicates from which it is extracted (Δ17O = 0.56 ± 0.06 ‰) but is comparable to the average SNC silicate composition (Δ17O ≈ 0.3 ‰). However, there is no consensus on the oxygen isotopic composition of water in SNCs because aliquots of water extracted from different samples (separate pieces of a single meteorite or from different meteorites) have different oxygen isotopic compositions [3]. Furthermore, carbonates and sulfates extracted from SNCs also possess distinct oxygen isotopic compositions [4]. The variation in oxygen isotopic composition among these phases most likely results from the existence of isotopically distinct oxygen reservoirs on Mars that were not equilibrated. On Earth, interaction of ozone (O3) and carbon dioxide (CO2) leads to a mass independent oxygen

  13. The influence of kinetics on the oxygen isotope composition of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

    2013-08-01

    Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

  14. U-Pb isotopic results for single shocked and polycrystalline zircons record 550-65.5-Ma ages for a K-T target site and 2700-1850-Ma ages for the Sudbury impact event

    NASA Technical Reports Server (NTRS)

    Krogh, T. E.; Kamo, S. L.; Bohor, B. F.

    1992-01-01

    The refractory mineral zircon develops distinct morphological features during shock metamorphism and retains these features under conditions that would anneal them in other minerals. In addition, weakly shocked zircon grains give primary ages for the impact site, while highly reconstituted (polycrystalline) single grains give ages that approach the age of the impact event. Data for a series of originally coeval grains will define a mixing line that gives both of these ages providing that no subsequent geological disturbances have overprinted the isotopic systematics. In this study, we have shown that the three zircon grain types described by Bohor, from both K-T distal ejecta (Fireball layer, Raton Basin, Colorado) and the Onaping Formation, represent a progressive increase in impact-related morphological change that coincides with a progressive increase in isotopic resetting in zircons from the ejecta and basement rocks. Unshocked grains are least affected by isotopic resetting while polycrystalline grains are most affected. U-Pb isotopic results for 12 of 14 single zircon grains from the Fireball layer plot on or close to a line recording a primary age of 550 +/- 10 Ma and a secondary age of 65.5 +/- 3 Ma. Data for the least and most shocked grains plot closest to the primary and secondary ages respectively. The two other grains each give ages between 300 and 350 Ma. This implies that the target ejecta was dominated by 550-Ma rocks and that the recrystallization features of the zircon were superimposed during the impact event at 65.5 Ma. A predominant age of 550 Ma for zircons from the Fireball layer provides an excellent opportunity to identify the impact site and to test the hypothesis that multiple impacts occurred at this time. A volcanic origin for the Fireball layer is ruled out by shock-related morphological changes in zircon and the fact that the least shocked grains are old. Basement Levack gneisses north of the Sudbury structure have a primary age of

  15. In situ U-Pb and Lu-Hf isotopic studies of zircons from the Sancheong-Hadong AMCG suite, Yeongnam Massif, Korea: Implications for the petrogenesis of ∼1.86 Ga massif-type anorthosite

    NASA Astrophysics Data System (ADS)

    Lee, Yuyoung; Cho, Moonsup; Yi, Keewook

    2017-05-01

    Isotopic and geochemical characteristics of Proterozoic anorthosite-mangerite-charnockite-granite (AMCG) suite have long been used for tracing the mantle-crustal source and magmatic evolution. We analyzed Lu-Hf isotopic compositions of zircon from the Sancheong-Hadong AMCG complex, Yeongnam Massif, Korea, in order to understand tectonomagmatic evolution of the Paleoproterozoic AMCG suite occurring at the southeastern margin of the North China Craton (NCC). The anorthositic rocks in this complex, associated with charnockitic and granitic gneisses, were recrystallized to eradicate magmatic features. In situ SHRIMP (sensitive high-resolution ion microprobe) U-Pb analyses of zircon from a leuconorite and an oxide-bearing gabbroic dyke yielded weighted mean 207Pb/206Pb ages of 1870 ± 2 Ma and 1861 ± 6 Ma, respectively. Charnockitic, granitic, and porphyroblastic gneisses yielded weighted mean 207Pb/206Pb zircon ages of 1861 ± 6 Ma, 1872 ± 6 Ma, and 1873 ± 4 Ma, respectively. These crystallization ages, together with our previous geochronological data for anorthosites (1862 ± 2 Ma), are indicative of episodic AMCG magmatism over an ∼10 Ma interval. Initial εHf(t) values of zircon analyzed from five anorthositic rocks and four felsic gneisses range from +2.1 to -6.1 and -0.3 to -5.4, respectively. Zircon Hf isotopic data in combination with available whole rock Sr-Nd isotopic data suggest that anorthositic parental magma was most likely derived from a mantle source and variably affected by crustal contamination. This crustal component is also reflected in charnockitic-granitic magmas produced primarily by the melting of lower crust. Taken together, the AMCG magmatism at 1.87-1.86 Ga in the Yeongnam Massif is most likely a late orogenic product of Paleoproterozoic NCC amalgamation tectonically linked to assembly of the Columbia supercontinent.

  16. Sediment Sulfur Isotopes Reflect Seawater Oxygen Rise in Neoarchean

    NASA Astrophysics Data System (ADS)

    Fakhraee, M.; Crowe, S.; Katsev, S.

    2017-12-01

    The oxygenation of the ocean-atmosphere system is recorded in S isotopes preserved in sedimentary pyrites. Disappearance of mass independent fractionation of S (S-MIF) around 2.45 Ga signals the first large-scale oxygenation of the atmosphere (the GOE), while a narrow range of pyritic δ34S during the Archean eon suggests limited oxidative cycling of S. Both δ34S and S-MIF ranges, however, undergo a clear and unexplained expansion in the Neoarchean between 2.7 and 2.45 Ga, indicating a change in global S-cycling. By analyzing the preservation patterns of isotopic signals with a 1D reaction-transport model, we show that the rock record points to the rise of oxygen in shallow marine environments around 2.7 billion years ago. The model tracks d34S and Δ33S isotopic transformations during early diagenesis in a reaction-transport framework. The results indicate that δ34S and MIF signatures in >2.7Ga sulfides require deposition from anoxic or minimally oxygenated seawater, whereas the 2.7-2.4 Ga expansion in both δ34S and D33S ranges points to at least localized accumulation oxygen to low μM levels, accompanied by a moderate rise in sulfate from low μM concentrations to up to 200 μM. In contrast to the role of oxygen in the atmosphere where it suppresses the production of MIF, oxygen in seawater at levels below 25 μM does not necessarily suppress the MIF preservation, which instead depends on the availability of reactive organic matter, sulfate, and electron acceptors for sulfide re-oxidation. The S-isotopes in Neoarchean sulfides thus paint a picture of gradual oxygenation of shallow marine environments under a nearly anoxic atmosphere where the atmospherically produced S isotopic signals are overprinted by increasingly oxidative diagenesis, rising sulfate levels, and increasing organic sedimentation.

  17. Continental crustal history in SE Asia: Insights from zircon geochronology

    NASA Astrophysics Data System (ADS)

    Sevastjanova, I.; Hall, R.; Gunawan, I.; Ferdian, F.; Decker, J.

    2012-12-01

    It is well known that SE Asia is underlain mostly by continental crust derived from Gondwana. However, there are still many uncertainties about the ages of protoliths, origin, arrival ages and history of different blocks, because much of the basement is unexposed. We have compiled previously published and new zircon U-Pb age and Hf isotope data from SE Asia. Our data set currently contains over 8400 U-Pb ages and over 600 Hf isotope analyses from sedimentary, metamorphic and igneous rocks and work is continuing to increase its size and the area covered. Zircons range in age from 3.4 Ga to near-zero. Archean zircons (>2.5 Ga) are rare in SE Asia and significant Archean populations (particularly zircons >2.8 Ga) are found only in East Java and the Sibumasu block of the Malay Peninsula. The presence of Archean zircons strongly suggests that the East Java and Sibumasu blocks were once situated near present-day Western Australia. Detrital Paleoproterozoic (ca. 1.9-1.8 Ga) zircons are abundant in many parts of SE Asia. In Sundaland (Malay Peninsula, Sumatra, West Java, Borneo) the most likely source for these zircons is the tin belt basement, but a north Australian source is more likely for eastern Indonesian samples. An early Mesoproterozoic (ca. 1.6-1.5 Ga) zircon population, particularly common in eastern Indonesia, is interpreted to be derived from central or northern Australia. Mesoproterozoic zircons, ca. 1.4 Ga, are common only on fragments that are now attached to or were previously part of the north Australian margin, such as the Bird's Head of New Guinea, Timor, Seram, Sulawesi and SW Borneo. Hf isotope characteristics of zircons from Seram are similar to those of zircons from eastern Australia. This supports the suggestion that Seram was part of the Australian margin. Late Meso- and early Neoproterozoic zircons (ca. 1.2-1.1 Ga, 900 Ma, and 600 Ma) are present, but not abundant, in SE Asia. Dominant Phanerozoic populations are Permian-Triassic, Cretaceous, and

  18. Preliminary results of oxygen isotope ratio measurement with a particle-gamma coincidence method

    NASA Astrophysics Data System (ADS)

    Borysiuk, Maciek; Kristiansson, Per; Ros, Linus; Abdel, Nassem S.; Elfman, Mikael; Nilsson, Charlotta; Pallon, Jan

    2015-04-01

    The possibility to study variations in the oxygen isotopic ratio with photon tagged nuclear reaction analysis (pNRA) is evaluated in the current work. The experiment described in the article was performed at Lund Ion Beam Analysis Facility (LIBAF) with a 2 MeV deuteron beam. Isotopic fractionation of light elements such as carbon, oxygen and nitrogen is the basis of many analytical tools in hydrology, geology, paleobiology and paleogeology. IBA methods provide one possible tool for measurement of isotopic content. During this experimental run we focused on measurement of the oxygen isotopic ratio. The measurement of stable isotopes of oxygen has a number of applications; the particular one driving the current investigation belongs to the field of astrogeology and specifically evaluation of fossil extraterrestrial material. There are three stable isotopes of oxygen: 16O, 17O and 18O. We procured samples highly enriched with all three isotopes. Isotopes 16O and 18O were easily detected in the enriched samples, but no significant signal from 17O was detected in the same samples. The measured yield was too low to detect 18O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with 16O was clearly visible.

  19. Hadean Oceanography: Experimental Constraints on the Development of the Terrestrial Hydrosphere and the Origin of Life on Earth

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ryerson, F J

    The oxygen isotopic compositions of the world's oldest mineral grains, zircon, have recently been used to infer the compositions of the rocks from which they crystallized. The results appear to require a source that had once experienced isotopic fractionation between clay minerals and liquid water, thereby implying the presence of liquid water at the Earth's surface prior to 4.4 billion years ago, less than 2 million years after accretion. This observation has important implications for the development of the Earth's continental crust. The inferred composition of the zircon source rock is directly dependent upon the oxygen isotopic fractionation between zirconmore » and melt, and zircon and water. These fractionation factors have not been determined experimentally, however, constituting the weak link in this argument. A series of experiments to measure these fractionation factors has been conducted. The experiments consist of finely powdered quartz, a polished single crystal of zircon and isotopically-enriched or isotopically normal water to provide a range of isotopic compositions. The experiments will be run until quartz is in isotopic equilibrium with water. Zircon was expected to partially equilibrate producing an oxygen isotopic diffusion profile perpendicular to the surface. Ion probe spot analysis of quartz and depth profiling of zircon will determine the bulk and surface isotopic compositions of the phases, respectively. The well-known quartz-water isotopic fractionation factors can be used to calculate the oxygen isotopic composition of the fluid, and with the zircon surface composition, the zircon-water fractionation factor. Run at temperatures up to 1000 C for as long as 500 hours have not produced diffusion profiles longer than 50 nm. The steep isotopic gradient at the samples surface precludes use of the diffusion profile for estimation on the surface isotopic composition. The short profiles may be the result of surface dissolution, although such

  20. Zircon growth in shear zones

    NASA Astrophysics Data System (ADS)

    Kaulina, Tatiana

    2013-04-01

    The possibility of direct dating of the deformation process is critical for understanding of orogenic belts evolution. Establishing the age of deformation by isotopic methods is indispensable in the case of uneven deformation overlapping, when later deformation inherits the structural plan of the early strains, and to distinguish them on the basis of the structural data only is impossible. A good example of zircon from the shear zones is zircon formed under the eclogite facies conditions. On the one hand, the composition of zircon speaks about its formation simultaneously to eclogitic paragenesis (Rubatto, Herman, 1999; Rubatto et al., 2003). On the other hand, geological studies show that mineral reactions of eclogitization are often held only in areas of shear deformations, which provides access of fluid to the rocks (Austrheim, 1987; Jamtveit et al., 2000; Bingen et al., 2004). Zircons from mafic and ultramafic rocks of the Tanaelv and Kolvitsa belts (Kola Peninsula, the Baltic Shield) have showed that the metamorphic zircon growth is probably controlled by the metamorphic fluid regime, as evidenced by an increase of zircon quantity with the degree of shearing. The internal structure of zircon crystals can provide an evidence of zircon growth synchronous with shearing. The studied crystals have a sector zoning and often specific "patchy" zoning (Fig. 1), which speaks about rapid change of growth conditions. Such internal structure can be compared with the "snowball" garnet structure reflecting the rotation of crystals during their growth under a shift. Rapidly changing crystallization conditions can also be associated with a small amount of fluid, where supersaturation is changing even at a constant temperature. Thus, the growth of metamorphic zircon in shear zones is more likely to occur in the fluid flow synchronous with deformation. A distinctive feature of zircons in these conditions is isometric shape and sector "patchy" zoning. The work was supported by

  1. Magma evolution as seen through zircon geochemistry: an example from the Southern Adamello Batholith, N. Italy

    NASA Astrophysics Data System (ADS)

    Broderick, C.; Schaltegger, U.; Gerdes, A.; Frick, D.; Guenther, D.; Brack, P.

    2012-04-01

    Zircon is an ubiquitous accessory mineral often used for U-Pb geochronology but is also an important recorder of geochemical information. The trace element and isotopic characteristics of zircon yield potential for tracking changes in an evolving magma through time. With recent advances in U-Pb zircon geochronology, 10-100 ka to Ma timescales are observed for incremental pluton construction (Michel et al., 2008, Schaltegger et al., 2009). In observed 100 ka timescales of zircon crystallization, can zircon record the processes that produce trace element variations in a magma? This study focuses on the Val Fredda Complex (VFC) in the southern tip of the 43 to 33 Ma Adamello batholith, N. Italy. The VFC displays complex relationships among mafic melts that were injected into solidifying felsic magmas. Single zircon crystals were dated using CA-ID-TIMS. With permil uncertainties on 206Pb/238U zircon dates, zircons reveal complexities within single populations. The mafic units crystallized potential autocrystic zircons over a duration of 100 - 150ka, whereas the felsic units record up to 200ka of zircon crystallization. In order to understand these complex zircon populations, we analyzed Hf isotopes and trace elements, on the same volume of zircon used for U-Pb dating, following the TIMS-TEA method (Schoene et al., 2010). This detailed zircon study will allow us to look at how magmas are evolving with time. Hf isotopes of VFC mafic zircons reveal distinct ɛHf values between the three mafic units and their ɛHf values remain consistent through time, whereas the VFC felsic units record more complexity in their ɛHf values. We observe changes such as increasing and slight decreases in ɛHf with time which suggest different processes are occurring to produce the different felsic units. Trace element ratios in zircon reveal differences which allow us to make distinctions between felsic and mafic units (e.g. Th/U, (Lu/Gd)N, REEs). The VFC records 200 ka of zircon

  2. Growth history of cultured pearl oysters based on stable oxygen isotope analysis

    NASA Astrophysics Data System (ADS)

    Nakashima, R.; Furuta, N.; Suzuki, A.; Kawahata, H.; Shikazono, N.

    2007-12-01

    We investigated the oxygen isotopic ratio in shells of the pearl oyster Pinctada martensii cultivated in embayments in Mie Prefecture, central Japan, to evaluate the biomineralization of shell structures of the species and its pearls in response to environmental change. Microsamples for oxygen isotope analysis were collected from the surfaces of shells (outer, middle, and inner shell layers) and pearls. Water temperature variations were estimated from the oxygen isotope values of the carbonate. Oxygen isotope profiles of the prismatic calcite of the outer shell layer reflected seasonal variations of water temperature, whereas those of nacreous aragonites of the middle and inner shell layers and pearls recorded temperatures from April to November, June to September, and July to September, respectively. Lower temperatures in autumn and winter might slow the growth of nacreous aragonites. The oxygen isotope values are controlled by both variations of water temperature and shell structures; the prismatic calcite of this species is useful for reconstructing seasonal changes of calcification temperature.

  3. Detrital zircon U-Pb geochronology, Lu-Hf isotopes and REE geochemistry constrains on the provenance and tectonic setting of Indochina Block in the Paleozoic

    NASA Astrophysics Data System (ADS)

    Wang, Ce; Liang, Xinquan; Foster, David A.; Fu, Jiangang; Jiang, Ying; Dong, Chaoge; Zhou, Yun; Wen, Shunv; Van Quynh, Phan

    2016-05-01

    In situ U-Pb geochronology, Lu-Hf isotopes and REE geochemical analyses of detrital zircons from Cambrian-Devonian sandstones in the Truong Son Belt, central Vietnam, are used to provide the information of provenance and tectonic evolution of the Indochina Block. The combined detrital zircon age spectra of all of the samples ranges from 3699 Ma to 443 Ma and shows with dominant age peaks at ca. 445 Ma and 964 Ma, along with a number of age populations at 618-532 Ma, 1160-1076 Ma, 1454 Ma, 1728 Ma and 2516 Ma. The zircon age populations are similar to those from time equivalent sedimentary sequences in continental blocks disintegrated from the East Gondwana during the Phanerozoic. The younger zircon grains with age peaks at ca. 445 Ma were apparently derived from middle Ordovician-Silurian igneous and metamorphic rocks in Indochina. Zircons with ages older than about 600 Ma were derived from other Gondwana terrains or recycled from the Precambrian basement of the Indochina Block. Similarities in the detrital zircon U-Pb ages suggest that Paleozoic strata in the Indochina, Yangtze, Cathaysia and Tethyan Himalayas has similar provenance. This is consistent with other geological constrains indicating that the Indochina Block was located close to Tethyan Himalaya, northern margin of the India, and northwestern Australia in Gondwana.

  4. Oxygen isotope analysis of bacterial and fungal manganese oxidation.

    PubMed

    Sutherland, K M; Wankel, S D; Hansel, C M

    2018-07-01

    The ability of micro-organisms to oxidize manganese (Mn) from Mn(II) to Mn(III/IV) oxides transcends boundaries of biological clade or domain. Many bacteria and fungi oxidize Mn(II) to Mn(III/IV) oxides directly through enzymatic activity or indirectly through the production of reactive oxygen species. Here, we determine the oxygen isotope fractionation factors associated with Mn(II) oxidation via various biotic (bacteria and fungi) and abiotic Mn(II) reaction pathways. As oxygen in Mn(III/IV) oxides may be derived from precursor water and molecular oxygen, we use a twofold approach to determine the isotope fractionation with respect to each oxygen source. Using both 18 O-labeled water and closed-system Rayleigh distillation approaches, we constrain the kinetic isotope fractionation factors associated with O atom incorporation during Mn(II) oxidation to -17.3‰ to -25.9‰ for O 2 and -1.9‰ to +1.8‰ for water. Results demonstrate that stable oxygen isotopes of Mn(III/IV) oxides have potential to distinguish between two main classes of biotic Mn(II) oxidation: direct enzymatic oxidation in which O 2 is the oxidant and indirect enzymatic oxidation in which superoxide is the oxidant. The fraction of Mn(III/IV) oxide-associated oxygen derived from water varies significantly (38%-62%) among these bio-oxides with only weak relationship to Mn oxidation state, suggesting Mn(III) disproportionation may account for differences in the fraction of mineral-bound oxygen from water and O 2 . Additionally, direct incorporation of molecular O 2 suggests that Mn(III/IV) oxides contain a yet untapped proxy of δ18OO2 of environmental O 2 , a parameter reflecting the integrated influence of global respiration, photorespiration, and several other biogeochemical reactions of global significance. © 2018 John Wiley & Sons Ltd.

  5. The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

    NASA Astrophysics Data System (ADS)

    Hayles, Justin; Bao, Huiming

    2015-06-01

    Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption-desorption, dissociation-association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2. Triple-oxygen-isotope labeled ceria powders are heated at 700 °C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (⩽10-4 mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰ ± 0.8‰ increase in the δ18O value of ceria after being heated in vacuum at 700 °C for 1 h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3-19% of its final structural oxygen from air, with a δ18O value of 2.1-4.1+7.7 ‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy

  6. Extinct 244Pu in ancient zircons.

    PubMed

    Turner, Grenville; Harrison, T Mark; Holland, Greg; Mojzsis, Stephen J; Gilmour, Jamie

    2004-10-01

    We have found evidence, in the form of fissiogenic xenon isotopes, for in situ decay of 244Pu in individual 4.1- to 4.2-billion-year-old zircons from the Jack Hills region of Western Australia. Because of its short half-life, 82 million years, 244Pu was extinct within 600 million years of Earth's formation. Detrital zircons are the only known relics to have survived from this period, and a study of their Pu geochemistry will allow us to date ancient metamorphic events and determine the terrestrial Pu/U ratio for comparison with the solar ratio.

  7. Oxygen Isotope Signatures of Biogenic Manganese(III/IV) Oxides

    NASA Astrophysics Data System (ADS)

    Sutherland, K. M.; Hansel, C. M.; Wankel, S. D.

    2015-12-01

    Manganese (Mn) oxide minerals are pervasive throughout a number of surface earth environments as rock varnishes, ferromanganese nodules, crusts around deep-sea vents, and cave deposits among many other marine, freshwater, and terrestrial deposits. Mn(III,IV) oxides are also among the strongest sorbents and oxidants in surface earth environments and are crucial to understanding the fate of organic matter in sedimentary environments. The precipitation of Mn oxide minerals proceeds via both abiotic and biotic oxidation pathways, the latter due to the indirect or direct activity of Mn(II)- oxidizing microorganisms, including bacteria and fungi. Although the precipitation of Mn oxides is believed to be primarily controlled by Mn(II)-oxidizing organisms in most surface earth environments, confirmation of this generally held notion has remained illusive and limits our understanding of their formation on Earth and beyond (e.g., Mars). Previous work provided evidence that O atom incorporation by specific Mn oxidation pathways may exhibit unique and predictable isotopic fractionation. In this study, we expand upon this evidence by measuring the oxygen isotope signature of several biogenic and abiogenic Mn oxide minerals synthesized under a range of oxygen-18 labeled water. These results allow us to determine the relative amount oxygen atoms derived from water and molecular oxygen that are incorporated in the oxide and shed light on corresponding isotope fractionation factors. Additionally, we show that, once precipitated, Mn oxide isotope signatures are robust with respect to aqueous oxygen isotope exchange. The study provides a foundation on which to study and interpret Mn oxides in natural environments and determine which environmental controls may govern Mn(II) oxidation.

  8. Sulfur in zircons: A new window into melt chemistry

    NASA Astrophysics Data System (ADS)

    Tang, H.; Bell, E. A.; Boehnke, P.; Barboni, M.; Harrison, T. M.

    2017-12-01

    The abundance and isotopic composition of sulfur are important tools for exploring the photochemistry of the atmosphere, the thermal history of mantle and igneous rocks, and ancient metabolic processes on the early Earth. Because the oldest terrestrial samples are zircons, we developed a new in-situ procedure to analyze the sulfur content of zircons using the CAMECA ims 1290 at UCLA. We analyzed zircons from three metaluminous/I-type granites (reduced and oxidized Peninsular range and Elba), which exhibit low sulfur abundance with the average of 0.5ppm, and one peraluminous/S-type zircon (Strathbogie Range), which shows an elevated sulfur level with the average of 1.5ppm. Additionally, we found that sulfur content ranges between 0.4 and 2.3 ppm in young volcanic zircons (St. Lucia). Our analyses of zircons from the Jack Hills, Western Australia, whose ages range between 3.4 and 4.1 Ga, show a variety of sulfur contents. Three out of the ten zircons are consistent with the sulfur contents of S-type zircons; the rest have low sulfur contents, which are similar to those of I-type zircons. The high sulfur content in some of these Jack Hills zircons can be interpreted as indicating their origin in either a S-type granite or a volcanic reservoir. We favor the former interpretation since the Ti-in-zircon temperatures of our Jack Hills zircons is lower than those of volcanic zircons. Future work will be undertaken to develop a systematic understanding of the relationship between melt volatile content, melt chemistry, and zircon sulfur content.

  9. How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

    NASA Astrophysics Data System (ADS)

    Price, Gregory; Grimes, Stephen

    2015-04-01

    The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

  10. Planetary Accretion, Oxygen Isotopes and the Central Limit Theorem

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Hill, Hugh G. M.; Vondrak, Richard R. (Technical Monitor)

    2001-01-01

    The accumulation of presolar dust into increasingly larger aggregates (CAIs and Chondrules, Asteroids, Planets) should result in a very drastic reduction in the numerical spread in oxygen isotopic composition between bodies of similar size, in accord with the Central Limit Theorem. Observed variations in oxygen isotopic composition are many orders of magnitude larger than would be predicted by a simple, random accumulation model that begins in a well-mixed nebula - no matter which size-scale objects are used as the beginning or end points of the calculation. This discrepancy implies either that some as yet unspecified process acted on the solids in the Solar Nebula to increase the spread in oxygen isotopic composition during each and every stage of accumulation or that the nebula was heterogeneous and maintained this heterogeneity throughout most of nebular history. Large-scale nebular heterogeneity would have significant consequences for many areas of cosmochemistry, including the application of some well-known isotopic systems to the dating of nebular events or the prediction of bulk compositions of planetary bodies on the basis of a uniform cosmic abundance.

  11. The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT).

    PubMed

    Slouka, Christoph; Kainz, Theresa; Navickas, Edvinas; Walch, Gregor; Hutter, Herbert; Reichmann, Klaus; Fleig, Jürgen

    2016-11-22

    The different properties of acceptor-doped (hard) and donor-doped (soft) lead zirconate titanate (PZT) ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La 3+ donor-doped, Fe 3+ acceptor-doped and La 3+ /Fe 3+ -co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT.

  12. The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT)

    PubMed Central

    Slouka, Christoph; Kainz, Theresa; Navickas, Edvinas; Walch, Gregor; Hutter, Herbert; Reichmann, Klaus; Fleig, Jürgen

    2016-01-01

    The different properties of acceptor-doped (hard) and donor-doped (soft) lead zirconate titanate (PZT) ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La3+ donor-doped, Fe3+ acceptor-doped and La3+/Fe3+-co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT. PMID:28774067

  13. Opening the closed box: lattice diffusion in zircon?

    NASA Astrophysics Data System (ADS)

    Wheeler, J.; MacDonald, J.; Goodenough, K. M.; Crowley, Q.; Harley, S.; Mariani, E.

    2015-12-01

    In principle, any radiogenic parent or daughter element can diffuse through any crystalline lattice. Given improved analytic techniques and mathematical models, geochronology is beginning to take such diffusion into account in a quantitative fashion. Whilst lattice diffusion compromises simple interpretation of radiometric data, it can, when combined with spatially resolved data, provide more detailed insight into thermal histories. In regions that have experienced particularly high temperatures diffusion may become significant in minerals normally thought to be reliably closed. We have modelled Pb diffusion in zircon, building on earlier work on Ar diffusion in micas - the mathematics being basically the same. We are motivated by some challenging isotope data from zircon in the Lewisian Complex of NW Scotland (a TTG region with a long Archaean and Proterozoic history). For example we have grains with old rims and younger cores. Whilst other explanations are possible, we show how lattice diffusion of Pb is plausible, using experimental diffusion data together with estimates of ultra-high temperatures from the region. We have modified a previous model for Ar diffusion ("Diffarg") to include variations in parent isotope concentration, so we can understand the consequences of U zonation within zircon grains during prolonged thermal histories. This is also relevant to asking why Pb has apparently not diffused in zircon from other UHT regions - or has it?

  14. Uniformly mantle-like δ18O in zircons from oceanic plagiogranites and gabbros

    NASA Astrophysics Data System (ADS)

    Grimes, Craig B.; Ushikubo, Takayuki; John, Barbara E.; Valley, John W.

    2011-01-01

    Lower ocean crust is primarily gabbroic, although 1-2% felsic igneous rocks that are referred to collectively as plagiogranites occur locally. Recent experimental evidence suggests that plagiogranite magmas can form by hydrous partial melting of gabbro triggered by seawater-derived fluids, and thus they may indicate early, high-temperature hydrothermal fluid circulation. To explore seawater-rock interaction prior to and during the genesis of plagiogranite and other late-stage magmas, oxygen-isotope ratios preserved in igneous zircon have been measured by ion microprobe. A total of 197 zircons from 43 plagiogranite, evolved gabbro, and hydrothermally altered fault rock samples have been analyzed. Samples originate primarily from drill core acquired during Ocean Drilling Program and Integrated Ocean Drilling Program operations near the Mid-Atlantic and Southwest Indian Ridges. With the exception of rare, distinctively luminescent rims, all zircons from ocean crust record remarkably uniform δ18O with an average value of 5.2 ± 0.5‰ (2SD). The average δ18O(Zrc) would be in magmatic equilibrium with unaltered MORB [δ18O(WR) ~ 5.6-5.7‰], and is consistent with the previously determined value for equilibrium with the mantle. The narrow range of measured δ18O values is predicted for zircon crystallization from variable parent melt compositions and temperatures in a closed system, and provides no indication of any interactions between altered rocks or seawater and the evolved parent melts. If plagiogranite forms by hydrous partial melting, the uniform mantle-like δ18O(Zrc) requires melting and zircon crystallization prior to significant amounts of water-rock interactions that alter the protolith δ18O. Zircons from ocean crust have been proposed as a tectonic analog for >3.9 Ga detrital zircons from the earliest (Hadean) Earth by multiple workers. However, zircons from ocean crust are readily distinguished geochemically from zircons formed in continental crustal

  15. Oxygen isotopes and the moon-forming giant impact.

    PubMed

    Wiechert, U; Halliday, A N; Lee, D C; Snyder, G A; Taylor, L A; Rumble, D

    2001-10-12

    We have determined the abundances of 16O, 17O, and 18O in 31 lunar samples from Apollo missions 11, 12, 15, 16, and 17 using a high-precision laser fluorination technique. All oxygen isotope compositions plot within +/-0.016 per mil (2 standard deviations) on a single mass-dependent fractionation line that is identical to the terrestrial fractionation line within uncertainties. This observation is consistent with the Giant Impact model, provided that the proto-Earth and the smaller impactor planet (named Theia) formed from an identical mix of components. The similarity between the proto-Earth and Theia is consistent with formation at about the same heliocentric distance. The three oxygen isotopes (delta17O) provide no evidence that isotopic heterogeneity on the Moon was created by lunar impacts.

  16. U-Pb ages and Hf isotopic composition of zircons in Austrian last glacial loess: constraints on heavy mineral sources and sediment transport pathways

    NASA Astrophysics Data System (ADS)

    Újvári, Gábor; Klötzli, Urs

    2015-07-01

    Loess sediments in Austria deposited ca. 30-20 ka ago yield different zircon age signatures for samples collected around Krems (SE Bohemian Massif; samples K23 and S1) and Wels (halfway between the Bohemian Massif and the Eastern Alps; sample A16). Cathodoluminescence (CL) imaging reveals both old, multistage zircons with complex growth histories and inherited cores, and young, first-cycle magmatic zircons. Paleoproterozoic ages between 2,200 and 1,800 Ma (K23 and S1), an age gap of 1,800-1,000 Ma for S1 and abundant Cadomian grains, indicate NW African/North Gondwanan derivation of these zircons. Also, A16 yields ages between 630 and 600 Ma that can be attributed to "Pan-African" orogenic processes. Significant differences are seen for the <500 Ma part of the age spectra with major age peaks at 493-494 and 344-335 Ma (K23 and S1), and 477 and 287 Ma (A16). All three samples show negative initial ɛHf signatures (-25 to -10, except one grain with +9.4) implying zircon crystallization from magmas derived by recycling of older continental crust. Hf isotopic compositions of 330- to 320-Ma-old zircons from S1 and K23 preclude a derivation from Bavarian Forest granites and intermediate granitoids. Rather, all the data suggest strong contributions of eroded local rocks (South Bohemian pluton, Gföhl unit) to loess material at the SE edge of the Bohemian Massif (K23 and S1) and sourcing of zircons from sediment donor regions in the Eastern Alps for loess at Wels (A16). We tentatively infer primary fluvial transport and secondary eolian reworking and re-deposition of detritus from western/southwestern directions. Finally, our data highlight that loess zircon ages are fundamentally influenced by fluvial transport, its directions, the interplay of sediment donor regions through the mixing of detritus and zircon fertility of rocks, rather than Paleowind directions.

  17. Nanogeochronology of discordant zircon measured by atom probe microscopy of Pb-enriched dislocation loops

    PubMed Central

    Peterman, Emily M.; Reddy, Steven M.; Saxey, David W.; Snoeyenbos, David R.; Rickard, William D. A.; Fougerouse, Denis; Kylander-Clark, Andrew R. C.

    2016-01-01

    Isotopic discordance is a common feature in zircon that can lead to an erroneous age determination, and it is attributed to the mobilization and escape of radiogenic Pb during its post-crystallization geological evolution. The degree of isotopic discordance measured at analytical scales of ~10 μm often differs among adjacent analysis locations, indicating heterogeneous distributions of Pb at shorter length scales. We use atom probe microscopy to establish the nature of these sites and the mechanisms by which they form. We show that the nanoscale distribution of Pb in a ~2.1 billion year old discordant zircon that was metamorphosed c. 150 million years ago is defined by two distinct Pb reservoirs. Despite overall Pb loss during peak metamorphic conditions, the atom probe data indicate that a component of radiogenic Pb was trapped in 10-nm dislocation loops that formed during the annealing of radiation damage associated with the metamorphic event. A second Pb component, found outside the dislocation loops, represents homogeneous accumulation of radiogenic Pb in the zircon matrix after metamorphism. The 207Pb/206Pb ratios measured from eight dislocation loops are equivalent within uncertainty and yield an age consistent with the original crystallization age of the zircon, as determined by laser ablation spot analysis. Our results provide a specific mechanism for the trapping and retention of radiogenic Pb during metamorphism and confirm that isotopic discordance in this zircon is characterized by discrete nanoscale reservoirs of Pb that record different isotopic compositions and yield age data consistent with distinct geological events. These data may provide a framework for interpreting discordance in zircon as the heterogeneous distribution of discrete radiogenic Pb populations, each yielding geologically meaningful ages. PMID:27617295

  18. The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

    NASA Astrophysics Data System (ADS)

    von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel

    2014-01-01

    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

  19. Biological Oxygen Productivity Over The Last Glacial Termination From Triple Oxygen Isotope Measurements

    NASA Astrophysics Data System (ADS)

    Blunier, T.; Bender, M. L.; Hendricks, M. B.

    The atmospheric oxygen isotope signature of O2 is linked to the oxygen signature of seawater through photosynthesis and respiration. Fractionation during these pro- cesses is mass dependent affecting 17O about half as much as 18O. A mass indepen- dent fractionation process takes place during isotope exchange between O2 and CO2 in the stratosphere (Thiemens, 1999; Luz et al., 1999). The magnitude of the mass- independent anomaly in the triple isotope composition of O2 depends on relative rates of biological O2 cycling and photochemical reactions in the stratosphere. Variations of this anomaly thus allows us to estimate changes of mass dependent O2 production by photosynthesis versus mass independent O2-CO2 exchange in the stratosphere. We reconstruct total oxygen productivity for the past from 17O and 18O measure- ments of O2 trapped in ice cores. With a box model we estimate that the total biogenic productivity was only 76-83 % of today for the glacial and was probably still lower than today during the glacial-interglacial transition and the early Holocene. In principle we can calculate the oxygen flux from the ocean biosphere if we know the oxygen flux from the land biosphere. Calculated ocean production is very sensitive to the estimate of land biosphere production. The latter term remains uncertain, however, and we can presently only constrain glacial ocean production to 88 to 140 % of the present value.

  20. Seasonality of Oxygen isotope composition in cow (Bos taurus) hair and its model interpretation

    NASA Astrophysics Data System (ADS)

    Chen, Guo; Schnyder, Hans; Auerswald, Karl

    2017-04-01

    Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (p<0.05) to the isotope composition in meteoric water in a regression analysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

  1. Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

    USGS Publications Warehouse

    Johnson, C.A.; Emsbo, P.; Poole, F.G.; Rye, R.O.

    2009-01-01

    Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a ??34S versus ??18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The ??34S versus ??18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

  2. Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

    NASA Astrophysics Data System (ADS)

    Johnson, Craig A.; Emsbo, Poul; Poole, Forrest G.; Rye, Robert O.

    2009-01-01

    Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a δ 34S versus δ 18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The δ 34S versus δ 18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H 2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

  3. An Early Permian epithermal gold system in the Tulasu Basin in North Xinjiang, NW China: Constraints from in situ oxygen-sulfur isotopes and geochronology

    NASA Astrophysics Data System (ADS)

    Dong, Leilei; Wan, Bo; Deng, Chen; Cai, Keda; Xiao, Wenjiao

    2018-03-01

    The Axi and Jingxi-Yelmand gold deposits, being the largest gold deposits in the Chinese North Tianshan, NW China, are located ca. l0 km apart in the Tulasu Basin, and are hosted by the Late Devonian - Early Carboniferous Dahalajunshan Formation. In situ LA-ICP-MS titanium analyses on quartz from the Axi and Jingxi-Yelmand deposits are broadly identical. Accordingly, the calculated ore-forming temperatures by Ti-in-quartz thermometer give average temperatures of 279 °C and 294 °C, respectively. Results of in situ SIMS analyses of oxygen and sulfur isotopes on quartz and pyrite from these two deposits are similar. Temperature-corrected fluids of the Axi deposit have δ18O values of 2.6-8.1‰ and δ34S values of 0.8-2.4‰, whereas the fluids of the Jingxi-Yelmand deposit have δ18O of 6.4-8.9‰ and δ34S of -0.4 to 4.0‰. The oxygen and sulfur isotopes from the two deposits indicate a magmatic origin. LA-ICP-MS zircon U-Pb ages of Aqialehe Formation sandstone provided a lower limit for the mineralization timing of the Axi deposit (288 Ma). In situ SIMS U-Pb analyses on entrapped zircon (297 Ma) and newly recognized 284.5 Ma columnar rhyolite implies that the Jingxi-Yelmand deposit formed in the Early Permian. Based on the magmatic affinity of the ore fluids, similar age and ore-formation temperatures, we propose that the Axi and Jingxi-Yelmand deposits comprise an epithermal gold system, which was driven by the same Permian magma in the Tulasu Basin. The ore geological features together with our new results indicate that the Axi and Jingxi-Yelmand deposits are intermediate and high sulfidation type epithermal deposits, respectively.

  4. Oxygen isotope and trace element evidence for three-stage petrogenesis of the youngest episode (260-79 ka) of Yellowstone rhyolitic volcanism

    NASA Astrophysics Data System (ADS)

    Loewen, Matthew W.; Bindeman, Ilya N.

    2015-10-01

    We report the first high-precision δ18O analyses of glass, δ18O of minerals, and trace element concentrations in glass and minerals for the 260-79 ka Central Plateau Member (CPM) rhyolites of Yellowstone, a >350 km3 cumulative volume of lavas erupted inside of 630 ka Lava Creek Tuff (LCT) caldera. The glass analyses of these crystal-poor rhyolites provide direct characterization of the melt and its evolution through time. The δ18Oglass values are low and mostly homogeneous (4.5 ± 0.14 ‰) within and in between lavas that erupted in four different temporal episodes during 200 ka of CPM volcanism with a slight shift to lower δ18O in the youngest episode (Pitchstone Plateau). These values are lower than Yellowstone basalts (5.7-6 ‰), LCT (5.5 ‰), pre-, and extracaldera rhyolites (~7-8 ‰), but higher than the earliest 550-450 ka post-LCT rhyolites (1-2 ‰). The glass δ18O value is coupled with new clinopyroxene analyses and previously reported zircon analyses to calculate oxygen isotope equilibration temperatures. Clinopyroxene records >900 °C near-liquidus temperatures, while zircon records temperatures <850 °C similar to zircon saturation temperature estimates. Trace element concentrations in the same glass analyzed for oxygen isotopes show evidence for temporal decreases in Ti, Sr, Ba, and Eu—related to Fe-Ti oxide and sanidine (±quartz) crystallization control, while other trace elements remain similar or are enriched through time. The slight temporal increase in glass Zr concentrations may reflect similar or higher temperature magmas (via zircon saturation) through time, while previosuly reported temperature decreases (e.g., Ti-in-quartz) might reflect changing Ti concentrations with progressive melt evolution. Multiple analyses of glass across single samples and in profiles across lava flow surfaces document trace element heterogeneity with compatible behavior of all analyzed elements except Rb, Nb, and U. These new data provide evidence for a

  5. Oxygen Isotopic Compositions of Solar Corundum Grains

    NASA Astrophysics Data System (ADS)

    Makide, Kentaro; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.

    2009-11-01

    Oxygen is one of the major rock-forming elements in the solar system and the third most abundant element of the Sun. Oxygen isotopic composition of the Sun, however, is not known due to a poor resolution of astronomical spectroscopic measurements. Several Δ17O values have been proposed for the composition of the Sun based on (1) the oxygen isotopic measurements of the solar wind implanted into metallic particles in lunar soil (< -20‰ by Hashizume & Chaussidon and ~ +26‰ by Ireland et al.), (2) the solar wind returned by the Genesis spacecraft (-27‰ ± 6‰ by McKeegan et al.), and (3) the mineralogically pristine calcium-aluminum-rich inclusions (CAIs) (-23.3‰ ± 1.9‰ by Makide et al. and -35‰ by Gounelle et al.). CAIs are the oldest solar system solids, and are believed to have formed by evaporation, condensation, and melting processes in hot nebular region(s) when the Sun was infalling (Class 0) or evolved (Class 1) protostar. Corundum (Al2O3) is thermodynamically the first condensate from a cooling gas of solar composition. Corundum-bearing CAIs, however, are exceptionally rare, suggesting either continuous reaction of the corundum condensates with a cooling nebular gas and their replacement by hibonite (CaAl12O19) or their destruction by melting together with less refractory condensates during formation of igneous CAIs. In contrast to the corundum-bearing CAIs, isolated micrometer-sized corundum grains are common in the acid-resistant residues from unmetamorphosed chondrites. These grains could have avoided multistage reprocessing during CAI formation and, therefore, can potentially provide constraints on the initial oxygen isotopic composition of the solar nebula, and, hence, of the Sun. Here we report oxygen isotopic compositions of ~60 micrometer-sized corundum grains in the acid-resistant residues from unequilibrated ordinary chondrites (Semarkona (LL3.0), Bishunpur (LL3.1), Roosevelt County 075 (H3.2)) and unmetamorphosed carbonaceous

  6. Spatial and temporal oxygen isotope trends at the northern tree-line in Eurasia

    NASA Astrophysics Data System (ADS)

    Saurer, Matthias; Schweingruber, Fritz; Vaganov, Eugene A.; Shiyatov, Stepan G.; Siegwolf, Rolf

    2002-05-01

    The oxygen isotope ratio of ice cores and sea-sediments is an extremely useful source of information on long-term climatic changes. A similar approach has been applied to the oxygen isotope ratio of tree rings to enable a pattern-based reconstruction of the isotope variations on the continents. We present an oxygen isotope map for northern Eurasia spanning from Norway to Siberia, that reflects the isotope distribution in the late 19th century, and compare it with an equivalent map for the present-day situation. The average isotope values of 130 trees show a large east-to-west gradient and are highly correlated with the isotope distribution of precipitation. Surprisingly, the 18O/16O ratio of the wood has been decreasing in the interior of the continent since the late 19th century, in contrast to the strong temperature increase recorded by meteorological data. From this isotope trend over time a change in the seasonality of precipitation can be inferred.

  7. Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

    NASA Astrophysics Data System (ADS)

    Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

    2017-12-01

    The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical

  8. Relict zircon U-Pb age and O isotope evidence for reworking of Neoproterozoic crustal rocks in the origin of Triassic S-type granites in South China

    NASA Astrophysics Data System (ADS)

    Gao, Peng; Zheng, Yong-Fei; Chen, Yi-Xiang; Zhao, Zi-Fu; Xia, Xiao-Ping

    2018-02-01

    Granites derived from partial melting of sedimentary rocks are generally characterized by high δ18O values and abundant relict zircons. Such relict zircons are valuable in tracing the source rocks of granites and the history of crustal anatexis. Here we report in-situ U-Pb ages, O isotopes and trace elements in zircons from Triassic granites in the Zhuguangshan and Jiuzhou regions, which are located in the Nanling Range and the Darongshan area, respectively, in South China. Zircon U-Pb dating yields magma crystallization ages of 236 ± 2 Ma for the Zhuguangshan granites and 246 ± 2 Ma to 252 ± 3 Ma for the Jiuzhou granites. The Triassic syn-magmatic zircons are characterized by high δ18O values of 10.1-11.9‰ in Zhuguangshan and 8.5-13.5‰ in Jiuzhou. The relict zircons show a wide range of U-Pb ages from 315 to 2185 Ma in Zhuguangshan and from 304 to 3121 Ma in Jiuzhou. Nevertheless, a dominant age peak of 700-1000 Ma is prominent in both occurrences, demonstrating that their source rocks were dominated by detrital sediments weathered from Neoproterozoic magmatic rocks. Taking previous results for regional granites together, Neoproterozoic relict zircons show δ18O values in a small range from 5 to 8‰ for the Nanling granites but a large range from 5 to 11‰ for the Darongshan granites. In addition, relict zircons of Paleozoic U-Pb age occur in the two granitic plutons. They exhibit consistently high δ18O values similar to the Triassic syn-magmatic zircons in the host granites. These Paleozoic relict zircons are interpreted as the peritectic product during transient melting of the metasedimentary rocks in response to the intracontinental orogenesis in South China. Therefore, the relict zircons of Neoproterozoic age are directly inherited from the source rocks of S-type granites, and those of Paleozoic age record the transient melting of metasedimentary rocks before intensive melting for granitic magmatism in the Triassic.

  9. Sources and Contributions of Oxygen During Microbial Pyrite Oxidation: the Triple Oxygen Isotopes of Sulfate

    NASA Astrophysics Data System (ADS)

    Ziegler, K.; Coleman, M. L.; Mielke, R. E.; Young, E. D.

    2008-12-01

    The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (< 3 days) is characterized by subtle and multiple changes in oxygen source and contribution that is likely due to the adjustment of the microbial metabolism from S to Fe2+-oxidation. A more detailed understanding of the microbial mechanisms and behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of

  10. Photosynthetic Fractionation of the Stable Isotopes of Oxygen and Carbon.

    PubMed Central

    Guy, R. D.; Fogel, M. L.; Berry, J. A.

    1993-01-01

    Isotope discrimination during photosynthetic exchange of O2 and CO2 was measured using enzyme, thylakoid, and whole cell preparations. Evolved oxygen from isolated spinach thylakoids was isotopically identical (within analytical error) to its source water. Similar results were obtained with Anacystis nidulans Richter and Phaeodactylum tricornutum Bohlin cultures purged with helium. For consumptive reactions, discrimination ([delta], where 1 + [delta]/1000 equals the isotope effect, k16/k18 or k12/k13) was determined by analysis of residual substrate (O2 or CO2). The [delta] for the Mehler reaction, mediated by ferredoxin or methylviologen, was 15.3[per mille (thousand) sign]. Oxygen isotope discrimination during oxygenation of ribulose-1,5-bisphosphate (RuBP) catalyzed by RuBP carboxylase/oxygenase (Rubisco) was 21.3[per mille (thousand) sign] and independent of enzyme source, unlike carbon isotope discrimination: 30.3[per mille (thousand) sign] for spinach enzyme and 19.6 to 23[per mille (thousand) sign] for Rhodospirillum rubrum and A. nidulans enzymes, depending on reaction conditions. The [delta] for O2 consumption catalyzed by glycolate oxidase was 22.7[per mille (thousand) sign]. The expected overall [delta] for photorespiration is about 21.7[per mille (thousand) sign]. Consistent with this, when Asparagus sprengeri Regel mesophyll cells approached the compensation point within a sealed vessel, the [delta]18O of dissolved O2 came to a steady-state value of about 21.5[per mille (thousand) sign] relative to the source water. The results provide improved estimates of discrimination factors in several reactions prominent in the global O cycle and indicate that photorespiration plays a significant part in determining the isotopic composition of atmospheric oxygen. PMID:12231663

  11. Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

    NASA Astrophysics Data System (ADS)

    Nielson, Kristine E.; Bowen, Gabriel J.

    2010-03-01

    Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

  12. Primary Data on U/Pb-Isotope Ages and Lu/Hf-Isotope Geochemical Systematization of Detrital Zircons from the Lopatinskii Formation (Vendian-Cambrian Transition Levels) and the Tectonic Nature of Teya-Chapa Depression (Northeastern Yenisei Ridge)

    NASA Astrophysics Data System (ADS)

    Kuznetsov, N. B.; Priyatkina, N. S.; Rud'ko, S. V.; Shatsillo, A. V.; Collins, W. J.; Romanyuk, T. V.

    2018-03-01

    The main results are presented on U/Pb-isotope dating of 100 detrital zircons and, selectively, on the Lu/Hf-isotope system of 43 grains from sandstones of the Lopatinskii formation (the lower stratigraphic level of the Chingasan group). Ages from 896 ± 51 to 2925 ± 38 Ma were obtained with a pronounced maximum of 1890 Ma in the curve of probability density, along with ɛHf estimates from +8.4 to-15.1, which allow one to throw doubt upon the molasse nature of the Lopatinskii formation.

  13. Precambrian-Cambrian provenance of Matinde Formation, Karoo Supergroup, northwestern Mozambique, constrained from detrital zircon U-Pb age and Lu-Hf isotope data

    NASA Astrophysics Data System (ADS)

    Bicca, Marcos Müller; Jelinek, Andrea Ritter; Philipp, Ruy Paulo; de Carvalho Lana, Cristiano; Alkmim, Ana Ramalho

    2018-02-01

    The Permian-Triassic time interval was a period of high sedimentation rates in the intracontinental Karoo rift basin of northwestern Mozambique, reflecting high exhumation rates in the surrounding high ground Precambrian-Cambrian basement and juxtaposed nappes. U-Pb LA-MC-ICPMS dating and Lu-Hf isotopic analysis of detrital zircons from the Late Permian-Early Triassic Matinde Formation of the Karoo Supergroup is used as a reliable proxy to map denudation patterns of source regions. Data allow discrimination of U-Pb age populations of ca. 1250-900 Ma, a secondary population between ca. 900-700 and a major contribution of ages around ca. 700-490 Ma. Zircon grains of the Mesoproterozoic age population present Mesoproterozoic (1000-1500 Ma) to Paleoproterozoic (1800-2300 Ma) Hf TDM ages, with positive (0 to +11) and negative εHf values (-3 to -15), respectively. The younger U-Pb age population also presents two different groups of zircon grains according to Lu-Hf isotopes. The first group comprise Paleoproterozoic (1800-2300 Ma) ages, with highly negative εHf values, between -10 and -22, and the second group exhibits Mesoproterozoic ages (1200-1500 Ma), with increased juvenile εHf values (ca. 0 to -5). These Hf isotopes reinforce the presence of unexposed ancient crust in this region. The oldest U-Pb age population resembles the late stages of Grenville Orogeny and the Rodinia Supercontinent geotectonic activity mostly represented by magmatic rocks, which are widely present in the basement of northern Mozambique. The juvenile Hf-isotope signature with an older age component is associated to rocks generated from subduction processes with crust assimilation by continental arcs, which we correlate to rocks of the Nampula Complex, south and east of the Moatize-Minjova Basin. The U-Pb ages between 900 and 700 Ma were correlated to the calc-alkaline magmatism registered in the Guro Suite, related to the breakup phase of Rodinia, and mark the western limit of the Moatize

  14. The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

    NASA Astrophysics Data System (ADS)

    von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.

    2013-12-01

    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported

  15. Implications of Bishop Tuff zircon U-Pb ages for rates of zircon growth and magma accumulation

    NASA Astrophysics Data System (ADS)

    Reid, M. R.; Schmitt, A. K.

    2012-12-01

    Rates of geologic processes obtained from natural studies rely on accurate geochronologic information. An important benchmark in geochronology as well as a valuable source of insights into the evolution of voluminous explosive eruptions is the >600 km3 Bishop Tuff (BT). A recently determined weighted mean 206Pb/238U date of 767.1±0.9 ka for a BT zircon population [1] is indistinguishable from the recalibrated 40Ar/39Ar sanidine date of 767.4±2.2 ka [2], potentially providing a key intercalibration point between astronomical and radio-isotopic dating approaches. Consequences of these results are linear zircon growth rates of >1×10-14 cm/sec and magma accumulation rates of >200 km3/ka. In contrast, spatially selective SIMS U-Pb dating of BT zircons yielded mean pre-eruption ages of 850 ka [3], a difference that raises questions about the validity of intercalibration between U-Pb and K-Ar dating methods and the history of magma accumulation. We obtained new SIMS analyses of the BT zircons using more spatially and analytically sensitive methods and verifying our accuracy against the TIMS dated Quaternary zircon 61.308A (2.488±0.002 Ma). Analyses were performed on zircon rims and on oriented cross-sections exposed during optical interferometry-calibrated serial sectioning removing the outermost ~31 μm. Sputtering by a 100 nA ion beam versus the normally employed 10-12 nA beam resulted in enhanced radiogenic Pb yields and analytical uncertainties for Quaternary zircon approaching the U-Pb age reproducibility of the primary zircon standard (~1-2 % for AS3). Ages obtained at ~31 μm depth (representing <5% of crystal growth in most cases) average 892±26ka (MSWD=0.29), corroborating previous evidence for residence times of several tens of ka. Rim ages average 781±22 ka (MSWD=0.61), overlapping Ar/Ar determinations of eruption age and corroborating the importance of near-eruption aged zircon growth. Our results confirm the presence of BT zircon domains that predate

  16. A non-zircon Hf isotope record in Archean black shales from the Pilbara craton confirms changing crustal dynamics ca. 3 Ga ago.

    PubMed

    Nebel-Jacobsen, Yona; Nebel, Oliver; Wille, Martin; Cawood, Peter A

    2018-01-17

    Plate tectonics and associated subduction are unique to the Earth. Studies of Archean rocks show significant changes in composition and structural style around 3.0 to 2.5 Ga that are related to changing tectonic regime, possibly associated with the onset of subduction. Whole rock Hf isotope systematics of black shales from the Australian Pilbara craton, selected to exclude detrital zircon components, are employed to evaluate the evolution of the Archean crust. This approach avoids limitations of Hf-in-zircon analyses, which only provide input from rocks of sufficient Zr-concentration, and therefore usually represent domains that already underwent a degree of differentiation. In this study, we demonstrate the applicability of this method through analysis of shales that range in age from 3.5 to 2.8 Ga, and serve as representatives of their crustal sources through time. Their Hf isotopic compositions show a trend from strongly positive εHf initial values for the oldest samples, to strongly negative values for the younger samples, indicating a shift from juvenile to differentiated material. These results confirm a significant change in the character of the source region of the black shales by 3 Ga, consistent with models invoking a change in global dynamics from crustal growth towards crustal reworking around this time.

  17. Oxygen isotopes as a tracer of phosphate sources and cycling in aquatic systems (Invited)

    NASA Astrophysics Data System (ADS)

    Young, M. B.; Kendall, C.; Paytan, A.

    2013-12-01

    The oxygen isotopic composition of phosphate can provide valuable information about sources and processes affecting phosphorus as it moves through hydrologic systems. Applications of this technique in soil and water have become more common in recent years due to improvements in extraction methods and instrument capabilities, and studies in multiple aquatic environments have demonstrated that some phosphorus sources may have distinct isotopic compositions within a given system. Under normal environmental conditions, the oxygen-phosphorus bonds in dissolved inorganic phosphate (DIP) can only be broken by enzymatic activity. Biological cycling of DIP will bring the phosphate oxygen into a temperature-dependent equilibrium with the surrounding water, overprinting any existing isotopic source signals. However, studies conducted in a wide range of estuarine, freshwater, and groundwater systems have found that the phosphate oxygen is often out of biological equilibrium with the water, suggesting that it is common for at least a partial isotopic source signal to be retained in aquatic systems. Oxygen isotope analysis on various potential phosphate sources such as synthetic and organic fertilizers, animal waste, detergents, and septic/wastewater treatment plant effluents show that these sources span a wide range of isotopic compositions, and although there is considerable overlap between the source groups, sources may be isotopically distinct within a given study area. Recent soil studies have shown that isotopic analysis of phosphate oxygen is also useful for understanding microbial cycling across different phosphorus pools, and may provide insights into controls on phosphorus leaching. Combining stable isotope information from soil and water studies will greatly improve our understanding of complex phosphate cycling, and the increasing use of this isotopic technique across different environments will provide new information regarding anthropogenic phosphate inputs and

  18. A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings.

    NASA Astrophysics Data System (ADS)

    Roden, J. S.; Farquhar, G. D.

    2008-12-01

    Stable isotopes ratios of carbon and oxygen in tree ring cellulose have been used to infer environmental change. Process-based models have been developed to clarify the potential of historic tree ring records for meaningful paleoclimatic reconstructions. However, isotopic variation can be influenced by multiple environmental factors making simplistic interpretations problematic. Recently, the dual isotope approach, where the variation in one stable isotope ratio (e.g. oxygen) is used to constrain the interpretation of variation in another (e.g. carbon), has been shown to have the potential to de-convolute isotopic analysis. However, this approach requires further testing to determine its applicability for paleo-reconstructions using tree-ring time series. We present a study where the information needed to parameterize mechanistic models for both carbon and oxygen stable isotope ratios were collected in controlled environment chambers for two species (Pinus radiata and Eucalyptus globulus). The seedlings were exposed to treatments designed to modify leaf temperature, transpiration rates, stomatal conductance and photosynthetic capacity. Both species were grown for over 100 days under two humidity regimes that differed by 20%. Stomatal conductance was significantly different between species and for seedlings under drought conditions but not between other treatments or humidity regimes. The treatments produced large differences in transpiration rate and photosynthesis. Treatments that effected photosynthetic rates but not stomatal conductance influenced carbon isotope discrimination more than those that influenced primarily conductance. The various treatments produced a range in oxygen isotope ratios of 7 ‰. Process models predicted greater oxygen isotope enrichment in tree ring cellulose than observed. The oxygen isotope ratios of bulk leaf water were reasonably well predicted by current steady-state models. However, the fractional difference between models that

  19. A Plant-Based Proxy for the Oxygen Isotope Ratio of Atmospheric Water Vapor

    NASA Astrophysics Data System (ADS)

    Helliker, B.

    2007-12-01

    Atmospheric water vapor is a major component of the global hydrological cycle, but the isotopic balance of vapor is largely unknown. It is shown here that the oxygen isotope ratio of leaf water in the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides (Spanish Moss) is controlled by the oxygen isotope ratio of atmospheric water vapor in both field and lab studies. Assuming that the leaf-water isotopic signature (and hence the atmospheric water vapor signature) is recorded in plant organic material, the atmospheric water vapor oxygen isotope ratios for Miami, Florida (USA) were reconstructed for several years from 1878 to 2005 using contemporary and herbarium specimens. T. usneoides ranges from Virginia, USA southwards through the tropics to Argentina, and the CAM epiphytic lifeform is widespread in other species. Therefore, epiphytes may be used to reconstruct the isotope ratio of atmospheric water for spatial scales that span over 60° of latitude and temporal scales that cover the last century of global temperature increase.

  20. Zircon U-Pb and Hf-O isotopes trace the architecture of polymetallic deposits: A case study of the Jurassic ore-forming porphyries in the Qin-Hang metallogenic belt, China

    NASA Astrophysics Data System (ADS)

    Zhao, Panlao; Yuan, Shunda; Mao, Jingwen; Santosh, M.; Zhang, Dongliang

    2017-11-01

    The Qin-Hang intra-continental porphyry-skarn Cu polymetallic belt (QHMB) is among the economically important metallogenic belts in South China. The significant differences in the size and metal assemblage of the Jurassic magmatic-hydrothermal ore deposits in this belt remain as an enigma. Here we employ zircon U-Pb and Hf-O isotopes of the Tongshanling and Baoshan Cu-Pb-Zn deposits in the central part of the QHMB to investigate the contrasting metallogenic architecture. Our SIMS zircon U-Pb data indicate that the Tongshanling and Baoshan granodiorite formed at 160 Ma. These rocks show high Mg# values, and negative zircon εHf(t) and high δ18O values suggesting that the magmas of the granodiorite porphyries were mainly generated through the anatexis of older crustal components triggered by the input of mantle-derived magma. The minor content of amphibole phenocrysts, low Sr/Y ratios, negative Eu anomaly, and low zircon Ce4 +/Ce3 + ratios indicate that the porphyries are relatively less oxidized with less water content compared with the ore-bearing porphyries in the Dexing and Yuanzhuding porphyry Cu deposits in the northern and southern part of the QHMB, suggesting that high magmatic water content and oxidation state are important prerequisites for the formation of large size porphyry-skarn copper deposits in the QHMB. The positive correlation between zircon εHf(t) values with the Cu reserves, as well as zircon δ18O values with the Cu/(Cu + Pb + Zn) ratios of the deposits indicate that the magmatic sources exerted a first-order control on the volume and metal assemblage of deposits in the QHMB. The Hf and Nd isotope contour maps indicate that the central part of the QHMB has high potential for Pb-Zn-dominated magmatic-hydrothermal deposits, whereas the northern and southern part of the QHMB are prospective for large Cu deposits. Our results have important implications in formulating regional exploration strategies for Jurassic porphyry-skarn Cu-Pb-Zn deposits in

  1. Using detrital zircons from river sands to constrain major tectono-thermal events of the Cathaysia Block, SE China

    NASA Astrophysics Data System (ADS)

    Xu, Yonghang; Wang, Christina Yan; Zhao, Taiping

    2016-07-01

    Detrital zircons from the Minjiang and Zhujiang Rivers in SE China have been analyzed for U/Pb ages and Lu-Hf isotopic compositions to constrain their provenance and the growth history of the continental crust of the Cathaysia Block. Zircon U/Pb ages show five major populations at 90-250 Ma, 400-500 Ma, 0.7-1.2 Ga, 1.6-2.0 Ga and 2.3-2.6 Ga. Proterozoic zircons have Hf isotopic signatures consistent with the remelted ancient crust and the involvement of juvenile crust. However, Phanerozoic zircons have Hf isotopic signatures indicative of reworked or recycled ancient crust. Crustal growth rates based on the two-stage Hf model ages of the detrital zircons indicate that 30% and 90% of present crust in the northeastern Cathaysia Block was formed by 2.5 Ga and 1.6 Ga, respectively, whereas <20% continental crust was formed by 2.5 Ga, and 80% by 1.6 Ga in the southwestern Cathaysia Block. Therefore, Neoarchean and Paleoproterozoic were two major periods of crustal growth of the Cathaysia Block. Our results also reveal that the tectono-thermal events at ∼370 Ma and ∼117 Ma may have occurred to the Wuyishan terrane in the northeastern Cathaysia Block. Jurassic zircon grains have Hf isotopic compositions more variable than Cretaceous grains, which may have been derived from different source rocks. The 140-120 Ma tectono-thermal events were likely related to the change of the subduction direction of the Paleo-Pacific plate from northward to northwestward at 140 Ma. The 112-90 Ma tectono-thermal events may be correlated with the rollback of the subducted paleo-Pacific plate at ∼110 Ma.

  2. Correcting speleothem oxygen isotopic variations for growth-rate controlled kinetic fractionation effects

    NASA Astrophysics Data System (ADS)

    Stoll, Heather; Moreno, Ana; Cacho, Isabel; Mendez Vicence, Ana; Gonzalez Lemos, Saul; Pirla Casasayas, Gemma; Cheng, Hai; Wang, Xianfeng; Edwards, R. Lawrence

    2015-04-01

    The oxygen isotopic signature may be the most widely used climate indicator in stalagmites, but recent experimental and theoretical studies indicate the potential for kinetic fractionation effects which may be significant, especially in situations where the primary signal from rainfall isotopic composition and cave temperature is limited to a few permil. Here we use a natural set of stalagmites to illustrate the magnitude of such effects and the potential for deconvolving kinetic signals from the primary temperature and rainfall signals. We compare isotopic records from 6 coeval stalagmites covering the interval 140 to 70 ka, from two proximal caves in NW Spain which experienced the same primary variations in temperature and rainfall d18O, but exhibit a large range in growth rates and temporal trends in growth rate. Stalagmites growing at faster rates near 50 microns/year have oxygen isotopic ratios more than 1 permil more negative than coeval stalagmites with very slow (5 micron/year) growth rates. Because growth rate variations also occur over time within any given stalagmite, the measured oxygen isotopic time series for a given stalagmite includes both climatic and kinetic components. Removal of the kinetic component of variation in each stalagmite, based on the dependence of the kinetic component on growth rate, is effective at distilling a common temporal evolution among the oxygen isotopic records of the multiple stalagmites. However, this approach is limited by the quality of the age model. For time periods characterized by very slow growth and long durations between dates, the presence of crypto-hiatus may result in average growth rates which underestimate the instantaneous speleothem deposition rates and which therefore underestimate the magnitude of kinetic effects. We compare the composite corrected oxygen isotopic record with other records of the timing of glacial inception in the North Atlantic realm.

