Sample records for u-pb isotope dilution

  1. An algorithm for U-Pb isotope dilution data reduction and uncertainty propagation

    NASA Astrophysics Data System (ADS)

    McLean, N. M.; Bowring, J. F.; Bowring, S. A.

    2011-06-01

    High-precision U-Pb geochronology by isotope dilution-thermal ionization mass spectrometry is integral to a variety of Earth science disciplines, but its ultimate resolving power is quantified by the uncertainties of calculated U-Pb dates. As analytical techniques have advanced, formerly small sources of uncertainty are increasingly important, and thus previous simplifications for data reduction and uncertainty propagation are no longer valid. Although notable previous efforts have treated propagation of correlated uncertainties for the U-Pb system, the equations, uncertainties, and correlations have been limited in number and subject to simplification during propagation through intermediary calculations. We derive and present a transparent U-Pb data reduction algorithm that transforms raw isotopic data and measured or assumed laboratory parameters into the isotopic ratios and dates geochronologists interpret without making assumptions about the relative size of sample components. To propagate uncertainties and their correlations, we describe, in detail, a linear algebraic algorithm that incorporates all input uncertainties and correlations without limiting or simplifying covariance terms to propagate them though intermediate calculations. Finally, a weighted mean algorithm is presented that utilizes matrix elements from the uncertainty propagation algorithm to propagate random and systematic uncertainties for data comparison between other U-Pb labs and other geochronometers. The linear uncertainty propagation algorithms are verified with Monte Carlo simulations of several typical analyses. We propose that our algorithms be considered by the community for implementation to improve the collaborative science envisioned by the EARTHTIME initiative.

  2. Neodymium Isotopic Compositions of the Titanite Reference Materials Used in U-Pb Geochronology

    NASA Astrophysics Data System (ADS)

    Ma, Q.; Yang, Y.; Zhao, Z.

    2017-12-01

    Titanite (CaTiSiO5) is a widespread mineral and preferentially incorporates considerable uranium and significant light rare earth elements (LREEs) in its structure. Geochronology based upon U-Pb and Pb-Pb analyses of titanite has proven to be useful for understanding the P-T-t evolution of many igneous, metamorphic and hydrothermally altered rock samples (Scott and St-Onge, 1995). In the meantime, Sm-Nd isotopic composition in single titanite can be used to obtain initial Nd isotope composition at the time of titanite crystallization when combined with its U-Pb age, making titanite the most versatile mineral for dating metamorphism and tracing hydrothermal source (Amelin et al., 2009). The widely utilized in situ analyses by SIMS and LA-(MC)-ICP-MS have emphasized the significance for uniform and homogeneous reference materials for external correction (Liu et al., 2012, Sun et al., 2012, Yang et al., 2014). Here, we present U-Pb ages and Sm-Nd isotope analyses of twelve natural titanite crystals (12YQ82, T004, Ontario, BLR-1, OLT1, Khan, Qinghu, TLS-36, NW-IOA, C253, Pakistan and MKED1) acquired by Agilent 7500a Q-ICP-MS and Neptune MC-ICP-MS, respectively, combined a 193 nm ArF excimer laser ablation system. For U-Pb dating, elemental fractionation and instrumental drift were externally corrected using MKED1 titanite standard, showing results of U-Pb analyses all within error of those recommended values. With respect to Sm-Nd isotopes, we employed the interference-free 147Sm/149Sm to deduct 144Sm isobaric interference on 144Nd, and the fractionation between 147Sm and 144Nd was calibrated using BLR-1 titanite, which is proved homogenous in Sm-Nd isotopic system. The obtained Sm-Nd isotopic compositions for natural titanite samples are all consistent with those values determined by isotope dilution (ID) MC-ICP-MS, demonstrating the precision and accuracy currently available for in situ Sm-Nd analyses. Our results demonstrate that BLR-1, OLT1 and Ontario titanites

  3. U-Pb Isotope Systematic of SNC Meteorites

    NASA Astrophysics Data System (ADS)

    Jagoutz, E.; Jotter, R.; Kubny, A.; Zartman, R.

    2005-12-01

    A stepwise dissolution technique was applied to several nakhlite meteorites that were heavily contaminated by terrestrial Pb. Pulverized samples were subjected to three acid leaches of increasing strength followed by HF-HNO3 digestion of the remaining residue. Using this procedure the major portion of the terrestrial contamination was removed in Leaches 1 and 2, while essentially uncontaminated Pb was recovered in Leach 3 and the Residue. We give further details here about some of the insights gained from this improved ability to distinguish between the primary and terrestrial Pb components in meteorites. Firstly, we ran one sample of Nakhla as a test of the procedure. The result showed L1 and L2 to be mainly dominated by terrestrial Pb while L3 yielded Pb close to the initial Pb of other Nakhlites. The Pb in the Res, however, was very radiogenic and had a 206Pb/204Pb relative to 207Pb/204Pb indicating a drastic increase of the U/Pb at 1.3 Ga. Furthermore, the relatively unradiogenic 208Pb/204Pb suggested that there might be zircon or other high U/Th mineral in the Res. We made an in-depth study on a thin-section using an electron microscope and found indeed tiny 10 m grains of Baddeleyeite. The same dissolution technique was then applied to other Nakhlites from the Antarctic NIPR collection and NASA (MIL) with similar results, indicating that all Nakhlites may have the same age. In addition, an identical initial Pb isotopic composition indicates that all of these meteorites were derived from the same homogeneous source. Moreover, it is strongly suggested by their initial Pb that the "olivine Shergottites", like SAU, DAG, Que, and Y, likewise come from this Nakhla source. While "normal" Shergottites like Shergotty, LA are from sources having a more evolved Pb isotopic composition. "Olivine Shergottites" are clearly younger than Nakhlites. Their Sm Nd and Rb Sr isotopic systems are highly disturbed. Analyzing the existing data we favor an age of 800 my for the

  4. Evaluation of the combined measurement uncertainty in isotope dilution by MC-ICP-MS.

    PubMed

    Fortunato, G; Wunderli, S

    2003-09-01

    The combination of metrological weighing, the measurement of isotope amount ratios by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) and the use of high-purity reference materials are the cornerstones to achieve improved results for the amount content of lead in wine by the reversed isotope dilution technique. Isotope dilution mass spectrometry (IDMS) and reversed IDMS have the potential to be a so-called primary method, with which close comparability and well-stated combined measurement uncertainties can be obtained. This work describes the detailed uncertainty budget determination using the ISO-GUM approach. The traces of lead in wine were separated from the matrix by ion exchange chromatography after HNO(3)/H(2)O(2) microwave digestion. The thallium isotope amount ratio ( n((205)Tl)/ n((203)Tl)) was used to correct for mass discrimination using an exponential model approach. The corrected lead isotope amount ratio n((206)Pb)/ n((208)Pb) for the isotopic standard SRM 981 measured in our laboratory was compared with ratio values considered to be the least uncertain. The result has been compared in a so-called pilot study "lead in wine" organised by the CCQM (Comité Consultatif pour la Quantité de Matière, BIPM, Paris; the highest measurement authority for analytical chemical measurements). The result for the lead amount content k(Pb) and the corresponding expanded uncertainty U given by our laboratory was:k(Pb)=1.329 x 10-10mol g-1 (amount content of lead in wine)U[k(Pb)]=1.0 x 10-12mol g-1 (expanded uncertainty U=kxuc, k=2)The uncertainty of the main influence parameter of the combined measurement uncertainty was determined to be the isotope amount ratio R(206,B) of the blend between the enriched spike and the sample.

  5. The 238U/235U isotope ratio of the Earth and the solar system: Constrains from a gravimetrically calibrated U double spike and implications for absolute Pb-Pb ages

    NASA Astrophysics Data System (ADS)

    Weyer, Stefan; Noordmann, Janine; Brennecka, Greg; Richter, Stephan

    2010-05-01

    The ratio of 238U and 235U, the two primordial U isotopes, has been assumed to be constant on Earth and in the solar system. The commonly accepted value for the 238U/235U ratio, which has been used in Pb-Pb dating for the last ~ 30 years, was 137.88. Within the last few years, it has been shown that 1) there are considerable U isotope variations (~1.3‰) within terrestrial material produced by isotope fractionation during chemical reactions [1-3] and 2) there are even larger isotope variations (at least 3.5‰) in calcium-aluminum-rich inclusions (CAIs) in meoteorites that define the currently accepted age of the solar system [4]. These findings are dramatic for geochronology, as a known 238U/235U is a requirement for Pb-Pb dating, the most precise dating technique for absolute ages. As 238U/235U variations can greatly affect the reported absolute Pb-Pb age, understanding and accurately measuring variation of the 238U/235U ratio in various materials is critical, With these new findings, the questions also arises of "How well do we know the average U isotope composition of the Earth and the solar system?" and "How accurate can absolute Pb-Pb ages be?" Our results using a gravimetrically calibrated 233U/236U double spike IRMM 3636 [5] indicate that the U standard NBL 950a, which was commonly used to define the excepted "natural" 238U/235U isotope ratio, has a slightly lower 238U/235U of 137.836 ± 0.024. This value is indistinguishable from the U isotope compositions for NBL 960 and NBL112A, which have been determined by several laboratories, also using the newly calibrated U double spike IRMM 3636 [6]. These findings provide new implications about the average U isotope composition of the Earth and the solar system. Basalts display a very tight range of U isotope variations (~0.25-0.32‰ relative to SRM 950a). Their U isotope composition is also very similar to that of chondrites [4], which however appear to show a slightly larger spread. Accepting terrestrial

  6. U-Th-Pb isotopic systematics of lunar norite 78235

    NASA Technical Reports Server (NTRS)

    Premo, W. R.; Tatsumoto, M.

    1991-01-01

    A pristine high-Mg noritic cumulate thought to be relict deep-seated lunar crust is studied with an eye to obtaining evidence of initial Pb isotopic composition and U/Pb ratios of early lunar magma sources and possibly of a primary magma ocean. A leaching procedure was conducted on polymineralic separates to assure the removal of secondary Pb components. The Pb from leached separates do not form a linear trend on the Pb-Pb diagram, indicating open-system behavior either from mixtures of Pb or postcrystallization disturbances. Calculated initial Pb compositions and corresponding U-238/Pb-204 (mu) values are presented, with the assumption of reasonably precise radiometric ages from the literature for norite 78236. The results obtained support the contention that high-Mg suite rocks are coeval with the ferroan anorthosites, both being produced during the earliest stages of lunar evolution.

  7. U, Th, and Pb isotopes in hot springs on the Juan de Fuca Ridge

    NASA Technical Reports Server (NTRS)

    Chen, J. H.

    1987-01-01

    Concentrations and isotopic compositions of U, Th, and Pb in three hydrothermal fluids from the Juan de Fuca Ridge were determined from samples obtained by the Alvin submersible. The samples were enriched in Pb and Th relative to deep-sea water, and were deficient in U. No clear relationship with Mg was found, suggesting nonideal mixing between the hot hydrothermal fluids and the cold ambient seawater. Values for U-234/U-238 have a seawater signature, and show a U-234 enrichment relative to the equilibrium value. The Pb isotopic composition has a uniform midocean ridge basalt signature, and it is suggested that Pb in these fluids may represent the best average value of the local oceanic crust.

  8. U-Pb isotope systematics and age of uranium mineralization, Midnite mine, Washington.

    USGS Publications Warehouse

    Ludwig, K. R.; Nash, J.T.; Naeser, C.W.

    1981-01-01

    Uranium ores at the Midnite mine, near Spokane, Washington, occur in phyllites and calcsilicates of the Proterozoic Togo Formation, near the margins of an anomalously uraniferous, porphyritic quartz monzonite of Late Cretaceous age. The present geometry of the ore zones is tabular, with the thickest zones above depressions in the pluton-country rock contact. Analyses of high-grade ores from the mine define a 207 Pb/ 204 Pb- 235 U/ 204 Pb isochron indicating an age of mineralization of 51.0 + or - 0.5 m.y. This age coincides with a time of regional volcanic activity (Sanpoil Volcanics), shallow intrusive activity, erosion, and faulting. U-Th-Pb isotopic ages of zircons from the porphyritic quartz monzonite in the mine indicate an age of about 75 m.y., hence the present orebodies were formed about 24 m.y. after its intrusion. The 51-m.y. time of mineralization probably represents a period of mobilization and redeposition of uranium by supergene ground waters, perhaps aided by mild heating and ground preparation and preserved by a capping of newly accumulated, impermeable volcanic rocks. It seems most likely that the initial concentration of uranium occurred about 75 m.y. ago, probably from relatively mild hydrothermal fluids in the contact-metamorphic aureole of the U-rich porphyritic quartz monzonite.Pitchblende, coffinitc, pyrite, marcasite, and hisingerite are the most common minerals in the uranium-bearing veinlets, with minor sphalerite and chalcopyrite. Coffinitc with associated marcasite is paragenetically later than pitchblende, though textural and isotopic evidence suggests no large difference in the times of pitchblende and colfinite formation.The U-Pb isotope systematics of total ores and of pitchblende-coffinite and pyrite-marcasite separates show that whereas open system behavior for U and Pb is essentially negligible for large (200-500 g) ore samples, Pb migration has occurred on a scale of 1 to 10 mm (out of pitchblende and coffinite and into pyrite

  9. 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

  10. Preliminary Report on U-Th-Pb Isotope Systematics of the Olivine-Phyric Shergottite Tissint

    NASA Technical Reports Server (NTRS)

    Moriwaki, R.; Usui, T.; Yokoyama, T.; Simon, J. I.; Jones, J. H.

    2014-01-01

    Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions, and trace element abundances.. These correlations have been interpreted as indicating the presence of a reduced, incompatible-element- depleted reservoir and an oxidized, incompatible-element-rich reservoir. The former is clearly a depleted mantle source, but there has been a long debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former clearly requires the ancient martian crust to be the enriched source (crustal assimilation), whereas the latter requires a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and U-Th-Pb concentration analyses of the olivine-phyric shergottite Tissint because U-Th-Pb isotope systematics have been intensively used as a powerful radiogenic tracer to characterize old crust/sediment components in mantle- derived, terrestrial oceanic island basalts. The U-Th-Pb analyses are applied to sequential acid leaching fractions obtained from Tissint whole-rock powder in order to search for Pb isotopic source components in Tissint magma. Here we report preliminary results of the U-Th-Pb analyses of acid leachates and a residue, and propose the possibility that Tissint would have experienced minor assimilation of old martian crust.

  11. 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.

  12. Feldspar palaeo-isochrons from early Archaean TTGs: Pb-isotope evidence for a high U/Pb terrestrial Hadean crust

    NASA Astrophysics Data System (ADS)

    Kamber, B. S.; Whitehouse, M. J.; Moorbath, S.; Collerson, K. D.

    2001-12-01

    Feldspar lead-isotope data for 22 early Archaean (3.80-3.82 Ga) tonalitic gneisses from an area south of the Isua greenstone belt (IGB),West Greenland, define a steep linear trend in common Pb-isotope space with an apparent age of 4480+/-77 Ma. Feldspars from interleaved amphibolites yield a similar array corresponding to a date of 4455+/-540 Ma. These regression lines are palaeo-isochrons that formed during feldspar-whole rock Pb-isotope homogenisation a long time (1.8 Ga) after rock formation but confirm the extreme antiquity (3.81 Ga) of the gneissic protoliths [1; this study]. Unlike their whole-rock counterparts, feldspar palaeo-isochrons are immune to rotational effects caused by the vagaries of U/Pb fractionation. Hence, comparison of their intercept with mantle Pb-isotope evolution models yields meaningful information regarding the source history of the magmatic precursors. The locus of intersection between the palaeo-isochrons and terrestrial mantle Pb-isotope evolution lines shows that the gneissic precursors of these 3.81 Ga gneisses were derived from a source with a substantially higher time-integrated U/Pb ratio than the mantle. Similar requirements for a high U/Pb source have been found for IGB BIF [2], IGB carbonate [3], and particularly IGB galenas [4]. Significantly, a single high U/Pb source that separated from the MORB-source mantle at ca. 4.3 Ga with a 238U/204Pb of ca. 10.5 provides a good fit to all these observations. In contrast to many previous models based on Nd and Hf-isotope evidence we propose that this reservoir was not a mantle source but the Hadean basaltic crust which, in the absence of an operating subduction process, encased the early Earth. Differentiation of the early high U/Pb basaltic crust could have occurred in response to gravitational sinking of cold mantle material or meteorite impact, and produced zircon-bearing magmatic rocks. The subchondritic Hf-isotope ratios of ca. 3.8 Ga zircons support this model [5] provided that

  13. Application of isotope dilution inductively coupled plasma mass spectrometry to the analysis of marine sediments

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

    McLaren, J.W.; Beauchemin, D.; Berman, S.S.

    1987-02-15

    Isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of 11 trace elements (Cr, Ni, Zn, Sr, Mo, Cd, Sn, Sb, Tl, Pb, and U) in the marine sediment reference materials MESS-1 and BCSS-1. Accuracy and, especially, precision are better than those that can be easily achieved by other ICP-MS calibration strategies, as long as isotopic equilibration is achieved and the isotopes used for the ratio measurement are free of isobaric interferences by molecular species. The measurement of the isotope ratios on unspiked samples provides a sensitive diagnostic of such interferences.

  14. Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH.

    PubMed

    Xie, Hong; Huang, Zhi-Yong; Cao, Ying-Lan; Cai, Chao; Zeng, Xiang-Cheng; Li, Jian

    2012-08-01

    Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p < 0.05) than the values estimated with L values, single chemical extractants and the Σ(BCR) values obtained with the BCR approach, respectively. A strong negative correlation (R(2) = 0.984) between E(24 h) values and soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted

  15. U-Pb isotopic systematics of shock-loaded and annealed baddeleyite: Implications for crystallization ages of Martian meteorite shergottites

    NASA Astrophysics Data System (ADS)

    Niihara, Takafumi; Kaiden, Hiroshi; Misawa, Keiji; Sekine, Toshimori; Mikouchi, Takashi

    2012-08-01

    Shock-recovery and annealing experiments on basalt-baddeleyite mixtures were undertaken to evaluate shock effects on U-Pb isotopic systematics of baddeleyite. Shock pressures up to 57 GPa caused fracturing of constituent phases, mosaicism of olivine, maskelynitization of plagioclase, and melting, but the phase transition from monoclinic baddeleyite structure to high-pressure/temperature polymorphs of ZrO2 was not confirmed. The U-Pb isotopic systems of the shock-loaded baddeleyite did not show a large-scale isotopic disturbance. The samples shock-recovered from 47 GPa were then employed for annealing experiments at 1000 or 1300 °C, indicating that the basalt-baddeleyite mixture was almost totally melted except olivine and baddeleyite. Fine-grained euhedral zircon crystallized from the melt was observed around the relict baddeleyite in the sample annealed at 1300 °C for 1 h. The U-Pb isotopic systems of baddeleyite showed isotopic disturbances: many data points for the samples annealed at 1000 °C plotted above the concordia. Both radiogenic lead loss/uranium gain and radiogenic lead gain/uranium loss were observed in the baddeleyite annealed at 1300 °C. Complete radiogenic lead loss due to shock metamorphism and subsequent annealing was not observed in the shock-loaded/annealed baddeleyites studied here. These results confirm that the U-Pb isotopic systematics of baddeleyite are durable for shock metamorphism. Since shergottites still preserve Fe-Mg and/or Ca zonings in major constituent phases (i.e. pyroxene and olivine), the shock effects observed in Martian baddeleyites seem to be less intense compared to that under the present experimental conditions. An implication is that the U-Pb systems of baddeleyite in shergottites will provide crystallization ages of Martian magmatic rocks.

  16. Ion microprobe U-Pb dating and strontium isotope analysis of biogenic apatite

    NASA Astrophysics Data System (ADS)

    Sano, Y.; Toyoshima, K.; Takahata, N.; Shirai, K.

    2012-12-01

    Conodonts are micro-fossils chemically composed of apatite which occurred in the body of one animal. They are guide fossils to show formation ages of sedimentary sequences with the highest resolution [1] and good samples to verify the dating method. We developed the ion microprobe U-Pb dating of apatite [2] and applied the method to a Carboniferous conodont [3] by using a SHRIMP II installed at Department of Earth and Planetary Sciences, Hiroshima University. Recently we have developed the NanoSIMS U-Pb dating method and successfully measured the formation ages of monazite [4] and zircon [5] at Atmosphere and Ocean Research Institute, University of Tokyo. In this work we carried out the NanoSIMS U-Pb dating of biogenic apatite such as conodont. Since the spot size of NanoSIMS is smaller than SHRIMP II, it is easier to have multi-spots on the single fragment of biogenic apatite. Based on the isochron method of U-Pb system, we have calculated the formation ages. They are consistent with those in literature. In order to study the chemical evolution of ocean during the past 600 Million years, strontium isotopes (87Sr/86Sr) of fossil marine carbonate such as coral skeletons and foraminifera tests were measured and compiled [6]. However they are not robust when the age is older than 500Ma, partly due to post-depositional histories. Apatite is more stable and more resistant to the alteration than carbonate [7]. Recently we have developed the method of NanoSIMS strontium isotopic analysis of a fish otolith, which composed of aragonite [8]. In this work we carried out the strontium isotopic analysis of biogenic apatite. The advantage of the ion microprobe technique over the TIMS (thermal ionization mass spectrometer) and MC-ICP-MS (multi-collector inductively coupled argon plasma mass spectrometer) method is preservation of the important textural context and to provide an opportunity for other simultaneous analytical work with high spatial resolution. This is the case for

  17. A combined Sm-Nd, Rb-Sr, and U-Pb isotopic study of Mg-suite norite 78238: Further evidence for early differentiation of the Moon

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

    Edmunson, J; E.Borg, L; Nyquist, L E

    2008-11-17

    Lunar Mg-suite norite 78238 was dated using the Sm-Nd, Rb-Sr, and U-Pb isotopic systems in order to constrain the age of lunar magma ocean solidification and the beginning of Mg-suite magmatism, as well as to provide a direct comparison between the three isotopic systems. The Sm-Nd isotopic system yields a crystallization age for 78238 of 4334 {+-} 37 Ma and an initial {var_epsilon}{sub Nd}{sup 143} value of -0.27 {+-} 0.74. The age-initial {var_epsilon}{sub Nd}{sup 143} (T-I) systematics of a variety of KREEP-rich samples, including 78238 and other Mg-suite rocks, KREEP basalts, and olivine cumulate NWA 773, suggest that lunar differentiationmore » was completed by 4492 {+-} 61 Ma assuming a Chondritic Uniform Reservoir bulk composition for the Moon. The Rb-Sr isotopic systematics of 78238 were disturbed by post-crystallization processes. Nevertheless, selected data points yield two Rb-Sr isochrons. One is concordant with the Sm-Nd crystallization age, 4366 {+-} 53 Ma. The other is 4003 {+-} 95 Ma and is concordant with an Ar-Ar age for 78236. The {sup 207}Pb-{sup 206}Pb age of 4333 {+-} 59 Ma is concordant with the Sm-Nd age. The U-Pb isotopic systematics of 78238 yield linear arrays equivalent to younger ages than the Pb-Pb system, and may reflect fractionation of U and Pb during sample handling. Despite the disturbed nature of the U-Pb systems, a time-averaged {mu} ({sup 238}U/{sup 204}Pb) value of the source can be estimated at 27 {+-} 30 from the Pb-Pb isotopic systematics. Because KREEP-rich samples are likely to be derived from source regions with the highest U/Pb ratios, the relatively low {mu} value calculated for the 78238 source suggests the bulk Moon does not have an exceedingly high {mu} value.« less

  18. Archean Pb Isotope Evolution: Implications for the Early Earth.

    NASA Astrophysics Data System (ADS)

    Vervoort, J. D.; Thorpe, R.; Albarede, F.; Blichert-Toft, J.

    2008-12-01

    The U-Pb isotope system provides us with a powerful tool for understanding the chemical evolution of the Earth. Pb isotopes in Archean rocks, however, have not been widely utilized because U mobility makes initial Pb isotope ratios from old silicate rocks difficult, if not impossible, to determine. Galenas in syngenetic volcanogenic massive sulfide (VMS) deposits, however, provide snapshots of initial Pb ratios because their Pb isotopic composition is time invariant at their formation (U/Pb=0). The Pb isotopic record from galenas from rocks of all age have been utilized for over 70 years to answer a wide range of scientific problems beginning with Al Nier's pioneering work analyzing Pb isotopes in the 1930's but are no longer widely used by the isotopic community because they have been produced by older TIMS techniques. We have begun a re-examination of Archean Pb by an extensive analysis of over 100 galena samples from Archean VMS deposits throughout the Superior and Slave Provinces in Canada as well as from other VMS deposits in Finland, South Africa and Western Australia. The goal of this work is to provide modern, high precision measurements and update an old, but venerable, Pb isotopic data set. We feel these data provide important constraints on not only the Pb isotopic evolution of the Earth, but planetary differentiation and recycling processes operating in the first 2 b.y. of Earth's history. Our analytical techniques include dissolving the Pb sulfide minerals, purifying them with ion chromatography, and analyzing them using MC-ICPMS at both Washington State University (Neptune) and Ecole Normale Superieure in Lyon, France (Nu). All Pb solutions are doped with Tl in order to correct for mass fractionation. In this abstract we report preliminary galena Pb isotope data from 6 VMS deposits in the Abitibi greenstone belt: Chibougamu, Matagami, Noranda, Normetal, Timmins, and Val d"Or. These deposits are all approximately 2.7 Ga in age but in detail vary from 2

  19. The U-Th-Pb, Sm-Nd, and Ar-Ar isotopic systematics of lunar meteorite Yamato-793169

    NASA Technical Reports Server (NTRS)

    Torigoye, Noriko; Misawa, Keji; Dalrymple, G. Brent; Tatsumoto, Mitsunobu

    1993-01-01

    U-Th-Pb, Sm-Nd, and (Ar-40)-(Ar-39) isotopic studies were performed on Yamato (Y)-793169, an unbrecciated diabasic lunar meteorite whose chemical composition is close to low Ti(LT) and very low-Ti (VLT) mare basalts. The isotopic data indicate that the meteorite was formed earlier than 3.9 Ga from a source with low U/Pb and high Sm/Nd and was distributed by a thermal event at 751 Ma. due to the small sample size (104 mg), a plagioclase crystal and glass grains were handpicked for Ar analysis, leaving four fractions for the U-Th-Pb and Sm-Nd studies; a fine-grained fraction (less than 63 microns; Fine) and three medium-grained fractions (63-150 microns). Medium-grained fractions were divided by density; a heavy fraction (rho greater than 3.3) consisting mainly of pyroxene (PX1), a lighter fraction (rho less than 2.8) consisting of plagioclase (PL), and a middle density fraction (predominantly pyroxene; PX2). The fractions were washed with acetone and alcohol, and then leached in 0.01 HBr and 0.1N HBr in order to remove any terrestrial Pb contamination. Analysis of the HBr leaches revealed that this meteorite was heavily contaminated with terrestrial Pb during its residence in Antarctic ice.

  20. Combined oxygen-isotope and U-Pb zoning studies of titanite: New criteria for age preservation

    DOE PAGES

    Bonamici, Chloe E.; Fanning, C. Mark; Kozdon, Reinhard; ...

    2015-02-11

    Here, titanite is an important U-Pb chronometer for dating geologic events, but its high-temperature applicability depends upon its retention of radiogenic lead (Pb). Experimental data predict similar rates of diffusion for lead (Pb) and oxygen (O) in titanite at granulite-facies metamorphic conditions (T = 650-800°C). This study therefore investigates the utility of O-isotope zoning as an indicator for U-Pb zoning in natural titanite samples from the Carthage-Colton Mylonite Zone of the Adirondack Mountains, New York. Based on previous field, textural, and microanalytical work, there are four generations (types) of titanite in the study area, at least two of which preservemore » diffusion-related δ 18O zoning. U-Th-Pb was analyzed by SIMS along traverses across three grains of type-2 titanite, which show well-developed diffusional δ 18O zoning, and one representative grain from each of the other titanite generations.« less

  1. 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

  2. Stable isotope dilution analysis of hydrologic samples by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Garbarino, John R.; Taylor, Howard E.

    1987-01-01

    Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

  3. Geochemical, isotopic (Sr-Nd-Pb) and geochronological (Ar-Ar and U-Pb) constraints on Quaternary bimodal volcanism of the Nigde Volcanic Complex (Central Anatolia, Turkey)

    NASA Astrophysics Data System (ADS)

    Aydin, F.; Siebel, W.; Uysal, I.; Ersoy, E. Y.; Schmitt, A. K.; Sönmez, M.; Duncan, R.

    2012-04-01

    The Nigde Volcanic Complex (NVC) is a major Late Neogene-Quaternary volcanic centre within the Cappadocian Volcanic Province of Central Anatolia. The Late Neogene evolution of the NVC generally initiated with the eruption of extensive andesitic-dacitic lavas and pyroclastic flow deposits, and minor basaltic lavas. This stage was followed by a Quaternary bimodal magma suite which forms Na-alkaline/transitional basaltic and high-K calc-alkaline to alkaline silicic volcanic rocks. In this study, we present new geochemical, isotopic (Sr-Nd-Pb) and geochronological (Ar-Ar and U-Pb) data for the bimodal volcanic suite within the NVC. Recent data suggest that the eruption of this suite took place ranges between ~650 and ~220 ka (Middle-Late Pleistocene). Silicic rocks consisting of rhyolite and associated pumice-rich pyroclastic fall out and surge deposits define a narrow range of 143Nd/144Nd isotope ratios (0.5126-0.5127), and show virtually no difference in Pb isotope composition (206Pb/204Pb = 18.84-18.87, 207Pb/204Pb = 15.64-15.67 and 208Pb/204Pb = 38.93-38.99). 87Sr/86Sr isotopic compositions of the silicic (0.704-0.705) and basaltic rocks (0.703-0.705) are rather similar reflecting a common source. The most mafic sample from basaltic rocks related to monogenetic cones is characterized by 87Sr/86Sr = 0.704, 143Nd/144Nd = 0.5127, 206Pb/204Pb = 18.80, 207Pb/204Pb = 15.60 and 208Pb/204Pb = 38.68. These values suggest a moderately depleted signature of the mantle source. The geochronological and geochemical data suggest that NVC silicic and basaltic rocks are genetically closely related to each other. Mantle derived differentiated basaltic melts which experienced low degree of crustal assimilation are suggested to be the parent melt of the rhyolites. Further investigations will focus on the spatial and temporal evolution of Quaternary bimodal magma suite in the NVC and the genetic relation between silicic and basaltic rocks through detailed oxygen isotope analysis and (U

  4. U-Th-Pb and Sm-Nd Isotopic Systematics of the Goalpara Ureilite

    NASA Astrophysics Data System (ADS)

    Torigoye, N.; Misawa, K.; Tatsumoto, M.

    1993-07-01

    One of the interesting features of ureilites is the light REE-enriched component that is dissolved by HNO3 leaching [1,2]. In this work, we performed acid-leaching of several mineral fractions from Goalpara ureilite for U-Th-Pb and Sm-Nd analyses. Olivine and pyroxene grains were hand-picked from 150-300- micrometer-sized fraction. Because they still contained carbon and metal sulfide they were further crushed to <63 micrometers and metal was removed with a hand magnet. These separates and whole-rock powders were washed by ethanol, and leached in 0.01N HBr, 1N HNO3, and in some cases, 7N HNO3. Concentrations of U, Th, and Pb in residues are 0.05-0.3 ppb, 0.1-0.7 ppb, and 5-100 ppb, respectively, corresponding to <=0.01X CI chondrites. Lead isotopic compositions of the residues are less radiogenic and close to Canon Diablo troilite (CDT) Pb [3] (Fig. 1). The U-Pb and Th-Pb ages of all the fractions are older than 4.5 Ga, indicating terrestrial Pb contamination (MT). Because of low concentration of U, Th, and Pb, a small amount of Pb can have a significant effect on the U-Pb and Th-Pb model ages. 238U/204Pb (mu) value of the least contaminated residue is 3, which is higher than mu (0.14-0.5) value of carbonaceous chondrites [3,4]. The higher mu value may be due to either volatile depletion by nebula fractionation or to depletion of Pb during segregation of sulfide that occurred prior to the formation of ureilite as an ultramafic cumulate. The Sm and Nd abundances in the residues are also extremely low; 0.4-2 ppb and 1-2.5 ppb, respectively, corresponding to 0.002-0.01X CI chondritic abundances. All the residues show high 147Sm/144Nd ratios (0.23 ~ 0.44), and the fraction with the highest Sm/Nd plots on the 4.55 Ga chondritic isochron (Fig. 2). The 1N HNO3 leachates do not contain light-REE-enriched components, except for the samples containing black metal-carbon phases, which also contain a large amount of terrestrial Pb in the residual fractions. Therefore

  5. Pb isotope compositions of modern deep sea turbidites

    NASA Astrophysics Data System (ADS)

    Hemming, S. R.; McLennan, S. M.

    2001-01-01

    Modern deep sea turbidite muds and sands collected from Lamont piston cores represent a large range in age of detrital sources as well as a spectrum of tectonic settings. Pb isotope compositions of all but three of the 66 samples lie to the right of the 4.56 Ga Geochron, and most also lie along a slope consistent with a time-integrated κ ( 232Th/ 238U) between 3.8 and 4.2. Modern deep sea turbidites show a predictable negative correlation between both Pb and Sr isotope ratios and ɛNd and ɛHf, clearly related to the age of continental sources. However, the consistency between Pb and Nd isotopes breaks down for samples with very old provenance ( ɛNd<-20) that are far less radiogenic than predicted by the negative correlation. The correlations among Sr, Nd and Hf isotopes also become more scattered in samples with very old provenance. The unradiogenic Pb isotopic character of modern sediments with Archean Nd model ages is consistent with a model where Th and U abundances of the Archean upper crust are significantly lower than the post-Archean upper crust.

  6. 206Pb-230Th-234U-238U and 207Pb-235U geochronology of Quaternary opal, Yucca Mountain, Nevada

    USGS Publications Warehouse

    Neymark, Leonid A.; Amelin, Yuri V.; Paces, James B.

    2000-01-01

    U–Th–Pb isotopic systems have been studied in submillimeter-thick outermost layers of Quaternary opal occurring in calcite–silica fracture and cavity coatings within Tertiary tuffs at Yucca Mountain, Nevada, USA. These coatings preserve a record of paleohydrologic conditions at this site, which is being evaluated as a potential high-level nuclear waste repository. The opal precipitated from groundwater is variably enriched in 234U (measured 234U/238U activity ratio 1.124–6.179) and has high U (30–313 ppm), low Th (0.008–3.7 ppm), and low common Pb concentrations (measured 206Pb/204Pb up to 11,370). It has been demonstrated that the laboratory acid treatment used in this study to clean sample surfaces and to remove adherent calcite, did not disturb U–Th–Pb isotopic systems in opal. The opal ages calculated from 206Pb∗/238U and 207Pb∗/235U ratios display strong reverse discordance because of excess radiogenic 206Pb∗ derived from the elevated initial 234U. The data are best interpreted using projections of a new four-dimensional concordia diagram defined by 206Pb∗/238U, 207Pb∗/235U, 234U/238Uactivity, and 230Th/238Uactivity. Ages and initial 234U/238U activity ratios have been calculated using different projections of this diagram and tested for concordance. The data are discordant, that is observed 207Pb∗/235U ages of 170 ± 32 (2σ) to 1772 ± 40 ka are systematically older than 230Th/U ages of 34.1 ± 0.6 to 452 ± 32 ka. The age discordance is not a result of migration of uranium and its decay products under the open system conditions, but a consequence of noninstantaneous growth of opal. Combined U–Pb and 230Th/U ages support the model of slow mineral deposition at the rates of millimeters per million years resulting in layering on a scale too fine for mechanical sampling. In this case, U–Pb ages provide more accurate estimates of the average age for mixed multiage samples than 230Th/U ages, because ages based on shorter

  7. U-Pb systematics in iron meteorites - Uniformity of primordial lead

    NASA Astrophysics Data System (ADS)

    Gopel, C.; Manhes, G.; Allegre, C. J.

    1985-08-01

    Pb isotopic compositions and U-Pb abundances were determined in the metal phase of six iron meteorites: Canyon Diablo IA, Toluca IA, Odessa IA, Youndegin IA, Deport IA, and Mundrabilla An. Prior to complete dissolution, samples were subjected to a series of leachings and partial dissolutions. Isotopic compositions and abundances of the etched Pb indicate a contamination by terrestrial Pb which is attributable to previous cutting of the meteorite. Pb isotopic compositions measured in the decontaminated samples are identical within 0.2 percent and essentially confirm the primordial Pb value defined by Tatsumoto et al. (1973). These data invalidate more radiogenic Pb isotopic compositions published for iron meteorites, which are the result of terrestrial Pb contamination introduced mainly by analytical procedure. The results of this study support the idea of a solar nebula which was isotopically homogeneous for Pb 4.55 Ga ago. The new upper limit for U-abundance in iron meteorites, 0.001 ppb, is in agreement with its expected thermodynamic solubility in the metal phase.

  8. Isotopic composition of Pb and Th in interplinian volcanics from Somma-Vesuvius volcano, Italy

    USGS Publications Warehouse

    Cortini, M.; Ayuso, R.A.; de Vivo, B.; Holden, P.; Somma, R.

    2004-01-01

    We present a detailed isotopic study of volcanic rocks emitted from Somma-Vesuvius volcano during three periods of interplinian activity: "Protohistoric" (3550 y B.P. to 79 A.D.), "Ancient Historic" (79 to 472 A.D.) and "Medieval" (472 to 1631 A.D.). Pb isotopic compositions of two acid leached fractions and whole rock residues of 37 whole rock samples (determined by Somma et al., 2001) show that each of the three interplinian periods is distinguished by small, systematic, and unique uranogenic and thorogenic Pb isotopic trends. This key and novel feature is compatible with the notion that the Pb isotopic data reflect small-scale source heterogeneity operating over relatively short periods of time. From this representative group of samples, a selected set of nine whole rocks were analysed for Th isotopes. 232Th/238U ratios in the source can be obtained independently from Pb and from Th isotopes. Those obtained from Pb isotopes represent source ratios, time-integrated over the whole age of the Earth; they range from 3.9 to 4.1. 232Th/238U obtained from Th isotopes are those of the present source. They are lower, and cluster around 3.5; this difference probably indicates recent U enrichment of the present source. The behaviour of Pb, as inferred by its isotopic ratios, is quite distinct from that of Sr and Nd isotopes: Pb isotope variations are not correlated to Sr or Nd isotope variations. The isotopic contrast is compatible with the idea that the isotopes were decoupled during magmatic production, evolution, and ascent through the crust. Thus, the Pb isotopes do not reflect the effects of the same processes as in the case of the Sr and Nd isotopes, or, as we also favor, they do not necessarily reflect the same source contributions into the magmas. Moreover, the Pb isotopic evolution of the interplinian rocks chiefly reflects mixing, driven by processes that are superimposed on, and independent of, other source contributions that determine the isotopic compositions

  9. U-Th-Pb and Rb-Sr systematics of Allende and U-Th-Pb systematics of Orgueil

    USGS Publications Warehouse

    Tatsumoto, M.; Unruh, D.M.; Desborough, G.A.

    1976-01-01

    U-Th-Pb systematics study of Allende inclusions showed that U, Th and Sr concentrations in Ca, Al (pyroxene)-rich chondrules and white and pinkish-white aggregate separates of Allende are five to ten times higher than those of the matrix, whereas Mg (olivine)-rich chondrules have U and Th concentrations about twice as high as the matrix. Th concentrations are extremely high in white aggregates and in pinkish-white (spinel-rich) aggregates while U and Sr concentrations in white aggregates are more than twice as high as those in pinkish-white aggregates. Large enrichment of these refractory elements in the white aggregates indicates that they contain high-temperature condensates from the solar nebula. The Pb concentrations in the inclusions are less than half of those in the whole rock and matrix, indicating that the matrix is a lower-temperature condensate. The isotopic composition of lead in the matrix is less radiogenic than that of the whole meteorite, whereas lead in Ca- and Al-rich chondrules and aggregates is extremely radiogenic. The 206Pb/204Pb ratio reaches as high as 55.9 in a white aggregate separate. The lead of Mg-rich chondrules is moderately radiogenic and the 206Pb/204Pb ratio ranges from 18 to 26. A striking linear relationship exists among leads in the chondrules, aggregates and matrix on the 207Pb/204Pb vs 204Pb/204Pb plot. The slope of the best fit line is 0.6188 ?? 0.0016, yielding an isochron age of 4553 ?? 4 m.y. The regression line passes through primordial lead values obtained from Canyon Diablo troilite. The data, when corrected for Canyon Diablo troilite Pb and plotted on a U-Pb concordia diagram, show that the pink and white aggregates and the Ca-Al-rich and Mg-rich inclusions have excess Pb and define a chord which intersects the concordia curve at 4548 ?? 25 m.y. and 107 ?? 70 m.y. The intercepts might correspond to the agglomeration age of the meteorite and a time of probably later disturbance, respectively. The matrix and some

  10. 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.

  11. Modern U-Pb chronometry of meteorites: advancing to higher time resolution reveals new problems

    USGS Publications Warehouse

    Amelin, Y.; Connelly, J.; Zartman, R.E.; Chen, J.-H.; Gopel, C.; Neymark, L.A.

    2009-01-01

    In this paper, we evaluate the factors that influence the accuracy of lead (Pb)-isotopic ages of meteorites, and may possibly be responsible for inconsistencies between Pb-isotopic and extinct nuclide timescales of the early Solar System: instrumental mass fractionation and other possible analytical sources of error, presence of more than one component of non-radiogenic Pb, migration of ancient radiogenic Pb by diffusion and other mechanisms, possible heterogeneity of the isotopic composition of uranium (U), uncertainties in the decay constants of uranium isotopes, possible presence of "freshly synthesized" actinides with short half-life (e.g. 234U) in the early Solar System, possible initial disequilibrium in the uranium decay chains, and potential fractionation of radiogenic Pb isotopes and U isotopes caused by alpha-recoil and subsequent laboratory treatment. We review the use of 232Th/238U values to assist in making accurate interpretations of the U-Pb ages of meteorite components. We discuss recently published U-Pb dates of calcium-aluminum-rich inclusions (CAIs), and their apparent disagreement with the extinct nuclide dates, in the context of capability and common pitfalls in modern meteorite chronology. Finally, we discuss the requirements of meteorites that are intended to be used as the reference points in building a consistent time scale of the early Solar System, based on the combined use of the U-Pb system and extinct nuclide chronometers.

  12. 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.

  13. Community-based Approaches to Improving Accuracy, Precision, and Reproducibility in U-Pb and U-Th Geochronology

    NASA Astrophysics Data System (ADS)

    McLean, N. M.; Condon, D. J.; Bowring, S. A.; Schoene, B.; Dutton, A.; Rubin, K. H.

    2015-12-01

    The last two decades have seen a grassroots effort by the international geochronology community to "calibrate Earth history through teamwork and cooperation," both as part of the EARTHTIME initiative and though several daughter projects with similar goals. Its mission originally challenged laboratories "to produce temporal constraints with uncertainties approaching 0.1% of the radioisotopic ages," but EARTHTIME has since exceeded its charge in many ways. Both the U-Pb and Ar-Ar chronometers first considered for high-precision timescale calibration now regularly produce dates at the sub-per mil level thanks to instrumentation, laboratory, and software advances. At the same time new isotope systems, including U-Th dating of carbonates, have developed comparable precision. But the larger, inter-related scientific challenges envisioned at EARTHTIME's inception remain - for instance, precisely calibrating the global geologic timescale, estimating rates of change around major climatic perturbations, and understanding evolutionary rates through time - and increasingly require that data from multiple geochronometers be combined. To solve these problems, the next two decades of uranium-daughter geochronology will require further advances in accuracy, precision, and reproducibility. The U-Th system has much in common with U-Pb, in that both parent and daughter isotopes are solids that can easily be weighed and dissolved in acid, and have well-characterized reference materials certified for isotopic composition and/or purity. For U-Pb, improving lab-to-lab reproducibility has entailed dissolving precisely weighed U and Pb metals of known purity and isotopic composition together to make gravimetric solutions, then using these to calibrate widely distributed tracers composed of artificial U and Pb isotopes. To mimic laboratory measurements, naturally occurring U and Pb isotopes were also mixed in proportions to mimic samples of three different ages, to be run as internal

  14. Genesis of the Bangbule Pb-Zn-Cu polymetallic deposit in Tibet, western China: Evidence from zircon U-Pb geochronology and S-Pb isotopes

    NASA Astrophysics Data System (ADS)

    Kan, Tian; Zheng, Youye; Gao, Shunbao

    2016-04-01

    The Banbule Pb-Zn-Cu skarn deposit is located in the Longger-Gongbujiangda volcanic magma arc in the Gangdese-Nyainqentanglha Plate. It is the only lead-zinc polymetallic deposit discovered in the westernmost Nyainqentanglha metallogenic belt. The measured and indicated resources include 0.9 Mt of Pb+Zn (4.77% Pb and 4.74% Zn, respectively), 6499 t of Cu, and 178 t of Ag (18.75g/t Ag). The orebodies mainly occur as lenses, veins and irregular shapes in the contact zone between the quartz-porphyry and limestone of the Upper Permian Xiala Formation, or in the boundaries between limestone and sandstone. Pb-Zn-Cu mineralization in the Banbule deposit is closely associated with skarns. The ore minerals are dominated by galena, sphalerite, chalcopyrite, bornite, and magnetite, with subordinate pyrite, malachite, and azurite. The gangue minerals are mainly garnet, actinolite, diopside, quartz, and calcite. The ore-related quartz-porphyry displays LA-ICP-MS zircon U-Pb age of 77.31±0.74 Ma. The δ34S values of sulfides define a narrow range of -0.8 to 4.7‰ indicating a magmatic source for the ore-forming materials. Lead isotopic systematics yield 206Pb/204Pb of 18.698 to 18.752, 207Pb/204Pb of 15.696 to 15.760, and 208Pb/204Pb of 39.097 to 39.320. The data points are constrained around the growth curves of upper crust and orogenic belt according to the tectonic discrimination diagrams. The calculated Δβ - Δγ values plot within the magmatic field according to the discrimination diagram of Zhu et al. (1995). The S-Pb isotopic data suggest that Bangbule is a typical skarn deposit, and the Pb-Zn-Cu mineralization is genetically related to the quartz-porphyry in the mining district. The discovery of the Bangbule deposit indicates that there is metallogenic potential in the westernmost Nyainqentanglha belt, which is of great importance for the exploration work in this area.

  15. Origin of the Early Sial Crust and U-Pb Isotope-Geochemical Heterogeneity of the Earth's Mantle

    NASA Astrophysics Data System (ADS)

    Mishkin, M. A.; Nozhkin, A. D.; Vovna, G. M.; Sakhno, V. G.; Veldemar, A. A.

    2018-02-01

    It is shown that presence of the Early Precambrian sial crust in the Indo-Atlantic segment of the Earth and its absence in the Pacific has been caused by geochemical differences in the mantle underlying these segments. These differences were examined on the basis of Nd-Hf and U-Pb isotopes in modern basalts. The U-Pb isotope system is of particular interest, since uranium is a member of a group of heat-generating radioactive elements providing heat for plumes. It is shown that in the Indo-Atlantic segment, a distribution of areas of the modern HIMU type mantle is typical, while it is almost completely absent in the Pacific segment. In the Archean, in the upper HIMU type paleo-mantle areas, plume generation and formation of the primordial basic crust occurred; this was followed by its remelting resulting in the appearance of an early sial crust forming cratons of the Indo-Atlantic segment.

  16. High spatial resolution U-Pb geochronology and Pb isotope geochemistry of magnetite-apatite ore from the Pea Ridge iron oxide-apatite deposit, St. Francois Mountains, southeast Missouri, USA

    USGS Publications Warehouse

    Neymark, Leonid; Holm-Denoma, Christopher S.; Pietruszka, Aaron; Aleinikoff, John N.; Fanning, C. Mark; Pillers, Renee M.; Moscati, Richard J.

    2016-01-01

    The Pea Ridge iron oxide-apatite (IOA) deposit is one of the major rhyolite-hosted magnetite deposits of the St. Francois Mountains terrane, which is located within the Mesoproterozoic (1.5–1.3 Ga) Granite-Rhyolite province in the U.S. Midcontinent. Precise and accurate determination of the timing and duration of oreforming processes in this deposit is crucial for understanding its origin and placing it within a deposit-scale and regional geologic context. Apatite and monazite, well-established U-Pb mineral geochronometers, are abundant in the Pea Ridge orebody. However, the potential presence of multiple generations of dateable minerals, processes of dissolution-reprecipitation, and occurrence of micrometer-sized intergrowths and inclusions complicate measurements and interpretations of the geochronological results. Here, we employ a combination of several techniques, including ID-TIMS and high spatial resolution geochronology of apatite and monazite using LA-SC-ICPMS and SHRIMP, and Pb isotope geochemistry of pyrite and magnetite to obtain the first direct age constraints on the formation and alteration history of the Pea Ridge IOA deposit. The oldest apatite TIMS 207Pb*/206Pb* dates are 1471 ± 1 and 1468 ± 1 Ma, slightly younger than (but within error of) the ~1474 to ~1473 Ma U-Pb zircon ages of the host rhyolites. Dating of apatite and monazite inclusions within apatite provides evidence for at least one younger metasomatic event at ~1.44 Ga, and possibly multiple superimposed metasomatic events between 1.47 and 1.44 Ga. Lead isotop analyses of pyrite show extremely radiogenic 206Pb/204Pb ratios up to ~80 unsupported by in situ U decay. This excess radiogenic Pb in pyrite may have been derived from the spatially associated apatite as apatite recrystallized several tens of million years after its formation. The low initial 206Pb/204Pb ratio of ~16.5 and 207Pb/204Pb ratio of ~15.4 for individual magnetite grains indicate closed U-Pb system behavior in

  17. Conventional U-Pb dating versus SHRIMP of the Santa Barbara Granite Massif, Rondonia, Brazil

    USGS Publications Warehouse

    Sparrenberger, I.; Bettencourt, Jorge S.; Tosdal, R.M.; Wooden, J.L.

    2002-01-01

    The Santa Ba??rbara Granite Massif is part of the Younger Granites of Rondo??nia (998 - 974 Ma) and is included in the Rondo??nia Tin Province (SW Amazonian Craton). It comprises three highly fractionated metaluminous to peraluminous within-plate A-type granite units emplaced in older medium-grade metamorphic rocks. Sn-mineralization is closely associated with the late-stage unit. U-Pb monazite conventional dating of the early-stage Serra do Cicero facies and late-stage Serra Azul facies yielded ages of 993 ?? 5 Ma and 989 ?? 13 Ma, respectively. Conventional multigrain U-Pb isotope analyses of zircon demonstrate isotopic disturbance (discordance) and the preservation of inherited older zircons of several different ages and thus yield little about the ages of Sn-granite magmatism. SHRIMP U-Pb ages for the Santa Ba??rbara facies association yielded a 207Pb/206Pb weighted-mean age of 978 ?? 13 Ma. The textural complexity of the zircon crystals of the Santa Ba??rbara facies association, the variable concentrations of U, Th and Pb, as well as the mixed inheritance of zircon populations are major obstacles to using conventional multigrain U-Pb isotopic analyses. Sm-Nd model ages and ??Nd (T) values reveal anomalous isotopic data, attesting to the complex isotopic behaviour within these highly fractionated granites. Thus, SHRIMP U-Pb zircon and conventional U-Pb monazite dating methods are the most appropriate to constrain the crystallization age of the Sn-bearing granite systems in the Rondo??nia Tin Province.

  18. U-Th-Pb age of the Barwell chondrite - Anatomy of a 'discordant' meteorite

    NASA Technical Reports Server (NTRS)

    Unruh, D. M.; Tatsumoto, M.; Hutchison, R.

    1979-01-01

    A Pb-Pb internal isochron for the Barwell L5-6 chondrite yields an age of 4.530 plus or minus 0.005 billion years, using the measured U-238/U-235 ratio of 135.24 plus or minus .17. If the terrestrial U isotope composition is used, an age of 4.559 billion years is obtained. The Pb isotopic composition is distinctly different from that of a terrestrial contaminant found in the fusion crust of the Barwell stone. When the U-Th-Pb data are plotted on the concordia diagram, the data define a line that intersects the concordia curve at approximately 4.53 and 0 billion years, and nearly all of the data plot above the concordia curve, regardless of the initial Pb correction. This discordancy and the Pb isotopic composition of the triolite are attributed to a recent reequilibration of Pb and not to terrestrial contamination.

  19. Pb isotopic constraints on the formation of the Dikulushi Cu-Pb-Zn-Ag mineralisation, Kundelungu Plateau (Democratic Republic of Congo)

    NASA Astrophysics Data System (ADS)

    Haest, Maarten; Schneider, Jens; Cloquet, Christophe; Latruwe, Kris; Vanhaecke, Frank; Muchez, Philippe

    2010-04-01

    Base metal-Ag mineralisation at Dikulushi and in other deposits on the Kundelungu Plateau (Democratic Republic of Congo) developed during two episodes. Subeconomic Cu-Pb-Zn-Fe polysulphide ores were generated during the Lufilian Orogeny (c. 520 Ma ago) in a set of E-W- and NE-SW-oriented faults. Their lead has a relatively unradiogenic and internally inhomogeneous isotopic composition (206Pb/204Pb = 18.07-18.49), most likely generated by mixing of Pb from isotopically heterogeneous clastic sources. These sulphides were remobilised and enriched after the Lufilian Orogeny, along reactivated and newly formed NE-SW-oriented faults into a chalcocite-dominated Cu-Ag mineralisation of high economic interest. The chalcocite samples contain only trace amounts of lead and show mostly radiogenic Pb isotope signatures that fall along a linear trend in the 207Pb/204Pb vs. 206Pb/204Pb diagram (206Pb/204Pb = 18.66-23.65; 207Pb/204Pb = 15.72-16.02). These anomalous characteristics reflect a two-stage evolution involving admixture of both radiogenic lead and uranium during a young fluid event possibly c. 100 Ma ago. The Pb isotope systematics of local host rocks to mineralisation also indicate some comparable young disturbance of their U-Th-Pb systems, related to the same event. They could have provided Pb with sufficiently radiogenic compositions that was added to less radiogenic Pb remobilised from precursor Cu-Pb-Zn-Fe polysulphides, whereas the U most likely originated from external sources. Local metal sources are also suggested by the 208Pb/204Pb-206Pb/204Pb systematics of combined ore and rock lead, which indicate a pronounced and diversified lithological control of the immediate host rocks on the chalcocite-dominated Cu-Ag ores. The Pb isotope systematics of polysulphide mineralisation on the Kundelungu Plateau clearly record a diachronous evolution.