  3. Meteorites and their parent bodies: Evidence from oxygen isotopes

    NASA Technical Reports Server (NTRS)

    Clayton, R. N.

    1978-01-01

    Isotopic abundance variations among meteorites are used to establish genetic associations between meteorite classes. Oxygen isotope distributions between group II E irons with H-group ordinary chondrites and enstatic meteorites indicate that the parent bodies were formed out of pre-solar material that was not fully mixed at the time condensation occurred within the solar nebula.

  4. Genesis of zircon megacrysts in Cenozoic alkali basalts and the heterogeneity of subcontinental lithospheric mantle, eastern China

    NASA Astrophysics Data System (ADS)

    Yu, Yao; Xu, Xisheng; Chen, Xiaoming

    2010-09-01

    Zircon megacrysts are found in alluvial deposits associated with Cenozoic basalts from Changle in Shandong Province, Mingxi in Fujian Province and Penglai in Hainan Province within the coastal area of eastern China. They are colourless, transparent to light brown-maroon, and some of them are up to 16 mm long. U-Pb ages of zircon megacrysts from Changle, Mingxi and Penglai are 19.2 ± 0.7 Ma, 1.2 ± 0.1 Ma and 4.1 ± 0.2 Ma respectively, slightly older than the eruption ages of their corresponding host rocks (16.05-18.87 Ma, 0.9-2.2 Ma, 3 Ma). ɛHf(t) values of zircon megacrysts are 9.02 ± 0.49, 6.83 ± 0.47, 4.46 ± 0.48 for Changle, Mingxi and Penglai, respectively, which indicates their mantle origin. We suggest that the zircon megacrysts originated from metasomatised lithospheric mantle and were later brought up quickly by the host basaltic magma. The euhedral forms, uniform internal structure and chemical homogeneity within a single grain suggest crystallization under stable conditions. Pronounced positive Ce anomalies and negligible Eu anomalies suggest oxidizing conditions and little or no fractional crystallization of plagioclase. The differences in Hf-isotope compositions among the zircon megacrysts from different localities are consistent with the Sr-Nd-Pb isotopic compositions of their respective host basalts. This indicates that the host basalts acquired their isotopic signatures from the lithospheric mantle from which the zircon megacrysts derived. These data document the lateral compositional heterogeneity in the upper mantle beneath eastern China. Like mantle xenoliths, zircon megacrysts also have the potential to fingerprint the composition and evolution of the subcontinental lithospheric mantle.

  5. Tracing source terranes using U-Pb-Hf isotopic analysis of detrital zircons: provenance of the Orhanlar Unit of the Palaeotethyan Karakaya subduction-accretion complex, NW Turkey

    NASA Astrophysics Data System (ADS)

    Ustaömer, Timur; Ayda Ustaömer, Petek; Robertson, Alastair; Gerdes, Axel

    2016-04-01

    Sandstones of the Late Palaeozoic-Early Mesozoic Karakaya Complex are interpreted to have accumulated along an active continental margin related to northward subduction of Palaeotethys. The age of deposition and provenance of the sandstones are currently being determined using radiometric dating of detrital zircons, coupled with dating of potential source terranes. Our previous work shows that the U-Pb-Hf isotopic characteristics of the sandstones of all but one of the main tectonostratigraphic units of the Karakaya Complex are compatible with a provenance that was dominated by Triassic and Permo-Carboniferous magmatic arc-type rocks, together with a minor contribution from Lower to Mid-Devonian igneous rocks (Ustaömer et al. 2015). However, one of the tectono-stratigraphic units, the Orhanlar Unit, which occurs in a structurally high position, differs in sedimentary facies and composition from the other units of the Karakaya Complex. Here, we report new isotopic age data for the sandstones of the Orhanlar Unit and also from an extensive, associated tectonic slice of continental metamorphic rocks (part of the regional Sakarya Terrane). Our main aim is to assess the provenance of the Orhanlar Unit sandstones in relation to the tectonic development of the Karakaya Complex as a whole. The Orhanlar Unit is composed of shales, sandstone turbidites and debris-flow deposits, which include blocks of Devonian radiolarian chert and Carboniferous and Permian neritic limestones. The sandstones are dominated by rock fragments, principally volcanic and plutonic rocks of basic-to-intermediate composition, metamorphic rocks and chert, together with common quartz, feldspar and mica. This modal composition contrasts significantly with the dominantly arkosic composition of the other Karakaya Complex sandstones. The detrital zircons were dated by the U-Pb method, coupled with determination of Lu-Hf isotopic compositions using a laser ablation microprobe attached to a multicollector

  6. Archean crustal evolution of the Narryer Gneiss Terrane, Western Australia, as revealed by the U-Pb age and Hf-isotope compositions of zircon from the granitic gneisses

    NASA Astrophysics Data System (ADS)

    Sylvester, P.; Souders, K.; Crowley, J. L.; Myers, J.

    2011-12-01

    The Narryer Gneiss Terrane of the Yilgarn Craton, Western Australia, is an important area for studies of early crustal evolution because of the preservation of (1) detrital zircons of Hadean to Archean age in the Jack Hills and Mt. Narryer metasedimentary belts, and (2) several widespread units of granitic gneisses emplaced between ca. 3.7 and 2.6 Ga. We have analyzed the U-Pb geochronology and Hf-isotope geochemistry of magmatic zircons from 38 samples of the granitic gneisses using laser ablation - (multicollector) - ICPMS. The sample suite is dominated by the Meeberrie gneiss, a banded quartz-microcline-oligoclase-biotite gneiss of monzogranite to granodiorite composition, and the Dugel gneiss, a leucocratic, pegmatite-layered syenogranite gneiss, but gneisses of dioritic to tonalitic composition, as well as less deformed granite sheets, are also represented. Magmatic zircons were identified on the basis of the preservation of oscillatory zoning in BSE and CL images, igneous Th/U ratios (>0.2), and concordant U-Pb isotopic systematics with low common Pb contents. The results indicate many of the gneisses are composed of the products of multiple magmatic events, as has been reported previously for samples of the Meeberrie gneiss (Kinny & Nutman, 1996, Precambrian Res. 78, 165-178). Major ages of magmatism preserved in the gneisses occurred at ca. 3685-3665 Ma, 3620-3565 Ma, 3495-3440 Ma, 3375-3330 Ma, and 3300-3260 Ma. The late granite sheets crystallized at 2710-2645 Ma. Hf-isotope compositions of the zircons trend to less radiogenic values with decreasing age, with ɛHf values of ca. 0 to -5 for 3.7-3.4 Ga gneisses, ca. -1 to -9 for 3.4-3.2 Ga gneisses and ca. -5 to -20 for the late granite sheets. The array of the Hf isotopic compositions with time for the entire sample set are fit well by a regression indicating a source reservoir with a 176Lu/177Hf of 0.022 extracted from the depleted mantle at 3.9 Ga. This suggests that the Narryer gneisses and late granite

  7. Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

    USGS Publications Warehouse

    Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

    2010-01-01

    Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

  8. Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

    PubMed

    Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky

    2012-09-30

    Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

  9. Fossil black smoker yields oxygen isotopic composition of Neoproterozoic seawater.

    PubMed

    Hodel, F; Macouin, M; Trindade, R I F; Triantafyllou, A; Ganne, J; Chavagnac, V; Berger, J; Rospabé, M; Destrigneville, C; Carlut, J; Ennih, N; Agrinier, P

    2018-04-13

    The evolution of the seawater oxygen isotopic composition (δ 18 O) through geological time remains controversial. Yet, the past δ 18 O seawater is key to assess past seawater temperatures, providing insights into past climate change and life evolution. Here we provide a new and unprecedentedly precise δ 18 O value of -1.33 ± 0.98‰ for the Neoproterozoic bottom seawater supporting a constant oxygen isotope composition through time. We demonstrate that the Aït Ahmane ultramafic unit of the ca. 760 Ma Bou Azzer ophiolite (Morocco) host a fossil black smoker-type hydrothermal system. In this system we analyzed an untapped archive for the ocean oxygen isotopic composition consisting in pure magnetite veins directly precipitated from a Neoproterozoic seawater-derived fluid. Our results suggest that, while δ 18 O seawater and submarine hydrothermal processes were likely similar to present day, Neoproterozoic oceans were 15-30 °C warmer on the eve of the Sturtian glaciation and the major life diversification that followed.

  10. Looking through the Zircon Kaleidoscope: Durations, Rates, and Fluxes in Silicic Magmatic System

    NASA Astrophysics Data System (ADS)

    Schaltegger, U.; Wotzlaw, J. F.

    2014-12-01

    The crystallization rate of zircon in a cooling magma depends on the cooling rate through the saturation interval in addition to compositional and kinetic factors. Repeated influx of hot magma over 10-20 ka leads to short-amplitude temperature oscillations, which are recorded by resorption/crystallization cycles of zircon. Plotting the number of dated zircons versus their high-precision U-Pb date results in curves that qualitatively relate to the evolution of magma temperature over time [1], [2]. The trace elemental, O and Hf isotopic composition of zircon gives indications about the degree of magma homogenization and thermal evolution. Zircons from systems with small volumes and magma fluxes record non-systematic chemical and Hf isotopic heterogeneity, suggesting crystallization in non-homogenized ephemeral magma batches. Such systems typically lead to small, mid-upper crustal plutons [3]. Zircons from large-volume crystal-poor rhyolites record initial heterogeneities and rapid amalgamation of smaller magma batches over 10 ka [4], while zircons from monotonous intermediates record magma evolution over several 100 ka with coherent fractionation trends suggesting homogenization and a coherent thermal evolution [2]. In both cases, volumes and flux rates were sufficient to produce large volumes of eruptible magma on very contrasting time scales. Zircon is therefore recording cyclic crystallization-rejuvenation processes during temperature fluctuations in intermediate to upper crustal magma reservoirs but may not relate to the physical pluton emplacement or eruption. We can quantify volumes, rates of magma influx, rates of cooling and crystallization, and the degree of convective homogenization from zircon data, and infer reservoir assembly and eruption trigger mechanisms. These parameters largely control the evolution of long-lived, low-flux silicic magmatic system typical for mid-to-upper crustal plutons, monotonous intermediates are characterized by intermediate

  11. Evidence of early Archean crust in northwest Gondwana, from U-Pb and Hf isotope analysis of detrital zircon, in Ediacaran surpacrustal rocks of northern Spain

    NASA Astrophysics Data System (ADS)

    Naidoo, Thanusha; Zimmermann, Udo; Vervoort, Jeff; Tait, Jenny

    2018-03-01

    The Mora Formation (Narcea Group) is one of the oldest Precambrian supracrustal successions in northern Spain. Here, we use U-Pb and in situ Hf isotope analysis on detrital zircon to determine its age and provenance. The youngest U-Pb dates constrain the maximum depositional age of the Mora Formation at 565 ± 11 Ma. Results indicate: (1) a dominant Ediacaran zircon population (33%; 565-633 Ma, Cadomian) within a spectrum of Neoproterozoic ages (40%; 636-996 Ma); and (2) smaller Mesoproterozoic (5%; 1004-1240 Ma), Palaeoproterozoic (11%; 1890-2476 Ma) and Archean (11%; 2519-3550 Ma) populations. Results here do not point to one specific cratonic source area; instead, detritus may have been derived from the West African craton and Amazonia, or even the concealed Iberian basement. The lack of 1.3-1.8 Ga grains suggests exclusion of the Sahara Craton as a major source, but this is not certain. This mixed composition favours a complex source history with reworking of detritus across terrane/craton boundaries. Hafnium isotope compositions indicate a range of crustal and juvenile sources, with initial ɛHf values between -15.8 and 11.1, and Hf model ages from 0.8 to 3.7 Ga. For Neoproterozoic zircons (80%), juvenile components (ɛHf(i) +10) may be related to Rodinia fragmentation and the onset of an active margin setting leading to the Cadomian orogeny. Palaeoproterozoic to Paleoarchean grains (20%) all have negative ɛHf values and Meso- to Eoarchean Hf model ages. This indicates an early (Archean) sialic crustal component for northwestern Gondwana.

  12. Atmosphere-ocean-lithosphere interactions during the Great Oxidation Event: insights from zircon δ18O

    NASA Astrophysics Data System (ADS)

    Spencer, C. J.; Partin, C. A.; Kirkland, C.; Shiels, C.; Raub, T. D.; Kinny, P.

    2016-12-01

    The Great Oxidation Event (GOE) records a precipitous atmospheric oxygen rise, perhaps by as much as three to four orders of magnitude within a few million years. The timescale of the GOE is primarily constrained by the rapid loss of mass-independently fractionated sulfur isotopes. The drastic surface changes associated with the GOE are reflected by the appearance of marine sulfate and manganese deposits, as well as increased redox-sensitive trace metal abundances in banded iron formations and shale. Each of these manifestations is recorded at the atmosphere-lithosphere or atmosphere-ocean interface. However, how the GOE affected the lithosphere beyond the atmosphere interface has received little attention to date. We present zircon δ18O data from Paleoproterozoic sedimentary successions in Western Australia and Canada that display a step-change from the <7.5‰ Archean background to 9-11‰ by 2.35 Ga. Intriguingly, the timing of this shift coincides with the timing of the GOE. As the subduction process has been shown to be a pre-existing condition to the GOE and the timing of this shift does not correspond to any known periods of enhanced supracrustal tectonic reworking (i.e. the Siderian tectonic `slowdown'), we propose this shift must be explained by the appearance of an isotopically distinct reservoir with high δ18O that was incorporated into subduction zone magmas. One likely candidate is marine sulfate evaporite deposits, which appear with the GOE. The incorporation of this enriched δ18O reservoir would have facilitated the step change seen in the zircon δ18O record. This signal may also be present to a much lower degree associated with the "whiffs" of atmospheric oxygen prior to the GOE.

  13. Magma reservoir dynamics at Toba caldera, Indonesia, recorded by oxygen isotope zoning in quartz

    PubMed Central

    Budd, David A.; Troll, Valentin R.; Deegan, Frances M.; Jolis, Ester M.; Smith, Victoria C.; Whitehouse, Martin J.; Harris, Chris; Freda, Carmela; Hilton, David R.; Halldórsson, Sæmundur A.; Bindeman, Ilya N.

    2017-01-01

    Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ18O values. Overall, Toba quartz crystals exhibit comparatively high δ18O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ18O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum ∆core−rim = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ18O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ18O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems. PMID:28120860

  14. Magma reservoir dynamics at Toba caldera, Indonesia, recorded by oxygen isotope zoning in quartz

    NASA Astrophysics Data System (ADS)

    Budd, David A.; Troll, Valentin R.; Deegan, Frances M.; Jolis, Ester M.; Smith, Victoria C.; Whitehouse, Martin J.; Harris, Chris; Freda, Carmela; Hilton, David R.; Halldórsson, Sæmundur A.; Bindeman, Ilya N.

    2017-01-01

    Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ18O values. Overall, Toba quartz crystals exhibit comparatively high δ18O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ18O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum Δcore-rim = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ18O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ18O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems.

  15. Magma reservoir dynamics at Toba caldera, Indonesia, recorded by oxygen isotope zoning in quartz.

    PubMed

    Budd, David A; Troll, Valentin R; Deegan, Frances M; Jolis, Ester M; Smith, Victoria C; Whitehouse, Martin J; Harris, Chris; Freda, Carmela; Hilton, David R; Halldórsson, Sæmundur A; Bindeman, Ilya N

    2017-01-25

    Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ 18 O values. Overall, Toba quartz crystals exhibit comparatively high δ 18 O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ 18 O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum ∆ core-rim  = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ 18 O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ 18 O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems.

  16. Oxygen isotope geochemistry of the amphiboles: isotope effects of cation substitutions in minerals

    NASA Astrophysics Data System (ADS)

    Kohn, Matthew J.; Valley, John W.

    1998-06-01

    The occurrence of coexisting amphiboles in rocks and the likelihood of concurrent isotope closure allows equilibrium oxygen isotope fractionations among the amphiboles to be recovered from natural samples. Oxygen isotope analyses of mineral separates using laser fluorination show that coexisting amphiboles increasingly partition 18O in the order: hornblende ≪ gedrite < cummingtonite ≤ anthophyllite. The observed fractionations at ˜575°C are: Δ(Ged-Hbl) = 0.8‰, Δ(Cum-Hbl) = 0.9, Δ(Cum-Ged) = 0.2, Δ(Ath-Ged) = 0.3, and Δ(Ath-Hbl) > 0.9. Previously published data for hornblende, actinolite, glaucophane, and garnet show that Δ(Act-Hbl) ˜ 0.2, Δ(Gln-Grt) ≫ 1, and Δ(Hbl-Grt) ˜ 0. Thus, glaucophane strongly partitions 18O relative to the calcic amphiboles. The fractionation between two amphiboles of arbitrary composition can be predicted from the known fractionations for mica endmembers, pyroxene endmembers, and exchange components such as CaAl(NaSi) -1, NaAl(CaMg) -1, CaMg -1, MgFe -1, FeMn -1, KNa -1, KAl( Si) -1, and Fe 3+Al -1. Applications of the exchange component method reproduce measured amphibole fractionations to within ±0.1 to ±0.2‰, whereas other predictive methods cause misfit for typical metamorphic hornblende of ≥0.5‰ at 575°C. Although the isotope effects of cation exchanges may be small at high-T, they magnify dramatically for minerals formed in surficial, diagenetic, and low-T metamorphic environments. Different composition clays are predicted to have equilibrium δ 18O differences of 2-9‰. If the isotope fractionation can be determined for one mineral endmember, then calibrated exchanges allow accurate prediction of the isotope fractionations for intermediate compositions of most ortho-, ring-, chain-, and sheet-silicates.

  17. Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

    NASA Astrophysics Data System (ADS)

    Sutherland, K. M.; Wankel, S. D.; Hansel, C. M.

    2016-12-01

    Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be

  18. Multiple sources for the origin of Late Jurassic Linglong adakitic granite in the Shandong Peninsula, eastern China: Zircon U-Pb geochronological, geochemical and Sr-Nd-Hf isotopic evidence

    NASA Astrophysics Data System (ADS)

    Ma, Liang; Jiang, Shao-Yong; Dai, Bao-Zhang; Jiang, Yao-Hui; Hou, Ming-Lan; Pu, Wei; Xu, Bin

    2013-03-01

    The Linglong granite is one of the most important Mesozoic plutons in the Shandong Peninsula, eastern China, and its petrogenesis has long been controversial, particularly with regard to the nature of source region and geodynamic setting. Our new precise zircon U-Pb dating results reveal that the Linglong granite was emplaced in the Late Jurassic (157-160 Ma). In addition, abundant inherited zircons are identified in the granite with four groups of age peaked at ~ 208, ~ 750, ~ 1800 and ~ 2450 Ma. Geochemical studies indicate that the Linglong granite is weakly peraluminous I-type granite, and is characterized by high SiO2, Sr and La, but low MgO, Y and Yb contents, strongly fractionated REE pattern and high Sr/Y and La/Yb ratios. It also exhibits high initial 87Sr/86Sr ratios (0.7097 to 0.7125), low ɛNd(t) (- 17.7 to - 20.3) and variable zircon ɛHf(t) (- 22.2 to - 8.7) values. Calculation of the zircon saturation temperature (TZr) reveals that the magma temperatures are 760 ± 20 °C, and the lowest TZr value of 740 °C may be close to initial magma temperature of this inheritance-rich rock. Interpretation of the elemental and isotopic data suggests that the Linglong granite has some affinities with the adakite, and was most likely derived from partial melting of thickened lower crust without any significant contribution of mantle components. The presence of a large number of inherited zircons and variable Sr-Nd-Hf isotopic compositions reveal that the Linglong granite probably has multiple sources consisting of the lower crust of both South China Block and North China Block, as well as the collision-related alkaline rocks and UHP metamorphic rocks. The continental arc-rifting related to the Izanagi plate subduction was the most likely geodynamic force for formation of the Jurassic Linglong adakatic granite in the Shandong Peninsula.

  19. Applications of primary and secondary inclusion assemblages for zircon petrogenesis and alteration

    NASA Astrophysics Data System (ADS)

    Bell, E. A.

    2017-12-01

    Igneous zircon often contains abundant mineral inclusions which represent a mixture of primary phases captured during crystallization in magma and secondary phases formed either during late-stage deuteric alteration of a solidifying pluton, during later metamorphism, or during detrital transport and diagenesis in groundwater. Microstructural examination of zircon from both magmatic and metamorphic rocks reveals varying abundances of clearly secondary phases filling cracks and potentially secondary phases in contact with cracks or in disturbed regions of the host zircon. We used EDS and WDS X-ray spectroscopy to examine crack-isolated, crack-intersecting, and crack-filling phases in zircon from Phanerozoic magmatic rocks (USA, Victoria), several Grenville (Blue Ridge, VA) orthogneisses, and detrital zircons in metasediments from Jack Hills, Mt. Narryer (Western Australia) and the Nuvvuagittuq supracrustal belt (northern Quebec). Orthogneiss and detrital zircon appear to retain primary inclusion compositions away from contact with cracks or disturbed regions of zircon (as distinguished by U-Pb). Characteristic trace element patterns associated with chemical alteration of zircon match well with the apparently dominant secondary phases in metasedimentary detrital zircons and magmatic zircon subjected to deuteric alteration. Additionally, high spatial resolution Pb isotopic analyses of secondary phosphates using the CAMECA ims1290 ion microprobe reveal preservation of multiple generations of metamorphic phosphate, in some cases juxtaposed within a single inclusion on the 5-10 micron scale. Zircon can therefore in many cases preserve the compositions of its primary inclusion cargo through later metamorphism. Zircon can also preserve information about individual hydrothermal or metamorphic events during the grain's residence in the crust.

  20. Petrogenesis of granodiorite in the Balong region, eastern Kunlun Orogen, China: Constraints from zircon U-Pb geochronology, geochemistry and Sr-Nd-Hf isotopes

    NASA Astrophysics Data System (ADS)

    Huang, X.; Li, H.; Wang, Y.; Liu, Y.

    2017-12-01

    Numerous granitoid intrusions that close to the Balong region have great scientific significance to reveal tectonic evolution and geodynamic background of eastern Kunlun Orogen (EKO). Balong granodiorite (BLG) is located at the northern of the EKO. It generally emplaced into the Proterozoic to Lower Palaeozoic rocks and contains abundant mafic microgranular enclaves. LA-ICP-MS zircon U-Pb dating of the BLG gives a 206Pb/238U age of 230.7±1.9 Ma, indicating that it was emplaced in the Late Triassic. The BLG is high-K calc-alkaline series and metaluminous, with SiO2 of 59.86 61.83%, K2O+Na2O of 5.98 6.40%, CaO of 4.95 5.77% and P2O5 of 0.14% 0.18%. The granodioritic rocks are enriched in LILE (Ba, Rb, Sr), but depleted in HFSE (Nb, Ta, P, Ti), with weak negative Eu anomalies (δEu=0.70 0.82). Mineralogy and geochemistry of the rocks show an affinity to I-type granite. The BLG, having (87Sr/86Sr)i ratios of 0.70819 to 0.70832, ɛNd(t) values of -5.27 to -5.75, and zircon ɛHf(t) values ranging from -3.86 to -1.34. The whole-rock Nd isotopic model ages (1432 1471 Ma) and zircon Hf isotopic model ages (1205 1357 Ma) indicate that the BLG is generated by partial melting of lower crust (Precambrian metabasaltic basement rocks) with different degree of involvement of mantle material. Combined with regional geological data, the granodiorite was derived from dehydration melting of mafic lower crustal rocks during the subduction of the Anyemaqen ocean lithosphere at Late Permian-Triassic in a subduction setting. Basaltic magma underplating and crust-mantle mixing are main mechanisms for the origin of large-scale I-type granitoid in Balong.

  1. Contrasting Granite Metallogeny through the Zircon Record: A Case Study from Myanmar.

    PubMed

    Gardiner, Nicholas J; Hawkesworth, Chris J; Robb, Laurence J; Whitehouse, Martin J; Roberts, Nick M W; Kirkland, Christopher L; Evans, Noreen J

    2017-04-07

    Granitoid-hosted mineral deposits are major global sources of a number of economically important metals. The fundamental controls on magma metal fertility are tectonic setting, the nature of source rocks, and magma differentiation. A clearer understanding of these petrogenetic processes has been forged through the accessory mineral zircon, which has considerable potential in metallogenic studies. We present an integrated zircon isotope (U-Pb, Lu-Hf, O) and trace element dataset from the paired Cu-Au (copper) and Sn-W (tin) magmatic belts in Myanmar. Copper arc zircons have juvenile εHf (+7.6 to +11.5) and mantle-like δ 18 O (5.2-5.5‰), whereas tin belt zircons have low εHf (-7 to -13) and heavier δ 18 O (6.2-7.7‰). Variations in zircon Hf and U/Yb reaffirm that tin belt magmas contain greater crustal contributions than copper arc rocks. Links between whole-rock Rb/Sr and zircon Eu/Eu* highlight that the latter can monitor magma fractionation in these systems. Zircon Ce/Ce* and Eu/Eu* are sensitive to redox and fractionation respectively, and here are used to evaluate zircon sensitivity to the metallogenic affinity of their host rock. Critical contents of Sn in granitic magmas, which may be required for the development of economic tin deposits, are marked by zircon Eu/Eu* values of ca. ≤0.08.

  2. Determining Oxygen Isotopic Fractionation between the ferrous sulfate, melanterite, and aqueous sulfate

    NASA Astrophysics Data System (ADS)

    Shulaker, D. Z.; Kohl, I.; Coleman, M. L.

    2011-12-01

    Studying regions on Earth that are analogous to Mars serve as case studies for studying astrobiology and planetary surface rock formation processes. Rio Tinto, Spain is very rich in iron sulfates, and has an environment that is possibly very similar to the former environment on Mars. Certain bacteria play significant roles in accelerating pyrite oxidation rates, the products of which contribute to the formation of ferrous sulfates, such as melanterite. During mineral crystallization in an aqueous solution, there are systematic isotopic differences between dissolved species and solid phases. Quantifying this fractionation enables isotopic analysis to be used to trace the original isotopic signature of the dissolved species. Isotope fractionation has been determined for minerals such as gypsum and epsomite, and from these results and theoretical predictions, it is expected that melanterite, a mineral potentially found on Mars, would be more enriched in oxygen-18 relative to the aqueous solution from which it crystallized.Thus, determining the oxygen-18 isotopic fractionation between melanterite and dissolved sulfate has many potential benefits for understanding surface processes on Mars and its past environment. To investigate the oxygen isotope fractionation for melanterite, acidic aqueous solutions saturated with dissolved hydrated ferrous sulfate were evaporated at 25 deg C and 40 deg C and under different conditions to induce different evaporation rates. During evaporation, the aqueous solution and crystallized melanterite were sampled at different stages. Oxygen-18 isotopic compositions were then measured. However, the fractionations observed in the experiments were opposite from predictions. At 25 deg C without enhanced evaporation, the dissolved sulfate was +5.5 per mil relative to the solid, while at 40 deg C it was +4.3 per mil. With enhanced evaporation, fractionation was +2.1 per mil, while at 40 deg C it was +3.6 per mil. In addition, at 40 deg C

  3. Oxygen Isotope Records in Modern Oyster Shells from Chi Ku, Tainan and Their Implication of Seasonality

    NASA Astrophysics Data System (ADS)

    Chen, Y. C.; Mii, H. S.; Li, K. T.

    2015-12-01

    To exam whether oxygen isotope records of Crassostrea gigasoysters can be used as proxies of environment, 133 cultivated oysters and 21 water samples were collected from Chi Ku area, Tainan City, southern Taiwan in December of 2012, and from March, 2013 to July, 2014. Instrumental air and water temperatures and precipitation records were obtained from a nearest Central Weather Bureau (CWB) station roughly 16 km north of Chi Ku. The oxygen and carbon isotope values of the ligamental area of the modern oyster shells are from -6.92‰ to -0.08‰ (-3.05 ± 1.17‰, N = 2280; 1σ; VPDB) and from -5.57‰ to 0.63‰ (-1.88 ± 0.81‰), respectively. Oxygen isotope values of the water samples are mainly between -0.28‰ and 0.74‰ (0.18 ± 0.29‰, N = 20; 1σ; VSMOW). However, water oxygen isotope value of -2.75‰ was observed for the water sample collected immediately after a typhoon heavy rainfall. Seasonal temperature fluctuation pattern of estimated oxygen isotope temperatures from modern shells is similar to that of CWB instrumental records. However, the oxygen isotope temperatures are respectively about 3 °C and 10°C higher than those of instrumental records for winter and summer. Higher estimated oxygen isotope temperatures are most likely caused by underestimated fraction of freshwater. We analyzed 5 archaeological oyster shells of Siraya culture (500~250B.P.) collected from Wu Chien Tuso North (WCTN) archaeological site of Tainan branch of Southern Taiwan Science Park to infer the harvest season of mollusks. Oxygen isotope values of the ligamental area of the archaeological oyster shells are between -5.98‰ and -1.26‰ (-3.34 ± 1.37‰, N = 60; 1σ), and carbon isotope values are between -3.21‰ and 0.60‰ (-2.04‰ ± 0.55‰). The oxygen isotope records of archaeological oyster shells also showed clear seasonality. Most of the oysters were collected in autumn and winter. Oxygen isotope values of archaeological oyster shells was 1‰ greater than that

  4. Seasonal oxygen isotopic variations in living planktonic foraminifera off Bermuda

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Williams, D.F.; Be, A.W.H.; Fairbanks, R.G.

    1979-10-26

    Seasonal variations in the oxygen-18/oxygen-16 ratio of calcite shells of living planktonic foraminifera in the Sargasso Sea off Bermuda are a direct function of surface water temperature. Seasonal occurrence as well as depth habitat are determining factors in the oxygen isotopic composition of planktonic foraminifera. These relationships may be used to determine the seasonal temperature contrast of oceans in the past.

  5. The Mesozoic metamorphic-magmatic events in the Medog area, the Eastern Himalayan Syntaxis: constraints from zircon U-Pb geochronology, trace elements and Hf isotope compositions in granitoids

    NASA Astrophysics Data System (ADS)

    Dong, Hanwen; Xu, Zhiqin; Li, Yuan; Liu, Zhao; Li, Huaqi

    2015-01-01

    Based on the regional geological mapping, several granitoid intrusions had been discovered in the Eastern Himalayan Syntaxis (EHS). In order to constrain their petrogenesis and discuss their relations with the regional tectonics, we carried out U-Pb dating, trace elements and Hf isotope geochemistry studies on zircons separated from the granitoid rocks, in the area of the EHS. In this contribution, the granitoid rocks are mainly composed of diorites (X20-1-6) and granitic gneissic rocks (X2-15-1). The U-Pb zircon dating of diorites yields a crystallization age of 193.8 ± 2.0 Ma. These zircon have ɛ Hf( t) values ranging from -6.48 to -0.05, indicating an involvement of ancient crustal materials in the generation of these igneous rocks. The zircons from the Medog granitic gneissic rock commonly show zoning structures. The REE patterns and abundances of the inherited cores are different from those of the oscillatory rims. The LA-ICP-MS U-Pb zircon in situ analyses indicate that: (1) the zircon cores give multi-stage magmatic event ages ranging from 516 to 1,826 Ma, of which six ages are converged on 1,330-911 Ma, it is considered that the migmatitic gneiss has been formed in this time, and (2) while the zircon rims yield 206Pb/238U weighted mean ages of 217.4 ± 3.0 Ma (MSWD = 3.2), which was interpreted to represent the ages of the Triassic anatexis. Their ɛ Hf( t) values range from -18.98 to -8.36 and -14.22 to 8.72, respectively. The timing of the anatexis in the Medog area is coeval with the widespread metamorphism in Lhasa terrane.

  6. [Research advances in identifying nitrate pollution sources of water environment by using nitrogen and oxygen stable isotopes].

    PubMed

    Mao, Wei; Liang, Zhi-wei; Li, Wei; Zhu, Yao; Yanng, Mu-yi; Jia, Chao-jie

    2013-04-01

    Water body' s nitrate pollution has become a common and severe environmental problem. In order to ensure human health and water environment benign evolution, it is of great importance to effectively identify the nitrate pollution sources of water body. Because of the discrepant composition of nitrogen and oxygen stable isotopes in different sources of nitrate in water body, nitrogen and oxygen stable isotopes can be used to identify the nitrate pollution sources of water environment. This paper introduced the fractionation factors of nitrogen and oxygen stable isotopes in the main processes of nitrogen cycling and the composition of these stable isotopes in main nitrate sources, compared the advantages and disadvantages of five pre-treatment methods for analyzing the nitrogen and oxygen isotopes in nitrate, and summarized the research advances in this aspect into three stages, i. e. , using nitrogen stable isotope alone, using nitrogen and oxygen stable isotopes simultaneously, and combining with mathematical models. The future research directions regarding the nitrate pollution sources identification of water environment were also discussed.

  7. A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water—USGS50 Lake Kyoga Water

    USGS Publications Warehouse

    Coplen, Tyler B.; Wassenaar, Leonard I; Mukwaya, Christine; Qi, Haiping; Lorenz, Jennifer M.

    2015-01-01

    This isotopic reference material, designated as USGS50, is intended as one of two reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer, of use especially for isotope-hydrology laboratories analyzing freshwater samples from equatorial and tropical regions.

  8. Detection of phosphohydrolytic enzyme activity through the oxygen isotope composition of dissolved phosphate

    NASA Astrophysics Data System (ADS)

    Colman, A. S.

    2016-02-01

    Phosphohydrolytic enzymes play an important role in phosphorus remineralization. As they release phosphate (Pi) from various organophosphorus compounds, these enzymes facilitate the transfer of oxygen atoms from water to the phosphoryl moieties. Most such enzymatic reactions impart a significant isotopic fractionation to the oxygen transferred. If this reaction occurs within a cell, then the resultant oxygen isotope signal is overprinted by continued recycling of the Pi. However, if this reaction occurs extracellularly, then the isotopic signal will be preserved until the Pi is transported back into a cell. Thus, the oxygen isotope composition of Pi (δ18Op) in an aquatic ecosystem can serve as a useful indicator of the mechanisms by which P is remineralized. We develop a time-dependent model illustrating the sensitivity of the δ18O of dissolved phosphate to various modes of P remineralization. The model is informed by cell lysis experiments that reveal the relative proportions of P­i that are directly liberated from cytosol vs. regenerated from co-liberated dissolved organic phosphorus compounds via extracellular hydrolysis. By incorporating both cellular uptake and release fluxes of P, we show that the degree of isotopic disequilibrium in an aquatic ecosystem can be a strong indicator of P remineralization mode. Apparent oxygen isotope equilibrium between Pi and water arises in this model as a steady-state scenario in which fractionation upon cellular uptake of Pi counterbalances the hydrolytic source flux of disequilibrated Pi. Low and high rates of extracellular phosphohydrolase activity are shown to produce steady-state δ18Op values that are respectively above or below thermodynamic equilibrium compositions.

  9. Oxygen isotope variation in stony-iron meteorites.

    PubMed

    Greenwood, R C; Franchi, I A; Jambon, A; Barrat, J A; Burbine, T H

    2006-09-22

    Asteroidal material, delivered to Earth as meteorites, preserves a record of the earliest stages of planetary formation. High-precision oxygen isotope analyses for the two major groups of stony-iron meteorites (main-group pallasites and mesosiderites) demonstrate that each group is from a distinct asteroidal source. Mesosiderites are isotopically identical to the howardite-eucrite-diogenite clan and, like them, are probably derived from the asteroid 4 Vesta. Main-group pallasites represent intermixed core-mantle material from a single disrupted asteroid and have no known equivalents among the basaltic meteorites. The stony-iron meteorites demonstrate that intense asteroidal deformation accompanied planetary accretion in the early Solar System.

  10. Stable isotope analysis of molecular oxygen from silicates and oxides using CO2 laser extraction

    NASA Technical Reports Server (NTRS)

    Perry, Eugene

    1996-01-01

    A laser-excited system for determination of the oxygen isotope composition of small quantities of silicate and oxide minerals was constructed and tested at JSC. This device is the first reported to use a commercially available helium cryostat to transfer and purify oxygen gas quantitatively within the system. The system uses oxygen gas instead of the conventional CO2 for mass spectrometer analyses. This modification of technique permits determination of all three stable oxygen isotopes, an essential requirement for oxygen isotope analysis of meteoritic material. Tests of the system included analysis of standard silicate materials NBS 28 and UWMG2 garnet, six SNC meteorites, and inclusions and chondrules from the Allende meteorite. Calibration with terrestrial standards was excellent. Meteorite values are close to published values and show no evidence of terrestrial oxygen contamination. The one limitation observed is that, in some runs on fine-grained SNC matrix material, sample results were affected by other samples in the sample holder within the reaction chamber. This reemphasizes the need for special precautions in dealing with fine-grained, reactive samples. Performance of the JSC instrument compares favorably with that of any other instrument currently producing published oxygen isotope data.

  11. Behaviour of Structural Carbonate Stable Carbon and Oxygen Isotope Compositions in Bioapatite During Burning of Bone

    NASA Astrophysics Data System (ADS)

    Munro, L. E.; Longstaffe, F. J.; White, C. D.

    2003-12-01

    Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by

  12. U-Pb zircon, geochemical and Sr-Nd-Hf-O isotopic constraints on age and origin of the ore-bearing intrusions from the Nurkazgan porphyry Cu-Au deposit in Kazakhstan

    NASA Astrophysics Data System (ADS)

    Shen, Ping; Pan, Hongdi; Seitmuratova, Eleonora; Jakupova, Sholpan

    2016-02-01

    Nurkazgan, located in northeastern Kazakhstan, is a super-large porphyry Cu-Au deposit with 3.9 Mt metal copper and 229 tonnage gold. We report in situ zircon U-Pb age and Hf-O isotope data, whole rock geochemical and Sr-Nd isotopic data for the ore-bearing intrusions from the Nurkazgan deposit. The ore-bearing intrusions include the granodiorite porphyry, quartz diorite porphyry, quartz diorite, and diorite. Secondary ion mass spectrometry (SIMS) zircon U-Pb dating indicates that the granodiorite porphyry and quartz diorite porphyry emplaced at 440 ± 3 Ma and 437 ± 3 Ma, respectively. All host rocks have low initial 87Sr/86Sr ratios (0.70338-0.70439), high whole-rock εNd(t) values (+5.9 to +6.3) and very high zircon εHf(t) values (+13.4 to +16.5), young whole-rock Nd and zircon Hf model ages, and consistent and slightly high zircon O values (+5.7 to +6.7), indicating that the ore-bearing magmas derived from the mantle without old continental crust involvement and without marked sediment contamination during magma emplacement. The granodiorite porphyry and quartz diorite porphyry are enriched in large ion lithophile elements (LILE) and light rare earth elements (LREE) and depleted in high-field strength elements (HFSE), Eu, Ba, Nb, Sr, P and Ti. The diorite and quartz diorite have also LILE and LREE enrichment and HFSE, Nb and Ti depletion, but have not negative Eu, Ba, Sr, and P anomalies. These features suggest that the parental magma of the granodiorite porphyry and quartz diorite porphyry originated from melting of a lithospheric mantle and experienced fractional crystallization, whereas the diorite and quartz diorite has a relatively deeper lithospheric mantle source region and has not experienced strong fractional crystallization. Based on these, together with the coeval ophiolites in the area, we propose that a subduction of the Balkhash-Junggar oceanic plate took place during the Early Silurian and the ore-bearing intrusions and associated Nurkazgan

  13. Petrology of Zircon-Bearing Diogenite Northwest Africa 10666

    NASA Technical Reports Server (NTRS)

    Tanner, T. B.; Jeffcoat, C. R.; Righter, M.; Berger, E. L.; Lapen, T. J.; Irving, A. J.; Kuehner, S. M.; Fujihara, G.

    2017-01-01

    The howardite, eucrite, and diogenite (HED) meteorites are a group of achondrites thought to be derived from the asteroid 4 Vesta, though there is active debate as to whether all diogenites are part of the HED suite. Petrologic investigation of the HED meteorite group provides a means of understanding early planetary differentiation processes and early evolution of planets in our solar system. Diogenites are predominantly coarse grained ortho-pyroxenites with some samples containing appreciable amounts of clinopyroxene, olivine, chromite, and plagioclase. Accessory metal, troilite, and apatite are common. Many diogenites are brecciated, however, there are few poorly to unbrecciated samples. Diogenites are important because they may represent the lower crust of 4 Vesta. Although Mg isotope data indicates that the sources of diogenites are ancient, their crystallization ages are difficult to constrain due to their protracted thermal histories. The limited chronologic data for diogenites also limits the ability to test petrogenetic connections with eucrites and even parent body. A reliable and high closure-temperature isotope system, such as U-Pb in zircon, is needed to address the timing of diogenite igneous crystallization. Description of the textures and mineralogy of diogenites are essential to their classification and understanding their formation, in particular, whether all phases are petrogenetically related. Here, we present detailed petrographic data from a rare zircon-bearing feldspathic diogenite, Northwest Africa (NWA) 10666 and provide textural evidence for igneous crystallization of the zircon.

  14. Nitrogen and Oxygen Isotopic Studies of the Marine Nitrogen Cycle

    NASA Astrophysics Data System (ADS)

    Casciotti, Karen L.

    2016-01-01

    The marine nitrogen cycle is a complex web of microbially mediated reactions that control the inventory, distribution, and speciation of nitrogen in the marine environment. Because nitrogen is a major nutrient that is required by all life, its availability can control biological productivity and ecosystem structure in both surface and deep-ocean communities. Stable isotopes of nitrogen and oxygen in nitrate and nitrite have provided new insights into the rates and distributions of marine nitrogen cycle processes, especially when analyzed in combination with numerical simulations of ocean circulation and biogeochemistry. This review highlights the insights gained from dual-isotope studies applied at regional to global scales and their incorporation into oceanic biogeochemical models. These studies represent significant new advances in the use of isotopic measurements to understand the modern nitrogen cycle, with implications for the study of past ocean productivity, oxygenation, and nutrient status.

  15. Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method

    USGS Publications Warehouse

    Casciotti, K.L.; Sigman, D.M.; Hastings, M. Galanter; Böhlke, J.K.; Hilkert, A.

    2002-01-01

    We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate.1Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO3-), lack of interference by other solutes, and ease of sample preparation.

  16. Tectonic Recycling in the Paleozoic Ouachita Assemblage from U-Pb Detrital Zircon Studies

    NASA Astrophysics Data System (ADS)

    Gleason, J. D.; Gehrels, G. E.; Finney, S. C.

    2001-05-01

    The Paleozoic Ouachita deep-marine clastic sedimentary assemblage records a complex provenance over the course of its 200 m.y. history, with evidence for mixed sources and multiple dispersal paths. Combined neodymium and U-Pb detrital zircon work has established that most of the assemblage in Arkansas and Oklahoma is derived from Laurentian sources, meaning that regardless of the multiple pathways by which sediment was delivered to Ouachita seafloor, the material had its ultimate origin on the North American continent. More detailed work is in progress to elucidate specific dispersal paths, in particular for the middle to late Ordovician when a major change in provenance is recorded, and during the Carboniferous when voluminous turbidites entered the basin. We sampled three formations for U-Pb detrital zircon studies: the lower Middle Ordovician Blakely Sandstone, the Upper Ordovician/Lower Silurian Blaylock Sandstone, and the Pennsylvanian Jackfork Group. Individual zircon ages from these units document a major change in provenance between deposition of the Blakely Sandstone and Blaylock Sandstone, which is also reflected in the neodymium isotopic signature. Both units have a large population of Grenvillian-age zircons (1.0-1.2 Ga), and a less abundant population of 1.3-1.4 Ga zircons likely derived from sources in the mid-continent region. The Blakely Sandstone also contains abundant Archean zircons (2.5-2.7 Ga, likely derived from the Superior Province), and one grain apparently derived from the Penokean orogen (1.9 Ga). Zircon morphology (highly rounded, spherical), combined with the pure quartz sandstone lithology of the Blakely Sandstone, indicates very mature sedimentary sources. We conclude that zircons from this source were recycled ultimately from source terranes in the North American craton. This is reinforced by neodymium isotopes (eNd = -15), paleocurrents (from the north) and olistoliths (1.3 Ga granites), the latter indicating that Blakely turbidites

  17. Influence of oxygen partial pressure on the composition and orientation of strontium-doped lead zirconate titanate thin films.

    PubMed

    Sriram, S; Bhaskaran, M; du Plessis, J; Short, K T; Sivan, V P; Holland, A S

    2009-01-01

    The influence of oxygen partial pressure during the deposition of piezoelectric strontium-doped lead zirconate titanate thin films is reported. The thin films have been deposited by RF magnetron sputtering in an atmosphere of high purity argon and oxygen (in the ratio of 9:1), on platinum-coated silicon substrates (heated to 650 degrees C). The influence of oxygen partial pressure is studied to understand the manner in which the stoichiometry of the thin films is modified, and to understand the influence of stoichiometry on the perovskite orientation. This article reports on the results obtained from films deposited at oxygen partial pressures of 1-5 mTorr. The thin films have been studied using a combination of X-ray photoelectron spectroscopy (XPS), glancing angle X-ray diffraction (GA-XRD), and atomic force microscopy (AFM). XPS analysis highlights the marked influence of variations in oxygen pressure during sputtering, observed by variations in oxygen concentration in the thin films, and in some cases by the undesirable decrease in lead concentration in the thin films. GA-XRD is used to study the relative variations in perovskite peak intensities, and has been used to determine the deposition conditions to attain the optimal combination of stoichiometry and orientation. AFM scans show the marked influence of the oxygen partial pressure on the film morphology.

  18. Hydrogen and oxygen isotope exchange reactions between clay minerals and water

    USGS Publications Warehouse

    O'Neil, J.R.; Kharaka, Y.K.

    1976-01-01

    The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

  19. Hydrogen and Oxygen Isotope Ratios in Body Water and Hair: Modeling Isotope Dynamics in Nonhuman Primates

    PubMed Central

    O’Grady, Shannon P.; Valenzuela, Luciano O.; Remien, Christopher H.; Enright, Lindsey E.; Jorgensen, Matthew J.; Kaplan, Jay R.; Wagner, Janice D.; Cerling, Thure E.; Ehleringer, James R.

    2012-01-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water (2H/1H, 18O/16O expressed as δ2H and δ18O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ2H and δ18O values of body water and a second model to predict the δ2H and δ18O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ2H and δ18O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ2H and δ18O values of gut water and the 18O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (αow). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of αow was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. PMID:22553163

  20. HAFNIAN ZIRCONS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    von Knorring, O.; Hornung, G.

    1961-06-17

    Two hafnia zircons were examined in detail, one from Mtoko in Southern Rhodesia, containing 21% HfO/sub 2/, and the other from Karibib in South-West Africa, with 31% HfO/sub 2/. In both cases the zircons are associated with the later tantalum-rich phase of mineralization. The Mtoko zircon forms small, mauve- colored, independent crystals in the albitic zone of the pegmatite. The zircon from Karibib occurs in larger reddish-brown masses, partly intergrown with minute manganotantalite crystals and set in a matrix of lithium-bearing mica, albite, quartz and kaolinized feldspar. Some crystals show dominant pyramid faces, with a suppressed prism. Both zircons exhibitmore » an intense golden-yellow fluorescence in UV light. The zircon from Karibib was found to be only weakly radioactive. Data are given concerning various properties of the two zircons. (P.C.H.)« less

  1. Sulfur and oxygen isotope fractionation during benzene, toluene, ethyl benzene, and xylene degradation by sulfate-reducing bacteria.

    PubMed

    Knöller, Kay; Vogt, Carsten; Richnow, Hans-Herrmann; Weise, Stephan M

    2006-06-15

    We examined the oxygen and sulfur isotope fractionation of sulfate during anaerobic degradation of toluene by sulfate-reducing bacteria in culture experiments with Desulfobacula toluolica as a type strain and with an enrichment culture Zz5-7 obtained from a benzene, toluene, ethylbenzene, and xylene (BTEX)-contaminated aquifer. Sulfur isotope fractionation can show considerable variation upon sulfate reduction and may react extremely sensitively to changes in environmental conditions. In contrast, oxygen isotope fractionation seems to be less sensitive to environmental changes. Our results clearly indicate that oxygen isotope fractionation is dominated by isotope exchange with ambient water. To verify our experimental results and to test the applicability of oxygen and sulfur isotope investigations under realistic field conditions, we evaluated isotope data from two BTEX-contaminated aquifers presented in the recent literature. On a field scale, bacterial sulfate reduction may be superimposed by processes such as dispersion, adsorption, reoxidation, or mixing. The dual isotope approach enables the identification of such sulfur transformation processes. This identification is vital for a general qualitative evaluation of the natural attenuation potential of the contaminated aquifer.

  2. Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

    NASA Astrophysics Data System (ADS)

    Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

  3. Elemental and Isotopic Tomography at Single-Atom-Scale in 4.0 and 2.4 Ga Zircons

    NASA Astrophysics Data System (ADS)

    Valley, J. W.; Reinhard, D. A.; Snoeyenbos, D.; Lawrence, D.; Martin, I.; Kelly, T. F.; Ushikubo, T.; Strickland, A.; Cavosie, A. J.

    2012-12-01

    Atom probe tomography can determine identity (mass/charge ratio) and 3-D position of individual atoms in minerals such as zircon. These data provide unique information for understanding the thermal history and mechanisms of mineral reaction and exchange, including radiation damage. Nine needle-shaped specimens ~100 nm in diameter (at the apex) were sampled from 2 zircons by FIB and analyzed with a local-electrode atom probe (LEAP), CAMECA LEAP 4000X HR. The LEAP uses pulsed-laser heating to field evaporate the tip of a zircon needle and accelerates the ions into a position-sensitive TOF-MS. With due care for complex isobaric interferences (molecules, multiple ionizations) and background correction, it is possible to individually identify up to 10E8 atoms/needle (36% detection efficiency) by mass/charge (MRP ~ 1000@ m/n=16Da) and position (X-Y-Z coordinates on 0.2 nm scale) (Kelly & Larson 2012). The 3-D distribution of Pb and Y differ at atom-scale in the 2 zircons. Zircon #1 (4007 Ma, Jack Hills, W. Australia, Cavosie 2005, Ushikubo et al. 2008, Bouvier et al. 2011) is homogeneous in Pb and Y. In contrast, incompatible elements, including Pb and Y, are concentrated in equant 5-10 nm dia. domains, spaced ~50 nm apart in zircon #2 (2438 Ma, Albion-Raft R-Grouse Ck core complex, Utah, Strickland et al. 2011). U is homogeneously distributed in both zircons. The analyzed domains suffered 4-8 x 10E15 α-decay events/mg due to U and Th decay and yet both zircons yield >97% concordant U-Pb ages by SIMS, suggesting annealing of radiation damage during the life of the zircons. The 207-Pb/206-Pb ratios for these nm-scale domains, as measured by LEAP, average 0.17 for the 2.4 Ga Zrc2 (3 needles) and 0.43 for the 4.0 Ga Zrc1 (5 needles). These ratios are less precise (±40% 2σ) due to ultra-small sample size, but are in excellent agreement with values measured by SIMS, 0.1684 and 0.4269, respectively. Thus Pb in both zircons is radiogenic. The Pb-Y-rich domains and lack of

  4. Dating the Indo-Asia collision in NW Himalaya: constraints from Sr-Nd isotopes and detrital zircon (U-Pb) and Hf isotopes of Paleogene-Neogene rocks in the Katawaz basin, NW Pakistan

    NASA Astrophysics Data System (ADS)

    Zhuang, Guangsheng; Najman, Yani; Millar, Ian; Chauvel, Catherine; Guillot, Stephane; Carter, Andrew

    2015-04-01

    The time of collision between the Indian and Asian plates is key for understanding the convergence history and the impact on climatic systems and marine geochemistry. Despite much active research, the fundamental questions still remain elusive regarding when and where the Indian plate collided with the Asian plate. Especially in the west Himalaya, the questions become more complex due to disputes on the amalgamation history of interoceanic Kohistan-Ladakh arcs (KLA) with Karakoram of the Asian plate and the Indian plate. Here, we present a result of multiple-isotopic geochemistry and geochronology study in the Katawaz Basin in NW Pakistan, a remnant oceanic basin on the western Indian plate which was the repository for the sediments eroded from the west Himalaya ( Qayyum et al., 1996, 1997a, 1997b, 2001; Carter et al., 2010), to evaluate the time and character of collision in this region. In this study, we analyzed 22 bulk mudstone samples for Sr-Nd isotopes and 11 medium-grained sandstones for detrital zircon (U-Pb) geochronology and Hf isotopes. We constructed the Cenozoic chronology in the Katawaz Basin based on our newly collected detrital zircon U-Pb ages and fission track ages. We present the first record of Katawaz chronology that constrained the Khojak Formation to be < 40 Ma to < 22 Ma. The result is consistent with the previous nanofossil study that constrained the upper part of underlying Nisai Formation to be the Middle to Late Eocene. Our current study revealed that the Katawaz sedimentary sequence ranges in age from Eocene to the earliest Miocene. The samples from the Nisai Formation show the 87Sr/86Sr - ɛNd values overlapping those of the end member of the Karakoram of Asian origin, revealing the arrival of Asian detritus on the Indian plate prior to 50 Ma. There are two parallel lines of evidence supporting this conclusion: (1) young zircon grains (< 120 Ma), characterizing the KLA and Karakoram, persistently exist throughout the whole sedimentary

  5. Middle Neoproterozoic (ca. 705-716 Ma) arc to rift transitional magmatism in the northern margin of the Yangtze Block: Constraints from geochemistry, zircon U-Pb geochronology and Hf isotopes

    NASA Astrophysics Data System (ADS)

    Wang, Ruirui; Xu, Zhiqin; Santosh, M.; Xu, Xianbing; Deng, Qi; Fu, Xuehai

    2017-09-01

    The South Qinling Belt in Central China is an important window to investigate the Neoproterozoic tectono-magmatic processes along the northern margin of the Yangtze Block. Here we present whole-rock geochemistry, zircon U-Pb geochronology and Lu-Hf isotopes of a suite of Middle Neoproterozoic intrusion from the Wudang Uplift in South Qinling. Zircon LA-ICP-MS U-Pb ages reveal that these rocks were formed at ca. 705-716 Ma. Geochemical features indicate that the felsic magmatic rocks are I-type granitoids, belong to calcic- to calc-alkaline series, and display marked negative Nb, Ta and Ti anomalies. Moreover, the enrichment of light rare earth elements (LREEs) and large ion lithophile elements (LILEs), combined with depletion of heavy rare earth elements (HREEs) support that these rocks have affinity to typical arc magmatic rocks formed in Andean-type active continental margins. The REE patterns are highly to moderately fractionated, with (La/Yb)N = 5.13-8.10 in meta-granites, and 2.32-2.35 in granodiorite. The granitoids have a wide range of zircon εHf(t) values (-29.91 to 14.76) and zircon Hf two-stage model ages (696-3482 Ma). We suggest that the ca. 705-716 Ma granitoids were sourced from different degrees of magma mixing between partial melting of the overlying mantle wedge triggered by hydrous fluids released from subducted materials and crustal melting. The hybrid magmas were emplaced in the shallow crust accompanied by assimilation and fractional crystallization (AFC). Both isotopic and geochemical data suggest that the ca. 705-716 Ma felsic magmatic rocks were formed along a continental arc. These rocks as well as the contemporary A-type granite may mark a transitional tectonic regime from continental arc to rifting, probably related to slab rollback during the oceanic subduction beneath the northern margin of Yangtze Block.

  6. Growth of the European abalone ( Haliotis tuberculata L.) in situ: Seasonality and ageing using stable oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Roussel, Sabine; Huchette, Sylvain; Clavier, Jacques; Chauvaud, Laurent

    2011-02-01

    The ormer, Haliotis tuberculata is the only European abalone species commercially exploited. The determination of growth and age in the wild is an important tool for fisheries and aquaculture management. However, the ageing technique used in the past in the field is unreliable. The stable oxygen isotope composition ( 18O/ 16O) of the shell depends on the temperature and oxygen isotope composition of the ambient sea water. The stable oxygen isotope technique, developed to study paleoclimatological changes in shellfish, was applied to three H. tuberculata specimens collected in north-west Brittany. For the specimens collected, the oxygen isotope ratios of the shell reflected the seasonal cycle in the temperature. From winter-to-winter cycles, estimates of the age and the annual growth increment, ranging from 13 to 55 mm per year were obtained. This study shows that stable oxygen isotopes can be a reliable tool for ageing and growth studies of this abalone species in the wild, and for validating other estimates.

  7. Oxygen isotope fractionation in the siderite-water system between 8.5 and 62 °C

    NASA Astrophysics Data System (ADS)

    van Dijk, Joep; Fernandez, Alvaro; Müller, Inigo A.; Lever, Mark; Bernasconi, Stefano M.

    2018-01-01

    The oxygen isotope composition of siderites can be used to deduce the temperature and/or oxygen isotope composition of the fluids from which they precipitated. Previous siderite-water oxygen isotope fractionation calibrations are not well constrained at temperatures below 33 °C where most of the siderite forms at the Earth's surface. Moreover, the few experimental low temperature calibration points available are possibly inaccurate as the corresponding siderites may not have formed in equilibrium with the solution. In this study, we synthesized siderite in the laboratory from 8.5 to 62 °C, using both active-degassing experiments and microbial cultures. We used the enzyme carbonic anhydrase, which significantly reduces the equilibration time of oxygen isotopes among all dissolved inorganic carbon (DIC) species and water to minimize siderite formation out of equilibrium. Our calibration is based on many more data points than previous calibrations and significantly reduces the uncertainty in siderite-water oxygen isotope fractionation in natural siderites formed at low temperatures. The best fit equation is 1000 * ln α = 19.67 ± 0.42(103/T) -36.27 ± 1.34 where α (1000+δ18Osiderite/1000+δ18Owater) is the fractionation factor and T is the temperature in Kelvin.

  8. Lifetime of an ocean island volcano feeder zone: constraints from U-Pb dating on coexisting zircon and baddeleyite, and 40/39Ar age determinations, Fuerteventura, Canary Islands

    USGS Publications Warehouse

    Allibon, James; Ovtcharova, Maria; Bussy, Francois; Cosca, Michael; Schaltegger, Urs; Bussien, Denise; Lewin, Eric

    2011-01-01

    High-precision isotope dilution - thermal ionization mass spectrometry (ID-TIMS) U-Pb zircon and baddeleyite ages from the PX1 vertically layered mafic intrusion Fuerteventura, Canary Islands, indicate initiation of magma crystallization at 22.10 ± 0.07 Ma. The magmatic activity lasted a minimum of 0.52 Ma. 40Ar/39Ar amphibole dating yielded ages from 21.9 ± 0.6 to 21.8 ± 0.3, identical within errors to the U-Pb ages, despite the expected 1% theoretical bias between 40Ar/39Ar and U-Pb dates. This overlap could result from (i) rapid cooling of the intrusion (i.e., less than the 0.3 to 0.6 Ma 40Ar/39Ar age uncertainties) from closure temperatures (Tc) of zircon (699-988 °C) to amphibole (500-600 °C); (ii) lead loss affecting the youngest zircons; or (iii) excess argon shifting the plateau ages towards older values. The combination of the 40Ar/39Ar and U/Pb datasets implies that the maximum amount of time PX1 intrusion took to cool below amphibole Tc is 0.8 Ma, suggesting PX1 lifetime of 520,000 to 800,000 Ma. Age disparities among coexisting baddeleyite and zircon (22.10 ± 0.07/0.08/0.15 Ma and 21.58 ± 0.15/0.16/0.31 Ma) in a gabbro sample from the pluton margin suggest complex genetic relationships between phases. Baddeleyite is found preserved in plagioclase cores and crystallized early from low silica activity magma. Zircon crystallized later in a higher silica activity environment and is found in secondary scapolite and is found close to calcite veins, in secondary scapolite that recrystallised from plagioclase. close to calcite veins. Oxygen isotope δ18O values of altered plagioclase are high (+7.7), indicating interaction with fluids derived from host-rock carbonatites. The coexistence of baddeleyite and zircon is ascribed to interaction of the PX1 gabbro with CO2-rich carbonatite-derived fluids released during contact metamorphism.

  9. Hydrogen and oxygen isotope ratios in body water and hair: modeling isotope dynamics in nonhuman primates.

    PubMed

    O'Grady, Shannon P; Valenzuela, Luciano O; Remien, Christopher H; Enright, Lindsey E; Jorgensen, Matthew J; Kaplan, Jay R; Wagner, Janice D; Cerling, Thure E; Ehleringer, James R

    2012-07-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water ((2)H/(1)H, (18)O/(16)O expressed as δ(2) H and δ(18)O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ(2)H and δ(18)O values of body water and a second model to predict the δ(2)H and δ(18)O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ(2)H and δ(18)O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ(2)H and δ(18)O values of gut water and the (18)O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (α(ow)). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of α(ow) was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. © 2012 Wiley Periodicals, Inc.

  10. Defining Uncertainty and Error in Planktic Foraminiferal Oxygen Isotope Measurements

    NASA Astrophysics Data System (ADS)

    Fraass, A. J.; Lowery, C.

    2016-12-01

    Foraminifera are the backbone of paleoceanography, and planktic foraminifera are one of the leading tools for reconstructing water column structure. Currently, there are unconstrained variables when dealing with the reproducibility of oxygen isotope measurements. This study presents the first results from a simple model of foraminiferal calcification (Foraminiferal Isotope Reproducibility Model; FIRM), designed to estimate the precision and accuracy of oxygen isotope measurements. FIRM produces synthetic isotope data using parameters including location, depth habitat, season, number of individuals included in measurement, diagenesis, misidentification, size variation, and vital effects. Reproducibility is then tested using Monte Carlo simulations. The results from a series of experiments show that reproducibility is largely controlled by the number of individuals in each measurement, but also strongly a function of local oceanography if the number of individuals is held constant. Parameters like diagenesis or misidentification have an impact on both the precision and the accuracy of the data. Currently FIRM is a tool to estimate isotopic error values best employed in the Holocene. It is also a tool to explore the impact of myriad factors on the fidelity of paleoceanographic records. FIRM was constructed in the open-source computing environment R and is freely available via GitHub. We invite modification and expansion, and have planned inclusions for benthic foram reproducibility and stratigraphic uncertainty.

  11. Dual sources of water overprinting on the low zircon δ18O metamorphic country rocks: Disequilibrium constrained through inverse modelling of partial reequilibration

    PubMed Central

    Wei, Chun-Sheng; Zhao, Zi-Fu

    2017-01-01

    Since water is only composed of oxygen and hydrogen, δ18O and δ2H values are thus utilized to trace the origin of water(s) and quantify the water-rock interactions. While Triassic high pressure (HP) and ultrahigh pressure (UHP) metamorphic rocks across the Dabie-Sulu orogen in central-eastern China have been well documented, postcollisional magmatism driven hydrothermal systems are little known. Here we show that two sources of externally derived water interactions were revealed by oxygen isotopes for the gneissic country rocks intruded by the early Cretaceous postcollisional granitoids. Inverse modellings indicate that the degree of disequilibrium (doD) of meteoric water interactions was more evident than that of magmatic one (−65 ± 1o vs. −20 ± 2°); the partial reequilibration between quartz and alkali feldspar oxygen isotopes with magmatic water was achieved at 340 °C with a water/rock (W/R) ratio of about 1.2 for an open-hydrothermal system; two-stage meteoric water interactions were unraveled with reequilibration temperatures less than 300 °C and W/R ratios around 0.4. The lifetime of fossil magmatic hydrothermal system overprinted on the low zircon δ18O orthogneissic country rocks was estimated to maintain up to 50 thousand years (Kyr) through oxygen exchange modellings. Four-stage isotopic evolutions were proposed for the magmatic water interacted gneiss. PMID:28091552

  12. 3-D Characterization of Detrital Zircon Grains and its Implications for Fluvial Transport, Mixing, and Preservation Bias

    NASA Astrophysics Data System (ADS)

    Markwitz, V.; Kirkland, C. L.; Mehnert, A.; Gessner, K.; Shaw, J.

    2017-12-01

    Detrital zircon studies can suffer from selective loss of provenance information due to U-Pb age discordance, metamictization, metamorphic overprinting and fluviatile transport processes. The relationship between isotopic composition and zircon grain shape, and how grain shape is modified during transport, is largely unknown. We combine X-ray tomography with U-Pb geochronology to quantify how fluvial transport affects 3-D zircon shape, detrital age signature, and grain density along the Murchison River, whose catchment comprises Eoarchean to Early Paleozoic source rocks in Western Australia. We acquired tomographic volumes and isotopic data from 373 detrital zircons to document changes in size, shape and density in transport direction, and explore how grain shape, age spectra and the proportion of discordant material vary along the channel. Results show that shape characteristics are sensitive to transport distance, stream gradient, proximity to source material, and whether the source consists of primary or recycled zircons. With increasing transport distance, grain lengths decrease more than their widths. Furthermore, the loss of metamict grains occurs at a near constant rate, resulting in a linear increase of mean calculated zircon density by ca. 0.03 g/cm3 per 100 km transport distance. 3-D grain shape is therefore strongly linked to detrital age signature, and mean grain density is a function of the absolute transport distance. 3-D shape characteristics provide valuable information on detrital zircon populations, including the interaction between source materials with fluvial transport processes, which significantly affects preservation bias and, by inference, the representativeness of the sampled data.

  13. 99 Tc NMR determination of the oxygen isotope content in 18 O-enriched water.

    PubMed

    Tarasov, Valerii P; Kirakosyan, Gayana А; German, Konstantin E

    2018-03-01

    99 Tc NMR has been suggested as an original method of evaluating the content of oxygen isotopes in oxygen-18-enriched water, a precursor for the production of radioisotope fluorine-18 used in positron emission tomography. To this end, solutions of NH 4 TcO 4 or NaTcO 4 (up to 0.28 mol/L) with natural abundance of oxygen isotopes in virgin or recycled 18 O-enriched water have been studied by 99 Tc NMR. The method is based on 16 O/ 17 O/ 18 O intrinsic isotope effects in the 99 Tc NMR chemical shifts, and the statistical distribution of oxygen isotopes in the coordination sphere of TcO 4 - and makes it possible to quantify the composition of enriched water by measuring the relative intensities of the 99 Tc NMR signals of the Tc 16 O 4-n 18 O n - isotopologues. Because the oxygen exchange between TcO 4 - and enriched water in neutral and alkaline solutions is characterized by slow kinetics, gaseous HCl was bubbled through a solution for a few seconds to achieve the equilibrium distribution of oxygen isotopes in the Tc coordination sphere without distortion of the oxygen composition of the water. Pertechnetate ion was selected as a probe due to its high stability in solutions and the significant 99 Tc NMR shift induced by a single 16 O→ 18 O substitution (-0.43 ± 0.01 ppm) in TcO 4 - and spin coupling constant 1 J( 99 Tc- 17 O) (131.46 Hz) favourable for the observation of individual signals of Tc 16 O 4-n 18 O n - isotopologues. Copyright © 2017 John Wiley & Sons, Ltd.

  14. Impact-shocked zircons: discovery of shock-induced textures reflecting increasing degrees of shock metamorphism

    USGS Publications Warehouse

    Bohor, B.F.; Betterton, W.J.; Krogh, T.E.

    1993-01-01

    Textural effects specifically characteristic of shock metamorphism in zircons from impact environments have not been reported previously. However, planar deformation features (PDF) due to shock metamorphism are well documented in quartz and other mineral grains from these same environments. An etching technique was developed that allows SEM visualization of PDF and other probable shock-induced textural features, such as granular (polycrystalline) texture, in zircons from a variety of impact shock environments. These textural features in shocked zircons from K/T boundary distal ejecta form a series related to increasing degrees of shock that should correlate with proportionate resetting of the UPb isotopic system. ?? 1993.

  15. Impact-shocked zircons: Discovery of shock-induced textures reflecting increasing degrees of shock metamorphism

    NASA Technical Reports Server (NTRS)

    Bohor, B. F.; Betterton, W. J.; Krogh, T. E.

    1993-01-01

    Textural effects specifically characteristic of shock metamorphism in zircons from impact environments have not been reported previously. However, planar deformation features (PDF) due to shock metamorphism are well documented in quartz and other mineral grains from these same environments. An etching technique was developed that allows scanning electron microscope (SEM) visualization of PDF and other probable shock-induced textural features, such as granular (polycrystalline) texture, in zircons from a variety of impact shock environments. These textural features in shocked zircons from K/T boundary distal ejecta form a series related to increasing degrees of shock that should correlate with proportionate resetting of the U-Pb isotopic system.

  16. Permian-Carboniferous arc magmatism in southern Mexico: U-Pb dating, trace element and Hf isotopic evidence on zircons of earliest subduction beneath the western margin of Gondwana

    NASA Astrophysics Data System (ADS)

    Ortega-Obregón, C.; Solari, L.; Gómez-Tuena, A.; Elías-Herrera, M.; Ortega-Gutiérrez, F.; Macías-Romo, C.

    2014-07-01

    Undeformed felsic to mafic igneous rocks, dated by U-Pb zircon geochronology between 311 and 255 Ma, intrude different units of the Oaxacan and Acatlán metamorphic complexes in southwestern Mexico. Rare earth element concentrations on zircons from most of these magmatic rocks have a typical igneous character, with fractionated heavy rare earths and negative Eu anomalies. Only inherited Precambrian zircons are depleted in heavy rare earth elements, which suggest contemporaneous crystallization in equilibrium with metamorphic garnet during granulite facies metamorphism. Hf isotopic signatures are, however, different among these magmatic units. For example, zircons from two of these magmatic units (Cuanana pluton and Honduras batholith) have positive ɛHf values (+3.8-+8.5) and depleted mantle model ages (using a mean crustal value of 176Lu/177Hf = 0.015) ( T DMC) ranging between 756 and 1,057 Ma, whereas zircons from the rest of the magmatic units (Etla granite, Zaniza batholith, Carbonera stock and Sosola rhyolite) have negative ɛHf values (-1 to -14) and model ages between 1,330 and 2,160 Ma. This suggests either recycling of different crustal sources or, more likely, different extents of crustal contamination of arc-related mafic magmas in which the Oaxacan Complex acted as the main contaminant. These plutons thus represent the magmatic expression of the initial stages of eastward subduction of the Pacific plate beneath the western margin of Gondwana, and confirm the existence of a Late Carboniferous-Permian magmatic arc that extended from southern North America to Central America.

  17. Zircon U-Pb Geochronology, Hf Isotopic Composition and Geological Implications of the Neoproterozoic Huashan Group in the Jingshan Area, Northern Yangtze Block, China

    NASA Astrophysics Data System (ADS)

    Yang, Z.; Yang, K.

    2015-12-01

    In the northern Yangtze Block, a clear angular unconformity between the Mesoproterozoic sequences (e.g. Dagushi Group) and the overlying Neoproterozoic strata (e.g. Huashan Group) marks the the Jinning orogeny. A combined study of Lu-Hf isotopes and U-Pb ages for detrital zircons from Huashan Group can provide information on the crustal evolution of sedimentary provenances and the timing of the Jinning orogeny. Detrital zircons from Huashan Group have two major U-Pb age populations of about 2.0Ga, 2.65Ga, and three subordinate age groups of about 0.82Ga, 2.5Ga, 2.9Ga with minor >3.0Ga ages. The youngest five analyses yield a weighted average age of 816±9Ma, which is consistent with that of interlayered basalt (824±9Ma, Deng et al., 2013) and roughly defines the minimum depositional age of Huashan Group. Detrital zircons of Huashan Group mostly have two stage Hf isotope model ages (TDM2) between 3.0 to 3.3Ga, indicating that the northern Yangtze Block experienced significant continental crustal growth during the Paleo- to Meso-archean. Similar U-Pb ages of detrital zircons have been obtained from Precambrian sedimentary rocks in the northern Yangtze Block from previous studies (Liu et al., 2008; Guo et al., 2014 and references therein). Recently, ca. 2.65Ga A-type granites had been reported from the Kongling and Huji area, which likely record the thermally stable lithosphere (Chen et al., 2013; Zhou et al., 2015). In combination with this study, it documents the widespread 2.6-2.7Ga magmatic rocks in the northern Yangtze Block. Zhao et al. (2013) demonstrated both the ca. 850Ma tonalite and trondhjemite of the Huangling igneous complex were formed in a continental arc setting. This suggests the Miaowan-Huashan oceanic basin proposed by Bader et al. (2013) has not been closed at ca. 850Ma. This evidence, together with the depositional age of the Huashan Group, indicates the Jinning orogeny took place at 850-820 Ma. [1] Bader et al., 2013 Tectonics [2] Deng et al

  18. The NO+O3 reaction: a triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly.

    PubMed

    Savarino, J; Bhattacharya, S K; Morin, S; Baroni, M; Doussin, J-F

    2008-05-21

    Atmospheric nitrate shows a large oxygen isotope anomaly (Delta 17 O), characterized by an excess enrichment of 17 O over 18 O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO(x), greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8+/-5)%(+/-2 sigma) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship Delta 17 O(NO2)=A x Delta 17 O(O3)+B, with A=1.18+/-0.07(+/-1 sigma) and B=(6.6+/-1.5)[per thousand](+/-1 sigma). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

  19. Oxygen Isotopic Fractionation During Evaporation of SiO2 in Vacuum and in H Gas

    NASA Astrophysics Data System (ADS)

    Nagahara, H.; Young, E. D.; Hoering, T. C.; Mysen, B. O.

    1993-07-01

    Chondritic components, chondrules, CAIs, and some parts of the matrix are believed to have formed and/or thermally processed in the solar nebula. If this scenario is the case, they should be fractionated for major and minor elements and isotopes according to the formation temperature. This is true for major and trace elements, but is not the case for isotopes. Differences in oxygen isotopic composition among meteorite groups are interpreted to be the results of mixing of gas and dust from different oxygen reservoirs, and the effect of isotopic fractionation is negligible for most meteorites except for rare CAIs. Davis et al. [1] studied the isotopic fractionation of SiO2, MgO, and forsterite and showed that oxygen isotopic fractionation from solid materials is very small, but that from liquid is significant. Evaporation in the solar nebula should, however, be in hydrogen gas, which is reactive with silicates. Therefore, the effect of hydrogen gas on the evaporation behaviors of silicates, including mode of evaporation, evaporation rate, and compositional and isotopic fractionation, should be studied. Nagahara [2] studied the evaporation rate of SiO2 in equilibrium, in constant evacuation (free evaporation), and in hydrogen, and showed that the rate in hydrogen gas is orders of magnitude larger than that in vacuum; the mode of evaporation also differs from that in vacuum. Oxygen isotopic fractionation during evaporation of SiO2 in constant evacuation and in hydrogen gas at two different total pressures are studied in the present study. The starting material is a single crystal of natural quartz, which should transform into high cristobalite at experimental conditions. The powdered starting material was kept in a graphite capsule without a cap and set in a vacuum chamber with and without hydrogen gas flow. Experimental temperature was 1600 degrees C. Oxygen isotopic compositions (^18O/^16O) were measured with the CO2laser heating fluorination technique. Oxygen

  20. Potentially biogenic carbon preserved in a 4.1 billion-year-old zircon.

    PubMed

    Bell, Elizabeth A; Boehnke, Patrick; Harrison, T Mark; Mao, Wendy L

    2015-11-24

    Evidence of life on Earth is manifestly preserved in the rock record. However, the microfossil record only extends to ∼ 3.5 billion years (Ga), the chemofossil record arguably to ∼ 3.8 Ga, and the rock record to 4.0 Ga. Detrital zircons from Jack Hills, Western Australia range in age up to nearly 4.4 Ga. From a population of over 10,000 Jack Hills zircons, we identified one >3.8-Ga zircon that contains primary graphite inclusions. Here, we report carbon isotopic measurements on these inclusions in a concordant, 4.10 ± 0.01-Ga zircon. We interpret these inclusions as primary due to their enclosure in a crack-free host as shown by transmission X-ray microscopy and their crystal habit. Their δ(13)CPDB of -24 ± 5‰ is consistent with a biogenic origin and may be evidence that a terrestrial biosphere had emerged by 4.1 Ga, or ∼ 300 My earlier than has been previously proposed.

  1. Potentially biogenic carbon preserved in a 4.1 billion-year-old zircon

    PubMed Central

    Bell, Elizabeth A.; Harrison, T. Mark; Mao, Wendy L.

    2015-01-01

    Evidence of life on Earth is manifestly preserved in the rock record. However, the microfossil record only extends to ∼3.5 billion years (Ga), the chemofossil record arguably to ∼3.8 Ga, and the rock record to 4.0 Ga. Detrital zircons from Jack Hills, Western Australia range in age up to nearly 4.4 Ga. From a population of over 10,000 Jack Hills zircons, we identified one >3.8-Ga zircon that contains primary graphite inclusions. Here, we report carbon isotopic measurements on these inclusions in a concordant, 4.10 ± 0.01-Ga zircon. We interpret these inclusions as primary due to their enclosure in a crack-free host as shown by transmission X-ray microscopy and their crystal habit. Their δ13CPDB of −24 ± 5‰ is consistent with a biogenic origin and may be evidence that a terrestrial biosphere had emerged by 4.1 Ga, or ∼300 My earlier than has been previously proposed. PMID:26483481

  2. From Mars Meteorites to Laboratory Investigations: Understanding Heterogeneous Photochemical Transformations Using Oxygen Triple Isotope Anomalies of Carbonates

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Smirnova, V.; Jackson, T. L.; Mang, L.; Thiemens, M. H.

    2016-12-01

    The planet Mars is unique in our solar system with a positive O-isotope anomaly observed in its bulk silicate and carbonates minerals ranging from 0.3 to 0.6 ‰. The carbonate isotopic signature can be used to reveal its origin, past history and atmosphere-hydrosphere-geosphere-interactions. Ozone is a powerful natural tracer of photochemical processes in Earth's atmosphere. It possess the highest enrichment in heavy isotopes δ17O ≈ δ18O (70-150‰) and oxygen isotopic anomaly (Δ17O = 30-40‰). The oxygen isotopic anomaly from ozone is transferred to other oxygen carrying molecules in the atmosphere through different mechanisms. Laboratory experiments were conducted with the JSC-Mars Simulant and iron oxide to investigate how this anomaly can be transferred to water and minerals under conditions similar to present day Mars. Three sets of laboratory experiments (O3-H2O-UV-minerals; O2-H2O-UV-minerals; O3-H2O-minerals) were performed. The oxygen triple isotopic analysis of product mineral carbonates formed from adsorbed CO2 reaction showed an oxygen isotopic anomaly (Δ17O = 0.4-3‰). The oxygen triple isotopic composition of water at photochemical equilibrium shifted towards ozone with Δ17O = 9‰ indicating reaction of ozone with water vapor via electronically excited oxygen atoms and transfer of the anomaly via hydroxyl radicals. HOx (HO, HO2) are extremely reactive and have very short life time (< μs), however, our data indicate that its signature is preserved through surficial interactions with adsorbed CO2 on mineral surfaces. Hydroxyl radicals may have played a significant role in heterogeneous photochemical transformations on mineral dust in the atmosphere of Mars and transfer of ozone anomaly to water and other oxygen bearing minerals through surficial reactions. Series of experiments were performed to constrain the amount of H2O required to preserve the oxygen isotope anomaly observed in carbonate minerals in the Martian meteorites. These

  3. Magmatic @d^1^8O in 4400-3900 Ma detrital zircons: A record of the alteration and recycling of crust in the Early Archean [rapid communication

    NASA Astrophysics Data System (ADS)

    Cavosie, A. J.; Valley, J. W.; Wilde, S. A.

    2005-07-01

    Ion microprobe analyses of δ 18O in 4400-3900 Ma igneous zircons from the Jack Hills, Western Australia, provide a record of the oxygen isotope composition of magmas in the earliest Archean. We have employed a detailed analysis protocol aimed at correlating spatially related micro-volumes of zircon concordant in U/Pb age with δ 18O and internal zoning. Simultaneous analysis of 18O and 16O with dual Faraday cup detectors, combined with frequent standardization, has yielded data with improved accuracy and precision over prior studies, and resulted in a narrower range of what is interpreted as magmatic δ 18O in > 3900 Ma zircons. Preserved magmatic δ 18O values from individual zircons (Zrc) range from 5.3‰ to 7.3‰ (VSMOW), and increasingly deviate from the mantle range of 5.3 ± 0.3‰ as zircons decrease in age from 4400 to 4200 Ma. Elevated δ 18O (Zrc) values up to 6.5‰ occur as early as 4325 Ma, which suggests that evolved rocks were incorporated into magmas within ˜230 Ma of Earth's accretion. Values of magmatic δ 18O (Zrc) as high as 7.3‰ are recorded in zircons by 4200 Ma, and are common thereafter. The protoliths of the magmas these zircons crystallized in were altered by low temperature interaction with liquid water near Earth's surface. These results provide the strongest evidence yet for the existence of liquid water oceans and supracrustal rocks by approximately 4200 Ma, and possibly as early as 4325 Ma. The range of magmatic δ 18O values in the 4400-3900 Ma zircons is indistinguishable from Archean igneous zircons, suggesting similar magmatic processes occurred over the first two billion years of recorded Earth history. Zircons with sub-solidus alteration histories, identified by the presence of disturbed internal zoning patterns, record δ 18O values both below (4.6‰) and above (10.3‰) the observed range for primary magmatic zircon, and are unreliable indicators of Early Archean magma chemistry.

  4. Alxa Block Provenance of Ediacaran (Sinian) Sediments in the Helanshan Area: Constraints from Hf Isotopes and U-Pb Geochronology of Detrital Zircons

    NASA Astrophysics Data System (ADS)

    Xiaopeng, D.

    2016-12-01

    The tectonic relationship between the Alxa Block and the North China Craton has long been controversial. The Helanshan area lies at the western margin of the Ordos Block and east of the Alxa Block (Fig.a), and it contains rocks of the lower Zhengmuguan and upper Tuerkeng formations that belong to the Ediacaran system. The Zhengmuguan Formation is made up of abyssal facies rocks including dolomite and glacial conglomerate with dropstones, and the Tuerkeng Formation consists of silty slate of the neritic facies. A discontinuity marks the boundary between the Tuerkeng Formation and the Early Cambrian Suyukou Formation, which is composed mainly of pebbly sandstone towards the base and sandstone towards the top, representing a change in sedimentary facies from terrestrial to littoral.The Neoproterozoic U-Pb ages of zircons from the Ediacaran and Early Cambrian sediments peak at 818 ± 4 Ma (n = 88) and 905 ± 8 Ma (n = 20), consistent with the Neoproterozoic age peaks found in the Precambrian basement of the Alxa Block(Fig.b). There are few Neoproterozoic zircons in the Neoproterozoic strata of the Langshan area, and there are no reports of Neoproterozoic zircons in the Zhuozishan area, northwest of Helanshan, or in the western margin of the neighboring Ordos Basin. A number of Neoproterozoic zircons are found in the Middle Cambrian to Middle Ordovician strata of the Niushoushan area. And while Niushoushan is part of the Hexi Corridor, it did not amalgamate with the NCC before the Early-Middle Cambrian. Therefore, the Neoproterozoic and Early Cambrian sediments in Helanshan record information about Neoproterozoic magmatic events in the Alxa Block, and indicate an Alxa Block provenance(Fig.c).The Hf isotopic characteristics of the Neoproterozoic zircons from the Ediacaran Zhengmuguan Formation in the Helanshan area (eHf(t) = -7.812 to 3.274, TDMC = 2211-1578 Ma, n = 10) are similar to those Neoproterozoic igneous zircons from the Langshan area (eHf(t) = -1.105 to 5

  5. Zircon U-Pb ages and Hf-O isotopes, and whole-rock Sr-Nd isotopes of the Bozhushan granite, Yunnan province, SW China: Constraints on petrogenesis and tectonic setting

    NASA Astrophysics Data System (ADS)

    Chen, Xiao-Cui; Hu, Rui-Zhong; Bi, Xian-Wu; Zhong, Hong; Lan, Jiang-Bo; Zhao, Cheng-Hai; Zhu, Jing-Jing

    2015-03-01

    The Bainiuchang silver-polymetallic ore deposit is a super-large deposit in the western part of the South China tungsten-tin province (or the Nanling tungsten-tin province). The deposit is spatially and temporally associated with the Bozhushan granite pluton. Our new data indicate that the Bozhushan granitoids formed at 86-87 Ma. The granitoids are geochemically consistent with A-type granite. The Bozhushan pluton consists predominantly of biotite granite that is characterized by weakly peraluminous to metaluminous compositions and high alkali contents (Na2O + K2O = 7.51-9.06 wt.%). The granitic rocks are enriched in large-ion lithophile elements (LILE) Rb, Th, U, and K, but relatively depleted in Ba and Sr. In addition, they have high Zr + Nb + Ce + Y contents (310-478 ppm) and high 10,000× Ga/Al ratios (2.7-3.1). The temperatures of the parental magmas for the Bozhushan granites are estimated to be 790-842 °C based on the zircon saturation thermometer. Isotopically, the Bozhushan granites are characterized by elevated initial 87Sr/86Sr ratios (0.7126-0.7257) and low εNd values (-11.2 to -12.4), and high δ18O values (7.91-9.58‰) and low εHf values (-9.5 to -6.1) for zircon crystals, which indicate a dominant continental crustal source. The two-stage Hf model ages vary from 1.53 to 1.86 Ga. The isotopic compositions support the interpretation that the granitic rocks formed by melting of the Meso- and Neoproterozoic metasedimentary basements of the Cathaysia block. These results, together with geological records in the other parts of the western Cathaysia block, suggest that the formation of the Bozhushan A-type granites is related to lithospheric extension and asthenospheric upwelling that are associated with the change of plate motion in Late-Cretaceous.

  6. A Quantitative, Time-Dependent Model of Oxygen Isotopes in the Solar Nebula: Step one

    NASA Technical Reports Server (NTRS)

    Nuth, J. A.; Paquette, J. A.; Farquhar, A.; Johnson, N. M.

    2011-01-01

    The remarkable discovery that oxygen isotopes in primitive meteorites were fractionated along a line of slope I rather than along the typical slope 0,52 terrestrial fractionation line occurred almost 40 years ago, However, a satisfactory, quantitative explanation for this observation has yet to be found, though many different explanations have been proposed, The first of these explanations proposed that the observed line represented the final product produced by mixing molecular cloud dust with a nucleosynthetic component, rich in O-16, possibly resulting from a nearby supernova explosion, Donald Clayton suggested that Galactic Chemical Evolution would gradually change the oxygen isotopic composition of the interstellar grain population by steadily producing O-16 in supernovae, then producing the heavier isotopes as secondary products in lower mass stars, Thiemens and collaborators proposed a chemical mechanism that relied on the availability of additional active rotational and vibrational states in otherwise-symmetric molecules, such as CO2, O3 or SiO2, containing two different oxygen isotopes and a second, photochemical process that suggested that differential photochemical dissociation processes could fractionate oxygen , This second line of research has been pursued by several groups, though none of the current models is quantitative,

  7. The 3.5 Ga granulites of the Bug polymetamorphic complex, Ukraine (U-Pb SHRIMP-II zircon data)

    NASA Astrophysics Data System (ADS)

    Lobach-Zhuchenko, Svetlana; Kaulina, Tatiana; Baltybaev, Shauket; Yurchenko, Anastasija; Balagansky, Victor; Skublov, Sergei; Sukach, Vitaliji

    2014-05-01

    and Cpx). Zircon U-Pb isotopic analysis was carried out using SHRIMP II ion microprobe technique at the Isotopic Centre of VSEGEI, St.-Petersburg. Six transparent grains of the (1) group form a discordia line with Concordia intercepts at 3499+/-33 Ma (and 2638+/-240 Ma (MSWD=2.3). According to internal textures and chemical composition of zircons their formation is associated with granulite metamorphism. The 207 Pb/ 206 Pb data for 11 grains from (3) group are highly variable in age from 3330+/-5 to 2356+/-7 Ma indicating isotopic disturbance. They do not form an isochrone, thus reliable determination of their age is not yet possible. Thus, the oldest granulitic event at 3499 ± 33 Ma has been identified and justified for rocks of the Bug polymetamorphic granulite complex. Recognition of this oldest granulite metamorphism proved possible due to preserved isotopic and geochemical features of zircon. The work was financially supported by program ONZ - 6.

  8. Resolution, the key to unlocking granite petrogenesis using zircon U-Pb - Lu-Hf studies

    NASA Astrophysics Data System (ADS)

    Tapster, Simon; Horstwood, Matthew; Roberts, Nick M. W.; Deady, Eimear; Shail, Robin

    2017-04-01

    Coarse-scale understanding of crustal evolution and source contributions to igneous systems has been drastically enhanced by coupled zircon U-Pb and Lu-Hf data sets. These are now common place and potentially offer advantages over whole-rock analyses by resolving heterogeneous source components in the complex crystal cargos of single hand-samples. However, the application of coupled zircon U-Pb and Lu-Hf studies to address detailed petrogenetic questions faces a crisis of resolution - On the one hand, micro-beam analytical techniques have high spatial resolution, capable of interrogating crystals with complex growth histories. Yet, the >1-2% temporal resolution of these techniques places a fundamental limitation on their utility for developing petrogenetic models. This limitation in data interpretation arises from timescales of crystal recycling or changes in source evolution that are often shorter than the U-Pb analytical precision. Conversely, high-precision CA-ID-TIMS U-Pb analysis of single whole zircons and solution MC-ICP-MS Lu-Hf isotopes of column washes (Hf masses equating to ca. 10-50 ng) have much greater temporal resolution (<0.1%), yet lack the spatial resolution to deal with complex crystal growth. Analyses homogenize any heterogeneity within the zircon and convolute the petrogenetic model. A balance must be struck between spatial and temporal resolution to address petrogenetic issues. Here, we demonstrate that micro-sampling of complex xenocryst-rich zircon crystals (e.g. <40 µm zircon tips) from the granitic post-Variscan Cornubian Batholith (SW England), in tandem with low-common Pb blank CA-ID-TIMS U-Pb chemistry, permits the analysis of zircon volumes that approach those of LA-ICPMS analyses, whilst simultaneously retaining the majority of the temporal resolution associated with the CA-ID-TIMS U-Pb technique. The low volume of zircon within these analyses may only provide <5 ng Hf, and therefore gaining useful precision from Lu-Hf isotopes is

  9. Triple oxygen isotope composition of leaf waters in Mpala, central Kenya

    NASA Astrophysics Data System (ADS)

    Li, Shuning; Levin, Naomi E.; Soderberg, Keir; Dennis, Kate J.; Caylor, Kelly K.

    2017-06-01

    Variations in triple oxygen isotopes have been used in studies of atmospheric photochemistry, global productivity and increasingly in studies of hydroclimate. Understanding the distribution of triple oxygen isotopes in plant waters is critical to studying the fluxes of oxygen isotopes between the atmosphere and hydrosphere, in which plants play an important role. In this paper we report triple oxygen isotope data for stem and leaf waters from Mpala, Kenya and explore how Δ17 O, the deviation from an expected relationship between 17O /16O and 18O /16O ratios, in plant waters vary with respect to relative humidity and deuterium excess (d-excess). We observe significant variation in Δ17 O among waters in leaves and stems from a single plant (up to 0.16‰ range in Δ17 O in leaf water in a plant over the course of a signal day), which correlates to changes in relative humidity. A steady state model for evaporation in leaf water reproduces the majority of variation in Δ17 O and d-excess we observed in leaf waters, except for samples that were collected in the morning, when relative humidity is high and the degree of fractionation in the system is minimal. The data and the steady state model indicate that the slope, λtransp, that links δ17 O and δ18 O values of stem and leaf waters and characterizes the fractionation during transpiration, is strongly influenced by the isotopic composition of ambient vapor when relative humidity is high. We observe a strong, positive relationship between d-excess and Δ17 O, with a slope 2.2 ± 0.2 per meg ‰-1, which is consistent with the observed relationship in tropical rainfall and in water in an evaporating open pan. The strong linear relationship between d-excess and Δ17 O should be typical for any process involving evaporation or any other fractionation that is governed by kinetic effects.

  10. Investigating the Direct Meltwater Effect in Terrestrial Oxygen-Isotope Paleoclimate Records Using an Isotope-Enabled Earth System Model

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhu, Jiang; Liu, Zhengyu; Brady, Esther C.

    Variations in terrestrial oxygen-isotope reconstructions from ice cores and speleothems have been primarily attributed to climatic changes of surface air temperature, precipitation amount, or atmospheric circulation. In this work, we demonstrate with the fully coupled isotope-enabled Community Earth System Model an additional process contributing to the oxygen-isotope variations during glacial meltwater events. This process, termed “the direct meltwater effect,” involves propagating large amounts of isotopically depleted meltwater throughout the hydrological cycle and is independent of climatic changes. We find that the direct meltwater effect can make up 15–35% of the δ 18O signals in precipitation over Greenland and eastern Brazilmore » for large freshwater forcings (0.25–0.50 sverdrup (10 6 m 3/s)). Model simulations further demonstrate that the direct meltwater effect increases with the magnitude and duration of the freshwater forcing and is sensitive to both the location and shape of the meltwater. These new modeling results have important implications for past climate interpretations of δ 18O.« less

  11. Investigating the Direct Meltwater Effect in Terrestrial Oxygen-Isotope Paleoclimate Records Using an Isotope-Enabled Earth System Model

    DOE PAGES

    Zhu, Jiang; Liu, Zhengyu; Brady, Esther C.; ...

    2017-12-28

    Variations in terrestrial oxygen-isotope reconstructions from ice cores and speleothems have been primarily attributed to climatic changes of surface air temperature, precipitation amount, or atmospheric circulation. In this work, we demonstrate with the fully coupled isotope-enabled Community Earth System Model an additional process contributing to the oxygen-isotope variations during glacial meltwater events. This process, termed “the direct meltwater effect,” involves propagating large amounts of isotopically depleted meltwater throughout the hydrological cycle and is independent of climatic changes. We find that the direct meltwater effect can make up 15–35% of the δ 18O signals in precipitation over Greenland and eastern Brazilmore » for large freshwater forcings (0.25–0.50 sverdrup (10 6 m 3/s)). Model simulations further demonstrate that the direct meltwater effect increases with the magnitude and duration of the freshwater forcing and is sensitive to both the location and shape of the meltwater. These new modeling results have important implications for past climate interpretations of δ 18O.« less

  12. Detrital Zircons From the Jack Hills and Mount Narryer, Western Australia: Geochronological, Morphological, and Geochemical Evidence for Diverse >4000 Ma Source Rocks

    NASA Astrophysics Data System (ADS)

    Crowley, J. L.; Myers, J. S.; Sylvester, P. J.; Cox, R. A.

    2004-05-01

    Detrital zircons from all major clastic units in the Jack Hills and Mount Narryer metasedimentary belts, Western Australia, were analyzed for morphology, internal zoning, inclusion mineralogy, age, and trace element concentrations (latter two obtained by laser-ablation microprobe ICPMS). The results show that zircons were derived from a wide diversity of rocks, including previously described, >4000 Ma grains that are older than any known terrestrial rocks. In three metaconglomerate samples from the western Jack Hills, 4200-3800 Ma zircons ("old grains") comprise 14% of the population, 3800-3600 Ma grains form only 2%, and 3550-3250 Ma zircons ("young grains") are dominant with a significant peak at 3380 Ma. Old and young grains are interpreted as being from similar rock types because they are indistinguishable in trace element concentrations, size (several hundred microns), morphology (subequant, typically fragmented), internal zoning (typically both oscillatory and sector), and U concentration (50-200 ppm). Many of these properties suggest an intermediate plutonic source, whereas an evolved granitic source was previously interpreted from rare-earth element and oxygen isotope data. Detrital zircons in quartzites and metaconglomerates at Mount Narryer differ significantly from zircons from the western Jack Hills. Old grains comprise only 3% (most of which are 4200-4100 Ma), 3800-3600 Ma zircons form 31%, and there are peaks at 3650, 3600, and 3500 Ma. Old and young grains have similar properties that suggest granitic sources, such as elongate prismatic morphology, oscillatory zoning, high U concentrations (100-600 ppm), and xenotime and monazite inclusions. Trace element concentrations are broadly similar to those in Jack Hills zircons, with notable exceptions being generally higher U, smaller Ce and Eu anomalies, and lower Nb/Ta. It is considered unlikely that Jack Hills zircons were derived from granitic gneisses that surround the metasedimentary belts because

  13. Quasi-free Proton Knockout Reactions on the Oxygen Isotopic Chain

    NASA Astrophysics Data System (ADS)

    Atar, Leyla; Aumann, Thomas; Bertulani, Carlos; Paschalis, Stefanos; R3B Collaboration

    2017-09-01

    It is well known from electron-induced knockout data that the single-particle (SP) strength is reduced to about 60-70% for stable nuclei in comparison to the independent particle model due to the presence of short- and long-range correlations. This finding has been confirmed by nuclear knockout reactions using stable and exotic beams, however, with a strong dependency on the proton-neutron asymmetry. The observed strong reduction of SP cross sections for the deeply bound valence nucleons in asymmetric nuclei is theoretically not understood. To understand this dependency quantitatively a complementary approach, quasi-free (QF) knockout reactions in inverse kinematics, is introduced. We have performed a systematic study of spectroscopic strength of oxygen isotopes using QF (p,2p) knockout reactions in complete kinematics at the R3B/LAND setup at GSI with secondary beams containing 13-24O. The oxygen isotopic chain covers a large variation of separ ation energies, which allow a systematic study of SF with respect to isospin asymmetry. We will present results on the (p,2p) cross sections for the entire oxygen isotopic chain obtained from a single experiment. By comparison with the Eikonal reaction theory the SF and reduction factors will be presented. The work is supported by GSI-TU Darmstadt cooperation and BMBF project 05P15RDFN1.

  14. Oxygen isotope evolution of the Lake Owyhee volcanic field, Oregon, and implications for low-δ18O magmas of the Snake River Plain - Yellowstone hotspot

    NASA Astrophysics Data System (ADS)

    Blum, T.; Kitajima, K.; Nakashima, D.; Valley, J. W.

    2013-12-01

    The Snake River Plain - Yellowstone (SRP-Y) hotspot trend is one of the largest known low-δ18O magmatic provinces, yet the timing and distribution of hydrothermal alteration relative to hotspot magmatism remains incompletely understood. Existing models for SRP-Y low-δ18O magma genesis differ regarding the timing of protolith alteration (e.g. Eocene vs. present), depth at which alteration occurs (e.g. 15 km vs. <5 km), and physical controls on the extent of alteration (e.g. caldera collapse, crustal scale fluid flow, etc.). We expand the existing oxygen isotope data set for zircon in the Lake Owyhee volcanic field (LOVF) of east central Oregon to further identify magmatic oxygen isotope trends within the field. These data offer insight into the timing of alteration and the extent of the greater SRP-Y low-δ18O province, as well as the conditions that generate large low-δ18O provinces. 16-14 Ma silicic volcanism in the LOVF is linked to the pre-14 Ma SRP-Y hotspot, with volcanism partially overlapping extension in the north-south trending Oregon-Idaho Graben (OIG). Ion microprobe analyses of zircons from 16 LOVF silicic lavas and tuffs reveal homogeneous zircons on both the single grain and hand sample scales: individual samples have 2 S.D. for δ18O ranging from 0.27 to 0.96‰ (SMOW), and sample averages ranging from 1.8 to 6.0‰, excluding texturally chaotic and/or porous zircons which have δ18O values as low as 0.0‰. All low-δ18O LOVF magmas, including the caldera-forming Tuff of Leslie Gulch and Tuff of Spring Creek, are confined to the OIG, although not all zircons from within the OIG have low δ18O values. The presence and sequence of low-δ18O magmas in the LOVF and adjacent central Snake River Plain (CSRP) cannot be explained by existing caldera subsidence or pre-hotspot source models. These data, however, combined with volumetrically limited low-δ18O material in the adjacent Idaho Batholith and Basin and Range, are consistent with low-δ18O magmas

  15. Uranium Stable Isotopes: A Proxy For Productivity Or Ocean Oxygenation?

    NASA Astrophysics Data System (ADS)

    Severmann, S.

    2015-12-01

    Uranium elemental abundances in sediments have traditionally been used to reconstruct primary productivity and carbon flux in the ocean. 238U/235U isotope compositions, in contrast, are currently understood to reflect the extent of bottom water anoxia in the ocean. A review of our current understanding of authigenic U enrichment mechanism into reducing sediments suggests that a revision of this interpretation is warranted. Specifically, the current interpretation of U isotope effects in suboxic vs. anoxic deposits has not taken into account the well-documented linear relationship with organic C burial rates. Although organic C rain rates (i.e., surface productivity) and bottom water oxygenation are clearly related, distinction between these two environmental controls is conceptually important as it relates to the mechanism of enhanced C burial and ultimately the strength of the biological pump. Here we will review new and existing data to test the hypothesis that the isotope composition of authigenic U in reducing sediments are best described by their relationship with parameters related to organic carbon delivery and burial, rather than bottom water oxygen concentration.

  16. Oxygen isotopes as a tool to quantify reservoir-scale CO2 pore-space saturation

    NASA Astrophysics Data System (ADS)

    Serno, Sascha; Flude, Stephanie; Johnson, Gareth; Mayer, Bernard; Boyce, Adrian; Karolyte, Ruta; Haszeldine, Stuart; Gilfillan, Stuart

    2017-04-01

    Structural and residual trapping of carbon dioxide (CO2) are two key mechanisms of secure CO2 storage, an essential component of Carbon Capture and Storage technology [1]. Estimating the amount of CO2 that is trapped by these two mechanisms is a vital requirement for accurately assessing the secure CO2 storage capacity of a formation, but remains a key challenge. Recent field [2,3] and laboratory experiment studies [4] have shown that simple and relatively inexpensive measurements of oxygen isotope ratios in both the injected CO2 and produced water can provide an assessment of the amount of CO2 that is stored by these processes. These oxygen isotope assessments on samples obtained from observation wells provide results which are comparable to other geophysical techniques. In this presentation, based on the first comprehensive review of oxygen isotope ratios measured in reservoir waters and CO2 from global CO2 injection projects, we will outline the advantages and potential limitations of using oxygen isotopes to quantify CO2 pore-space saturation. We will further summarise the currently available information on the oxygen isotope composition of captured CO2. Finally, we identify the potential issues in the use of the oxygen isotope shifts in the reservoir water from baseline conditions to estimate accurate saturations of the pore space with CO2, and suggest how these issues can be reduced or avoided to provide reliable CO2 pore-space saturations on a reservoir scale in future field experiments. References [1] Scott et al., (2013) Nature Climate Change, Vol. 3, 105-111 doi:10.1038/nclimate1695 [2] Johnson et al., (2011) Chemical Geology, Vol. 283, 185-193 http://dx.doi.org/10.1016/j.ijggc.2016.06.019 [3] Serno et al., (2016) IJGGC, Vol. 52, 73-83 http://dx.doi.org/10.1016/j.ijggc.2016.06.019 [4] Johnson et al., (2011) Applied Geochemistry, Vol. 26 (7) 1184-1191 http://dx.doi.org/10.1016/j.apgeochem.2011.04.007

  17. Empirical constraints on the effects of radiation damage on helium diffusion in zircon

    NASA Astrophysics Data System (ADS)

    Anderson, Alyssa J.; Hodges, Kip V.; van Soest, Matthijs C.

    2017-12-01

    In this study, we empirically evaluate the impact of radiation damage on zircon (U-Th)/He closure temperatures for a suite of zircon crystals from the slowly cooled McClure Mountain syenite of south-central Colorado, USA. We present new zircon, titanite, and apatite conventional (U-Th)/He dates, zircon laser ablation (U-Th)/He and U-Pb dates, and zircon Raman spectra for crystals from the syenite. Titanite and apatite (U-Th)/He dates range from 447 to 523 Ma and 88.0 to 138.9 Ma, respectively, and display no clear correlation between (U-Th)/He date and effective uranium concentration. Conventional zircon (U-Th)/He dates range from 230.3 to 474 Ma, while laser ablation zircon (U-Th)/He dates show even greater dispersion, ranging from 5.31 to 520 Ma. Dates from both zircon (U-Th)/He datasets decrease with increasing alpha dose, indicating that most of the dispersion can be attributed to radiation damage. Alpha dose values for the dated zircon crystals range from effectively zero to 2.15 × 1019 α /g, spanning the complete damage spectrum. We use an independently constrained thermal model to empirically assign a closure temperature to each dated zircon grain. If we assume that this thermal model is robust, the zircon radiation damage accumulation and annealing model of Guenthner et al. (2013) does not accurately predict closure temperatures for many of the analyzed zircon crystals. Raman maps of the zircons dated by laser ablation document complex radiation damage zoning, sometimes revealing crystalline zones in grains with alpha dose values suggestive of amorphous material. Such zoning likely resulted in heterogeneous intra-crystalline helium diffusion and may help explain some of the discrepancies between our empirical findings and the Guenthner et al. (2013) model predictions. Because U-Th zoning is a common feature in zircon, radiation damage zoning is likely to be a concern for most ancient, slowly cooled zircon (U-Th)/He datasets. Whenever possible, multiple

  18. Carbon, Hydrogen, and Oxygen Isotope Ratios of Cellulose from Plants Having Intermediary Photosynthetic Modes 1

    PubMed Central

    Sternberg, Leonel O'Reilly; Deniro, Michael J.; Ting, Irwin P.

    1984-01-01

    Carbon and hydrogen isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from species of greenhouse plants having different photosynthetic modes were determined. When hydrogen isotope ratios are plotted against carbon isotope ratios, four clusters of points are discernible, each representing different photosynthetic modes: C3 plants, C4 plants, CAM plants, and C3 plants that can shift to CAM or show the phenomenon referred to as CAM-cycling. The combination of oxygen and carbon isotope ratios does not distinguish among the different photosynthetic modes. Analysis of the carbon and hydrogen isotope ratios of cellulose nitrate should prove useful for screening different photosynthetic modes in field specimens that grew near one another. This method will be particularly useful for detection of plants which show CAM-cycling. PMID:16663360

  19. Oxygen isotope variations in phosphate of deer bones

    NASA Astrophysics Data System (ADS)

    Luz, Boaz; Cormie, Allison B.; Schwarcz, Henry P.

    1990-06-01

    Variations of δ 18O of bone phosphate (δ p) of white tailed deer were studied in samples with wide geographic distribution in North America. Bones from the same locality have similar isotopic values, and the difference between specimens (0.4‰) is not large relative to the measurement error (0.3‰). The total range of δ p values is about 12‰. This indicates that deer use water from a relatively small area, and thus their δ p indicates local environmental conditions. Multiple regression analysis between oxygen isotope composition of deer bone phosphate and of local relative humidity and precipitation (δ w) yields a high correlation coefficient (0.95). This correlation is significantly better than the linear correlation (0.81) between δ p and δ w of precipitation alone. Thus δ p depends on both isotopic composition of precipitation and on relative humidity. This is because deer obtain most of their water from leaves, the isotopic composition of which is partly controlled by relative humidity through evaporation/transpiration.

  20. Oxygen isotope fractionation in the CaCO3-DIC-H2O system

    NASA Astrophysics Data System (ADS)

    Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

    2017-10-01

    The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

  1. Finding the "true" age: ways to read high-precision U-Pb zircon dates

    NASA Astrophysics Data System (ADS)

    Schaltegger, U.; Schoene, B.; Ovtcharova, M.; Sell, B. K.; Broderick, C. A.; Wotzlaw, J.

    2011-12-01

    Refined U-Pb dating techniques, applying an empirical chemical abrasion treatment prior to analysis [1], and using a precisely calibrated double isotope Pb, U EARTHTIME tracer solution, have led to an unprecedented <0.1% precision and accuracy of obtained 206Pb/238U dates of single zircon crystals or fragments. Results very often range over 10e4 to 10e6 years and cannot be treated as statistically singular age populations. The interpretation of precise zircon U-Pb ages is biased by two problems: (A) Post-crystallization Pb loss from decay damaged areas is considered to be mitigated by applying chemical abrasion techniques. The success of such treatment can, however, not be assumed a priori. The following examples demonstrate that youngest zircons are not biased by lead loss but represent close-to-youngest zircon growth: (i) coincidence of youngest zircon dates with co-magmatic titanite in tonalite; (ii) coincidence with statistically equivalent clusters of 206Pb/238U dates from zircon in residual melts of cogenetic mafic magmas; (iii) youngest zircons in ash beds of sedimentary sequences do not violate the stratigraphic superposition, whereas conventional statistical interpretation (mean or median values) does; (iv) results of published inter-laboratory cross-calibration tests using chemical abrasion on natural zircon crystals of the same sample arrive at the same 206Pb/238U result within <0.1% (e.g., [2]); (v) Youngest crystals coincide in age with the astronomical age of hosting cyclic sediments. Residual lead loss may, however, still be identified in the case of single, significantly younger dates (>3 sigma), and are common in many pre-Triassic and hydrothermally altered rocks. (B) Pre-eruptive/pre-intrusive growth is found to be the main reason for scattered zircon ages in igneous rocks. Zircons crystallizing from the final magma batch are called autocrystic [3]. Autocrystic growth will happen in a moving or stagnant magma shortly before or after the

  2. SHRIMP U-Pb dating, trace elements and the Lu-Hf isotope system of coesite-bearing zircon from amphibolite in the SW Sulu UHP terrane, eastern China

    NASA Astrophysics Data System (ADS)

    Liu, Fulai; Gerdes, Axel; Zeng, Lingsen; Xue, Huaimin

    2008-06-01

    In this study, we link mineral inclusion data, trace element analyses, U-Pb age and Hf isotope composition obtained from distinct zircon domains of complex zircon to unravel the origin and multi-stage metamorphic evolution of amphibolites from the Sulu ultrahigh-pressure (UHP) terrane, eastern China. Zircon grains separated from amphibolites from the CCSD-MH drill hole (G12) and Niushan outcrop (G13) were subdivided into two main types based on cathodoluminescence (CL) and Laser Raman spectroscopy: big dusty zircons with inherited cores and UHP metamorphic rims and small clear zircons. Weakly zoned, grey-white luminescent inherited cores preserve mineral inclusions of Cpx + Pl + Ap ± Qtz indicative of a mafic igneous protolith. Dark grey luminescent overgrowth rims contain the coesite eclogite-facies mineral inclusion assemblage Coe + Grt + Omp + Phe + Ap, and formed at T = 732-839 °C and P = 3.0-4.0 GPa. In contrast, white luminescent small clear zircons preserve mineral inclusions formed during retrograde HP quartz eclogite to LP amphibolite-facies metamorphism (T = 612-698 °C and P = 0.70-1.05 GPa). Inherited zircons from both samples yield SHRIMP 206Pb/238U ages of 695-520 Ma with an upper intercept age of 800 ± 31 Ma. The UHP rims yield consistent Triassic ages around 236-225 and 239-225 Ma for G12 and G13 with weighted means of 229 ± 3 and 231 ± 3 Ma, respectively. Small clear zircons from both samples give 206Pb/238U ages around 219-210 Ma with a weighted mean of 214 ± 3 Ma, interpreted as the age of retrograde quartz eclogite-facies metamorphism. Matrix amphibole from both samples indicate Ar-Ar ages of 209 ± 0.7 and 207 ± 0.7 Ma, respectively, probably dating late amphibolite-facies retrogression. The data suggest subduction of Neoproterozoic mafic igneous rocks to UHP conditions in Middle Triassic (∼230 Ma) times and subsequent exhumation to an early HP (∼214 Ma) and a late LP stage (∼208 Ma) over a period of ∼16 and 6 Myr, respectively

  3. High Pressure Behavior of Zircon at Room Temperature

    NASA Astrophysics Data System (ADS)

    Reichmann, H. J.; Rocholl, A.

    2016-12-01

    Zircon, ZrSiO4, is an ubiquitous mineral in the Earth's crust, forming under a wide range of metamorphic and igneous conditions. Its high content in certain trace elements (REE, Hf, Th, U) and due to its isotopic information, together with its chemical and physical robustness makes zircon an unique geochemical tool and geochronometer. Despite its geological importance there is a disagreement regarding the responds of zircon to elevated pressure, especially about the commencement of a pressure - induced structural phase transition. At elevated pressure zircon (I41/amd) undergoes a pressure induced phase transition to the scheelite structure (I41/a) . In the low pressure and high pressure phase, the (SiO4)4- tetrahedral units are present. However, the onset of the phase transition at room temperature is not well defined: zircon - scheelite transitions have been reported in a pressure regime ranging from 20 to 30 GPa (e.g. Ono et al., 2004). To clarify this issue, we performed Raman spectroscopy measurement up to 60 GPa on a non-metamict single crystal zircon sample (reference material 91500; Wiedenbeck et al., 1995; Wiedenbeck et al., 2004). A closer look at the external lattice modes at 201 cm-1 shows a decreasing of the wavenumbers with increasing pressure up to 21 GPa followed by a steep increase. The lattice modes at 213 and 224 cm-1 also exhibit a subtle kink in this pressure range. This pressure coincides with that one reported for the zircon - scheelite transition (van Westrenen et al., 2004). Another interesting issue is the behavior of the internal modes at higher pressures. The ν3 stretching modes at about 1000 cm-1show distinct discontinuities at 31 GPa accompanied by the emerging of new features in the Raman spectrum suggesting another, pressure triggered modification in the zircon structure. References: Ono, Funakoshi, Nakajima, Tange, and Katsura (2004) Contr. Mineral. Petrol., 147, 505-509. Van Westrenen, Frank, Hanchar, Fei, Finch, and Zha (2004

  4. Ancient and modern rhyolite: Using zircon trace element compositions to examine the origin of volcanic rocks

    NASA Astrophysics Data System (ADS)

    Klemetti, E. W.; Lackey, J.; Starnes, J.; Wooden, J. L.

    2011-12-01

    along with crystal fractionation. At a given Hf concentration, the Th/U of Mineral King rhyolites are lower than Okataina rhyolites. Yb/Sm are, on average, lower for Mineral King rhyolite at a given Hf than in the Okataina rhyolites. At high Hf concentrations (>12000 ppm), Mineral King rhyolites show a wide range of Yb/Sm (<100 to 500). A xenocrystic zircon with an age of ~1.63 Ga was found in one Mineral King rhyolite suggesting crustal melting/assimilation was also important during the evolution in the younger rhyolites in the pendant. Additionally, bulk zircon oxygen isotopic analyses from Mineral King rhyolites show a change from more mantle-like values δ18O at 196 Ma (+5.3%) to higher values at 136 Ma (+6.8%), evidence of increasing input of continental crust. In all, the differences in the trace element and isotopic compositions between the Okataina and Mineral King zircon likely reflect the difference in the crustal thickness and composition of their respective crustal settings, but also reflect the particular volcanic environment.

  5. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

    Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

  6. Timing of metasomatism in a subcontinental mantle: evidence from zircon at Finero (Italy)

    NASA Astrophysics Data System (ADS)

    Badanina, I. Yu.; Malitch, K. N.

    2012-04-01

    The Finero phlogopite-peridotite represents a metasomatized residual mantle harzburgite, exposed at the base of the lower-crust section in the Ivrea Zone, Western Alps (Hartmann and Wedepohl 1993). It forms the core of a concentrically zoned sequence of internal layered gabbro, amphibole-rich peridotite and external gabbro. The phlogopite peridotite contains small-size chromitite bodies, with a suite of accessory minerals such as phlogopite, apatite, Ca-Mg carbonates, zirconolite, zircon, thorianite and uraninite, proposed to form during alkaline-carbonatitic metasomatism process within the mantle (Zaccarini et al. 2004). In this study, the combined application of a non-destructive technique to separate zircon from their host rocks (see details at http://www.natires.com) and in-situ analytical technique for compositional and isotopic analysis (SHRIMP-II at Russian Geological Research Institute, St. Petersburg) has provided new more detailed age constraints on the formation of chromitite and related metasomatic events within a mantle tectonite at Finero. Chromitite samples derived from the dump in the prospecting trenches of Rio Creves. In thin sections, zircon occurs as relatively large (up to 200 μm) grains characterized by subhedral to euhedral shapes. Separated grains of zircon form two distinct populations. Dominant zircon population is pale pink and characterized by different shapes (subhedral, subrounded or elongated). In cathodoluminescense, the main set of population is represented by complex grains, which show development of core-rim relationship (most likely recrystallized rim on a preserved core). Subordinate zircon grains are colourless. They are characterized by a smoky cathodoluminescense, with almost no internal pattern. Three main U-Pb age clusters have been recognized. The youngest age cluster, typical for subordinate colourless zircon population and rims in complex grains of dominant pale pink population, show two concordant 206Pb/238U ages (e

  7. Estimation of oxygen isotope in source water of tree-ring cellulose in Indonesia using tree-ring oxygen isotope model

    NASA Astrophysics Data System (ADS)

    Hisamochi, R.; Watanabe, Y.; Kurita, N.; Sano, M.; Nakatsuka, T.; Matsuo, M.; Yamamoto, H.; Sugiyama, J.; Tsuda, T.; Tagami, T.

    2016-12-01

    Oxygen isotope composition (δ18O) of tree-ring cellulose has been used as paleoclimate proxy because its origin is atmospheric precipitation. However, interpretation of tree-ring cellulose δ18O is not simple because source water of tree-ring cellulose (the water took up by tree) is not atmospheric precipitation but soil water or ground water in growing season, precisely. In this study, we investigate the relationship between source water of tree-ring cellulose and precipitation in order to improve interpretation of tree-ring cellulose δ18O as paleoclimate proxy. We collected ten teak (Tectona grandis) plantation samples in Java Island, Indonesia. Teak is deciduous tree and grows in rainy season. Samples were cut into annual rings after cellulose extraction. δ18O of individual rings were measured by TCEA-IRMS at the Research Institute of Humanity and Nature. We calculatedδ18O of source water by means of tree-ring oxygen isotope model and then comparedδ18O of source water and that of monthly atmospheric precipitation at Jakarta (GNIP; Global Network of isotopes in Precipitation). Source waterδ18O shows two types of significant correlation withδ18O in atmospheric precipitation. One is positive correlation withδ18O of atmospheric precipitation in previous rainy season. Another is negative correlation with δ18O of atmospheric precipitation in beginning of the growing season. The former indicates that soil water in growing season contains rainfall in previous rainy season and teak mainly takes it up. The latter is difficult to interpret. It may be related to soil moisutre in beginning of growing season.

  8. Origin and evolution of multi-stage felsic melts in eastern Gangdese belt: Constraints from U-Pb zircon dating and Hf isotopic composition

    NASA Astrophysics Data System (ADS)

    Guo, Liang; Zhang, Hong-Fei; Harris, Nigel; Pan, Fa-Bin; Xu, Wang-Chun

    2011-11-01

    This integrated study of whole rock geochemistry, zircon U-Pb dating and Hf isotope composition for seven felsic rocks from the Nyingchi Complex in eastern Himalayan syntaxis has revealed a complex magmatic history for the eastern Gangdese belt. This involves multiple melt sources and mechanisms that uniquely identify the tectonic evolution of this part of the Himalayan orogen. Our U-Pb zircon dating reveals five stages of magmatic or anatectic events: 165, 81, 61, 50 and 25 Ma. The Jurassic granitic gneiss (165 Ma) exhibits εHf(t) values of + 1.4 to + 3.5. The late Cretaceous granite (81 Ma) shows variable εHf(t) values from - 0.9 to + 6.2, indicating a binary mixing between juvenile and old crustal materials. The Paleocene granodioritic gneiss (61 Ma) has εHf(t) values of + 5.4 to + 8.0, suggesting that it originated from partial melting of a juvenile crustal material. The Eocene anatexis is recorded in the leucosome, which has Hf isotopic composition similar to that of the Jurassic granite, indicating that the leucosome could be derived from partial melting of the Jurassic granite. The late Oligocene biotite granite (25 Ma) shows adakitic geochemical characteristics, with Sr/Y = 49.3-56.6. The presence of a large number of inherited zircons and negative εHf(t) values suggest that it sourced from anatexis of crustal materials. In contrast to the Gangdese batholiths that are mainly derived from juvenile crustal source in central Tibet, the old crustal materials play an important role for the magma generation of the felsic rocks, suggesting the existence of a crustal basement in the eastern Gangdese belt. These correspond to specific magmatic evolution stages during the convergence between India and Asia. The middle Jurassic granitic gneiss resulted from the northward subduction of the Neo-Tethyan oceanic slab. The late Cretaceous magmatism is probably related to the ocean ridge subduction. The Paleocene-Eocene magmatism, metamorphism and anatexis are

  9. Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

    2016-06-01

    We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the

  10. Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

    NASA Astrophysics Data System (ADS)

    Brookman, Tom H.; Ambrose, Stanley H.

    2012-09-01

    Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

  11. Oxygen isotopes of phosphatic compounds - Application for marine particulate matter, sediments and soils

    USGS Publications Warehouse

    McLaughlin, K.; Paytan, A.; Kendall, C.; Silva, S.

    2006-01-01

    The phosphate oxygen isotopic composition in naturally occurring particulate phosphatic compounds (??18Op) can be used as a tracer for phosphate sources and to evaluate the cycling of phosphorus (P) in the environment. However, phosphatic compounds must be converted to silver phosphate prior to isotopic analysis, a process that involves digestion of particulate matter in acid. This digestion will hydrolyze some of the phosphatic compounds such that oxygen from the acid solution will be incorporated into the sample as these phosphatic compounds are converted to orthophosphate (PO 43-). To determine the extent of incorporation of reagent oxygen into the sample, we digested various phosphatic compounds in both acid amended with H218O (spiked) and unspiked acid and then converted the samples to silver phosphate for ??18Op analysis. Our results indicate that there is no isotopic fractionation associated with acid digestion at 50??C. Furthermore, we found that reagent oxygen incorporation is a function of the oxygen to phosphorus ratio (O:P) of the digested compound whereby the percentage of reagent oxygen incorporated into the sample is the same as that which is required to convert all of the P-compounds into orthophosphate. Based on these results, we developed a correction for reagent oxygen incorporation using simple mass balance, a procedure that allows for the determination of the ??18O p of samples containing a mixture of phosphatic compounds. We analyzed a variety of environmental samples for ??18O p to demonstrate the utility of this approach for understanding sources and cycling of P. ?? 2005 Elsevier B.V. All rights reserved.

  12. Marked spatial gradient in the topographic evolution of the Andes spanning the Chilean flat-slab transition: evidence from stable isotope paleoaltimetry and zircon double dating

    NASA Astrophysics Data System (ADS)

    Hoke, G. D.; McPhillips, D. F.; Giambiagi, L.; Garzione, C. N.; Mahoney, J. B.; Strecker, M. R.

    2015-12-01

    The major changes in the subduction angle of the Nazca plate are often hypothesized to have important consequences for the tectonic evolution of the Andes. Temporal and spatial patterns of topographic growth and exhumation are indicators that should help elucidate any linkages to subduction angle. Here, we combine observations from stable isotope paleoaltimetry with detrital zircon double dating between 30 and 35°S to demonstrate a consistent increase in surface and rock uplift in the Andes south of 32°S. The stable isotope data are from Miocene pedogenic carbonates collected from seven different basin sequences spanning different tectonic and topographic positions in the range. Paleoelevations between 1 km and 1.9 km are calculated using modern local isotope-elevation gradients along with carbonate-formation temperatures determined from clumped isotope studies in modern soils. Present day, low elevation foreland localities were at their present elevations during the Miocene, while three of the intermontane basins experienced up to 2 km of surface uplift between the end of deposition during the late Miocene and present. Detrital zircon (U-Th-Sm)/He and U-Pb double dating in three modern drainage basins (Tunuyán, Arroyo Grande and Río de los Patos) reveals clear Miocene exhumation signals south of the flat slab with no recent exhumation apparent at 32°S. The exhumation pattern is consistent with paleoaltimetry results. Interestingly, the maximum inferred surface uplift is greatest where the crust is thinnest, and the timing of the observed changes in elevation and exhumation has not been linked to any documented episodes of large-magnitude crustal shortening in the eastern half of the range. The spatial pattern of surface uplift and exhumation seems to mimic the Pampean flat slab's geometry, however, it could be equally well explained by eastward migration of a crustal root via ductile deformation in the lower crust and is not related to flat-slab subduction.

  13. Potentially biogenic carbon preserved in a 4.1 billion-year-old zircon

    DOE PAGES

    Bell, Elizabeth A.; Boehnke, Patrick; Harrison, T. Mark; ...

    2015-10-19

    Here, evidence of life on Earth is manifestly preserved in the rock record. However, the microfossil record only extends to ~3.5 billion years (Ga), the chemofossil record arguably to ~3.8 Ga, and the rock record to 4.0 Ga. Detrital zircons from Jack Hills, Western Australia range in age up to nearly 4.4 Ga. From a population of over 10,000 Jack Hills zircons, we identified one >3.8-Ga zircon that contains primary graphite inclusions. Here, we report carbon isotopic measurements on these inclusions in a concordant, 4.10 ± 0.01-Ga zircon. We interpret these inclusions as primary due to their enclosure in amore » crack-free host as shown by transmission X-ray microscopy and their crystal habit. Their δ 13C PDB of –24 ± 5‰ is consistent with a biogenic origin and may be evidence that a terrestrial biosphere had emerged by 4.1 Ga, or ~300 My earlier than has been previously proposed.« less

  14. Potentially biogenic carbon preserved in a 4.1 billion-year-old zircon

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bell, Elizabeth A.; Boehnke, Patrick; Harrison, T. Mark

    Here, evidence of life on Earth is manifestly preserved in the rock record. However, the microfossil record only extends to ~3.5 billion years (Ga), the chemofossil record arguably to ~3.8 Ga, and the rock record to 4.0 Ga. Detrital zircons from Jack Hills, Western Australia range in age up to nearly 4.4 Ga. From a population of over 10,000 Jack Hills zircons, we identified one >3.8-Ga zircon that contains primary graphite inclusions. Here, we report carbon isotopic measurements on these inclusions in a concordant, 4.10 ± 0.01-Ga zircon. We interpret these inclusions as primary due to their enclosure in amore » crack-free host as shown by transmission X-ray microscopy and their crystal habit. Their δ 13C PDB of –24 ± 5‰ is consistent with a biogenic origin and may be evidence that a terrestrial biosphere had emerged by 4.1 Ga, or ~300 My earlier than has been previously proposed.« less

  15. Ground Based Observation of Isotopic Oxygen in the Martian Atmosphere Using Infrared Heterodyne Spectroscopy

    NASA Technical Reports Server (NTRS)

    Smith, R. L.; Kostiuk, T.; Livengood, T. A.; Fast, K. E.; Hewagama, T.; Delgado, J. D.; Sonnabend, G.

    2010-01-01

    Infrared heterodyne spectra of isotopic CO2 in the Martian atmosphere were obtained using the Goddard Heterodyne Instrument for Planetary Wind and Composition, HIPWAC, which was interfaced with the 3-meter telescope at the NASA Infrared Telescope Facility- Spectra were colle cted at a resolution of lambda/delta lambda=10(exp 7). Absorption fea tures of the CO2 isotopologues have been identified from which isotop ic ratios of oxygen have been determined. The isotopic ratios O-17/O -16 and O-18/O-16 in the Martian atmosphere can be related to Martian atmospheric evolution and can be compared to isotopic ratios of oxyg en in the Earth's atmosphere. Isotopic carbon and oxygen are importa nt constraints on any theory for the erosion of the Martian primordia l atmosphere and the interaction between the atmosphere and surface o r subsurface chemical reservoirs. This investigation explored the pr esent abundance of the stable isotopes of oxygen in Mars' atmospheric carbon dioxide by measuring rovibrational line absorption in isotop ic species of CO2 using groundbased infrared heterodyne spectroscopy in the vicinity of the 9.6 micron and 10.6 micron CO2 lasing bands. T he target transitions during this observation were O-18 C-12 O-16 as well as O-178 C-12 O-16 and O-16 C-113 O-16 at higher resolving power of lambda/delta lambda=10(exp 7) and with high signal-to-noise ratio (longer integration time) in order to fully characterize the absorpt ion line profiles. The fully-resolved lineshape of both the strong n ormal-isotope and the weak isotopic CO2 lines were measured simultane ously in a single spectrum.

  16. Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

    USGS Publications Warehouse

    Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.

    2012-01-01

    Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

  17. In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael E.; Engrand, Cecile; Gounelle, Matthieu; Zolensky, Mike E.

    2001-01-01

    We have measured the oxygen isotopic composition of several components of Tagish Lake by ion microprobe. This meteorite constitutes the best preserved sample of C2 matter presently available for study. It presents two different lithologies (carbonate-poor and -rich) which have fairly comparable oxygen isotopic composition, with regard to both the primary or secondary minerals. For the olivine and pyroxene grains, their delta O-18 values range from - 10.5% to + 7.4% in the carbonate-poor lithology, with a mean Delta O-17 value of - 3.7 2.4%. In the carbonate-rich lithology, delta O-18 varies from - 7.9% to + 3.3%, and the mean Delta O-17 value is - 4.7 +/- 1.4%. Olivine inclusions (Fo(sub >99)) with extreme O-16-enrichment were found in both lithologies: delta O-18 = - 46.1 %, delta O-187= - 48.3% and delta O-18 = - 40.6%, delta O-17 = - 41.2% in the carbonate-rich lithology; delta O-18 = - 41.5%, delta O-17 = -43.4%0 in the carbonate-poor lithology. Anhydrous minerals in the carbonate-poor lithology are slightly more O-16-rich than in the carbonate-rich one. Four low-iron manganese-rich (LIME) olivine grains do not have an oxygen isotopic composition distinct from the other "normal" olivines. The phyllosilicate matrix presents the same range of oxygen isotopic compositions in both lithologies: delta O-18 from approximately 11 % to approximately 6%, with an average Delta. O-17 approximately 0%. Because the bulk Tagish Lake oxygen isotopic composition given by Brown et al. is on the high end of our matrix analyses, we assume that this "bulk Tagish Lake" composition probably only represents that of the carbonate-rich lithology. Calcium carbonates have delta O-18 values up to 35%, with Delta O-17 approximately 0.5%0. Magnetite grains present very high Delta O-17 values approximately + 3.4%0 +/- 1.2%. Given our analytical uncertainties and our limited carbonate data, the matrix and the carbonate seem to have formed in isotopic equilibrium. In that case, their large

  18. Bulk Oxygen-Isotope Compositions of Different Lithologies in Sutter's Mill

    NASA Astrophysics Data System (ADS)

    Ziegler, K.; Garvie, L. A. J.

    2013-09-01

    We correlate mineralogy data with bulk oxygen-isotope data of the clay-rich and the ol-rich lithologies in order to assess the possibility of more than one parent material, and the possibility of different alteration environments on the parent body.