  20. Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

    NASA Astrophysics Data System (ADS)

    Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

    2015-12-01

    Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity

  1. Integrated Extraction Chromatographic Separation of the Lithophile Elements Involved in Long-Lived Radiogenic Isotope Systems (Rb-Sr, U-Th-Pb, Sm-Nd, La-Ce, and Lu-Hf) Useful in Geochemical and Environmental Sciences.

    PubMed

    Pin, Christian; Gannoun, Abdelmouhcine

    2017-02-21

    A fast and efficient sample preparation method in view of isotope ratio measurements is described, allowing the separation of 11 elements involved, either as "parent" or as "daughter" isotopes, in six radiogenic isotope systems used as chronometers and tracers in earth, planetary, and environmental sciences. The protocol is based on small extraction chromatographic columns, used either alone or in tandem, through which a single nitric acid solution is passed, without any intervening evaporation step. The columns use commercially available extraction resins (Sr resin, TRU resin, Ln resin, RE resin, and again Ln resin for isolating Sr and Pb, LREE then La-Ce-Nd-Sm, Lu(Yb), and Hf, Th, and U, respectively) along with an additional, in-house prepared resin for separating Rb. A simplified scheme is proposed for samples requiring the separation of Sr, Pb, Nd, and Hf only. Adverse effects of troublesome major elements (Fe 3+ , Ti) are circumvented by masking with ascorbic acid and hydrofluoric acid, respectively. Typical recoveries in the 85-95% range are achieved, with procedural blanks of 10-100 pg, negligible with regard to the amounts of analytes processed. The fractions separated are suitable for high precision isotope ratio measurements by TIMS or MC-ICP-MS, as demonstrated by the repeat analyses of several international reference materials of basaltic composition for 87 Sr/ 86 Sr, 208,207,206 Pb/ 204 Pb, 143 Nd/ 144 Nd, 176 Hf/ 177 Hf, and 230 Th/ 232 Th. Concentration data could be obtained by spiking and equilibrating the sample with appropriate isotopic tracers before the onset of the separation process and, finally, measuring the isotope ratios modified by the isotope dilution process.

  2. Pb isotope geochemistry of Piton de la Fournaise historical lavas

    NASA Astrophysics Data System (ADS)

    Vlastélic, Ivan; Deniel, Catherine; Bosq, Chantal; Télouk, Philippe; Boivin, Pierre; Bachèlery, Patrick; Famin, Vincent; Staudacher, Thomas

    2009-07-01

    Variations of Pb isotopes in historical lavas (1927-2007) from Piton de la Fournaise are investigated based on new (116 samples) and published (127 samples) data. Lead isotopic signal exhibits smooth fluctuations (18.87 < 206Pb/ 204Pb < 18.94) on which superimpose unradiogenic spikes ( 206Pb/ 204Pb down to 18.70). Lead isotopes are decoupled from 87Sr/ 86Sr and 143Nd/ 144Nd, which display small and barely significant variations, respectively. No significant change of Pb isotope composition occurred during the longest (> 3 years) periods of inactivity of the volcano (1939-1942, 1966-1972, 1992-1998), supporting previous inferences that Pb isotopic variations occur mostly during and not between eruptions. Intermediate compositions (18.904 < 206Pb/ 204Pb < 18.917) bracket the longest periods of quiescence. In this respect, the highly frequent occurrence of an intermediate composition (18.90 < 206Pb/ 204Pb < 18.91), which clearly defines an isotopic baseline during the most recent densely sampled period (1975-2007), either suggests direct sampling of plume melts or sampling of a voluminous magma reservoir that buffers Pb isotopic composition. Deviations from this prevalent composition occurred during well-defined time periods, namely 1977-1986 (radiogenic signature), 1986-1990 and 1998-2005 (unradiogenic signatures). The three periods display a progressive isotopic drift ending by a rapid return (mostly during a single eruption) to the isotopic baseline. The isotopic gradients could reflect progressive emptying of small magma reservoirs or magma conduits, which are expected to be more sensitive to wall-rock interactions than the main magma chamber. These gradients provide a lower bound ranging from 0.1 to 0.17 km 3 for the size of the shallow magma storage system. The isotopic shifts (March 1986, January 1990 and February 2005) are interpreted as refilling the plumbing system with deep melts that have not interacted with crustal components. The volume of magma erupted

  3. Gluconeogenesis from labeled carbon: estimating isotope dilution

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

    Kelleher, J.K.

    1986-03-01

    To estimate the rate of gluconeogenesis from steady-state incorporation of labeled 3-carbon precursors into glucose, isotope dilution must be considered so that the rate of labeling of glucose can be quantitatively converted to the rate of gluconeogenesis. An expression for the value of this isotope dilution can be derived using mathematical techniques and a model of the tricarboxylic acid (TCA) cycle. The present investigation employs a more complex model than that used in previous studies. This model includes the following pathways that may affect the correction for isotope dilution: 1) flux of 3-carbon precursor to the oxaloacetate pool via acetyl-CoAmore » and the TCA cycle; 2) flux of 4- or 5-carbon compounds into the TCA cycle; 3) reversible flux between oxaloacetate (OAA) and pyruvate and between OAA and fumarate; 4) incomplete equilibrium between OAA pools; and 5) isotope dilution of 3-carbon tracers between the experimentally measured pool and the precursor for the TCA-cycle OAA pool. Experimental tests are outlined which investigators can use to determine whether these pathways are significant in a specific steady-state system. The study indicated that flux through these five pathways can significantly affect the correction for isotope dilution. To correct for the effects of these pathways an alternative method for calculating isotope dilution is proposed using citrate to relate the specific activities of acetyl-CoA and OAA.« less

  4. 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

  5. Distinct 238U/235U ratios and REE patterns in plutonic and volcanic angrites: Geochronologic implications and evidence for U isotope fractionation during magmatic processes

    NASA Astrophysics Data System (ADS)

    Tissot, François L. H.; Dauphas, Nicolas; Grove, Timothy L.

    2017-09-01

    Angrites are differentiated meteorites that formed between 4 and 11 Myr after Solar System formation, when several short-lived nuclides (e.g., 26Al-26Mg, 53Mn-53Cr, 182Hf-182W) were still alive. As such, angrites are prime anchors to tie the relative chronology inferred from these short-lived radionuclides to the absolute Pb-Pb clock. The discovery of variable U isotopic composition (at the sub-permil level) calls for a revision of Pb-Pb ages calculated using an ;assumed; constant 238U/235U ratio (i.e., Pb-Pb ages published before 2009-2010). In this paper, we report high-precision U isotope measurement for six angrite samples (NWA 4590, NWA 4801, NWA 6291, Angra dos Reis, D'Orbigny, and Sahara 99555) using multi-collector inductively coupled plasma mass-spectrometry and the IRMM-3636 U double-spike. The age corrections range from -0.17 to -1.20 Myr depending on the samples. After correction, concordance between the revised Pb-Pb and Hf-W and Mn-Cr ages of plutonic and quenched angrites is good, and the initial (53Mn/55Mn)0 ratio in the Early Solar System (ESS) is recalculated as being (7 ± 1) × 10-6 at the formation of the Solar System (the error bar incorporates uncertainty in the absolute age of Calcium, Aluminum-rich inclusions - CAIs). An uncertainty remains as to whether the Al-Mg and Pb-Pb systems agree in large part due to uncertainties in the Pb-Pb age of CAIs. A systematic difference is found in the U isotopic compositions of quenched and plutonic angrites of +0.17‰. A difference is also found between the rare earth element (REE) patterns of these two angrite subgroups. The δ238U values are consistent with fractionation during magmatic evolution of the angrite parent melt. Stable U isotope fractionation due to a change in the coordination environment of U during incorporation into pyroxene could be responsible for such a fractionation. In this context, Pb-Pb ages derived from pyroxenes fraction should be corrected using the U isotope composition

  6. 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

  7. 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

    beyond the scope of typical solution MC-ICP-MS techniques. However, we demonstrate that an uncertainty level of ca. 1 ɛHf can be achieved with as little as 0.4 ng Hf through the use of low-volume solution introduction methods - thus bridging the gap in resolving power between in-situ and isotope dilution coupled zircon U-Pb - Lu-Hf studies. We demonstrate the potential of this approach to unravel intra- and inter-sample heterogeneity and address models for granite genesis using a new regional data set for 21 samples encompassing all major granite types within the Early Permian Cornubian Batholith (SW England). The data provide a refined chronological framework for magma source evolution over 20 Myrs of crust-mantle melt extraction and upper crustal batholith construction. The resulting petrogenetic model will also be evaluated through the lens of low- temporal resolution commonly employed in granitic zircon U-Pb - Lu-Hf studies in order to highlight the enhanced insights into geological processes gained though our approach. The current limitations to data interpretation and directions of future research will be discussed.

  8. Simultaneous determination of iron, cadmium, zinc, copper, nickel, lead, and uranium in seawater by stable isotope dilution spark source mass spectrometry

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

    Mykytiuk, A.P.; Russell, D.S.; Sturgeon, R.E.

    Trace concentrations (ng/mL) of Fe, Cd, Zn, Cu, Ni, Pb, U, and Co have been determined in seawater by stable isotope dilution spark source mass spectrometry. The seawater samples were preconcentrated on the ion exchanger Chelex-100 and the concentrate was evaporated on a graphite or silver electrode. The results are compared with those obtained by graphite furnace atomic absorption spectrometry and inductively coupled plasma emission spectrometry. The technique avoids the use of calibration standards and is capable of producing results in cases where the analyte is only partially recovered. 2 tables.

  9. Pb isotope constaints on the extent of crustal recycling into a steady state mantle

    NASA Technical Reports Server (NTRS)

    Galer, S. J. G.; Goldstein, S. L.; Onions, R. K.

    1988-01-01

    Isotopic and geochemical evidence was discussed against recycling of continental crust into the mantle. Element ratios such as Sm/Nd, Th/Sc, and U/Pb in sedimentary masses have remained relatively constant throughout Earth history, and this can only be reconciled with steady state recycling models if new crustal materials added from the mantle have had similar ratios. Such recycling models would also require shorter processing times for U, Th, and Pb through the mantle than are geodynamically reasonable. Models favoring subduction of pelagic sediments as the only recycling mechanism fail to account for the Pb isotopic signature of the mantle. Recycling of bulk crust with Pb isotopic compositions similar to those expected for primitive mantle would be permissable with available data, but there appear to be no plausible tectonic mechanisms to carry this out.

  10. U Pb ages of angrites

    NASA Astrophysics Data System (ADS)

    Amelin, Yuri

    2008-01-01

    Precise U-Pb ages, determined with double spike ( 202Pb- 205Pb) thermal ionization m1ass spectrometry, are reported for angrites Angra dos Reis (AdoR), Lewis Cliff 86010 (LEW), and D'Orbigny. Nineteen of 23 acid-washed pyroxene fractions from these meteorites and whole rock fractions from D'Orbigny contain between 0.5 and 1.3 pg of total common Pb, indistinguishable from analytical blank. Measured 206Pb/ 204Pb ratios in these fractions are between 6300 and 14,100 for AdoR, 1160-4500 for LEW, and 608-8500 for D'Orbigny. Blank-corrected 206Pb/ 204Pb ratios for all three meteorites vary from 2160 to over 100,000. These fractions yielded precise and reproducible 207Pb ∗/ 206Pb ∗ dates with the average values of 4557.65 ± 0.13 Ma for AdoR, 4558.55 ± 0.15 Ma for LEW, and 4564.42 ± 0.12 Ma for D'Orbigny. Pb-Pb isochrons including data with slightly elevated common Pb, and U-Pb upper concordia intercepts, yield similar dates. The implications of these new Pb-isotopic ages of angrites are threefold. First, they demonstrate that AdoR and LEW are not coeval, and the group of "slowly cooled" angrites is therefore genetically diverse. Second, the new age of LEW suggests an upward revision of 53Mn- 53Cr "absolute" ages by 0.7 Ma. Third, a precise age of D'Orbigny allows consistent linking of the 53Mn- 53Cr and 26Al- 26Mg extinct nuclide chronometers to the absolute lime scale.

  11. 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.

  12. Two mineralization events in the Baiyinnuoer Zn-Pb deposit in Inner Mongolia, China: Evidence from field observations, S-Pb isotopic compositions and U-Pb zircon ages

    NASA Astrophysics Data System (ADS)

    Jiang, Si-Hong; Chen, Chun-Liang; Bagas, Leon; Liu, Yuan; Han, Ning; Kang, Huan; Wang, Ze-Hai

    2017-08-01

    The Xing-Mong Orogenic Belt (XMOB) is located in the eastern part of the Central Asian Orogenic Belt (CAOB) and has experienced multiple tectonic events. The Baiyinnuoer Pb-Zn deposit may be a rare case that documents two periods of mineralization in the tectonically complex XMOB. There are two types of Pb-Zn mineralization in the deposit: (1) skarn-type ore, hosted by the skarn in the contact zone between marble and granodiorite and within the marble and (2) vein-type ore, hosted by crystal tuff and feldspar porphyry. This study revealed that the host rocks, mineral assemblages, mineralization occurrences, S-Pb isotopes, and ages between the two types of ore are notably different. Zircon U-Pb dating indicates that the granodiorite was emplaced in the Early Triassic (244 ± 1 to 242 ± 1 Ma), the crystal tuff was deposited in the Early Cretaceous (140 ± 1 to 136 ± 1 Ma), and the feldspar porphyry was intruded in the Early Cretaceous (138 ± 2 to 136 ± 2 Ma). The first skarn mineralization occurred at ∼240 Ma and the second vein-type Pb-Zn mineralization took place between 136 and 129 Ma. Thus the Triassic orebodies were overprinted by Early Cretaceous mineralization. The sphalerite and galena from the skarn mineralization have higher δ34S values (-4.7 to +0.3‰) than the sphalerite, galena and aresenopyrite from the vein-type mineralization (-7.5 to -4.2‰), indicating different sulfur sources or ore-forming processes for the two types of mineralization. The Pb isotopic compositions of the two types of ore are very similar, suggesting similar lead sources. Geochemistry and Nd-Pb-Hf isotopic systematics of the igneous rocks in the region show that the Triassic granodiorite was generated from hybridization of mafic and felsic magmas due to strong crust-mantle interaction under the collisional setting that resulted following the closure of the Paleo-Asian Ocean and the collision of North China and Siberian cratons at the end of the Permian; while the

  13. U-Pb Dating of Calcite by LA-ICPMS

    NASA Astrophysics Data System (ADS)

    Hacker, B. R.; Kylander-Clark, A. R.; Holder, R. M.; Nuriel, P.

    2016-12-01

    An emerging frontier area in geochronology is U-Pb dating of carbonate minerals by laser-ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The spate of papers over the last few years applying LA-ICPMS to carbonate dating stems from the capability of LA-ICPMS to deal with the variable, and often low, U/Pb ratios of carbonate. LA-ICPMS is an excellent tool for efficiently screening out samples with low U/Pb ratios and provides the ability to measure many spots with different U/Pb ratios and obtain dates free of assumptions about the composition of common Pb. Because this technique is in its infancy, important questions remain. What percentage of carbonate samples have high enough U/Pbc ratios that they can be dated? What percentage of samples yield isochronous datasets? What are the limits on precision and accuracy of carbonate U/Pb dates? What is the best analytical method in the absence of isotopically homogeneous reference materials? Through the generosity of our colleagues we have acquired 8 reference materials ranging in age from 3 to 250 Ma. We have analyzed 125 unknowns from a variety of locations using a 193 nm ns laser with an 80-100 μm spot and a Nu Plasma HR-ES. We measure 207Pb/206Pb using NIST 614 glass and then calculate a 206Pb/238U correction factor based on the measured vs. known ages of the reference materials. Sixty of these samples ( 50%) have high enough U/Pb ratios that they can be dated. There is great heterogeneity among the sample suites: some have no datable samples, whereas one suite of 68 samples yielded 53 datable rocks. Of the samples with high U/Pbc ratios, a majority yielded isochronous U-Pb data, indicating that the U-Pb system closed at a given time and was not subsequently disturbed.

  14. Simultaneous in situ determination of both U-Th-Pb and Sm-Nd isotopes in monazite by laser ablation using a magnetic sector ICP-MS and a multicollector ICP-MS

    NASA Astrophysics Data System (ADS)

    Goudie, D. J.; Fisher, C. M.; Hanchar, J. M.; Davis, W. J.; Crowley, J. L.; Ayers, J. C.

    2012-12-01

    We present a method for the simultaneous in situ determination of U-Th-Pb and Sm-Nd isotopes in monazite, using a laser ablation (LA) system coupled to both a magnetic sector inductively coupled plasma mass spectrometer (HR) ICP-MS and a multicollector (MC) ICP-MS. The ablated material is split using a glass Y-connector and transported simultaneously to both mass spectrometers via helium carrier gas. The MC-ICP-MS is configured to provide relative Ce, Gd, and Eu contents, in addition to Sm and Nd. This approach obtains both age (U-Pb), tracer isotope (Sm-Nd), and REE element data (Ce, Gd, and Eu), in the same ablation volume, thus reducing sampling problems associated with fine-scale zoning and other internal structures. The accuracy and precision of the U-Pb data are demonstrated using six well characterized monazite reference materials from the Geological Survey of Canada (three of which are currently used as SHRIMP standards) and agree well with previously determined ID-TIMS ages. The accuracy of the Sm-Nd isotopic data was assessed by comparison to TIMS measurements on a well-characterized in-house monazite standard. The dual LA-ICP-MS method was applied to the Birch Creek Pluton (BCP) in the White Mountains, California in a case study to test the utility of U-Th-Pb dating coupled with Sm-Nd (and Ce, Gd, Eu) isotopic data for solving geologic problems. Previous work on the Cretaceous BCP [1] used Th-Pb ages coupled with O isotopic data to constrain hydrothermal fluid events, as recorded in monazite. The original study suggested that the high delta 18O monazite in Paleozoic country rocks adjacent to the BCP grew in response to fluid alternation associated with the intrusion of the BCP, based on overlapping age with the BCP. New monazite split-stream U-Pb and Sm-Nd data show that monazite from the BCP pluton and monazite from altered country rock have homogenous and overlapping initial Nd isotopic composition, further strengthening the proposal that monazite in

  15. 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

  16. 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

  17. Common Pb isotope mapping of UHP metamorphic zones in Dabie orogen, Central China: Implication for Pb isotopic structure of subducted continental crust

    NASA Astrophysics Data System (ADS)

    Shen, Ji; Wang, Ying; Li, Shu-Guang

    2014-10-01

    We report Pb isotopic compositions for feldspars separated from 57 orthogneisses and 2 paragneisses from three exhumed UHPM slices representing the North Dabie zone, the Central Dabie zone and the South Dabie zone of the Dabie orogen, central-east China. The feldspars from the gneisses were recrystallized during Triassic continental subduction and UHP metamorphism. Precursors of the orthogneisses are products of Neoproterozoic bimodal magmatic events, those in north Dabie zone emplaced into the lower crust and those in central and south Dabie zones into middle or upper crust, respectively. On a 207Pb/204Pb vs. 206Pb/204Pb diagram, almost all orthogneisses data lie to the left of the 0.23 Ga paleogeochron and plot along the model mantle evolution curve with the major portion of the data plotting below it. On a 208Pb/204Pb vs. 206Pb/204Pb diagram the most of data of north Dabie zone extend in elongate arrays along the lower crustal curve and others extend between the lower crustal curve to near the mantle evolution curve for the plumbotectonics model. This pattern demonstrates that the Pb isotopic evolution of the feldspars essentially ended at 0.23 Ga and the orthogneiss protoliths were principally dominated by reworking of ancient lower crust with some addition of juvenile mantle in the Neoproterozoic rifting tectonic zone. According to geological evolution history of the locally Dabie orogen, a four-stage Pb isotope evolution model including a long time evolution between 2.0 and 0.8 Ga with a lower crust type U/Pb ratio (μ = 5-6) suggests that magmatic emplacement levels of the protoliths of the orthogneisses in the Dabie orogen at 0.8 Ga also play an important role in the Pb evolution of the exhumed UHPM slices, corresponding to their respective Pb characters at ca. 0.8-0.23 Ga. For example, north Dabie zone requires low μ values (3.4-9.6), while central and south Dabie zones require high μ values (10.9-17.2). On the other hand, Pb isotopic mixing between

  18. Subduction and melting processes inferred from U-Series, Sr Nd Pb isotope, and trace element data, Bicol and Bataan arcs, Philippines

    NASA Astrophysics Data System (ADS)

    DuFrane, S. Andrew; Asmerom, Yemane; Mukasa, Samuel B.; Morris, Julie D.; Dreyer, Brian M.

    2006-07-01

    We present U-series, Sr-Nd-Pb isotope, and trace element data from the two principal volcanic chains on Luzon Island, developed over oppositely dipping subduction zones, to explore melting and mass transfer processes beneath arcs. The Bataan (western) and Bicol (eastern) arcs are currently subducting terrigenous and pelagic sediments, respectively, which have different trace element and isotopic compositions. The range of ( 230Th/ 238U) disequilibria for both arcs is 0.85-1.15; only lavas from Mt. Mayon (Bicol arc) have 230Th activity excesses. Bataan lavas have higher 87Sr/ 86Sr and lower 143Nd/ 144Nd than Bicol lavas ( 87Sr/ 86Sr = 0.7042-0.7046, 143Nd/ 144Nd = 0.51281-0.51290 vs. 87Sr/ 86Sr = 0.70371-0.70391, 143Nd/ 144Nd = 0.51295-0.51301) and both arcs show steep linear arrays towards sediment values on 207Pb/ 204Pb vs. 206Pb/ 204Pb diagrams. Analysis of incompatible element and isotopic data allows identification of a sediment component that, at least in part, was transferred as a partial melt to the mantle wedge peridotite. Between 1% and 5% sediment melt addition can explain the isotopic and trace element variability in the rocks from both arcs despite the differences in sediment supply. We therefore propose that sediment transfer to the mantle wedge is likely mechanically or thermally limited. It follows that most sediments are either accreted, reside in the sub-arc lithosphere, or are recycled into the convecting mantle. However, whole-sale sediment recycling into the upper mantle is unlikely in light of the global mid-ocean ridge basalt data. Fluid involvement is more difficult to characterize, but overall the Bicol arc appears to have more fluid influence than the Bataan arc. Rock suites from each arc can be related by a dynamic melting process that allows for 230Th ingrowth, either by dynamic or continuous flux melting, provided the initial ( 230Th/ 232Th) of the source is ˜0.6-0.7. The implication of either model is that inclined arrays on the U

  19. Pb isotope signatures in the North Atlantic: initial results from the U.S. GEOTRACES North Atlantic Transect

    NASA Astrophysics Data System (ADS)

    Noble, A.; Echegoyen-Sanz, Y.; Boyle, E. A.

    2012-12-01

    This study presents Pb isotope data from the US GEOTRACES North Atlantic Transect (US-GT-NAT) sampled during two cruises that took place during Fall 2010 and 2011. Almost all of the Pb in the modern ocean is derived from anthropogenic sources, and the North Atlantic has received major Pb inputs from the United States and Europe due to emissions from leaded gasoline and high temperature industrial processes. During the past three decades, Pb fluxes to the North Atlantic have decreased following the phasing out of leaded gasoline in the United States and Europe. Following the concentrations and isotope ratios of Pb in this basin over time reveals the temporal evolution of Pb in this highly-affected basin. The Pb isotope signatures reflect the relative importance of changing inputs from the United States and Europe as leaded gasoline was phased out faster in the United States relative to Europe. In the western North Atlantic, a shallow (~100-200m) low Pb-206/Pb-207 ratio feature was observed near the Subtropical Underwater salinity peak at many stations across the transect, coincident with shallow subsurface maxima in Pb concentration. This water mass originates from high-salinity surface water near 25°N (Defant), which is in the belt of European-Pb-gas-contaminated African aerosols, which we confirmed by Pb-206/Pb-207 ~ 1.17 from upper ocean samples from US-GT-NAT station 18 (23.24degN,38.04degW). At the Mid-Atlantic Ridge station, Pb scavenging onto iron oxides and sulfide was observed by a decrease in Pb concentrations within the TAG hydrothermal plume, although the isotopic signature within the plume was slightly (~3 permil) lower than the surrounding waters possibly indicating a small contribution of hydrothermal Pb or preferential uptake of the lighter isotope. In the Mediteranean Outflow plume near Lisbon, Pb-206/Pb-207 (~1.178) is also strongly influenced by European Pb. Further results from the section will be presented as more data will be available by the

  20. U-Th-Pb systematics. [geochemical analysis on lunar rocks

    NASA Technical Reports Server (NTRS)

    Nunes, P. D.; Tatsumoto, M.

    1974-01-01

    The following boulder samples are analyzed for U, Th, and Pb concentrations and for Pb isotopic compositions: 72275,53/matrix; 72275,73/matrix; 72275,81/dark rind, clast #1; 72275,117/white interior, clast #1; 72255,49/Civet Cat clast; 72255,54/light gray matrix; and 72255,67/dark gray matrix.

  1. Anorogenic nature of magmatism in the Northern Baikal volcanic belt: Evidence from geochemical, geochronological (U-Pb), and isotopic (Pb, Nd) data

    USGS Publications Warehouse

    Neymark, L.A.; Larin, A.M.; Nemchin, A.A.; Ovchinnikova, G.V.; Rytsk, E. Yu

    1998-01-01

    The Northern Baikal volcanic belt has an age of 1.82-1.87 Ga and extends along the boundary between the Siberian Platform and the Baikal foldbelt. The volcanic belt is composed of volcanics of the Akitkan Group and granitic rocks of the Irel and Primorsk complexes. The geochemistry of the rocks points to the intraplate anorogenic nature of the belt. U-Pb zircon dating of the Chuya granitoids revealed that they are older (2020-2060 Ma) than the Northern Baikal volcanic belt and, thus, cannot be regarded as its component. Data on the Pb isotopic system of feldspars from the granitoids confirm the contemporaneity of all volcanic rocks of the belt except the volcanics of the upper portion of the Akitkan Group (Chaya Formation). Our data suggest its possibly younger (???1.3 Ga) age. The isotopic Nd and Pb compositions of the acid volcanic rocks provide evidence of the heterogeneity of their crustal protoliths. The volcanics of the Malaya Kosa Formation have ??Nd(T) = -6.1, ??2 = 9.36, and were most probably produced with the participation of the U-depleted lower continental crust of Archean age. Other rocks of the complex show ??Nd(T) from -0.1 to -2.4, ??2 = 9.78, and could have been formed by the recycling of the juvenile crust. The depletion of the Malaya Kosa volcanics in most LILEs and HFSEs compared with other acid igneous rocks of the belt possibly reflects compositional differences between the Late Archean and Early Proterozoic crustal sources. The basaltic rocks of the Malaya Kosa Formation (??Nd varies from -4.6 to -5.4) were produced by either the melting of the enriched lithospheric mantle or the contamination of derivatives of the depleted mantle by Early Archean lower crustal rocks, which are not exposed within the area. Copyright ?? 1998 by MAEe Cyrillic signK Hay??a/Interperiodica Publishing.

  2. Weathering During Glacial-Interglacial Cycles Based on Pb Isotopes at Orphan Knoll, NW Atlantic

    NASA Astrophysics Data System (ADS)

    Flynn, S. N.; Martin, E. E.