  19. Late magmatic stage of the zoned Caleu pluton (Central Chile): insights from zircon crystallization conditions

    NASA Astrophysics Data System (ADS)

    Molina, P. G.; Parada, M.; Gutierrez, F. J.; Chang-Qiang, M.; Jianwei, L.; Yuanyuan, L.

    2012-12-01

    The Caleu pluton consists of three N-S elongated lithological zones: Gabbro-Diorite Zone (GDZ), Tonalite Zone (TZ) and Granodiorite Zone (GZ); western, middle and eastern portions of the pluton, respectively. The zones are thought to be previously differentiated in a common, isotopically depleted (Sr-Nd), subjacent magma reservoir at a 4 kbar equivalent depth. The emplacement should have occurred at the climax of the Cretaceous rifting. We present preliminary results of U238/Pb206 zircon geochronology; zircon saturation, Tsat(Zrn), and crystallization temperatures (Ti-in-Zrn); as well as relative oxidation states at time of crystallization, based on: (i) the sluggish REE and HFSE subsolidus diffusivities in zircon; (ii) the behavior of Ti4+↔Si4+ and Ce4+↔Zr4+ isovalent replacement, in addition to a constrained TiO2 activity in almost all typical crustal rocks; and (iii) relative oxidation states at time of crystallization, respectively. The latter are obtained by interpolation of the partition coefficients of trivalent (REE) and tetravalent (HFSE) curves in Onuma diagrams for each zircon, and then estimating relative Ce(IV)/Ce(III) ratios. Results obtained from 4 samples (a total of 77 zircon grains) collected from the three mentioned lithological zones indicate U/Pb ages of approximately 99.5 ±1.5 Ma, 96.8 ±0.6 Ma, and 94.4 +2.2 -0.8 Ma; and Ti-in Zrn ranges of ca. 720-870°C, ca. 680-820°C and ca. 750-840°C, for the GDZ, TZ and GZ samples, respectively. On the other hand Tsat(Zrn) of ca. 750-780°C in the TZ, and ca. 830-890°C in the GZ, were obtained. As expected saturation temperatures are similar or higher than Ti-in-Zrn obtained in zircon grains of TZ and GZ, respectively. Cathodoluminiscence images in zircon suggest a magmatic origin, due to absence of complex zoning patterns and fairly well conserved morphologies. Exceptionally the GDZ sample zircons show evidence of inheritance, indicating a xenocrystic and/or antecrystic origin. A relative Ce

  20. In situ location and U-Pb dating of small zircon grains in igneous rocks using laser ablation-inductively coupled plasma-quadrupole mass spectrometry

    NASA Astrophysics Data System (ADS)

    Sack, Patrick J.; Berry, Ron F.; Meffre, Sebastien; Falloon, Trevor J.; Gemmell, J. Bruce; Friedman, Richard M.

    2011-05-01

    A new U-Pb zircon dating protocol for small (10-50 μm) zircons has been developed using an automated searching method to locate zircon grains in a polished rock mount. The scanning electron microscope-energy-dispersive X ray spectrum-based automated searching method can routinely find in situ zircon grains larger than 5 μm across. A selection of these grains was ablated using a 10 μm laser spot and analyzed in an inductively coupled plasma-quadrupole mass spectrometer (ICP-QMS). The technique has lower precision (˜6% uncertainty at 95% confidence on individual spot analyses) than typical laser ablation ICP-MS (˜2%), secondary ion mass spectrometry (<1%), and isotope dilution-thermal ionization mass spectrometry (˜0.4%) methods. However, it is accurate and has been used successfully on fine-grained lithologies, including mafic rocks from island arcs, ocean basins, and ophiolites, which have traditionally been considered devoid of dateable zircons. This technique is particularly well suited for medium- to fine-grained mafic volcanic rocks where zircon separation is challenging and can also be used to date rocks where only small amounts of sample are available (clasts, xenoliths, dredge rocks). The most significant problem with dating small in situ zircon grains is Pb loss. In our study, many of the small zircons analyzed have high U contents, and the isotopic compositions of these grains are consistent with Pb loss resulting from internal α radiation damage. This problem is not significant in very young rocks and can be minimized in older rocks by avoiding high-U zircon grains.

  1. Oxygen and carbon isotopic growth record in a reef coral from the florida keys and a deep-sea coral from blake plateau

    USGS Publications Warehouse

    Emiliani, C.; Harold, Hudson J.; Shinn, E.A.; George, R.Y.

    1978-01-01

    Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.

  2. Triple oxygen isotope composition of tropospheric carbon dioxide and terrestrial carbonates

    NASA Astrophysics Data System (ADS)

    Hofmann, M. E.; Horváth, B.; Pack, A.

    2011-12-01

    The triple oxygen isotope composition of tropospheric CO2 is a potential new tracer in urban air studies and for biosphere-atmosphere interactions [1]. In this study, we are analyzing CO2 from different provenances in order to trace the influx of anthropogenic CO2 to urban air and to test predictions on the stratosphere-troposphere exchange flux. Since July 2010, we are monitoring the triple oxygen isotope composition of CO2 in urban air in a two-week interval. For this purpose, carbon dioxide was extracted from ~450L of ambient air on the campus of the University of Göttingen using a Russian Doll type cryogenic trap [2]. The CO2 was analyzed by CO2-CeO2 equilibration at 685°C and subsequent IR laser fluorination of CeO2 and CF-irmMS [3]. All triple oxygen isotope data are reported as Δ17OTFL values relative to the terrestrial fractionation line (TFL) with a slope βTFL=0.5251 and an intercept γTFL=-0.014%. On average, the Δ17OTFL value of ambient CO2 was -0.11±0.05% (SD) with a seasonal cycle of 0.04±0.01%. Lower Δ17O values were observed during wintertime. In order to test the potential of Δ17O as a tracer for anthropogenic CO2, we analyzed CO2 from different combustion processes. Our results showed that the Δ17O anomaly of tropospheric O2 [4] is passed on fully, or partially to the combustion CO2 [5]. We estimate that elevated anthropogenic emission during wintertime could be responsible for a decrease in Δ17O of urban air CO2 of -0.02±0.01%. In order to predict the triple oxygen isotope composition of tropospheric CO2 on a global scale, we revised the box model calculation from Hoag et al. [1]. For the exponent β for CO2-water equilibrium, we assume that βCO2-water=0.522±0.001 [6]. Furthermore, we took into account that the Δ17OTFL value of CO2 released from soils is affected by kinetic fractionation. Thus, we obtained a Δ17OTFL value for global tropospheric CO2 of -0.13%. The model calculation agrees well with the Δ17OTFL value determined for

  3. Oxygen Isotopes and Origin of Opal in an Antarctic Ureilite

    NASA Astrophysics Data System (ADS)

    Downes, H.; Beard, A. D.; Franchi, I. A.; Greenwood, R. C.

    2016-08-01

    Fragments of opal (SiO2.nH2O) in several internal chips of a single Antarctic polymict ureilite meteorite Elephant Moraine (EET) 83309 have been studied by NanoSIMS to determine their oxygen isotope compositions and hence constrain their origin.

  4. Dual temperature effects on oxygen isotopic ratio of shallow-water coral skeleton: Consequences on seasonal and interannual records

    NASA Astrophysics Data System (ADS)

    Juillet-Leclerc, A.; Reynaud, S.

    2009-04-01

    Oxygen isotopic ratio from coral skeleton is regarded for a long time as promising climate archives at seasonal scale. Although in isotopic disequilibrium relative to seawater, it is supposed to obey to the isotope thermometer. Indeed, coral oxygen isotopic records are strongly temperature dependent, but d18O-temperature calibrations derived from different corals are highly variable. The isotope thermometer assumption does not take into account vital effects due to biogenic origin of the mineral. Corals are animals living in symbiosis with algae (zooxanthellae). Interactions between symbiont photosynthesis and coral skeleton carbonation have been abundantly observed but they remain poorly understood and the effects of photosynthesis on coral growth and skeleton oxygen ratio are ignored. Coral cultured under two light conditions enabled to relate metabolic parameters and oxygen isotopic variability with photosynthetic activity. By examining responses provided by each colony they revealed that photosynthesis significantly affected d18O, by an opposite sense compared with the sole temperature influence. Since temperature and light changes are associated during seasonal variations, this complicates the interpretation of seasonal record. Additionally, this complexity is amplified because photosynthetic activity is also directly impacted by temperature variability. Thus, the annual isotopic amplitude due to the "physical" temperature influence is partly compensated through photosynthesis. Similar opposite effect is also shown by extension rate of the cultured colonies. First, we will examine and quantify consequences of photosynthesis on growth rate and oxygen isotopic signature, from cultured corals. Second, we will consider the consequences of this vital effect on data series, at seasonal and interannual time scales.

  5. Using Oxygen and Carbon Isotopic Signatures in Order to Infer Climatic and Dietary Information in Roman Edessa, Greece

    NASA Astrophysics Data System (ADS)

    Michael, Dimitra-Ermioni; Dotsika, Elissavet

    2017-12-01

    Even though many isotopic studies have been conducted on ancient populations from Greece for the purpose of dietary reconstruction; mostly through carbon and nitrogen isotopic signals of bone collagen, less attention has been given to the utility of apatite signatures (oxygen and carbon) as dietary and palaeoenvironmental tools. Moreover, until recently the isotopic signal of tooth enamel for both the purposes of environmental and dietary reconstructions has been rarely assessed in ancient Greek societies. Therefore, the present study aims to provide with novel isotopic information regarding Edessa; a town in Northern Greece, during the Roman period. The current study primarily aims to explore the possible differentiation between the present climatic conditions in Edessa in relation to those occurring at the Roman period. Secondly, this study aims to reveal the significant utility of enamel isotopic signatures (carbon and oxygen) in palaeoenvironmental and palaeodietary studies regarding ancient human remains. The isotopic analyses have been conducted at the Stable Isotope and Radiocarbon Unit of INN, NCSR “Demokritos”. The population of Roman Edessa (2nd-4th c. AD) consists of 22 individuals, providing with 19 bone samples and 16 enamel ones. The mean enamel oxygen value is at -7.7 ±1.1 %0, the bone apatite mean oxygen value at -9.2 ±1.9 %0, and finally the mean carbon enamel value is at -11.7 ±1.2 %0. Oxygen values probably indicate that Edessa had a cooler climate during the Roman times in relation to present conditions, even though more research should be carried out in order to be more certain. In addition, the possible existence of non-local individuals has been revealed through the oxygen teeth enamel-bone apatite spacing. Finally, the carbon enamel signature has pointed out possible differentiations between the adult and the juvenile diet. Based on Edessa’s findings, the stated study strongly encourages the enamel oxygen and carbon isotopic signals

  6. Coeval Formation of Zircon Megacrysts and Host Magmas in the Eifel Volcanic Field (Germany) Based on High Spatial Resolution Petrochronology

    NASA Astrophysics Data System (ADS)

    Schmitt, Axel; Klitzke, Malte; Gerdes, Axel; Ludwig, Thomas; Schäfer, Christof

    2017-04-01

    Zircon megacrysts (approx. 0.5-6 mm in diameter) from the Quaternary West and East Eifel volcanic fields, Germany, occur as euhedral crystals in porous K-spar rich plutonic ejecta clasts, and as partially resorbed xenocrysts in tephrite lava. Their relation to the host volcanic rocks has remained contentious because the dominantly basanitic to phonolitic magma compositions in the Eifel are typically zircon undersaturated. We carried out a detailed microanalytical study of zircon megacrysts from seven locations (Emmelberg and Rockeskyll in the West Eifel; Bellerberg, Laacher See, Mendig, Rieden, and Wehr in the East Eifel). Crystals were embedded in epoxy, sectioned to expose interiors through grinding with abrasives, diamond-polished, and mapped by optical microscopy, backscattered electron, and cathodoluminescence imaging. Subsequently, isotope-specific analysis using secondary ionization mass spectrometry (SIMS) and laser ablation inductively coupled mass spectrometry (LA-ICP-MS) was carried out placing 100 correlated spots on 20 selected crystals. Concordant U-Th disequilibrium and U-Pb ages determined by SIMS are between ca. 430 ka (Rieden) and 170 ka (Mendig) and indicate that the megacryst zircons crystallized almost always briefly before eruption. A significant gap between zircon megacryst crystallization (ca. 230 ka) and eruption (ca. 45 ka) ages was only detected for the Emmelberg location. SIMS trace element abundances (e.g., rare earth elements) vary by orders-of-magnitude and correlate with domain boundaries visible in cathodoluminescence; trace element patterns match those reported for zircon from syenitic origins. Isotopic compositions are homogeneous within individual crystals, but show some heterogeneity between different crystals from the same locality. Average isotopic values (δ18O SMOW = +5.3±0.6 ‰ by SIMS; present-day ɛHf = +1.7±2.5 ‰ by LA-ICP-MS; 1 standard deviation), however, are consistent with source magmas being dominantly mantle

  7. Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid

    Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasingmore » synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.« less

  8. High Precision Oxygen Three Isotope Analysis of Wild-2 Particles and Anhydrous Chondritic Interplanetary Dust Particles

    NASA Technical Reports Server (NTRS)

    Nakashima, D.; Ushikubo, T.; Zolensky, Michael E.; Weisberg, M. K.; Joswiak, D. J.; Brownlee, D. E.; Matrajt, G.; Kita, N. T.

    2011-01-01

    One of the most important discoveries from comet Wild-2 samples was observation of crystalline silicate particles that resemble chondrules and CAIs in carbonaceous chondrites. Previous oxygen isotope analyses of crystalline silicate terminal particles showed heterogeneous oxygen isotope ratios with delta(sup 18)O to approx. delta(sup 17)O down to -50% in the CAI-like particle Inti, a relict olivine grain in Gozen-sama, and an olivine particle. However, many Wild-2 particles as well as ferromagnesian silicates in anhydrous interplanetary dust particles (IDPs) showed Delta(sup 17)O values that cluster around -2%. In carbonaceous chondrites, chondrules seem to show two major isotope reservoirs with Delta(sup 17)O values at -5% and -2%. It was suggested that the Delta(sup 17)O = -2% is the common oxygen isotope reservoir for carbonaceous chondrite chondrules and cometary dust, from the outer asteroid belt to the Kuiper belt region. However, a larger dataset with high precision isotope analyses (+/-1-2%) is still needed to resolve the similarities or distinctions among Wild-2 particles, IDPs and chondrules in meteorites. We have made signifi-cant efforts to establish routine analyses of small particles (< or =10micronsm) at 1-2% precision using IMS-1280 at WiscSIMS laboratory. Here we report new results of high precision oxygen isotope analyses of Wild-2 particles and anhydrous chondritic IDPs, and discuss the relationship between the cometary dust and carbonaceous chondrite chondrules.

  9. Determining the oxygen isotope composition of evapotranspiration with eddy covariance

    USDA-ARS?s Scientific Manuscript database

    The oxygen isotope componsition of evapotranspiration (dF) represents an important tracer in the study of biosphere-atmosphere interactions, hydrology, paleoclimate, and carbon cycling. Here we demonstrate direct measurement of dF based on eddy covariance (EC) and tunable diode laser (EC-TDL) techni...

  10. Oxygen isotopes in crystalline silicates of comet Wild 2: A comparison of oxygen isotope systematics between Wild 2 particles and chondritic materials

    NASA Astrophysics Data System (ADS)

    Nakashima, Daisuke; Ushikubo, Takayuki; Joswiak, David J.; Brownlee, Donald E.; Matrajt, Graciela; Weisberg, Michael K.; Zolensky, Michael E.; Kita, Noriko T.

    2012-12-01

    Oxygen three-isotope ratios of nine crystalline silicate particles from comet Wild 2 were measured to investigate oxygen isotope systematics of cometary materials. We are able to analyze particles as small as 4 μm using an ion microprobe with a˜1×2 μm beam by locating the analysis spots with an accuracy of ±0.4 μm. Three particles of Mn-rich forsterite, known as low-iron, manganese-enriched (LIME) olivine, showed extremely 16O-rich signatures (δ18O, δ17O˜-50‰), similar to refractory inclusions in chondrites. The three Mn-rich forsterite particles may have formed by condensation from an 16O-rich solar nebula gas. Other particles consist of olivine and/or pyroxene with a wide range of Mg# [=molar MgO/(FeO+MgO) %] from 60 to 96. Their oxygen isotope ratios plot nearly along the carbonaceous chondrite anhydrous mineral (CCAM) and Young and Russell lines with Δ17O(=δ17O-0.52×δ18O) values of -3.0‰ to +2.5‰. These data are similar to the range observed from previous analyses of Wild 2 crystalline silicates and those of chondrules in carbonaceous chondrites. Six particles extracted from Stardust track 77 show diverse chemical compositions and isotope ratios; two Mn-rich forsterites, FeO-poor pigeonite, and three FeO-rich olivines with a wide range of Δ17O values from -24‰ to +1.6‰. These results confirmed that the original projectile that formed track 77 was an aggregate (>6 μm) of silicate particles that formed in various environments. The Δ17O values of ferromagnesian Wild 2 particles (including data from previous studies) increase from ˜-23‰ to+2.5‰ with decreasing Mg#: Δ17O values of Mn-rich forsterite particles (Mg#=98-99.8) cluster at -23‰, those of FeO-poor particles (Mg#=95-97) cluster at -2‰, and those of FeO-rich particles (Mg#≤90) scatter mainly from -1.5‰ to+2.5‰. Compared to chondrules in primitive chondrites, the systematic trend between Mg# and Δ17O among the Wild 2 particles is most similar to that reported for CR

  11. Multiple taxon multiple locality approach to providing oxygen isotope evidence for warm-blooded theropod dinosaurs

    NASA Astrophysics Data System (ADS)

    Fricke, Henry C.; Rogers, Raymond R.

    2000-09-01

    Oxygen isotope ratios of fossil remains of coexisting taxa from several different localities can be used to help investigate dinosaur thermoregulation. Focusing on the Late Cretaceous, oxygen isotope ratios of crocodile tooth enamel from four separate localities exhibit less of a decrease with latitude than do ratios of tooth enamel from coexisting theropod dinosaurs. A shallower latitudinal gradient for crocodiles is consistent with how oxygen isotope ratios should vary for heterothermic animals having body temperatures coupled with their environments (“cold blooded”), while a steeper gradient for theropods is consistent with how these ratios should vary for homeothermic animals having constant body temperatures independent of their environments (“warm blooded”). This inferred homoethermy in theropods is likely due to higher rates of metabolic heat production relative to crocodiles and is not an artifact of body size.

  12. Negative Oxygen Isotope Effect in Manganites with an Ordered Cation Arrangement in a High Magnetic Field

    NASA Astrophysics Data System (ADS)

    Taldenkov, A. N.; Snegirev, V. V.; Babushkina, N. A.; Kalitka, V. S.; Kaul', A. R.

    2018-03-01

    The oxygen isotope effect in PrBaMn2 16-18 O5.97 manganite with an ordered cation arrangement is studied. The field dependences of magnetic susceptibility and magnetization are measured in the temperature range 100-270 K and magnetic fields up to 32 T. A significant increase in the temperature of the spin-reorientation antiferromagnet-ferromagnet phase transition is detected in samples enriched in heavy oxygen 18O (negative isotope effect). The transition temperature and the isotope effect depend strongly on the magnetic field. An H-T phase diagram is plotted for samples with various isotope compositions. An analysis of the experimental results demonstrates that the detected negative isotope effect and the giant positive isotope effect revealed earlier in doped manganites have the same nature. The mechanisms of appearance of isotope effects are discussed in terms of the double exchange model under a polaron narrowing of the free carrier band.

  13. Lithium in Jack Hills zircons: Evidence for extensive weathering of Earth's earliest crust

    NASA Astrophysics Data System (ADS)

    Ushikubo, Takayuki; Kita, Noriko T.; Cavosie, Aaron J.; Wilde, Simon A.; Rudnick, Roberta L.; Valley, John W.

    2008-08-01

    In situ Li analyses of 4348 to 3362 Ma detrital zircons from the Jack Hills, Western Australia by SIMS reveal that the Li abundances (typically 10 to 60 ppm) are commonly over 10,000 times higher than in zircons crystallized from mantle-derived magmas and in mantle-derived zircon megacrysts (typically < 2 ppb). High Li concentrations in zircons (10 to 250 ppm) have also been found in igneous zircons from three continental parent rocks: granites, Li-rich pegmatites, and migmatites in pelitic metasediment. The substitution of trivalent cations (REEs and Y) in zircon correlates with Li + 1 and P + 5 , suggesting that an interstitial site for Li, as well as the xenotime substitution for P, provides charge balance for REEs. Li is thus fixed in the zircon structure by coupled substitutions, and diffusive changes in [Li] composition are rate-limited by slow diffusion of REEs. The Jack Hills zircons also have fractionated lithium isotope ratios ( δ7Li = - 19 to + 13‰) about five times more variable than those recorded in primitive ocean floor basalts (2 to 8‰), but similar to continental crust and its weathering products. Values of δ7Li below - 10‰ are found in zircons that formed as early as 4300 Ma. The high Li compositions indicate that primitive magmas were not the source of Jack Hills zircons and the fractionated values of δ7Li suggest that highly weathered regolith was sampled by these early Archean magmas. These new Li data provide evidence that the parent magmas of ancient zircons from Jack Hills incorporated materials from the surface of the Earth that interacted at low temperature with liquid water. These data support the hypothesis that continental-type crust and oceans existed by 4300 Ma, within 250 million years of the formation of Earth and the low values of δ7Li suggest that weathering was extensive in the early Archean.

  14. Assessment of oceanic productivity with the triple-isotope composition of dissolved oxygen.

    PubMed

    Luz, B; Barkan, E

    2000-06-16

    Plant production in the sea is a primary mechanism of global oxygen formation and carbon fixation. For this reason, and also because the ocean is a major sink for fossil fuel carbon dioxide, much attention has been given to estimating marine primary production. Here, we describe an approach for estimating production of photosynthetic oxygen, based on the isotopic composition of dissolved oxygen of seawater. This method allows the estimation of integrated oceanic productivity on a time scale of weeks.

  15. Zircon ages in granulite facies rocks: decoupling from geochemistry above 850 °C?

    NASA Astrophysics Data System (ADS)

    Kunz, Barbara E.; Regis, Daniele; Engi, Martin

    2018-03-01

    Granulite facies rocks frequently show a large spread in their zircon ages, the interpretation of which raises questions: Has the isotopic system been disturbed? By what process(es) and conditions did the alteration occur? Can the dates be regarded as real ages, reflecting several growth episodes? Furthermore, under some circumstances of (ultra-)high-temperature metamorphism, decoupling of zircon U-Pb dates from their trace element geochemistry has been reported. Understanding these processes is crucial to help interpret such dates in the context of the P-T history. Our study presents evidence for decoupling in zircon from the highest grade metapelites (> 850 °C) taken along a continuous high-temperature metamorphic field gradient in the Ivrea Zone (NW Italy). These rocks represent a well-characterised segment of Permian lower continental crust with a protracted high-temperature history. Cathodoluminescence images reveal that zircons in the mid-amphibolite facies preserve mainly detrital cores with narrow overgrowths. In the upper amphibolite and granulite facies, preserved detrital cores decrease and metamorphic zircon increases in quantity. Across all samples we document a sequence of four rim generations based on textures. U-Pb dates, Th/U ratios and Ti-in-zircon concentrations show an essentially continuous evolution with increasing metamorphic grade, except in the samples from the granulite facies, which display significant scatter in age and chemistry. We associate the observed decoupling of zircon systematics in high-grade non-metamict zircon with disturbance processes related to differences in behaviour of non-formula elements (i.e. Pb, Th, U, Ti) at high-temperature conditions, notably differences in compatibility within the crystal structure.

  16. The oxygen isotope enrichment of leaf-exported assimilates--does it always reflect lamina leaf water enrichment?

    PubMed

    Gessler, Arthur; Brandes, Elke; Keitel, Claudia; Boda, Sonja; Kayler, Zachary E; Granier, André; Barbour, Margaret; Farquhar, Graham D; Treydte, Kerstin

    2013-10-01

    The oxygen stable isotope composition of plant organic matter (OM) (particularly of wood and cellulose in the tree ring archive) is valuable in studies of plant-climate interaction, but there is a lack of information on the transfer of the isotope signal from the leaf to heterotrophic tissues. We studied the oxygen isotopic composition and its enrichment above source water of leaf water over diel courses in five tree species covering a broad range of life forms. We tracked the transfer of the isotopic signal to leaf water-soluble OM and further to phloem-transported OM. Observed leaf water evaporative enrichment was consistent with values predicted from mechanistic models taking into account nonsteady-state conditions. While leaf water-soluble OM showed the expected (18)O enrichment in all species, phloem sugars were less enriched than expected from leaf water enrichment in Scots pine (Pinus sylvestris), European larch (Larix decidua) and Alpine ash (Eucalyptus delegatensis). Oxygen atom exchange with nonenriched water during phloem loading and transport, as well as a significant contribution of assimilates from bark photosynthesis, can explain these phloem (18)O enrichment patterns. Our results indicate species-specific uncoupling between the leaf water and the OM oxygen isotope signal, which is important for the interpretation of tree ring data. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

  17. Influence of crystal phases on electro-optic properties of epitaxially grown lanthanum-modified lead zirconate titanate films

    NASA Astrophysics Data System (ADS)

    Masuda, Shin; Seki, Atsushi; Masuda, Yoichiro

    2010-02-01

    We describe here how we have improved the crystal qualities and controlled the crystal phase of the lanthanum-modified lead zirconate titanate (PLZT) film without changing the composition ratio using an oxygen-pressure crystallization process. A PLZT film deposited on a SrTiO3 substrate with the largest electro-optic (EO) coefficient of 498 pm/V has been achieved by controlling the crystal phase of the film. Additionally, a fatigue-free lead zirconate titanate (PZT) capacitor with platinum electrodes has been realized by reducing the oxygen vacancies in the films.

  18. On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

    NASA Astrophysics Data System (ADS)

    Bauska, T.; Hodell, D. A.; Walters, G.

    2016-12-01

    Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous

  19. Trace element chemistry of zircons from oceanic crust: A method for distinguishing detrital zircon provenance

    USGS Publications Warehouse

    Grimes, Craig B.; John, Barbara E.; Kelemen, P.B.; Mazdab, F.K.; Wooden, J.L.; Cheadle, Michael J.; Hanghoj, K.; Schwartz, J.J.

    2007-01-01

    We present newly acquired trace element compositions for more than 300 zircon grains in 36 gabbros formed at the slow-spreading Mid-Atlantic and Southwest Indian Ridges. Rare earth element patterns for zircon from modern oceanic crust completely overlap with those for zircon crystallized in continental granitoids. However, plots of U versus Yb and U/Yb versus Hf or Y discriminate zircons crystallized in oceanic crust from continental zircon, and provide a relatively robust method for distinguishing zircons from these environments. Approximately 80% of the modern ocean crust zircons are distinct from the field defined by more than 1700 continental zircons from Archean and Phanerozoic samples. These discrimination diagrams provide a new tool for fingerprinting ocean crust zircons derived from reservoirs like that of modern mid-ocean ridge basalt (MORB) in both modern and ancient detrital zircon populations. Hadean detrital zircons previously reported from the Acasta Gneiss, Canada, and the Narryer Gneiss terrane, Western Australia, plot in the continental granitoid field, supporting hypotheses that at least some Hadean detrital zircons crystallized in continental crust forming magmas and not from a reservoir like modern MORB. ?? 2007 The Geological Society of America.

  20. Oxygen isotopic relationships between the LEW85332 carbonaceous chondrite and CR chondrites

    NASA Technical Reports Server (NTRS)

    Prinz, M.; Weisberg, M. K.; Clayton, R. N.; Mayeda, T. K.

    1993-01-01

    LEW85332, originally described as a unique C3 chondrite, was shown to be a C2 chondrite with important linkages to the CR clan. An important petrologic aspect of LEW85332 is that it contains anhydrous chondrules and hydrated matrix, and new oxygen isotopic data on chondrules, matrix and whole rock are consistent with the petrology. Chondrules fall on the equilibrated chondrite line (ECL), with a slope near 1, which goes through ordinary chondrite chondrules. This contrasts with the CR chondrule line which has a lower slope due to hydrated components. LEW85332 chondrules define a new carbonaceous chondrite chondrule line, parallel to the anhydrous CV chondrule line (CCC), consistent with the well-established concept of two oxygen isotopic reservoirs. Matrix and whole rock fall on the CR line. The whole rock composition indicates that the chondrite is dominated by chondrules, and that most of them contain light oxygen similar to that of anhydrous olivine and pyroxene separates in the Renazzo and Al Rais CR chondrites.

  1. Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis.

    PubMed

    Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans-Hermann

    2017-05-01

    In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS 18 O/ 16 O monitoring for future method development is proposed.

  2. Oxygen isotopic fractionation of O₂ during adsorption and desorption processes using molecular sieve at low temperatures.

    PubMed

    Ahn, Insu; Kusakabe, Minoru; Lee, Jong Ik

    2014-06-15

    Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in

  3. The formation and alteration of the Renazzo-like carbonaceous chondrites I: Implications of bulk-oxygen isotopic composition

    NASA Astrophysics Data System (ADS)

    Schrader, Devin L.; Franchi, Ian A.; Connolly, Harold C., Jr.; Greenwood, Richard C.; Lauretta, Dante S.; Gibson, Jenny M.

    2011-01-01

    To better understand the role of aqueous alteration on the CR chondrite parent asteroid, a whole-rock oxygen isotopic study of 20 meteorites classified as Renazzo-like carbonaceous chondrites (CR) was conducted. The CR chondrites analyzed for their oxygen isotopes were Dhofar 1432, Elephant Moraine (EET) 87770, EET 92042, EET 96259, Gao-Guenie (b), Graves Nunataks (GRA) 95229, GRA 06100, Grosvenor Mountains (GRO) 95577, GRO 03116, LaPaz Ice Field (LAP) 02342, LAP 04720, Meteorite Hills (MET) 00426, North West Africa (NWA) 801, Pecora Escarpment (PCA) 91082, Queen Alexandra Range (QUE) 94603, QUE 99177, and Yamato-793495 (Y-793495). Three of the meteorites, Asuka-881595 (A-881595), GRA 98025, and MET 01017, were found not to be CR chondrites. The remaining samples concur petrographically and with the well-established oxygen-isotope mixing line for the CR chondrites. Their position along this mixing line is controlled both by the primary oxygen-isotopic composition of their individual components and their relative degree of aqueous alteration. Combined with literature data and that of this study, we recommend the slope for the CR-mixing line to be 0.70 ± 0.04 (2σ), with a δ 17O-intercept of -2.23 ± 0.14 (2σ). Thin sections of Al Rais, Shişr 033, Renazzo, and all but 3 samples analyzed for oxygen isotopes were studied petrographically. The abundance of individual components is heterogeneous among the CR chondrites, but FeO-poor chondrules and matrix are the most abundant constituents and therefore, dominate the whole-rock isotopic composition. The potential accreted ice abundance, physico-chemical conditions of aqueous alteration (e.g. temperature and composition of the fluid) and its duration control the degree of alteration of individual CR chondrites. Combined with literature data, we suggest that LAP 02342 was exposed to lower temperature fluid during alteration than GRA 95229. With only two falls, terrestrial alteration of the CR chondrites complicates the

  4. Mechanisms of strain accommodation in plastically-deformed zircon under simple shear deformation conditions during amphibolite-facies metamorphism

    NASA Astrophysics Data System (ADS)

    Kovaleva, Elizaveta; Klötzli, Urs; Wheeler, John; Habler, Gerlinde

    2018-02-01

    crust, and, possibly, the timing of deformation, if the isotopic systems of deformed zircon were reset.

  5. Climatic forcing of carbon-oxygen isotopic covariance in temperate-region marl lakes

    NASA Technical Reports Server (NTRS)

    Drummond, C. N.; Patterson, W. P.; Walker, J. C.

    1995-01-01

    Carbon and oxygen stable isotopic compositions of lacustrine carbonate from a southeastern Michigan marl lake display linear covariance over a range of 4.0% Peedee belemnite (PDB) in oxygen and 3.9% (PDB) in carbon. Mechanisms of delta 13 C-delta 18 O coupling conventionally attributed to lake closure in arid-region basins are inapplicable to hydrologically open lake systems. Thus, an alternative explanation of isotopic covariance in temperate region dimictic marl lakes is required. We propose that isotopic covariance is a direct record of change in regional climate. In short-residence-time temperate-region lake basins, summer meteoric precipitation is enriched in 18O relative to winter values, and summer organic productivity enriches epilimnic dissolved inorganic carbon in 13C. Thus, climate change toward longer summers and/or shorter winters could result in greater proportions of warm-month meteoric precipitation, longer durations of warm-month productivity, and net long-term enrichment in carbonate 18O and 13C. Isotopic covariance observed in the Michigan marl lake cores is interpreted to reflect postglacial warming from 10 to 3 ka followed by cooler mean annual temperature, a shift toward greater proportions of seasonal summer precipitation, a shortening of the winter season, or some combination of these three factors.

  6. Comparison of the oxygen and hydrogen isotopes in the juices of fast-growing vegetables and slow-growing fruits.

    PubMed

    Bong, Yeon-Sik; Lee, Kwang-Sik; Shin, Woo-Jin; Ryu, Jong-Sik

    2008-09-01

    We have analyzed the oxygen and hydrogen isotopic composition of juices from fruits and vegetables collected from a small orchard in order to investigate the differences in isotopic enrichment and evaporation intensity between fast-growing vegetables and slow-growing fruits grown under the same climatic conditions. The oxygen and hydrogen isotope levels were much higher in the juices of the fruits and vegetables than in the source waters in which they grew because of evaporation effects. According to our data, fast-growing vegetables are subject to greater evaporation than slow-growing fruits. An evaporation experiment using the source water showed that the oxygen and hydrogen isotopic composition of the 60-80% residual fraction was similar to that of the isotopically enriched grape juice, whereas those of the plume and tomato juices were very close to that of the 80-90% residual fraction, thus proving the effect of evaporation. Copyright (c) 2008 John Wiley & Sons, Ltd.

  7. Oxygen isotope composition of mafic magmas at Vesuvius

    NASA Astrophysics Data System (ADS)

    Dallai, L.; Cioni, R.; Boschi, C.; D'Oriano, C.

    2009-12-01

    The oxygen isotope composition of olivine and clinopyroxene from four plinian (AD 79 Pompeii, 3960 BP Avellino), subplinian (AD 472 Pollena) and violent strombolian (Middle Age activity) eruptions were measured to constrain the nature and evolution of the primary magmas of the last 4000 years of Mt. Vesuvius activity. A large set of mm-sized crystals was accurately separated from selected juvenile material of the four eruptions. Crystals were analyzed for their major and trace element compositions (EPMA, Laser Ablation ICP-MS), and for 18O/16O ratios. As oxygen isotope composition of uncontaminated mantle rocks on world-wide scale is well constrained (δ18Oolivine = 5.2 ± 0.3; δ18Ocpx = 5.6 ± 0.3 ‰), the measured values can be conveniently used to monitor the effects of assimilation/contamination of crustal rocks in the evolution of the primary magmas. Instead, typically uncontaminated mantle values are hardly recovered in Italian Quaternary magmas, mostly due to the widespread occurrence of crustal contamination of the primary magmas during their ascent to the surface (e.g. Alban Hills, Ernici Mts., and Aeolian Islands). Low δ18O values have been measured in olivine from Pompeii eruption (δ18Oolivine = 5.54 ± 0.03‰), whereas higher O-compositions are recorded in mafic minerals from pumices or scoria of the other three eruptions. Measured olivine and clinopyroxene share quite homogeneous chemical compositions (Olivine Fo 85-90 ; Diopside En 45-48, respectively), and represent phases crystallized in near primary mafic magmas, as also constrained by their trace element compositions. Data on melt inclusions hosted in crystals of these compositions have been largely collected in the past demonstrating that they crystallized from mafic melt, basaltic to tephritic in composition. Published data on volatile content of these melt inclusions reveal the coexistence of dissolved water and carbon dioxide, and a minimum trapping pressure around 200-300 MPa, suggesting

  8. Refined Proterozoic evolution of the Gawler Craton, South Australia, through U-Pb zircon geochronology

    USGS Publications Warehouse

    Fanning, C.M.; Flint, R.B.; Parker, A.J.; Ludwig, K. R.; Blissett, A.H.

    1988-01-01

    Through the application of both conventional U-Pb zircon analyses and small-sample U-Pb isotopic analyses, the nature and timing of tectonic events leading to the formation of the Gawler Craton have been defined more precisely. Constraints on deposition of Early Proterozoic iron formation-bearing sediments have been narrowed down to the period 1960-1847 Ma. Deformed acid volcanics, including the economically important Moonta Porphyry, have zircon ages of ??? 1790 and 1740 Ma. The voluminous acid Gawler Range Volcanics and correlatives to the east were erupted over a short interval at 1592 ?? 2 Ma, and were intruded by anorogenic granites at ??? 1575 Ma. Small-sample zircon analyses proved to be an extremely valuable adjunct to conventional analyses, generally yielding more-concordant data which forced a curved discordia through an upper intercept slightly younger than from a conventional straight-line discordia. ?? 1988.

  9. Generation and Evolution of Quaternary Magmas Beneath Tengchong: Sr-Nd-Pb-Hf Isotope and Zircon U-series Age Constraints

    NASA Astrophysics Data System (ADS)

    Zou, H.; Ma, M.; Fan, Q.; Xu, B.; Li, S. Q.; Zhao, Y.; King, D. T., Jr.

    2017-12-01

    The Tengchong volcanic field on the southeastern margin of the Tibetan Plateau represents rare Quaternary volcanic eruptions on the plateau. The Quaternary Tengchong volcanic field formed high-potassium calc-alkaline volcanic rocks that include trachybasalts, basaltic trachyandesites, trachyandesites, and dacites. Herein, we present comprehensive Nd-Sr-Pb-Hf isotopic and elemental data for trachybasalts, basaltic trachyandesites, and trachyandesites from four young Tengchong volcanoes at Maanshan, Dayingshan, Heikongshan, and Laoguipo, in order to understand their magma genesis and evolution. Nd-Sr-Pb-Hf isotopes for the primitive Tengchong magma (trachybasalts with SiO2 <52.5 wt. % and MgO >5.5% wt. %) reflect a heterogeneous enriched mantle source. High Th/U, Th/Ta, and Rb/Nb ratios and Nd-Sr-Pb-Hf isotope characteristics of the primitive magmas suggest that the enriched mantle beneath Tengchong formed as a result of subduction of clay-rich sediments, which probably came from the Indian continental plate. Partial melting of the enriched mantle was generated by deep continental subduction coupled with recent regional extension in the Tengchong area. With regard to the evolved magmas (basaltic trachyandesites and trachyandesites), good correlations between SiO2 content and the ratios 87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb, and 177Hf/176Hf strongly suggest that the combined assimilation and fractional crystallization (AFC) was an important process during magma evolution to form these basaltic trachyandesites and trachyandesites. Uranium-series zircon dating on these evolved lavas from Tengchong is used to constrain their magma evolution and residence timescales.

  10. A Critical Look at the Combined Use of Sulfur and Oxygen Isotopes to Study Microbial Metabolisms in Methane-Rich Environments

    PubMed Central

    Antler, Gilad; Pellerin, André

    2018-01-01

    Separating the contributions of anaerobic oxidation of methane and organoclastic sulfate reduction in the overall sedimentary sulfur cycle of marine sediments has benefited from advances in isotope biogeochemistry. Particularly, the coupling of sulfur and oxygen isotopes measured in the residual sulfate pool (δ18OSO4 vs. δ34SSO4). Yet, some important questions remain. Recent works have observed patterns that are inconsistent with previous interpretations. We differentiate the contributions of oxygen and sulfur isotopes to separating the anaerobic oxidation of methane and organoclastic sulfate reduction into three phases; first evidence from conventional high methane vs. low methane sites suggests a clear relationship between oxygen and sulfur isotopes in porewater and the metabolic process taking place. Second, evidence from pure cultures and organic matter rich sites with low levels of methane suggest the signatures of both processes overlap and cannot be differentiated. Third, we take a critical look at the use of oxygen and sulfur isotopes to differentiate metabolic processes (anaerobic oxidation of methane vs. organoclastic sulfate reduction). We identify that it is essential to develop a better understanding of the oxygen kinetic isotope effect, the degree of isotope exchange with sulfur intermediates as well as establishing their relationships with the cell-specific metabolic rates if we are to develop this proxy into a reliable tool to study the sulfur cycle in marine sediments and the geological record. PMID:29681890

  11. Oxygen isotope values in bone carbonate and collagen are consistently offset for New World monkeys

    PubMed Central

    Crowley, Brooke Erin

    2014-01-01

    Stable oxygen isotopes are increasingly used in ecological research. Here, I present oxygen isotope (δ18O) values for bone carbonate and collagen from howler monkeys (Alouatta palliata), spider monkeys (Ateles geoffroyi) and capuchins (Cebus capucinus) from three localities in Costa Rica. There are apparent differences in δ18Ocarbonate and δ18Ocollagen among species. Monkeys from moist forest have significantly lower isotope values than those from drier localities. Because patterns are similar for both substrates, discrimination (Δ) between δ18Ocarbonate and δ18Ocollagen is relatively consistent among species and localities (17.6 ± 0.9‰). Although this value is larger than that previously obtained for laboratory rats, consistency among species and localities suggests it can be used to compare δ18Ocarbonate and δ18Ocollagen for monkeys, and potentially other medium-bodied mammals. Establishing discrimination for oxygen between these substrates for wild monkeys provides a foundation for future environmental and ecological research on modern and ancient organisms. PMID:25392315

  12. Sea Surface Temperature and Seawater Oxygen Isotope Variability Recorded in a Madagascar Coral Record

    NASA Astrophysics Data System (ADS)

    Zinke, J.; Dullo, W. Chr; Eisenhauer, A.

    2003-04-01

    We analysed a 336 year coral oxygen isotope record off southwest Madagascar in the Mozambique Channel. Based on temporal variability of skeletal oxygen isotopes annual mean sea surface temperatures are reconstructed for the period from 1659 to 1995. Sr/Ca ratios were measured for selected windows with monthly resolution (1973 to 1995, 1863 to 1910, 1784 to 1809, 1688 to 1710) to validate the SST reconstructions derived from oxygen isotopes. The coral proxy data were validated against gridded SST data sets. The coral oxygen isotope record is coherent with Kaplan-SST and GISST2.3b on an interdecadal frequency of 17 years, which is the most prominent frequency band observed in this region. The Sr/Ca-SST agree well with SST observations in the validation period (1863 to 1910), whereas the d18O derived SST show largest discrepencies during this time interval. By taking into account the SST values derived from coral Sr/Ca, we were able to reconstruct d18O seawater variability. This indicates that d18O seawater variations contributed significantly to interannual and interdecadal variations in coral d18O. We propose that the local surface-ocean evaporation-precipitation balance and remote forcing by ENSO via South Equatorial Current and/or Indonesian throughflow variability may contribute to observed d18O variability. Our results indicate that coral d18O may be used to reconstruct temporal variations in the fresh water balance within the Indian Ocean on interannual to interdecadal time scales.

  13. Seasonal temperature and precipitation recorded in the intra-annual oxygen isotope pattern of meteoric water and tree-ring cellulose

    NASA Astrophysics Data System (ADS)

    Schubert, Brian A.; Jahren, A. Hope

    2015-10-01

    Modern and ancient wood is a valuable terrestrial record of carbon ultimately derived from the atmosphere and oxygen inherited from local meteoric water. Many modern and fossil wood specimens display rings sufficiently thick for intra-annual sampling, and analytical techniques are rapidly improving to allow for precise carbon and oxygen isotope measurements on very small samples, yielding unprecedented resolution of seasonal isotope records. However, the interpretation of these records across diverse environments has been problematic because a unifying model for the quantitative interpretation of seasonal climate parameters from oxygen isotopes in wood is lacking. Towards such a model, we compiled a dataset of intra-ring oxygen isotope measurements on modern wood cellulose (δ18Ocell) from 33 globally distributed sites. Five of these sites represent original data produced for this study, while the data for the other 28 sites were taken from the literature. We defined the intra-annual change in oxygen isotope value of wood cellulose [Δ(δ18Ocell)] as the difference between the maximum and minimum δ18Ocell values determined within the ring. Then, using the monthly-resolved dataset of the oxygen isotope composition of meteoric water (δ18OMW) provided by the Global Network of Isotopes in Precipitation database, we quantified the empirical relationship between the intra-annual change in meteoric water [Δ(δ18OMW)] and Δ(δ18Ocell). We then used monthly-resolved datasets of temperature and precipitation to develop a global relationship between Δ(δ18OMW) and maximum/minimum monthly temperatures and winter/summer precipitation amounts. By combining these relationships we produced a single equation that explains much of the variability in the intra-ring δ18Ocell signal through only changes in seasonal temperature and precipitation amount (R2 = 0.82). We show how our recent model that quantifies seasonal precipitation from intra-ring carbon isotope profiles can be

  14. An evaluation of the zircon method of isotopic dating in the Southern Arabian Craton

    USGS Publications Warehouse

    Cooper, J.A.; Stacey, J.S.; Stoeser, D.G.; Fleck, R.J.

    1979-01-01

    A zircon study has been made on eleven samples of igneous rocks from the Saudi Arabian Craton. Ages of sized and magnetic fractions of zircon concentrates show variable degrees of discordance which seem to result from a very young disturbance that produces linear arrays in the Concordia plot. Model age calculations based on a statistically and geologically reasonable lower intercept produce very consistent internal relationships. The Pan African Orogeny, considered to be responsible for loss of radiogenic argon and strontium from minerals of many rocks, does not appear to have affected the zircon data, even though uplift had exposed the rocks of the Arabian Shield at that time. Tonalite, granodiorite, and crosscutting leucoadamellite bodies in the southern part of the An Nimas Bathylith yield ages in the time range 820-760 Ma. A narrow time range of 660 to 665 million years was indicated for ages of widely separated and compositionally different intrusive bodies all to the east of the An Nimas Bathylith. This work suggests that the younger end of the age spectrum established from regional K-Ar and Rb-Sr measurements may be underestimated, and that magmatic activity could be more episodic than previously assumed.

  15. U-Pb Dating of Unabraded Detrital Zircon Metamorphic Rims in the Nanaimo Basin, British Columbia

    NASA Astrophysics Data System (ADS)

    Boivin, M. P.; Guest, B.; Matthews, W.

    2016-12-01

    Thin metamorphic rims on detrital zircons from the Nanaimo Basin in SW British Columbia offer a unique opportunity to further constrain the source of these zircons, helping to resolve the long standing Baja BC controversy. Here we present an analytical approach for dating thin zircon rims and use it to show that zircons from the Nanaimo Basin are most likely derived from metamorphic rocks in southern California. Conventional in-situ laser ablation sample preparation typically requires mounting and polishing zircon grains to expose their core. However, in order to date these thin metamorphic zircon rims a depth-profiling approach on unabraded grains was employed. Zircon grains from the Upper Cretaceous Geoffrey, Spray, and Gabriola formations of the Nanaimo Group exposed on Denman and Hornby Islands (British Columbia) were sorted into five groups based on morphology. The zircons were then mounted on tape along with several grains of a well-characterised zircon reference material to validate the uncertainty of the method. The zircons were then imaged using a Zygo Zescope optical profilometer in order to correct for grain-to-grain variations in elevation relative to mounting medium and ensure consistent laser focus. Backscatter electron images (BSE) were used to further characterised the grains and optimize the location of laser ablation targets. Zircons were ablated using a Resonetics 193 nm excimer laser and uranium and lead isotopic ratios were measured using an Agilent 7700 quadrupole mass spectrometer. A low frequency laser repetition rate extended the data collection period on relatively thin zircon rims. Our results show that metamorphic zircon growth occurred in two main phases at 100 Ma and 77 Ma suggesting two sources of detrital zircons with differing metamorphic histories were present in the catchment area. The timing of metamorphism of the source area for the Nanaimo basin is inconsistent with derivation from sources in the Rocky Mountains (Lemhi sub

  16. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

    NASA Astrophysics Data System (ADS)

    Boshers, D.; Granger, J.; Bohlke, J. K.

    2016-12-01

    Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

  17. The age of unusual xenogenic zircons from Yakutian kimberlites

    NASA Astrophysics Data System (ADS)

    Vladykin, N. V.; Lepekhina, E. A.

    2009-12-01

    Several spindle-shaped grains of zircon, which have a small size (<0.25 mm) and a distinct purplish pink coloration were found in the crushed samples of kimberlites from the Aykhal, Komsomolskaya-Magnitnaya, Botuobinskaya (Siberian platform), and Nyurbinskaya (Yakutia) pipes and olivine lamproites of the Khani massif (West Aldan). U-Pb SHRIMP II zircon dating performed at the VSEGEI Center for Isotopic Research yielded the ages of 1870-1890 Ma for the pipes of the Western province (Aykhal and Komsomolskaya) and 2200-2750 Ma for the pipes of the eastern province (Nyurbinskaya and Botuobinskaya), which allowed us to consider these zircons to be xenogenic to kimberlites. Although these zircons resemble in their age and color those from the granulite xenoliths in the Udachnaya pipe [2], no other granulite minerals are found there. Thus, major geological events in the mantle and lower crust, which led to the formation of zircon-bearing rocks, happened at 1800-1900 Ma in the northern part of the kimberlite province, whereas in the Eastern part of the province (Nakyn field) these events were much older (2220-2700 Ma). It is known that the period of 1800-1900 Ma in the Earth’s history was accompanied by intense tectonic movements and widespread alkaline-carbonatite magmatism. This magmatism was related to plume activity responsible for overheating the large portions of the mantle to the temperatures at which some diamonds in mantle rocks would burn (northern part of the kimberlite province). In the Nakyn area, the mantle underwent few or no geological processes at that time, and perhaps for this reason this area hosts more diamondiferous kimberlites. The age of olivine lamproites from the Khani massif is 2672-2732 Ma. Thus, these are some of the world’s oldest known K-alkaline rocks.

  18. Measurement of infiltration rates in urban sewer systems by use of oxygen isotopes.

    PubMed

    De Bénédittis, J; Bertrand-Krajewski, J L

    2005-01-01

    The paper presents the principle of a method to measure infiltration rates in sewer systems based on the use of oxygen isotopes and its application in Lyon (France). In the urban area of Lyon, significant differences in delta 18O that can reach 3 per thousand are observed between the oxygen isotopic compositions of groundwater originating from Rhone, Saone and from their associated alluvial aquifers. Drinking water supplying Lyon results mainly from pumping in the Rhone alluvial aquifer. Therefore, in some areas, the difference of isotopic composition between wastewater resulting from the consumption of drinking water and local groundwater can be used to measure infiltration in sewer systems. The application in the catchment of Ecully shows that the infiltration flow rate presents strong fluctuations at an hourly scale: it varies between 15 and 40 m3/h. This variability could be explained by non-constant discharges of pumping and by variations of the water level in the sewer.

  19. Triple oxygen isotope systematics of structurally bonded water in gypsum

    NASA Astrophysics Data System (ADS)

    Herwartz, Daniel; Surma, Jakub; Voigt, Claudia; Assonov, Sergey; Staubwasser, Michael

    2017-07-01

    The triple oxygen isotopic composition of gypsum mother water (gmw) is recorded in structurally bonded water in gypsum (gsbw). Respective fractionation factors have been determined experimentally for 18O/16O and 17O/16O. By taking previous experiments into account we suggest using 18αgsbw-gmw = 1.0037; 17αgsbw-gmw = 1.00195 and θgsbw-gmw = 0.5285 as fractionation factors in triple oxygen isotope space. Recent gypsum was sampled from a series of 10 ponds located in the Salar de Llamara in the Atacama Desert, Chile. Total dissolved solids (TDS) in these ponds show a gradual increase from 23 g/l to 182 g/l that is accompanied by an increase in pond water 18O/16O. Gsbw falls on a parallel curve to the ambient water from the saline ponds. The offset is mainly due to the equilibrium fractionation between gsbw and gmw. However, gsbw represents a time integrated signal biased towards times of strong evaporation, hence the estimated gmw comprises elevated 18O/16O compositions when compared to pond water samples taken on site. Gypsum precipitation is associated with algae mats in the ponds with lower salinity. No evidence for respective vital effects on the triple oxygen isotopic composition of gypsum hydration water is observed, nor are such effects expected. In principle, the array of δ18Ogsbw vs. 17Oexcess can be used to: (1) provide information on the degree of evaporation during gypsum formation; (2) estimate pristine meteoric water compositions; and (3) estimate local relative humidity which is the controlling parameter of the slope of the array for simple hydrological situations. In our case study, local mining activities may have decreased deep groundwater recharge, causing a recent change of the local hydrology.

  20. Box-modeling of bone and tooth phosphate oxygen isotope compositions as a function of environmental and physiological parameters.

    PubMed

    Langlois, C; Simon, L; Lécuyer, Ch

    2003-12-01

    A time-dependent box model is developed to calculate oxygen isotope compositions of bone phosphate as a function of environmental and physiological parameters. Input and output oxygen fluxes related to body water and bone reservoirs are scaled to the body mass. The oxygen fluxes are evaluated by stoichiometric scaling to the calcium accretion and resorption rates, assuming a pure hydroxylapatite composition for the bone and tooth mineral. The model shows how the diet composition, body mass, ambient relative humidity and temperature may control the oxygen isotope composition of bone phosphate. The model also computes how bones and teeth record short-term variations in relative humidity, air temperature and delta18O of drinking water, depending on body mass. The documented diversity of oxygen isotope fractionation equations for vertebrates is accounted for by our model when for each specimen the physiological and diet parameters are adjusted in the living range of environmental conditions.

  1. Analysis of Atmospheric Nitrate Deposition in Lake Tahoe Using Multiple Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    McCabe, J. R.; Michalski, G. M.; Hernandez, L. P.; Thiemens, M. H.; Taylor, K.; Kendall, C.; Wankel, S. D.

    2002-12-01

    Lake Tahoe in the Sierra Nevada Mountain Range is world renown for its depth and water clarity bringing 2.2 million visitors per year resulting in annual revenue of \\1.6 billion from tourism. In past decades the lake has suffered from decreased water clarity (from 32 m plate depth to less than 20), which is believed to be largely the result of algae growth initiated by increased nutrient loading. Lake nutrients have also seen a shift from a nitrogen limited to a phosphorous limited system indicating a large increase in the flux of fixed nitrogen. Several sources of fixed nitrogen of have been suggested including surface runoff, septic tank seepage from ground water and deposition from the atmosphere. Bio-available nitrogen in the form of nitrate (NO_{3}$-) is a main component of this system. Recent studies have estimated that approximately 50% of the nitrogen input into the lake is of atmospheric origin (Allison et al. 2000). However, the impact and magnitude of atmospheric deposition is still one of the least understood aspects of the relationship between air and water quality in the Basin (TRPA Threshold Assessment 2002). The utility of stable isotopes as tracers of nitrate reservoirs has been shown in several studies (Bohlke et al. 1997, Kendall and McDonnell 1998, Durka et al. 1994). Stable nitrogen (δ15N) and oxygen (δ18O) isotopes have been implemented in a dual isotope approach to characterize the various nitrate sources to an ecosystem. While δ18O distinguishes between atmospheric and soil sources of nitrate, processes such as denitrification can enrich the residual nitrate in δ18O leaving a misleading atmospheric signature. The benefit of δ15N as a tracer for NO3- sources is the ability to differentiate natural soil, fertilizer, and animal or septic waste, which contain equivalent δ18O values. The recent implementation of multiple oxygen isotopes to measure Δ17O in nitrate has proven to be a more sensitive tracer of atmospheric deposition. The

  2. Climatic and environmental controls on speleothem oxygen-isotope values

    NASA Astrophysics Data System (ADS)

    Lachniet, Matthew S.

    2009-03-01

    Variations in speleothem oxygen-isotope values ( δ18O) result from a complicated interplay of environmental controls and processes in the ocean, atmosphere, soil zone, epikarst, and cave system. As such, the controls on speleothem δ18O values are extremely complex. An understanding of the processes that control equilibrium and kinetic fractionation of oxygen isotopes in water and carbonate species is essential for the proper interpretation of speleothem δ18O as paleoclimate and paleoenvironmental proxies, and is best complemented by study of site-specific cave processes such as infiltration, flow routing, drip seasonality and saturation state, and cave microclimate, among others. This review is a process-based summary of the multiple controls on δ18O in the atmosphere, soil, epikarst, and speleothem calcite, illustrated with case studies. Primary controls of δ18O in the atmosphere include temperature and relative humidity through their role in the multiple isotope "effects". Variability and modifications of water δ18O values in the soil and epikarst zones are dominated by evaporation, mixing, and infiltration of source waters. The isotopically effective recharge into a cave system consists of those waters that participate in precipitation of CaCO 3, resulting in calcite deposition rates which may be biased to time periods with optimal dripwater saturation state. Recent modeling, experimental, and observational data yield insight into the significance of kinetic fractionation between dissolved carbonate phases and solid CaCO 3, and have implications for the 'Hendy' test. To assist interpretation of speleothem δ18O time series, quantitative and semi-quantitative δ18O-climate calibrations are discussed with an emphasis on some of the difficulties inherent in using modern spatial and temporal isotope gradients to interpret speleothems as paleoclimate proxy records. Finally, several case studies of globally significant speleothem paleoclimate records are

  3. Molybdenite Re-Os, zircon U-Pb dating and Lu-Hf isotopic analysis of the Xiaerchulu Au deposit, Inner Mongolia Province, China

    NASA Astrophysics Data System (ADS)

    Wang, Jia-xin; Nie, Feng-Jun; Zhang, Xue-ni; Jiang, Si-hong

    2016-09-01

    The Xiaerchulu Au deposit, located in the Southern Orogenic Belt (SOB) of Western Inner Mongolia (WIM), is hosted in an Early Permian (271-261 Ma) volcanic-plutonic sequence. Mineralization took place in silicified biotite granites or along the contact zone between the Neoproterozoic Baiyinbaolage Group and the biotite granite. In order to constrain the timing of the Xiaerchulu mineralization and discuss the petrogenesis of the hosting granites, molybdenite Re-Os, and zircon U-Pb and, Lu-Hf, and REE, geochemical, and Sr-Nd isotopic studies were completed in this study. We measured Re-Os isotopes of six molybdenite samples from the main ore body, which yielded a weighted average model age of 261.7 ± 1.5 Ma with a MSWD of 0.55, indicating that the time of mineralization was at ca. 262 Ma. High precision U-Pb dating for the studied granites yields Permian 206Pb/238U ages ranging from 271 to 269 Ma. These age data confirm that both the intrusion and related mineralization were initiated in Early Permian period. These granites are strongly peraluminous with A/CNK = 1.11-1.12, high SiO2-K2O contents, as well as containing biotite and muscovite, indicating a petrogenesis of typical S-type granites, the above consideration is also consistent with the result of discrimination diagrams. The Re contents of molybdenite, εNd(t), and zircon εHf(t), as well as the 176Hf/177Hf values of the granites, fall into the ranges from 1.153 to 2.740 μg/g, - 11.1 to - 9.3, - 8.8 to - 0.9, and 0.282358 to 0.282688, respectively. All of this evidence suggests that the metals were derived from a predominantly crustal source, the granites originated from crust in an extensional setting, and the rejuvenation of the continent may have play an important role during the ore-forming processes of the Early Permian epoch.

  4. Birth and demise of the Rheic Ocean magmatic arc(s): Combined U-Pb and Hf isotope analyses in detrital zircon from SW Iberia siliciclastic strata

    NASA Astrophysics Data System (ADS)

    Pereira, M. F.; Gutíerrez-Alonso, G.; Murphy, J. B.; Drost, K.; Gama, C.; Silva, J. B.

    2017-05-01

    Paleozoic continental reconstructions indicate that subduction of Rheic oceanic lithosphere led to collision between Laurussia and Gondwana which was a major event in the formation of the Ouachita-Appalachian-Variscan orogenic belt and the amalgamation of Pangea. However, arc systems which record Rheic Ocean subduction are poorly preserved. The preservation of Devonian detrital zircon in Late Devonian-Early Carboniferous siliciclastic rocks of SW Iberia, rather than arc-related igneous rocks indicates that direct evidence of the arc system may have been largely destroyed by erosion. Here we report in-situ detrital zircon U-Pb isotopic analyses of Late Devonian-Early Carboniferous siliciclastic rocks from the Pulo do Lobo Zone, which is a reworked Late Paleozoic suture zone located between Laurussia and Gondwana. Detrital zircon age spectra from the Pulo do Lobo Zone Frasnian formations show striking similarities, revealing a wide range of ages dominated by Neoproterozoic and Paleoproterozoic grains sourced from rocks typical of peri-Gondwanan terranes, such as Avalonia, the Meguma terrane and the Ossa-Morena Zone. Pulo do Lobo rocks also include representative populations of Mesoproterozoic and Early Silurian zircons that are typical of Avalonia and the Meguma terrane which are absent in the Ossa-Morena Zone. The Famennian-Tournaisian formations from the Pulo do Lobo Zone, however, contain more abundant Middle-Late Devonian zircon indicating the contribution from a previously unrecognized source probably related to the Rheic Ocean magmatic arc(s). The Middle-Late Devonian to Early Carboniferous zircon ages from the siliciclastic rocks of SW Iberia (South Portuguese, Pulo do Lobo and Ossa-Morena zones) have a wide range in εHfT values (- 8.2 to + 8.3) indicating the likely crystallization from magmas formed in a convergent setting. The missing Rheic Ocean arc was probably built on a Meguma/Avalonia type basement. We propose for the Pulo do Lobo Zone that the

  5. Triple oxygen isotopes in biogenic and sedimentary carbonates

    NASA Astrophysics Data System (ADS)

    Passey, Benjamin H.; Hu, Huanting; Ji, Haoyuan; Montanari, Shaena; Li, Shuning; Henkes, Gregory A.; Levin, Naomi E.

    2014-09-01

    The 17O anomaly (Δ17O) of natural waters has been shown to be sensitive to evaporation in a way analogous to deuterium excess, with evaporated bodies of water (e.g., leaf waters, lake waters, animal body waters) tending to have lower Δ17O than primary meteoric waters. In animal body water, Δ17O relates to the intake of evaporated waters, evaporative effluxes of water, and the Δ17O value of atmospheric O2, which itself carries signatures of global carbon cycling and photochemical reactions in the stratosphere. Carbonates have the potential to record the triple oxygen isotope compositions of parent waters, allowing reconstruction of past water compositions, but such investigations have awaited development of methods for high-precision measurement of Δ17O of carbonate. We describe optimized methods based on a sequential acid digestion/reduction/fluorination approach that yield Δ17O data with the high precision (∼0.010‰, 1σ) needed to resolve subtle environmental signals. We report the first high-precision Δ17O dataset for terrestrial carbonates, focusing on vertebrate biogenic carbonates and soil carbonates, but also including marine invertebrates and high-temperature carbonates. We determine apparent three-isotope fractionation factors between the O2 analyte derived from carbonate and the parent waters of the carbonate. These in combination with appropriate temperature estimates (from clumped isotope thermometry, or known or estimated body temperatures) are used to calculate the δ18O and Δ17O of parent waters. The clearest pattern to emerge is the strong 17O-depletion in avian, dinosaurian, and mammalian body water (from analyses of eggshell and tooth enamel) relative to meteoric waters, following expected influences of evaporated water (e.g., leaf water) and atmospheric O2 on vertebrate body water. Parent waters of the soil carbonates studied here have Δ17O values that are similar to or slightly lower than global precipitation. Our results suggest

  6. Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

    USGS Publications Warehouse

    Qi, Haiping; Lorenz, Jennifer M.; Coplen, Tyler B.; Tarbox, Lauren V.; Mayer, Bernhard; Taylor, Steve

    2014-01-01

    RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

  7. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

    NASA Technical Reports Server (NTRS)

    Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.

    2012-01-01

    MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

  8. Oxygen isotope anomaly observed in water vapor from Alert, Canada and the implication for the stratosphere

    PubMed Central

    Lin, Ying; Clayton, Robert N.; Huang, Lin; Nakamura, Noboru; Lyons, James R.

    2013-01-01

    To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003−2005 at Alert station, Canada (82°30′N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ17O and δ18O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λMDF(H2O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003−2005. An oxygen isotopic anomaly of Δ17O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ17O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930−1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ17O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l'Environnement, Gif sur Yvette, France, had 17Oexcess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water. PMID:24009339

  9. Late accretion to the Moon recorded in zircon (U-Th)/He thermochronometry

    NASA Astrophysics Data System (ADS)

    Kelly, Nigel M.; Flowers, Rebecca M.; Metcalf, James R.; Mojzsis, Stephen J.

    2018-01-01

    We conducted zircon (U-Th)/He (ZHe) analysis of lunar impact-melt breccia 14311 with the aim of leveraging radiation damage accumulated in zircon over extended intervals to detect low-temperature or short-lived impact events that have previously eluded traditional isotopic dating techniques. Our ZHe data record a coherent date vs. effective Uranium concentration (eU) trend characterized by >3500 Ma dates from low (≤75 ppm) eU zircon grains, and ca. 110 Ma dates for high (≥100 ppm) eU grains. A progression between these date populations is apparent for intermediate (75-100 ppm) eU grains. Thermal history modeling constrains permissible temperatures and cooling rates during and following impacts. Modeling shows that the data are most simply explained by impact events at ca. 3950 Ma and ca. 110 Ma, and limits allowable temperatures of heating events between 3950-110 Ma. Modeling of solar cycling thermal effects at the lunar surface precludes this as the explanation for the ca. 110 Ma ZHe dates. We propose a sample history characterized by zircon resetting during the ca. 3950 Ma Imbrium impact event, with subsequent heating during an impact at ca. 110 Ma that ejected the sample to the vicinity of its collection site. Our data show that zircon has the potential to retain 4He over immense timescales (≥3950 Myrs), thus providing a valuable new thermochronometer for probing the impact histories of lunar samples, and martian or asteroidal meteorites.