    2017-12-01

    Seawater Pb isotopes extracted from FeMn oxyhydroxide coatings on deep sea sediments preserve a record of regional variations in continental weathering intensity. Crocket et al. (2012) documented a distinct increase in seawater Pb isotopes across Termination I (TI) at IODP Sites U1302/03 on Orphan Knoll in the NW Atlantic which they attributed to an increase in weathering intensity associated with ice sheet retreat. Deglaciation during Termination II (TII) was more rapid than TI due to higher insolation forcing and elevated CO2 levels. This rapid warming followed Heinrich Stadial 11 (HS11) cooling and circulation changes, but was not interrupted by a Younger Dryas-type reversal in warming. In this study, Pb isotopic data from leachates of the <63 µm fraction of bulk sediment from TII at Sites U1302/03 are used to test whether changes in weathering are a feature of terminations and whether differences in the character of the termination translate to differences in the weathering response. We analyzed the clay/silt fraction to minimize preformed FeMn oxyhydroxides associated with IRD. All three Pb isotopic systems display similar patterns. Seawater 206Pb/204Pb values are 19.5 during MIS 6, reach a minimum of 18.7 during HS11, increase in < 1 ky to 20.6 in MIS 5e, and then vary between 19.9 - 20.5 across MIS 5e-d. In comparison to the TI study (Crocket et al., 2009), the TII HS is defined by a minimum in Pb isotopes that suggests suppressed chemical weathering during cooling and ice sheet advance. The increase in 206Pb/204Pb during TII indicates a rapid increase in weathering at high latitudes following glacial retreat. This result is consistent with a negative shift in ɛNd values during TII observed farther south on Bermuda Rise and interpreted as increased weathering of old continental material (Deaney et al. 2017). Future research on TII at Orphan Knoll includes analyses of detrital Pb isotopes to isolate the impact of changes in source material versus weathering

  3. Connecting the U-Th and U-Pb Chronometers: New Algorithms and Applications

    NASA Astrophysics Data System (ADS)

    McLean, N. M.; Smith, C. J. M.; Roberts, N. M. W.; Richards, D. A.

    2016-12-01

    The U-Th and U-Pb geochronometers are important clocks for separate intervals of the geologic timescale. U-Th dates exploit disequilibrium in the 238U intermediate daughter isotopes 234U and 230Th, and are often used to date corals and speleothems that are zero age through 800 ka. The U-Pb system relies on secular equilibrium decay of 238U to 206Pb and 235U to 207Pb over longer timescales, and can be used to date samples from <1 Ma to 4.5 Ga. Disequilibrium plays a role in young U-Pb dates, but only as a nuisance correction. Both chronometers can produce dates with uncertainties <0.1% near the center of their applicable age ranges, but become less precise at their intersection, when the 238U decay chain approaches secular equilibrium and there has been little time for ingrowth of radiogenic Pb. However, if measurements or assumptions about both chronometers can be made, then they can be combined into a single, more informed date. Coupling the datasets can improve their precision and accuracy and help interrogate the assumptions that underpin each. Working with this data is difficult for two reasons. The Bateman equations are long and cumbersome for U decay chains that include 238U, 234U, 230Th, 226Ra, 206Pb and 235U, 231Pa, and 207Pb. Also, Pb measurements often comprise varying amounts of radiogenic Pb from locally heterogeneous U concentrations mixed with varying amounts of common Pb. At present there is no established, flexible computational framework to combine information from measurements and/or assumptions of these parameters, and no way to visualize and interpret the results. We present new algorithms to quickly and accurately solve the system of differential equations defined by both of the uranium decay chains and the linear regression through the U-Pb isochron. The results are illustrated on a new concordia diagram, where the concordia curve is determined by measured and/or assumed U-series disequilibrium and can have unfamiliar topologies. We

  4. 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

  5. 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.

  6. Whole-rock Pb and Sm-Nd isotopic constraints on the growth of southeastern Laurentia during Grenvillian orogenesis

    USGS Publications Warehouse

    Fisher, C.M.; Loewy, S.L.; Miller, C.F.; Berquist, P.; Van Schmus, W. R.; Hatcher, R.D.; Wooden, J.L.; Fullagar, P.D.

    2010-01-01

    The conventional view that the basement of the southern and central Appalachians represents juvenile Mesoproterozoic crust, the final stage of growth of Laurentia prior to Grenville collision, has recently been challenged. New whole-rock Pb and Sm-Nd isotopic data are presented from Meso protero zoic basement in the southern and central Appalachians and the Granite-Rhyolite province, as well as one new U-Pb zircon age from the Granite-Rhyolite province. These data, combined with existing data from Mesoproterozoic terranes throughout southeastern Laurentia, further substantiate recent suggestions that the southern and central Appalachian basement is exotic with respect to Laurentia. Sm-Nd isotopic compositions of most rocks from the southern and central Appalachian basement are consistent with progressive growth through reworking of the adjacent Granite-Rhyolite province. However, Pb isotopic data, including new analyses from important regions not sampled in previous studies, do not correspond with Pb isotopic compositions of any adjacent crust. The most distinct ages and isotopic compositions in the southern and central Appalachian basement come from the Roan Mountain area, eastern Tennessee-western North Carolina. The data set indicates U-Pb zircon ages up to 1.8 Ga for igneous rocks, inherited and detrital zircon ages >2.0 Ga, Sm-Nd depleted mantle model (TDM) ages >2.0 Ga, and the most elevated 207Pb/204Pb observed in southeastern Laurentia. The combined U-Pb geochronologic and Sm-Nd and Pb isotopic data preclude derivation of southern and central Appalachian basement from any nearby crustal material and demonstrate that Grenville age crust in southeastern Laurentia is exotic and probably was transferred during collision and assembly of Rodinia. These new data better define the boundary between the exotic southern and central Appalachian basement and adjacent Laurentian Granite-Rhyolite province. ?? 2010 Geological Society of America.

  7. Final report of the key comparison CCQM-K98: Pb isotope amount ratios in bronze

    NASA Astrophysics Data System (ADS)

    Vogl, Jochen; Yim, Yong-Hyeon; Lee, Kyoung-Seok; Goenaga-Infante, Heidi; Malinowskiy, Dmitriy; Ren, Tongxiang; Wang, Jun; Vocke, Robert D., Jr.; Murphy, Karen; Nonose, Naoko; Rienitz, Olaf; Noordmann, Janine; Näykki, Teemu; Sara-Aho, Timo; Ari, Betül; Cankur, Oktay

    2014-01-01

    Isotope amount ratios are proving useful in an ever increasing array of applications that range from studies unravelling transport processes, to pinpointing the provenance of specific samples as well as trace element quantification by using isotope dilution mass spectrometry (IDMS). These expanding applications encompass fields as diverse as archaeology, food chemistry, forensic science, geochemistry, medicine and metrology. However, to be effective tools, the isotope ratio data must be reliable and traceable to enable the comparability of measurement results. The importance of traceability and comparability in isotope ratio analysis has already been recognized by the Inorganic Analysis Working Group (IAWG) within the CCQM. While the requirements for isotope ratio accuracy and precision in the case of IDMS are generally quite modest, 'absolute' Pb isotope ratio measurements for geochemical applications as well as forensic provenance studies require Pb isotope ratio measurements of the highest quality. To support present and future CMCs on isotope ratio determinations, a key comparison was urgently needed and therefore initiated at the IAWG meeting in Paris in April 2011. The analytical task within such a comparison was decided to be the measurement of Pb isotope amount ratios in water and bronze. Measuring Pb isotope amount ratios in an aqueous Pb solution tested the ability of analysts to correct for any instrumental effects on the measured ratios, while the measurement of Pb isotope amount ratios in a metal matrix sample provided a real world test of the whole chemical and instrumental procedure. A suitable bronze material with a Pb mass fraction between 10 and 100 mg•kg-1 and a high purity solution of Pb with a mass fraction of approximately 100 mg•kg-1 was available at the pilot laboratory (BAM), both offering a natural-like Pb isotopic composition. The mandatory measurands, the isotope amount ratios n(206Pb)/n(204Pb), n(207Pb)/n(204Pb) and n(208Pb)/n(204Pb

  8. 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

  9. U-Pb SHRIMP dating of uraniferous opals

    USGS Publications Warehouse

    Nemchin, A.A.; Neymark, L.A.; Simons, S.L.

    2006-01-01

    U-Pb and U-series analyses of four U-rich opal samples using sensitive high-resolution ion microprobe (SHRIMP) demonstrate the potential of this technique for the dating of opals with ages ranging from several tens of thousand years to millions of years. The major advantages of the technique, compared to the conventional thermal ionisation mass spectrometry (TIMS), are the high spatial resolution (???20 ??m), the ability to analyse in situ all isotopes required to determine both U-Pb and U-series ages, and a relatively short analysis time which allows obtaining a growth rate of opal as a result of a single SHRIMP session. There are two major limitations to this method, determined by both current level of development of ion probes and understanding of ion sputtering processes. First, sufficient secondary ion beam intensities can only be obtained for opal samples with U concentrations in excess of ???20 ??g/g. However, this restriction still permits dating of a large variety of opals. Second, U-Pb ratios in all analyses drifted with time and were only weakly correlated with changes in other ratios (such as U/UO). This drift, which is difficult to correct for, remains the main factor currently limiting the precision and accuracy of the U-Pb SHRIMP opal ages. Nevertheless, an assumption of similar behaviour of standard and unknown opals under similar analytical conditions allowed successful determination of ages with precisions of ???10% for the samples investigated in this study. SHRIMP-based U-series and U-Pb ages are consistent with TIMS dating results of the same materials and known geological timeframes. ?? 2005 Elsevier B.V. All rights reserved.

  10. Assessment of the Pb-Pb and U-Pb chronometry of the early solar system

    NASA Astrophysics Data System (ADS)

    Tera, Fouad; Carlson, Richard W.

    1999-06-01

    An evaluation of early solar system chronometry by the Pb-Pb and U-Pb methods is provided. Specifically, three consequential factors are examined: procedure of age calculation, extent of terrestrial Pb contamination, and initial Pb isotopic composition. On a Pb-Pb diagram, high temperature inclusions of the Allende meteorite are tightly organized into a well-defined line (inside a potentially dispersive mixing field), which is consistent with the inclusions containing initial Pb that is more primitive than that of Cañon Diablo troilite (PAT). Consequences of the possible existence of a pre-PAT Pb to the evolution history of the solar nebula are discussed. Phosphates from the ordinary chondrite St. Séverin appear to be contaminated by terrestrial Pb, a condition that renders age calculation based on subtraction of PAT inaccurate. The Pb-Pb mixing line of these phosphates indicates an age of 4.558 Ga. Interestingly, Angra dos Reis phosphate and pyroxene, as well as pyroxene of the other angrite Lewis Cliff 86010 fall precisely on the line defined by St. Séverin phosphates. Whole rocks of ordinary chondrites are pictorially and explicitly shown to be seriously contaminated with terrestrial Pb, thus their single-stage U-Pb ages may not be suitable markers of time. Because their true crystallization ages are often younger than the whole rocks, and because of the possibility of multistage evolution, phosphates of ordinary chondrites may yield single-stage ages older than their true crystallization ages. A hypothetical numerical demonstration is provided. On the basis of revised ages and new observations we provide an ;updated; chronometry for the early solar system.

  11. 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.

  12. Lead Isotope Geochemistry of Mississippi Valley-Type Pb-Zn Deposits of the Ozark Region, U.S. Midcontinent: Constraints on the Origin of Ore Metals

    NASA Astrophysics Data System (ADS)

    Potra, A.

    2015-12-01

    The Ozark region of the U.S. midcontinent is one of the world's most important provinces of MVT mineralization, hosting world-class ore deposits. The ores in the Tri-State (TS) and Northern Arkansas (NA) districts, dominated by sphalerite, are mainly hosted by platform carbonate rocks and vary in age from Ordovician and Mississippian for NA and Mississippian for TS. The deposits are considered to have formed from a regional hydrothermal flow system consisting of sedimentary brines discharged from the Arkoma basin and adjacent platform during the Late Pennsylvanian to Early Permian Ouachita orogeny. New MC-ICP-MS Pb isotope analyses of sphalerites are presented in order to compare and contrast the isotopic signature of ores from the NA and TS districts with those from other MVT districts from central and eastern US and trace metal sources. The Pb isotope ratios of ores from the TS District (208Pb/204Pb between 40.7443 and 41.2626; 207Pb/204Pb between 15.8633 and 15.9571; 206Pb/204Pb between 21.8373 and 22.1956) plot in an area that is superimposed on the Pb isotope field defined by samples from the Central Missouri District, suggesting similar metal sources. The sphalerites are less radiogenic than samples from the Upper Mississippi Valley District, but more radiogenic than samples from any other MVT district. Sphalerites from the NA District have lower Pb isotope values (208Pb/204Pb between 39.4633 and 40.8863; 207Pb/204Pb between 15.8216 and 15.9176; 206Pb/204Pb between 20.2396 and 21.6438) than the TS District ores; they plot below the field defined by samples from the Illinois-Kentucky district and overlap the field defined by ores from the Southeast Missouri (Viburnum and Old Lead Belt) district, implying similar metal sources. Current data suggest that basement of Grenvillian age (1 - 1.2 by), thought to be present in Arkansas, to the south of the Viburnum Trend, may be a likely source of the radiogenic Pb component. Pb data from ores in the NA and the

  13. 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.

  14. High precision time calibration of the Permo-Triassic boundary mass extinction by U-Pb geochronology

    NASA Astrophysics Data System (ADS)

    Baresel, Björn; Bucher, Hugo; Brosse, Morgane; Schaltegger, Urs

    2014-05-01

    U-Pb dating using Chemical Abrasion, Isotope Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS) is the analytical method of choice for geochronologists, who are seeking highest temporal resolution and a high degree of accuracy for single grains of zircon. The use of double-isotope tracer solutions, cross-calibrated and assessed in different EARTHTIME labs, coinciding with the reassessment of the uranium decay constants and further improvements in ion counting technology led to unprecedented precision better than 0.1% for single grain, and 0.05% for population ages, respectively. These analytical innovations now allow calibrating magmatic and biological timescales at resolution adequate for both groups of processes. To construct a revised and high resolution calibrated time scale for the Permian-Triassic boundary (PTB) we use (i) high-precision U-Pb zircon age determinations of a unique succession of volcanic ash beds interbedded with shallow to deep water fossiliferous sediments in the Nanpanjiang Basin (South China) combined with (ii) accurate quantitative biochronology based on ammonoids and conodonts and (iii) carbon isotope excursions across the PTB. Using these alignments allows (i) positioning the PTB in different depositional environments and (ii) solving age/stratigraphic contradictions generated by the index, water depth-controlled conodont Hindeodus parvus, whose diachronous first occurrences are arbitrarily used for placing the base of the Triassic. This new age framework provides the basis for a combined calibration of chemostratigraphic records with high-resolution biochronozones of the Late Permian and Early Triassic. Besides the general improvement of the radio-isotopic calibration of the PTB at the ±100 ka level, this will also lead to a better understanding of cause and effect relations involved in this mass extinction.

  15. Pb-isotopic systematics of lunar highland rocks (>3.9 Ga): Constraints on early lunar evolution

    USGS Publications Warehouse

    Premo, W.R.; Tatsumoto, M.; Misawa, K.; Nakamuka, N.; Kita, N.I.

    1999-01-01

    The present lead (Pb)-isotopic database of over 200 analyses from nearly 90 samples of non-mare basalt, lunar highland rocks (>3.9 Ga) delineate at least three isotopically distinct signatures that in some combination can be interpreted to characterize the systematics of the entire database. Two are fairly new sets of lunar data and are typical of Pb data from other solar-system objects, describing nearly linear arrays slightly above the 'geochron' values, with 207Pb/206Pb values 500). Although the age and origin of this exotic Pb is not well constrained, it is interpreted to be related to the entrapment of incompatible-element-rich (U, Th) melts within the lunar upper mantle and crust between 4.36 and 4.46 Ga (urKREEP residuum?). The latest discovered Pb signature is found only in lunar meteorites and is characterized by relatively low source ?? values between 10 and 50 at 3.9 Ga. The fact that most lunar crustal rocks (>3.9 Ga) exhibit high 207Pb/206Pb values requires that they were derived from, mixed with, or contaminated by Pb produced from early-formed, high-?? sources. The ubiquity of these U-Pb characteristics in the sample collection is probably an artifact of Apollo and Luna sampling sites, all located on the near side of the Moon, which was deeply excavated during the basin-forming event(s). However, the newest Pb-isotopic data support the idea that the Moon originally had a ?? value of ~8 to 35, slightly elevated from Earth values, and that progressive U-Pb fractionations occurred within the Moon during later stages of differentiation between 4.36 and 4.46 Ga.

  16. U-Th-Pb systematics in three Apollo 14 basalts and the problem of initial Pb in lunar rocks.

    NASA Technical Reports Server (NTRS)

    Tera, F.; Wasserburg, G. J.

    1972-01-01

    The isotopic composition of Pb and the elemental concentration of U, Th and Pb were measured on 'total' rock samples 14053, 14073 and 14310 and on mineral separates of 14310 and 14053. These are the first Pb-U isochrons obtained for lunar basalts and indicate a reasonable solution to the previous discrepancy between the different methods of 'absolute' age determination. The resulting U-Pb isochron ages are compatible with the Rb-Sr and K-Ar ages on the same rocks. However, it is not possible to establish a precise time of 'crystallization' from the Pb-U data because of the small angle of intersection between the linear arrays and the concordia curve. These data show that total rock model ages do not in general yield crystallization ages. The data on 14310 and 14053 show that these rocks were formed containing a highly radiogenic initial lead which accounts for the excessively high total rock model ages by the U-Th-Pb method. The data prove that at the time of extrusion of some basalts, unsupported lead with extremely high Pb-207/Pb-206 ratios was added to the lunar surface.

  17. Simultaneous determination of the quantity and isotopic ratios of uranium in individual micro-particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS).

    PubMed

    Park, Jong-Ho; Choi, Eun-Ju

    2016-11-01

    A method to determine the quantity and isotopic ratios of uranium in individual micro-particles simultaneously by isotope dilution thermal ionization mass spectrometry (ID-TIMS) has been developed. This method consists of sequential sample and spike loading, ID-TIMS for isotopic measurement, and application of a series of mathematical procedures to remove the contribution of uranium in the spike. The homogeneity of evaporation and ionization of uranium content was confirmed by the consistent ratio of n((233)U)/n((238)U) determined by TIMS measurements. Verification of the method was performed using U030 solution droplets and U030 particles. Good agreements of resulting uranium quantity, n((235)U)/n((238)U), and n((236)U)/n((238)U) with the estimated or certified values showed the validity of this newly developed method for particle analysis when simultaneous determination of the quantity and isotopic ratios of uranium is required. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. 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).

  19. Age of uranium mineralization at the Jabiluka and Ranger deposits, Northern Territory, Australia: New U- Pb isotope evidence.

    USGS Publications Warehouse

    Ludwig, K. R.; Grauch, R.I.; Nutt, C.J.; Nash, J.T.; Frishman, D.; Simmons, K.R.

    1987-01-01

    The Ranger and Jabiluka uranium deposits are the largest in the Alligator Rivers uranium field, which contains at least 20% of the world's low-cost uranium reserves. Ore occurs in early Proterozoic metasediments, below an unconformity with sandstones of the 1.65 b.y.-old Kombolgie Formation. This study has used U-Pb isotope data from a large number of whole-rock drill core samples with a variety of mineral assemblages and textures. Both Ranger and Jabiluka reflect a common, profound isotopic disturbance at about 400 to 600 m.y. This disturbance, which was especially pronounced at Jabiluka, may correspond to the development of basins and associated basalt flows to the W and SW.-from Authors

  20. Isotopic chemical weathering behaviour of Pb derived from a high-Alpine Holocene lake-sediment record

    NASA Astrophysics Data System (ADS)

    Gutjahr, Marcus; Süfke, Finn; Gilli, Adrian; Anselmetti, Flavio; Glur, Lukas; Eisenhauer, Anton

    2017-04-01

    Several studies assessing the chemical weathering systematics of Pb isotopes provided evidence for the incongruent release of Pb from source rocks during early stages of chemical weathering, resulting in runoff compositions more radiogenic (higher) than the bulk source-rock composition [e.g. 1]. Deep NW Atlantic seawater Pb isotope records covering the last glacial-interglacial transition further support these findings. Clear excursions towards highly radiogenic Pb isotopic input in the deep NW Atlantic seen during the early Holocene, hence after the large-scale retreat of the Laurentide Ice Sheet in North America, are interpreted to be controlled by preferential release of radiogenic Pb from U- and Th-rich mineral phases during early stages of chemical weathering that are less resistant to chemical dissolution than other rock-forming mineral phases [2-4]. To date, however, no terrestrial Pb isotope record exists that could corroborate the evidence from deep marine sites for efficient late deglacial weathering and washout of radiogenic Pb. We present a high-resolution adsorbed Pb isotope record from a sediment core retrieved from Alpine Lake Grimsel (1908 m.a.s.l.) in Switzerland, consisting of 117 Pb compositions over the past 10 kyr. This high-Alpine study area is ideally located for incipient and prolonged chemical weathering studies. The method used to extract the adsorbed lake Pb isotope signal is identical to previous marine approaches targeting the authigenic Fe-Mn oxyhydroxides fraction within the lake sediments [5, 6]. The Pb isotope compositions are further accompanied by various elemental ratios derived from the same samples that equally trace climatic boundary conditions in the Grimsel Lake area. The Pb isotopic composition recorded in Lake Grimsel is remarkably constant throughout the majority of the Holocene until ˜2.5 ka BP, despite variable sediment composition and -age, and isotopically relatively close to the signature of the granitic source rock

  1. Variations in Pb concentrations and Pb-isotope ratios in soils collected along an east-west transect across the United States

    NASA Astrophysics Data System (ADS)

    Smith, David; Woodruff, Laurel; Reimann, Clemens; Flem, Belinda

    2014-05-01

    Soil A-horizon and C-horizon samples were collected along a 4000 km long transect cutting the USA from the west to the east coast. For purposes of site selection, the transect was divided into approximately 40-km segments. For each segment, a 1-km2 target area was selected at random. Soil A- and C-horizon samples were collected at a site within each target area that was most representative of the surrounding landscape. The samples were air-dried at ambient temperature, disaggregated, and sieved through a 2-mm stainless steel screen. The <2-mm material was crushed to <150 µm in a ceramic mill prior to chemical analysis. Lead was analyzed in all the A- and C-horizon samples by inductively coupled plasma-mass spectrometry following a 4-acid digestion. The complete dataset can be found in Smith et al., 2005. Pb-isotope ratio measurements were carried out on 159 soil A-horizon and 137 soil C-horizon samples on an inductively coupled sector field plasma mass spectrometer (SF-ICP-MS; ELEMENT 1, Finnigan MAT) in the laboratory of the Geological Survey of Norway (NGU), following a 7 N HNO3 digestion. Lead concentrations along the transect show (1) generally higher values in the soil A-horizon than the C-horizon (median 21 vs. 16.5 mg/kg), (2) an increase in the median value of the soil A-horizon for the central to eastern U.S. (Missouri to Maryland) when compared to the western U.S. (California to Kansas) (median 26 vs. 20 mg/kg) and (3) a higher A/C ratio for the central to eastern US (1.35 vs. 1.14). Lead isotopes show a distinct trend across the U.S., with the highest 206Pb/207Pb ratios occurring in the centre (Missouri, median A-horizon: 1.245; C-horizon: 1.251) and the lowest at both coasts (e.g. California, median A-horizon: 1.195; C-horizon:1.216). The soil C-horizon samples show generally higher 206Pb/207Pb ratios than the A-horizon (median C-horizon: 1.224; A-horizon: 1.219). The 206Pb/207Pb isotope ratios in the soil A horizon show a correlation with the total

  2. Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

    NASA Astrophysics Data System (ADS)

    Marzouk, E. R.; Chenery, S. R.; Young, S. D.

    2013-12-01

    The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values. Quantify the isotopically exchangeable fractions of Zn, Cd and Pb (E-values), and assess their local and regional variability, using multi-element stable isotope dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop

  3. 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

  4. 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

  5. Isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS) for the certification of lead and cadmium in environmental standard reference materials.

    PubMed

    Murphy, K E; Beary, E S; Rearick, M S; Vocke, R D

    2000-10-01

    Lead (Pb) and cadmium (Cd) have been determined in six new environmental standard reference materials (SRMs) using isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS). The SRMs are the following: SRM 1944, New York-New Jersey Waterway Sediment, SRMs 2583 and 2584, Trace Elements in Indoor Dust, Nominal 90 mg/kg and 10,000 mg/kg Lead, respectively, SRMs 2586 and 2587, Trace Elements in Soil Containing Lead from Paint, Nominal 500 mg/kg and 3,000 mg/kg Lead, respectively, and SRM 2782, Industrial Sludge. The capabilities of ID ICP-MS for the certification of Pb and Cd in these materials are assessed. Sample preparation and ratio measurement uncertainties have been evaluated. Reproducibility and accuracy of the established procedures are demonstrated by determination of gravimetrically prepared primary standard solutions and by comparison with isotope dilution thermal ionization mass spectrometry (ID TIMS). Material heterogeneity was readily demonstrated to be the dominant source of uncertainty in the certified values.

  6. Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

    USGS Publications Warehouse

    Neymark, L.A.; Amelin, Y.V.

    2008-01-01

    Extreme U and Pb isotope variations produced by disequilibrium in decay chains of 238U and 232Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my-1) contain excess 206Pb and 208Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable 206Pb/238U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect 207Pb/235U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages. Opal and calcite from outer (younger) portions of coatings have 230Th/U ages from 94.6 ?? 3.7 to 361.3 ?? 9.8 ka and initial 234U/238U activity ratios (AR) from 4.351 ?? 0.070 to 7.02 ?? 0.12, which indicate 234U enrichment from percolating water. Present-day 234U/238U AR is ???1 in opal/chalcedony from older portions of the coatings. The 207Pb/235U ages of opal/chalcedony samples range from 0.1329 ?? 0.0080 to 9.10 ?? 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my-1, in good agreement with previous results. Measured 234U/238U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ?? 0.006 to 2.091 ?? 0.006 and are >1 in most samples. The range of 87Sr/86Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool. In the U-poor calcite samples, measured 206Pb/207Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both 206Pb and 207Pb derived from Rn diffusion and from direct ??-recoil from U-rich opal. Calcite from coatings devoid of opal

  7. A comparative analysis of alpha-decay half-lives for even-even 178Pb to 234U isotopes

    NASA Astrophysics Data System (ADS)

    Hosseini, S. S.; Hassanabadi, H.; Zarrinkamar, S.

    2018-02-01

    The feasibility for the alpha decay from the even-even transitions of 178Pb to 234U isotopes has been studied within the Coulomb and proximity potential model (CPPM). The alpha decay half-lives are considered from different theoretical approaches using Semi-empirical formula of Poenaru et al. (SemFIS), the Universal Decay law (UDL) of Qi et al., Akrawy-Dorin formula of Akrawy and Poenaru (ADF), the Scaling law of Brown (SLB) and the Scaling Law of Horoi et al. (SLH). The numerical results obtained by the CPPM and compared with other method as well the experimental data.

  8. Re-Os, Sm-Nd, U-Pb, and stepwise lead leaching isotope systematics in shear-zone hosted gold mineralization: genetic tracing and age constraints of crustal hydrothermal activity

    NASA Astrophysics Data System (ADS)

    Frei, R.; Nägler, Th. F.; Schönberg, R.; Kramers, J. D.