  10. Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils.

    PubMed

    Tian, Liyan; Guo, Qingjun; Zhu, Yongguan; He, Huijun; Lang, Yunchao; Hu, Jian; Zhang, Han; Wei, Rongfei; Han, Xiaokun; Peters, Marc; Yang, Junxing

    2016-12-01

    Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ 18 O P ) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L -1 NaHCO 3 (pH = 8.5), 0.1 mol L -1 NaOH and 1 mol L -1 HCl) of agricultural soils from the Beijing area. The δ 18 O P results of the water extracts and NaHCO 3 extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ 18 O P value of the water extracts and NaHCO 3 extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ 18 O P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ 18 O P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ 18 O p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.

  11. Spatial and Temporal Trends in Stable Carbon and Oxygen Isotope Ratios of Juvenile Winter Flounder

    EPA Science Inventory

    Isotopic ratios of fish otoliths have been used in numerous studies as natural tags or markers to aid the study of connectivity among fish populations. We investigated the use of spatial and temporal changes in the stable carbon and oxygen isotope ratios of otoliths to different...

  12. Forensic applications of nitrogen and oxygen isotopes in tracing nitrate sources in urban environments

    USGS Publications Warehouse

    Silva, S.R.; Ging, P.B.; Lee, R.W.; Ebbert, J.C.; Tesoriero, A.J.; Inkpen, E.L.

    2002-01-01

    Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing ??15N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

  13. Chemical evolution of Himalayan leucogranites based on an O, U-Pb and Hf study of zircon

    NASA Astrophysics Data System (ADS)

    Hopkinson, Thomas N.; Warren, Clare J.; Harris, Nigel B. W.; Hammond, Samantha J.; Parrish, Randall R.

    2015-04-01

    Crustal melting is a characteristic process at convergent plate margins, where crustal rocks are heated and deformed. Miocene leucogranite sheets and plutons are found intruded into the high-grade metasedimentary core (the Greater Himalayan Sequence, GHS) across the Himalayan orogen. Previously-published Himalayan whole-rock data suggest that these leucogranites formed from a purely meta-sedimentary source, isotopically similar to those into which they now intrude. Bulk rock analyses carry inherent uncertainties, however: they may hide contributions from different contributing sources, and post-crystallization processes such as fluid interaction may significantly alter the original chemistry. In contrast, zircon is more able to retain precise information of the contributing sources of the melt from which it crystallises whilst its resistant nature is impervious to post-magmatic processes. This multi-isotope study of Oligocene-Miocene leucogranite zircons from the Bhutan Himalaya, seeks to differentiate between various geochemical processes that contribute to granite formation. Hf and O isotopes are used to detect discrete changes in melt source while U-Pb isotopes provide the timing of zircon crystallisation. Our data show that zircon rims of Himalayan age yield Hf-O signatures that lie within the previously reported whole-rock GHS field, confirming the absence of a discernible mantle contribution to the leucogranite source. Importantly, we document a decrease in the minimum ɛHf values during Himalayan orogenesis through time, correlating to a change in Hf model age from 1.4 Ga to 2.4 Ga. Nd model ages for the older Lesser Himalayan metasediments (LHS) that underthrust the GHS are significantly older than those for the GHS (2.4-2.9 Ga compared with 1.4-2.2 Ga), and as such even minor contributions of LHS material incorporated into a melt would significantly increase the resulting Hf model age. Hence our leucogranite data suggest either a change of source within

  14. Mo isotope record of shales points to deep ocean oxygenation in the early Paleoproterozoic

    NASA Astrophysics Data System (ADS)

    Asael, Dan; Scott, Clint; Rouxel, Olivier; Poulton, Simon; Lyons, Timothy; Javaux, Emmanuelle; Bekker, Andrey

    2014-05-01

    Two steps in Earth's surface oxidation lie at either end of the Proterozoic Eon. The first step, known as the Great Oxidation Event (GOE), occurred at ca. 2.32 Ga (1), when atmospheric oxygen first exceeded 0.001% of present atmospheric levels (2). The second step, occurred at ca. 0.58 Ga, resulting in the pervasive oxygenation of the deep oceans, a feature that persisted through most of the Phanerozoic (3). The conventional model envisions two progressive and unidirectional increases in free oxygen. However, recent studies have challenged this simplistic view of the GOE (4, 5). A dramatic increase and decline in Earth oxidation state between 2.3 and 2.0 Ga is now well supported (6-9) and raises the question of how well-oxygenated the Earth surface was in the immediate aftermath of the GOE. In order to constrain the response of the deep oceans to the GOE, we present a study of Mo isotope composition and Mo concentration from three key early Paleoproterozoic black shale units with ages ranging from 2.32 to 2.06 Ga. Our results suggest high and unstable surface oxygen levels at 2.32 Ga, leading to an abrupt increase in Mo supply to the still globally anoxic ocean, and producing extreme seawater Mo isotopic enrichments in these black shales. We thus infer a period of significant Mo isotopic Rayleigh effects and non-steady state behaviour of the Mo oceanic system at the beginning of the GOE. Between 2.2-2.1 Ga, we observe smaller Mo isotopic variations and estimate the δ98Mo of seawater to be 1.42 ± 0.27 ‰W conclude that oxygen levels must have stabilized at a relatively high level and that the deep oceans were oxygenated for the first time in Earth's history. By ca. 2.06 Ga, immediately after the Lomagundi Event, the Mo isotopic composition decreased dramatically to δ98MoSW = 0.80 ± 0.21 o reflecting the end of deep ocean oxygenation and the return of largely anoxic deep oceans. References: [1] A. Bekker et al., 2004, Nature 427, 117-20. [2] A. Pavlov and J

  15. Differential lead retention in zircons: implications for nuclear waste containment.

    PubMed

    Gentry, R V; Sworski, T J; McKown, H S; Smith, D H; Eby, R E; Christie, W H

    1982-04-16

    An innovative ultrasensitive technique was used for lead isotopic analysis of individual zircons extracted from granite core samples at depths of 960, 2170, 2900, 3930, and 4310 meters. The results show that lead, a relatively mobile element compared to the nuclear waste-related actinides uranium and thorium, has been highly retained at elevated temperatures (105 degrees to 313 degrees C) under conditions relevant to the burial of synthetic rock waste containers in deep granite holes.

  16. Triple Oxygen Isotope Measurement of Nitrate to Analyze Impact of Aircraft Emissions

    NASA Astrophysics Data System (ADS)

    Chan, Sharleen

    With 4.9% of total anthropogenic radiative forcing attributed to aircraft emissions, jet engines combust copious amounts of fuel producing gases including: NOx (NO + NO2), SOx, VOC's and fine particles [IPCC (1999), IPCC (2007), Lee et al., 2009]. The tropospheric non-linear relationships between NOx, OH and O3 contribute uncertainties in the ozone budget amplified by poor understanding of the NOx cycle. In a polluted urban environment, interaction of gases and particles produce various new compounds that are difficult to measure with analytical tools available today [Thiemens, 2006]. Using oxygen triple isotopic measurement of NO3 to investigate gas to particle formation and chemical transformation in the ambient atmosphere, this study presents data obtained from aerosols sampled at NASA's Dryden Aircraft Operations Facility (DAOF) in Palmdale, CA during January and February, 2009 and Los Angeles International Airport (LAX) during Fall 2009, Winter 2010, and Spring 2010. The aerosols collected from jet aircraft exhaust in Palmdale exhibit an oxygen isotope anomaly (Delta17O =delta 17O -0.52 delta18O) increase with photochemical age of particles (-0.22 to 26.41‰) while NO3 concentration decreases from 53.76 - 5.35ppm with a radial distance from the jet dependency. Bulk aerosol samples from LAX exhibit seasonal variation with Delta17 O and NO3 concentration peaking in winter suggesting multiple sources and increased fossil fuel burning. Using oxygen triple isotopes of NO3, we are able to distinguish primary and secondary nitrate by aircraft emissions allowing new insight into a portion of the global nitrogen cycle. This represents a new and potentially important means to uniquely identify aircraft emissions on the basis of the unique isotopic composition of jet aircraft emissions.

  17. Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

    PubMed

    Keedakkadan, Habeeb Rahman; Abe, Osamu

    2015-04-30

    The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic

  18. Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Groundwater Samples

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lee, Brady D.; Moran, James J.; Nims, Megan K.

    Report summarizing stable oxygen and hydrogen isotope analysis of two groundwater samples from the B-Complex. Results from analyses were compared to perched water and pore water analyses performed previously.

  19. Magmatic zircon Lu-Hf isotopic record of juvenile addition and crustal reworking in the Gawler Craton, Australia

    NASA Astrophysics Data System (ADS)

    Reid, Anthony J.; Payne, Justin L.

    2017-11-01

    New in situ zircon Lu-Hf isotopic data are presented from magmatic rocks distributed across the Gawler Craton, Australia. These rocks range in composition from granite to gabbro, with the majority being granite or granodiorite and moderately peraluminous in composition. The new Lu-Hf isotopic data, together with previously published data, provide insight into the magmatic evolution of the craton and crust and mantle interaction through time. Increased juvenile content of magmatic rocks correlate with periods of extensional tectonism, in particular basin formation and associated magmatism during the Neoarchean to earliest Paleoproterozoic (c. 2555-2480 Ma), Middle Paleoproterozoic (c. 2020-1710 Ma) and Late Paleoproterozoic (c. 1630-160 Ma). In contrast, magmatic rocks associated with periods of orogenic activity show greater proportions of crustal derivation, particularly the magmatic rocks generated during the c. 1730-1690 Ma Kimban Orogeny. The final two major magmatic events of the Gawler Craton at c. 1630-1604 Ma and c. 1595-1575 Ma both represent periods of juvenile input into the Gawler Craton, with εHf(t) values extending to as positive as + 8. However, widespread crustal melting at this time is also indicated by the presence of more evolved εHf(t) values to - 6.5. The mixing between crust and mantle sources during these two youngest magmatic events is also indicated by the range in two stage depleted mantle model ages (TDMc) between 1.76 Ga and 2.51 Ga. Significant mantle input into the crust, particularly during formation of the c. 1595-1575 Ma Hiltaba Suite and Gawler Range Volcanics, likely facilitated the widespread crustal magmatism of this time period. Viewed spatially, average εHf(t) and TDMc values highlight three of the major shear zones within the Gawler Craton as potentially being isotopic as well as structural boundaries. Differences in isotopic composition across the Coorabbie Shear Zone in the western Gawler Craton, the Middle Bore Fault in

  20. Oxygen isotope values in bone carbonate and collagen are consistently offset for New World monkeys.

    PubMed

    Crowley, Brooke Erin

    2014-11-01

    Stable oxygen isotopes are increasingly used in ecological research. Here, I present oxygen isotope (δ(18)O) values for bone carbonate and collagen from howler monkeys (Alouatta palliata), spider monkeys (Ateles geoffroyi) and capuchins (Cebus capucinus) from three localities in Costa Rica. There are apparent differences in δ(18)Ocarbonate and δ(18)Ocollagen among species. Monkeys from moist forest have significantly lower isotope values than those from drier localities. Because patterns are similar for both substrates, discrimination (Δ) between δ(18)Ocarbonate and δ(18)Ocollagen is relatively consistent among species and localities (17.6 ± 0.9‰). Although this value is larger than that previously obtained for laboratory rats, consistency among species and localities suggests it can be used to compare δ(18)Ocarbonate and δ(18)Ocollagen for monkeys, and potentially other medium-bodied mammals. Establishing discrimination for oxygen between these substrates for wild monkeys provides a foundation for future environmental and ecological research on modern and ancient organisms. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

  1. "Taconic" arc magmatism in the central Brooks Range, Alaska: New U-Pb zircon geochronology and Hf isotopic data from the lower Paleozoic Apoon assemblage of the Doonerak fenster

    NASA Astrophysics Data System (ADS)

    Strauss, J. V.; Hoiland, C. W.; Ward, W.; Johnson, B.; McClelland, W.

    2015-12-01

    The Doonerak fenster in the central Brooks Range, AK, exposes an important package of early Paleozoic volcanic and sedimentary rocks called the Apoon assemblage, which are generally interpreted as para-autochthonous basement to the Mesozoic-Cenozoic Brookian fold-thrust belt. Recognition in the 1970's of a major pre-Mississippian unconformity within the window led to correlations between Doonerak and the North Slope (sub-) terrane of the Arctic Alaska Chukotka microplate (AACM); however, the presence of arc-affinity volcanism and the apparent lack of pre-Mississippian deformation in the Apoon assemblage makes this link tenuous and complicates Paleozoic tectonic reconstructions of the AACM. Previous age constraints on the Apoon assemblage are limited to a handful of Middle Cambrian-Silurian paleontological collections and five K-Ar and 40Ar/39Ar hornblende ages from mafic dikes ranging from ~380-520 Ma. We conducted U-Pb geochronologic and Hf isotopic analyses on igneous and sedimentary zircon from the Apoon assemblage to test Paleozoic links with the North Slope and to assess the tectonic and paleogeographic setting of the Doonerak region. U-Pb analyses on detrital zircon from Apoon rocks yield a spectrum of unimodal and polymodal age populations, including prominent age groups of ca. 420-490, 960-1250, 1380­-1500, 1750-1945, and 2650-2830 Ma. Hf isotopic data from the ca. 410-490 Ma age population are generally juvenile (~7-10 ɛHf), implying a distinct lack of crustal assimilation during Ordovician-Silurian Doonerak arc magmatism despite its proximity to a cratonic source terrane as indicated by an abundance of Archean and Proterozoic zircon in the interbedded siliciclastic strata. These data are in stark contrast to geochronological data from the non-Laurentian portions of the AACM, highlighting a prominent tectonic boundary between Laurentian- and Baltic-affinity rocks at the Doonerak window and implying a link to "Taconic"-age arc magmatism documented along

  2. [Hydrogen and oxygen isotopes of lake water and geothermal spring water in arid area of south Tibet].

    PubMed

    Xiao, Ke; Shen, Li-Cheng; Wang, Peng

    2014-08-01

    The condition of water cycles in Tibet Plateau is a complex process, and the hydrogen and oxygen isotopes contain important information of this process. Based on the analysis of isotopic composition of freshwater lake, saltwater lake and geothermal water in the southern Tibetan Plateau, this study investigated water cycling, composition and variation of hydrogen and oxygen isotopes and the influencing factors in the study area. The study found that the mean values of delta18O and deltaD in Daggyaima lake water (-17.0 per thousand for delta18O and -138. 6 per thousand for deltaD), Langcuo lake water (-6.4 per thousand for delta18O and -87.4 per thousand for deltaD) and Dagejia geothermal water (-19.2 per thousand for delta18 and -158.2 per thousand for deltaD) all showed negative delta18O and deltaD values in Tibetan Plateau by the influence of altitude effects. Lake water and geothermal water were influenced by evaporation effects in inland arid area, and the slope of evaporation line was less than 8. Deuterium excess parameters of lake water and geothermal water were all negative. The temperature of geothermal reservoirs in Dagejia geothermal field was high,and oxygen shift existed in the relationship of hydrogen and oxygen isotopes.

  3. Ultrafiltration by a compacted clay membrane-I. Oxygen and hydrogen isotopic fractionation

    USGS Publications Warehouse

    Coplen, T.B.; Hanshaw, B.B.

    1973-01-01

    Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01 N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disc compacted to a porosity of 35 per cent by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5%. and in O18 by 0.8%. relative to the residual solution. No additional isotopic fractionation due to a salt filtering mechanism was observed at NaCl concentrations up to 0.01 N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. ?? 1973.

  4. A change in the geodynamics of continental growth 3 billion years ago.

    PubMed

    Dhuime, Bruno; Hawkesworth, Chris J; Cawood, Peter A; Storey, Craig D

    2012-03-16

    Models for the growth of continental crust rely on knowing the balance between the generation of new crust and the reworking of old crust throughout Earth's history. The oxygen isotopic composition of zircons, for which uranium-lead and hafnium isotopic data provide age constraints, is a key archive of crustal reworking. We identified systematic variations in hafnium and oxygen isotopes in zircons of different ages that reveal the relative proportions of reworked crust and of new crust through time. Growth of continental crust appears to have been a continuous process, albeit at variable rates. A marked decrease in the rate of crustal growth at ~3 billion years ago may be linked to the onset of subduction-driven plate tectonics.

  5. Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

    NASA Astrophysics Data System (ADS)

    Kawasaki, Noriyuki; Simon, Steven B.; Grossman, Lawrence; Sakamoto, Naoya; Yurimoto, Hisayoshi

    2018-01-01

    TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of

  6. Three-Body Forces and the Limit of Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Otsuka, Takaharu; Suzuki, Toshio; Holt, Jason D.; Schwenk, Achim; Akaishi, Yoshinori

    2010-07-01

    The limit of neutron-rich nuclei, the neutron drip line, evolves regularly from light to medium-mass nuclei except for a striking anomaly in the oxygen isotopes. This anomaly is not reproduced in shell-model calculations derived from microscopic two-nucleon forces. Here, we present the first microscopic explanation of the oxygen anomaly based on three-nucleon forces that have been established in few-body systems. This leads to repulsive contributions to the interactions among excess neutrons that change the location of the neutron drip line from O28 to the experimentally observed O24. Since the mechanism is robust and general, our findings impact the prediction of the most neutron-rich nuclei and the synthesis of heavy elements in neutron-rich environments.

  7. Dolomite clumped isotope constraints on the oxygen isotope composition of the Phanerozoic Sea

    NASA Astrophysics Data System (ADS)

    Ryb, U.; Eiler, J. M.

    2017-12-01

    The δ18O value of the Phanerozoic Sea has been debated several decades, largely motivated by an 8‰ increase in δ18O of sedimentary carbonates between the Cambrian and the present. Some previous studies have interpreted this increase to be a primary depositional signal, resulting from an increase in the 18O content of ocean water over time, or from a decrease in ocean temperature increasing the oxygen isotope fractionation between seawater and carbonates. In contrast, other studies have interpreted lower δ18O compositions as the products of diagenetic alteration at elevated burial temperatures. Here, we show that the Phanerozoic dolomite δ18O record overlaps with that of well-preserved calcite fossils, and use carbonate clumped isotope measurements of Cambrian to Pleistocene dolomites to calculate their formation temperatures and the isotopic compositions of their parent-waters. The observed variation in dolomite δ18O is largely explained by dolomite formation at burial temperatures of up to 158°C. The δ18O values of dolomite parent-waters range -2 to +12‰ and are correlated with formation temperatures. Such correlation is consistent with the modification of seawater (0±2‰, VSMOW) toward isotopically heavier compositions through water-rock reactions at elevated burial temperatures. The similarity between the dolomite and calcite δ18O records, and published clumped isotope-based calculations of water compositions, suggests that like dolomite, temporal variations of the calcite δ18O record may also be largely driven by diagenetic alteration. Finally, the relationship we observe between temperature of dolomitization and d18O of dolomite suggests platform carbonates generally undergo dolomitization through reaction with modified marine waters, and that there is no evidence those waters were ever significantly lower in d18O than the modern ocean.

  8. Textural and U-Pb systematics (CA-TIMS) of stepwise leaching in zircon from granophyres in the Archean Stillwater Complex

    NASA Astrophysics Data System (ADS)

    Wall, C. J.; Scoates, J. S.; Friedman, R. M.; Meurer, W. P.

    2011-12-01

    The chemical abrasion-TIMS method or CA-TIMS uses a high-temperature annealing treatment to remove the effects of Pb-loss from radiation damaged parts of the zircon lattice and allows for highly precise and accurate U-Pb dating [1]. Zircon with high U-Th concentrations can be strongly metamict and it is not yet clear how effective the chemical abrasion treatment is when applied to these types of grains. In this study, we evaluate the link between the textural response and U-Pb systematics of zircon during chemical leaching for a granophyric rock from the Archean Stillwater Complex in Montana. The sample was selected based on the high abundance of zircon and the high degree of metamictization of the grains. Untreated and leached zircon grains were analyzed by scanning electron microscopy (SEM) and isotope dilution thermal ionization mass spectrometry (ID-TIMS). In thin section, zircon grains are euhedral in morphology and tend to be associated with amphibole-rich zones. Under the SEM, zircon grains typically have two distinct zones, a Ca-rich amorphous zone in the core and a more intact outer shell. Five acid-leaching steps were carried out on grains with each step increasing in temperature and acid strength until the zircon residue completely dissolved (starting at a 50% strength HF/HNO3 mixture at 100°C for 4 hours and finishing at full strength acid at 170°C for 4 hours). SEM imaging was conducted on grains after each step with a noticeable change in the morphology of the grains. As the leaching progressed, the acid leach created large pathways through the crystal lattice until only grain fragments remained, in some cases even boring large holes into the centre of the zircon grain. The acid preferentially dissolved the more soluble Ca-rich zones leaving behind fragile zircon "shells". U-Pb results of untreated grains are highly discordant (37-80%) and yield a chord with an upper intercept age of 1981 ± 140 Ma, whereas leached grains are slightly less

  9. UPb ages of zircon rims: A new analytical method using the air-abrasion technique

    USGS Publications Warehouse

    Aleinikoff, J.N.; Winegarden, D.L.; Walter, M.

    1990-01-01

    We present a new technique for directly dating, by conventional techniques, the rims of zircons. Several circumstances, such as a xenocrystic or inherited component in igneous zircon and metamorphic overgrowths on igneous cores, can result in grains with physically distinct age components. Pneumatic abrasion has been previously shown by Krogh to remove overgrowths and damaged areas of zircon, leaving more resistant and isotopically less disturbed parts available for analysis. A new abrader design, which is capable of very gently grinding only tips and interfacial edges of even needle-like grains, permits easy collection of abraded material for dating. Five examples demonstrate the utility of the "dust-collecting" technique, including two studies that compare conventional, ion microprobe and abrader data. Common Pb may be strongly concentrated in the outermost zones of many zircons and this Pb is not easily removed by leaching (even in weak HF). Thus, the benefit of removing only the outermost zones (and avoiding mixing of age components) is somewhat compromised by the much higher common Pb contents which result in less precise age determinations. A very brief abrasion to remove the high common Pb zones prior to collection of material for dating is selected. ?? 1990.

  10. The role of detrital zircons in Hadean crustal research

    NASA Astrophysics Data System (ADS)

    Nebel, Oliver; Rapp, Robert P.; Yaxley, Gregory M.

    2014-03-01

    Meso-Archean sedimentary sequences at Mt. Narryer and the Jack Hills of the Narryer Terrane in Western Australia's Yilgarn Craton contain detrital zircon grains with ages as old as 4.37 Ga, the oldest preserved terrestrial matter. These grains are rare remnants of Hadean (4.5-4.0 Ga) terrestrial crust and their survival stems from the crystallographic properties of zircon during crustal reworking: they are resistant to physical and chemical weathering. Zircons are further suitable for single grain, precise age determinations making them a unique archive of the crustal past. Only a small proportion of all detrital zircons from the Narryer Terrane show Hadean age spectra and younger overgrowth rims on all 'Hadean' grains indicate multiple recycling events. Numerous studies that applied a spectacular range of analytical tools and proxies have been undertaken to decipher the geochemical nature of these zircons' host rocks, in order to place constraints on Hadean geodynamics and the processes responsible for creating the earliest terrestrial crust. Their elemental and isotope budget and mineral inclusions have helped to develop an emerging picture of a water-rich, evolved Hadean crust. However, subsequent studies have challenged this view and it seems that each piece of new evidence indicative of an early, evolved continental crust has non-unique interpretations also permissive of mafic to ultra-mafic crust. In this review we examine these disparate interpretations and their possible implications and conclude that at least parts of the earliest terrestrial crust were hydrated. However, to date there is no conclusive evidence for preserved granitic, continental crust. The protoliths of the Hadean detrital zircons were likely acidic in nature, yet the composition of the greater terrane from which these melts were derived was probably mafic. It remains unclear if the zircons formed in a geodynamic environment that includes Hadean subduction. We suspect that the Hadean

  11. Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

    NASA Astrophysics Data System (ADS)

    Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

    2017-08-01

    Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

  12. Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

    NASA Astrophysics Data System (ADS)

    Henkes, Gregory A.; Passey, Benjamin H.; Grossman, Ethan L.; Shenton, Brock J.; Yancey, Thomas E.; Pérez-Huerta, Alberto

    2018-05-01

    Surface temperature is among the most important parameters describing planetary climate and habitability, and yet there remains considerable debate about the temperature evolution of the Earth's oceans during the Phanerozoic Eon (541 million years ago to present), the time during which complex metazoan life radiated on Earth. Here we critically assess the emerging record of Phanerozoic ocean temperatures based on carbonate clumped isotope thermometry of fossil brachiopod and mollusk shells, and we present new data that fill important gaps in the Late Paleozoic record. We evaluate and reject the hypothesis that solid-state reordering of 13C-18O bonds has destroyed the primary clumped isotope temperature signal of most fossils during sedimentary burial at elevated temperatures. The resulting Phanerozoic record, which shows a general coupling between tropical seawater temperatures and atmospheric carbon dioxide (CO2) levels since the Paleozoic, indicates that tropical temperatures during the icehouse climate of the Carboniferous period were broadly similar to present (∼25-30 °C), and suggests that benthic metazoans were able to thrive at temperatures of 35-40 °C during intervals of the early and possibly the latest Paleozoic when CO2 levels were likely 5-10× higher than present-day values. Equally important, there is no resolvable trend in seawater oxygen isotope ratios (δ18 O) over the past ∼500 million years, indicating that the average temperature of oxygen exchange between seawater and the oceanic crust has been high (∼270 °C) since at least the early Paleozoic, which points to mid-ocean ridges as the dominant locus of water-rock interaction over the past half-billion years.

  13. Oxygen isotopes in garnet and accessory minerals to constrain fluids in subducted crust

    NASA Astrophysics Data System (ADS)

    Rubatto, Daniela; Gauthiez-Putallaz, Laure; Regis, Daniele; Rosa Scicchitano, Maria; Vho, Alice; Williams, Morgan

    2017-04-01

    Fluids are considered a fundamental agent for chemical exchanges between different rock types in the subduction system. Constraints on the sources and pathways of subduction fluids thus provide crucial information to reconstruct subduction processes. Garnet and U-Pb accessory minerals constitute some of the most robust and ubiquitous minerals in subducted crust and can preserve multiple growth zones that track the metamorphic evolution of the sample they are hosted in. Microbeam investigation of the chemical (major and trace elements) and isotopic composition (oxygen and U-Pb) of garnet and accessory minerals is used to track significant fluid-rock interaction at different stages of the subduction system. This approach requires consideration of the diffusivity of oxygen isotopes particularly in garnet, which has been investigated experimentally. The nature of the protolith and ocean floor alteration is preserved in relict accessory phases within eclogites that have been fully modified at HP conditions (e.g. Monviso and Dora Maira units in the Western Alps). Minerals in the lawsonite-blueschists of the Tavsanli zone in Turkey record pervasive fluid exchange between mafic and sedimentary blocks at the early stage of subduction. High pressure shear zones and lithological boundaries show evidence of intense fluid metasomatism at depth along discontinuities in Monviso and Corsica. In the UHP oceanic crust of the Zermatt-Saas Zone, garnet oxygen isotopes and tourmaline boron isotopes indicate multistage fluid infiltration during prograde metamorphism. Localized exchanges of aqueous fluids are also observed in the subducted continental crust of the Sesia-Lanzo Zone. In most cases analyses of distinct mineral zones enable identification of multiple pulses of fluids during the rock evolution.

  14. TEMORA 1: A new zircon standard for Phanerozoic U-Pb geochronology

    USGS Publications Warehouse

    Black, L.P.; Kamo, S.L.; Allen, C.M.; Aleinikoff, J.N.; Davis, D.W.; Korsch, R.J.; Foudoulis, C.

    2003-01-01

    The role of the standard is critical to the derivation of reliable U-Pb zircon ages by micro-beam analysis. For maximum reliability, it is critically important that the utilised standard be homogeneous at all scales of analysis. It is equally important that the standard has been precisely and accurately dated by an independent technique. This study reports the emergence of a new zircon standard that meets those criteria, as demonstrated by Sensitive High Resolution Ion MicroProbe (SHRIMP), isotope dilution thermal ionisation mass-spectrometry (IDTIMS) and excimer laser ablation- inductively coupled plasma-mass-spectrometry (ELA-ICP-MS) documentation. The TEMORA 1 zircon standard derives from the Middledale Gabbroic Diorite, a high-level mafic stock within the Palaeozoic Lachlan Orogen of eastern Australia. Its 206Pb/238U IDTIMS age has been determined to be 416.75??0.24 Ma (95% confidence limits), based on measurement errors alone. Spike-calibration uncertainty limits the accuracy to 416.8??1.1 Ma for U-Pb intercomparisons between different laboratories that do not use a common spike. ?? 2003 Published by Elsevier Science B.V. All rights reserved.

  15. Brittle-ductile deformation effects on zircon crystal-chemistry and U-Pb ages: an example from the Finero Mafic Complex (Ivrea-Verbano Zone, western Alps)

    NASA Astrophysics Data System (ADS)

    Langone, Antonio; José Alberto, Padrón-Navarta; Zanetti, Alberto; Mazzucchelli, Maurizio; Tiepolo, Massimo; Giovanardi, Tommaso; Bonazzi, Mattia

    2016-04-01

    correlation between internal zircon structures, chemistry, U-Pb isotope ratios and mylonitic fabric. U-Pb data return highly discordant and variable ages: in particular, the 206Pb/238U ages range from Carboniferous to Triassic within the same zircon grain. The youngest 206Pb/238U data derive from narrow axial stripes oriented parallel or at low angle with respect to the foliation planes. These stripes are characterized by an overall HREE, Y, U and Th enrichment possibly reflecting deformation of the grain in presence of interstitial fluid phases, likely related to a concomitant magmatic activity. Deformation related structures (cracks and fractures) within zircon grains acted as fast-diffusion pathways allowing fluids to modify the geochemistry and isotopic systems of zircon. Our results suggest that fluid-assisted brittle-ductile deformation can severely modify the trace elements and isotopic composition of zircon with unexpected patterns constrained by stress regime. In similar cases, our observations suggest that, for a more appropriate interpretation of the petrologic evolution and age variability, a direct characterization of the internal structures of zircons still placed in their microtextural site is highly recommended.

  16. The mechanism of oxygen isotopic fractionation during fungal denitrification - A pure culture study

    NASA Astrophysics Data System (ADS)

    Wrage-Moennig, Nicole; Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Annette; Lewicka-Szczebak, Dominika; Well, Reinhard

    2014-05-01

    Nitrous oxide (N2O) from soil denitrification originates from bacteria and - to an unknown extent - also from fungi. During fungal denitrification, oxygen (O) exchange takes place between H2O and intermediates of the denitrification process as in bacterial exchange[1,2]. However, information about enzymes involved in fungal O exchanges and the associated fractionation effects is lacking. The objectives of this study were to estimate the O fractionation and O exchange during the fungal denitrifying steps using a conceptual model[2] adapted from concepts for bacterial denitrification[3], implementing controls of O exchange proposed by Aerssens, et al.[4] and using fractionation models by Snider et al.[5] Six different pure fungal cultures (five Hypocreales, one Sordariales) known to be capable of denitrification were incubated under anaerobic conditions, either with nitrite or nitrate. Gas samples were analyzed for N2O concentration and its isotopic signatures (SP, average δ15N, δ18O). To investigate O exchange, both treatments were also established with 18O-labelled water as a tracer in the medium. The Hypocreales strains showed O exchange mainly at NO2- reductase (Nir) with NO2- as electron acceptor and no additional O exchange at NO3- reductase (Nar) with NO3- as electron acceptor. The only Hypocreales species having higher O exchange with NO3- than with NO2- also showed O exchange at Nar. The Sordariales species tested seems capable of O exchange at NO reductase (Nor) additionally to O exchange at Nir with NO2-. The data will help to better interpret stable isotope values of N2O from soils. .[1] D. M. Kool, N. Wrage, O. Oenema, J. Dolfing, J. W. Van Groenigen. Oxygen exchange between (de)nitrification intermediates and H2O and its implications for source determination of NO?3- and N2O: a review. Rapid Commun. Mass Spec. 2007, 21, 3569. [2] L. Rohe, T.-H. Anderson, B. Braker, H. Flessa, A. Giesemann, N. Wrage-Mönnig, R. Well. Fungal Oxygen Exchange between

  17. Fractionation of Nitrogen and Oxygen Isotopes and Roles of Bacteria during Denitrification

    NASA Astrophysics Data System (ADS)

    Kang, J.; Buyanjargal, A.; Jeen, S. W.

    2017-12-01

    Nitrate in groundwater can cause health and environmental problems when not properly treated. The purpose of this study was to develop a treatment method for nitrate in groundwater using organic carbon-based reactive mixtures (i.e., wood chips and gravel) through column experiments and to evaluate reaction mechanisms responsible for the treatment. The column experiments were operated for a total of 19 months. The results from the geochemical analyses for the experiments suggest that cultures of denitrifying bacteria used organic carbon while utilizing nitrate as their electron acceptor via denitrification process. Proteobacteria was the most abundant phylum in all samples, accounting for 45.7% of the bacterial reads, followed by Firmicutes (22.6%) and Chlorobi (10.6%). Bacilli, Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria_c consisted of 32, 30, 23, 11, and 2% of denitrifying bacteria class. The denitrification process caused fractionation of nitrogen and oxygen isotopes of nitrate while nitrate concentration decreased. When fitted to the Rayleigh's fractionation model, enrichment factors (ɛ) were 11.5‰ and 5.6‰ for 15N and 18O isotopes, respectively. Previous studies suggested that nitrogen isotope enrichment factors of denitrification are within the range of 4.7 to 40‰ and oxygen isotopic enrichment factors are between 8 and 18.3‰. This study shows that nitrate in groundwater can be effectively treated using passive treatment systems, such as permeable reactive barriers (PRBs), and denitrificaton is the dominant process reponsible for the removal of nitrate.

  18. Oxygen Isotope Variability within Nautilus Shell Growth Bands

    PubMed Central

    2016-01-01

    Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis of oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. To create the observed range of δ18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands. PMID:27100183

  19. Oxygen isotope variability within Nautilus shell growth bands

    DOE PAGES

    Linzmeier, Benjamin J.; Kozdon, Reinhard; Peters, Shanan E.; ...

    2016-04-21

    Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis ofmore » oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ 18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ 18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. In addition, to create the observed range of δ 18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands.« less

  20. [Temporal and spatial variations of hydrogen and oxygen isotopes in Tuojia River and its influencing factors.

    PubMed

    Wu, Hong Bao; Zhao, Qiang; Qin, Xiao Bo; Gao, Qing Zhu; Lyu, Cheng Wen

    2018-05-01

    The characteristics of hydrogen and oxygen stable isotopes in river is important for regional hydrologic cycle research. To uncover water supply sources in subtropical agricultural basin from a perspective of stable isotopes, field measurements were conducted in four reaches (S 1 , S 2 , S 3 and S 4 ) of Tuojia River from April to August 2017. We analyzed the spatial and temporal variations in hydrogen and oxygen isotopes and deuterium excess parameters and their relationship with precipitation, altitude and water quality. Results showed that hydrogen and oxygen isotopes and deuterium excess values ranged from -43.17‰ to -26.43‰ (-35.50‰±5.44‰), -7.94‰ to -5.70‰ (-6.86‰±0.74‰), and 16.77‰ to 23.49‰ (19.39‰±1.95‰), respectively. Under the influence of monsoon circulation, hydrogen and oxygen isotopes showed substantial seasonal variation, with spring (δD: -29.88‰±3.31‰; δ 18 O: -6.18‰±0.57‰) > summer (δD: -39.25‰±2.65‰; δ 18 O: -7.32‰±0.42‰). The spatial distribution of hydrogen and oxygen isotopes values increased fluctuantly with the position from the sampling site to the river's source, with δD: S 1 <S 4 <S 3 <S 2 , and δ 18 O: S 1 <S 3 <S 4 <S 2 . The deuterium excess values had no significant temporal variation, while it spatially increased gradually with the river levels. The slope and intercept of water line in this river were smaller than that of the local meteoric water line, suggesting that precipitation was the primary water source for this river. At the seasonal scale, both δD and δ 18 O were significantly negatively correlated with water temperature (δD: r=-0.92; δ 18 O: r=-0.88) and δ 18 O was negatively correlated with altitude (r=-0.96). At spatial scale, δ 18 O had a significantly positive correlation with water temperature. The δD and δ 18 O had negative correlation with precipitation, but being not statistically significant.

  1. Mechanisms and timescales of generating eruptible rhyolitic magmas at Yellowstone caldera from zircon and sanidine geochronology and geochemistry

    USGS Publications Warehouse

    Stelten, Mark; Cooper, Kari M.; Vazquez, Jorge A.; Calvert, Andrew T.; Glessner, Justin G

    2015-01-01

    We constrain the physical nature of the magma reservoir and the mechanisms of rhyolite generation at Yellowstone caldera via detailed characterization of zircon and sanidine crystals hosted in three rhyolites erupted during the (ca. 170 – 70 ka) Central Plateau Member eruptive episode – the most recent post-caldera magmatism at Yellowstone. We present 238U-230Th crystallization ages and trace-element compositions of the interiors and surfaces (i.e., unpolished rims) of individual zircon crystals from each rhyolite. We compare these zircon data to 238U- 230Th crystallization ages of bulk sanidine separates coupled with chemical and isotopic data from single sanidine crystals. Zircon age and trace-element data demonstrate that the magma reservoir that sourced the Central Plateau Member rhyolites was long-lived (150 – 250 kyr) and genetically related to the preceding episode of magmatism, which occurred ca. 256 ka. The interiors of most zircons in each rhyolite were inherited from unerupted material related to older stages of Central Plateau Member magmatism or the preceding late Upper Basin Member magmatism (i.e., are antecrysts). Conversely, most zircon surfaces crystallized near the time of eruption from their host liquids (i.e., are autocrystic). The repeated recycling of zircon interiors from older stages of magmatism demonstrates that sequentially erupted Central Plateau Member rhyolites are genetically related. Sanidine separates from each rhyolite yield 238U-230Th crystallization ages at or near the eruption age of their host magmas, coeval with the coexisting zircon surfaces, but are younger than the coexisting zircon interiors. Chemical and isotopic data from single sanidine crystals demonstrate that the sanidines in each rhyolite are in equilibrium with their host melts, which considered along with their near-eruption crystallization ages suggests that nearly all CPM sanidines are autocrystic. The paucity of antecrystic sanidine crystals relative to

  2. The Origin of the Chinese Central Tianshan Block in the Southern Central Asian Orogenic Belt: Evidence from Detrital Zircon Study

    NASA Astrophysics Data System (ADS)

    Huang, Z.; Long, X.; Yuan, C.

    2016-12-01

    The Chinese Central Tianshan Block (CTB) is one of the oldest continental fragments in the southern Central Asian Orogenic Belt (CAOB). Although it is vital for understanding the evolution of the CAOB, its origin has been poorly studied. The CTB was previously suggested to have been originated from the North China, the South China, the Tarim cratons or the East European Craton (Baltica). A total of 165 concordant U-Pb and Hf isotopic analyses of detrital zircon are obtained from three meta-sediments in the CTB, including one meta-sandstone from Xingxingxia formation and one meta-sandstone as well as one quartzite from Kawabulake formation. Detrital zircon grains from the Xingxingxia and Kawabulake formations are dominated by respective youngest age populations at 1002 Ma and 930-960 Ma, providing constraints on the maximum depositional ages for these two formations. Zircon grains from the meta-sediments have very similar age distributions, with two dominant peaks at 0.93-1.0 Ga and 1.0-1.6 Ga and a minor peak at 2.3-2.7 Ga. They have similar Hf isotopic signatures, suggesting that the meta-sediments in the CTB share similar sedimentary provenance. The early Neoproterozoic detrital zircon grains are mainly local-derived, whereas the Paleo-Mesoproterozoic grains are both autochthonous and allochthonous. The occurrence of these Mesoproterozoic and Neoproterozoic zircon grains are coincident with the Nuna breakup and the Rodinia assembly. This suggests that the CTB might experience the tectonic switching of the Nuna to the Rodinia. The distinct Meso-Neoproterozoic age patterns and Hf isotopic compositions of these detrital grains from the CTB and the surrounding blocks indicate that the CTB was not located close to the North China, the South China or the Tarim cratons in Precambrian. Our new data suggest that the CTB was most likely once a part of the East European Craton before the Neoproterozoic. This study was supported by National Basic Research Program of China

  3. Heterogenous Oxygen Isotopic Composition of a Complex Wark-Lovering Rim and the Margin of a Refractory Inclusion from Leoville

    NASA Technical Reports Server (NTRS)

    Simon, J. I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.

    2014-01-01

    Wark-Lovering (WL) rims [1] surrounding many refractory inclusions represent marker events in the early evolution of the Solar System in which many inclusions were exposed to changes in pressure [2], temperature [3], and isotopic reservoirs [4-7]. The effects of these events can be complex, not only producing mineralogical variability of WL rims [2], but also leading to mineralogical [8-10] and isotopic [7, 11, 12] changes within inclusion interiors. Extreme oxygen isotopic heterogeneity measured in CAIs has been explained by mixing between distinct oxygen gas reservoirs in the nebula [13]. Some WL rims contain relatively simple mineral layering and/or are isotopically homogeneous [14, 15]. As part of a larger effort to document and understand the modifications observed in some CAIs, an inclusion (L6) with a complex WL rim from Leoville, a member of the reduced CV3 subgroup was studied. Initial study of the textures and mineral chemistry was presented by [16]. Here we present NanoSIMS oxygen isotopic measurements to complement these petrologic observations.

  4. Reconciliation of late Quaternary sea levels derived from coral terraces at Huon Peninsula with deep sea oxygen isotope records

    NASA Astrophysics Data System (ADS)

    Chappell, John; Omura, Akio; Esat, Tezer; McCulloch, Malcolm; Pandolfi, John; Ota, Yoko; Pillans, Brad

    1996-06-01

    A major discrepancy between the Late Quaternary sea level changes derived from raised coral reef terraces at the Huon Peninsula in Papua New Guinea and from oxygen isotopes in deep sea cores is resolved. The two methods agree closely from 120 ka to 80 ka and from 20 ka to 0 ka (ka = 1000 yr before present), but between 70 and 30 ka the isotopic sea levels are 20-40 m lower than the Huon Peninsula sea levels derived in earlier studies. New, high precision U-series age measurements and revised stratigraphic data for Huon Peninsula terraces aged between 30 and 70 ka now give similar sea levels to those based on deep sea oxygen isotope data planktonic and benthic δ 18O data. Using the sea level and deep sea isotopic data, oxygen isotope ratios are calculated for the northern continental ice sheets through the last glacial cycle and are consistent with results from Greenland ice cores. The record of ice volume changes through the last glacial cycle now appears to be reasonably complete.

  5. U Pb zircon age, geochemical and Sr Nd Pb Hf isotopic constraints on age and origin of alkaline intrusions and associated mafic dikes from Sulu orogenic belt, Eastern China

    NASA Astrophysics Data System (ADS)

    Liu, Shen; Hu, Ruizhong; Gao, Shan; Feng, Caixia; Qi, Youqiang; Wang, Tao; Feng, Guangying; Coulson, Ian M.

    2008-12-01

    Post-orogenic alkaline intrusions and associated mafic dikes from the Sulu orogenic belt of eastern China consist of quartz monzonites, A-type granites and associated mafic dikes. We report here U-Pb zircon ages, geochemical data and Sr-Nd-Pb-Hf isotopic data for these rocks. The SHRIMP U-Pb zircon analyses yield consistent ages ranging from 120.3 ± 2.1 Ma to 126.9 ± 1.9 Ma for five samples from the felsic rocks, and two crystallization ages of 119.0 ± 1.7 Ma and 120.2 ± 1.9 Ma for the mafic dikes. The felsic rocks and mafic dikes are characterized by high ( 87Sr/ 86Sr) i ranging from 0.7079 to 0.7089, low ɛNd( t) values from - 15.3 to - 19.2, 206Pb/ 204Pb = 16.54-17.25, 207Pb/ 204Pb = 15.38-15.63, 208Pb/ 204Pb = 37.15-38.45, and relatively uniform ɛHf( t) values of between - 21.6 ± 0.6 and - 23.7 ± 1.0, for the magmatic zircons. The results suggest that they were derived from a common enriched lithospheric mantle source that was metasomatized by foundered lower crustal eclogitic materials before magma generation. Geochemical and isotopic characteristics imply that the primary magma to these rocks originated through partial melting of ancient lithospheric mantle that was variably hybridized by melts derived from foundered lower crustal eclogite. The mafic dikes may have been generated by subsequent fractionation of clinopyroxene, whereas the felsic rocks resulted from fractionation of potassium feldspar, plagioclase and ilmenite or rutile. Both were not affected by crustal contamination. Combined with previous studies, these findings provide new evidence that the intense lithospheric thinning beneath the Sulu belt of eastern China occurred between 119 and 127 Ma, and that this was caused by the removal of the lower lithosphere (mantle and lower crust).

  6. Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

    USGS Publications Warehouse

    Balci, N.; Shanks, Wayne C.; Mayer, B.; Mandernack, K.W.

    2007-01-01

    To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2

  7. Low δ18O zircons from the Bruneau-Jarbidge eruptive center: a key to crustal anatexis along the track of the Yellowstone hotspot

    NASA Astrophysics Data System (ADS)

    Cathey, H. E.; Nash, B. P.; Seligman, A. N.; Valley, J. W.; Kita, N.; Allen, C. M.; Campbell, I. H.; Vazquez, J. A.; Wooden, J. L.

    2011-12-01

    The Bruneau-Jarbidge eruptive center (BJEC) in the central Snake River Plain, Idaho, USA consists of the Cougar Point Tuff (CPT), a series of ten, high-temperature (900-1000°C) voluminous ignimbrites produced over the explosive phase of volcanism (12.8 - 10.5 Ma) and more than a dozen equally high-temperature rhyolite lava flows produced during the effusive phase (10.5 - 8 Ma). Spot analyses by ion microprobe of oxygen isotope ratios in 210 zircons demonstrate that all of the eruptive units of the BJEC are characterized by zircon δ18O values ≤ 2.5%, thus documenting the largest low δ18O silicic volcanic province known on Earth (>104 km3). There is no evidence for voluminous normal δ18O magmatism at the BJEC that precedes generation of low δ18O magmas as there is at other volcanic centers that generate low δ18O magmas such as Heise and Yellowstone. At these younger volcanic centers of the hotspot track, such low δ18O magmas represent ~45 % and ~20% respectively of total eruptive volumes. Zircons in all BJEC tuffs and lavas studied (23 units) document strong 18O depletion (median CPT δ18OZrc = 1.0 %, post-CPT lavas = 1.5%) with the third member of the CPT recording an excursion to minimum δ18O values (δ18OZrc= -1.8 %) in a supereruption > 2% lower than other voluminous low δ18O rhyolites known worldwide (δ18OWR ≤0.9 vs. 3.4%). Subsequent units of the CPT and lavas record a progressive recovery in δ18OZrc to ~2.5% over a ~ 4 m.y. interval (12 to 8 Ma). We present detailed evidence of unit-to-unit systematic patterns in O isotopic zoning in zircons (i.e. direction and magnitude of Δcore-rim), spectrum of δ18O in individual units, and zircon inheritance patterns established by re-analysis of spots for U-Th-Pb isotopes by LA-ICPMS and SHRIMP. In conjunction with mineral thermometry and magma compositions, these patterns are difficult to reconcile with the well-established model for "cannibalistic" low δ18O magma genesis at Heise and Yellowstone. We

  8. Origin and age of zircon-bearing chromitite layers from the Finero phlogopite peridotite (Ivrea-Verbano Zone, Western Alps) and geodynamic consequences

    NASA Astrophysics Data System (ADS)

    Zanetti, Alberto; Giovanardi, Tommaso; Langone, Antonio; Tiepolo, Massimo; Wu, Fu-Yuan; Dallai, Luigi; Mazzucchelli, Maurizio

    2016-10-01

    An investigation has been performed on three chromitite layers segregated in dunite bodies of the Phlogopite Peridotite mantle unit in the Finero complex (FPP, Ivrea-Verbano Zone, Southern Alps) aimed at providing new constraints to their origin and evolution. Field relationships, the sub-chondritic Hf isotopic composition of the zircons (εHf(188) as low as - 5.4), the heavy O isotopic composition of zircons and pyroxenes (δ18O up to 6.9‰), the strict similarity of the trace element composition between the clinopyroxenes and amphiboles from the chromitites and those from the phlogopite harzburgites and pyroxenites forming the typical FPP association, as well as the REE composition of zircons, which approaches equilibrium with the associate clinopyroxene, suggest that the studied chromitites were segregated from melts, highly contaminated from continental crust, during the pervasive cycle of metasomatism recorded by the FPP. An LA-ICP-HRMS survey of chromitite zircon grains has provided Early Jurassic U-Pb ages mostly between 199 ± 3 Ma and 178 ± 2 Ma, with a pronounced peak at 187 Ma. Relevant exceptions are inherited domains of two grains giving Triassic ages of 242 ± 7 Ma and 229 ± 7 Ma, and a third homogeneous zircon giving 208 ± 3 Ma. Our geochronological data and those reported in the literature show that the FPP chromitites have zircon populations with different internal CL textures, but the same sub-chondritic Hf isotopic composition, which define an overall U-Pb age span from 290 Ma to 180. The segregation of the chromitite layers and the main pervasive metasomatism likely occurred in the Early Permian (in a post-collisional, transtensional setting) or before (possibly, in a subduction-related setting). The rejuvenation of the zircon ages was accompanied by a progressive disappearance of the internal zoning, interpreted as the result of a prolonged residence at mantle depths with progressive re-equilibration of the U-Pb system due to thermal

  9. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream

    PubMed Central

    Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

    2016-01-01

    ABSTRACT Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ15NNO2− and δ18ONO2−, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of “Candidatus Nitrosocaldus.” The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ18O value of nitrite produced from ammonia oxidation varied with the δ18O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ18ONO2− in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. IMPORTANCE Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying

  10. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream.

    PubMed

    Nishizawa, Manabu; Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

    2016-08-01

    Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of

  11. Investigating the direct meltwater effect in oxygen-isotope records using an isotope-enabled Earth system model

    NASA Astrophysics Data System (ADS)

    Zhu, J.; Liu, Z.; Brady, E. C.; Otto-Bliesner, B. L.; Marcott, S. A.; Zhang, J.; Wang, X.; Noone, D.; Nusbaumer, J. M.; Wong, T. E.; Jahn, A.

    2017-12-01

    Oxygen isotopes (δ18O) in both terrestrial and marine paleoclimate archives have long been used to study the climate evolution of the late Quaternary. Based on the high-latitude "temperature effect" and the tropical "amount effect", the δ18O variations in ice cores and speleothems have been primarily interpreted as changes in surface air temperature and regional precipitation amount, respectively, although recent studies suggest that other climate processes may also play a role. However, one long-overlooked assumption for these climatic interpretations is that the δ18O variations in the terrestrial records can be exclusively explained by changes in climate variables. This assumption could be violated during past glacial meltwater events, as the meltwater discharged into the ocean by icebergs or surface runoff is considerably depleted in δ18O compared to the surface ocean. This depleted meltwater can significantly decrease the isotope composition of the seawater it deposits and propagate within the hydrological cycle to directly influence the δ18O values in adjacent precipitation (the direct effect), without involving any changes in the climate state (the indirect effect). Here, by conducting water isotope-enabled climate simulations, we aim to quantify the direct meltwater effect on the terrestrial δ18O records. We find that, for large meltwater events in the northern North Atlantic Ocean (e.g., around 0.25 Sv lasting 300 years), the direct meltwater effect contributes more than 15% and 35% of the total δ18O changes in the precipitation over Greenland and the eastern Brazil, respectively. Model simulations further demonstrate that the direct meltwater effect increases with the magnitude and duration of meltwater, and it is sensitive to both the location and the shape of the freshwater forcing. We argue that the direct meltwater effect on δ18O records could also be significant in other regions and for other terrestrial oxygen-isotope records, as long as the

  12. Partitioning water and carbon fluxes in a Mediterranean oak woodland using stable oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Dubbert, Maren; Piayda, Arndt; Cuntz, Matthias; Correia, Alexandra; Silva, Filipe Costa e.; Pereira, Joao; Werner, Christiane

    2014-05-01

    Water is a key factor driving ecosystem productivity, especially in water-limited ecosystems. A separation of the component fluxes is needed to gain a functional understanding on the development of net ecosystem water fluxes and their coupling with biogeochemical cycles. Oxygen isotope signatures are valuable tracers for water movements within the ecosystem because of the distinct isotopic compositions of water in soil and vegetation. In the past, determination of isotopic signatures of evaporative or transpirational fluxes has been challenging since measurements of water vapor isotopes were difficult to obtain using cold-trap methods, delivering data with low time resolution. Recent developments in laser spectroscopy now enable direct high frequency measurements of the isotopic composition of atmospheric water vapor (δv), evapotranspiration (δET), and its components and allow validations of common modeling approaches for estimating δE and δT based on Craig and Gordon (1965). Here, a novel approach was used, combining a custom build flow-through gas-exchange branch chamber with a Cavity Ring-Down Spectrometer in a Mediteranean cork-oak woodland where two vegetation layers respond differently to drought: oak-trees (Quercus suber L.) avoid drought due to their access to ground water while herbaceous plants survive the summer as seeds. We aimed at 1) testing the Craig and Gordon equation for soil evaporation against directly measured δE and 2) quantifying the role of non-steady-state transpiration under natural conditions. Thirdly, we used this approach to quantify the impact of the understory herbaceous vegetation on ecosystem carbon and water fluxes throughout the year and disentangle how ET components of the ecosystem relate to carbon dioxide exchange. We present one year data comparing modeled and measured stable oxygen isotope signatures (δ18O) of soil evaporation, confirming that the Craig and Gordon equation leads to good agreement with measured δ18O of

  13. Covariance of oxygen and hydrogen isotopic composition in plant water: Species effects

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Cooper, L.W.; DeNiro, M.J.

    1989-12-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species-specific factors on leaf water enrichment of D and {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leafmore » water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 18}O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes.« less

  14. The carbon and oxygen isotope records of reef-dwelling foraminifers subjected to five varied pCO2 seawater

    NASA Astrophysics Data System (ADS)

    Hikami, M.; Ishimura, T.; Suzuki, A.; Nojiri, Y.; Kawahata, H.

    2013-12-01

    Ocean acidification (OA) in response to rising atmospheric pCO2 is generally expected to reduce rates of calcification by reef calcifying organisms, with potentially severe implications for coral reef ecosystems. Reef dwelling foraminifera is one of the most important primary and carbonate producers in coral reef environments. Their shells are composed of high-Mg calcite and they are host to algal endosymbionts. In our previous culture experiment with two algal reef dwelling foraminifers, Amphisorus kudakajimensis and Calcarina gaudichaudii in the seawater of five different pCO2 conditions, net calcification of A. kudakajimensis was reduced under higher pCO2, whereas net calcification of C. gaudichaudii showed continued increasing trend with pCO2. These contrasting responses between the two species are possibly due to differences in calcification mechanisms and to links between calcification by the foraminifers and photosynthesis by the algal endosymbionts. But the factors affecting these calcification mechanisms are poorly understood. In this study, to get a better understanding of the effect of OA on their calcification, we cultured three reef dwelling foraminifers: Amphisorus hemprichii, belong to imperforate species, Baculogypsina sphaerulata, and C. gaudichaudii belong to perforate species, in the seawater of five different pCO2 conditions and we address the response of carbon and oxygen isotopes of the carbonate shells of foraminifers. The oxygen isotope ratio of cultured foraminiferal tests under five varied pCO2 seawater indicated no significant correlation to pCO2 values. On the other hand, the carbon isotope ratio of foraminiferal tests indicated heavy trend with rising pCO2 in all species. Alteration of carbonate chemistry result from ocean acidification may be effect strongly on carbon isotope composition relate to metabolic system (i.e. photosynthesis and respiration). In perforate species, both of oxygen and carbon isotope ratio were lighter than that

  15. Multiple Hadean crystallization and reworking events preserved in individual Jack Hills zircon grains

    NASA Astrophysics Data System (ADS)

    Bellucci, Jeremy; Nemchin, Alexander; Whitehouse, Martin; Snape, Joshua

    2017-04-01

    Five Hadean (>3.9 Ga) aged zircon grains from the Jack Hills metasedimentary belt have been investigated by an improved secondary ion mass spectrometry scanning ion image technique. This technique has the ability to obtain accurate and precise full U-Pb systematics on a scale <5 μm, as well as document the spatial distribution of U, Th and Pb. All five of the grains investigated here have complex cathodoluminescence patterns that correlate to different U, Th, and Pb concentration domains. The age determinations for these different chemical zones indicate multiple reworking events that are preserved in each grain and have affected the primary crystalized zircon on the scale of <10 μm, smaller than traditional ion microprobe spot analyses. These new scanning ion images and age determinations suggest that roughly half, if not all, previous analyses, including those of trace elements and various isotope systems, could have intersected several domains of unfractured zircon, thus making the interpretation of any trace element, Hf, or O isotopic data tenuous. Lastly, all of the grains analyzed here preserve at least two distinguishable 207Pb/206Pb ages. These ages are preserved in core-rim and/or complex internal textural relationships. These secondary events took place during at ca. 4.3, 4.2, 4.1, 4.0, and 3.7 Ga potentially indicating a sequence of magmatic and/or metamorphic events that recycled some volume of early crust during the Hadean and into Paleo- to Mesoarchean several times with an apparent periodicity of ca. 100 Ma.

  16. Oxygen Isotope Ratios of Magnetite in CI-Like Clasts from a Polymict Ureilite

    NASA Technical Reports Server (NTRS)

    Kita, N. T.; Defouilloy, C.; Goodrich, C. A.; Zolensky, M. E.

    2017-01-01

    Polymict ureilites contain a variety of Less than or equal to mm to cm sized non-ureilitic clasts, many of which can be identifed as chondritic and achondritic meteorite types. Among them, dark clasts have been observed in polymict ureilites that are similar to CI chondrites in mineralogy, containing phyllosilicates, magnetite, sulfide and carbonates. Bulk oxygen isotope analyses of a dark clast in Nilpena plot along the CCAM line and above the terrestrial fractionation line, on the O-poor extension of the main group ureilite trend and clearly different from bulk CI chondrites. One possible origins of such dark clast is that they represent aqueously altered precursors of ureilite parent body (UPB) that were preserved on the cold surface of the UPB. Oxygen isotope analyses of dark clasts are key to better understanding their origins. Oxygen isotope ratios of magnetite are of special interest because they reflect the compositions of the fluids in asteroidal bodies. In primitive chondrites, Delta O (= Delta O - 0.52× Delta O) values of magnetites are always higher than those of the bulk meteorites and represent minimum Delta O values of the initial O-poor aqueous fluids in the parent body. Previous SIMS analyses on magnetite and fayalite in dark clasts from the DaG 319 polymict ureilite were analytically difficult due to small grain sizes, though data indicated positive Delta O values of 3-4 per mille, higher than that of the dark clast in Nilpena (1.49per mille).

  17. Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Oerter, Erik; Singleton, Michael; Davisson, Lee

    The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

  18. Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

    DOE PAGES

    Oerter, Erik; Singleton, Michael; Davisson, Lee

    2017-10-22

    The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

  19. Triple oxygen and hydrogen isotopes of gypsum hydration water for quantitative paleo-humidity reconstruction

    NASA Astrophysics Data System (ADS)

    Gázquez, Fernando; Morellón, Mario; Bauska, Thomas; Herwartz, Daniel; Surma, Jakub; Moreno, Ana; Staubwasser, Michael; Valero-Garcés, Blas; Delgado-Huertas, Antonio; Hodell, David A.

    2018-01-01

    Atmospheric relative humidity is an important parameter affecting vegetation yet paleo-humidity proxies are scarce and difficult to calibrate. Here we use triple oxygen (δ17O and δ18O) and hydrogen (δD) isotopes of structurally-bound gypsum hydration water (GHW) extracted from lacustrine gypsum to quantify past changes in atmospheric relative humidity. An evaporation isotope-mass-balance model is used together with Monte Carlo simulations to determine the range of climatological conditions that simultaneously satisfy the stable isotope results of GHW, and with statistically robust estimates of uncertainty. We apply this method to reconstruct the isotopic composition of paleo-waters of Lake Estanya (NE Spain) and changes in normalized atmospheric relative humidity (RHn) over the last glacial termination and Holocene (from ∼15 to 0.6 cal. kyrs BP). The isotopic record indicates the driest conditions occurred during the Younger Dryas (YD; ∼12-13 cal. kyrs BP). We estimate a RHn of ∼40-45% during the YD, which is ∼30-35% lower than today. Because of the southward displacement of the Polar Front to ∼42°N, it was both windier and drier during the YD than the Bølling-Allerød period and Holocene. Mean atmospheric moisture gradually increased from the Preboreal to Early Holocene (∼11 to 8 cal. kyrs BP, 50-60%), reaching 70-75% RHn from ∼7.5 cal. kyrs BP until present-day. We demonstrate that combining hydrogen and triple oxygen isotopes in GHW provides a powerful tool for quantitative estimates of past changes in relative humidity.

  20. Zircon U-Pb ages, Hf isotope data, and tectonic implications of Early-Middle Triassic granitoids in the Ailaoshan high-grade metamorphic belt of Southeast Tibet

    NASA Astrophysics Data System (ADS)

    Wu, Wenbin; Liu, Junlai; Chen, Xiaoyu; Zhang, Lisheng

    2017-04-01

    The Ailaoshan tectonic belt, where the effects of the Paleo-Tethyan ocean evolution and Indian-Eurasian plate collision are superimposed, is one of the most significant geological discontinuities in western Yunnan province of southeast Tibet. An Ailaoshan micro-block within the belt is bounded by the Ailaoshan suture zone to the west and the Red River Fault to the east, and consists of low- and high-grade metamorphic belts. Late Permian-Middle Triassic granitoids that are widely distributed to the west of the Ailaoshan suture zone and within the Ailaoshan micro-block may yield significant information on the Tethyan tectonic evolution of the Ailaoshan tectonic belt. This study reports new LA-ICP-MS zircon U-Pb geochronology and Hf isotope data of four granitoids from the Ailaoshan high-grade metamorphic belt. Zircon grains from the Yinjie granitoid do not have inherited cores and yield a weighted mean U-Pb age of 247.1 ± 2.0 Ma. The zircon ɛ Hf( t) values range from 7.8 to 12.1, and Hf model ages from 775 to 546 Ma, indicating that the granitoid was derived from juvenile crust. The rims of zircons from the Majie and Yuanjiang granitoids yield weighted mean U-Pb ages of 239.5 ± 1.8 and 237.9 ± 2.6 Ma, respectively, whereas the cores yield ages of 1608-352 Ma. The ɛ Hf( t) values of zircon rims range from -20.4 to -5.3, yielding Hf model ages from 2557 to 1606 Ma and suggesting that the source magma of the Majie and Yuanjiang granitoids was derived from ancient crust. An additional granitoid located near the Majie Village yields a zircon U-Pb age of 241.2 ± 1.0 Ma. Based on our geochronological and geochemical data, combined with geological observations, we propose that the Ailaoshan micro-block was derived from the western margin of the Yangtze block, and is comparable to the Zhongzan and Nam Co micro-blocks. The presence of late Permian mafic rocks with rift-related geochemical characteristics within the Ailaoshan micro-block, together with granitoids derived

  1. The pressure dependence of oxygen-isotope-exchange rates between solution and apical oxygens on the UO 2(OH) 4 2- ion

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Harley, Steven J.; Ohlin, C. Andre; Johnson, Rene L.

    2011-04-06

    The pressure dependence of isotope exchange rate was determined for apical oxygen atoms in the UO 2(OH) 4 2-(aq) ion. The results can be interpreted to indicate an associative character of the reaction.

  2. Uranium-Lead Zircon Ages and Sr, Nd, and Pb Isotope Geochemistry of Selected Plutonic Rocks from Western Idaho

    USGS Publications Warehouse

    Unruh, Daniel M.; Lund, Karen; Kuntz, Mel A.; Snee, Lawrence W.

    2008-01-01

    Across the Salmon River suture in western Idaho, where allochthonous Permian to Cretaceous oceanic rocks are juxtaposed against Proterozoic North American rocks, a wide variety of plutonic rocks are exposed. Available data indicate much variation in composition, source, and structural state of these plutons. The plutonic rocks were long described as the western border zone of the Cretaceous Idaho batholith but limited pre-existing age data indicate more complicated origins. Because the affinity and age of the plutonic rocks cannot be reliably determined from field relations, TIMS U-Pb dating in conjunction with Sr, Nd, and Pb isotopic studies of selected plutons across the suture in western Idaho were undertaken. The data indicate three general groups of plutons including (1) those that intruded the island arc terranes during the Triassic and Jurassic, those that intruded near the western edge of oceanic rocks along the suture in the Early Cretaceous, and the plutons of the Idaho batholith that intruded Proterozoic North American rocks in the Late Cretaceous. Plutons that intruded Proterozoic North American rocks commonly include xenocrystic zircons and in several cases, ages could not be determined. The least radiogenic Sr and most radiogenic Nd are found among the Blue Mountains superterrane island arc samples. Suture-zone plutons have isotopic characteristics that span the range between Idaho batholith and island arc samples but mostly follow island arc signatures. Plutons of the Idaho batholith have the most radiogenic initial Pb and Sr ratios and the least radiogenic Nd of the samples analyzed.