    1998-06-01

    A combined Re-Os, Sm-Nd, U-Pb, and stepwise Pb leaching (PbSL) isotope study of hydrothermal (Mo-W)-bearing minerals and base metal sulfides from two adjacent shear zone hosted gold deposits (RAN, Kimberley) in the Harare-Shamva greenstone belt (Zimbabwe) constrain the timing of the mineralizing events to two periods. During an initial Late Archean event (2.60 Ga) a first molybdenite-scheelite bearing paragenesis was deposited in both shear zone systems, followed by a local reactivation of the shear systems during an Early Proterozoic (1.96 Ga) tectono-thermal overprint, during which base metal sulfides and most of the gold was (re-)deposited. While PbSL has revealed an open-system behavior of the U-Pb systematics in molybdenite and wolframite from the RAN mine, initial Archean Re-Os ages are still preserved implying that this system in these minerals was more resistant to the overprint. A similar retentivity could be shown for the Sm-Nd system in scheelite and powellite associated with the above ore minerals. Re-Os isotopic data from the Proterozoic mineralization in the Kimberley mine point to a recent gain of Re, most pronouncedly affecting Fe-rich sulfides such as pyrrhotite. A significant Re-loss in powellitic scheelite (an alteration phase of molybdenite-bearing scheelite), coupled with a marked loss of U in W-Mo ore minerals, complements the observation of a major Re uptake in Fe-sulfides during oxidizing conditions in a weathering environment. Pyrrhotite under these conditions behaves as an efficient Re-sink. Lead isotope signatures from PbSL residues of molybdenite, powellite, and quartz indicate a continental crustal source and/or contamination for the mineralizing fluid by interaction of the fluids with older sedimentary material as represented by the direct host country rocks. Our investigation reveals the potential of the Re-Os isotopic system applied to crustal hydrothermal ore minerals for genetic tracing and dating purposes. The simplified chemical

  9. Origin of the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Evidence from regional Pb and Sr isotope sources

    USGS Publications Warehouse

    Ayuso, R.A.; Kelley, K.D.; Leach, D.L.; Young, L.E.; Slack, J.F.; Wandless, G.; Lyon, A.M.; Dillingham, J.L.

    2004-01-01

    Pb and Sr isotope data were obtained on the shale-hosted Zn-Pb-Ag Red Dog deposits (Qanaiyaq, Main, Aqqaluk, and Paalaaq), other shale-hosted deposits near Red Dog, and Zn-Pb-Ag sulfide and barite deposits in the western and central Brooks Range. The Red Dog deposits and other shale-hosted Zn-Pb-Ag deposits near Red Dog are hosted in the Mississippian Kuna Formation, which is underlain by a sequence of marine-deltaic clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. Ag-Pb-Zn vein-breccias are found in the Endicott Group. Galena formed during the main mineralization stages in the Red Dog deposits and from the Anarraaq and Wulik deposits have overlapping Pb isotope compositions in the range 206Pb/204Pb = 18.364 to 18.428, 207Pb/204Pb = 15.553 to 15.621, and 208Pb/204Pb = 38.083 to 38.323. Galena and sphalerite formed during the main ore-forming stages in the Red Dog deposits define a narrow field on standard uranogenic and thorogenic Pb isotope diagrams. Lead in sulfides of the Red Dog district is less radiogenic (238U/204Pb: ?? = 9.51-9.77) than is indicated by the average crustal lead evolution model (?? = 9.74), a difference consistent with a long history of evolution at low ratios of ?? before the Carboniferous. The homogeneous regional isotopic reservoir of Pb may indicate large-scale transport and leaching of minerals with various ?? ratios and Th/Pb ratios. Younger and genetically unrelated fluids did not significantly disturb the isotopic compositions of galena and sphalerite after the main mineralization event in the Red Dog district. Some pyrite shows evidence of minor Pb remobilization. The overall lead isotope homogeneity in the shale-hosted massive sulfide deposits is consistent with three types of control: a homogeneous regional source, mixing of lead during leaching of a thick sedimentary section and fluid transport, or mixing at the site of deposition. Isotopic variability of the hydrothermal fluids, as represented by galena

  10. U-Th-Pb isotope data indicate phanerozoic age for oxidation of the 3.4 Ga Apex Basalt

    NASA Astrophysics Data System (ADS)

    Li, Weiqiang; Johnson, Clark M.; Beard, Brian L.

    2012-02-01

    The occurrence of ferric oxides in Archean rocks has played an important role in discussions on the amount of free oxygen in the atmosphere of the ancient Earth. Recognizing that post-Archean weathering may also produce oxide minerals, drill cores have been used to obtain samples beneath the depth of Phanerozoic weathering. The first core of the Archean Biosphere Drilling Project (ABDP-1) documented hematite as alteration products in 3.4 Ga basalts from the Marble Bar area of the Pilbara Craton, NW Australia, and this has been used to infer the presence of an O2-bearing atmosphere in the Archean. It is possible, however, that despite recovery of samples from > 100 m depth, oxidation of the basalts occurred much younger than the depositional age. In this study, the age of oxidation of the Apex Basalt from the ABDP-1 drill core at Marble Bar is constrained by U-Th-Pb geochronology. Lead and U concentrations of the basalts from the ABDP-1 drill core vary greatly, between < 1-58 ppm and 0.08-1.04 ppm, respectively, whereas Th contents are more restricted (0.24-0.71 ppm). 206Pb/204Pb ratios are non-radiogenic and vary from 12.44 to 14.69. The linear array in terms of 206Pb/204Pb-207Pb/204Pb variations does not reflect an age but reflects two-component mixing between a non-radiogenic "ore lead" end member and a radiogenic "basalt lead" end member. The samples do not form isochrons on 238U/204Pb-206Pb/204Pb, 235U/204Pb-207Pb/204Pb, or 232Th/204Pb-208Pb/204Pb diagrams, indicating post-formation U and Pb addition. Comparison of measured U/Th ratios with "model" U/Th ratios calculated based on 208Pb/204Pb-206Pb/204Pb variations indicates that U enrichment most likely occurred in the last 200 Ma. The degree of U enrichment in the samples is correlated with Fe(III)/FeTotal ratios, indicating that U addition and oxidation were related, most likely reflecting penetration of oxygenated surface waters in the Phanerozoic along bedding planes and shear zones. These results

  11. U-Th-Pb, Rb-Sr, and Sm-Nd isotopic systematics of lunar troctolitic cumulate 76535 - Implications on the age and origin of this early lunar, deep-seated cumulate

    NASA Technical Reports Server (NTRS)

    Premo, Wayne R.; Tatsumoto, M.

    1992-01-01

    The U-Th-Pb, Rb-Sr, and Sm-Nd isotopic systematics of four lightly leached residues of pristine, high-Mg, troctolitic cumulate 76535 were analyzed in order to determine their ages and magma sources. The data indicate that the cumulate was in isotopic equilibrium with a fluid or magma characterized by a high U-238/Pb-204 (mu) value of 600 at 4.236 Ga. Two and three stage Pb evolution calculations define even greater source mu values of about 1000, assuming low lunar initial mu values between 5 and 40 prior to about 4.43 Ga. These results are similar to mu values for KREEP sources and are also consistent with values from 78235, suggesting that at least some high-Mg suite rocks were derived from magma sources with high-mu values similar to KREEP, and support that idea that these rocks postdate primary lunar differentiation and formation of ferroan anorthosites.

  12. Pacific 187Os/188Os isotope chemistry and U-Pb geochronology: Synchroneity of global Os isotope change across OAE 2

    NASA Astrophysics Data System (ADS)

    Du Vivier, A. D. C.; Selby, D.; Condon, D. J.; Takashima, R.; Nishi, H.

    2015-10-01

    Studies of OAE 2 sections beyond the Atlantic Ocean, Western Interior Seaway (WIS) and European pelagic shelf are limited. Here, we present initial osmium isotope stratigraphy (187Os/188Os-Osi) from two proto-Pacific sites that span the Cenomanian-Turonian boundary interval (CTBI): the Yezo Group (YG) section, Hokkaido, Japan, and the Great Valley Sequence (GVS), California, USA; to evaluate the 187Os/188Os seawater chemistry of the proto-Pacific. Additionally we combine new 206Pb/238U zircon CA-ID-TIMS geochronology from five volcanic tuff horizons of the Yezo Group section to test and facilitate inter-basinal integration with the WIS using radio-isotopically constrained age-depth models for both sections, and quantitatively constrain the absolute timing and duration of events across the CTBI. The YG shows an almost identical Osi profile to that of the WIS, and very similar to that of other sites of the proto-Atlantic and European pelagic oceans (Turgeon and Creaser, 2008; Du Vivier et al., 2014). The characteristics of the Osi profile are radiogenic and heterogeneous (∼0.55-0.85) prior to the OAE 2, and synchronous with the inferred OAE 2 onset the Osi abruptly become unradiogenic and remain relatively homogeneous (∼0.20-0.30) before showing a gradual return to more radiogenic Osi (∼ 0.70) throughout the middle to late OAE 2. A206Pb/238U zircon age of an interbedded tuff (HK017) in the adjacent horizon to the first unradiogenic Osi value constrains the age of the Osi inflection at 94.44 ± 0.14 Ma. This age, including uncertainty, agrees with the interpolated age of the same point in the Osi profile (94.28 ± 0.25 Ma) in the only other dated OAE 2 section, the WIS; indicating a coeval shift in seawater chemistry associated with volcanism at the OAE 2 onset at the levels of temporal resolution (ca. 0.1 Myr). Further, prior to the onset of OAE 2 an enhanced radiogenic inflection in the Osi profile of the YG is correlative, within uncertainty, with a similar

  13. Isotopic equilibration between dissolved and suspended particulate lead in the Atlantic Ocean - Evidence from Pb-210 and stable Pb isotopes

    NASA Technical Reports Server (NTRS)

    Sherrell, Robert M.; Boyle, Edward A.; Hamelin, Bruno

    1992-01-01

    Vertical profiles of, on one hand, the stable Pb isotopic composition, and on the other, the ratio of total Pb to Pb-210 in suspended particles, are noted to closely track contemporaneous depth variations in these ratios for dissolved Pb throughout the upper 2 km of the Sargasso Sea near Bermuda. A simple flux model suggests that the effect of deep ocean scavenging processes on the flux and isotopic composition of Pb sinking on large particles was minor throughout the preanthropogenic, and most of the anthropogenic era: but it has become more important as surface inputs decrease to preleaded gasoline levels, perhaps exceeding the contribution of surface-derived Pb flux in the next decade.

  14. Late Proterozoic charnockites in Orissa, India: A U-Pb and Rb-Sr isotopic study

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

    Aftalion, M.; Bowes, D.R.; Dash, B.

    1988-11-01

    Charnockite formation in the Angul district of Orissa took place between 1088 + 26/ -17 Ma, the U-Pb zircon upper intercept crystallization age of a leptynite neosome, and 957 +8/ -4-956 {plus minus} 4 Ma, the U-Pb zircon-monazite upper intercept and U-Pb monazite crystallization ages of a granite. Confirmation of the Proterozoic age of the charnockites is given by (1) a U-Pb zircon upper intercept 1159 + 59/ -30 Ma age and a Rb-Sr whole-rock 1080 {plus minus} 65 Ma age for an augen gneiss which pre-dates the leptynite, and (2) U-Pb monazite ages of 973 {plus minus} 5,964 {plusmore » minus} 4, and 953 {plus minus} 4 Ma for a gray quartzofeldspathic gneiss, the augen gneiss, and the leptynite, respectively: these late Proterozoic dates are interpreted as representing ages recorded during charnockitization. The ca. 950-980 Ma charnockite- and granite-forming events are related to the evolution of mantle-derived, CO{sub 2}-bearing basic magma emplaced into the deeper levels of an extensional tectonic-transcurrent fault regime. The ca. 1100-1150 Ma tectonothermal and igneous events represent compressional tectonism in reactivated crystalline basement in the late mid-Proterozoic Eastern Ghats orogenic belt.« less

  15. New high precision U-Pb calibration of the late Early-Triassic (Smithian-Spathian Boundary, South China)

    NASA Astrophysics Data System (ADS)

    Widmann, Philipp; Leu, Marc; Goudemand, Nicolas; Schaltegger, Urs; Bucher, Hugo

    2017-04-01

    Following the Permian-Triassic mass extinction (PTME), the Early Triassic is characterized by large short-lived perturbations of the global carbon cycle associated with radiation and extinction pulses of the biota. More stable conditions resumed in the Middle Triassic (Anisian). The exact ages and duration of these short-lived but intense radiation-extinction events as well as carbon cycle perturbations are poorly constrained and a robust intercalibration of U-Pb dates, biochronozones and carbon isotope fluctuations is still lacking. An accurate and precise time frame is essential in order to quantify the dynamics of the underlying mechanistic processes and to assess the validity of the various explanatory scenarios. The most drastic Early Triassic extinction occurred at the Smithian-Spathian boundary (SSB) and is associated with a globally recognized sharp positive excursion of the marine d13C signal. Based on the most recently published ages for the Permian-Triassic boundary (251.938 ± 0.029 Ma, Baresel et al., 2016) and for the Early-Middle Triassic boundary (247.05 ± 0.16 Ma, Ovtcharova et al., 2015), we know the Early Triassic lasted 4.9 myr. However, neither the position of the SSB nor the durations of the major biotic and abiotic events around the SSB are constrained by radiometric dates. Here, we will present new high precision, chemical abrasion, isotope dilution, thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb ages from single zircon crystals, sampled from closely spaced volcanic ash layers that bracket the SSB in the Nanpanjiang Basin (Guizhou province, South China). These ash layers are found in a mixed carbonate-siliciclastic, conodont-rich sedimentary succession (Luolou Formation) that is well calibrated biochronologically. We obtained best estimates of the ages of the SSB and associated events by applying Bayesian age modelling. References: Baresel, B., Bucher, H., Brosse, M., Cordey, F., Guodun, K., and Schaltegger, U., 2016. Precise age

  16. An extremely low U Pb source in the Moon: UThPb, SmNd, RbSr, and 40Ar 39Ar isotopic systematics and age of lunar meteorite Asuka 881757

    USGS Publications Warehouse

    Misawa, K.; Tatsumoto, M.; Dalrymple, G.B.; Yanai, K.

    1993-01-01

    We have undertaken UThPb, SmNd, RbSr, and 40Ar 39Ar isotopic studies on Asuka 881757, a coarse-grained basaltic lunar meteorite whose chemical composition is close to low-Ti and very low-Ti (VLT) mare basalts. The PbPb internal isochron obtained for acid leached residues of separated mineral fractions yields an age of 3940 ?? 28 Ma, which is similar to the U-Pb (3850 ?? 150 Ma) and Th-Pb (3820 ?? 290 Ma) internal isochron ages. The Sm-Nd data for the mineral separates yield an internal isochron age of 3871 ?? 57 Ma and an initial 143Nd 144Nd value of 0.50797 ?? 10. The Rb-Sr data yield an internal isochron age of 3840 ?? 32 Ma (??(87Rb) = 1.42 ?? 10-11 yr-1) and a low initial 87Sr 86Sr ratio of 0.69910 ?? 2. The 40Ar 39Ar age spectra for a glass fragment and a maskelynitized plagioclase are relatively flat and give a weighted mean plateau age of 3798 ?? 12 Ma. We interpret these ages to indicate that the basalt crystallized from a melt 3.87 Ga ago (the Sm-Nd age) and an impact event disturbed the Rb-Sr system and completely reset the K-Ar system at 3.80 Ga. The slightly higher Pb-Pb age compared to the Sm-Nd age could be due to the secondary Pb (from terrestrial and/or lunar surface Pb contamination) that remained in the residues after acid leaching. Alternatively, the following interpretation is also possible; the meteorite crystallized at 3.94 Ga (the Pb-Pb age) and the Sm-Nd, Rb-Sr, and K-Ar systems were disturbed by an impact event at 3.80 Ga. The crystallization age obtained here is older than those reported for low-Ti basalts (3.2-3.5 Ga) and for VLT basalts (3.4 Ga), but similar to ages of some mare basalts, indicating that the basalt may have formed from a magma related to a basin-forming event (Imbrium?). The age span for VLT basalts from different sampling sites suggest that they were erupted over a wide area during an interval of at least ~500 million years. The impact event that thermally reset the K-Ar system of Asuka 881757 must have been post

  17. A Sequential Leach Method and Pb Isotope Approach to Studying Apatite Weathering in Granitoid Soils at Hubbard Brook Experimental Forest, NH, USA

    NASA Astrophysics Data System (ADS)

    Nezat, C. A.; Blum, J. D.

    2005-12-01

    Easily dissolved minerals such as calcite and apatite can be important in controlling stream and ground water chemistry even though these minerals are only present in trace amounts in granitoid rocks. Because of its solubility, apatite, a calcium phosphate mineral, may be a significant source of essential nutrients (especially phosphorous) for vegetation, and has been shown to strongly influence stream and soil water composition (e.g, calcium, strontium and rare earth elements). There are additional sources of Ca (e.g., feldspars, hornblende) and P (e.g., organic matter or bound to Fe and Al oxides) in granitoid soils. In order to distinguish the chemical constituents of apatite from other pools in the bulk soil, we selectively dissolved apatite with a dilute acid leach, and measured Pb isotopic ratios of apatite, feldspar, and leachates. We tested the leaching procedure on mineral separates and verified that a dilute nitric solution primarily dissolves apatite. Silicates were dissolved in subsequent steps by successively stronger acids. We then applied this method to bulk soils collected from several soil pits across a small watershed at the Hubbard Brook Experimental Forest (HBEF), New Hampshire, USA, to determine the spatial distribution of Ca and P pools, and determine the depth of apatite depletion in the soil. We also measured Pb isotope ratios in the soil leachates to distinguish among the various sources of Pb (e.g., apatite, feldspars and anthropogenic sources). We found that Pb in the dilute nitric leach of the HBEF organic soils is dominated by anthropogenic sources and that Pb from apatite becomes increasingly important with depth.

  18. Radioisotope dilution analyses of geological samples using 236U and 229Th

    USGS Publications Warehouse

    Rosholt, J.N.

    1984-01-01

    The use of 236U and 229Th in alpha spectrometric measurements has some advantages over the use of other tracers and measurement techniques in isotope dilution analyses of most geological samples. The advantages are: (1) these isotopes do not occur in terrestrial rocks, (2) they have negligible decay losses because of their long half lives, (3) they cause minimal recoil contamination to surface-barrier detectors, (4) they allow for simultaneous determination of the concentration and isotopic composition of uranium and thorium in a variety of sample types, and (5) they allow for simple and constant corrections for spectral inferences, 0.5% of the 238U activity is subtracted for the contribution of 235U in the 236U peak and 1% of the 229Th activity is subtracted from the 230Th activity. Disadvantages in using 236U and 229Th are: (1) individual separates of uranium and thorium must be prepared as very thin sources for alpha spectrometry, (2) good resolution in the spectrometer system is required for thorium isotopic measurements where measurement times may extend to 300 h, and (3) separate calibrations of the 236U and 229Th spike solution with both uranium and thorium standards are required. The use of these tracers in applications of uranium-series disequilibrium studies has simplified the measurements required for the determination of the isotopic composition of uranium and thorium because of the minimal corrections needed for alpha spectral interferences. ?? 1984.

  19. Applications of UThPb isotope systematics to the problems of radioactive waste disposal

    USGS Publications Warehouse

    Stuckless, J.S.

    1986-01-01

    Concentrations of U, Th and Pb, and the isotopic composition of Pb for whole-rock samples of granitoids show: (1) that open-system behavior is nearly universal in the surface and near-surface environment; and (2) that elemental mobility is possible to depths of several hundred meters. Several identified or at least postulated factors that control U and/or Pb mobility include: (1) the mineralogical sites for U and its daughter products; (2) access of groundwater to these sites; (3) the volume of circulating water; and (4) the chemistry of the groundwater. Studies of granitic samples from peralkaline complexes in the Arabian Shield have shown that most samples lost less than 20% of their U during recent exposure to the near-surface environment. Most of the U in these samples appears to be firmly bound in zircons. In contrast, most surface and shallow drill-core samples of the granite of Lankin Dome (Granite Mountains, Wyoming) have lost ??? 70% of their U. Most of the U in these samples is weakly bound in biotite and epidote-family minerals. The granite recovered during the Illinois Deep Drill Hole Project (Stephenson County, Illinois) is mineralogically similar to the granite of Lankin Dome, but this granite lost radiogenic Pb rather than U, probably as a result of exposure to groundwater that had a markedly different chemistry from that in the Granite Mountains. Studies of the Sherman Granite (Wyoming) and the Go??temar Granite (southeastern Sweden) have shown that U and/or Pb mobility is greatest in and near fractured rock. The greater mobility is interpreted to be the result of both a larger water/rock ratio in the fractured rock and exposure to water over an increased surface area (and consequently a greater number of uranium sites). Several types of geochemical and mineralogic data can be used to identify rock-water interaction in granites; however, if rock samples have favorable radiogenic to common Pb ratios, both the amount and approximate timing of U or Pb

  20. Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats.

    PubMed

    Nakata, Hokuto; Nakayama, Shouta M M; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B; Saengtienchai, Aksorn; Ishizuka, Mayumi

    2017-01-10

    Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown ( Rattus norvegicus , n = 43) and black ( R. rattus , n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed.

  1. Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats

    PubMed Central

    Nakata, Hokuto; Nakayama, Shouta M. M.; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B.; Saengtienchai, Aksorn; Ishizuka, Mayumi

    2017-01-01

    Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown (Rattus norvegicus, n = 43) and black (R. rattus, n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed. PMID:28075384

  2. Formation ages and evolution of Shergotty and its parent planet from U-Th-Pb systematics

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Wasserburg, G. J.

    1986-01-01

    The isotopic composition of Pb from Shergotty, Zagami, and EETA 79001 meteorites was determined for different phases. Using phases with low U-238/Pb-204 ratio, the initial leads of these meteorites were defined. Samples from all three meteorites were shown to have distinct initial leads, and, thus to have evolved from different reservoirs over most of solar system history in a low U-238/Pb-204 environment. It follows that the parent planet of the shergottites has a high Pb-204 concentration relative to U and must also be high in other volatiles. The possibility of the Martian origin of the SNC-type meteorites is discussed.

  3. Pb concentrations and isotopic record preserved in northwest Greenland snow.

    PubMed

    Kang, Jung-Ho; Hwang, Heejin; Han, Changhee; Hur, Soon Do; Kim, Seong-Joong; Hong, Sungmin

    2017-11-01

    We present high-resolution lead (Pb) concentrations and isotopic ratios from a northwest Greenland snow pit covering a six-year period between 2003 and 2009. Pb concentrations ranged widely from 2.7 pg g -1 to 97.3 pg g -1 , with a mean concentration of 21.6 pg g -1 . These values are higher than those recorded for the pre-industrial period. Pb concentrations exhibit seasonal spikes in winter-spring layers. Crustal Pb enrichment factors (EF) suggest that the northwest Greenland snow pit is highly enriched with Pb of predominantly anthropogenic origin. The 206 Pb/ 207 Pb ratios ranged from 1.144 to 1.169 with a mean value of 1.156, which fall between less radiogenic Eurasian-type and more radiogenic Canadian-type signatures. This result suggests that several potential source areas of Pb impact on northwest Greenland. Abrupt changes in Pb concentrations and Pb isotope ratios were observed and related to seasonal shifts in source regions of aerosol transport. The 206 Pb/ 207 Pb isotope ratio increased gradually between 2003 and 2009. The similarity of the three-isotope plot ( 206 Pb/ 207 Pb versus 208 Pb/ 207 Pb) between some of our samples and Chinese urban aerosols suggests a steadily increasing contribution of Chinese Pb to northwest Greenland snow. Copyright © 2017. Published by Elsevier Ltd.

  4. Petrogenesis of the Yaochong granite and Mo deposit, Western Dabie orogen, eastern-central China: Constraints from zircon U-Pb and molybdenite Re-Os ages, whole-rock geochemistry and Sr-Nd-Pb-Hf isotopes

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Xu, Zhaowen; Qiu, Wenhong; Li, Chao; Yu, Yang; Wang, Hao; Su, Yang

    2015-05-01

    The Dabie orogen is among the most famous continent-continent collisional orogenic belts in the world, and is characterized by intensive post-collisional extension, magmatism and Mo mineralization. However, the genetic links between the mineralization and the geodynamic evolution of the orogen remain unresolved. In this paper, the Yaochong Mo deposit and its associated granitic stocks were investigated to elucidate this issue. Our new zircon U-Pb ages yielded an Early Cretaceous age (133.3 ± 1.3 Ma) for the Yaochong granite, and our molybdenite Re-Os dating gave a similar age (135 ± 1 Ma) for the Mo deposit. The Yaochong stock is characterized by high silica and alkali but low Mg, Fe and Ca. It is enriched in light rare earth elements (LREEs) and large ion lithophile elements (LILEs: Rb, K, Th and U), but strongly depleted in heavy REEs, and high field strength elements (HFSEs: Nb, Ta, Ti and Y). The Yaochong granite has initial 87Sr/86Sr ratios of 0.7087-0.7096, and Pb isotopic ratios of (206Pb/204Pb)i = 16.599-16.704, (207Pb/204Pb)i = 15.170-15.618 and (208Pb/204Pb)i = 36.376-38.248. The granite has εNd(t) of -18.0 to -16.3 and εHf(t) values of -26.5 to -20.0. All these data indicate that the Yaochong granite is a high-K calc-alkaline fractionated I-type granite, and may have originated from partial melting of the thickened Yangtze continental crust. The Mo ores also show low radiogenic Pb isotopes similar to the Yaochong stock. Medium Re content in molybdenite (21.8-74.8 ppm) also suggests that the ore-forming materials were derived from the thickened lower crust with possibly minor mixing with the mantle. Similar to the Eastern Dabie orogen, the thickened crust beneath the Western Dabie orogen may also have experienced tectonic collapse, which may have exerted fundamental geodynamic controls on the two-stage Mo mineralization in the region.

  5. 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.

  6. 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

  7. Pb-, Sr- and Nd-Isotopic systematics and chemical characteristics of cenozoic basalts, Eastern China

    USGS Publications Warehouse

    Peng, Z.C.; Zartman, R.E.; Futa, K.; Chen, D.G.

    1986-01-01

    Forty-eight Paleogene, Neogene and Quaternary basaltic rocks from northeastern and east-central China have been analyzed for major-element composition, selected trace-element contents, and Pb, Sr and Nd isotopic systematics. The study area lies entirely within the marginal Pacific tectonic domain. Proceeding east to west from the continental margin to the interior, the basalts reveal an isotopic transition in mantle source material and/or degree of crustal interaction. In the east, many of the rocks are found to merge both chemically and isotopically with those previously reported from the Japanese and Taiwan island-arc terrains. In the west, clear evidence exists for component(s) of Late Archean continental lithosphere to be present in some samples. A major crustal structure, the Tan-Lu fault, marks the approximate boundary between continental margin and interior isotopic behaviors. Although the isotopic signature of the western basalts has characteristics of lower-crustal contamination, a subcrustal lithosphere, i.e. an attached mantle keel, is probably more likely to be the major contributor of their continental "flavor". The transition from continental margin to interior is very pronounced for Pb isotopes, although Sr and Nd isotopes also combine to yield correlated patterns that deviate strikingly from the mid-ocean ridge basalt (MORB) and oceanic-island trends. The most distinctive chemical attribute of this continental lithosphere component is its diminished U Pb as reflected in the Pb isotopic composition when compared to sources of MORB, oceanic-island and island-arc volcanic rocks. Somewhat diminished Sm Nd and elevated Rb Sr, especially in comparison to the depleted asthenospheric mantle, are also apparent from the Nd- and Sr-isotopic ratios. ?? 1986.

  8. 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.

  9. Matrix effects for elemental fractionation within ICPMS: applications for U-Th-Pb geochronology

    NASA Astrophysics Data System (ADS)

    Chen, W.