  3. What can zircon ages from the Jack Hills detrital zircon suite really tell us about Hadean geodynamics?

    NASA Astrophysics Data System (ADS)

    Whitehouse, Martin; Nemchin, Alexander

    2015-04-01

    As the only direct sample of the Hadean Earth, detrital zircon grains from the Jack Hills, Western Australia, have been the subject of intense investigation over the almost three decades since their discovery. A wide variety of geochemical and isotopic analyses of these grains, as well as their mineral inclusions, have been used variously to support two fundamentally different models for Hadean geodynamics: (i) Some form of (not necessarily modern-style) plate recycling generating felsic (continental-type?) crust at the boundaries [1, 2], or conversely (ii) the persistence of a long-lived, stagnant basaltic lid within which magmatism occurred as a result of internal temperature perturbations and/or impacts [3, 4], a model also generally consistent with a wide range of observations from post-Hadean geochemical reservoirs. Despite the considerable time and resources expended, the majority of these studies uncritically accept the individual U-Pb zircon ages, even though their veracity is key to many of the interpretations [5, 6]. We report here the results of an in-depth evaluation of all published (and new) U-Pb ages from the Jack Hills zircon suite in order to define age populations that can be used with a high degree of confidence in geodynamic interpretations. A notable problem in the interpretation of U-Pb data from ancient zircon grains (including those as young as the Neoarchean) is that disturbance of the systematics even several 100 Ma after crystallization causes data to spread along the concordia curve without becoming discernably discordant within the relatively large error bounds associated with U/Pb ages from in situ dating methods (e.g. SIMS). While 207Pb/206Pb ages are typically more precise, individually they provide no means to detect Pb-loss-induced younging. However, if two or preferably more analyses have been made in the same zircon growth zone, a reasonable evaluation of the possibility of Pb-loss can be made. In the available Jack Hills zircon

  4. Multi-mode Li diffusion in natural zircons: Evidence for diffusion in the presence of step-function concentration boundaries

    NASA Astrophysics Data System (ADS)

    Tang, Ming; Rudnick, Roberta L.; McDonough, William F.; Bose, Maitrayee; Goreva, Yulia

    2017-09-01

    Micron- to submicron-scale observations of Li distribution and Li isotope composition profiles can be used to infer the mechanisms of Li diffusion in natural zircon. Extreme fractionation (20-30‰) within each single crystal studied here confirms that Li diffusion commonly occurs in zircon. Sharp Li concentration gradients frequently seen in zircons suggest that the effective diffusivity of Li is significantly slower than experimentally determined (Cherniak and Watson, 2010; Trail et al., 2016), otherwise the crystallization/metamorphic heating of these zircons would have to be unrealistically fast (years to tens of years). Charge coupling with REE and Y has been suggested as a mechanism that may considerably reduce Li diffusivity in zircon (Ushikubo et al., 2008; Bouvier et al., 2012). We show that Li diffused in the direction of decreasing Li/Y ratio and increasing Li concentration (uphill diffusion) in one of the zircons, demonstrating charge coupling with REE and Y. Quantitative modeling reveals that Li may diffuse in at least two modes in natural zircons: one being slow and possibly coupled with REE+Y, and the other one being fast and not coupled with REE+Y. The partitioning of Li between these two modes during its diffusion may depend on the pre-diffusion substitution mechanism of REE and Y in the zircon lattice. Based on our results, sharp Li concentration gradients are not indicative of limited diffusion, and can be preserved at temperatures >700 °C on geologic timescales. Finally, large δ7 Li variations observed in the Hadean Jack Hills zircons may record kinetic fractionation, rather than a record of ancient intense weathering in the granite source materials.

  5. Baseline shifts in coral skeletal oxygen isotopic composition: a signature of symbiont shuffling?

    NASA Astrophysics Data System (ADS)

    Carilli, J. E.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

    2013-06-01

    Decades-long records of the stable isotopic composition of coral skeletal cores were analyzed from four sites on the Mesoamerican Reef. Two of the sites exhibited baseline shifts in oxygen isotopic composition after known coral bleaching events. Changes in pH at the calcification site caused by a change in the associated symbiont community are invoked to explain the observed shift in the isotopic composition. To test the hypothesis that changes in symbiont clade could affect skeletal chemistry, additional coral samples were collected from Belize for paired Symbiodinium identification and skeletal stable isotopic analysis. We found some evidence that skeletal stable isotopic composition may be affected by symbiont clade and suggest this is an important topic for future investigation. If different Symbiodinium clades leave consistent signatures in skeletal geochemical composition, the signature will provide a method to quantify past symbiont shuffling events, important for understanding how corals are likely to respond to climate change.

  6. Ti-in-zircon thermometry: applications and limitations

    NASA Astrophysics Data System (ADS)

    Fu, Bin; Page, F. Zeb; Cavosie, Aaron J.; Fournelle, John; Kita, Noriko T.; Lackey, Jade Star; Wilde, Simon A.; Valley, John W.

    2008-08-01

    The titanium concentrations of 484 zircons with U-Pb ages of ˜1 Ma to 4.4 Ga were measured by ion microprobe. Samples come from 45 different igneous rocks (365 zircons), as well as zircon megacrysts (84) from kimberlite, Early Archean detrital zircons (32), and zircon reference materials (3). Samples were chosen to represent a large range of igneous rock compositions. Most of the zircons contain less than 20 ppm Ti. Apparent temperatures for zircon crystallization were calculated using the Ti-in-zircon thermometer (Watson et al. 2006, Contrib Mineral Petrol 151:413-433) without making corrections for reduced oxide activities (e.g., TiO2 or SiO2), or variable pressure. Average apparent Ti-in-zircon temperatures range from 500° to 850°C, and are lower than either zircon saturation temperatures (for granitic rocks) or predicted crystallization temperatures of evolved melts (˜15% melt residue for mafic rocks). Temperatures average: 653 ± 124°C (2 standard deviations, 60 zircons) for felsic to intermediate igneous rocks, 758 ± 111°C (261 zircons) for mafic rocks, and 758 ± 98°C (84 zircons) for mantle megacrysts from kimberlite. Individually, the effects of reduced a_{TiO2} or a_{SiO2}, variable pressure, deviations from Henry’s Law, and subsolidus Ti exchange are insufficient to explain the seemingly low temperatures for zircon crystallization in igneous rocks. MELTs calculations show that mafic magmas can evolve to hydrous melts with significantly lower crystallization temperature for the last 10-15% melt residue than that of the main rock. While some magmatic zircons surely form in such late hydrous melts, low apparent temperatures are found in zircons that are included within phenocrysts or glass showing that those zircons are not from evolved residue melts. Intracrystalline variability in Ti concentration, in excess of analytical precision, is observed for nearly all zircons that were analyzed more than once. However, there is no systematic change in Ti

  7. Validation of chlorine and oxygen isotope ratio analysis to differentiate perchlorate sources and to document perchlorate biodegradation

    USGS Publications Warehouse

    Paul B. Hatzinger,; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua

    2013-01-01

    Increased health concerns about perchlorate (ClO4-) during the past decade and subsequent regulatory considerations have generated appreciable interest in source identification. The key objective of the isotopic techniques described in this guidance manual is to provide evidence concerning the origin of ClO4- in soils and groundwater and, more specifically, whether that ClO4- is synthetic or natural. Chlorine and oxygen isotopic analyses of ClO4- provide the primary direct approach whereby different sources of ClO4- can be distinguished from each other. These techniques measure the relative abundances of the stable isotopes of chlorine (37Cl and 35Cl) and oxygen (18O, 17O, and 16O) in ClO4- using isotope-ratio mass spectrometry (IRMS). In addition, the relative abundance of the radioactive chlorine isotope 36Cl is measured using accelerator mass spectrometry (AMS). Taken together, these measurements provide four independent quantities that can be used to distinguish natural and synthetic ClO4- sources, to discriminate different types of natural ClO4-, and to detect ClO4- biodegradation in the environment. Other isotopic, chemical, and geochemical techniques that can be applied in conjunction with isotopic analyses of ClO4- to provide supporting data in forensic studies are also described.

  8. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.

    2015-07-01

    The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Femore » isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II) aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II) aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II) aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a

  9. Tooth enamel maturation reequilibrates oxygen isotope compositions and supports simple sampling methods

    NASA Astrophysics Data System (ADS)

    Trayler, Robin B.; Kohn, Matthew J.

    2017-02-01

    Oxygen isotope and major element zoning patterns of several disparate ungulate teeth were collected to evaluate the timing and geometry of enamel formation, records of isotope zoning, and tooth enamel sampling strategies. Isotopic zoning in mammalian tooth enamel encodes a sub-annual time series of isotopic variation of an animal's body water composition, with a damping factor that depends on the specifics of how enamel mineralizes. Enamel formation comprises two stages: precipitation of appositional enamel with a high CO3:PO4 ratio, followed by precipitation of maturational enamel with a lower CO3:PO4. If appositional and maturational enamel both contribute to isotope compositions (but with different CO3:PO4), and if isotope compositions vary seasonally, paired δ18O values from CO3 and PO4 profiles should show a spatial separation. CO3 isotope patterns should be shifted earlier seasonally than PO4 isotope patterns. Such paired profiles for new and published data show no resolvable shifts, i.e. CO3 and PO4 δ18O profiles show coincident maxima and minima. This coincidence suggests that enamel maturation reequilibrates appositional isotope compositions. If enamel maturation establishes enamel isotope compositions, the geometry of maturation, not apposition, should be considered when devising sampling protocols. X-ray maps of Ca zoning show that the majority of enamel (inner and middle layers) mineralizes heavily at a high angle to the external tooth surface and the enamel-dentine junction over length scales of 2-4 mm, while the outer enamel surface mineralizes more slowly. These data suggest that isotopic sampling strategies should parallel maturational geometry and focus on interior enamel to improve data fidelity. The magnitude of isotopic damping is also smaller than implied in previous studies, so tooth enamel zoning more closely reflects original body water isotopic variations than previously assumed.

  10. The mineralogical and chronological evidences of subducted continent material in deep mantle: diamond, zircon and rutile separated from the Horoman peridotite of Japan

    NASA Astrophysics Data System (ADS)

    Li, Y.; Yang, J.; Nida, K.; Yamamoto, S.; Lin, Y.; Li, Q.; Tian, M.; Kon, Y.; Komiya, T.; Maruyama, S.

    2017-12-01

    The Horoman peridotite complex is an Alpine-type orogenic lherzolite massif of upper-mantle in the Hidaka metamorphic belt, Hokkaido, Japan. The peridotite complex is composed of dunite, harzburgite, spinel lherzolite and plagioclase lherzolite, exhibits a conspicuous layered structure, which is a product of a Cretaceous to early Paleogene arc-trench system formed by westward subduction of an oceanic plate between the paleo-Eurasian and paleo-North American Plates. Various combinations of diamond, corundum, moissanite, zircon, monazite, rutile, and kyanite have been separated from spinel harzburgite (700 kg) and lherzolite (500 kg), respectively. The carbon isotopes analyses of diamond grains by Nano-SIMS yielded significant light carbon isotopes feature as δ13 CPDB values ranging from -29.2 ‰ to -17.2 ‰, with an average of -22.8±0.32 ‰. Zircon grains occur as sub-angular to round in morphological characteristics, similar to zircons of crustal sedimentary rocks. Many zircons contain small inclusions, comprise of quartz, apatite, rutile and muscovite. The U-Pb age of zircon grains analyzed using LA-ICP-MS and SIMS gave a wide age range, from the Jurassic to Archean (ca 159 - 3131 Ma). In the zircon age histogram, four age groups were identified; the age peaks are 2385 Ma, 1890 Ma, 1618 Ma and 1212 Ma, respectively. On the other hand, U-Pb ages of rutile grains analyzed using SIMS gave a peak of 370 Ma in age histogram. The mineralogical and chronological evidences of numerous crustal minerals in peridotite of Horoman suggest that the ancient continent material was subducted in deep mantle and recycled through the upper mantle by multicycle subduction processes.

  11. Coordinated U–Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

    Here, we present the results of a coordinated SIMS U–Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ~4.33 Ga, however they differ in thatmore » only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ≤300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb– 206Pb ages of 4.33 Ga. These grains are our best

  12. Coordinated U-Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

    NASA Astrophysics Data System (ADS)

    Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

    2017-04-01

    We present the results of a coordinated SIMS U-Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ∼4.33 Ga, however they differ in that only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ⩽300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb-206Pb ages of 4.33 Ga. These grains are our best constraints on

  13. Coordinated U–Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

    DOE PAGES

    Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

    2016-12-28

    Here, we present the results of a coordinated SIMS U–Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ~4.33 Ga, however they differ in thatmore » only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ≤300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb– 206Pb ages of 4.33 Ga. These grains are our best

  14. Generation and Reworking of Archaean and Hadean Crust

    NASA Astrophysics Data System (ADS)

    Hawkesworth, C.; Kemp, T.; Storey, C.; Dhuime, B.

    2008-12-01

    Combined Hf and O isotopes in well-dated zircons are increasingly used to investigate the age of the crustal source rocks of detrital and inherited zircons. O isotopes are used to screen out samples that may have a sediment contribution in the parental magma, since sediments yield hybrid model ages that are difficult to interpret. Mafic and granitic rocks also have different Lu/Hf ratios, and so in principle the Hf isotope ratios of zircons can be used to investigate the broad composition of the average crust. The unradiogenic Hf isotope compositions of the Jack Hills zircons from Western Australia indicate the existence of enriched (crustal) reservoirs by at least 4.3 Ga (Y. Amelin et al., 1998, Nature v. 399, p. 252- 255; T. M. Harrison et al., 2005, Science, v. 310, p. 1947-1950). We report in situ Hf isotope analyses of the Jack Hills zircons in which the Pb isotope age information is measured concurrently with the Hf isotope data. The simple data arrays provide clear evidence for Earth differentiation at 4.5 Ga, with the production of both continental crust-like material and a mafic crustal reservoir with higher Lu/Hf. The continued resampling of this reservoir over at least 1.5 Ga argues for a substantial stabilised volume of mafic crust, and, in tandem with oxygen isotope data, the existence of Hadean continents. Zircons remain poor windows into the upper mantle. We therefore investigate Nd isotopes in well-dated titanites; they have closure temperatures for Pb in the range 600-750oC and they can retain cores with distinct age and REE chemistry to subsequent rim overgrowths. Nd isotopes offer a complementary approach to Hf in zircon that can be used to construct the both depleted mantle evolution and crustal growth curves.

  15. Evidence for rapid climate change in North America during the latest Paleocene thermal maximum: oxygen isotope compositions of biogenic phosphate from the Bighorn Basin (Wyoming)

    NASA Astrophysics Data System (ADS)

    Fricke, Henry C.; Clyde, William C.; O'Neil, James R.; Gingerich, Philip D.

    1998-07-01

    Oxygen isotope records of Cenozoic sea water temperatures indicate that a rapid warming event known as the Latest Paleocene Thermal Maximum (LPTM) occurred during the otherwise gradual increase in world temperatures during the Late Paleocene and Early Eocene. Oxygen isotope analysis of the carbonate and phosphate components of hydroxyapatite found in mammalian tooth enamel and body scales of river-dwelling fish from the Bighorn Basin in Wyoming were made to investigate corresponding changes in the terrestrial climate. A comparison of carbonate and phosphate isotope data from modern and fossil material indicates that some diagenetic alteration of the fossil material has occurred, although systematically larger intra-tooth ranges in the oxygen isotope composition of carbonate indicate that it is more likely to have been affected than phosphate. Carbonate and phosphate from the ecologically diverse mammals and fishes both record a shift to higher oxygen isotope ratios at the same time and of the same duration as the LPTM. These shifts reflect a change in the isotopic composition of regional precipitation, which in turn provides the first evidence for continental climate change during the LPTM. Assuming the present-day relation between the oxygen isotope composition of precipitation and temperature applies to conditions in the past, and that animal physiology and behavior is relatively invariant over time, the isotopic shift is equivalent to an increase of surface temperature in western North America of several degrees. This result is consistent with the magnitude of high-latitude ocean warming, and provides a basis for relating marine and terrestrial oxygen isotope records to records of terrestrial biotic change.

  16. Oxygenation of Ediacaran Ocean recorded by iron isotopes

    NASA Astrophysics Data System (ADS)

    Fan, Haifeng; Zhu, Xiangkun; Wen, Hanjie; Yan, Bin; Li, Jin; Feng, Lianjun

    2014-09-01

    The increase in atmospheric oxygen during the late Neoproterozoic Era (ca. 800-542 Ma) may have stimulated the oxygenation of the deep oceans and the evolution of macroscopic multicellular organisms. However, the mechanism and magnitude of Neoproterozoic oxygenation remain uncertain. We present Fe isotopes, Fe species and other geochemical data for two sections of the Doushantuo Formation (ca. 635-551 Ma) deposited after the Nantuo glacial episode in the Yangtze Gorge area, South China. It is highlighted that highly positive δ56Fe values reflect a lower oxidation rate of Fe(II)aq under ferruginous conditions, and in turn near zero δ56Fe values indicate oxidizing conditions. Our study suggests that during the deposition of the bottom of Member II of the Doushantuo Formation the shallow seawater was oxic, but the deep water was characterized by ferruginous conditions, which is consistent with a redox chemical stratification model. Subsequent anoxic conditions under shallow seawater, represented by positive δ56Fe and negative δ13Ccarb excursions, should be ascribed to the upwelling of Fe(II)aq and dissolved organic carbon (DOC)-rich anoxic deep seawater. The oxidation of Fe (II)aq and DOC-rich anoxic deep seawater upon mixing with oxic shallow water provides an innovative explanation for the well-known negative δ13Ccarb excursions (ENC2) and positive δ56Fe excursions in the middle of Doushantuo Formation. Meanwhile, the upwelling Fe (II)aq- and DOC-rich anoxic deep seawater could increase photosynthetic activity. The balance between oxygen consumption and production was most important criteria for the oxygenation of Early Ediacaran Ocean and diversity of eukaryotic organisms.

  17. High-precision measurement of (186)Os/(188)Os and (187)Os/(188)Os: isobaric oxide corrections with in-run measured oxygen isotope ratios.

    PubMed

    Chu, Zhu-Yin; Li, Chao-Feng; Chen, Zhi; Xu, Jun-Jie; Di, Yan-Kun; Guo, Jing-Hui

    2015-09-01

    We present a novel method for high precision measurement of (186)Os/(188)Os and (187)Os/(188)Os ratios, applying isobaric oxide interference correction based on in-run measurements of oxygen isotopic ratios. For this purpose, we set up a static data collection routine to measure the main Os(16)O3(-) ion beams with Faraday cups connected to conventional 10(11) amplifiers, and (192)Os(16)O2(17)O(-) and (192)Os(16)O2(18)O(-) ion beams with Faraday cups connected to 10(12) amplifiers. Because of the limited number of Faraday cups, we did not measure (184)Os(16)O3(-) and (189)Os(16)O3(-) simultaneously in-run, but the analytical setup had no significant influence on final (186)Os/(188)Os and (187)Os/(188)Os data. By analyzing UMd, DROsS, an in-house Os solution standard, and several rock reference materials, including WPR-1, WMS-1a, and Gpt-5, the in-run measured oxygen isotopic ratios were proven to present accurate Os isotopic data. However, (186)Os/(188)Os and (187)Os/(188)Os data obtained with in-run O isotopic compositions for the solution standards and rock reference materials show minimal improvement in internal and external precision, compared to the conventional oxygen correction method. We concluded that, the small variations of oxygen isotopes during OsO3(-) analytical sessions are probably not the main source of error for high precision Os isotopic analysis. Nevertheless, use of run-specific O isotopic compositions is still a better choice for Os isotopic data reduction and eliminates the requirement of extra measurements of the oxygen isotopic ratios.

  18. Connection between ENSO and Asian Summer Monsoon Precipitation Oxygen Isotope

    NASA Astrophysics Data System (ADS)

    Cai, Z.; Tian, L.

    2016-12-01

    In an effort to understand the connection between El Niño Southern Oscillation (ENSO) and Asian Summer Monsoon (ASM) precipitation oxygen isotope, this study investigates the spatial and interannual patterns in summer (JJAS) monsoon precipitation δ18O and satellite water vapor isotope retrievals, especially those patterns associated with convection and vapor transport. Both precipitation and vapor isotope values exhibit a "V" shaped longitudinal pattern in their spatial variations, reflecting the gradual rainout and increase in convective intensity along vapor transport routes. In order to understand interannual variations, an ASM precipitation δ18O index (ASMOI) is introduced to measure the temporal variations in regional precipitation δ18O; and these variations are consistent with central Indo-Pacific convection and cloud-top height. The counter variations in the ASMOI in El Niño and La Niña years confirm the existence of a positive isotope- ENSO response (e.g., high values corresponding to warm phases) over the eastern Indian Ocean and southeastern Asia (80°E-120°E/10°S-30°N) as a response to changes in convection. However, JJAS vapor δD over the western Pacific (roughly east of 120oE) varies in opposition, due to the influence of water vapor transport. This opposite variation does not support the interpretation of precipitation isotope-ENSO relationship as changing proportion of vapor transported from different regions, but rather condensation processes associated with convection. These findings are important for studying past ASM and ENSO activity from various isotopic archives and have implications for the study of the atmospheric water cycle.

  19. Laser Spectroscopic Study on Oxygen Isotope Effects in Ozone Surface Decomposition

    NASA Astrophysics Data System (ADS)

    Minissale, Marco; Boursier, Corinne; Elandaloussi, Hadj; Te, Yao; Jeseck, Pascal; Rouille, Christian; Zanon-Willette, Thomas; Janssen, Christof

    2016-04-01

    The isotope kinetics of ozone formation in the Chapman reaction [1] O + O2 + M → O3 + M (1) provides the primary example for a chemically induced oxygen isotope anomaly and is associated with large [2] and mass independent [3] oxygen isotope enrichments in the product molecule, linked to a symmetry selection in the ozone formation kinetics [4-5]. The isotopic composition of ozone and its transfer to other molecules is a powerful tracer in the atmospheric and biogeochemical sciences [6] and serves as a primary model for a possible explanation of the oxygen isotopic heterogeneity in the Solar system [7-8]. Recently, the isotope fractionation in the photolytic decomposition process O3 + hν → O2 + O (2) using visible light has been studied in detail [9-10]. Much less is currently known about the isotope fractionation in the dry deposition or in the gas phase thermal decomposition of ozone O3 + M → O2 + O +M. (3) Here we report on first spectroscopic studies of non-photolytic ozone decomposition using a cw-quantum cascade laser at 9.5 μm. The concentration of individual ozone isotopomers (16O3,16O16O17O, and 16O17O16O) in a teflon coated reaction cell is followed in real time at temperatures between 25 and 150 °C. Observed ozone decay rates depend on homogeneous (reaction (3)) processes in the gas phase and on heterogeneous reactions on the wall. A preliminary analysis reveals agreement with currently recommended ozone decay rates in the gas phase and the absence of a large symmetry selection in the surface decomposition process, indicating the absence of a mass independent fractionation effect. This result is in agreement with previous mass spectrometer (MS) studies on heterogeneous ozone formation on pyrex [11], but contradicts an earlier MS study [12] on ozone surface decomposition on pyrex and quartz. Implications for atmospheric chemistry will be discussed. [1] Morton, J., Barnes, J., Schueler, B. and Mauersberger, K. J. Geophys. Res. 95, 901 - 907 (1990

  20. Cellular Metabolic Activity and the Oxygen and Hydrogen Stable Isotope Composition of Intracellular Water and Metabolites

    NASA Astrophysics Data System (ADS)

    Kreuzer-Martin, H. W.; Hegg, E. L.

    2008-12-01

    Intracellular water is an important pool of oxygen and hydrogen atoms for biosynthesis. Intracellular water is usually assumed to be isotopically identical to extracellular water, but an unexpected experimental result caused us to question this assumption. Heme O isolated from Escherichia coli cells grown in 95% H218O contained only a fraction of the theoretical value of labeled oxygen at a position where the O atom was known to be derived from water. In fact, fewer than half of the oxygen atoms were labeled. In an effort to explain this surprising result, we developed a method to determine the isotope ratios of intracellular water in cultured cells. The results of our experiments showed that during active growth, up to 70% of the oxygen atoms and 50% of the hydrogen atoms in the intracellular water of E. coli are generated during metabolism and can be isotopically distinct from extracellular water. The fraction of isotopically distinct atoms was substantially less in stationary phase and chilled cells, consistent with our hypothesis that less metabolically-generated water would be present in cells with lower metabolic activity. Our results were consistent with and explained the result of the heme O labeling experiment. Only about 40% of the O atoms on the heme O molecule were labeled because, presumably, only about 40% of the water inside the cells was 18O water that had diffused in from the culture medium. The rest of the intracellular water contained 16O atoms derived from either nutrients or atmospheric oxygen. To test whether we could also detect metabolically-derived hydrogen atoms in cellular constituents, we isolated fatty acids from log-phase and stationary phase E. coli and determined the H isotope ratios of individual fatty acids. The results of these experiments showed that environmental water contributed more H atoms to fatty acids isolated in stationary phase than to the same fatty acids isolated from log-phase cells. Stable isotope analyses of

  1. New triple oxygen isotope data of bulk and separated fractions from SNC meteorites: Evidence for mantle homogeneity of Mars

    NASA Astrophysics Data System (ADS)

    Ali, Arshad; Jabeen, Iffat; Gregory, David; Verish, Robert; Banerjee, Neil R.

    2016-05-01

    We report precise triple oxygen isotope data of bulk materials and separated fractions of several Shergotty-Nakhla-Chassigny (SNC) meteorites using enhanced laser-assisted fluorination technique. This study shows that SNCs have remarkably identical Δ17O and a narrow range in δ18O values suggesting that these meteorites have assimilated negligibly small surface materials (<5%), which is undetectable in the oxygen isotope compositions reported here. Also, fractionation factors in coexisting silicate mineral pairs (px-ol and mask-ol) further demonstrate isotopic equilibrium at magmatic temperatures. We present a mass-dependent fractionation line for bulk materials with a slope of 0.526 ± 0.016 (1SE) comparable to the slope obtained in an earlier study (0.526 ± 0.013; Franchi et al. 1999). We also present a new Martian fractionation line for SNCs constructed from separated fractions (i.e., pyroxene, olivine, and maskelynite) with a slope of 0.532 ± 0.009 (1SE). The identical fractionation lines run above and parallel to our terrestrial fractionation line with Δ17O = 0.318 ± 0.016‰ (SD) for bulk materials and 0.316 ± 0.009‰ (SD) for separated fractions. The conformity in slopes and Δ17O between bulk materials and separated fractions confirm oxygen isotope homogeneity in the Martian mantle though recent studies suggest that the Martian lithosphere may potentially have multiple oxygen isotope reservoirs.

  2. Devonian climate and reef evolution: Insights from oxygen isotopes in apatite

    NASA Astrophysics Data System (ADS)

    Joachimski, M. M.; Breisig, S.; Buggisch, W.; Talent, J. A.; Mawson, R.; Gereke, M.; Morrow, J. R.; Day, J.; Weddige, K.

    2009-07-01

    Conodonts, microfossils composed of carbonate-fluor apatite, are abundant in Palaeozoic-Triassic sediments and have a high potential to preserve primary oxygen isotope signals. In order to reconstruct the palaeotemperature history of the Devonian, the oxygen isotope composition of apatite phosphate was measured on 639 conodont samples from sequences in Europe, North America and Australia. The Early Devonian (Lochkovian; 416-411 Myr) was characterized by warm tropical temperatures of around 30 °C. A cooling trend started in the Pragian (410 Myr) with intermediate temperatures around 23 to 25 °C reconstructed for the Middle Devonian (397-385 Myr). During the Frasnian (383-375 Myr), temperatures increased again with temperatures to 30 °C calculated for the Frasnian-Famennian transition (375 Myr). During the Famennian (375-359 Myr), surface water temperatures slightly decreased. Reconstructed Devonian palaeotemperatures do not support earlier views suggesting the Middle Devonian was a supergreenhouse interval, an interpretation based partly on the development of extensive tropical coral-stromatoporoid communities during the Middle Devonian. Instead, the Devonian palaeotemperature record suggests that Middle Devonian coral-stromatoporoid reefs flourished during cooler time intervals whereas microbial reefs dominated during the warm to very warm Early and Late Devonian.

  3. Using Oxygen Isotopic Values in Order to Infer Palaeoclimatic Differences between Northern and Central-Southern Greece

    NASA Astrophysics Data System (ADS)

    Michael, Dimitra-Ermioni; Dotsika, Elissavet

    2017-12-01

    Even though isotopic analyses have been extensively implemented on human skeletal remains for the purpose of dietary reconstruction, less attention has been given to the ingested water and thus to the investigation of palaeoclimatic conditions. In particular, oxygen isotopic fingerprinting has never been applied on human skeletal remains from Greece for the abovementioned purpose before. The basic aim of the present study is to compare climatic conditions from two ancient populations, deriving from two different ecological locations; Edessa (Greek Macedonia; 2nd-4th c. AD) and Thebes (Sterea Hellas, 13th-14th c. AD). Oxygen values in Edessa are at -7.69 ±1.13 ‰ and -9.18 ±1.88 ‰ for tooth enamel and bone apatite respectively. On the other hand, oxygen signals in Thebes are at -5.8 ±2.16 ‰ and -9.23 ±1.3 % for the enamel and bone apatite respectively. The utility of oxygen isotopic signatures for the purpose of palaeoclimatic investigation lies on the fact that the ratio of 18 to 16O of meteoric precipitation, expressed as δ18O per mill (‰), relative to the international standard (vSMOW) varies geographically by temperature, humidity, evaporation, distance to the sea, altitude and latitude. Therefore, results as expected, point out that Edessa do presents more negative enamel isotopic values in relation to Thebes, however the noted difference is not observed for the bone apatite samples. The lack of bone apatite differentiation between sites could be attributed to cultural diversity (particularly in Thebes), shift in dietary habits due to migration or social status, climatic fluctuations within each site or to possible diagenetic alteration of bone apatite samples.

  4. Coupling of Uranium and Thorium Series Isotope Systematics for Age Determination of Late Pleistocene Zircons using LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Sakata, S.; Hirakawa, S.; Iwano, H.; Danhara, T.; Hirata, T.

    2014-12-01

    Zircon U-Th-Pb dating method is one of the most important tools for estimating the duration of magmatism by means of coupling of uranium, actinium and thorium decay series. Using U-Pb dating method, its reliability is principally guaranteed by the concordance between 238U-206Pb and 235U-207Pb ages. In case of dating Quaternary zircons, however, the initial disequilibrium effect on 230Th and 231Pa should be considered. On the other hands, 232Th-208Pb dating method can be a simple but powerful approach for investigating the age of crystallization because of negligible influence from initial disequilibrium effect. We have developed a new correction model for accurate U-Pb dating of the young zircon samples by taking into consideration of initial disequilibrium and a U-Pb vs Th-Pb concordia diagram for reliable age calibration was successfully established. Hence, the U-Th-Pb dating method can be applied to various zircons ranging from Hadean (4,600 Ma) to Quaternary (~50 ka) ages, and this suggests that further detailed information concerning the thermal history of the geological sequences can be made by the coupling of U-Th-Pb, fission track and Ar-Ar ages. In this presentation, we will show an example of U-Th-Pb dating for zircon samples from Sambe Volcano (3 to 100 ka), southwest Japan and the present dating technique using LA-ICP-MS.

  5. Oxygen isotope constraints on the alteration temperatures of CM chondrites

    NASA Astrophysics Data System (ADS)

    Verdier-Paoletti, Maximilien J.; Marrocchi, Yves; Avice, Guillaume; Roskosz, Mathieu; Gurenko, Andrey; Gounelle, Matthieu

    2017-01-01

    We report a systematic oxygen isotopic survey of Ca-carbonates in nine different CM chondrites characterized by different degrees of alteration, from the least altered known to date (Paris, 2.7-2.8) to the most altered (ALH 88045, CM1). Our data define a continuous trend that crosses the Terrestrial Fractionation Line (TFL), with a general relationship that is indistinguishable within errors from the trend defined by both matrix phyllosilicates and bulk O-isotopic compositions of CM chondrites. This bulk-matrix-carbonate (BMC) trend does not correspond to a mass-dependent fractionation (i.e., slope 0.52) as it would be expected during fluid circulation along a temperature gradient. It is instead a direct proxy of the degree of O-isotopic equilibration between 17,18O-rich fluids and 16O-rich anhydrous minerals. Our O-isotopic survey revealed that, for a given CM, no carbonate is in O-isotopic equilibrium with its respective surrounding matrix. This precludes direct calculation of the temperature of carbonate precipitation. However, the O-isotopic compositions of alteration water in different CMs (inferred from isotopic mass-balance calculation and direct measurements) define another trend (CMW for CM Water), parallel to BMC but with a different intercept. The distance between the BMC and CMW trends is directly related to the temperature of CM alteration and corresponds to average carbonates and serpentine formation temperatures of 110 °C and 75 °C, respectively. However, carbonate O-isotopic variations around the BMC trend indicate that they formed at various temperatures ranging between 50 and 300 °C, with 50% of the carbonates studied here showing precipitation temperature higher than 100 °C. The average Δ17O and the average carbonate precipitation temperature per chondrite are correlated, revealing that all CMs underwent similar maximum temperature peaks, but that altered CMs experienced protracted carbonate precipitation event(s) at lower temperatures than

  6. Could a secular increase in organic burial explain the rise of oxygen? Insights from a geological carbon cycle model constrained by the carbon isotope record

    NASA Astrophysics Data System (ADS)

    Krissansen-Totton, J.; Kipp, M.; Catling, D. C.

    2017-12-01

    The stable isotopes of carbon in marine sedimentary rock provide a window into the evolution of the Earth system. Conventionally, a relatively constant carbon isotope ratio in marine sedimentary rocks has been interpreted as implying constant organic carbon burial relative to total carbon burial. Because organic carbon burial corresponds to net oxygen production from photosynthesis, it follows that secular changes in the oxygen source flux cannot explain the dramatic rise of oxygen over Earth history. Instead, secular declines in oxygen sink fluxes are often invoked as causes for the rise of oxygen. However, constant fractional organic burial is difficult to reconcile with tentative evidence for low phosphate concentrations in the Archean ocean, which would imply lower marine productivity and—all else being equal—less organic carbon burial than today. The conventional interpretation of the carbon isotope record rests on the untested assumption that the isotopic ratio of carbon inputs into the ocean reflect mantle isotopic values throughout Earth history. In practice, differing rates of carbonate and organic weathering will allow for changes in isotopic inputs, as suggested by [1] and [2]. However, these inputs can not vary freely because large changes in isotopic inputs would induce secular trends in carbon reservoirs, which are not observed in the isotope record. We apply a geological carbon cycle model to all Earth history, tracking carbon isotopes in crustal, mantle, and ocean reservoirs. Our model is constrained by the carbon isotope record such that we can determine the extent to which large changes in organic burial are permitted. We find both constant organic burial and 3-5 fold increases in organic burial since 4.0 Ga can be reconciled with the carbon isotope record. Changes in the oxygen source flux thus need to be reconsidered as a possible contributor to Earth's oxygenation. [1] L. A. Derry, Organic carbon cycling and the lithosphere, in Treatise on

  7. Seasonality of bottom water temperature in the northern North Sea reconstructed from the oxygen isotope composition of the bivalve Arctica islandica

    NASA Astrophysics Data System (ADS)

    Trofimova, Tamara; Andersson, Carin; Bonitz, Fabian

    2017-04-01

    The seasonality of temperature changes is an important characteristic of climate. However, observational data for the ocean are only available for the last 150 year from a limited number of locations. Prior to 18th century information is only available from proxy reconstructions. The vast majority of such reconstructions depend on land-based archives, primarily from dendrochronology. Established marine proxy records for the ocean, especially at high latitudes, are both sparsely distributed and poorly resolved in time. Therefore, the identification and development of proxies for studying key ocean processes at sub-annual resolution that can extend the marine instrumental record is a clear priority in marine climate science. In this study, we have developed a record of early Holocene seasonal variability of bottom water temperature from the Viking Bank in the northern most North Sea. This area is of a particular interest since the hydrography is controlled by the inflow of Atlantic water. The reconstruction is based on the oxygen isotope composition of the growth increments in two sub-fossil shells of Arctica islandica (Bivalvia), dated to 9600-9335 cal. yr BP. By combining radiocarbon dating and sclerochronological techniques a floating chronology spanning over 200 years was constructed. Using the chronology as an age model, oxygen isotope measurements from 2 shells were combined into a 22-years long record. The results from this oxygen isotope record are compared with stable oxygen isotope profiles from modern shells to estimate changes in the mean state and seasonality between present and early Holocene. Shell-derived oxygen isotope values together with ice-volume corrected oxygen isotope values for the seawater were used to calculate bottom-water temperatures on a sub-annual time-scale. Preliminary results of the reconstructed early Holocene bottom water temperature indicate higher seasonality and lower minimum temperature compared to the present.

  8. Using Nitrogen and Oxygen Isotope Compositions of Nitrate to Distinguish Contaminant Sources in Hanford Soil and Groundwater

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Conrad, Mark; Bill, Markus

    2008-08-01

    The nitrogen ({delta}{sup 15}N) and oxygen ({delta}{sup 18}O) isotopic compositions of nitrate in the environment are primarily a function of the source of the nitrate. The ranges of isotopic compositions for nitrate resulting from common sources are outlined in Figure 1 from Kendall (1998). As noted on Figure 1, processes such as microbial metabolism can modify the isotopic compositions of the nitrate, but the effects of these processes are generally predictable. At Hanford, nitrate and other nitrogenous compounds were significant components of most of the chemical processes used at the site. Most of the oxygen in nitrate chemicals (e.g., nitricmore » acid) is derived from atmospheric oxygen, giving it a significantly higher {delta}{sup 18}O value (+23.5{per_thousand}) than naturally occurring nitrate that obtains most of its oxygen from water (the {delta}{sup 18}O of Hanford groundwater ranges from -14{per_thousand} to -18{per_thousand}). This makes it possible to differentiate nitrate from Hanford site activities from background nitrate at the site (including most fertilizers that might have been used prior to the Department of Energy plutonium production activities at the site). In addition, the extreme thermal and chemical conditions that occurred during some of the waste processing procedures and subsequent waste storage in select single-shell tanks resulted in unique nitrate isotopic compositions that can be used to identify those waste streams in soil and groundwater at the site (Singleton et al., 2005; Christensen et al., 2007). This report presents nitrate isotope data for soil and groundwater samples from the Hanford 200 Areas and discusses the implications of that data for potential sources of groundwater contamination.« less

  9. Paired N and O isotopic analysis of nitrate and nitrite in the Arabian Sea oxygen deficient zone

    NASA Astrophysics Data System (ADS)

    Martin, T. S.; Casciotti, K. L.

    2017-03-01

    The Arabian Sea is home to one of the three main oceanic oxygen deficient zones (ODZs). We present paired nitrogen (N) and oxygen (O) isotope measurements of nitrate (NO3-) and nitrite (NO2-) from the central Arabian Sea in order to understand the effects of N biogeochemistry on the distribution of these species in the low oxygen waters. Within the ODZ, NO2- accumulated in a secondary NO2- maximum (SNM), though the shape and magnitude of the SNM, along with the isotopic composition of NO3- and NO2-, were highly dependent on the location within the ODZ. We also explored water mass mixing within the Arabian Sea as an explanatory factor in the distribution of NO2- in the SNM. The intrusion of Persian Gulf Water at depth may influence the shape of the NO2- peak by introducing small amounts of dissolved oxygen (O2), favoring NO2- oxidation. There was also evidence that vertical mixing may play a role in shaping the top of the SNM peak. Finally, we present evidence for NO2- oxidation and NO2- reduction co-occurring within the ODZ, as has been previously suggested in the Arabian Sea, as well as in other ODZs. The decoupling of the N and O isotopes of NO3-, deviating from the expected 1:1 ratio for dissimilatory NO3- reduction, indicates that NO2- oxidation has a significant influence on the isotopic composition of NO3-. Additionally, the N isotopes of NO2- were generally fit well by Rayleigh curves for NO2- oxidation. However, the removal of dissolved inorganic nitrogen (DIN) within the domain reflects the importance of NO2- reduction to N2.

  10. Analysis of the interdecadal variability of summer precipitation in central Japan using a reconstructed 106 year long oxygen isotope record from tree ring cellulose

    NASA Astrophysics Data System (ADS)

    Kurita, Naoyuki; Nakatsuka, Takeshi; Ohnishi, Keiko; Mitsutani, Takumi; Kumagai, Tomo'omi

    2016-10-01

    We present a unique proxy for reconstructing the interannual variability of summer precipitation associated with the quasi-stationary front (Baiu front) in central Japan. The rainfall from the Baiu front has a relatively lower oxygen isotopic composition than other types of nonfrontal precipitation. The variability in the oxygen isotopes in summer rainfall is closely related to the Baiu frontal activity. In this study we used a mechanistic tree ring isotope model to reconstruct a 106 year long oxygen isotopic composition of precipitation during the early rainy season (June) based on the oxygen isotopic compositions of the annual rings of Chamaecyparis obtusa Endl trees from central Japan. The year-to-year variations of the isotopes over the most recent 25 years are associated with several teleconnection patterns that often lead to the Baiu precipitation anomalies in central Japan (such as the Pacific-Japan (PJ) pattern, Silk Road pattern, and wave train pattern along the polar jet). Yet none of these external forcing mechanisms apply further back in time. From the 1950s to 1980s, the interannual isotopic variability is predominantly related to local factors such as anomalous intensification/weakening of the Bonin High. Before the 1950s, the variability of the oxygen isotopic composition of precipitation is mainly associated with a wave train pattern along the polar jet. The isotopic variability is predominantly linked to the PJ pattern, while the PJ index is correlated with El Niño-Southern Oscillation. These findings suggest that the teleconnection patterns influencing Baiu precipitation variability vary according to interdecadal time scales during the twentieth century.

  11. Thermophysiology of Tyrannosaurus rex: Evidence from Oxygen Isotopes.

    PubMed

    Barrick, R E; Showers, W J

    1994-07-08

    The oxygen isotopic composition of vertebrate bone phosphate (delta(p)) is related to ingested water and to the body temperature at which the bone forms. The delta(p) is in equilibrium with the individual's body water, which is at a physiological steady state throughout the body. Therefore, intrabone temperature variation and the mean interbone temperature differences of well-preserved fossil vertebrates can be determined from the deltap variation. Values of delta(p) from a well-preserved Tyrannosaurus rex suggest that this species maintained homeothermy with less than 4 degrees C of variability in body temperature. Maintenance of homeothermy implies a relatively high metabolic rate that is similar to that of endotherms.

  12. Coordinated Petrography and Oxygen Isotopic Compositions of Al-Rich Chondrules from CV3 Chondrites

    NASA Astrophysics Data System (ADS)

    Zhang, M. M.; Lin, Y. T.; Tang, G. Q.; Li, X. H.

    2017-07-01

    In this study, we coordinated the petrology, bulk compositions and oxygen isotope compositions of 12 ARCs from Allende and Leoville and Ningqiang chondrites in order to elucidate any potential genetic relationships between ARCs, CAIs and FMCs.

  13. Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

    USGS Publications Warehouse

    Truesdell, A.H.

    1974-01-01

    Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275??C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO2 which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl2 and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (103 ln ??) between 1 molal solutions and pure water at 25, 100, and 275??C are: NaCl 0.0, -1.5, +1.0; KCl 0.0, -1.0, +2.0; LiCl -1.0, -0.6, -0.5; CaCl2 -0.4, -1.8, +0.8; MgCl2 -1.1, -0.7, -0.3; MgSO4 -1.1, +0.1, -; NaF (0.8 m) 0.0, -1.5, -0.3; and NH4Cl (0.55 m) 0.0, -1.2, -1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required. ?? 1974.

  14. Importance of the Lu-Hf isotopic system in studies of planetary chronology and chemical evolution

    USGS Publications Warehouse

    Patchett, P.J.

    1983-01-01

    The 176Lu-176Hf isotope method and its applications in earth sciences are discussed. Greater fractionation of Lu/Hf than Sm/Nd in planetary magmatic processes makes 176Hf 177Hf a powerful geochemical tracer. In general, proportional variations of 176Hf 177Hf exceed those of 143Nd l44Nd by factors of 1.5-3 in terrestrial and lunar materials. Lu-Hf studies therefore have a major contribution to make in understanding of terrestrial and other planetary evolution through time, and this is the principal importance of Lu-Hf. New data on basalts from oceanic islands show unequivocally that whereas considerable divergences occur in 176Hf 177Hf- 87Sr 86Sr and 143Nd l44Nd- 87Sr 86Sr diagrams, 176Hf 177Hf and 143Nd 144Nd display a single, linear isotopic variation in the suboceanic mantle. These discordant 87Sr 86Sr relationships may allow, with the acquisition of further Hf-Nd-Sr isotopic data, a distinction between processes such as mantle metasomatism, influence of seawater-altered material in the magma source, or recycling of sediments into the mantle. In order to evaluate the Hf-Nd isotopic correlation in terms of mantle fractionation history, there is a need for measurements of Hf distribution coefficients between silicate minerals and liquids, and specifically for a knowledge of Hf behavior in relation to rareearth elements. For studying ancient terrestrial Hf isotopic variations, the best quality Hf isotope data are obtained from granitoid rocks or zircons. New data show that very U-Pb discordant zircons may have upwardly-biased 176Hf 177Hf, but that at least concordant to slightly discordant zircons appear to be reliable carriers of initial 176Hf 177Hf. Until the controls on addition of radiogenic Hf to zircon are understood, combined zircon-whole rock studies are recommended. Lu-Hf has been demonstrated as a viable tool for dating of ancient terrestrial and extraterrestrial samples, but because it offers little advantage over existing methods, is unlikely to find

  15. Zircon U-Pb and molybdenite Re-Os geochronology and Sr-Nd-Pb-Hf isotopic constraints on the genesis of the Xuejiping porphyry copper deposit in Zhongdian, Northwest Yunnan, China

    NASA Astrophysics Data System (ADS)

    Leng, Cheng-Biao; Zhang, Xing-Chun; Hu, Rui-Zhong; Wang, Shou-Xu; Zhong, Hong; Wang, Wai-Quan; Bi, Xian-Wu

    2012-10-01

    The Xuejiping porphyry copper deposit is located in northwestern Yunnan Province, China. Tectonically, it lies in the southern part of the Triassic Yidun island arc. The copper mineralization is mainly hosted in quartz-dioritic and quartz-monzonitic porphyries which intruded into clastic-volcanic rocks of the Late Triassic Tumugou Formation. There are several alteration zones including potassic, strong silicific and phyllic, argillic, and propylitic alteration zones from inner to outer of the mineralized porphyry bodies. The ages of ore-bearing quartz-monzonitic porphyry and its host andesite are obtained by using the zircon SIMS U-Pb dating method, with results of 218.3 ± 1.6 Ma (MSWD = 0.31, N = 15) and 218.5 ± 1.6 Ma (MSWD = 0.91, N = 16), respectively. Meanwhile, the molybdenite Re-Os dating yields a Re-Os isochronal age of 221.4 ± 2.3 Ma (MSWD = 0.54, N = 5) and a weighted mean age of 219.9 ± 0.7 Ma (MSWD = 0.88). They are quite in accordance with the zircon U-Pb ages within errors. Furthermore, all of them are contemporary with the timing of the Garzê-Litang oceanic crust subduction in the Yidun arc. Therefore, the Xuejiping deposit could be formed in a continental margin setting. There are negative ɛNd(t) values ranging from -3.8 to -2.1 and relatively high initial 87Sr/86Sr ratios from 0.7051 to 0.7059 for the Xuejiping porphyries and host andesites. The (206Pb/204Pb)t, (207Pb/204Pb)t and (208Pb/204Pb)t values of the Xuejiping porphyries and host andesites vary from 17.899 to 18.654, from 15.529 to 15.626, and from 37.864 to 38.52, respectively, indicative of high radiogenic Pb isotopic features. In situ Hf isotopic analyses on zircons by using LA-MC-ICP-MS exhibit that there are quite uniform and slightly positive ɛHf(t) values ranging from -0.2 to +3.2 (mostly between 0 and +2), corresponding to relatively young single-stage Hf model ages from 735 Ma to 871 Ma. These isotopic features suggest that the primary magmas of the Xuejiping porphyries and

  16. Zircon Lu-Hf isotope systematics and U-Pb geochronology, whole-rock Sr-Nd isotopes and geochemistry of the early Jurassic Gokcedere pluton, Sakarya Zone-NE Turkey: a magmatic response to roll-back of the Paleo-Tethyan oceanic lithosphere

    NASA Astrophysics Data System (ADS)

    Karsli, Orhan; Dokuz, Abdurrahman; Kandemir, Raif

    2017-05-01

    The early Mesozoic was a critical era for the geodynamic evolution of the Sakarya Zone as transition from accretion to collision events in the region. However, its complex evolutionary history is still debated. To address this issue, we present new in situ zircon U-Pb ages and Lu-Hf isotope data, whole-rock Sr-Nd isotopes, and mineral chemistry and geochemistry data of plutonic rocks to better understand the magmatic processes. The Gokcedere pluton is mainly composed of gabbro and gabbroic diorite. LA-ICP-MS zircon U-Pb dating reveals that the pluton was emplaced in the early Jurassic (177 Ma). These gabbros and gabbroic diorites are characterized by relatively low SiO2 content of 47.09 to 57.15 wt% and high Mg# values varying from 46 to 75. The samples belong to the calc-alkaline series and exhibit a metaluminous I-type character. Moreover, they are slightly enriched in large ion lithophile elements (Rb, Ba, Th and K) and light rare earth elements and depleted in high field strength elements (Nb and Ti). Gabbroic rocks of the pluton have a depleted Sr-Nd isotopic composition, including low initial 87Sr/86Sr ranging from 0.705124 to 0.705599, relatively high ɛ Nd ( t) values varying from 0.1 to 3.5 and single-stage Nd model ages ( T DM1 = 0.65-0.95 Ga). In situ zircon analyses show that the rocks have variable and positive ɛ Hf ( t) values (4.6 to 13.5) and single-stage Hf model ages ( T DM1 = 0.30 to 0.65 Ga). Both the geochemical signature and Sr-Nd-Hf isotopic composition of the gabbroic rocks reveal that the magma of the studied rocks was formed by the partial melting of a depleted mantle wedge metasomatized by slab-derived fluids. The influence of slab fluids is mirrored by their trace-element characteristics. Trace-element modeling suggests that the primary magma was generated by a low and variable degree of partial melting ( 5-15%) of a depleted and young lithospheric mantle wedge consisting of phlogopite- and spinel-bearing lherzolite. Heat to melt the

  17. Oxygen Isotopes Archived in Subfossil Chironomids: Advancing a Promising Proxy for Lake Water Isotopes

    NASA Astrophysics Data System (ADS)

    Lasher, G. E.; Axford, Y.; Blair, N. E.

    2017-12-01

    Oxygen isotopes measured in subfossil chironomid head capsules (aquatic insect remains) in lake sediments are beginning to offer paleoclimate insights from previously under-studied areas of the world. Since the first published pilot study demonstrated the potential of chironomid δ18O to record lake water δ18O (Wooller et al., 2004), subsequent work has refined our understanding of this proxy: confirming via lab cultures that growth water controls head capsule δ18O (Wang et al., 2009), refining laboratory pretreatment protocols, and further validating the method by demonstrating strong agreement between carbonate and chironomid-derived paleo-isotope records (Verbruggen et al., 2009, 2010, 2011). However, outstanding questions remain, including the seasonality of chironomid growth, possible species-dependent vital effects, and diagenetic effects on the protein-chitin complex that comprise chironomid cuticles. To address some of these questions, we summarize available data from paired modern chironomid-lake water δ18O values from around the world and discuss climatic and environmental factors affecting chironomid isotopic signatures. We also present new data on the resistance of these subfossils to diagenesis and degradation throughout the late Quaternary using Fourier Transform Infrared Spectroscopy (FT-IR) and Pyrolysis Gas Chromatography Mass Spectrometry (Py-GC/MS) of chironomid remains up to >100,000 years old. As chironomids are nearly ubiquitous in lakes globally and, we argue, molecularly stable through glacial and interglacial cycles, this proxy has the potential to greatly expand the spatial and temporal resolution of Quaternary paleo-isotopes and thus climate records. In addition to reviewing and presenting new methodological advances, we also present applications of chironomid δ18O from millennial- to centennial-scale Holocene Greenland lake records.

  18. Oxygen isotope variations at the margin of a CAI records circulation within the solar nebula.

    PubMed

    Simon, Justin I; Hutcheon, Ian D; Simon, Steven B; Matzel, Jennifer E P; Ramon, Erick C; Weber, Peter K; Grossman, Lawrence; DePaolo, Donald J

    2011-03-04

    Micrometer-scale analyses of a calcium-, aluminum-rich inclusion (CAI) and the characteristic mineral bands mantling the CAI reveal that the outer parts of this primitive object have a large range of oxygen isotope compositions. The variations are systematic; the relative abundance of (16)O first decreases toward the CAI margin, approaching a planetary-like isotopic composition, then shifts to extremely (16)O-rich compositions through the surrounding rim. The variability implies that CAIs probably formed from several oxygen reservoirs. The observations support early and short-lived fluctuations of the environment in which CAIs formed, either because of transport of the CAIs themselves to distinct regions of the solar nebula or because of varying gas composition near the proto-Sun.

  19. Hydrogen and oxygen stable isotope ratios of milk in the United States.

    PubMed

    Chesson, Lesley A; Valenzuela, Luciano O; O'Grady, Shannon P; Cerling, Thure E; Ehleringer, James R

    2010-02-24

    Models of hydrogen and oxygen incorporation in human tissues recognize the impact of geographic location on the isotopic composition of fluid intake, but inputs can include nonlocal beverages, such as milk. Milk and cow drinking water were collected from dairies, and commercially available milk was purchased from supermarkets and fast food restaurants. It was hypothesized that milk water delta(2)H and delta(18)O values record geographic location information. Correlations between milk water isotope ratios and purchase location tap water were significant. However, the amount of variation in milk delta(2)H and delta(18)O values explained by tap water was low, suggesting a single estimation of fluid input isotope ratios may not always be adequate in studies. The delta(2)H and delta(18)O values of paired milk and cow drinking water were related, suggesting potential for geographical origin assignment using stable isotope analysis. As an application example, milk water delta(18)O values were used to predict possible regions of origin for restaurant samples.

  20. U-Pb isotopic systematics of zircons from prograde and retrograde transition zones in high-grade orthogneisses, Sri Lanka

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Baur, N.; Liew, T.C.; Todt, W.

    1991-07-01

    The authors present U-Pb zircon isotopic data from locally restricted prograde (arrested in situ charnockitization) and retrograde metamorphic transition zones, which are well exposed in Proterozoic orthogneisses tectonically interbanded with granulite facies supracrustal rocks of the Highland Group in Sri Lanka. These granitoid rocks yield apparent ages of 1942 {plus minus} 22 Ma, {approximately} 770 Ma, {approximately} 660 Ma, and {approximately} 560 Ma. All samples show severe Pb-loss some 550-560 Ma ago. The main phase of granulite-formation could not be dated unambiguously but is bracketed between {approximately} 660 Ma and {approximately} 550 Ma. The pervasive Pb-loss event around 550-560 Mamore » reflects the end of this period of high-grade metamorphism and was associated with widespread igneous activity and retrogression. This is constrained by the 550 {plus minus} 3 Ma intrusion age for a post-tectonic granite. They relate this late phase of thermal activity to crustal uplift of the Sri Lankan granulites. This data unambiguously prove the high-grade history of the Sri Lanka gneisses to be a late Precambrian event that may be related to the Pan-African evolution along the eastern part of Africa.« less

  1. Laboratory investigations of stable carbon and oxygen isotope ratio data enhance monitoring of CO2 underground

    NASA Astrophysics Data System (ADS)

    Barth, Johannes A. C.; Myrttinen, Anssi; Becker, Veith; Nowak, Martin; Mayer, Bernhard

    2014-05-01

    Stable carbon and oxygen isotope data play an important role in monitoring CO2 in the subsurface, for instance during carbon capture and storage (CCS). This includes monitoring of supercritical and gaseous CO2 movement and reactions under reservoir conditions and detection of potential CO2 leakage scenarios. However, in many cases isotope data from field campaigns are either limited due to complex sample retrieval or require verification under controlled boundary conditions. Moreover, experimentally verified isotope fractionation factors are also accurately known only for temperatures and pressures lower than commonly found in CO2 reservoirs (Myrttinen et al., 2012). For this reason, several experimental series were conducted in order to investigate effects of elevated pressures, temperatures and salinities on stable carbon and oxygen isotope changes of CO2 and water. These tests were conducted with a heateable pressure device and with glass or metal gas containers in which CO2 reacted with fluids for time periods of hours to several weeks. The obtained results revealed systematic differences in 13C/12C-distributions between CO2 and the most important dissolved inorganic carbon (DIC) species under reservoir conditions (CO2(aq), H2CO3 and HCO3-). Since direct measurements of the pH, even immediately after sampling, were unreliable due to rapid CO2 de-gassing, one of the key results of this work is that carbon isotope fractionation data between DIC and CO2 may serve to reconstruct in situ pH values. pH values reconstructed with this approach ranged between 5.5 and 7.4 for experiments with 60 bars and up to 120 °C and were on average 1.4 pH units lower than those measured with standard pH electrodes directly after sampling. In addition, pressure and temperature experiments with H2O and CO2 revealed that differences between the oxygen isotope ratios of both phases depended on temperature, water-gas ratios as well as salt contents of the solutions involved. Such

  2. Oxygen isotope fractionation between bird bone phosphate and drinking water.

    PubMed

    Amiot, Romain; Angst, Delphine; Legendre, Serge; Buffetaut, Eric; Fourel, François; Adolfssen, Jan; André, Aurore; Bojar, Ana Voica; Canoville, Aurore; Barral, Abel; Goedert, Jean; Halas, Stanislaw; Kusuhashi, Nao; Pestchevitskaya, Ekaterina; Rey, Kevin; Royer, Aurélien; Saraiva, Antônio Álamo Feitosa; Savary-Sismondini, Bérengère; Siméon, Jean-Luc; Touzeau, Alexandra; Zhou, Zhonghe; Lécuyer, Christophe

    2017-06-01

    Oxygen isotope compositions of bone phosphate (δ 18 O p ) were measured in broiler chickens reared in 21 farms worldwide characterized by contrasted latitudes and local climates. These sedentary birds were raised during an approximately 3 to 4-month period, and local precipitation was the ultimate source of their drinking water. This sampling strategy allowed the relationship to be determined between the bone phosphate δ 18 O p values (from 9.8 to 22.5‰ V-SMOW) and the local rainfall δ 18 O w values estimated from nearby IAEA/WMO stations (from -16.0 to -1.0‰ V-SMOW). Linear least square fitting of data provided the following isotopic fractionation equation: δ 18 O w  = 1.119 (±0.040) δ 18 O p  - 24.222 (±0.644); R 2  = 0.98. The δ 18 O p -δ 18 O w couples of five extant mallard ducks, a common buzzard, a European herring gull, a common ostrich, and a greater rhea fall within the predicted range of the equation, indicating that the relationship established for extant chickens can also be applied to birds of various ecologies and body masses. Applied to published oxygen isotope compositions of Miocene and Pliocene penguins from Peru, this new equation computes estimates of local seawater similar to those previously calculated. Applied to the basal bird Confuciusornis from the Early Cretaceous of Northeastern China, our equation gives a slightly higher δ 18 O w value compared to the previously estimated one, possibly as a result of lower body temperature. These data indicate that caution should be exercised when the relationship estimated for modern birds is applied to their basal counterparts that likely had a metabolism intermediate between that of their theropod dinosaur ancestors and that of advanced ornithurines.

  3. Oxygen isotope fractionation between bird bone phosphate and drinking water

    NASA Astrophysics Data System (ADS)

    Amiot, Romain; Angst, Delphine; Legendre, Serge; Buffetaut, Eric; Fourel, François; Adolfssen, Jan; André, Aurore; Bojar, Ana Voica; Canoville, Aurore; Barral, Abel; Goedert, Jean; Halas, Stanislaw; Kusuhashi, Nao; Pestchevitskaya, Ekaterina; Rey, Kevin; Royer, Aurélien; Saraiva, Antônio Álamo Feitosa; Savary-Sismondini, Bérengère; Siméon, Jean-Luc; Touzeau, Alexandra; Zhou, Zhonghe; Lécuyer, Christophe

    2017-06-01

    Oxygen isotope compositions of bone phosphate (δ18Op) were measured in broiler chickens reared in 21 farms worldwide characterized by contrasted latitudes and local climates. These sedentary birds were raised during an approximately 3 to 4-month period, and local precipitation was the ultimate source of their drinking water. This sampling strategy allowed the relationship to be determined between the bone phosphate δ18Op values (from 9.8 to 22.5‰ V-SMOW) and the local rainfall δ18Ow values estimated from nearby IAEA/WMO stations (from -16.0 to -1.0‰ V-SMOW). Linear least square fitting of data provided the following isotopic fractionation equation: δ18Ow = 1.119 (±0.040) δ18Op - 24.222 (±0.644); R 2 = 0.98. The δ18Op-δ18Ow couples of five extant mallard ducks, a common buzzard, a European herring gull, a common ostrich, and a greater rhea fall within the predicted range of the equation, indicating that the relationship established for extant chickens can also be applied to birds of various ecologies and body masses. Applied to published oxygen isotope compositions of Miocene and Pliocene penguins from Peru, this new equation computes estimates of local seawater similar to those previously calculated. Applied to the basal bird Confuciusornis from the Early Cretaceous of Northeastern China, our equation gives a slightly higher δ18Ow value compared to the previously estimated one, possibly as a result of lower body temperature. These data indicate that caution should be exercised when the relationship estimated for modern birds is applied to their basal counterparts that likely had a metabolism intermediate between that of their theropod dinosaur ancestors and that of advanced ornithurines.

  4. The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

    NASA Astrophysics Data System (ADS)

    von Sperber, C.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

    2015-07-01

    Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (myo-inositol hexakisphosphate, IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields available Pi and less phosphorylated inositol derivates as products. The hydrolysis of organic P compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'-monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as a substrate were prepared. During the hydrolysis of IP6 by phytase, four of the six Pi were released, and one oxygen atom from water was incorporated into each Pi. This incorporation of oxygen from water into Pi was subject to an apparent inverse isotopic fractionation (ϵ ~ 6 to 10 ‰), which was similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ~ 7 ‰), where less than three Pi were released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ~ -12 ‰), similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ϵ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking

  5. The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

    NASA Astrophysics Data System (ADS)

    Sperber, C. v.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

    2015-03-01

    Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields plant available inorganic phosphate (Pi) and less phosphorylated inositol derivates as products. The hydrolysis of organic P-compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as substrate were prepared. During the hydrolysis of IP6 by phytase, four Pi are released, and one oxygen atom from water is incorporated into each Pi. This incorporation of oxygen from water into Pi is subject to an apparent inverse isotopic fractionation (ϵ ∼ 6 to 10‰), which is similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ∼ 7‰) where less than three Pi are released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ∼ -12‰), again similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ɛ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking substrate-dependency of

  6. Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Cao, Xiaobin; Liu, Yun

    2011-12-01

    With a growing interest in small 17O-anomaly, there is a pressing need for the precise ratio, ln 17α/ln 18α, for a particular mass-dependent fractionation process (MDFP) (e.g., for an equilibrium isotope exchange reaction). This ratio (also denoted as " θ") can be determined experimentally, however, such efforts suffer from the demand of well-defined process or a set of processes in addition to high precision analytical capabilities. Here, we present a theoretical approach from which high-precision ratios for MDFPs can be obtained. This approach will complement and serve as a benchmark for experimental studies. We use oxygen isotope exchanges in equilibrium processes as an example. We propose that the ratio at equilibrium, θE ≡ ln 17α/ln 18α, can be calculated through the equation below: θa-bE=κa+(κa-κb){ln18βb}/{ln18α} where 18βb is the fractionation factor between a compound "b" and the mono-atomic ideal reference material "O", 18αa-b is the fractionation factor between a and b and it equals to 18βa/ 18βb and κ is a new concept defined in this study as κ ≡ ln 17β/ln 18β. The relationship between θ and κ is similar to that between α and β. The advantages of using κ include the convenience in documenting a large number of θ values for MDFPs and in estimating any θ values using a small data set due to the fact that κ values are similar among O-bearing compounds with similar chemical groups. Frequency scaling factor, anharmonic corrections and clumped isotope effects are found insignificant to the κ value calculation. However, the employment of the rule of geometric mean (RGM) can significantly affect the κ value. There are only small differences in κ values among carbonates and the structural effect is smaller than that of chemical compositions. We provide κ values for most O-bearing compounds, and we argue that κ values for Mg-bearing and S-bearing compounds should be close to their high temperature limitation (i.e., 0.5210 for

  7. Ceramic with zircon coating

    NASA Technical Reports Server (NTRS)

    Wang, Hongyu (Inventor)

    2003-01-01

    An article comprises a silicon-containing substrate and a zircon coating. The article can comprise a silicon carbide/silicon (SiC/Si) substrate, a zircon (ZrSiO.sub.4) intermediate coating and an external environmental/thermal barrier coating.

  8. Digesting the data - Effects of predator ingestion on the oxygen isotopic signature of micro-mammal teeth

    NASA Astrophysics Data System (ADS)

    Barham, Milo; Blyth, Alison J.; Wallwork, Melinda D.; Joachimski, Michael M.; Martin, Laure; Evans, Noreen J.; Laming, Belinda; McDonald, Bradley J.

    2017-11-01

    Biogenic minerals such as dental apatite have become commonly analysed archives preserving geochemical indicators of past environmental conditions and palaeoecologies. However, post-mortem, biogenic minerals are modified due to the alteration/replacement of labile components, and recent moves to utilise micro-mammal tooth δ18O signatures for refined Cenozoic terrestrial palaeoclimate reconstructions has lacked consideration of the chemical effects of predator digestion. Here, the physical and chemical condition of laboratory-raised mouse (Mus musculus) teeth have been investigated in conjunction with their bulk phosphate and tissue-specific δ18O values prior, and subsequent, to ingestion and excretion by various predator species (owls, mammals and a reptile). Substantial variability (up to 2‰) in the δ18O values of both undigested teeth and those ingested by specific predators suggests significant natural heterogeneity of individual prey δ18O. Statistically distinct, lower δ18O values (∼0.7‰) are apparent in teeth ingested by barn owls compared to undigested controls as a result of the chemically and enzymatically active digestive and waste-pellet environments. Overall, dentine tissues preserve lower δ18O values than enamel, while the greatest modification of oxygen isotope signals is exhibited in the basal enamel of ingested teeth as a result of its incompletely mineralised state. However, recognition of 18O-depletion in chemically purified phosphate analyses demonstrates that modification of original δ18O values is not restricted to labile oxygen-bearing carbonate and organic phases. The style and magnitude of digestive-alteration varies with predator species and no correlation was identified between specific physical or minor/trace-element (patterns or concentrations) modification of ingested teeth and disruption of their primary oxygen isotope values. Therefore, there is a current lack of any screening tool for oxygen isotope disruption as a result

  9. Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria

    NASA Astrophysics Data System (ADS)

    Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.

    2012-04-01

    Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7

  10. Oxygen isotope reservoirs in the outer asteroid belt inferred from oxygen isotope systematics of chondrule olivines and isolated forsterite and olivine grains in Tagish Lake-type carbonaceous chondrites, WIS 91600 and MET 00432

    NASA Astrophysics Data System (ADS)

    Yamanobe, Masakuni; Nakamura, Tomoki; Nakashima, Daisuke

    2018-03-01

    To understand oxygen isotope ratios and redox conditions of the chondrule formation environments of the outer rigions of the asteroid belt, we analyzed major element concentrations and oxygen isotope ratios of olivine grains in chondrules, isolated forsterite, and isolated olivine from the WIS 91600 and MET 00432 carbonaceous chondrites, which are thought to have originated from D-type asteroids located in the outer asteroid belt. The oxygen isotope ratios of individual chondrules and isolated grains show a wide variation in δ18O from -9.9‰ to +9.1‰ along the carbonaceous chondrite anhydrous mineral (CCAM) and primitive chondrule mineral (PCM) lines. The Δ17O (= δ17O - 0.52 × δ18O) values of the measured objects increase with decreasing Mg#; i.e., FeO-poor objects (Mg# > 90; type I chondrules and isolated forsterites) mainly have Δ17O values of ca. -6‰, and FeO-rich objects (Mg# < 90; type II chondrules and isolated olivines) have Δ17O values ranging from -3‰ to +2‰. Similar trends are observed for ferromagnesian silicate particles from comet Wild2 and CR chondrite chondrules, particularly in terms of FeO-rich objects with Δ17O values ranging from -3‰ to +2‰. It is suggested that FeO-rich objects formed in the outer regions of the asteroid belt and were transported to the outer solar nebular regions where comet Wild2 formed.

  11. Ancient xenocrystic zircon in young volcanic rocks of the southern Lesser Antilles island arc

    NASA Astrophysics Data System (ADS)

    Rojas-Agramonte, Yamirka; Williams, Ian S.; Arculus, Richard; Kröner, Alfred; García-Casco, Antonio; Lázaro, Concepción; Buhre, Stephan; Wong, Jean; Geng, Helen; Echeverría, Carlos Morales; Jeffries, Teresa; Xie, Hangqian; Mertz-Kraus, Regina

    2017-10-01

    The Lesser Antilles arc is one of the best global examples in which to examine the effects of the involvement of subducted sediment and crustal assimilation in the generation of arc crust. Most of the zircon recovered in our study of igneous and volcaniclastic rocks from Grenada and Carriacou (part of the Grenadines chain) is younger than 2 Ma. Within some late Paleogene to Neogene ( 34-0.2 Ma) lavas and volcaniclastic sediments however, there are Paleozoic to Paleoarchean ( 250-3469 Ma) xenocrysts, and Late Jurassic to Precambrian zircon ( 158-2667 Ma) are found in beach and river sands. The trace element characteristics of zircon clearly differentiate between different types of magmas generated in the southern Lesser Antilles through time. The zircon population from the younger arc (Miocene, 22-19 Ma, to Present) has minor negative Eu anomalies, well-defined positive Ce anomalies, and a marked enrichment in heavy rare earth elements (HREE), consistent with crystallization from very oxidized magmas in which Eu2 + was in low abundance. In contrast, zircon from the older arc (Eocene to mid-Oligocene, 30-28 Ma) has two different REE patterns: 1) slight enrichment in the light (L)REE, small to absent Ce anomalies, and negative Eu anomalies and 2) enriched High (H)REE, positive Ce anomalies and negative Eu anomalies (a similar pattern is observed in the xenocrystic zircon population). The combination of positive Ce and negative Eu anomalies in the zircon population of the older arc indicates crystallization from magmas that were variably, but considerably less oxidized than those of the younger arc. All the igneous zircon has positive εHf(t), reflecting derivation from a predominantly juvenile mantle source. However, the εHf(t) values vary significantly within samples, reflecting considerable Hf isotopic heterogeneity in the source. The presence of xenocrystic zircon in the southern Lesser Antilles is evidence for the assimilation of intra-arc crustal sediments and

  12. Crustal-scale recycling in caldera complexes and rift zones along the Yellowstone hotspot track: O and Hf isotopic evidence in diverse zircons from voluminous rhyolites of the Picabo volcanic field, Idaho

    USGS Publications Warehouse

    Drew, Dana L.; Bindeman, Ilya N.; Watts, Kathryn E.; Schmitt, Axel K.; Fu, Bin; McCurry, Michael

    2013-01-01

    Rhyolites of the Picabo volcanic field (10.4–6.6 Ma) in eastern Idaho are preserved as thick ignimbrites and lavas along the margins of the Snake River Plain (SRP), and within a deep (>3 km) borehole near the central axis of the Yellowstone hotspot track. In this study we present new O and Hf isotope data and U–Pb geochronology for individual zircons, O isotope data for major phenocrysts (quartz, plagioclase, and pyroxene), whole rock Sr and Nd isotope ratios, and whole rock geochemistry for a suite of Picabo rhyolites. We synthesize our new datasets with published Ar–Ar geochronology to establish the eruptive framework of the Picabo volcanic field, and interpret its petrogenetic history in the context of other well-studied caldera complexes in the SRP. Caldera complex evolution at Picabo began with eruption of the 10.44±0.27 Ma (U–Pb) Tuff of Arbon Valley (TAV), a chemically zoned and normal-δ18O (δ18O magma=7.9‰) unit with high, zoned 87Sr/86Sri (0.71488–0.72520), and low-εNd(0) (−18) and εHf(0) (−28). The TAV and an associated post caldera lava flow possess the lowest εNd(0) (−23), indicating ∼40–60% derivation from the Archean upper crust. Normal-δ18O rhyolites were followed by a series of lower-δ18O eruptions with more typical (lower crustal) Sr–Nd–Hf isotope ratios and whole rock chemistry. The voluminous 8.25±0.26 Ma West Pocatello rhyolite has the lowest δ18O value (δ18Omelt=3.3‰), and we correlate it to a 1,000 m thick intracaldera tuff present in the INEL-1 borehole (with published zircon ages 8.04–8.35 Ma, and similarly low-δ18O zircon values). The significant (4–5‰) decrease in magmatic-δ18O values in Picabo rhyolites is accompanied by an increase in zircon δ18O heterogeneity from ∼1‰ variation in the TAV to >5‰ variation in the late-stage low-δ18O rhyolites, a trend similar to what is characteristic of Heise and Yellowstone, and which indicates remelting of variably hydrothermally altered tuffs

  13. The oxygen isotope composition of baddeleyite and a test of crystal orientation effects during SIMS analysis

    NASA Astrophysics Data System (ADS)

    Ibanez-Mejia, M.; DesOrmeau, J. W.; Eddy, M. P.; Kitajima, K.; Valley, J. W.

    2017-12-01

    Baddeleyite, the monoclinic polymorph of ZrO2, is a relatively common accessory phase in undersaturated and alkaline igneous rocks that is rapidly developing into a widely-used tool for studying the age and initial 176Hf/177Hf composition of many terrestrial and planetary rocks that typically lack zircon. The prospect of combining U-Pb-Hf data from baddeleyite with δ18O information, as regularly done with zircon, could prove a very powerful addition to the `analytical toolbox' of the igneous petrologist and for studies of crust and mantle evolution. However, the oxygen isotope systematics of this mineral remain poorly explored, as are the potential analytical hurdles involved in obtaining accurate spatially-resolved δ18O data by SIMS. Here, we report laser fluorination δ18O measurements from two baddeleyite megacrysts from Kovdor (δ18O = 0.24 ± 0.11 ‰) and Phalaborwa (4.58 ± 0.11 ‰), which were subsequently analyzed by SIMS to explore their compositional homogeneity and potential as reference materials for correcting instrumental mass fractionation (IMF). Randomly oriented grain fragments analyzed by SIMS were subsequently mapped using high-resolution EBSD, such that the incidence angle of the Cs+ primary ion beam relative to the baddeleyite crystallographic axes could be determined for each spot. We found that: a) δ18O values for both crystals reproduce fairly well, but several apparent outliers (ca. 10% of all data) were measured with no evident correlation to orientation, cracks or inclusions, suggesting these might not be ideal standards; b) there is a systematic difference in mean measured IMFs of ca. 0.6 ‰ between the two baddeleyite crystals; c) mean 16OH/16O values for Phalaborwa (2.5x10-4) are significantly higher than those of Kovdor (2.9x10-6), suggesting that different degrees of radiation damage affect IMF; and d) there is no statistically significant correlation in our dataset (n= 96 spot analyses) between IMF and crystallographic

  14. Geochemistry, thermometry and isotope ratios on the same zircon crystals: the tandem use of quadrupole LA-ICPMS and CA-TIMS

    NASA Astrophysics Data System (ADS)

    Olin, P. H.; Schmitz, M. D.; Crowley, J. L.

    2011-12-01

    Current trends in igneous petrology include the extraction of diverse geochemical information from smaller sample targets by ever more efficient and cost effective means. Igneous zircons are repositories of several types of petrogenetic information, such as magmatic crystallization ages obtained using U-Pb geochronology, magmatic temperatures using Ti-in-zircon geothermometry, and magmatic differentiation and/or mixing trends using trace element contents. Here we demonstrate a tandem quadrupole LA-ICPMS and CA-TIMS approach on single zircon crystals and within domains in single crystals, which extracts all of these data from a single laser spot analysis and then guides the acquisition of CA-TIMS ages at precisions relevant to magmatic histories. We present data from zircon-bearing intrusive and extrusive rocks spanning the compositional spectrum, and highlight results from silicic volcanic rocks with different affinities. The utility of our approach is illustrated in zircons from the Temora diorite, a commonly used standard material which we analysed using 25-μm ablation spots placed on dozens of grains which had been previously annealed and chemically abraded prior to mounting in epoxy. Our LA-ICPMS results illustrate a 3- to 5-fold variation in trace element concentrations and trace element ratios over >150 degrees of cooling as estimated from Ti-in-zircon thermometry. Some geochemical parameters (e.g., Nb/Ta variations and Eu anomalies) are consistent with crystal fractionation during progressive crystallization, while others are bimodal (e.g., Hf and U contents), suggesting the mixing of crystal/magma batches prior to final solidification. LA-ICPMS U-Pb spot ages reproduce the accepted CA-TIMS age within 2% precision and accuracy, while our CA-TIMS results on the same grains constrain the development of the observed geochemical variability to within 100 ka. Other zircon standard materials to be presented include Plesovich syenite, FC1 gabbro, and R33 diorite

  15. New Insights on the Recrystallization and New Growth of Extensively Radiation-damaged Zircon

    NASA Astrophysics Data System (ADS)

    Hanchar, J. M.; Schmitz, M. D.; Wirth, R.

    2012-12-01

    Approximately 10 grams of cm-sized nearly metamict zircon crystals from the Saranac Prospect in the Bancroft District of Ontario were combined by breaking into small pieces and then ground under ethanol to a fine powder with an agate mortar and pestle in order to make enough homogeneously mixed material for multiple powder X-Ray and diffraction scans, high-resolution transmission electron microscopy (HR-TEM) measurements, and chemical abrasion isotope dilution thermal ionization mass spectrometry (CA-TIMS). While these large zircon crystals ground to a powder have a larger surface area and not in the same physical state (i.e., brown and metamict) as what is typically analyzed in single zircon CA-ID-TIMS U-Pb analysis (clear euhedral grains), the physical and chemical changes that occur during the heat treatment used in CA-TIMS are thought to be similar processes. Aliquots of the ground zircon powder were annealed in situ using a Pt furnace in a powder diffractometer during which time simultaneous powder diffraction patterns were acquired starting at 25°C, at elevated temperature (from 500°C to 1400°C) at selected time intervals, and then again at 25°C. The powder X-ray diffraction results indicate that below ~900°C the recrystallization of the zircon powder commences but is incomplete, even after 36 hours, with diffuse low intensity diffraction peaks. At 1150°C the zircon powder shows significant recrystallization. At 1150°C, the recrystallization is essentially complete in less than one hour. Before heating the zircon powder samples consisted of clear, transparent to brown, translucent, complexly zoned fragments. After heating at 900°C the zircon powder retained a smaller percentage of clear or brown complexly zoned fragments, while the majority of material had transformed to oscillatory or irregularly zoned, dominantly white opaque microcrystalline fragments. The clear fragments were hypothesized to be preexisting original crystalline zircon, the brown

  16. The Pressure Dependence of Oxygen Isotope Exchange Rates Between Solution and Apical Oxygen Atoms on the [UO2(OH)4]2- Ion

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Harley, Steven J.; Ohlin, C. André; Johnson, Rene L.

    2011-04-06

    Under pressure: The pressure dependence of isotope exchange rate was determined for apical oxygen atoms in the [UO2(OH)4]2-(aq) ion (see picture). The results can be interpreted to indicate an associative character of the reaction.

  17. Chemical abrasion-SIMS (CA-SIMS) U-Pb dating of zircon from the late Eocene Caetano caldera, Nevada

    USGS Publications Warehouse

    Watts, Kathryn E.; Coble, Matthew A.; Vazquez, Jorge A.; Henry, Christopher D.; Colgan, Joseph P.; John, David A.

    2016-01-01

    μm for CA and non-CA Caetano, R33 and TEMORA-2 zircons, and do not indicate variations in secondary ion sputtering rates due to chemical or structural changes from the CA treatment. Our new data underscore the potential for cryptic Pb-loss to go unrecognized in other geologically young magmatic centers that do not have zircons with high U, statistically discordant isotope ratios, high common Pb, or metamict textures.

  18. Extinct Plutonium Geochemistry of Ancient Hadean Zircons

    NASA Astrophysics Data System (ADS)

    Turner, G.; Gilmour, J.; Crowther, S.; Busfield, A.; Mojzsis, S.; Harrison, M.

    2005-12-01

    The abundance of 244Pu in the early solar system has important implications for r-process nucleosynthesis and models of noble gas transport within the Earth's mantle. Our recent discovery(1) of xenon isotopes from the in-situ decay of 244Pu in ancient Jack Hills zircons promises to provide a new time-sensitive window on the first 500 Ma of Earth history. We have extended this initial work by the use of resonance ioniisation mass spectrometry to analyse xenon released by stepped heating from 17 individual zircons with Pb-Pb ages in the range 3.95 to 4.18 Ga. Our immediate objectives are to determine the causes of variations in the inferred Pu/U ratios and in the longer term to determine the initial Pu/U ratio of the Earth. The Pu/U ratios calculated for individual zircons may be expected to vary as a result of igneous fractionation and also from differential loss of Pu and U fission xenon in the last 4 Ga. We have studied the effects of xenon loss by irradiating the zircons with thermal neutrons to generate xenon from 235U neutron fission in order to determine U/Xe ratios and apparent ages. 131Xe/134Xe and 132Xe/134Xe ratios can be used to calculate the relative contributions from 244Pu and 238U spontaneous fission and 235U neutron fission. The measured Pu/U ratios (back calculated to 4.56 Ga on the basis of the individual Pb-Pb ages) range from zero to 0.012. The highest ratio in our initial study was 0.008 (note that the published ratio has been revised upwards on the basis of improved decay parameters for 238U spontaneous fission). Comparison of Pb-Pb and U-Xe ages indicate varying amounts of xenon loss, over 50% in some cases. While this accounts for some of the variability in the inferred Pu/U, igneous fractionation may also play a part, and we are currently attempting to investigate this by a comparison with REE abundances. Reference: (1) Turner et al. (2004) Science, 306, 89-91.

  19. Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts.

    PubMed

    Michalski, Greg; Kolanowski, Michelle; Riha, Krystin M

    2015-01-01

    Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ(15)N values of synthetic and natural nitrates were 0 ± 2 ‰ similar to the air N2 from which they are derived. The δ(18)O values of synthetic nitrates were 23 ± 3 ‰, similar to air O2, and natural nitrate fertilizer δ(18)O values (55 ± 5 ‰) were similar to those observed in atmospheric nitrate. The Δ(17)O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ(17)O values of 18 ± 2 ‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.

  20. CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

    PubMed

    Lyons, J R; Young, E D

    2005-05-19

    The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

  1. Identification of Anthropogenic CO2 Using Triple Oxygen and Clumped Isotopes.

    PubMed

    Laskar, Amzad H; Mahata, Sasadhar; Liang, Mao-Chang

    2016-11-01

    Quantification of contributions from various sources of CO 2 is important for understanding the atmospheric CO 2 budget. Considering the number and diversity of sources and sinks, the widely used proxies such as concentration and conventional isotopic compositions (δ 13 C and δ 18 O) are not always sufficient to fully constrain the CO 2 budget. Additional constraints may help in understanding the mechanisms of CO 2 production and consumption. The anomaly in triple oxygen isotopes or 17 O excess (denoted by Δ 17 O) and molecules containing two rare isotopes, called clumped isotopes, are two recently developed tracers with potentials to independently constrain some important processes that regulate CO 2 in the atmosphere. The clumped isotope for CO 2 , denoted by Δ 47 , is the excess of 13 C 16 O 18 O over a random distribution of isotopes in a CO 2 molecule. We measured the concentrations of δ 13 C, δ 18 O, Δ 17 O, and Δ 47 in air CO 2 samples collected from the Hsuehshan tunnel (length: 12.9 km), and applied linear and polynomial regressions to obtain the fossil fuel end-members for all these isotope proxies. The other end-members, the values of all these proxies for background air CO 2 , are either assumed or taken as the values obtained over the tunnel and ocean. The fossil fuel (anthropogenic) CO 2 end-member values for δ 13 C, δ 18 O, Δ 17 O, and Δ 47 are estimated using the two component mixing approach: the derived values are -26.76 ± 0.25‰, 24.57 ± 0.33‰, -0.219 ± 0.021‰, and 0.267 ± 0.036‰, respectively. These four major CO 2 isotope tracers along with the concentration were used to estimate the anthropogenic contribution in the atmospheric CO 2 in urban and suburban locations. We demonstrate that Δ 17 O and Δ 47 have the potential to independently estimate anthropogenic contribution, and the advantages of these two over the conventional isotope proxies are discussed.

  2. Isotopic evidence for the diversity of late Quaternary loess in Nebraska: Glaciogenic and nonglaciogenic sources

    USGS Publications Warehouse

    Aleinikoff, John N.; Muhs, Daniel R.; Bettis, E. Arthur; Johnson, William C.; Fanning, C. Mark; Benton, Rachel

    2008-01-01

    Pb isotope compositions of detrital K-feldspars and U-Pb ages of detrital zircons are used as indicators for determining the sources of Peoria Loess deposited during the last glacial period (late Wisconsin, ca. 25–14 ka) in Nebraska and western Iowa. Our new data indicate that only loess adjacent to the Platte River has Pb isotopic characteristics suggesting derivation from this river. Most Peoria Loess in central Nebraska (up to 20 m thick) is non-glaciogenic, on the basis of Pb isotope ratios in K-feldspars and the presence of 34-Ma detrital zircons. These isotopic characteristics suggest derivation primarily from the Oligocene White River Group in southern South Dakota, western Nebraska, southeastern Wyoming, and northeastern Colorado. The occurrence of 10–25 Ma detrital zircons suggests additional minor contributions of silt from the Oligocene-Miocene Arikaree Group and Miocene Ogallala Group. Isotopic data from detrital K-feldspar and zircon grains from Peoria Loess deposits in eastern Nebraska and western Iowa suggest that the immediate source of this loess was alluvium of the Missouri River. We conclude that this silt probably is of glaciogenic origin, primarily derived from outwash from the western margin of the Laurentide Ice Sheet. Identification of the White River Group as the main provenance of Peoria Loess of central Nebraska and the Missouri River valley as the immediate source of western Iowa Peoria Loess indicates that paleowind directions during the late Wisconsin were primarily from the northwest and west, in agreement with earlier studies of particle size and loess thickness variation. In addition, the results are in agreement with recent simulations of non-glaciogenic dust sources from linked climate-vegetation modeling, suggesting dry, windy, and minimally vegetated areas in parts of the Great Plains during the last glacial period.

  3. Improved Quaternary North Atlantic stratigraphy using relative paleointensity (RPI), oxygen isotopes, and magnetic excursions (Invited)

    NASA Astrophysics Data System (ADS)

    Channell, J. E.

    2013-12-01

    Improving the resolution of Quaternary marine stratigraphy is one of the major challenges in paleoceanography. IODP Expedition 303/306, and ODP Legs 162 and 172, have yielded multiple high-resolution records (mean sedimentation rates in the 7-20 cm/kyr range) of relative paleointensity (RPI) that are accompanied by oxygen isotope data and extend through much of the Quaternary. Tandem fit of RPI and oxygen isotope data to calibrated templates (LR04 and PISO), using the Match protocol, yields largely consistent stratigraphies, implying that both RPI and oxygen isotope data are dominated by regional/global signals. Based on the recent geomagnetic field, RPI can be expected to be a global signal (i.e. dominated by the axial dipole field) when recorded at sedimentation rates less than several decimeters/kyr. Magnetic susceptibility, on the other hand, is a local/regional lithologic signal, and therefore less useful for long-distance correlation. Magnetic excursions are directional phenomena and, when adequately recorded, are manifest as paired reversals in which the virtual geomagnetic poles (VGPs) reach high latitudes in the opposite hemisphere, and they occupy minima in RPI records. Reversed VGPs imply that excursions are attributable to the main axial dipole, and therefore provide global stratigraphy. The so-called Iceland Basin excursion is recorded at many IODP/ODP sites and lies at the MIS 6/7 boundary at ~188 ka, with a duration of 2-3 kyr. Other excursions in the Brunhes chron are less commonly recorded because their duration (perhaps <~1 kyr) requires sedimentation rates >20 cm/kyr to be adequately recorded. On the other hand, several excursions within the Matuyama Chron are more commonly recorded in North Atlantic drift sediments due to relatively elevated durations. With some notable exceptions (e.g. Iberian Margin), high quality RPI records from North Atlantic sediments, together with magnetic excursions, can be used in tandem with oxygen isotope data to

  4. Developing Zircon as a Probe of Planetary Impact History

    NASA Astrophysics Data System (ADS)

    Wielicki, Matthew

    2014-12-01

    The identification of Meteor Crater in Arizona as an extraterrestrial impact by Eugene Shoemaker provided the first evidence of this geologic phenomenon and opened the door to a new field of research that has eventually lead to the identification of over ~150 terrestrial impact structures. Subsequently impacts have been evoked in the formation of the moon, delivery of volatiles and bio-precursors to early Earth, creation of habitats for the earliest life and, in more recent times, major mass extinction events. However, understanding the impact flux to the Earth-Moon system has been complicated by the constant weathering and erosion at Earth's surface and the complex nature of impactite samples such that only a hand full of terrestrial craters have been accurately and precisely dated. Currently 40Ar/39Ar step-heating analysis of impactite samples is commonly used to infer impact ages but can be problematic due to the presence of relic clasts, incomplete 40Ar outgassing or excess 40Ar, and recoil and shock effects. The work presented here attempts to develop zircon geochronology to probe planetary impact histories as an alternative to current methods and provides another tool by which to constrain the bolide flux to the Earth-Moon system. Zircon has become the premier geo-chronometer in earth science and geochemical investigation of Hadean zircon from Western Australia has challenged the long-standing, popular conception that the near-surface Hadean Earth was an uninhabitable and hellish world; Zircons may preserve environmental information regarding their formation and thus provide a rare window into conditions on early Earth. Isotopic and petrologic analyses of these ancient grains have been interpreted to suggest that early Earth was more habitable than previously envisioned, with water oceans, continental crust, and possibly even plate tectonics. The Hadean is also suspected to be a time of major planetary bombardment however identifying impact signatures within

  5. Bioapatite Recrystallization During Burning and its Effects on Phosphate Stable Oxygen Isotope Composition

    NASA Astrophysics Data System (ADS)

    Munro, L. E.; Longstaffe, F. J.; White, C. D.

    2003-04-01

    Stable oxygen isotopic compositions of phosphate from mammal bones are commonly used in palaeoenvironmental reconstructions. However, preservation of the primary bone oxygen isotopic composition is of concern during post-mortem alteration. Particularly in studies of archaeological interest, bone samples are often obtained from contexts where they have been heated, either in middens, or near hearths. Hence, in addition to alteration resulting from natural diagenetic processes, burning may also have contributed to modification of the primary oxygen isotopic signal. Various techniques can be employed to evaluate the degree of preservation of bone during burning. Anthropologists commonly use colour comparisons (Munsell Colour Chart) to assess the temperature of burning. Recrystallization of the carbonated hydroxyapatite, i.e., bioapatite, in bone is more rigorously assessed using X-ray diffraction and infra-red spectroscopy. In this study, freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned, incrementally burned, colour-typed, ground to a standardized grain-size (45<63mm), and analysed using differential thermal analysis (DTA), thermogravimetric analysis (TGA), rotating anode X-ray diffraction (XRD), and Fourier transform infra-red spectroscopy (FTIR). Heating temperatures ranged from 25 to 900^oC, increasing in intervals of 25^oC. Two major stages of weight loss were recorded in the DTA/TGA data, 25-260^oC representing dehydration, and 270-600^oC reflecting incineration of organic matter. The end-product (900^oC) resembled pure hydroxyapatite. XRD patterns of the bioapatite remained virtually unchanged from 25-250^oC, after which peak intensity, sharpness and the XRD crystallinity index (XRD CI) increased from 0.80 at 250^oC to 1.26 at 900^oC. FTIR patterns showed analogous behaviour, demonstrating minimal fluctuations in the FTIR crystallinity

  6. Kinetic theory of oxygen isotopic exchange between minerals and water

    USGS Publications Warehouse

    Criss, R.E.; Gregory, R.T.; Taylor, H.P.

    1987-01-01

    Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

  7. Growth patterns of an intertidal gastropod as revealed by oxygen isotope analysis

    NASA Astrophysics Data System (ADS)

    Bean, J. R.; Hill, T. M.; Guerra, C.

    2007-12-01

    The size and morphology of mollusk shells are affected by environmental conditions. As a result, it is difficult to assess growth rate, population age structure, shell morphologies associated with ontogenetic stages, and to compare life history patterns across various environments. Oxygen isotope analysis is a useful tool for estimating minimum ages and growth rates of calcium carbonate secreting organisms. Calcite shell material from members of two northern California populations of the intertidal muricid gastropod Acanthinucella spirata was sampled for isotopic analysis. Individual shells were sampled from apex to margin, thus providing a sequential record of juvenile and adult growth. A. spirata were collected from a sheltered habitat in Tomales Bay and from an exposed reef in Bolinas. Abiotic factors, such as temperature, wave exposure, and substrate consistency, and biotic composition differ significantly between these sites, possibly resulting in local adaptations and variation in life history and growth patterns. Shell morphology of A. spirata changes with age as internal shell margin thickenings of denticle rows associated with external growth bands are irregularly accreted. It is not known when, either seasonally and/or ontogentically, these thickenings and bands form or whether inter or intra-populational variation exists. Preliminary results demonstrate the seasonal oxygen isotopic variability present at the two coastal sites, indicating 5-6 degC changes from winter to summertime temperatures; these data are consistent with local intertidal temperature records. Analysis of the seasonal patterns indicate that: 1) differences in growth rate and seasonal growth patterns at different ontogenetic stages within populations, and 2) differences in growth patterns and possibly age structure between the two A. spirata populations. These findings indicate that isotopic analyses, in addition to field observations and morphological measurements, are necessary to

  8. Detrital zircon study along the Tsangpo River, SE Tibet

    NASA Astrophysics Data System (ADS)

    Liang, Y.; Chung, S.; Liu, D.; O'Reilly, S. Y.; Chu, M.; Ji, J.; Song, B.; Pearson, N. J.

    2004-12-01

    The interactions among tectonic uplift, river erosion and alluvial deposition are fundamental processes that shape the landscape of the Himalayan-Tibetan orogen since its creation from early Cenozoic time. To better understand these processes around the eastern Himalayan Syntaxis, we conducted a study by systematic sampling riverbank sediments along the Tsangpo River, SE Tibet. Detrital zircons separated from the sediments were subjected to U-Pb dating by the SHRIMP II at the Beijing SHRIMP Center and then in-situ measurements of Hf isotope ratios using LA-MC-ICPMS at GEMOC. These results, together with U-Pb ages and Hf isotope data that we recently obtained for the Transhimalayan plutonic and surrounding basement rocks, allow a more quantitative examination of the provenance or protosource areas for the river sediments. Consequently, the percentage inputs from these source areas can be estimated. Our study indicates that, before the Tsangpo River flows into the Namche Barwa Syntaxis of the eastern Himalayas where the River forms a 180° Big Bend gorge and crosscuts the Himalayan sequences, the Gangdese batholith that crops out just north of the River appear to be an overwhelming source accounting for ˜50 % of the bank sediments. The Tethyan Himalayan sequences south of the River are the second important source, with an input of ˜25 %. The proportion of sediment supply changes after the River enters the Big Bend gorge and turns to south: ˜25 % of detrital zircons are derived from the Greater Himalayas so that the input from the Tethyan Himalayas decreases (< 10 %) despite those from the Gangdese batholith remains high ( ˜40 %). Comparing with the sediment budget of the Brahmaputra River in the downstream based on literature Sr, Nd and Os isotope information, which suggests dominant ( ˜90-60 %) but subordinate ( ˜10-40 %) contributions by the (Greater and Lesser) Himalayan and Tibetan (including Tethyan Himalayan) rocks, respectively, the change is interpreted

  9. [Impacts of dominated landscape types on hydrogen and oxygen isotope effects of spring water in the Hani Rice Terraces].

    PubMed

    Jiao, Yuan Mei; Liu, Cheng Jing; Liu, Xin; Liu, Zhi Lin; Ding, Yin Ping

    2017-07-18

    Analysis of hydrogen and oxygen stable isotopes is an effective method to track the water cycle in watershed. Impact of landscape pattern on the isotope effects of spring water is a new interdisciplinary topic between landscape ecology and isotope hydrology. Taking the Quanfuzhuang River basin located in the core area of UNESCO World Cultural Heritage of Honghe Hani Rice Terrace as the object, collecting the monthly samples of 78 points of spring water and 39 precipitation at altitude of 1500 m (terraces), 1700 m (terraces) and 1900 m (forest) from March 2015 to March 2016, we analyzed the hydrogen and oxygen stable isotopes of water samples under the different landscape types. The results indicated that the dominated landscape types were forests and rice terraces, being 66.6% and 22.1% of the whole landscape area respectively, and they had a spatial vertical pattern of forest located at the mountain top and rice terraces at the down-slope. The correlation analysis showed that the spring water not only came from the precipitation, but also from other water sources which had a more positive δ 18 O and δD values, the spring water in up-slope forests mainly came from precipitation, while that in down-slope rice terraces came from precipitation, ri-ver water, rice terrace water and under ground water. Therefore, the mixing effects of spring water δ 18 O and δD were more significant in rice terraces. The overall altitude effect of the hydrogen and oxygen stable isotopes in spring water was obvious. The linear decreasing rates of δ 18 O and δD values were -0.125‰·(100 m) -1 and -0.688‰·(100 m) -1 , respectively. The deuterium surplus value increased with the altitude because of the impacts of landscape pattern and the local cycle of water isotopes. In summary, the dominant landscape types had a significant impact on the hydrogen and oxygen isotopes of spring water, which could be used as response indicator to reveal the impacts of landscape pattern on

  10. Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

    NASA Technical Reports Server (NTRS)

    Snead, C. J.; Keller, L. P.; McKeegan, K. D.; Messenger, S.

    2016-01-01

    Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass

  11. Using thallium isotopes in the 2.63 Ga Jeerinah Formation from Hamersley Basin, Western Australia, to constrain ancient seafloor oxygenation

    NASA Astrophysics Data System (ADS)

    Holdaway, B. J.; Owens, J. D.; Nielsen, S.; Anbar, A. D.; Ostrander, C. M.

    2017-12-01

    Understanding the chemical and biological innovation and evolution of the global ocean is pivotal in understanding the processes for how early life on Earth and potentially habitable planets advanced. Previous research on early-Earth oxygenation has revealed a rise in atmospheric [O2] 2.32 billion years ago, coined the Great Oxidation Event, or GOE. Many lines of evidence, however, suggest continental oxidative weathering as early as 3.0 Ga, with possibilities of complementary ocean oxygenation. Modeling of the geochemical data suggests small oxygen "oases" prior to whiffs of O2, or even widespread oxygen-rich margins. However, constraining the extent and timing of oceanic oxygenation is difficult as proxies fall short in detecting early ocean oxygenation. Importantly, the formation and preservation of manganese (Mn) in the form of manganese-oxides requires an oxygenated water-column that penetrates the sediment-water interface. Until recently, tracking the global burial of Mn-oxides was very difficult, largely compounded by an incomplete ancient geologic record. Here we use thallium (Tl), a new and novel isotope system to better constrain marine [O2], specifically by constraining the global burial of Mn-oxides. Recently, it has been shown that modern seawater Tl isotope composition is faithfully recorded in anoxic to euxinic (anoxic and sulfidic) sediments. Nearly all isotopic inputs: riverine, dust, volcanic, hydrothermal, and benthic recycling of Tl into the ocean are constant with ɛ205Tl -2. In contrast, the two primary outputs impart significant fractionations, these outputs being the burial of Mn-oxides (ɛ205Tl +12) and altered oceanic crust (ɛ205Tl -10). Thus, seawater is mainly dictated by the mass balance of the outputs (Mn-oxides and altered oceanic crust) which, for short-term events, is likely driven by the amount of Mn-oxide burial. Tl isotope analyses of the dominantly euxinic 2.5 Ga Mt. McRae Shale from the Hamersley Basin, Western Australia

  12. The 230Th correction is the 1st priority for accurate dates of young zircons: U/Th partitioning experiments and measurements

    NASA Astrophysics Data System (ADS)

    Krawczynski, M.; McLean, N.

    2017-12-01

    One of the most accurate and useful ways of determining the age of rocks that formed more than about 500,000 years ago is uranium-lead (U-Pb) geochronology. Earth scientists use U-Pb geochronology to put together the geologic history of entire regions and of specific events, like the mass extinction of all non-avian dinosaurs about 66 million years ago or the catastrophic eruptions of supervolcanoes like the one currently centered at Yellowstone. The mineral zircon is often utilized because it is abundant, durable, and readily incorporates uranium into its crystal structure. But it excludes thorium, whose isotope 230Th is part of the naturally occurring isotopic decay chain from 238U to 206Pb. Calculating a date from the relative abundances of 206Pb and 238U therefore requires a correction for the missing 230Th. Existing experimental and observational constraints on the way U and Th behave when zircon crystallizes from a melt are not known precisely enough, and thus currently the uncertainty in dates introduced by they `Th correction' is one of the largest sources of systematic error in determining dates. Here we present preliminary results on our study of actinide partitioning between zircon and melt. Experiments have been conducted to grow zircon from melts doped with U and Th that mimic natural magmas at a range of temperatures, and compositions. Synthetic zircons are separated from their coexisting glass and using high precision and high-spatial-resolution techniques, the abundance and distribution of U and Th in each phase is determined. These preliminary experiments are the beginning of a study that will result in precise determination of the zircon/melt uranium and thorium partition coefficients under a wide variety of naturally occurring conditions. This data will be fit to a multidimensional surface using maximum likelihood regression techniques, so that the ratio of partition coefficients can be calculated for any set of known parameters. The results of

  13. Zircon U-Pb chronology, geochemistry and Sr-Nd-Pb isotopic compositions of the Volcanic Rocks in the Elashan area, NW China: petrogenesis and tectonic implications

    NASA Astrophysics Data System (ADS)

    Zhou, H.; Wei, J.; Shi, W.; Li, P.; Chen, M.; Zhao, X.

    2017-12-01

    Elashan area is located in the intersection of the East Kunlun Orogenic Belt (EKOB) and the West Qinling Orogenic (WQOB). We present petrology, zircon U-Pb ages, whole-rock geochemistry and Sr-Nd-Pb isotopic compositions from the andesite and felsic volcanic rocks (rhyolite and rhyolitic tuffs) in Elashan group volcanic rock. The LA-ICP-MS zircon U-Pb age data indicate that the volcanic rocks are emplaced at 250 247 Ma. The volcanic rocks have high -K and aluminum - peraluminous characteristics, A/CNK = 1.07 1.82, δ ranges from 1.56 2.95, the main body is calc-alkaline rock. They are enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs) and depleted in some high field strength elements (HFSEs, e.g., Nb, Ta, P and Ti), while having a flat heavy REE (HREEs) pattern. The ∑REE values of 178.68 to 298.11 ppm, average 230.50 ppm. The LREE/HREE values of 4.39 to 11.78 ppm, average 6.77 ppm. REE fractionation is obvious, REE distribution curve was right smooth, and have slightly negative Eu anomalies (Eu/Eu*=0.44-0.80, average 0.60), which as similar to the island arc volcanic rocks. The volcanic rocks have initial 87Sr/86Sr ratios of 0.71028-0.71232, ɛNd(t) values of -6.7 to -7.6, with T2DM-Nd ranging from 1561 to 1640 Ma. Pb isotopic composition (206 Pb / 204 Pb)t = 18.055 18.330, (207 Pb / 204 Pb)t = 15.586 15.618, (208 Pb / 204 Pb)t = 37.677 38.332. Geochemical and Sr-Nd-Pb isotopes indicates that Elashan group volcanic magma derived mainly from the lower crust. Elashan group volcanic rocks is the productive East Kunlun block and West Qinling block collision, which makes the thicken crust caused partial melting in the study area. The source rocks is probably from metamorphic sandstone of Bayankala. But with Y-Nb and Rb-(Y+Nb), R1-R2 and Rb/10-Hf-Ta*3 diagrams showing that intermediate-acid rocks mainly formed in volcanic arc-collision environment, probably the collision event is short , therefore rocks retain the original island

  14. Phosphorus cycling in forest ecosystems: insights from oxygen isotopes in phosphate

    NASA Astrophysics Data System (ADS)

    Pistocchi, Chiara; Tamburini, Federica; Bünemann, Else; Frossard, Emmanuel

    2015-04-01

    The current view on the phosphorus (P) cycle in forest ecosystems relies mostly on measurements and correlations of pools, and to a lower extent on measurement of fluxes. We have no direct insight into the processes phosphate goes through at the ecosystem level, and into the relative importance of organic and mineral pools in sustaining P nutrition of trees. The analysis of oxygen isotopes associated to P (18Op) is expected to bring this type of information. The German Priority Program SPP 1685 aims to test the overall hypothesis that the P-depletion of soils drives forest ecosystems from P acquiring systems (efficient mobilization of P from the mineral phase) to P recycling systems (highly efficient cycling of P). Our contribution to this project will consist in studying the relative importance of biological and geochemical processes in controlling the P cycle in temperate beech forest ecosystems in Germany along a gradient of decreasing soil P availability. We will follow the fate of phosphate from litter fall to the uptake of P by plants via P release by decomposition of organic matter or after release from P-containing minerals, by using a multi-isotope approach (O in water and phosphate plus 33P). To address our research question we will rely on measurements in experimental forest sites and on laboratory incubations of the organic layer or the mineral soil. We present here the first results issued from the 2014 sampling on three study sites, where we characterized the P pools in surface soil horizons by a sequential extraction (modified after Tiessen and Moir, 2007) and we analysed the 18Op of the resin extractable- and microbial-P fractions. Contrary to what was previously found (e.g. Tamburini et al. 2012) the isotopic composition of these fractions in most of the samples does not reflect the equilibrium value (as the result of the dominance of the pyrophosphatase activity on the other enzymatic processes, Blake et al. 2005). Depending on the P availability

  15. Characteristics of zircon suitable for REE extraction

    NASA Astrophysics Data System (ADS)

    Watanabe, Y.; Hoshino, M.

    2011-12-01

    Zircons (ZrSiO4) from Naegi and Ohro granitic pegmatites, Japan and from Saigon alkaline basalt, Vietnam, were mineralogically characterized by inductively couples plasma mass spectrometry (ICP-MS), electron-microprobe analysis (EMPA), X-ray powder diffraction, micro-Raman spectroscopy and leaching experiment. The powder XRD and Raman spectra analyses show that the degree of crystallinity decreases from Saigon, to Ohro and Naegi zircons. Quantitative analytical results by the EMPA indicate that the Naegi and Ohro zircon samples contain a large amount of REE2O3, while REE contents in Saigon zircon are below detection limit. The leaching experiments for the present zircons under the condition of a solvent 1M-HCl, at a room temperature to 250 °C and retention time of 30h resulted in about 100 %, 50 % and 1 % recoveries of REE from the Naegi, Ohro and Saigon zircons, respectively. Leaching experiments for the Naegi zircon under the condition of a solvent 1N-HCl, heating temperature of 50 °C, 100 °C, 150 °C and 200 °C, and retention time 30h, showed that a significant amount of REE was leached out at a temperature above 150 °C. However, the leaching experiments of the Naegi and Ohro zircons at room temperature (about 25 °C) show that REE were hard to be leached. These results indicates that both low crystallinity of zircon and higher leaching temperature are requisite for effective leaching of REE from zircon.

  16. Zircon morphology and U-Pb geochronology of seven metaluminous and peralkaline post-orogenic granite complexes of the Arabian Shield, Kingdom of Saudi Arabia

    USGS Publications Warehouse

    Aleinikoff, John Nicholas; Stoeser, D.B.

    1988-01-01

    The U-Pb zircon method was used to determine the ages of seven metaluminous-to-peralkaline post-orogenic granites located throughout the Late Proterozoic Arabian Shield of Saudi Arabia. Zircons from the metaluminous rocks are prismatic, with length-to-width ratios of about 2-4:1 and small pyramidal terminations. In contrast, zircons from three of the four peralkaline complexes either lack well developed prismatic faces (are pseudo-octahedral) or are anhedral. Some of the zircons from the peralkaline granites contain inherited radiogenic lead. This complicates interpretation of the isotopic data and. in many cases, may make the U-Pb method unsuitable for determining the age of a peralkaline granite. Zircons in the metaluminous granites do not contain inheritance and thus, best-fit chords calculated through the data have upper concordia intercepts that indicate the age of intrusion, and lower intercepts that indicate simple episodic lead loss. The results show that these granites were emplaced during multiple intrusive episodes from 670 to 510 Ma (Late Proterozoic to Cambrian).

  17. Looking Backwards in Time to the Early Earth Using the Lens of Stable Isotope Geodynamic Cycles

    NASA Astrophysics Data System (ADS)

    Gregory, R. T.

    2016-12-01

    weathering and the subduction of abyssal plain sediments represents true continental recycling and characteristic times for the age of the continents are consistent with modern chemical weathering rates. Two records, zircon and quartz oxygen isotopes, may be recording the transition from the water-world to the modern earth.

  18. Oxygen Isotopes in Intra-Back Arc Basalts from the Andean Southern Volcanic Zone

    NASA Astrophysics Data System (ADS)

    Parks, B. H.; Wang, Z.; Saal, A. E.; Frey, F. A.; Blusztajn, J.

    2013-12-01

    The chemical compositions of volcanic rocks from the Andean Southern Volcanic Zone (SVZ) reflect complex and dynamic interactions among the subducting oceanic lithosphere, the mantle wedge, and the overlying continental crust. Oxygen isotope ratios of olivine phenocrysts can be a useful means to identifying their relative contributions to the arc magmatism. In this study, we report high-precision oxygen-isotope ratios of olivine phenocrysts in a set of intra-back arc basalts from the SVZ. The samples were collected from monogenetic cinder cones east of the volcanic front (35-39 degrees S), and have been geochemically well-characterized with major and trace element contents, and Sr-Nd-Pb isotope compositions. Compared to lavas from the volcanic front, these intra-back arc lavas have similar radiogenic isotope, and a more alkalic and primitive (higher MgO content) chemical composition. We determined the oxygen-isotope ratios using the CO2-laser-fluorination method set up at the Department of Geology and Geophysics, Yale University following the techniques reported in Wang et al (2011). The samples were analyzed with standards of Gore Mountain Garnet (5.77×0.12‰ 1σ; Valley et al., 1995) and Kilbourne Hole Olivine (5.23×0.07‰ 1σ; Sharp, 1990) in order to account for minor changes in the vacuum line during analyses. The obtained δ18OSMOW values of olivine phenocrysts from the intra-back arc basalts vary from 4.98×0.01 to 5.34×0.01‰. This range, surprisingly, is similar to the δ18O values of olivines from mantle peridotites (5.2×0.2‰). Preliminary results indicate significant correlations of 87Sr/86Sr, 143Nd/144Nd and trace element ratios of the basaltic matrix with the δ18O values of olivine phenocrysts, indicating at least three components involved in the formation of the arc volcanism. By comparing the δ18O with the variations of major and trace element contents (e.g., MgO, TiO2 and Ni), and trace element ratios (e.g. Ba/Nb), we evaluate the effects

  19. Scanning ion imaging - a potent tool in SIMS U -Pb zircon geochronology

    NASA Astrophysics Data System (ADS)

    Whitehouse, M. J.; Fedo, C.; Kusiak, M.; Nemchin, A.

    2012-12-01

    The application of high spatial resolution (< 15-20 μm lateral) U-Pb data obtained by sec-ondary ion mass spectrometers (SIMS) coupled with textural information from scanning electron microscope (SEM) based cathodoluminescence (CL) and/or back-scattered elec-tron (BSE) characterisation, has revolutionised geochronology over the past 25 years, re-vealing complexities of crustal evolution from zoned zircons. In addition to ge-ochronology, such studies now commonly form the basis of broader investigations using O- and Hf- isotopes and trace elements obtained from the same growth zone as age, circumventing ambiguities commonly present in bulk-rock isotope studies. The choice of analytical beam diameter is often made to maximise the precision of data obtained from a given area of analysis within an identifiable growth zone. In cases where zircons yield poorly constrained internal structures in SEM, high spatial resolution spot analyses may yield uninterpretable and/or meaningless mixed ages by inadvertent sampling across regions with real age differences. Scanning ion imaging (SII) has the potential to generate accurate and precise geochrono-logical data with a spatial resolution down to ca. 2 μm, much higher than that of a normal spot analysis. SII acquisition utilises a rastered primary beam to image an area of the sample with a spatial resolution dependent on the selected primary beam diameter. On the Cameca ims1270/80 instruments, the primary beam scanning is coupled with the dynamic transfer optical system (DTOS) which deflects the secondary ions back on to the ion optical axis of the instrument regardless of where in the raster illuminated area the ions originated. This feature allows retention of a high field magnification (= high transmission) mode and the ability to operate the mass spectrometer at high mass resolution without any compromise in the quality of the peak shape. Secondary ions may be detected either in a sequential (peak hopping) mono

  20. Air abrasion experiments in U-Pb dating of zircon

    USGS Publications Warehouse

    Goldich, S.S.; Fischer, L.B.

    1986-01-01

    Air abrasion of zircon grains can remove metamict material that has lost radiogenic Pb and zircon overgrowths that were added during younger events and thereby improve the precision of the age measurements and permit closer estimates of the original age. Age discordance that resulted from a single disturbance of the U-Pb isotopic decay systems, as had been demonstrated by T.E. Krogh, can be considerably reduced, and, under favorable conditions, the ages brought into concordancy. Two or more events complicate the U-Pb systematics, but a series of abrasion experiments can be helpful in deciphering the geologic history and in arriving at a useful interpretation of the probable times of origin and disturbances. In east-central Minnesota, U.S.A., Penokean tonalite gneiss is dated at 1869 ?? 5 Ma, and sheared granite gneiss is shown to have been a high-level granite intrusion at 1982 ?? 5 Ma in the McGrath Gneiss precursor. Tonalite gneiss and a mafic granodiorite in the Rainy Lake area, Ontario, Canada, are dated at 2736 ?? 16 and 2682 ?? 4 Ma, respectively. The tonalitic phase of the Morton Gneiss, southwestern Minnesota, is dated at 3662 ?? 42 Ma. ?? 1986.

  1. Detrital zircon provenance of Mesoproterozoic to Cambrian arenites in the Western United States and Northwestern Mexico

    USGS Publications Warehouse

    Stewart, John H.; Gehrels, G.E.; Barth, A.P.; Link, P.K.; Christie-Blick, N.; Wrucke, C.T.

    2001-01-01

    U-Pb isotopic dating of detrital zircon from supracrustal Proterozoic and Cambrian arenites from the western United States and northern Mexico reveal three main age groups, 1.90 to 1.62 Ga, 1.45 to 1.40 Ga, and 1.2 to 1.0 Ga. Small amounts of zircons with ages of 3.1 to 2.5 Ga, 1.57 Ga, 1.32 Ga, 1.26 Ga, 0.7 Ga, and 0.5 Ga are also present. Detrital zircons ranging in age from 1.90 to 1.62 Ga and from 1.45 to 1.40 Ga are considered to have been derived from Proterozoic crystalline basement rocks of these known ages, and probably in part from reworked Proterozoic supracrustal sedimentary rocks, of the western United States. The 1.2 to 1.0 Ga detrital zircon ages from California, Arizona, and Sonora are characterized by distinct spikes (1.11 Ga, in particular) in the age-probability plots. These spikes are interpreted to indicate the influx of zircon from major silicic volcanic fields. Igneous rocks such as the Pikes Peak Granite (1.093 Ga) of Colorado, and the Aibo Granite (1.110 Ga) of Sonora, Mexico, may represent the deeply eroded roots of such volcanic fields. Samples from farther north along the Cordilleran margin that contain abundant 1.2-1.0 Ga detrital zircons do not show spikes in the age distribution, but rather ages spread out across the entire 1.2-1.0 Ga range. These age spectra resemble those for detrital zircons from the Grenville province, which is considered their source. Less common detrital zircons had a variety of sources. Zircons ranging in age from 3.36 to 2.31 Ga were apparently derived from inland parts of the North American continent from Wyoming to Canada. Zircons of about 1.577 Ga are highly unusual and may have had an exotic source; they may have come from Australia and been deposited in North America when Australia and North America were juxtaposed as part of the hypothetical Rodinian supercontinent. Detrital zircon of ??1.320 Ga apparently had the same source as that for tuff (1.320 Ga) in the Pioneer Shale of the Apache Group in Arizona

  2. U-Pb zircon geochronology and evolution of some Adirondack meta-igneous rocks

    NASA Technical Reports Server (NTRS)

    Mclelland, J. M.

    1988-01-01

    An update was presented of the recent U-Pb isotope geochronology and models for evolution of some of the meta-igneous rocks of the Adirondacks, New York. Uranium-lead zircon data from charnockites and mangerites and on baddeleyite from anorthosite suggest that the emplacement of these rocks into a stable crust took place in the range 1160 to 1130 Ma. Granulite facies metamorphism was approximately 1050 Ma as indicated by metamorphic zircon and sphene ages of the anorthosite and by development of magmatitic alaskitic gneiss. The concentric isotherms that are observed in this area are due to later doming. However, an older contact metamorphic aureole associated with anorthosite intrusion is observed where wollastonite develops in metacarbonates. Zenoliths found in the anorthosite indicate a metamorphic event prior to anorthosite emplacement. The most probable mechanism for anorthosite genesis is thought to be ponding of gabbroic magmas at the Moho. The emplacement of the anorogenic anorthosite-mangerite-charnockite suite was apparently bracketed by compressional orogenies.

  3. Phosphate oxygen isotope ratios as a tracer for sources and cycling of phosphate in North San Francisco Bay, California

    USGS Publications Warehouse

    McLaughlin, K.; Kendall, C.; Silva, S.R.; Young, M.; Paytan, A.

    2006-01-01

    A seasonal analysis assesing variations in the oxygen isotopic composition of dissolved inorganic phosphate (DIP) was conducted in the San Francisco Bay estuarine system, California. Isotopic fractionation of oxygen in DIP (exchange of oxygen between phosphate and environmental water) at surface water temperatures occurs only as a result of enzyme-mediated, biological reactions. Accordingly, if phospate demand is low relative to input and phosphate is not heavily cycled in the ecosystem, the oxygen isotopic composition of DIP (?? 18Op) will reflect the isotopic composition of the source of phosphate to the system. Such is the case for the North San Francisco Bay, an anthropogenically impacted estuary with high surface water phosphate concentrations. Variability in the ?? 18Op in the bay is primarily controlled by mixing of water masses with different ??18Op signatures. The ??18Op values range from 11.4??? at the Sacramento River to 20.1??? at the Golden Gate. Deviations from the two-component mixing model for the North Bay reflect additional, local sources of phosphate to the estuary that vary seasonally. Most notably, deviations from the mixing model occur at the confluence of a major river into the bay during periods of high river discharge and near wastewater treatment outlets. These data suggest that ??18Op can be an effective tool for identifying P point sources and understanding phosphate dynamics in estuarine systems. Copyright 2006 by the American Geophysical Union.

  4. Proterozoic tectonostratigraphy and paleogeography of central Madagascar derived from detrital zircon U-Pb age populations

    USGS Publications Warehouse

    Cox, R.; Coleman, D.S.; Chokel, C.B.; DeOreo, S.B.; Wooden, Joseph L.; Collins, A.S.; De Waele, B.; Kroner, A.

    2004-01-01

    Detrital zircon U‐Pb ages determined by SHRIMP distinguish two clastic sequences among Proterozoic metasedimentary rocks from central Madagascar. The Itremo Group is older: zircon data, stromatolite characteristics, and carbon isotope data all point to a depositional age around 1500–1700 Ma. The Molo Group is younger, deposited between ∼620 Ma (the age of the youngest zircon) and ∼560 Ma (the age of metamorphic overgrowths on detrital cores). Geochronologic provenance analysis of the Itremo Group points to sources in East Africa as well as local sources in central and southern Madagascar but provides no evidence for a detrital contribution from northern and eastern Madagascar nor from southern India. Detrital zircon and sedimentologic similarities between rocks of the Itremo Group and the Zambian Muva Supergroup suggest a lithostratigraphic correlation between the two. The Molo Group has a strong 1000–1100 Ma detrital signature that also indicates an east African provenance and suggests a Neoproterozoic geographic connection with Sri Lanka but shows no indication of input from the Dharwar craton and eastern Madagascar. Central Madagascar was probably juxtaposed with the Tanzanian craton in the Paleo‐ and Mesoproterozoic, whereas northern and eastern Madagascar were connected to India. Internal assembly of Madagascar postdates Neoproterozoic Molo Group sedimentation and is likely to have occurred at about 560 Ma.

  5. Zircon U-Pb age, Lu-Hf isotope, mineral chemistry and geochemistry of Sundamalai peralkaline pluton from the Salem Block, southern India: Implications for Cryogenian adakite-like magmatism in an aborted-rift

    NASA Astrophysics Data System (ADS)

    Renjith, M. L.; Santosh, M.; Li, Tang; Satyanarayanan, M.; Korakoppa, M. M.; Tsunogae, T.; Subba Rao, D. V.; Kesav Krishna, A.; Nirmal Charan, S.

    2016-01-01

    The Sundamalai peralkaline pluton is one among the Cryogenian alkaline plutons occurring in the Dharmapuri Rift Zone (DRZ) of the Salem Block in the Southern Granulite Terrane (SGT) of India. Here we present zircon U-Pb age and Lu-Hf isotopic composition, mineral chemistry and geochemistry of the pluton to explore the petrogenesis and geodynamic implications. Systematic modal variation of orthoclase, Na-plagioclase, Ca-amphibole (ferro-edenite and hastingsite) and quartz developed quartz-monzonite and granite litho units in the Sundamalai pluton. Thermometry based on amphibole-plagioclase pair suggests that the pluton was emplaced and solidified at around 4.6 kbar pressure with crystallization of the major phases between 748 and 661 °C. Estimated saturation temperature of zircon (712-698 °C) is also well within this range. However, apatite saturation occurred at higher temperatures between 835 and 870 °C, in contrast with monazite saturation (718-613 °C) that continued up to the late stage of crystallization. Estimated oxygen fugacity values (log fO2: -14 to -17) indicate high oxidation state for the magma that stabilized titanite and magnetite. The magmatic zircons from Sundamalai pluton yielded a weighted mean 206Pb/238U age of 832.6 ± 3.2 Ma. Geochemically, the Sundamalai rocks are high-K to shoshonitic, persodic (Na2O/K2O ratio > 1), silica-saturated (SiO2:65-72 wt.%), and peralkaline in composition (aluminum saturation index, ASI < 1; Alkalinity index, AI < 0). The initial magma was mildly metaluminous which evolved to strongly peralkaline as result of fractional crystallization (plagioclase effect) controlled differentiation between quartz-monzonite and granite. Both rock types have high content of Na2O (5.1-6.3 wt.%), Ba (350-2589 ppm) and Sr (264-1036 ppm); low content of Y (8.7-17 ppm) and Yb (0.96-1.69 ppm); elevated ratios of La/Yb (11-46) and Sr/Y (46-69) and are depleted in Ti, with a positive Sr anomaly suggesting an adakite-like composition and

  6. Record of Hybridization Preserved in Zircon, Aztec Wash Pluton, NV

    NASA Astrophysics Data System (ADS)

    Bromley, S. A.; Miller, C. F.; Claiborne, L. L.; Wooden, J. L.; Mazdab, F. K.

    2007-12-01

    The mid-Miocene Aztec Wash pluton comprises a smaller granite zone and a larger, highly heterogeneous zone in which evidence for interaction between basaltic and granitic magmas is ubiquitous. Granitic rocks in both zones show textural and compositional evidence for crystal accumulation and melt fractionation. In the heterogeneous zone, basalts have chilled, crenulate margins against granitic rocks, and there is widespread evidence for mechanical contamination of each lithology (coarse resorbed alkali feldspar in fine-grained mafic rock; mafic enclaves in granite). "Grey rocks" of intermediate composition are exposed on dm to 100's of m-scale as enclaves, pods, and initially subhorizontal sheets. They are variable texturally, but most are dominantly fine- grained and equigranular. Textures of grey rocks are consistent with rapid solidification from melt-rich magma, and, in combination with isotopic compositions intermediate between felsic and mafic rocks of the pluton, suggest an origin by near-complete homogenization of a hybrid melt (Bleick et al. 2005; Ericksen 2005). The elemental chemistry of zircon preserves information about the evolving magmatic environment in which it was hosted (Claiborne et al., 2006). Owing to its slow dissolution rate, it has the potential to survive periods of undersaturation with only partial resorption. Thus, it may record drastic shifts in T and melt chemistry that would accompany mafic-felsic hybridization. We are investigating zircon zoning patterns by cathodoluminescence (CL) and elemental compositions by SHRIMP-RG to evaluate the record of processes that they preserve. Temperatures of zircon growth are estimated using Ti-in-zircon thermometry (Watson et al. 2006), assuming a(TiO2) of ca. 0.7 (sphene +/-ilmenite are ubiquitous). Zircons from the granite zone yield estimated T's of 700-860 C, whereas those from grey rocks range from 710- 910 C. While both granite and grey zircon populations show dramatic T variations among and

  7. Stable Carbon and Oxygen Isotope Ratios of Otoliths Differentiate Winter Flounder (Pseudopleuonectes americanus) Habitats

    EPA Science Inventory

    Stable carbon (13C) and oxygen (18O) isotope ratios were measured in otoliths of juvenile winter flounder (Pseudopleuronectes americanus) collected from 18 nursery areas along the coast of Rhode Island, USA. Samples were obtained during June and July of 2002 from locations tha...

  8. Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

    PubMed

    Killingsworth, Bryan A; Bao, Huiming; Kohl, Issaku E

    2018-05-17

    Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .

  9. Evaporation Induced Oxygen Isotope Fractionation in Impact Ejecta

    NASA Astrophysics Data System (ADS)

    Macris, C. A.; Young, E. D.; Kohl, I. E.; zur Loye, T. E.

    2017-12-01

    Tektites are natural glasses formed as quenched impact melt ejecta. Because they experienced extreme heating while entrained in a hot impact vapor plume, tektites allow insight into the nature of these ephemeral events, which play a critical role in planetary accretion and evolution. During tektite formation, the chemical and isotopic composition of parent materials may be modified by (1) vapor/liquid fractionation at high T in the plume, (2) incorporation of meteoric water at the target site, (3) isotope exchange with atmospheric oxygen (if present), or some combination of the three. Trends from O isotope studies reveal a dichotomy: some tektite δ18O values are 4.0-4.5‰ lower than their protoliths (Luft et al. 1987; Taylor & Epstein 1962), opposite in direction to a vaporization induced fractionation; increases in δ18O with decreasing SiO2 in tektites (Taylor & Epstein 1969) is consistent with vapor fractionation. Using an aerodynamic levitation laser furnace (e.g. Macris et al. 2016), we can experimentally determine the contributions of processes (1), (2) and (3) above to tektite compositions. We conducted a series of evaporation experiments to test process (1) using powdered tektite fused into 2 mm spheres and heated to 2423-2473 K for 50-90 s while levitated in Ar in the furnace. Mass losses were from 23 to 26%, reflecting evaporation of Si and O from the melt. The starting tektite had a δ18O value of 10.06‰ (±0.01 2se) and the residues ranged from 13.136‰ (±0.006) for the least evaporated residue to 14.30‰ (±0.02) for the most evaporated (measured by laser fluorination). The increase in δ18O with increasing mass loss is consistent with Rayleigh fractionation during evaporation, supporting the idea that O isotopes are fractionated due to vaporization at high T in an impact plume. Because atmospheric O2 and water each have distinctive Δ17O values, we should be able to use departures from our measured three-isotope fractionation law to evaluate

  10. Isotope exchange in oxide-containing catalyst

    NASA Technical Reports Server (NTRS)

    Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

    1989-01-01

    A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

  11. Quantifying time in sedimentary successions by radio-isotopic dating of ash beds

    NASA Astrophysics Data System (ADS)

    Schaltegger, Urs

    2014-05-01

    , e.g., Schoene et al. 2012), which then becomes transferred into volcanic ashes as excess dispersion of 238U-206Pb dates (see, e.g., Guex et al. 2012). Zircon is crystallizing in the magmatic liquid shortly before the volcanic eruption; we therefore aim at finding the youngest zircon date or youngest statistically equivalent cluster of 238U-206Pb dates as an approximation of ash deposition (Wotzlaw et al. 2013). Time gaps between last zircon crystallization and eruption ("Δt") may be as large as 100-200 ka, at the limits of analytical precision. Understanding the magmatic crystallization history of zircon is the fundamental background for interpreting ash bed dates in a sedimentary succession. Ash beds of different stratigraphic position and age my be generated within different magmatic systems, showing different crystallization histories. A sufficient number of samples (N) is therefore of paramount importance, not to lose the stratigraphic age control in a given section, and to be able to discard samples with large Δt - but, how large has to be "N"? In order to use the youngest zircon or zircons as an approximation of the age of eruption and ash deposition, we need to be sure that we have quantitatively solved the problem of post-crystallization lead loss - but, how can we be sure?! Ash bed zircons are prone to partial loss of radiogenic lead, because the ashes have been flushed by volcanic gases, as well as brines during sediment compaction. We therefore need to analyze a sufficient number of zircons (n) to be sure not to miss the youngest - but, how large has to be "n"? Analysis of trace elements or oxygen, hafnium isotopic compositions in dated zircon may sometimes help to distinguish zircon that is in equilibrium with the last magmatic liquid, from those that are recycled from earlier crystallization episodes, or to recognize zircon with partial lead loss (Schoene et al. 2010). Respecting these constraints, we may arrive at accurate correlation of periods of

  12. Forward Modeling of Oxygen Isotope Variability in Tropical Andean Ice Cores

    NASA Astrophysics Data System (ADS)

    Vuille, M. F.; Hurley, J. V.; Hardy, D. R.