    2016-12-01

    Recent development in instruments provides significant technical supports for daily, quick, money saving geochemical analyses. Laser ablation ICPMS stands out due to these reasons, especially for the U-Th-Pb isotopic dating. Matrix-matched external standardization is by far the most common approach used in U-Th-Pb dating via LA-ICPMS. However, matrix-effects between standard and sample for in-situ dating have shown to be both significant and insignificant. It remains mysterious whether a well matrix-matched standard is needed for U-Th-Pb dating by LA-ICPMS. This study provides an experimental framework for the understanding of matrix effects induced elemental fractionation for U-Th-Pb associated with ICPMS. A preliminary study on the influence of varied U, Th and Pb amounts on their fractionations has been carried out. Experimental data show that different U, Th and Pb contents result in varied 238U/206Pb and 232Th/208Pb ratios. The fractionations of U/Pb and Th/Pb increase with the increasing contents (1 ppb to 100 ppb) with a strong positive anomaly at 10 ppb. Matrixes representing minerals frequently used in dating have been investigated for the influences on U/Pb and Th/Pb fractionations, which suggest a complicated effect. Little fractionations observed between mineral pairs (e.g., monazite and apatite; zircon and perovskite; rutile and perovskite; xenotime and baddeleyite), whereas large fractionations identified for other minerals (e.g., zircon and baddeleyite; monazite and sphene; rutile and baddeleyite). Single element matrix (i.e., Si, P, Ca, Zr, Ti) has been studied to identify their effects on the fractionations. U/Pb ratio increases with the increasing Si and P contents, whereas it decreases for Zr, Ca and Ti. Th/Pb ratio increases with increasing Si contents, decreases for P and Zr, and increases first then decreases for Ca and Ti. Above all, different matrix and U, Th and Pb amounts show distinct U/Pb and Th/Pb fractionations within ICPMS. The

  10. 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

  11. Pb isotopes of Gorgona Island (Colombia): isotopic variations correlated with magma type

    NASA Astrophysics Data System (ADS)

    Dupré, B.; Echeverría, L. M.

    1984-02-01

    Lead isotopic results obtained on komatiites and basalts from Gorgona Island provide evidence of large isotopic variations within a restricted area (8 × 2.5 km). The variations are correlated with differences in volcanic rock type. The highest isotopic ratios ( 206Pb/ 204Pb˜ 19.75 ) correspond to tholeiites which make up most of the island. The lowest ratios (18.3) correspond to the komatiites of the west coast of the island. Other rock types (komatiites of the east coast, K-tholeiites, picrites and tuffs) have isotopic characteristics intermediate between these two extreme values. These results are explained by the existence of two distinct mantle source regions, and by mixing or contamination between them.

  12. Exsolution lamellae as fast diffusion pathways in rutile: implications for U-Pb thermochronology and Zr thermometry

    NASA Astrophysics Data System (ADS)

    Smye, A.; Seman, S.; Roberts, N. M. W.; Condon, D. J.; Davis, B.

    2017-12-01

    Geophysical processes impart characteristic thermal signatures to the lithosphere. Near-continuous thermal histories can be obtained from inversion of intracrystalline U-Pb age profiles in rutile and apatite provided that it can be shown that profile formed in response to Fickian-type diffusion. Here, we present the results of a combined LA-ICPMS and ID-TIMS U-Pb study on rutile grains from two garnet-bearing granulite xenoliths from a kimberlite in the Archean Slave province. Interpreted using numerical models, we show that the rutile U-Pb isotope systematics are consistent with slow-cooling following crystallization at 1.2 Ga, contemporaneous with the Mackenzie dike swarm. However, inversion of rutile U-Pb age gradients is complicated by the ubiquitous presence of ilmenite exsolution lamellae. We show that these lamellae act as fast diffusion pathways for Pb and High Field Strength Elements, including Zr. This has important implications for the use of rutile as a U-Pb themochronometer and as a single-phase thermometer.

  13. 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

  14. 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.

  15. U-Pb geochronology and Hf-Nd isotope compositions of the oldest Neoproterozoic crust within the Cadomian orogen: new evidence for a unique juvenile terrane

    NASA Astrophysics Data System (ADS)

    Samson, S. D.; D'Lemos, R. S.; Blichert-Toft, J.; Vervoort, J.

    2003-03-01

    New U-Pb dates, combined with Nd and Hf isotopic data, from rocks within the Port Morvan area of the Baie de St Brieuc region of Brittany identify a unique portion of the Neoproterozoic Cadomia terrane. Two gneisses near Port Morvan yielded U-Pb dates of 754.6±0.8 Ma and 746.0±0.9 Ma, ages that are more than 130 Myr older than the oldest units formed during the main phase of early Cadomian magmatism. Two trondhjemite boulders from the monogenetic facies of the Cesson conglomerate yielded identical ages of 665.2±0.5 Ma and 665.5±0.7 Ma, and a cobble from the polygenetic facies yields a 207Pb- 206Pb date of 637±2 Ma. Individual detrital zircons from a sandstone associated with the Cesson conglomerates yield concordant U-Pb dates ranging from 650±3 Ma to 624.1±0.6 Ma. Initial ɛNd values for the rocks in this region range from +5.0 to +6.6, indicative of a substantial input from depleted mantle. Initial ɛHf values determined on zircons from these Neoproterozoic rocks, including the detrital zircons, range from +6.7 to +14.5, consistent with the Nd isotopic results. Maximum initial ɛHf values for two 2 Ga Icartian gneisses, considered basement to Cadomia, average +8.4 and +8.7. In contrast to the results of the Port Morvan rocks, 616-608 Ma syn-tectonic intrusions from Normandy and the British Channel Islands all have negative initial ɛNd values (-10.4 to -8.3) consistent with significant contamination by ancient crust such as the 2 Ga gneisses. The oldest arc-related magmas should have interacted most extensively with Cadomian basement, buffering younger mantle-derived magmas that were generated in subsequent magmatic episodes. The rocks within the Port Morvan region are thus inconsistent as examples of the earliest Cadomian intrusions as they show no evidence of interaction with 2 Ga basement. Instead, the older ages and mantle-like isotopic composition of these rocks suggest they are part of an independent terrane that formed prior to, and independently

  16. Guideline on Isotope Dilution Mass Spectrometry

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

    Gaffney, Amy

    Isotope dilution mass spectrometry is used to determine the concentration of an element of interest in a bulk sample. It is a destructive analysis technique that is applicable to a wide range of analytes and bulk sample types. With this method, a known amount of a rare isotope, or ‘spike’, of the element of interest is added to a known amount of sample. The element of interest is chemically purified from the bulk sample, the isotope ratio of the spiked sample is measured by mass spectrometry, and the concentration of the element of interest is calculated from this result. Thismore » method is widely used, although a mass spectrometer required for this analysis may be fairly expensive.« less

  17. U-Th-Pb measurements of Luna 20 soil

    USGS Publications Warehouse

    Tatsumoto, M.

    1973-01-01

    The concentrations of uranium, thorium and lead and the lead isotopic composition of Luna 20 soil were determined. The data indicate that the Luna 20 soil is mainly a mixture of highland anorthosites and low-K basalt, but little KREEP basalt. The U-Th-Pb systematics are discussed in comparison with other lunar soils, especially with Apollo 16 soils which were collected from a 'typical' highland region. The data fit well in the Apollo 16 soil array on a U-Pb evolution diagram, and they exhibit excess lead relative to uranium. This relationship appears to be a characteristic of highland localities. Considering the previous observations of lunar samples, we infer that lead enrichment in the soil relative to uranium occurred between 3.2 and 3.9 b.y. ago and that the soil was disturbed by 'third events' about 2.0 b.y. ago. A lunar evolution model is discussed. ?? 1973.

  18. U-Th-Pb systematics of some Apollo 17 lunar samples and implications for a lunar basin excavation chronology

    NASA Technical Reports Server (NTRS)

    Nunes, P. D.; Tatsumoto, M.; Unruh, D. M.

    1974-01-01

    U, Th, and Pb concentrations and lead isotopic compositions of selected Apollo 17 soil and rock samples are presented. Concordia treatments of U-Pb whole samples of Apollo 17 mare basalts and highland rocks probably reflect several early thermal events about 4.5 b.y. old more consistently than do U-Pb ages of samples collected at other lunar sites. We propose that all lunar U-Th-Pb data reflect a multistate U-Pb evolution history most easily understood as being related to a complex planetesimal bombardment history of the moon which apparently dominated lunar events from about 4.5 to about 3.9 b.y. ago. Semi-distinct events at about 4.0, about 4.2, and 4.4-4.5 b.y. are evident on whole-rock frequency versus Pb-207/Pb-206 age histograms. Each of these events may reflect multiple cratering episodes. For mare basalts, complete resetting of the source rock U-Pb systems owing to Pb loss relative to U was apparently often approached after a major planetesimal impact.

  19. Automating U-Pb IDTIMS data reduction and reporting: Cyberinfrastructure meets geochronology

    NASA Astrophysics Data System (ADS)

    Bowring, J. F.; McLean, N.; Walker, J. D.; Ash, J. M.

    2009-12-01

    We demonstrate the efficacy of an interdisciplinary effort between software engineers and geochemists to produce working cyberinfrastructure for geochronology. This collaboration between CIRDLES, EARTHTIME and EarthChem has produced the software programs Tripoli and U-Pb_Redux as the cyber-backbone for the ID-TIMS community. This initiative incorporates shared isotopic tracers, data-reduction algorithms and the archiving and retrieval of data and results. The resulting system facilitates detailed inter-laboratory comparison and a new generation of cooperative science. The resolving power of geochronological data in the earth sciences is dependent on the precision and accuracy of many isotopic measurements and corrections. Recent advances in U-Pb geochronology have reinvigorated its application to problems such as precise timescale calibration, processes of crustal evolution, and early solar system dynamics. This project provides a heretofore missing common data reduction protocol, thus promoting the interpretation of precise geochronology and enabling inter-laboratory comparison. U-Pb_Redux is an open-source software program that provides end-to-end support for the analysis of uranium-lead geochronological data. The system reduces raw mass spectrometer data to U-Pb dates, allows users to interpret ages from these data, and then provides for the seamless federation of the results, coming from many labs, into a community web-accessible database using standard and open techniques. This EarthChem GeoChron database depends also on keyed references to the SESAR sample database. U-Pb_Redux currently provides interactive concordia and weighted mean plots and uncertainty contribution visualizations; it produces publication-quality concordia and weighted mean plots and customizable data tables. This initiative has achieved the goal of standardizing the data elements of a complete reduction and analysis of uranium-lead data, which are expressed using extensible markup

  20. Variable microstructural response of baddeleyite to shock metamorphism in young basaltic shergottite NWA 5298 and improved U-Pb dating of Solar System events

    NASA Astrophysics Data System (ADS)

    Darling, James R.; Moser, Desmond E.; Barker, Ivan R.; Tait, Kim T.; Chamberlain, Kevin R.; Schmitt, Axel K.; Hyde, Brendt C.

    2016-06-01

    The accurate dating of igneous and impact events is vital for the understanding of Solar System evolution, but has been hampered by limited knowledge of how shock metamorphism affects mineral and whole-rock isotopic systems used for geochronology. Baddeleyite (monoclinic ZrO2) is a refractory mineral chronometer of great potential to date these processes due to its widespread occurrence in achondrites and robust U-Pb isotopic systematics, but there is little understanding of shock-effects on this phase. Here we present new nano-structural measurements of baddeleyite grains in a thin-section of the highly-shocked basaltic shergottite Northwest Africa (NWA) 5298, using high-resolution electron backscattered diffraction (EBSD) and scanning transmission electron microscopy (STEM) techniques, to investigate shock-effects and their linkage with U-Pb isotopic disturbance that has previously been documented by in-situ U-Pb isotopic analyses. The shock-altered state of originally igneous baddeleyite grains is highly variable across the thin-section and often within single grains. Analyzed grains range from those that preserve primary (magmatic) twinning and trace-element zonation (baddeleyite shock Group 1), to quasi-amorphous ZrO2 (Group 2) and to recrystallized micro-granular domains of baddeleyite (Group 3). These groups correlate closely with measured U-Pb isotope compositions. Primary igneous features in Group 1 baddeleyites (n = 5) are retained in high shock impedance grain environments, and an average of these grains yields a revised late-Amazonian magmatic crystallization age of 175 ± 30 Ma for this shergottite. The youngest U-Pb dates occur from Group 3 recrystallized nano- to micro-granular baddeleyite grains, indicating that it is post-shock heating and new mineral growth that drives much of the isotopic disturbance, rather than just shock deformation and phase transitions. Our data demonstrate that a systematic multi-stage microstructural evolution in

  1. 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.

  2. Tracing the recently increasing anthropogenic Pb inputs into the East China Sea shelf sediments using Pb isotopic analysis.

    PubMed

    Wang, Deli; Zhao, Zhiqi; Dai, Minhan

    2014-02-15

    This study examined the Pb content and Pb isotopic composition in a sediment core taken from the East China Sea (ECS) shelf, and it was observed that since 2003 the increasing anthropogenic Pb inputs have impacted as far as the ECS shelf sediments. The ECS shelf sediments were generally characterized with low bulk Pb contents (12.5-15.0 μg/g) and relatively lithogenic Pb isotopic signatures (both HCl-leached and residual fractions). However, elevated Pb records along with lighter Pb isotopic signals have occurred in the post-2003 sediments, as a result of a small but increasing anthropogenic Pb contribution from the heavily human perturbed coastal sediments due to the sharply increasing coal consumption in mainland China since 2003. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. Application of isotope dilution technique in vitamin A nutrition.

    PubMed

    Wasantwisut, Emorn

    2002-09-01

    The isotope dilution technique involving deuterated retinol has been developed to quantitatively estimate total body reserves of vitamin A in humans. The technique provided good estimates in comparison to hepatic vitamin A concentrations in Bangladeshi surgical patients. Kinetic studies in the United States, Bangladesh, and Guatemala indicated the mean equilibration time of 17 to 20 days irrespective of the size of hepatic reserves. Due to the controversy surrounding the efficacy of a carotene-rich diet on improvement of vitamin A status, the isotope dilution technique was proposed to pursue this research question further (IAEA's coordinated research program). In the Philippines, schoolchildren with low serum retinol concentrations showed significant improvement in total body vitamin A stores following intake of carotene-rich foods (orange fruits and vegetables), using a three-day deuterated-retinol-dilution procedure. When Chinese kindergarten children were fed green and yellow vegetables during the winter, their total body vitamin A stores were sustained as compared to a steady decline of vitamin A stores in the control children. Likewise, daily consumption of purified beta-carotene or diet rich in provitamin A carotenoids were shown to prevent a loss in total body vitamin A stores among Thai lactating women during the rice-planting season. These studies demonstrate potentials of the isotope dilution technique to evaluate the impact of provitamin A carotenoid intervention programs.

  4. 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

  5. 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.

  6. 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.

  7. Heterogeneity in the 238U/235U Ratios of Angrites.

    NASA Astrophysics Data System (ADS)

    Tissot, F.; Dauphas, N.; Grove, T. L.

    2016-12-01

    Angrites are differentiated meteorites of basaltic composition, of either volcanic or plutonic origin, that display minimal post-crystallization alteration, metamorphism, shock or impact brecciation. Because quenched angrites cooled very rapidly, all radiochronometric systems closed simultaneously in these samples. Quenched angrites are thus often used as anchors for cross-calibrating short-lived dating methods (e.g., 26Al-26Mg) and the absolute dating techniques (e.g, Pb-Pb). Due to the constancy of the 238U/235U ratio in natural samples, Pb-Pb ages have long been calculated using a "consensus" 238U/235U ratio, but the discovery of resolvable variations in the 238U/235U ratio of natural samples, means that the U isotopic composition of the material to date also has to be determined in order to obtain high-precision Pb-Pb ages. We set out (a) to measure at high-precision the 238U/235U ratio of a large array of angrites to correct their Pb-Pb ages, and (b) to identify whether all angrites have a similar U isotopic composition, and, if not, what were the processes responsible for this variability. Recently, Brennecka & Wadhwa (2012) suggested that the angrite-parent body had a homogeneous 238U/235U ratio. They reached this conclusion partly because they propagated the uncertainties of the U isotopic composition of the various U double spikes that they used onto the final 238U/235U ratio the sample. Because this error is systematic (i.e., it affects all samples similarly), differences in the δ238U values of samples corrected by the same double spike are better known than one would be led to believe if uncertainties on the spike composition are propagated. At the conference, we will present the results of the high-precision U isotope analyses for six angrite samples: NWA 4590, NWA 4801, NWA 6291, Angra dos Reis, D'Orbigny, and Sahara 99555. We will show that there is some heterogeneity in the δ238U values of the angrites and will discuss the possible processes by

  8. Evaluating the provenance of Permian-Triassic and Palaeocene-Eocene ash beds by high precision U-Pb and Lu-Hf isotopic analyses of zircons: linking local sedimentary records to global events

    NASA Astrophysics Data System (ADS)

    Eivind Augland, Lars; Jones, Morgan; Planke, Sverre; Svensen, Henrik; Tegner, Christian

    2016-04-01

    Zircons are a powerful tool in geochronology and isotope geochemistry, as their affinity for U and Hf in the crystal structure and the low initial Pb and Lu allow for precise and accurate dating by U-Pb ID-TIMS and precise and accurate determination of initial Hf isotopic composition by solution MC-ICP-MS analysis. The U-Pb analyses provide accurate chronostratigraphic controls on the sedimentary successions and absolute age frames for the biotic evolution across geological boundaries. Moreover, the analyses of Lu-Hf by solution MC-ICP-MS after Hf-purification column chemistry provide a powerful and robust fingerprinting tool to test the provenance of individual ash beds. Here we focus on ash beds from Permian-Triassic and Palaeocene successions in Svalbard and from the Palaeocene-Eocene Thermal Maximum (PETM) in Fur, Denmark. Used in combination with whole rock geochemistry from the ash layers and the available geochemical and isotopic data from potential source volcanoes, these data are used to evaluate the provenance of the Permian-Triassic and Palaeocene ashes preserved in Svalbard and PETM ashes in Denmark. If explosive eruptions from volcanic centres such as the Siberian Traps and the North Atlantic Igneous Province (NAIP) can be traced to distal basins as ash layers, they provide robust tests of hypotheses of global synchronicity of environmental changes and biotic crises. In addition, the potential correlation of ash layers with source volcanoes will aid in constraining the extent of explosive volcanism in the respective volcanic centres. The new integrated data sets will also contribute to establish new reference sections for the study of these boundary events when combined with stable isotope data and biostratigraphy.

  9. U-Pb isotopic evidence for the accretion of a continental microplate in the Zalm region of the Saudi Arabian Shield.

    USGS Publications Warehouse

    Stacey, J.S.; Agar, R.A.

    1985-01-01

    This area includes three of the main tectonic units of the Arabian Shield: the Afif continental terrain, the Nabitah suture with its associated mobile belt, and the Asir ensimatic arc terrain. U/Pb zircon data from a pelitic garnet-sillimanite gneiss show that the Kabib formation in the S of the Afif terrain may be as old as 1770 m.y. Pb and Rb/Sr isotopic data in the Zalm region reveal a change in the nature of the underlying crust, from continental basement in the NE to less radiogenic marginal arc rocks in the SW. Miogeosynclinal continental shelf facies of the Siham group lie unconformably over the Kabid formation. U/Pb zircon age determinations show that this 'Andean' continental margin developed before approx 720 m.y. and the emplacement of calc-alkaline plutonic rocks continued until approx 690 m.y. During the period 685-640 m.y. the continental Afif microplate collided with the Asir terrain as part of the Nabitah orogeny. At approx 640 m.y. age the Najd strike-slip faulting commenced, with a dextral phase that controlled emplacement of granite plutons as well as the development of large pull-apart grabens. Some of the latter were floored by new oceanic crust and filled with volcanosedimentary rocks of the Bani Ghayy group.-R.A.H.

  10. 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.

  11. Modeling crust-mantle evolution using radiogenic Sr, Nd, and Pb isotope systematics

    NASA Astrophysics Data System (ADS)

    Kumari, Seema; Paul, Debajyoti

    2015-04-01

    The present-day elemental and isotopic composition of Earth's terrestrial reservoirs can be used as geochemical constraints to study evolution of the crust-mantle system. A flexible open system evolutionary model of the Earth, comprising continental crust (CC), upper depleted mantle (UM) -source of mid-ocean ridge basalts (MORB), and lower mantle (LM) reservoir with a D" layer -source of ocean island basalts (OIB), and incorporating key radioactive isotope systematics (Rb-Sr, Sm-Nd, and U-Th-Pb), is solved numerically at 1 Ma time step for 4.55 Ga, the age of the Earth. The best possible solution is the one that produces the present-day concentrations as well as isotopic ratios in terrestrial reservoirs, compiled from published data. Different crustal growth scenarios (exponential, episodic, early and late growth), proposed in earlier studies, and its effect on the evolution of isotope systematics of terrestrial reservoirs is studied. Model simulations strongly favor a layered mantle structure satisfying majority of the isotopic constraints. In the successful model, which is similar to that proposed by Kellogg et al. (1999), the present-day UM comprises of 60% of mantle mass and extends to a depth 1600 km, whereas the LM becomes non-primitive and more enriched than the bulk silicate Earth, mainly due to addition of recycled crustal material. Modeling suggest that isotopic evolution of reservoirs is affected by the mode of crustal growth. Only two scenarios satisfied majority of the Rb-Sr and Sm-Nd isotopic constraints but failed to reproduce the present-day Pb-isotope systematics; exponential growth of crust (mean age, tc=2.3 Ga) and delayed and episodic growth (no growth for initial 900 Ma, tc=2.05 Ga) proposed by Patchett and Arndt (1986). However, assuming a slightly young Earth (4.45 Ga) better satisfies the Pb-isotope systematics. Although, the delayed crustal growth model satisfied Sr-Nd isotopic constraints, presence of early Hadean crust (4.03 and 4.4 Ga

  12. 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.

  13. High-Precision U-Pb Geochronology of Ice River Perovskite: A Possible Interlaboratory and Intertechnique EARTHTIME Standard

    NASA Astrophysics Data System (ADS)

    Burgess, S. D.; Bowring, S. A.; Heaman, L. M.

    2012-12-01

    Accurate and precise U-Pb geochronology of accessory phases other than zircon are required for dating some LIP basalts or determining the temporal patterns of kimberlite pipes, for example. Advances in precision and accuracy lead directly to an increase in the complexity of questions that can be posed. U-Pb geochronology of perovskite (CaTiO3) has been applied to silica-undersaturated basalts, carbonatites, alkaline igneous rocks, and kimberlites. Most published IDTIMS perovskite dates have 2-sigma precisions at the ~0.2% level for weighted mean 206Pb/238U dates, much less than possible with IDTIMS analyses of zircons, which limits the applicability of perovskite in high-precision applications. Precision on perovskite dates is lower than zircon because of common Pb, which in some cases can be up to 50% of the total Pb and must be corrected for and accurately partitioned between blank and initial. Relatively small changes in the composition of common Pb can result in inaccurate but precise dates. In many cases minerals with significant common Pb are corrected using Stacey and Kramers (1975) two stage Pb evolution model. This can be done without serious consequence to the final date for minerals with high U/Pb ratios. In the more common case where U/Pb ratios are relatively low and the proportion of common Pb is large, applying a model-derived Pb isotopic composition rather than measuring it directly can introduce percent-level inaccuracy to dates calculated with precisely known U/Pb ratios. Direct measurement of the common Pb composition can be done on a U-poor mineral that co-crystallized with perovskite; feldspar and clinopyroxene are commonly used. Clinopyroxene can contain significant in-grown radiogenic Pb and our experiments indicate that it is not eliminated by aggressive step-wise leaching. The U/Pb ratio in clinopyroxene is generally low (20 < mu < 50) but significant. Other workers (e.g. Kamo et al., 2003; Corfu and Dahlgren, 2008), have used two methods

  14. U-Th-Pb systematics of some Apollo 16 lunar samples

    NASA Technical Reports Server (NTRS)

    Nunes, P. D.; Tatsumoto, M.; Knight, R. J.; Unruh, D. M.; Doe, B. R.

    1973-01-01

    U, Th, and Pb concentrations and lead isotopic compositions of Apollo 16 samples are interpreted as follows: (1) an early period of lunar differentiation of either global or regional scale occurred about 4.47 b.y. ago; (2) the Imbrian impact event affected many Apollo 16 samples about 3.99 b.y. ago; (3) some Apollo 16 metaclastic rocks and breccias contain a large amount of KREEP-like material; (4) lead produced in the early history of the moon has been concentrated in lunar highland soils yielding high Pb-207/Pb-206 ratios corresponding to apparent ages of more than 4.8 b.y.; and (5) South Ray Crater soils reflect the approximately 2-b.y.-old event previously proposed for the Apollo 12 and 14 samples.

  15. 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.

  16. Time-scale calibration by U-Pb geochronology: Examples from the Triassic Period

    NASA Astrophysics Data System (ADS)

    Mundil, R.

    2009-05-01

    U-Pb zircon geochronology, pioneered by Tom Krogh, is a cornerstone for the calibration of the time scale. Before Krogh's innovations, U-Pb geochronology was essentially limited by laboratory blank Pb (typically hundreds of nanograms) inherent in the then existing zircon dissolution and purification methods. The introduction of high pressure HF dissolution combined with miniature ion exchange columns (1) reduced the blank by orders of magnitude and allowed mass-spectrometric analyses of minute amounts of material (picograms of Pb and U). Krogh also recognized the need for minimizing the effects of Pb loss, and the introduction of the air-abrasion technique was the method of choice for two decades (2), until the development of the combined annealing and chemical abrasion technique resulted in essentially closed system zircons (3). These are the prerequisite for obtaining precise (permil-level) and accurate radio-isotopic ages of individual zircons contained in primary volcanic ash deposits, which are primary targets for the calibration of the time scale if they occur within fossil bearing sediments. A prime example is the calibration of the Triassic time scale which improved significantly using these techniques. The ages for the base and the top of the Triassic are constrained by U-Pb ages to 252.3 (4) and 201.5 Ma (5), respectively. These dates also constrain the ages of major extinction events at the Permian-Triassic and Triassic-Jurassic boundaries, and are statistically indistinguishable from ages obtained for the Siberian Traps and volcanic products from the Central Atlantic Magmatic Province, respectively, suggesting a causal link. Ages for these continental volcanics, however, are mostly from the K-Ar (40Ar/39Ar) system which requires accounting and correcting for a systematic bias of ca 1 % between U-Pb and 40Ar/39Ar isotopic ages (the 40Ar/39Ar ages being younger) (6). Robust U-Pb age constraints also exist for the Induan- Olenekian boundary (251.2 Ma, (7

  17. Pb isotopes in drinking water: a new strategy for detection of low Pb sources

    EPA Science Inventory

    Source detection of low concentrations of Pb in water, for instance less than 15 µg L-1, may require a new methodology as the tolerances of Pb in drinking water are further reduced. It appears that the isotope properties of Pb may aid discrimination among natural sources and anth...

  18. Characterization of a new candidate isotopic reference material for natural Pb using primary measurement method.

    PubMed

    Nonose, Naoko; Suzuki, Toshihiro; Shin, Ki-Cheol; Miura, Tsutomu; Hioki, Akiharu

    2017-06-29

    A lead isotopic standard solution with natural abundance has been developed by applying a mixture of a solution of enriched 208 Pb and a solution of enriched 204 Pb ( 208 Pb- 204 Pb double spike solution) as bracketing method. The amount-of-substance ratio of 208 Pb: 204 Pb in this solution is accurately measured by applying EDTA titrimetry, which is one of the primary measurement methods, to each enriched Pb isotope solution. Also metal impurities affecting EDTA titration and minor lead isotopes contained in each enriched Pb isotope solution are quantified by ICP-SF-MS. The amount-of-substance ratio of 208 Pb: 204 Pb in the 208 Pb- 204 Pb double spike solution is 0.961959 ± 0.000056 (combined standard uncertainty; k = 1). Both the measurement of lead isotope ratios in a candidate isotopic standard solution and the correction of mass discrimination in MC-ICP-MS are carried out by coupling of a bracketing method with the 208 Pb- 204 Pb double spike solution and a thallium internal addition method, where thallium solution is added to the standard and the sample. The measured lead isotope ratios and their expanded uncertainties (k = 2) in the candidate isotopic standard solution are 18.0900 ± 0.0046 for 206 Pb: 204 Pb, 15.6278 ± 0.0036 for 207 Pb: 204 Pb, 38.0626 ± 0.0089 for 208 Pb: 204 Pb, 2.104406 ± 0.00013 for 208 Pb: 206 Pb, and 0.863888 ± 0.000036 for 207 Pb: 206 Pb. The expanded uncertainties are about one half of the stated uncertainty for NIST SRM 981, for 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, or one eighth, for 208 Pb: 206 Pb and 207 Pb: 206 Pb, The combined uncertainty consists of the uncertainties due to lead isotope ratio measurements and the remaining time-drift effect of mass discrimination in MC-ICP-MS, which is not removed by the coupled correction method. In the measurement of 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, the latter contribution is two or three times larger than the former. When the coupling of

  19. 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.

  20. A century long sedimentary record of anthropogenic lead (Pb), Pb isotopes and other trace metals in Singapore.

    PubMed

    Chen, Mengli; Boyle, Edward A; Switzer, Adam D; Gouramanis, Chris

    2016-06-01

    Reconstructing the history of metal deposition in Singapore lake sediments contributes to understanding the anthropogenic and natural metal deposition in the data-sparse Southeast Asia. To this end, we present a sedimentary record of Pb, Pb isotopes and eleven other metals (Ag, As, Ba, Cd, Co, Cr, Cu, Ni, Tl, U and Zn) from a well-dated sediment core collected near the depocenter of MacRitchie Reservoir in central Singapore. Before the 1900s, the sedimentary Pb concentration was less than 2 mg/kg for both soil and sediment, with a corresponding (206)Pb/(207)Pb of ∼1.20. The Pb concentration increased to 55 mg/kg in the 1990s, and correspondingly the (206)Pb/(207)Pb decreased to less than 1.14. The (206)Pb/(207)Pb in the core top sediment is concordant with the (206)Pb/(207)Pb signal of aerosols in Singapore and other Southeast Asian cities, suggesting that Pb in the reservoir sediment was mainly from atmospheric deposition. Using the Pb concentration in the topmost layer of sediment, the estimated atmospheric Pb flux in Singapore today is ∼1.6 × 10(-2) g/m(2) yr. The concentrations of eleven other metals preserved in the sediment were also determined. A principal component analysis showed that most of the metals exhibit an increasing trend towards 1990s with a local concentration peak in the mid-20(th) century. Copyright © 2016. Published by Elsevier Ltd.

  1. The mesoproterozoic Beaverhead impact structure and its tectonic setting, Montana-Idaho: 40Ar/39 and U-Pb isotopic constraints

    USGS Publications Warehouse

    Kellogg, K.S.; Snee, L.W.; Unruh, D.M.

    2003-01-01

    New 40Ar/39Ar and uranium-lead (U-Pb) zircon data from the Beaverhead impact structure, first identified by extensive shatter coning of Proterozoic quartzite and gneiss from the Beaverhead Mountains near the Montana-Idaho border, indicate that the structure formed at or after 900 Ma. The 40Ar/39Ar age spectra from fine-grained muscovite and biotite from a breccia zone in high-grade gneiss show significant argon loss but yield dates for highest-temperature steps that cluster between 899 and 908 Ma. The dated minerals probably formed by recrystallization of impact glass, so on both geologic and isotopic grounds, the dates probably represent the minimum age of impact. U-Pb data for zircons from the same breccia are strongly discordant and yield an upper intercept apparent age of 2464 ?? 56 Ma and a lower intercept apparent age of 779 ?? 69 Ma. Another brecciated gneiss about 7 km to the northeast that does not contain secondary mica does contain zircons that yield a concordant apparent age of 2455 ?? 9 Ma. Nearby gneiss that neither is brecciated nor contains shatter cones yields an apparent age of 2451 ?? 46 Ma. The 40Ar/39Ar results constrain the age of the shatter-coned quartzite and indicate that it is >900 Ma and possibly correlative with the Gunsight Formation of the Mesoproterozoic Lemhi Group. The upper intercept U-Pb age of ???2450 Ma from all three dated samples also shows that the Paleoproterozoic basement rocks of the area are among the youngest in the mostly Archean Wyoming province of North America. The impact site lies near the margin of the province, along the northeast-trending Great Falls tectonic zone, and the relatively young crustal age may reflect Early Proterozoic marginal accretion.

  2. Pb-isotopic Features of Primitive Rocks from Hess Deep: Distinguishing between EPR and Cocos-Nazca Mantle Source(s)

    NASA Astrophysics Data System (ADS)

    Jean, M. M.; Falloon, T.; Gillis, K. M.

    2014-12-01

    We have acquired high-precision Pb-isotopic signatures of primitive lithologies (basalts/gabbros) recovered from IODP Expedition 345.The Hess Deep Rift, located in the vicinity of the Galapagos triple junction (Cocos, Nazca, and Pacific), is viewed as one the best-studied tectonic windows into fast-spreading crust because a relatively young (<1.5 Ma) cross section of oceanic crust. This allows for (1) characterization of the mantle source(s) at Hess Deep, (2) insight into the extent of isotopic homogeneity or heterogeneity in the area, and (3) constrain the relative contributions from the intruding Cocos-Nazca spreading center. The observed Pb-isotopic variation at Hess Deep covers almost the entire range of EPR MORB (10°N to -5°S). Hess Deep samples range from 208Pb (37.3-38.25), 207Pb (15.47-15.58), 206Pb (17.69-18.91). These compositions suggest that this part of Hess Deep mantle is no more isotopically homogeneous than EPR mantle. Two distinct arrays are also observed: 208Pb-enriched (r2=0.985; n=30) and 208Pb-depleted (r2=0.988; n=6). The 208Pb/204Pb isotopes indicates that the Pb-source for some of the samples at Hess Deep had very low Th/U ratios, whereas other areas around the Galapagos microplate seem to have more "normal" ratios. These trends are less apparent when viewed with 207Pb-isotopes. Instead, the majority of basalts and gabbros follow the NHRL, however, at the depleted-end of this array a negative excursion to more enriched compositions is observed. This negative but linear trend could signify an alteration trend or mixing with an EMI-type mantle source, yet this mixing is not observed with 208Pb. This trend is also observed at Pito Deep, which has similar origins to Hess Deep (Barker et al., 2008; Pollack et al., 2009). The Galapagos region has been considered a testing ground for mixing of HIMU, Enriched Mantle, and Depleted Mantle reservoirs (e.g., Schilling et al., 2002). According to our data, however, an EPR-component must also be

  3. Early Proterozoic crustal evolution: Geochemical and NdPb isotopic evidence from metasedimentary rocks, southwestern North America

    NASA Astrophysics Data System (ADS)

    McLennan, S. M.; Hemming, S. R.; Taylor, S. R.; Eriksson, K. A.

    1995-03-01

    Early Proterozoic (1.8-1.7 Ga) metasedimentary rocks in northern New Mexico and southern Colorado, USA, can be divided into turbidite successions (commonly volcanogenic) associated with mafic/felsic metavolcanic successions (e.g., Irving Fm.) and stable shelf quartzite-pelite successions of shallow marine origin (e.g., Hondo Gp.). Metapelites from the turbidite successions reported here have low K2O/Na2O, low Th/U (<3.0), low to moderate Th/Sc (0.1-0.6), and slight negative Eu-anomalies, although regionally, negative Eu-anomalies in such rocks are common. At the time of sedimentation (ca. 1.7-1.8 Ga), ɛNd values were in the range +3 to +7, indistinguishable from associated metavolcanic and plutonic rocks. Similarly, lead isotopic data scatter about a 1.7 Ga reference isochron. Low κ (232Th/238U) values for the Irving Formation are consistent with derivation from crustal sources similar to the southern Colorado/northern New Mexico lead isotope crustal province. These data are further consistent with a volcanic arc related origin. In contrast, stable shelf metapelites have high K2O/Na2O, variable but commonly high Th/U (2.0-7.0), moderate to high Th/Sc (0.5-1.4), and substantial negative Eu-anomalies. Although compositions are rather variable, they are typical of post-Archean shales. Neodymium isotopes are surprisingly radiogenic with ɛNd(1.7 Ga) in the range -0.2 to +4. Lead isotopic data for the least radiogenic samples also are consistent with a dominantly juvenile source and on a 207Pb/204Pb vs. 206Pb/204Pb diagram, data scatter slightly above the 1.7 Ga reference isochron, suggesting minor components of significantly older material. Lead isotopic systematics suggest that a major component of the provenance was derived from the immediately associated metavolcanic-plutonic terranes, consistent with suggestions of a first-cycle origin, but with an Archean component. Isotopic data restrict the Archean component to about 10%, on average, and no more than 25% in

  4. Repeated kimberlite magmatism beneath Yakutia and its relationship to Siberian flood volcanism: Insights from in situ U-Pb and Sr-Nd perovskite isotope analysis

    NASA Astrophysics Data System (ADS)

    Sun, Jing; Liu, Chuan-Zhou; Tappe, Sebastian; Kostrovitsky, Sergey I.; Wu, Fu-Yuan; Yakovlev, Dmitry; Yang, Yue-Heng; Yang, Jin-Hui

    2014-10-01

    We report combined U-Pb ages and Sr-Nd isotope compositions of perovskites from 50 kimberlite occurrences, sampled from 9 fields across the Yakutian kimberlite province on the Siberian craton. The new U-Pb ages, together with previously reported geochronological constraints, suggest that kimberlite magmas formed repeatedly during at least 4 episodes: Late Silurian-Early Devonian (419-410 Ma), Late Devonian-Early Carboniferous (376-347 Ma), Late Triassic (231-215 Ma), and Middle/Late Jurassic (171-156 Ma). Recurrent kimberlite melt production beneath the Siberian craton - before and after flood basalt volcanism at 250 Ma - provides a unique opportunity to test existing models for the origin of global kimberlite magmatism. The internally consistent Sr and Nd isotope dataset for perovskites reveals that the Paleozoic and Mesozoic kimberlites of Yakutia have distinctly different initial radiogenic isotope compositions. There exists a notable increase in the initial 143Nd/144Nd ratios through time, with an apparent isotopic evolution that is intermediate between that of Bulk Earth and Depleted MORB Mantle. While the Paleozoic samples range between initial 87Sr/86Sr of 0.7028-0.7034 and 143Nd/144Nd of 0.51229-0.51241, the Mesozoic samples show values between 0.7032-0.7038 and 0.51245-0.51271, respectively. Importantly, perovskites from all studied Yakutian kimberlite fields and age groups have moderately depleted initial εNd values that fall within a relatively narrow range between +1.8 and +5.5. The perovskite isotope systematics of the Yakutian kimberlites are interpreted to reflect magma derivation from the convecting upper mantle, which appears to have a record of continuous melt depletion and crustal recycling throughout the Phanerozoic. The analyzed perovskites neither record highly depleted nor highly enriched isotopic components, which had been previously identified in likely plume-related Siberian Trap basalts. The Siberian craton has frequently been suggested

  5. Effects of interaction between ultramafic tectonite and mafic magma on Nd-Pb-Sr isotopic systems in the Neoproterozoic Chaya Massif, Baikal-Muya ophiolite belt

    NASA Astrophysics Data System (ADS)

    Amelin, Yuri V.; Ritsk, Eugeni Yu.; Neymark, Leonid A.

    1997-04-01

    Sm-Nd, Rb-Sr and U-Pb isotopic systems have been studied in minerals and whole rocks of harzburgites and mafic cumulates from the Chaya Massif, Baikal-Muya ophiolite belt, eastern Siberia, in order to determine the relationship between mantle ultramafic and crustal mafic sections. Geological relations in the Chaya Massif indicate that the mafic magmas were emplaced into, and interacted with older solid peridotite. Hand picked, acid-leached, primary rock-forming and accessory minerals (olivine, orthopyroxene, clinopyroxene and plagioclase) from the two harzburgite samples show coherent behavior and yield 147Sm/ 144Nd- 143Nd/ 144Nd and 238U/ 204Pb- 206Pb/ 204Pb mineral isochrons, corresponding to ages of 640 ± 58 Ma (95% confidence level) and 620 ± 71 Ma, respectively. These values are indistinguishable from the crystallization age of the Chaya mafic units of 627 ± 25 Ma (a weighted average of internal isochron Sm-Nd ages of four mafic cumulates). The Rb-Sr and Sm-Nd isotopic systems in the harzburgite whole-rock samples were disturbed by hydrothermal alteration. These alteration-related isotopic shifts mimic the trend of variations in primary isotopic compositions in the mafic sequence, thus emphasizing that isotopic data for ultramafic rocks should be interpreted with great caution. On the basis of initial Sr and Nd values, ultramafic and mafic rocks of the Chaya Massif can be divided into two groups: (1) harzburgites and the lower mafic unit gabbronorites withɛ Nd = +6.6 to +7.1 andɛ Sr = -11 to -16; and (2) websterite of the lower unit and gabbronorites of the upper mafic unit:ɛ Nd = +4.6 to +6.1 andɛ Sr = -8 to -9. Initial Pb isotopic ratios are identical in all rocks studied, with mean values of 206Pb/ 204Pb= 16.994 ± 0.023 and 207Pb/ 204Pb= 15.363 ± 0.015. The similarity of ages and initial isotopic ratios within the first group indicates that the isotopic systems in the pre-existing depleted peridotite were reset by extensive interaction with

  6. Effects of interaction between ultramafic tectonite and mafic magma on Nd-Pb-Sr isotopic systems in the Neoproterozoic Chaya Massif, Baikal-Muya ophiolite belt

    USGS Publications Warehouse

    Amelin, Y.V.; Ritsk, E. Yu; Neymark, L.A.

    1997-01-01

    Sm-Nd, Rb-Sr and U-Pb isotopic systems have been studied in minerals and whole rocks of harzburgites and mafic cumulates from the Chaya Massif, Baikal-Muya ophiolite belt, eastern Siberia, in order to determine the relationship between mantle ultramafic and crustal mafic sections. Geological relations in the Chaya Massif indicate that the mafic magmas were emplaced into, and interacted with older solid peridotite. Hand picked, acid-leached, primary rock-forming and accessory minerals (olivine, orthopyroxene, clinopyroxene and plagioclase) from the two harzburgite samples show coherent behavior and yield 147Sm/144Nd- 143Nd/144Nd and 238U/204Pb-206Pb/204Pb mineral isochrons, corresponding to ages of 640 ?? 58 Ma (95% confidence level) and 620 ?? 71 Ma, respectively. These values are indistinguishable from the crystallization age of the Chaya mafic units of 627 ?? 25 Ma (a weighted average of internal isochron Sm-Nd ages of four mafic cumulates). The Rb-Sr and Sm-Nd isotopic systems in the harzburgite whole-rock samples were disturbed by hydrothermal alteration. These alteration-related isotopic shifts mimic the trend of variations in primary isotopic compositions in the mafic sequence, thus emphasizing that isotopic data for ultramafic rocks should be interpreted with great caution. On the basis of initial Sr and Nd values, ultramafic and mafic rocks of the Chaya Massif can be divided into two groups: (1) harzburgites and the lower mafic unit gabbronorites with ??Nd = +6.6 to +7.1 and ??Sr = -11 to -16; and (2) websterite of the lower unit and gabbronorites of the upper mafic unit: ??Nd = + 4.6 to + 6.1 and ??Sr = - 8 to -9. Initial Pb isotopic ratios are identical in all rocks studied, with mean values of 206Pb/204Pb = 16.994 ?? 0.023 and 207Pb/204Pb = 15.363 ?? 0.015. The similarity of ages and initial isotopic ratios within the first group indicates that the isotopic systems in the pre-existing depleted peridotite were reset by extensive interaction with basaltic

  7. Some Pb and Sr isotopic measurements on eclogites from the Roberts Victor mine, South Africa

    USGS Publications Warehouse

    Manton, W.I.; Tatsumoto, M.

    1971-01-01

    Five nodules of eclogite, one nodule of garnet peridotite and one sample of kimberlite from the Roberts Victor mine were analyzed for concentrations of U, Th, Pb, Rb and Sr and isotopic compositions of Pb and Sr. In the eclogites, U content ranges from 0.09 to 0.26 ppm, Th from 0.35 to 1.1 ppm, Pb from 0.79 to 5.5 ppm, Rb from 2.1 to 28 ppm and Sr from 133 to 346 ppm; 206Pb/204Pb ratios range from 14.8 to 18.5, 207Pb/204Pb from 14.9 to 15.7, 208Pb/204Pb from 35.2 to 38.5. The garnet peridotite contains 0.22 ppm U, 0.97 ppm Th, 1.05 ppm Pb, 6.9 ppm Rb and 108 ppm Sr and the kimberlite contains 2.5 ppm U, 30 ppm Th, 37 ppm Pb, 113 ppm Rb and 2040 ppm Sr. The lead in the eclogites has two components, a lead pyroextractable at 1100-1200?? and a non-pyroextractable residual lead. In three of the eclogites, which are to some extent altered, a proportion of the pyroextractable lead may be contaminating lead from the kimberlite, but an altered kyanite eclogite does not appear to be contaminated by this same kimberlite. The pyroextractable lead from a less altered eclogite contains a much larger proportion of 206Pb. Compositions calculated for the residual leads vary greatly. In many of the pyroextraction runs the primary eclogitic phases disappeared and the new phases plagioclase, clinopyroxene and a magnetic iron compound were formed. Why part of the lead should have been retained by these new phases is not understood. ?? 1971.

  8. Uranium isotopic compositions of the crust and ocean: Age corrections, U budget and global extent of modern anoxia

    NASA Astrophysics Data System (ADS)

    Tissot, François L. H.; Dauphas, Nicolas

    2015-10-01

    the variability of the 238U/235U ratio on Pb-Pb and U-Pb ages and provide analytical formulas to calculate age corrections as a function of the age and isotopic composition of the sample. The crustal ratio may be used in calculation of Pb-Pb and U-Pb ages of continental crust rocks and minerals when the U isotopic composition is unknown. In cosmochemistry, the search for 247Cm (t1/2 = 15.6 Myr), an extinct short-lived radionuclide that decays into 235U, is important for understanding how r-process nuclides were synthesized in stars and learning about the astrophysical context of solar system formation (Chen and Wasserburg, 1981; Wasserburg et al., 1996; Nittler and Dauphas, 2006; Brennecka et al., 2010b; Tissot et al., 2015). In both terrestrial and extraterrestrial samples, variations in the 238U/235U ratio affect Pb-Pb ages (and depending on the analytical protocols, U-Pb ages). Therefore, samples dated by these techniques need to have their U isotopic compositions measured (Stirling et al., 2005, 2006; Weyer et al., 2008; Amelin et al., 2010; Brennecka et al., 2010b; Brennecka and Wadhwa, 2012; Connelly et al., 2012; Goldmann et al., 2015) or uncertainties on the U isotopic composition should be propagated into age calculations. In low temperature aqueous geochemistry, U isotopic fractionation between U4+ and U6+ (driven in part by nuclear field shift effects; Bigeleisen, 1996; Schauble, 2007; Abe et al., 2008), makes U isotopes potential tracers of paleoredox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011a; Kendall et al., 2013, 2015; Asael et al., 2013; Andersen et al., 2014; Dahl et al., 2014; Goto et al., 2014; Noordmann et al., 2015). The present paper aims at constraining some aspects of the global budget of uranium in the modern oceans using 238U/235U isotope variations, which involves characterizing the U isotopic composition of seawater and several reservoirs involved in the uranium oceanic budget

  9. U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, USA: An integrated SEM, EMPA, TIMS, and SHRIMP study

    USGS Publications Warehouse

    Aleinikoff, J.N.; Wintsch, R.P.; Fanning, C.M.; Dorais, M.J.

    2002-01-01

    U-Pb ages for zircon and titanite from a granodioritic gneiss in the Glastonbury Complex, Connecticut, have been determined using both isotope dilution thermal ionization mass spectrometry (TIMS) and the sensitive high resolution ion microprobe (SHRIMP). Zircons occur in three morphologic populations: (1) equant to stubby, multifaceted, colorless, (2) prismatic, dark brown, with numerous cracks, and (3) elongate, prismatic, light tan to colorless. Cathodoluminescence (CL) imaging of the three populations shows simple concentric oscillatory zoning. The zircon TIMS age [weighted average of 207Pb/206Pb ages from Group 3 grains-450.5 ?? 1.6 Ma (MSWD=1.11)] and SHRIMP age [composite of 206Pb/238 U age data from all three groups-448.2 ?? 2.7 Ma (MSWD = 1.3)], are interpreted to suggest a relatively simple crystallization history. Titanite from the granodioritic gneiss occurs as both brown and colorless varieties. Scanning electron microscope backscatter (BSE) images of brown grains show multiple cross-cutting oscillatory zones of variable brightness and dark overgrowths. Colorless grains are unzoned or contain subtle wispy or very faint oscillatory zoning. Electron microprobe analysis (EMPA) clearly distinguishes the two populations. Brown grains contain relatively high concentrations of Fe2O3, Ce2O3 (up to ~ 1.5 wt.%), Nb2O5, and Zr. Cerium concentration is positively correlated with total REE + Y concentration, which together can exceed 3.5 wt.%. Oscillatory zoning in brown titanite is correlated with variations in REE concentrations. In contrast, colorless titanite (both as discrete grains and overgrowths on brown titanite) contains lower concentrations of Y, REE, Fe2O3, and Zr, but somewhat higher Al2O3 and Nb2O5. Uranium concentrations and Th/U discriminate between brown grains (typically 200-400 ppm U; all analyses but one have Th/U between about 0.8 and 2) and colorless grains (10-60 ppm U; Th/U of 0-0.17). In contrast to the zircon U-Pb age results, SHRIMP U-Pb

  10. Pb and Sr isotope measurements by inductively coupled plasma mass spectrometer: efficient time management for precision improvement

    NASA Astrophysics Data System (ADS)

    Monna, F.; Loizeau, J.-L.; Thomas, B. A.; Guéguen, C.; Favarger, P.-Y.

    1998-08-01

    One of the factors limiting the precision of inductively coupled plasma mass spectrometry is the counting statistics, which depend upon acquisition time and ion fluxes. In the present study, the precision of the isotopic measurements of Pb and Sr is examined. The time of measurement is optimally shared for each isotope, using a mathematical simulation, to provide the lowest theoretical analytical error. Different algorithms of mass bias correction are also taken into account and evaluated in term of improvement of overall precision. Several experiments allow a comparison of real conditions with theory. The present method significantly improves the precision, regardless of the instrument used. However, this benefit is more important for equipment which originally yields a precision close to that predicted by counting statistics. Additionally, the procedure is flexible enough to be easily adapted to other problems, such as isotopic dilution.

  11. 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

  12. Sr, Nd and Pb isotopes in Proterozoic intrusives astride the Grenville Front in Labrador: Implications for crustal contamination and basement mapping

    USGS Publications Warehouse

    Ashwal, L.D.; Wooden, J.L.; Emslie, R.F.

    1986-01-01

    We report Sr, Nd and Pb isotopic compositions of mid-Proterozoic anorthosites and related rocks (1.45-1.65 Ga) and of younger olivine diabase dikes (1.4 Ga) from two complexes on either side of the Grenville Front in Labrador. Anorthositic or diabasic samples from the Mealy Mountains (Grenville Province) and Harp Lake (Nain-Churchill Provinces) complexes have very similar major, minor and trace element compositions, but distinctly different isotopic signatures. All Mealy Mountains samples have ISr = 0.7025-0.7033, ??{lunate}Nd = +0.6 to +5.6 and Pb isotopic compositions consistent with derivation from a mantle source depleted with respect to Nd/Sm and Rb/Sr. Pb isotopic compositions for the Mealy Mountains samples are slightly more radiogenic than model mantle compositions. All Harp Lake samples have ISr = 0.7032-0.7066, ??{lunate}Nd = -0.3 to -4.4 and variable, but generally unradiogenic 207Pb 204Pb and 206Pb 204Pb compared to model mantle, suggesting mixing between a mantle-derived component and a U-depleted crustal contaminant. Crustal contaminants are probably a variety of Archean high-grade quartzofeldspathic gneisses with low U/Pb ratios and include a component that must be isotopically similar to the early Archean (>3.6 Ga) Uivak gneisses of Labrador or the Amitsoq gneisses of west Greenland. This would imply that the ancient gneiss complex of coastal Labrador and Greenland is larger than indicated by present surface exposure and may extend in the subsurface as far west as the Labrador Trough. If Harp Lake and Mealy Mountains samples were subjected to the same degree of contamination, as suggested by their chemical similarities, then the Mealy contaminants must be much younger, probably early or middle Proterozoic in age. The Labrador segment of the Grenville Front, therefore, appears to coincide with the southern margin of the Archean North Atlantic craton and may represent a pre mid-Proterozoic suture. ?? 1986.

  13. Petrogenesis of ultramafic xenoliths from Hawaii inferred from Sr, Nd, and Pb isotopes

    NASA Astrophysics Data System (ADS)

    Okano, Osamu; Tatsumoto, Mitsunobu

    Isotopic compositions of Nd, Sr, and Pb in xenoliths in the Honolulu volcanic series from the Salt Lake Crater (H-type) are similar to those of the host post-erosional basalts, but are distinct from the magma sources of Koolau shield tholeiites and MORB. In contrast, one spinel Iherzolite (K-type) has isotopic compositions of Nd and Sr that are close to those of Koolau tholeiite rather than to the other Hawaiian basalts. Previous studies have shown that Sr isotopic composition of the xenoliths and the host basalt and that trace element concentrations in minerals of garnet Iherzolites from Honolulu basalt were nearly in equilibrium with the host magma, indicating that Honolulu volcanics were derived from garnet Iherzolite or similar material. However, differences exist among the isotopic compositions (especially Nd) of the xenoliths indicating that they are accidental inclusions from upper layers. The similarity in isotopic compositions between xenoliths and Honolulu basalt suggests that the source areas in the mantle are chemically similar. Correlation of 238U/204Pb vs. 206Pb/204Pb of chrome diopside separated from the H-type spinel Iherzolites indicates that the xenoliths are 80±36 Ma, which corresponds to the lithosphere age of the Hawaiian site. This age is consistent with petrological studies [e.g., Sen and Leeman, 1991] which have found that the spinel Iherzolite inclusions are derived from the lithosphere wall rocks. The ɛNd = ˜+8 of the H-xenoliths is slightly lower than that for the East Pacific Rise MORB indicating that the xenoliths are derived from a trace element depleted source similar to the MORB residue. If the garnet Iherzolite xenoliths are derived from mixture of spinel Iherzolite with intrusive pyroxenite, then the source of the pyroxenite contained little plume component. The one exceptional spinel Iherzolite xenolith may be a residue of Koolau-like tholeiitic magma or may have been metasomatized by Koolau volcanism in the deep lithosphere

  14. Pb-concentrations and Pb-isotope ratios in soils collected along an east-west transect across the United States

    USGS Publications Warehouse

    Reimann, Clemens; Smith, David B.; Woodruff, Laurel G.; Flem, Belinda

    2011-01-01

    Analytical results for Pb-concentrations and isotopic ratios from ca. 150 samples of soil A horizon and ca. 145 samples of soil C horizon collected along a 4000-km east–west transect across the USA are presented. Lead concentrations along the transect show: (1) generally higher values in the soil A-horizon than the C-horizon (median 21 vs. 16.5 mg/kg), (2) an increase in the median value of the soil A-horizon for central to eastern USA (Missouri to Maryland) when compared to the western USA (California to Kansas) (median 26 vs. 20 mg/kg) and (3) a higher A/C ratio for the central to eastern USA (1.35 vs. 1.14). Lead isotopes show a distinct trend across the USA, with the highest 206Pb/207Pb ratios occurring in the centre (Missouri, median A-horizon: 1.245; C-horizon: 1.251) and the lowest at both coasts (e.g., California, median A-horizon: 1.195; C-horizon: 1.216). The soil C-horizon samples show generally higher 206Pb/207Pb ratios than the A-horizon (median C-horizon: 1.224; A-horizon: 1.219). The 206Pb/207Pb-isotope ratios in the soil A horizon show a correlation with the total feldspar content for the same 2500-km portion of the transect from east-central Colorado to the Atlantic coast that shows steadily increasing precipitation. No such correlation exists in the soil C horizon. The data demonstrate the importance of climate and weathering on both Pb-concentration and 206Pb/207Pb-isotope ratios in soil samples and natural shifts thereof in the soil profile during soil-forming processes.