    2016-12-01

    Ice core records from the tropical Andes serve as important archives of past tropical Pacific SST variability and changes in monsoon intensity upstream over the Amazon basin. Yet the interpretation of the oxygen isotopic signal in these ice cores remains controversial. Based on 10 years of continuous on-site glaciologic, meteorologic and isotopic measurements at the summit of the world's largest tropical ice cap, Quelccaya, in southern Peru, we developed a process-based physical forward model (proxy system model), capable of simulating intraseasonal, seasonal and interannual variability in delta-18O as observed in snow pits and short cores. Our results highlight the importance of taking into account post-depositional effects (sublimation and isotopic enrichment) to properly simulate the seasonal cycle. Intraseasonal variability is underestimated in our model unless the effects of cold air incursions, triggering significant monsoonal snowfall and more negative delta-18O values, are included. A number of sensitivity test highlight the influence of changing boundary conditions on the final snow isotopic profile. Such tests also show that our model provides much more realistic data than applying direct model output of precipitation delta-18O from isotope-enabled climate models (SWING ensemble). The forward model was calibrated with and run under present-day conditions, but it can also be driven with past climate forcings to reconstruct paleo-monsoon variability and investigate the influence of changes in radiative forcings (solar, volcanic) on delta-18O variability in Andean snow. The model is transferable and may be used to render a paleoclimatic context at other ice core locations.

  13. A search for thermal excursions from ancient extraterrestrial impacts using Hadean zircon Ti-U-Th-Pb depth profiles.

    PubMed

    Abbott, Sunshine S; Harrison, T Mark; Schmitt, Axel K; Mojzsis, Stephen J

    2012-08-21

    Few terrestrial localities preserve more than a trace lithic record prior to ca. 3.8 Ga greatly limiting our understanding of the first 700 Ma of Earth history, a period inferred to have included a spike in the bolide flux to the inner solar system at ca. 3.85-3.95 Ga (the Late Heavy Bombardment, LHB). An accessible record of this era may be found in Hadean detrital zircons from the Jack Hills, Western Australia, in the form of μm-scale epitaxial overgrowths. By comparing crystallization temperatures of pre-3.8 Ga zircon overgrowths to the archive of zircon temperature spectra, it should, in principle, be possible to identify a distinctive impact signature. We have developed Ti-U-Th-Pb ion microprobe depth profiling to obtain age and temperature information within these zircon overgrowths and undertaken a feasibility study of its possible use in identifying impact events. Of eight grains profiled in this fashion, four have overgrowths of LHB-era age. Age vs. temperature profiles reveal a period between ca. 3.85-3.95 Ga (i.e., LHB era) characterized by significantly higher temperatures (approximately 840-875 °C) than do older or younger zircons or zircon domains (approximately 630-750 °C). However, temperatures approaching 900 °C can result in Pb isotopic exchange rendering interpretation of these profiles nonunique. Coupled age-temperature depth profiling shows promise in this role, and the preliminary data we report could represent the first terrestrial evidence for impact-related heating during the LHB.

  14. U-Pb and Hf isotope analysis of detrital zircons from Mesozoic strata of the Gravina belt, southeast Alaska

    NASA Astrophysics Data System (ADS)

    Yokelson, Intan; Gehrels, George E.; Pecha, Mark; Giesler, Dominique; White, Chelsi; McClelland, William C.

    2015-10-01

    The Gravina belt consists of Upper Jurassic through Lower Cretaceous marine clastic strata and mafic-intermediate volcanic rocks that occur along the western flank of the Coast Mountains in southeast Alaska and coastal British Columbia. This report presents U-Pb ages and Hf isotope determinations of detrital zircons that have been recovered from samples collected from various stratigraphic levels and from along the length of the belt. The results support previous interpretations that strata in the western portion of the Gravina belt accumulated along the inboard margin of the Alexander-Wrangellia terrane and in a back-arc position with respect to the western Coast Mountains batholith. Our results are also consistent with previous suggestions that eastern strata accumulated along the western margin of the inboard Stikine, Yukon-Tanana, and Taku terranes and in a fore-arc position with respect to the eastern Coast Mountains batholith. The history of juxtaposition of western and eastern assemblages is obscured by subsequent plutonism, deformation, and metamorphism within the Coast Mountains orogen, but may have occurred along an Early Cretaceous sinistral transform system. Our results are inconsistent with models in which an east-facing subduction zone existed along the inboard margin of the Alexander-Wrangellia terrane during Late Jurassic-Early Cretaceous time.

  15. Temperature and atmospheric CO2 concentration estimates through the PETM using triple oxygen isotope analysis of mammalian bioapatite

    PubMed Central

    Gehler, Alexander; Pack, Andreas

    2016-01-01

    The Paleocene–Eocene Thermal Maximum (PETM) is a remarkable climatic and environmental event that occurred 56 Ma ago and has importance for understanding possible future climate change. The Paleocene–Eocene transition is marked by a rapid temperature rise contemporaneous with a large negative carbon isotope excursion (CIE). Both the temperature and the isotopic excursion are well-documented by terrestrial and marine proxies. The CIE was the result of a massive release of carbon into the atmosphere. However, the carbon source and quantities of CO2 and CH4 greenhouse gases that contributed to global warming are poorly constrained and highly debated. Here we combine an established oxygen isotope paleothermometer with a newly developed triple oxygen isotope paleo-CO2 barometer. We attempt to quantify the source of greenhouse gases released during the Paleocene–Eocene transition by analyzing bioapatite of terrestrial mammals. Our results are consistent with previous estimates of PETM temperature change and suggest that not only CO2 but also massive release of seabed methane was the driver for CIE and PETM. PMID:27354522

  16. Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

    PubMed

    LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M

    2009-06-01

    Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the

  17. Stabel Carbon and Oxygen Isotope Ratios of Otoliths from Juvenile and Adult Winter Flounder

    EPA Science Inventory

    This study was designed to determine if stable carbon (13C) and oxygen (18O) isotope ratios in otoliths could be used to differentiate the locations that serve as important nursery areas for winter flounder along the Rhode Island, USA coastline. In recent years the populations ...

  18. Lu-Hf systematics of magmatic zircons reveal a Proterozoic crustal boundary under the Cretaceous Pioneer batholith, Montana

    NASA Astrophysics Data System (ADS)

    Foster, David A.; Mueller, Paul A.; Heatherington, Ann; Gifford, Jennifer N.; Kalakay, Thomas J.

    2012-06-01

    Lu-Hf systematics of magmatic zircons from quartz diorite and granodiorite plutons of the Late Cretaceous Pioneer batholith, Montana, indicate involvement of distinctly different crustal sources in the petrogensis of individual components of the batholith. Plutons of the eastern Pioneer batholith contain magmatic zircons with initial ɛHf values of - 28 to - 34 that crystallized in magmas likely derived from dominantly Archean and earliest Paleoproterozoic crust. Contemporaneous granodiorite in the western Pioneer batholith contains magmatic zircons with initial ɛHf values ranging from - 9 to - 33, but dominated by values between - 18 and - 22, which suggest a mixture of Paleoproterozoic and possible Mesoproterozoic sources. These data suggest that distinct segments of crust juxtaposed and produced during formation of the Great Falls tectonic zone (1.78-1.86 Ga) and the Belt basin (~ 1.43-1.47 Ga) contributed to magmatic compositions in the batholith and that these contributions are recorded in the magmatic zircons. The contrasting ɛHf distributions between eastern and western components of the Pioneer batholith suggest that an important crustal and/or lithospheric boundary underlies the Pioneer batholith. The Hf-isotopic results also suggest that the high P-wave velocity lower crust of the northern Rocky Mountains did not form in a single event.

  19. Do oxygen stable isotopes track precipitation moisture source in vascular plant dominated peatlands?

    NASA Astrophysics Data System (ADS)

    Charman, D.; Amesbury, M. J.; Newnham, R.; Loader, N.; Goodrich, J. P.; Gallego-Sala, A. V.; Royles, J.; Keller, E. D.; Baisden, W. T.

    2014-12-01

    Variations in the isotopic composition of precipitation are determined by fractionation processes which occur during temperature and humidity dependent phase changes associated with evaporation and condensation. Oxygen stable isotope ratios have therefore been frequently used as a source of palaeoclimate data from a variety of proxy archives. Exploitation of this record from ombrotrophic peatlands, where the source water used in cellulose synthesis is derived solely from precipitation, has been mostly limited to Northern Hemisphere Sphagnum-dominated bogs, with limited application in the Southern Hemisphere (SH) or in peatlands dominated by vascular plants. Throughout New Zealand (NZ), the preserved root matrix of the restionaceous wire rush (Empodisma spp.) forms deep peat deposits. NZ provides an ideal location to undertake empirical research into oxygen isotope fractionation in vascular peatlands because sites are ideally suited to single taxon analysis, preserve potentially high resolution full Holocene palaeoclimate records and are situated in the climatically sensitive SH mid-latitudes. Crucially, large gradients exist in the mean isotopic composition of precipitation across NZ, caused primarily by the relative influence of different climate modes. We test the capacity for δ18O analysis of Empodisma alpha cellulose from ombrotrophic restiad peatlands in NZ to provide a methodology for developing palaeoclimate records. We took surface plant, water and precipitation samples over spatial (six sites spanning >10° latitude) and temporal (monthly measurements over one year) gradients. We found a strong link between the isotopic compositions of surface root water, the most likely source water for plant growth, and precipitation in both datasets. Back-trajectory modelling of precipitation moisture source for rain days prior to sampling showed clear seasonality in the temporal data that was reflected in surface root water. The link between source water and plant

  20. The impact of moisture sources on the oxygen isotope composition of precipitation at a continental site in central Europe

    NASA Astrophysics Data System (ADS)

    Krklec, Kristina; Domínguez-Villar, David; Lojen, Sonja

    2018-06-01

    The stable isotope composition of precipitation records processes taking place within the hydrological cycle. Potentially, moisture sources are important controls on the stable isotope composition of precipitation, but studies focused on this topic are still scarce. We studied the moisture sources contributing to precipitation at Postojna (Slovenia) from 2009 to 2013. Back trajectory analyses were computed for the days with precipitation at Postojna. The moisture uptake locations were identified along these trajectories using standard hydrometeorological formulation. The moisture uptake locations were integrated in eight source regions to facilitate its comparison to the monthly oxygen isotope composition (δ18O values) of precipitation. Nearly half of the precipitation originated from continental sources (recycled moisture), and >40% was from central and western Mediterranean. Results show that moisture sources do not have a significant impact on the oxygen isotope composition at this site. We suggest that the large proportion of recycled moisture originated from transpiration rather than evaporation, which produced water vapour with less negative δ18O values. Thus the difference between the oceanic and local vapour source was reduced, which prevented the distinction of the moisture sources based on their oxygen isotope signature. Nevertheless, δ18O values of precipitation are partially controlled by climate parameters, which is of major importance for paleoclimate studies. We found that the main climate control on Postojna δ18O values of precipitation is the surface temperature. Amount effect was not recorded at this site, and the winter North Atlantic Oscillation (NAO) does not impact the δ18O values of precipitation. The Western Mediterranean Oscillation (WeMO) was correlated to oxygen stable isotope composition, although this atmospheric pattern was not a control. Instead we found that the link to δ18O values results from synoptic scenarios affecting We

  1. Can Lightning Produce Significant Levels of Mass-Independent Oxygen Isotopic Fractionation in Nebular Dust?

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A.; Paquette, John A.; Farquhar, Adam

    2012-01-01

    Based on recent evidence that oxide grains condensed from a plasma will contain oxygen that is mass independently fractionated compared to the initial composition of the vapor, we present a first attempt to evaluate the potential magnitude of this effect on dust in the primitive solar nebula. This assessment relies on previous studies of nebular lightning to provide reasonable ranges of physical parameters to form a very simple model to evaluate the plausibility that lightning could affect a significant fraction of nebular dust and that such effects could cause a significant change in the oxygen isotopic composition of solids in the solar nebula over time. If only a small fraction of the accretion energy is dissipated as lightning over the volume of the inner solar nebula, then a large fraction of nebular dust will be exposed to lightning. If the temperature of such bolts is a few percent of the temperatures measured in terrestrial discharges, then dust will vaporize and recondense in an ionized environment. Finally, if only a small average decrease is assumed in the O-16 content of freshly condensed dust, then over the last 5 million years of nebular accretion the average delta O-17 of the dust could increase by more than 30 per mil. We conclude that it is possible that the measured " slope 1" oxygen isotope line measured in meteorites and their components represents a time-evolution sequence of nebular dust over the last several million years of nebular evolution O-16-rich materials formed first, then escaped further processing as the average isotopic composition of the dust graduaUy became increasingly depleted in O-16 .

  2. Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

    USGS Publications Warehouse

    Kim, Sang-Tae; Gebbinck, Christa Klein; Mucci, Alfonso; Coplen, Tyler B.

    2014-01-01

    To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

  3. Variability in magnesium, carbon and oxygen isotope compositions, and trace element contents of brachiopod shells: implications for paleoceanographic studies

    NASA Astrophysics Data System (ADS)

    Rollion-Bard, Claire; Saulnier, Ségolène; Vigier, Nathalie; Schumacher, Aimryc; Chaussidon, Marc; Lécuyer, Christophe

    2016-04-01

    Magnesium content in the ocean is ≈ 1290 ppm and is one of the most abundant elements. It is involved in the carbon cycle via the dissolution and precipitation of carbonates, especially Mg-rich carbonates as dolomites. The Mg/Ca ratio of the ocean is believed to have changed through time. The causes of these variations, i.e. hydrothermal activity change or enhanced precipitation of dolomite, could be constrained using the magnesium isotope composition (δ26Mg) of carbonates. Brachiopods, as marine environmental proxies, have the advantage to occur worldwide in a depth range from intertidal to abyssal, and have been found in the geological record since the Cambrian. Moreover, as their shell is in low-Mg calcite, they are quite resistant to diagenetic processes. Here we report δ26Mg, δ18O, δ13C values along with trace element contents of one modern brachiopod specimen (Terebratalia transversa) and one fossil specimen (Terebratula scillae, 2.3 Ma). We combined δ26Mg values with oxygen and carbon isotope compositions and trace element contents to look for possible shell geochemical heterogeneities in order to investigate the processes that control the Mg isotope composition of brachiopod shells. We also evaluate the potential of brachiopods as a proxy of past seawater δ26Mg values. The two investigated brachiopod shells present the same range of δ26Mg variation (up to 2 ‰)). This variation cannot be ascribed to changes in environmental parameters, i.e. temperature or pH. As previously observed, the primary layer of calcite shows the largest degree of oxygen and carbon isotope disequilibrium relative to seawater. In contrast, the δ26Mg value of this layer is comparable to that of the secondary calcite layer value. In both T. scillae and T. transversa, negative trends are observable between magnesium isotopic compositions and oxygen and carbon isotopic compositions. These trends, combined to linear relationships between δ26Mg values and REE contents, are best

  4. Detrital zircons and Earth system evolution

    NASA Astrophysics Data System (ADS)

    McKenzie, R.

    2016-12-01

    Zircon is a mineral commonly produced in silicic magmatism. Therefore, due to its resilience and exceedingly long residence times in the continental crust, detrital zircon records can be used to track processes associated with silicic magmatism throughout Earth history. In this contribution I will address the potential role of preservational biases in zircon record, and further discuss how zircon datasets can be used to help better understand the relationship between lithospheric and Earth system evolution. I will use large compilations of zircon data to trace the composition and weatherability of the continental crust, to evaluate temporal rates of crustal recycling, and finally to track spatiotemporal variation in continental arc magmatism and volcanic CO2 outgassing throughout Earth history. These records demonstrate that secular changes in plate tectonic regimes played a prominent role in modulating conditions of the ocean+atmosphere system and long-term climate state for the last 3 billion years.

  5. New zircon U-Pb LA-ICP-MS ages and Hf isotope data from the Central Pontides (Turkey): Geological and geodynamic constraints

    NASA Astrophysics Data System (ADS)

    Çimen, Okay; Göncüoğlu, M. Cemal; Simonetti, Antonio; Sayit, Kaan

    2018-05-01

    The Central Pontides in northern Anatolia is located on the accretionary complex formed by the closure of Neotethyan Intra-Pontide Ocean between the southern Eurasian margin (Istanbul-Zonguldak Terrane) and the Cimmerian Sakarya Composite Terrane. Among other components of the oceanic lithosphere, it comprises not yet well-dated felsic igneous rocks formed in arc-basin as well as continent margin settings. In-situ U-Pb age results for zircons from the arc-basin system (öangaldağ Metamorphic Complex) and the continental arc (Devrekani Metadiorite and Granitoid) yield ages of 176 ± 6 Ma, 163 ± 9 Ma and 165 ± 3 Ma, respectively. Corresponding in-situ average (initial) 176Hf/177Hf initial ratios are 0.28261 ± 0.00003, 0.28267 ± 0.00002 and 0.28290 ± 0.00004 for these units and indicative of a subduction-modified mantle source. The new U-Pb ages and Hf isotope data from these oceanic and continental arc units together with regional geological constraints support the presence of a multiple subduction system within the Intra-Pontide Ocean during the Middle Jurassic.

  6. Ion Microprobe Measurements of Comet Dust and Implications for Models of Oxygen Isotope Heterogeneity in the Solar System

    NASA Technical Reports Server (NTRS)

    Snead, C. J.; McKeegan, K. D.; Keller, L. P.; Messenger, S.

    2017-01-01

    The oxygen isotopic compositions of anhydrous minerals in carbonaceous chondrites reflect mixing between a O-16-rich and O-17, O18-rich reservoir. The UV photodissociation of CO (i.e. selfshielding) has been proposed as a mass-independent mechanism for producing these isotopically distinct reservoirs. Self-shielding models predict the composition for the CO gas reservoir to be O-16-rich, and that the accreting primordial dust was in isotopic equilibrium with the gaseous reservoir [1, 2]. Self-shielding also predicts that cometary water, presumed to represent the O-17, O-18-rich reservoir, should be enriched in O-17 and O-18, with compositions of 200 -1000per mille, and that the interaction with this O-17, O-18-rich H2O reservoir altered the compositions of the primordial dust toward planetary values. The bulk composition of the solar nebula, which may be an approximation to the 16O-rich gaseous reservoir, has been constrained by the Genesis results [3]. However, material representing the O-17, O-18-rich end-member is rare [4], and dust representing the original accreting primordial dust has been challenging to conclusively identify in current collections. Anhydrous dust from comets, which accreted in the distal cold regions of the nebula at temperatures below approximately 30K, may provide the best opportunity to measure the oxygen isotope composition of primordial dust. Chondritic porous interplanetary dust particles (CP-IDPs) have been suggested as having cometary origins [5]; however, until direct comparisons with dust from a known comet parent body were made, link between CP-IDPs and comets remained circumstantial. Oxygen isotope analyses of particles from comet 81P/Wild 2 collected by NASA's Stardust mission have revealed surprising similarities to minerals in carbonaceous chondrites which have been interpreted as evidence for large scale radial migration of dust components from the inner solar nebula to the accretion regions of Jupiter- family comets [6

  7. The pre-Atlantic Hf isotope evolution of the east Laurentian continental margin: Insights from zircon in basement rocks and glacial tillites from northern New Jersey and southeastern New York

    NASA Astrophysics Data System (ADS)

    Zirakparvar, N. Alex; Setera, Jacob; Mathez, Edmond; Vantongeren, Jill; Fossum, Ryanna

    2017-02-01

    This paper presents laser ablation U-Pb age and Hf isotope data for zircons from basement rocks and glacial deposits in northern New Jersey and southeastern New York. The purpose is to understand the eastern Laurentian continental margin's Hf isotope record in relation to its geologic evolution prior to the opening of the Atlantic Ocean. The basement samples encompass a Meso- to Neoproterozoic continental margin arc, an anatectic magmatic suite, as well as a Late Ordovician alkaline igneous suite emplaced during post-orogenic melting of the lithospheric mantle. Additional samples were collected from terminal moraines of two Quaternary continental ice sheets. Across the entire dataset, zircons with ages corresponding to the timing of continental margin arc magmatism ( 1.4 Ga to 1.2 Ga) have positive εHf(initial) values that define the more radiogenic end of a crustal evolution array. This array progresses towards more unradiogenic εHf(initial) values along a series of low 176Lu/177Hf (0.022 to 0.005) trajectories during subsequent anatectic magmatism ( 1.2 Ga to 1.0 Ga) and later metamorphic and metasomatic re-working ( 1.0 Ga to 0.8 Ga) of the continental margin arc crust. In contrast, nearly chondritic εHf(initial) values from the Late Ordovician alkaline magmas indicate that the Laurentian margin was underlain by a re-fertilized mantle source. Such a source may have developed by subduction enrichment of the mantle wedge beneath the continental margin during the Mesoproterozoic. Additionally, preliminary data from a metasedimentary unit of unknown provenance hints at the possibility that some of the sediments occupying this portion of the Laurentian margin prior to the Ordovician were sourced from crust older than 1.9 Ga.

  8. Tracing the Impact of Aviation on the Atmospheric Nitrate With Oxygen Triple Isotopes

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Jackson, T. L.; Chan, S.; Hill, A.; Chakraborty, S.; Thiemens, M. H.

    2014-12-01

    The aviation industry is responsible for ~ 5% of anthropogenic climate change. Jet emission affects ~ in 25 mile radii from airports produce fine particles and concomitant pulmonary and cardio-vascular diseases. These unregulated emissions are of particular concerns for the health of local residents and environment in general due to rapid increase in worldwide air travel in 21st century. The accurate measurement of emissions from airports therefore requires development of new tools that quantification of aviation related emissions against other road traffic and hence to assess its local and global impacts and provide deeper understanding of nitrate in the environment in general, including the stratosphere where contrails are inadequately detailed Triple oxygen isotopic analysis of particulate nitrate from a DC 8 engine during a controlled experiment in Palmdale, CA documented the emission of nitric acid (~31 ng.m-3) at ~ 1m. The oxygen triple isotopic composition of nitrate emitted directly from the jet had δ18O values (22±1‰) identical to air O2 (δ18O = 23.5‰) with a mass dependent isotopic signature (Δ17O = 0), thus providing a unique isotopic signature of jet nitrate. A year long sampling campaign at one of the world's busiest airports, the Los Angeles International airport showed the contribution of NO3 varies from 60 to 90% in summer and winter with variations largely attributed to the change in road traffic as air traffic remains fairly constant throughout the year at LAX. The next step in this is to detect these contributions at distal sites and use this as a signal carrier of atmospheric nitrate and its transport in general in the global biogeochemical system. These aspects will be discussed in the presentation.

  9. U-Pb systematics of zircon and titanite from the Gardnos impact structure, Norway: Evidence for impact at 546 Ma?

    NASA Astrophysics Data System (ADS)

    Kalleson, E.; Corfu, F.; Dypvik, H.

    2009-05-01

    Zircon and titanite were investigated in impactites of the Gardnos structure, a crater formed in Sveconorwegian (ca. 1 Ga) crust, which was then overridden in the Devonian by Caledonian nappes. Observed deformation features in zircons are granular texture, planar microstructures, and likely the incorporation of organic carbon during impact causing black staining of the zircon grains. The grains were studied by scanning electron microscopy (SEM) and cathode luminescence (CL) and dated by U-Pb isotope dilution - thermo-ionization mass spectrometry (ID-TIMS). Zircon grains without impact related features have U-Pb data showing moderate discordance (5-13%) and indicating formation ages mostly in the range of 1600-1000 Ma, except detrital zircon ages as old as >2481 Ma, reflecting the diversity of target rocks in the area. Titanite with concordant ages of 995-999 Ma dates metamorphism during final juxtaposition of the Telemarkia on the Idefjorden terrane to the east. Zircon grains with demonstrated or presumed shock features yield highly discordant (14-40%) U-Pb data, with a majority of them plotting along an array with a lower intercept of about 340 Ma reflecting the influence of the Caledonian orogeny and recent Pb-loss. One zircon grain was totally reset at 379 Ma during late Caledonian metamorphism, which also caused local growth of new titanite. A specific group of zircon grains yields data with relatively high discordance for moderate U contents, and five of these analyses, including that of a grain with proven granular or aggregate texture, fit a discordia line with an upper intercept of 546 ± 5 Ma. These features are interpreted as indicating zircon break-down to an amorphous state during impact, with subsequent recrystallization into microcrystalline aggregates causing extensive to complete Pb loss. We further suggest that their crystallinity prevented Pb loss during the Caledonian orogeny, while the small subgrain size and increasing metamictisation allowed

  10. Zircon-scale insights into the history of a Supervolcano, Bishop Tuff, Long Valley, California, with implications for the Ti-in-zircon geothermometer

    USGS Publications Warehouse

    Reid, M.R.; Vazquez, J.A.; Schmitt, A.K.

    2011-01-01

    Zircon has the outstanding capacity to record chronological, thermal, and chemical information, including the storage history of zoned silicic magma reservoirs like the one responsible for the Bishop Tuff of eastern California, USA. Our novel ion microprobe approach reveals that Bishop zircon rims with diverse chemical characteristics surround intermediate domains with broadly similar compositions. The highest Y, REE, U, and Th concentrations tend to accompany the largest excesses in Y + REE3+:P beyond what can be explained by xenotime substitution in zircon. Apparent Ti-in-zircon temperatures of <720??C for zircon rims are distinctly lower than most of the range in eruption temperatures, as estimated from FeTi-oxide equilibria and zircon solubility at quench. While permissive of crystallization of zircon at near-solidus conditions, the low Ti-in-zircon temperatures are probably better explained by sources of inaccuracy in the temperature estimates. After apparently nucleating from different melts, zircons from across the Bishop Tuff compositional spectrum may have evolved to broadly similar chemical and thermal conditions and therefore it is possible that there was no significant thermal gradient in the magma reservoir at some stage in its evolution. There is also no compelling evidence for punctuated heat ?? chemical influxes during the intermediate stages of zircon growth. Judging by the zircon record, the main volume of the erupted magma evolved normally by secular cooling but the latest erupted portion is characterized by a reversal in chemistry that appears to indicate perfusion of the magma reservoir by-or zircon entrainment in-a less evolved melt from the one in which the zircons had previously resided. ?? 2010 Springer-Verlag.

  11. Distinguishing wild vs. stocked lake trout (Salvelinus namaycush) in Lake Ontario: Evidence from carbon and oxygen stable isotope values of otoliths

    USGS Publications Warehouse

    Schaner, T.; Patterson, W.P.; Lantry, B.F.; O'Gorman, R.

    2007-01-01

    We investigated the potential for using carbon and oxygen isotope values of otolith carbonate as a method to distinguish naturally produced (wild) lake trout (Salvelinus namaycush) from hatchery-reared lake trout in Lake Ontario. We determined δ 13C(CaCO3) and δ 18O(CaCO3) values of otoliths from juvenile fish taken from two hatcheries, and of otoliths from wild yearlings. Clear differences in isotope values were observed between the three groups. Subsequently we examined otoliths from large marked and unmarked fish captured in the lake, determining isotope values for regions of the otolith corresponding to the first year of life. Marked (i.e., stocked) fish showed isotope ratios similar to one of the hatchery groups, whereas unmarked fish, (wild fish or stocked fish that lost the mark) showed isotope ratios similar either to one of the hatchery groups or to the wild group. We interpret these data to suggest that carbon and oxygen isotope values can be used to determine the origin of lake trout in Lake Ontario, if a catalogue of characteristic isotope values from all candidate years and hatcheries is compiled.

  12. Oxygen isotope composition of evapotranspiration and its relation to C4 photosynthetic discrimination

    USDA-ARS?s Scientific Manuscript database

    The oxygen isotope ratio of water (18 O-H2O) and carbon dioxide (18 O-CO2) is an important signal of global change and can provide constraints on the coupled carbon-water cycle. Here, simultaneous observations of 18O-H2O (liquid and vapor phases) and 18 O-CO2 were used to investigate the relation be...

  13. Ab initio study of nitrogen and position-specific oxygen kinetic isotope effects in the NO + O3 reaction

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2016-12-01

    Ab initio calculations have been carried out to investigate nitrogen (k15/k14) and position-specific oxygen (k17/k16O & k18/k16) kinetic isotope effects (KIEs) for the reaction between NO and O3 using CCSD(T)/6-31G(d) and CCSD(T)/6-311G(d) derived frequencies in the complete Bigeleisen equations. Isotopic enrichment factors are calculated to be -6.7‰, -1.3‰, -44.7‰, -14.1‰, and -0.3‰ at 298 K for the reactions involving the 15N16O, 14N18O, 18O16O16O, 16O18O16O, and 16O16O18O isotopologues relative to the 14N16O and 16O3 isotopologues, respectively (CCSD(T)/6-311G(d)). Using our oxygen position-specific KIEs, a kinetic model was constructed using Kintecus, which estimates the overall isotopic enrichment factors associated with unreacted O3 and the oxygen transferred to NO2 to be -19.6‰ and -22.8‰, respectively, (CCSD(T)/6-311G(d)) which tends to be in agreement with previously reported experimental data. While this result may be fortuitous, this agreement suggests that our model is capturing the most important features of the underlying physics of the KIE associated with this reaction (i.e., shifts in zero-point energies). The calculated KIEs will useful in future NOx isotopic modeling studies aimed at understanding the processes responsible for the observed tropospheric isotopic variations of NOx as well as for tropospheric nitrate.

  14. Etching fission tracks in zircons

    USGS Publications Warehouse

    Naeser, C.W.

    1969-01-01

    A new technique has been developed whereby fission tracks can be etched in zircon with a solution of sodium hydroxide at 220??C. Etching time varied between 15 minutes and 5 hours. Colored zircon required less etching time than the colorless varieties.

  15. Zircon U-Pb geochronology, Sr-Nd-Hf isotopic composition and geological significance of the Late Triassic Baijiazhuang and Lvjing granitic plutons in West Qinling Orogen

    NASA Astrophysics Data System (ADS)

    Duan, Meng; Niu, Yaoling; Kong, Juanjuan; Sun, Pu; Hu, Yan; Zhang, Yu; Chen, Shuo; Li, Jiyong

    2016-09-01

    The Qinling Orogen was a consequence of continental collision of the South China Craton with the North China Craton in the Triassic and caused widespread granitoid magmatism. However, the petrogenesis of these granitoids remains controversial. In this paper, we choose the Baijiazhuang (BJZ) and Lvjing (LJ) plutons in the West Qinling Orogen for a combined study of the zircon U-Pb geochronology, whole-rock major and trace element compositions and Sr-Nd-Hf isotopic characteristics. We obtained zircon crystallization ages of 216 Ma and 212 Ma for the BJZ and the LJ plutons, respectively. The granitoid samples from both plutons have high K2O metaluminous to peraluminous compositions. They are enriched in large ion lithophile elements (LILEs), light rare earth elements (LREEs) and depleted in high field-strength elements (HFSEs) with significant negative Eu anomalies. The BJZ samples have initial Sr isotopic ratios of 0.7032 to 0.7078, εNd(t) of - 10.99 to - 8.54 and εHf (t) of - 10.22 to - 6.41. The LJ granitoids have initial Sr isotopic ratios of 0.7070 to 0.7080, εNd(t) of - 5.37 to - 4.58 and εHf(t) of - 3.64 to - 1.78. The enriched isotopic characteristics of the two plutons are consistent with their source being dominated by ancient continental crust. However, two BJZ samples show depleted Sr isotope compositions, which may infer possible involvement of mantle materials. Mantle-derived melt, which formed from partial melting of mantle wedge peridotite facilitated by dehydration of the subducted/subducting Mianlue ocean crust, provide the required heat for the crustal melting while also contributing to the compositions of these granitoids. That is, the two granitic plutons are magmatic responses to the closure of the Mianlue ocean basin and the continental collision between the Yangtze and South Qinling crustal terranes. (143Nd/144Nd)i = (143Nd/144Nd) - (147Sm/144Nd) × (eλt - 1), εNd(t) = [(143Nd/144Nd) / (143Nd/144Nd)CHUR(t) - 1] × 104, (143Nd/144Nd

  16. At what conditions does zircon grow/dissolve during high-T metamorphism? Relating zircon textures to PT-conditions

    NASA Astrophysics Data System (ADS)

    Kunz, Barbara E.; Regis, Daniele; Manzotti, Paola; Engi, Martin

    2015-04-01

    A key question in ziconology is when and how zircon grows during metamorphism. To shed light on zircon forming processes and the corresponding PT-conditions during high-T metamorphism a case study was undertaken. The Ivrea Zone (N-Italy) exposes a lower continental crustal section in which a continuous metamorphic field gradient from amphibolite to granulite facies is documented. This field gradient is thought to reflect protracted heating during late Paleozoic times, with a probable high-T peak in the Permian. We present first results from a primarily textural study supported by U-Pb ages, Th/U ratios and Ti-in-Zrn thermometry. Four types of zircon were identified based on their overgrowth proportions and the preservation of detrital cores. Zircon grains were thus classified as Type1 - detrital grains with no overgrowth or very narrow rims (300 Ma) and appears to reflect an early dehydration phase. Rim2b has Permian ages (median 275 Ma), is by far the most common overgrowth type, found in a wide PT-range. Its development appears related to biotite breakdown. Rim3 is texturally indicative of magmatic zircon, occurs only in diatexites. Rim4 is the latest overgrowth and is locally found at all metamorphic grades. Textural features suggest late fluid-related recrystallization of existing zircon. At lowest grade (675±35°C, 6±2 kbar) zircons show type1 only, overgrowths are too thin to clearly identify the rim type. Further upgrade (~700°C, 7 kbar) type1 and type2 dominate. Type2 zircons show rim1, rim2a and occasionally rim4. At the Mu-out isograd (750±50°C, 8.2±1.4 kbar) most zircons are of type2, now with rim2b instead of 2a, in addition to rim1 and rim4. Near and in granulite facies (to 800°C, 8±2 kbar) mostly zircon type2 and type4 are present. While rim1 gets more narrow with increasing metamorphic grade, rim2b grows significantly thicker. Occasionally rim2a and rim4 occur. Close to the Bt-out isograd (~860°C, 9.2±1.7 kbar), mostly type3 and type4 are

  17. Interpreting species-specific variation in tree-ring oxygen isotope ratios among three temperate forest trees

    Treesearch

    Xin Song; Kenneth S. Clark; Brent R. Helliker

    2014-01-01

    Although considerable variation has been documented in tree-ring cellulose oxygen isotope ratios (δ18Ocell) among co-occurring species, the underlying causes are unknown. Here, we used a combination of field measurements and modelling to investigate the mechanisms behind variations in late-wood δ

  18. From opening to subduction of an oceanic domain constrained by LA-ICP-MS U-Pb zircon dating (Variscan belt, Southern Armorican Massif, France)

    NASA Astrophysics Data System (ADS)

    Paquette, J.-L.; Ballèvre, M.; Peucat, J.-J.; Cornen, G.

    2017-12-01

    In the Variscan belt of Western Europe, the lifetime and evolution of the oceanic domain is poorly constrained by sparse, outdated and unreliable multigrain ID-TIMS U-Pb zircon dating. In this article, we present a complete in situ LA-ICP-MS dataset of about 300 U-Pb zircon analyses obtained on most of the ophiolitic and eclogitic outcrops of Southern Brittany, comprising new dating of previously published zircon populations and newly discovered rock samples. In situ dating and cathodo-luminescence imaging of each zircon grain yields new absolute time-constraints on the evolution of the Galicia-Moldanubian Ocean. The new results confirm that the opening of this oceanic domain is well defined at about 490 Ma. In contrast, the generally-quoted 400-410 Ma-age for the high-pressure event related to the subduction of the oceanic crust is definitely not recorded in the zircons of the eclogites. In light of these new data, we propose that the obduction of oceanic rocks occurred at about 370-380 Ma while the high-pressure event is recorded at 355 Ma in only a few zircon grains of some eclogite samples. Additionally, this large scale dating project demonstrates that the zircons from eclogites do not systematically recrystallise during the high pressure event and consequently their U-Pb systems do not record that metamorphism systematically. These zircons rather preserve the isotopic memory of the magmatic crystallization of their igneous protolith. Another example of an eclogite sample from the French Massif Central illustrates the frequent mistake in the interpretation of the ages of the early hydrothermal alteration of zircons in the oceanic crust versus partial or complete recrystallization during eclogite facies metamorphism.

  19. The activity-composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: III. Vapor-liquid water equilibration of NaCl solutions to 350°C

    NASA Astrophysics Data System (ADS)

    Horita, Juske; Cole, David R.; Wesolowski, David J.

    1995-03-01

    The effect of dissolved NaCl on equilibrium oxygen and hydrogen isotope fractionation factors between liquid water and water vapor was precisely determined in the temperature range from 130-350°C, using two different types of apparatus with static or dynamic sampling techniques of the vapor phase. The magnitude of the oxygen and hydrogen isotope effects of NaCl is proportional to the molality of liquid NaCl solutions at a given temperature. Dissolved NaCl lowers appreciably the hydrogen isotope fractionation factor between liquid water and water vapor over the entire temperature range. NaCl has little effect on the oxygen isotope fractionation factor at temperatures below about 200°C, with the magnitude of the salt effect gradually increasing from 200-350°C. Our results are at notable variance with those of Truesdell (1974) and Kazahaya (1986), who reported large oxygen and hydrogen isotope effects of NaCl with very complex dependencies on temperature and NaCl molality. Our high-temperature results have been regressed along with our previous results between 50 and 100°C (Horita et al., 1993a) and the low-temperature literature data to simple equations which are valid for NaCl solutions from 0 to at least 5 molal NaCl in the temperature range from 10-350°C. Our preliminary results of oxygen isotope fractionation in the system CaCO3-water ± NaCl at 300°C and 1 kbar are consistent with those obtained from the liquid-vapor equilibration experiments, suggesting that the isotope salt effects are common to systems involving brines and any other coexisting phases or species (gases, minerals, dissolved species, etc.). The observed NaCl isotope effects at elevated temperatures should be taken into account in the interpretation of isotopic data of brine-dominated natural systems.

  20. Moisture transport across Canada: evidence from stable oxygen and deuterium isotope values of lakes and rivers

    NASA Astrophysics Data System (ADS)

    Oakley, J. R.; Patterson, W. P.

    2008-12-01

    Global warming models often contain a prediction of changes in precipitation, yet modern moisture cycling is poorly understood. Stable oxygen and deuterium isotope values of several thousand lake and river water samples collected from 2004 to 2008 throughout Canada and the Northern United States provide a means to evaluate variations in the movement of moisture across the northern North American continent. Our particular focus is on the moisture tracking in the province of Saskatchewan. The dominant moisture source for Saskatchewan is the Gulf of Mexico, though precipitation contains some water from the Pacific and Arctic Oceans as well. By sampling locations multiple times, we established time series of isotope variability that we can relate to meteorological variation. A series of cross-plots of oxygen to deuterium isotopes for each year exhibits an increase in slope from year to year that reflects an increase in humidity and/or precipitation throughout the Prairies from 2004 to 2008. We define the influence of temperature, precipitation and humidity on the change in slope for each suite of samples. Ultimately, by combining our evidence of moisture transport with a grid of long-term secular records from lakes, speleothems and tree-ring isotope variability, we can not only reconstruct changes in atmospheric circulation through time, but also better predict what will happen in the future under various global climate change scenarios.

  1. Oxygen isotopic evidence for accretion of Earth's water before a high-energy Moon-forming giant impact.

    PubMed

    Greenwood, Richard C; Barrat, Jean-Alix; Miller, Martin F; Anand, Mahesh; Dauphas, Nicolas; Franchi, Ian A; Sillard, Patrick; Starkey, Natalie A

    2018-03-01

    The Earth-Moon system likely formed as a result of a collision between two large planetary objects. Debate about their relative masses, the impact energy involved, and the extent of isotopic homogenization continues. We present the results of a high-precision oxygen isotope study of an extensive suite of lunar and terrestrial samples. We demonstrate that lunar rocks and terrestrial basalts show a 3 to 4 ppm (parts per million), statistically resolvable, difference in Δ 17 O. Taking aubrite meteorites as a candidate impactor material, we show that the giant impact scenario involved nearly complete mixing between the target and impactor. Alternatively, the degree of similarity between the Δ 17 O values of the impactor and the proto-Earth must have been significantly closer than that between Earth and aubrites. If the Earth-Moon system evolved from an initially highly vaporized and isotopically homogenized state, as indicated by recent dynamical models, then the terrestrial basalt-lunar oxygen isotope difference detected by our study may be a reflection of post-giant impact additions to Earth. On the basis of this assumption, our data indicate that post-giant impact additions to Earth could have contributed between 5 and 30% of Earth's water, depending on global water estimates. Consequently, our data indicate that the bulk of Earth's water was accreted before the giant impact and not later, as often proposed.

  2. Isotopic fractionation of oxygen and carbon in decomposed lower-mantle inclusions in diamond

    DOE PAGES

    Kaminsky, Felix; Matzel, Jennifer; Jacobsen, Ben; ...

    2015-07-25

    Two carbonatitic mineral assemblages, calcite + wollastonite and calcite + monticellite, which are encapsulated in two diamond grains from the Rio Soriso basin in the Juina area, Mato Grosso State, Brazil, were studied utilizing the NanoSIMS technique. The assemblages were formed as the result of the decomposition of the lower-mantle assemblage calcite + CaSi-perovskite + volatile during the course of the diamond ascent under pressure conditions from 15 to less than 0.8 GPa. The oxygen and carbon isotopic compositions of the studied minerals are inhomogeneous. They fractionated during the process of the decomposition of primary minerals to very varying values:more » δ 18O from –3.3 to +15.4 ‰ SMOW and δ 13C from –2.8 to +9.3 ‰ VPDB. As a result, these values significantly extend the mantle values for these elements in both isotopically-light and isotopically-heavy areas.« less

  3. Isotopic exchange in mineral-fluid systems. IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H 2O and layer silicate-H 2O systems

    NASA Astrophysics Data System (ADS)

    Cole, David R.

    2000-03-01

    Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. We tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H 2O and layer silicate-H 2O at 300 and 350°C, respectively. Witherite (BaCO 3), strontianite (SrCO 3) and calcite (CaCO 3) were reacted with pure H 2O for different lengths of time (271-1390 h) at 300°C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H 2O for durations ranging from 132 to 3282 h at 350°C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. Changes in the mean grain diameters were particularly significant in experiments involving withertite, strontianite and biotite. The variations in the extent of oxygen isotope exchange were measured as a function of time, and fit to a pseudo-first order rate model that accounted for the change in surface area of the solid during reaction. The isotopic rates (ln r) for the carbonate-H 2O system are -20.75 ± 0.44, -18.95 ± 0.62 and -18.51 ± 0.48 mol O m -2 s -1 for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H 2O systems are -23.99 ± 0.89, -23.14 ± 0.74 and -22.40 ± 0.66 mol O m -2 s -1 for muscovite, biotite and chlorite, respectively. The rates for the carbonate-H 2O systems increase in order from calcite to strontianite to witherite. This order

  4. Accretionary history of the Altai-Mongolian terrane: perspectives from granitic zircon U-Pb and Hf-isotope data

    NASA Astrophysics Data System (ADS)

    Cai, Keda; Sun, Min; Xiao, Wenjiao

    2014-05-01

    The Central Asian Orogenic Belt (CAOB) consists of many tectonic terranes with distinct origin and complicated evolutionary history. Understanding of individual block is crucial to reconstruct the geodynamic history of the gigantic accetionary collage. This study presents zircon U-Pb ages and Hf isotopes for the granitoid rocks in the Russian Altai mountain range (including Gorny Altai, Altai-Mongolian terrane and CTUS suture zone between them), in order to clarify the timing of granitic magmatism, source nature, continental crustal growth and tectonic evolution. Our dating results suggest that granitic magmatism of the Russian Altai mountain range occurred in three major episodes including 445~429 Ma, 410~360 Ma and ~241 Ma. Most of the zircons within the Paleozoic granitoids present comparable positive ɛHf(t) values and Neoproterozoic crustal model ages, which favor the interpretation that the juvenile crustal materials produced in the early stage of CAOB were probably dominant sources for the Paleozoic magmatism in the region. The inference is also supported by widespread occurrence of short-lived juvenile materials including ophiolites, seamount relics and arc assemblages in the north CAOB. Consequently, the Paleozoic massive granitic rocks maybe not represent continental crustal growth at the time when they were emplaced, but rather record reworking of relatively juvenile Proterozoic crustal rocks although mantle-derived mafic magma was possibly involved to sever as heat engine during granitic magma generation. The Early Triassic granitic intrusion may be product in an intra-plate environment, as the case of same type rocks in the adjacent areas. The positive ɛHf(t) values (1.81~7.47) and corresponding Hf model ages (0.80~1.16 Ga) together with evidence of petrology are consistent with the interpretation that the parental magma of the Triassic granitic intrusion was produced from enriched mantle-derived sources under an usually high temperature condition

  5. Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands).

    PubMed

    Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

    2016-10-01

    Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ(18)Ocalc and δ(13)Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ(18)Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in (18)O relative to (16)O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ(18)Ocalc value of eggshell calcite to the δ(18)Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ(13)Ccalc and δ(18)Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ(13)Ccalc and high δ(18)Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

  6. Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands)

    NASA Astrophysics Data System (ADS)

    Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

    2016-10-01

    Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ18Ocalc and δ13Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ18Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in 18O relative to 16O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ18Ocalc value of eggshell calcite to the δ18Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ13Ccalc and δ18Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ13Ccalc and high δ18Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

  7. Timescales for the evolution of oxygen isotope compositions in the solar nebula

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.; Bergin, E. A.; Ciesla, F. J.; Davis, A. M.; Desch, S. J.; Hashizume, K.; Lee, J.-E.

    2009-09-01

    We review two models for the origin of the calcium-, aluminum-rich inclusion (CAI) oxygen isotope mixing line in the solar nebula: (1) CO self-shielding, and (2) chemical mass-independent fractionation (MIF). We consider the timescales associated with formation of an isotopically anomalous water reservoir derived from CO self-shielding, and also the vertical and radial transport timescales of gas and solids in the nebula. The timescales for chemical MIF are very rapid. CO self-shielding models predict that the Sun has Δ 17O SMOW ˜ -20‰ (Clayton, 2002), and chemical mass-independent fractionation models predict Δ 17O SMOW ˜0‰. Preliminary Genesis results have been reported by McKeegan et al. (McKeegan K. D., Coath C. D., Heber, V., Jarzebinski G., Kallio A. P., Kunihiro T., Mao P. H. and Burnett D. S. (2008b) The oxygen isotopic composition of captured solar wind: first results from the Genesis. EOS Trans. AGU 89(53), Fall Meet. Suppl., P42A-07 (abstr)) and yield a Δ 17O SMOW of ˜ -25‰, consistent with a CO self-shielding scenario. Assuming that subsequent Genesis analyses support the preliminary results, it then remains to determine the relative contributions of CO self-shielding from the X-point, the surface of the solar nebula and the parent molecular cloud. The relative formation ages of chondritic components can be related to several timescales in the self-shielding theories. Most importantly the age difference of ˜1-3 My between CAIs and chondrules is consistent with radial transport from the outer solar nebula (>10 AU) to the meteorite-forming region, which supports both the nebular surface and parent cloud self-shielding scenarios. An elevated radiation field intensity is predicted by the surface shielding model, and yields substantial CO photolysis (˜50%) on timescales of 0.1-1 My. An elevated radiation field is also consistent with the parent cloud model. The elevated radiation intensities may indicate solar nebula birth in a medium to large

  8. A search for thermal excursions from ancient extraterrestrial impacts using Hadean zircon Ti-U-Th-Pb depth profiles

    PubMed Central

    Abbott, Sunshine S.; Harrison, T. Mark; Schmitt, Axel K.; Mojzsis, Stephen J.

    2012-01-01

    Few terrestrial localities preserve more than a trace lithic record prior to ca. 3.8 Ga greatly limiting our understanding of the first 700 Ma of Earth history, a period inferred to have included a spike in the bolide flux to the inner solar system at ca. 3.85–3.95 Ga (the Late Heavy Bombardment, LHB). An accessible record of this era may be found in Hadean detrital zircons from the Jack Hills, Western Australia, in the form of μm-scale epitaxial overgrowths. By comparing crystallization temperatures of pre-3.8 Ga zircon overgrowths to the archive of zircon temperature spectra, it should, in principle, be possible to identify a distinctive impact signature. We have developed Ti-U-Th-Pb ion microprobe depth profiling to obtain age and temperature information within these zircon overgrowths and undertaken a feasibility study of its possible use in identifying impact events. Of eight grains profiled in this fashion, four have overgrowths of LHB-era age. Age vs. temperature profiles reveal a period between ca. 3.85–3.95 Ga (i.e., LHB era) characterized by significantly higher temperatures (approximately 840–875 °C) than do older or younger zircons or zircon domains (approximately 630–750 °C). However, temperatures approaching 900 °C can result in Pb isotopic exchange rendering interpretation of these profiles nonunique. Coupled age-temperature depth profiling shows promise in this role, and the preliminary data we report could represent the first terrestrial evidence for impact-related heating during the LHB. PMID:22869711

  9. Zircon age-temperature-compositional spectra in plutonic rocks

    DOE PAGES

    Samperton, Kyle M.; Bell, Elizabeth A.; Barboni, Mélanie; ...

    2017-08-23

    We present that geochronology can resolve dispersed zircon dates in plutonic rocks when magma cooling time scales exceed the temporal precision of individual U-Pb analyses; such age heterogeneity may indicate protracted crystallization between the temperatures of zircon saturation (T sat) and rock solidification (T solid). Diffusive growth models predict asymmetric distributions of zircon dates and crystallization temperatures in a cooling magma, with volumetrically abundant old, hot crystallization at T sat decreasing continuously to volumetrically minor young, cold crystallization at T solid. We present integrated geochronological and geochemical data from Bergell Intrusion tonalites (Central Alps, Europe) that document zircon compositional changemore » over hundreds of thousands of years at the hand-sample scale, indicating melt compositional evolution during solidification. Ti-in-zircon thermometry, crystallization simulation using MELTS software, and U-Pb dates produce zircon mass-temperature-time distributions that are in excellent agreement with zircon growth models. In conclusion, these findings provide the first quantitative validation of longstanding expectations from zircon saturation theory by direct geochronological investigation, underscoring zircon’s capacity to quantify supersolidus cooling rates in magmas and resolve dynamic differentiation histories in the plutonic rock record.« less

  10. Zircon age-temperature-compositional spectra in plutonic rocks

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Samperton, Kyle M.; Bell, Elizabeth A.; Barboni, Mélanie

    We present that geochronology can resolve dispersed zircon dates in plutonic rocks when magma cooling time scales exceed the temporal precision of individual U-Pb analyses; such age heterogeneity may indicate protracted crystallization between the temperatures of zircon saturation (T sat) and rock solidification (T solid). Diffusive growth models predict asymmetric distributions of zircon dates and crystallization temperatures in a cooling magma, with volumetrically abundant old, hot crystallization at T sat decreasing continuously to volumetrically minor young, cold crystallization at T solid. We present integrated geochronological and geochemical data from Bergell Intrusion tonalites (Central Alps, Europe) that document zircon compositional changemore » over hundreds of thousands of years at the hand-sample scale, indicating melt compositional evolution during solidification. Ti-in-zircon thermometry, crystallization simulation using MELTS software, and U-Pb dates produce zircon mass-temperature-time distributions that are in excellent agreement with zircon growth models. In conclusion, these findings provide the first quantitative validation of longstanding expectations from zircon saturation theory by direct geochronological investigation, underscoring zircon’s capacity to quantify supersolidus cooling rates in magmas and resolve dynamic differentiation histories in the plutonic rock record.« less

  11. On the Use of Biomineral Oxygen Isotope Data to Identify Human Migrants in the Archaeological Record: Intra-Sample Variation, Statistical Methods and Geographical Considerations

    PubMed Central

    Lightfoot, Emma; O’Connell, Tamsin C.

    2016-01-01

    Oxygen isotope analysis of archaeological skeletal remains is an increasingly popular tool to study past human migrations. It is based on the assumption that human body chemistry preserves the δ18O of precipitation in such a way as to be a useful technique for identifying migrants and, potentially, their homelands. In this study, the first such global survey, we draw on published human tooth enamel and bone bioapatite data to explore the validity of using oxygen isotope analyses to identify migrants in the archaeological record. We use human δ18O results to show that there are large variations in human oxygen isotope values within a population sample. This may relate to physiological factors influencing the preservation of the primary isotope signal, or due to human activities (such as brewing, boiling, stewing, differential access to water sources and so on) causing variation in ingested water and food isotope values. We compare the number of outliers identified using various statistical methods. We determine that the most appropriate method for identifying migrants is dependent on the data but is likely to be the IQR or median absolute deviation from the median under most archaeological circumstances. Finally, through a spatial assessment of the dataset, we show that the degree of overlap in human isotope values from different locations across Europe is such that identifying individuals’ homelands on the basis of oxygen isotope analysis alone is not possible for the regions analysed to date. Oxygen isotope analysis is a valid method for identifying first-generation migrants from an archaeological site when used appropriately, however it is difficult to identify migrants using statistical methods for a sample size of less than c. 25 individuals. In the absence of local previous analyses, each sample should be treated as an individual dataset and statistical techniques can be used to identify migrants, but in most cases pinpointing a specific homeland should

  12. Oxygen isotope systematics of chondrules in the Murchison CM2 chondrite and implications for the CO-CM relationship

    NASA Astrophysics Data System (ADS)

    Chaumard, Noël; Defouilloy, Céline; Kita, Noriko T.

    2018-05-01

    High-precision oxygen three-isotope measurements of olivine and pyroxene were performed on 29 chondrules in the Murchison CM2 chondrite by secondary ion mass spectrometry (SIMS). The oxygen isotope ratios of analyzed chondrules all plot very close to the primitive chondrule minerals (PCM) line. In each of 24 chondrules, the olivine and/or pyroxene grains analyzed show indistinguishable oxygen isotope ratios. Exceptions are minor occurrences of isotopically distinguished relict olivine grains, which were found in nine chondrules. The isotope homogeneity of these phenocrysts is consistent with a co-magmatic crystallization of olivine and pyroxene from the final chondrule melts and a significant oxygen isotope exchange between the ambient gas and the melts. Homogeneous type I chondrules with Mg#'s of 98.9-99.5 have host chondrule Δ17O values ranging from -6.0‰ to -4.1‰, with one exception (Δ17O: -1.2‰; Mg#: 99.6). Homogeneous chondrules with Mg#'s <96, including four type II chondrules (Mg# ∼65-70), have Δ17O values of around -2.5‰. Five type I chondrules (Mg# ≥99) have internally heterogeneous oxygen isotope ratios with Δ17O values ranging from -6.5‰ to -4.0‰, similar to those of host chondrule values. These heterogeneous chondrules have granular or porphyritic textures, convoluted outlines, and contain numerous metal grains dispersed within fine-grained silicates. This is consistent with a low degree of melting of the chondrule precursors, possibly because of a low temperature of the melting event and/or a shorter duration of melting. The Δ17O values of relict olivine grains in nine chondrules range from -17.9‰ to -3.4‰, while most of them overlap the range of the host chondrule values. Similar to those reported from multiple carbonaceous chondrites (Acfer 094, Y-82094, CO, and CV), the Δ17O ∼ -5‰ and high Mg# (≥99) chondrules, which might derive from a reduced reservoir with limited dust enrichments (∼50 × Solar System), dominate

  13. HIGH ARSENIC CONCENTRATIONS AND ENRICHED SULFUR AND OXYGEN ISOTOPES IN A FRACTURED-BEDROCK GROUND-WATER SYSTEM

    EPA Science Inventory

    Elevated arsenic concentrations are coincident with enriched sulfur and oxygen isotopes of sulfate in bedrock ground water within Kelly's Cove watershed, Northport, Maine, USA. Interpretation of the data is complicated by the lack of correlations between sulfate concentrations an...

  14. Archean crustal evolution in the Southern São Francisco craton, Brazil: Constraints from U-Pb, Lu-Hf and O isotope analyses

    NASA Astrophysics Data System (ADS)

    Albert, Capucine; Farina, Federico; Lana, Cristiano; Stevens, Gary; Storey, Craig; Gerdes, Axel; Dopico, Carmen Martínez

    2016-12-01

    In this study we present U-Pb and Hf isotope data combined with O isotopes in zircon from Neoarchean granitoids and gneisses of the southern São Francisco craton in Brazil. The basement rocks record three distinct magmatic events: Rio das Velhas I (2920-2850 Ma), Rio das Velhas II (2800-2760 Ma) and Mamona (2750-2680 Ma). The three sampled metamorphic complexes (Bação, Bonfim and Belo Horizonte) have distinct εHf vs. time arrays, indicating that they grew as separate terranes. Paleoarchean crust is identified as a source which has been incorporated into younger magmatic rocks via melting and mixing with younger juvenile material, assimilation and/or source contamination processes. The continental crust in the southern São Francisco craton underwent a change in magmatic composition from medium- to high-K granitoids in the latest stages, indicating a progressive HFSE enrichment of the sources that underwent anatexis in the different stages and possibly shallowing of the melting depth. Oxygen isotope data shows a secular trend towards high δ18O (up to 7.79‰) indicating the involvement of metasediments in the petrogenesis of the high potassium granitoids during the Mamona event. In addition, low δ18O values (down to 2.50‰) throughout the Meso- and Neoarchean emphasize the importance of meteoritic fluids in intra-crustal magmatism. We used hafnium isotope modelling from a compilation of detrital zircon compositions to constrain crustal growth rates and geodynamics from 3.50 to 2.65 Ga. The modelling points to a change in geodynamic process in the southern São Francisco craton at 2.9 Ga, from a regime dominated by net crustal growth in the Paleoarchean to a Neoarchean regime marked by crustal reworking. The reworking processes account for the wide variety of granitoid magmatism and are attributed to the onset of continental collision.

  15. The oxygen isotope partition function ratio of water and the structure of liquid water

    USGS Publications Warehouse

    O'Neil, J.R.; Adami, L.H.

    1969-01-01

    By means of the CO2-equilibration technique, the temperature dependence and absolute values of the oxygen isotope partition function ratio of liquid water have been determined, often at 1?? intervals, from -2 to 85??. A linear relationship between In (Q2/Q1) (H2O) and T-1 was obtained that is explicable in terms of the Bigeleisen-Mayer theory of isotopic fractionation. The data are incompatible with conventional, multicomponent mixture models of water because liquid water behaves isotopically as a singly structured homogeneous substance over the entire temperature range studied. A two-species model of water is proposed in which approximately 30% of the hydrogen bonds in ice are broken on melting at 0?? and in which this per cent of monomer changes by only a small amount over the entire liquid range. Because of the high precision and the fundamental property determined, the isotopic fractionation technique is particularly well suited to the detection of thermal anomalies. No anomalies were observed and those previously reported are ascribed to under-estimates of experimental error.

  16. Magmatic Longevity Constrained by ID-TIMS U-Pb Dating of Zircon and Titanite

    NASA Astrophysics Data System (ADS)

    Szymanowski, D.; Wotzlaw, J. F.; Ellis, B. S.; Bachmann, O.; Von Quadt, A.

    2016-12-01

    Clues about the timescales and thermal conditions associated with the growth and evacuation of large silicic magma reservoirs are frequently drawn from radiometric dating, diffusion modelling, or thermomechanical modelling. A growing amount of petrological and geochronological evidence, supported by thermal modelling, suggests that many silicic magma reservoirs may exist for some 104-106 years in the form of high-crystallinity mushes at relatively low temperatures ( 700-750°C; [1-3]). Geochronological studies addressing this issue typically utilise the U-Pb system in zircon capable of recording extended periods of crystallisation, particularly in evolved calc-alkaline systems that spend most of their lifetime zircon-saturated. In this study, we integrate U-Pb dating of zircon and titanite to investigate the longevity of the magma reservoir that produced the Kneeling Nun Tuff, a 35 Ma, >900 km3 crystal-rich rhyolitic super-eruption from the Mogollon-Datil volcanic field in New Mexico (USA). High-precision ID-TIMS U-Pb dates of single crystals of both zircon and titanite independently record a continuous crystallisation history over >400,000 years. We combine the dating of both accessory phases with textural, major, trace element and isotopic studies of single crystals, placing tight constraints on the thermal conditions of magma accumulation and storage while recording differentiation and rejuvenation processes within the magma reservoir. The results suggest a protracted `cool' upper-crustal storage of magma prior to the Kneeling Nun Tuff eruption followed by a melting event which reduced the magma crystallinity and conditioned it for eruption. [1] Bachmann & Bergantz (2004), J. Petrol. 45, 1565-1582. [2] Gelman et al. (2013), Geology 41, 759-762. [3] Cooper & Kent (2014), Nature 506, 480-483.

  17. Oxygen and nitrogen isotope effects duing nitrification and denitrification occuring in Midwesern soils

    NASA Astrophysics Data System (ADS)

    Michalski, G. M.; Wilkens, B.; Sanchez, A. V.; Yount, J.

    2017-12-01

    The processes of nitrification and denitrification are key steps in the biogeochemical cycling of N and are a main control on ecosystem productivity. These processes are ephemeral and often difficult to assess across wide spatial and temporal scales. Natural abundance stable isotopes are a way of potentially assessing these two processes across multiple scales. We have conducted incubation experiments to assess the N and O isotope effects occurring during denitrification in soils typical of the Midwestern United States. Nitrification was examined by incubating soils amended with ammonium (with a known δ15N) mixed with H2O and O2 that had different δ18O values and then measured the δ15N and δ18O of the product nitrate. The fraction of nitrate oxygen arising from H2O and O2 was determined along with the N and O kinetic isotope effect (KIE). For denitrification, nitrate with a known δ15N, δ17O, and δ18O, was incubated in anaerobic soils from 12-48 hours. The residual nitrate was analyzed for isotope change and the KIE for O and N as well as exchange with H2O was determined. These data can be useful for interpreting nitrate isotopes in agricultural fields as a way off assessing nitrification and denitrification is agricultural ecosystems such as the IML-CZO.

  18. Oxygen isotope evidence for submarine hydrothermal alteration of the Del Puerto ophiolite, California

    USGS Publications Warehouse

    Schiffman, P.; Williams, A.E.; Evarts, R.C.

    1984-01-01

    The oxygen isotope compositions and metamorphic mineral assemblages of hydrothermally altered rocks from the Del Puerto ophiolite and overlying volcaniclastic sedimentary rocks at the base of the Great Valley sequence indicate that their alteration occurred in a submarine hydrothermal system. Whole rock ??18O compositions decrease progressively down section (with increasing metamorphic grade): +22.4??? (SMOW) to +13.8 for zeolite-bearing volcaniclastic sedimentary rocks overlying the ophiolite; +19.6 to +11.6 for pumpellyite-bearing metavolcanic rocks in the upper part of the ophiolite's volcanic member; +12.3 to +8.1 for epidote-bearing metavolcanic rocks in the lower part of the volcanic member; +8.5 to +5.7 for greenschist facies rocks from the ophiolite's plutonic member; +7.6 to +5.8 for amphibolite facies or unmetamorphosed rocks from the plutonic member. Modelling of fluid-rock interaction in the Del Puerto ophiolite indicates that the observed pattern of upward enrichment in whole rock ??18O can be best explained by isotopic exchange with discharging 18O-shifted seawater at fluid/rock mass ratios near 2 and temperatures below 500??C. 18O-depleted plutonic rocks necessarily produced during hydrothermal circulation were later removed as a result of tectonism. Submarine weathering and later burial metamorphism at the base of the Great Valley sequence cannot by itself have produced the zonation of hydrothermal minerals and the corresponding variations in oxygen isotope compositions. The pervasive zeolite and prehnite-pumpellyite facies mineral assemblages found in the Del Puerto ophiolite may reflect its origin near an island arc rather than deep ocean spreading center. ?? 1984.

  19. Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

    USGS Publications Warehouse

    Young, M.B.; McLaughlin, K.; Kendall, C.; Stringfellow, W.; Rollog, M.; Elsbury, K.; Donald, E.; Paytan, A.

    2009-01-01

    The oxygen isotopic composition of dissolved inorganic phosphate (δ18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ18O p to be a useful tool for source tracking, the δ18Op of phosphate sources must be distinguishable from one another; however, the δ18Op of potential sources has not been well characterized. We measured the δ18O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ18Op values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and δ18Op can be used for identifying phosphate sources to aquatic systems.

  20. Permian A-type rhyolites of the Muráň Nappe, Inner Western Carpathians, Slovakia: in-situ zircon U-Pb SIMS ages and tectonic setting

    NASA Astrophysics Data System (ADS)

    Ondrejka, Martin; Li, Xian-Hua; Vojtko, Rastislav; Putis, Marian; Uher, Pavel; Sobocký, Tomas

    2018-04-01

    Three representative A-type rhyolitic rock samples from the Muráň Nappe of the inferred Silicic Unit of the Inner Western Carpathians (Slovakia) were dated using the high-precision SIMS U-Pb isotope technique on zircons. The geochronological data presented in this paper is the first in-situ isotopic dating of these volcanic rocks. Oscillatory zoned zircon crystals mostly revealed concordant Permian (Guadalupian) ages: 266.6 ± 2.4 Ma in Tisovec-Rejkovo (TIS-1), 263.3 ± 1.9 Ma in Telgárt-Gregová Hill (TEL-1) and 269.5 ± 1.8 Ma in Veľká Stožka-Dudlavka (SD-2) rhyolites. The results indicate that the formation of A-type rhyolites and their plutonic equivalents are connected to magmatic activity during the Permian extensional tectonics and most likely related to the Pangea supercontinent break-up.