  15. Determination of copper by isotopic dilution.

    PubMed

    Faquim, E S; Munita, C S

    1994-01-01

    A rapid and selective method was used for the determination of copper by isotopic dilution employing substoichiometric extraction with dithizone in carbon tetrachloride. The appropriate pH range for the substoichiometric extraction was 2-7. In the analysis, even a large excess of elements forming extractable complexes with dithizone does not interfere. The accuracy and precision of the method were evaluated. The method has been applied to analysis of reference materials, wheat flour, wine, and beer.

  16. 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.

  17. Determination of cadmium in sediments by diluted HCI extraction and isotope dilution ICP-MS.

    PubMed

    Terán-Baamonde, Javier; Soto-Ferreiro, Rosa-María; Carlosena, Alatzne; Andrade, José-Manuel; Prada, Darío

    2018-08-15

    Isotope dilution ICP-MS is proposed to measure the mass fraction of Cd extracted by diluted HCl in marine sediments, using a fast and simple extraction procedure based on ultrasonic probe agitation. The 111 Cd isotope was added before the extraction to achieve isotope equilibration with native Cd solubilized from the sample. The parameters affecting trueness and precision of isotope ratio measurements were evaluated carefully and subsequently corrected in order to minimize errors; they were: detector dead time, spectral interferences, mass discrimination factor and optimum sample/spike ratio. The mass fraction of Cd extracted was compared with the sum of the certified contents of the three steps of the sequential extraction procedure of the Standards, Measurements and Testing Programme (SM&T) analysing the BCR 701 sediment to validate the method. The certified and measured values agreed, giving a measured / certified mass fraction ratio of 1.05. Further, the extraction procedure itself was studied by adding the enriched isotope after the extraction step, which allowed verifying that analyte losses occurred during this process. Two additional reference sediments with certified total cadmium contents were also analysed. The method provided very good precision (0.9%, RSD) and a low detection limit, 1.8 ng g -1 . The procedural uncertainty budget was estimated following the EURACHEM Guide by means of the 'GUM Workbench' software, obtaining a relative expanded uncertainty of 1.5%. The procedure was applied to determine the bioaccessible mass fraction of Cd in sediments from two environmentally and economically important areas of Galicia (rias of Arousa and Vigo, NW of Spain). Copyright © 2018 Elsevier B.V. All rights reserved.

  18. Discrimination of the Cigarettes Geographical Origin by DRC-ICP-MS Measurements of Pb Isotope Compositions

    NASA Astrophysics Data System (ADS)

    Guo, W.; Hu, S.; Jin, L.

    2014-12-01

    Trace Pb are taken up with the same isotopic ratios as is present in the source soil, and the isotopic composition of Pb could used to reflect these sources and provide powerful indicators of the geographic origin of agriculture products derived from vegetative matter. We developed a simple and high throughput method, which based on DRC-ICP-MS for determination of Pb isotope ratios for discriminating the geographic origin of cigarettes. After acid digestion procedure, the cigarette digested solutions were directly analyzed by ICP-QMS with a DRC pressurized by the non-reactive gas Ne. In the DRC, Ne molecules collision with Pb ions and improves Pb isotope ratios precision 3-fold, which may be due to the collisional dampling smoothes out the ion beam fluctuations. Under the optimum DRC rejection parameter Q (RPq = 0.45), the main matrix components (K, Na, Ca, Mg, Al, Fe etc.) originating from cigarettes were filtered out. Mass discrimination of 208Pb/206Pb ratio in Ne DRC mode increased 0.3% compared to the standard mode, the mass bias due to the in-cell Ne gas collision can be accurately corrected by NIST 981 Pb isotope standard. This method was verified by a tobacco reference material CTV-OTL-2. Results of 208Pb/206Pb and 207Pb/206Pb were 2.0848 ± 0.0028 (2δ) and 0.8452 ± 0.0011 (2δ) for CTA-VTL-2, which were agreed with the literature values (208Pb/206Pb = 2.0884 ± 0.0090 and 207Pb/206Pb = 0.8442 ± 0.0032). The precision of Pb isotope ratios (208Pb/206Pb and 207Pb/206Pb) for the cigarette samples are ranged from 0.01 to 0.08% (N = 5). It has sufficient precision to discriminate 91 different brand cigarettes originated from four different geographic regions (Shown in Fig).

  19. A New Pb Isotope Perspective on Oceanic Basalts: Reading Between the Lines

    NASA Astrophysics Data System (ADS)

    Galer, S. J.; Abouchami, W.; Eisele, J.; Haase, K.; Moller, H.; Regelous, M.; Hofmann, A. W.

    2001-12-01

    Recent high-precision Pb isotope analyses ( ~100 ppm) obtained using double and triple spikes demonstrate that much of the scatter in previous, conventionally obtained data is analytical in origin. Here we pool together all the currently available high-precision Pb isotope data on oceanic basalts to provide a new "sharpened up" picture of the gross Pb isotope heterogeneity in the mantle. These Pb isotope data are from MORB glasses from the East Pacific Rise (EPR) and South Atlantic (26° S, Ascension), seven Hawaiian volcanoes, Pitcairn, Rurutu, the Azores (all MPI data), Mangaia (Woodhead, 1996), and St. Helena and Iceland (Thirlwall, 2000), totalling around 250 samples. The high-precision data for a given location do not form the "clouds" in Pb-Pb isotope space seen in conventional literature data. Rather, each data set forms tight linear arrays in both Pb isotope spaces. More surprising, though, is that the samples lying on a given array cover a limited geographic extent: (1) In the case of the EPR, six distinct arrays are found, each of which is confined to a particular range in latitude along the ridge, corresponding to length-scales of ~100 to 5000 km. The same is true of MORB samples from the South Atlantic (2) Distinct arrays are resolved for individual volcanoes along the Hawaiian chain, indicating that the heterogeneities within the Hawaiian plume are tapped in a long-lived and highly systematic fashion. It is also quite clear that these data are not readily interpretable in terms of mixing between notional end-member "components" in the mantle. For example, the EM1 "component" present in Pitcairn is quite clearly different in Pb isotope space from that sampled by Koolau. Similarly, the HIMU "component" present in the Austral-Cook chain is distinct in the islands Mangaia and Rurutu, and is not the same as that found in St. Helena. In all of these cases it is impossible to find common crossing points of the arrays in both Pb isotope spaces. Moreover, none

  20. 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

  1. Combined apatite fission track and U-Pb dating by LA-ICPMS

    NASA Astrophysics Data System (ADS)

    Chew, D. M.; Donelick, R. A.

    2012-04-01

    fractionation are challenges in apatite U-Pb dating by LA-ICPMS. Isochron-based approaches to common Pb correction require a significant spread in common Pb / radiogenic Pb ratios. This is not usually possible on individual detrital apatite grains and hence the 204Pb-, 207Pb- and 208Pb-correction methods are preferred. Uranium concentration measurements by ICPMS employ large peak jumps (the internal standard is a Ca isotope) which require a quadrupole or a rapid-scanning magnetic-sector LA-ICPMS system. These single-collector instruments require a prohibitively long dwell time on the low intensity 204Pb peak to measure it accurately and hence the 207Pb- and 208Pb-correction methods are preferred. Uranium-concentration measurements in fission-track dating require well-constrained ablation depths during analysis and hence spot analyses are preferred to rastering. Laser-induced U-Pb fractionation is corrected for by sample-standard bracketing using a variety of apatite standards (Durango, Emerald Lake, Fish Canyon Tuff, Kovdor, Otter Lake and McClure Mountain syenite). Of these, Emerald Lake (Chew et al., 2011) and McClure Mountain syenite apatite are recommended as primary standards with Durango apatite making a suitable secondary standard. Offline data-reduction uses custom-written software for ICPMS data processing (the UPbICP package of Ray Donelick) or the freeware IOLITE data-reduction package of Paton et al. (2010).

  2. Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios.

    PubMed

    Yoo, Eun-Jin; Lee, Jung-A; Park, Jae-Seon; Lee, Khanghyun; Lee, Won-Seok; Han, Jin-Seok; Choi, Jong-Woo

    2014-02-01

    This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the (203)Tl/(205)Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios ((207)Pb/(206)Pb) found were 0.85073 ± 0.0004~0.85373 ± 0.0003 for the main stream, while they were 0.83736 ± 0.0010 for the tributary and 0.84393 ± 0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60%. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.

  3. U-Pb Ages of Lunar Apatites

    NASA Technical Reports Server (NTRS)

    Vaughan, J.; Nemchin, A. A.; Pidgeon, R. T.; Meyer, Charles

    2006-01-01

    Apatite is one of the minerals that is rarely utilized in U-Pb geochronology, compared to some other U-rich accessory phases. Relatively low U concentration, commonly high proportion of common Pb and low closure temperature of U-Pb system of apatite inhibit its application as geochronological tool when other minerals such as zircon are widely available. However, zircon appear to be restricted to certain type of lunar rocks, carrying so called KREEP signature, whereas apatite (and whitlockite) is a common accessory mineral in the lunar samples. Therefore, utilizing apatite for lunar chronology may increase the pool of rocks that are available for U-Pb dating. The low stability of U-Pb systematics of apatite may also result in the resetting of the system during meteoritic bombardment, in which case apatite may provide an additional tool for the study of the impact history of the Moon. In order to investigate these possibilities, we have analysed apatites and zircons from two breccia samples collected during the Apollo 14 mission. Both samples were collected within the Fra Mauro formation, which is interpreted as a material ejected during the impact that formed the Imbrium Basin.

  4. Assay Methods for 238U, 232Th, and 210Pb in Lead and Calibration of 210Bi Bremsstrahlung Emission from Lead

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

    Orrell, John L.; Aalseth, Craig E.; Arnquist, Isaac J.

    2016-02-13

    Assay methods for measuring 238U, 232Th, and 210Pb concentrations in refined lead are presented. The 238U and 232Th concentrations are assayed via inductively coupled plasma mass spectrometry (ICP-MS) after anion exchange column separation on dissolved lead samples. The 210Pb concentration is inferred through α-spectroscopy of a daughter isotope, 210Po, after chemical precipitation separation on dissolved lead samples. Subsequent to the 210Po α-spectroscopy assay, a method for evaluating 210Pb concentrations in solid lead samples was developed via measurement of bremsstrahlung radiation from β-decay of a daughter isotope, 210Bi, by employing a 14-crystal array of high purity germanium (HPGe) detectors. Ten sourcesmore » of refined lead were assayed. The 238U concentrations were <34 microBq/kg and the 232Th concentrations ranged <0.6 – 15 microBq/kg, as determined by the ICP-MS assay method. The 210Pb concentrations ranged from ~0.1 – 75 Bq/kg, as inferred by the 210Po α-spectroscopy assay method.« less

  5. The Proterozoic of NW Mexico revisited: U-Pb geochronology and Hf isotopes of Sonoran rocks and their tectonic implications

    NASA Astrophysics Data System (ADS)

    Solari, L. A.; González-León, C. M.; Ortega-Obregón, C.; Valencia-Moreno, M.; Rascón-Heimpel, M. A.

    2018-04-01

    Several Proterozoic basement units crop out in the Sonora State of NW Mexico, and the same can be correlated with crustal provinces of southern Laurentia in the neighboring southwestern USA. Zircon U-Pb and Hf isotopic determinations in more than 300 grains separated from igneous and metaigneous rocks from these units indicate that the crystalline basement in Sonora is made up of different components, which are from west to east: (1) The Caborca-Mojave province to the west, characterized by the so-called Bámori Complex, have U-Pb ages between 1696 and 1772 Ma, with moderately juvenile to slightly evolved ɛHf values, yielding T DM ages of ca. 2.1-2.4 Ga; (2) in the intermediate area, east of Hermosillo, the Palofierral and La Ramada orthogneiss units yield an age of 1640 and 1703 Ma, respectively, both having juvenile ɛHf with the Palofierral overlapping the depleted mantle curve at ca. 1.65 Ga; and (3) in the northeastern Sonora, samples from the southern extension of the Mazatzal province, represented by the Pinal Schist, yielded ages between 1674 and 1694 Ma, with moderately juvenile to juvenile ɛHf values and a T DM age of ca. 1.9 Ga. In addition, a suite of post-tectonic granites was also studied in Caborca (San Luis granite) as well as in northeastern Sonora (Cananea granite), both yielding ages of ca. 1.44 Ga with moderately juvenile ɛHf values ranging from -1 to +8 and T DM dates of ca. 1.8-1.9 Ga and 1.6-1.7 Ga, respectively. These two isotopically contrasting provinces may imply the existence of a Proterozoic paleo-suture. However, if the Palofierral gneiss, of which the Hf signature straddles the depleted mantle array, is taken as the source for the 1.44 Ga Cananea granite, then the location of such a suture zone should lay farther south than the proposed trace of the Mojave-Sonora megashear.

  6. U-Pb Geochronology of Hydrous Silica (Siebengebirge, Germany)

    NASA Astrophysics Data System (ADS)

    Tomaschek, Frank; Nemchin, Alexander; Geisler, Thorsten; Heuser, Alexander; Merle, Renaud

    2015-04-01

    Low-temperature, hydrous weathering eventually leads to characteristic products such as silica indurations. Elevated U concentrations and the ability of silica to maintain a closed system permits silica to be dated by the U-Pb method, which, in turn, will potentially allow constraining the timing of near-surface processes. To test the feasibility of silica U-Pb geochronology, we sampled opal and chalcedony from the Siebengebirge, Germany. This study area is situated at the terminus of the Cenozoic Lower Rhine Basin on the Rhenish Massif. The investigated samples include silicified gravels from the Mittelbachtal locality, renowned for the embedded wood opal. Structural characterization of the silica phases (Raman spectroscopy) was combined with in situ isotopic analyses, using ion microprobe and LA-ICPMS techniques. In the Siebengebirge area fluviatile sediments of Upper Oligocene age were covered by an extended trachyte tuff at around 25 Ma. Silica is known to indurate some domains within the tuff and, in particular, certain horizons within the subjacent fluviatile sediments ('Tertiärquarzite'). Cementation of the gravels occurred during at least three successive growth stages: early paracrystalline silica (opal-CT), fibrous chalcedony, and late microcrystalline quartz. It has traditionally been assumed that this silica induration reflects intense weathering, more or less synchronous with the deposition of the volcanic ashes. Results from U-Pb geochronology returned a range of discrete 206Pb-238U ages, recording a protracted silicification history. For instance, we obtained 22 ± 1 Ma for opal-CT cement from a silicified tuff, 16.6 ± 0.5 Ma for silicified wood and opal-CT cement in the fluviatile gravels, as well as 11 ± 1 Ma for texturally late chalcedony. While silicification of the sampled tuff might be contemporaneous with late-stage basalts, opaline silicification of the subjacent sediments and their wood in the Mittelbachtal clearly postdates active

  7. Constraints on a Late Cretaceous uplift, denudation, and incision of the Grand Canyon region, southwestern Colorado Plateau, USA, from U-Pb dating of lacustrine limestone

    NASA Astrophysics Data System (ADS)

    Hill, Carol A.; Polyak, Victor J.; Asmerom, Yemane; P. Provencio, Paula

    2016-04-01

    The uplift and denudation of the Colorado Plateau is important in reconstructing the geomorphic and tectonic evolution of western North America. A Late Cretaceous (64 ± 2 Ma) U-Pb age for the Long Point limestone on the Coconino Plateau, which overlies a regional erosional surface developed on Permo-Triassic formations, supports unroofing of the Coconino Plateau part of Grand Canyon by that time. U-Pb analyses of three separate outcrops of this limestone gave ages of 64.0 ± 0.7, 60.5 ± 4.6, and 66.3 ± 3.9 Ma, which dates are older than a fossil-based, early Eocene age. Samples of the Long Point limestone were dated using the isotope dilution isochron method on well-preserved carbonates having high-uranium and low-lead concentrations. Our U-Pb ages on the Long Point limestone place important constraints on the (1) time of tectonic uplift of the southwestern Colorado Plateau and Kaibab arch, (2) time of denudation of the Coconino Plateau, and (3) Late Cretaceous models of paleocanyon incision west of, or across, the Kaibab arch. We propose that the age of the Long Point limestone, interbedded within the Music Mountain Formation in the Long Point area, represents a period of regional aggradation and a time of drainage blockage northward and eastward across the Kaibab arch, with possible diversion of northward drainage on the Coconino Plateau westward around the arch via a Laramide paleo-Grand Canyon.

  8. An update of the Pb isotope inventory in post leaded-petrol Singapore environments.

    PubMed

    Carrasco, Gonzalo; Chen, Mengli; Boyle, Edward A; Tanzil, Jani; Zhou, Kuanbo; Goodkin, Nathalie F

    2018-02-01

    Pb is a trace metal that tracks anthropogenic pollution in natural environments. Despite recent leaded petrol phase out around Southeast Asia, the region's growth has resulted in continued exposure of Pb from a variety of sources. In this study, sources of Pb into Singapore, a highly urbanised city-state situated in the central axis of Southeast Asia, are investigated using isotopic ratios and concentrations. We compiled data from our previous analyses of aerosols, incineration fly ash and sediments, with new data from analyses of soil from gas stations, water from runoff and round-island coastal seawater to obtain a spatio-temporal overview of sources of Pb into the Singapore environment. Using 206 Pb/ 207 Pb ratio, we identified three main Pb source origins: natural Pb (1.215 ± 0.001), historic/remnant leaded petrol (1.123 ± 0.013), and present-day industrial and incinerated waste (1.148 ± 0.005). Deep reservoir sediments bore larger traces of Pb from leaded petrol, but present-day runoff waters and coastal seawater were a mix of industrial and natural sources with somewhat variable concentrations. We found temporal variability in Pb isotopic ratio in aerosols indicating alternating transboundary Pb sources to Singapore that correspond to seasonal changes in monsoon winds. By contrast, seasonal monsoon circulation did not significantly influence isotopic ratios of coastal seawater Pb. Instead, seawater Pb was driven more by location differences, suggesting stronger local-scale drivers of Pb such as point sources, water flushing, and isotope exchange. The combination of multiple historic and current sources of Pb shown in this study highlights the need for continued monitoring of Pb in Southeast Asia, especially in light of emerging industries and potential large sources of Pb such as coal combustion. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. U–Pb, Rb–Sr, and U-series isotope geochemistry of rocks and fracture minerals from the Chalk River Laboratories site, Grenville Province, Ontario, Canada

    USGS Publications Warehouse

    Neymark, Leonid; Peterman, Zell E.; Moscati, Richard J.; Thivierge, R. H.

    2013-01-01

    As part of the Geologic Waste Management Facility feasibility study, Atomic Energy of Canada Ltd. (AECL) is evaluating the suitability of the Chalk River Laboratories (CRL) site in Ontario, situated in crystalline rock of the southwestern Grenville Province, for the possible development of an underground repository for low- and intermediate-level nuclear waste. This paper presents petrographic and trace element analyses, U–Pb zircon dating results, and Rb–Sr, U–Pb and U-series isotopic analyses of gneissic drill core samples from the deep CRG-series characterization boreholes at the CRL site. The main rock types intersected in the boreholes include hornblende–biotite (±pyroxene) gneisses of granitic to granodioritic composition, leucocratic granitic gneisses with sparse mafic minerals, and garnet-bearing gneisses with variable amounts of biotite and/or hornblende. The trace element data for whole-rock samples plot in the fields of within-plate, syn-collision, and volcanic arc-type granites in discrimination diagrams used for the tectonic interpretation of granitic rocks.Zircons separated from biotite gneiss and metagranite samples yielded SHRIMP-RG U–Pb ages of 1472 ± 14 (2σ) and 1045 ± 6 Ma, respectively, in very good agreement with widespread Early Mesoproterozoic plutonic ages and Ottawan orogeny ages in the Central Gneiss Belt. The Rb–Sr, U–Pb, and Pb–Pb whole-rock errorchron apparent ages of most of the CRL gneiss samples are consistent with zircon U–Pb age and do not indicate substantial large-scale preferential element mobility during superimposed metamorphic and water/rock interaction processes. This may confirm the integrity of the rock mass, which is a positive attribute for a potential nuclear waste repository. Most 234U/238U activity ratios (AR) in whole rock samples are within errors of the secular equilibrium value of one, indicating that the rocks have not experienced any appreciable U loss or gain within the past 1

  10. Rates of carbonate soil evolution from carbon, U- and Th-series isotope studies: Example of the Astian sands (SE France)

    NASA Astrophysics Data System (ADS)

    Barbecot, Florent; Ghaleb, Bassam; Hillaire-Marcel, Claude

    2015-04-01

    In carbonate rich soils, C-isotopes (14C, 13C) and carbonate mass budget may inform on centennial to millennial time scale dissolution/precipitation processes and weathering rates, whereas disequilibria between in the U- and Th-decay series provide tools to document high- (228Ra-228Th-210Pb) to low- (234U, 230Th, 231Pa, 226Ra) geochemical processes rate, covering annual to ~ 1Ma time scales, governing both carbonate and silicate soil fractions. Because lithology constitutes a boundary condition, we intend to illustrate the behavior of such isotopes in soils developed over Astian sands formation (up to ~ 30% carbonate) from the Béziers area (SE France). A >20 m thick unsaturated zone was sampled firstly along a naturally exposed section, then in a cored sequence. Geochemical and mineralogical analyses, including stable isotopes and 14C-measurements, were complemented with 228U, 234U, 230Th, 226Ra, 210Pb and 228Th, 232Th measurements. Whereas the upper 7 m depict geochemical and isotopic features forced by dissolution/precipitation processes leading to variable radioactive disequilibria, but overall deficits in more soluble elements of the decay series, the lower part of the sequence shows strong excesses in 234U and 230Th over parent isotopes (i.e., 238U and 234U, respectively). These features might have been interpreted as the result of successive phases of U-loss and gains. However, 226Ra and 230Th are in near-equilibrium, thus leading to conclude at a more likely slow enrichment process in both 234Th(234U) and 230Th, which we link to dissolved U-decay during groundwater recharge events. In addition, 210Pb deficits (vs parent 226Ra) are observed down to 12 m along the natural outcropping section and below the top-soil 210Pb-excess in the cored sequence, due to gaseous 222Rn-diffusion over the cliff outcrop. Based on C-isotope and chemical analysis, reaction rates at 14C-time scale are distinct from those estimates at the short- or long-lived U-series isotopes

  11. Stable isotope tracer dilution for quantifying very low-density lipoprotein-triacylglycerol kinetics in man.

    PubMed

    Sidossis, Labros S; Magkos, Faidon; Mittendorfer, Bettina; Wolfe, Robert R

    2004-08-01

    A number of approaches have been employed in the past to measure very low-density lipoprotein (VLDL) triacylglycerol (TG) kinetics in humans in vivo, varying in the selection of tracer and mode of administration. All, however, make use of labeled TG precursors and more or less complicated mathematical models to derive the kinetic parameters of interest. The aim of the present study was to develop a conceptually straightforward method, based on the traditional tracer infusion technique, for quantifying VLDL-TG production rates in man using stable isotopes. Our approach involves ingestion of [U-13C3]glycerol to endogenously label the glycerol in VLDL-TG, plasmapheresis, isolation of the newly 13C-labeled VLDL from plasma, and administration within the next 2-3 days via a primed constant autologous reinfusion. This procedure produces enough tracer for a priming dose plus 2-3 h of infusion. In the physiological conditions examined (basal and hyperglycemic states, fat- and carbohydrate-rich diets), with almost 3-fold ranging VLDL-TG pool sizes, a steady state in plasma VLDL-TG glycerol tracer-to-tracee ratio was readily achieved within 2 h. Consequently, calculations are made according to the isotope dilution principle, thus avoiding assumptions implicit in more complicated models. The stable isotope VLDL-TG tracer dilution method offers an alternative and reliable tool for the determination of endogenous VLDL-TG kinetics in man under a variety of metabolic states. Copyright 2003 Elsevier Ltd.

  12. Assessment of the U-Th-Pb system in two Archean metabasalts - Deciphering the complex histories of sulfides and silicates using acid leaching methods

    NASA Astrophysics Data System (ADS)

    Smith, Patrick E.; Farquhar, Ronald M.; Tatsumoto, Mitsunobo

    1989-08-01

    A detailed U-Th-Pb isotopic study of two Archean basalts from two greenstone belts in the eastern Wawa Subprovince of the Canadian shield was carried out on samples that were either dissolved at once or leached in either 1N HNO3, 2N HCl, or 6N HCl. The abundances and isotopic compositions from these samples suggest that variable disturbances had occurred in both rock systems, which can be attributed to Pb mobility, particularly in the form of sulphide addition at various times, and, in one case, by recent Pb loss. The Pb isotopic compositions of the sulphides record late events which affected the greenstone terrains. The results also indicate that the sulphides and silicate rocks could have originated from a common source. The isotopic compositions of the basalt suggest that, in the Archean, both depleted and enriched mantle sources existed beneath the Wawa Subprovince.

  13. Oceanic Pb-isotopic sources of proterozoic and paleozoic volcanogenic massive sulfide deposits on Prince of Wales Island and vicinity, southeastern Alaska

    USGS Publications Warehouse

    Ayuso, Robert A.; Karl, Susan M.; Slack, John F.; Haeussler, Peter J.; Bittenbender, Peter E.; Wandless, Gregory A.; Colvin, Anna

    2005-01-01

    samples from the massive sulfide deposits in the Moira Sound unit plot on a different trend (206Pb/204Pb=17.375–19.418, 207Pb/204Pb=15.361–15.519, 208Pb/204Pb=36.856–37.241) from the steep slope defined by the massive sulfide deposits in the Wales Group. In comparison, the Pb-isotopic ratios of Devonian polymetallic (Pb-Zn-Au-Ag) quartz-sulfide veins vary widely ( 206Pb/204Pb=18.339–18.946, 207Pb/204Pb=15.447–15.561, 208Pb/204Pb=37.358–38.354), straddling the slope defined by the massive sulfide deposits in the Moira Sound unit. The general decrease in 207Pb/204Pb ratio in these deposits, relative to the average crustal Pb-evolution curve, suggests that the most likely lead sources were those associated with oceanic volcanic rocks. The massive sulfide deposits in the Wales Group may have resided within an intraoceanic tectonic setting where the mantle was the predominant contributor of metals. Some contribution from reworked arc material or recycled older, hydrothermally altered oceanic crust (including pelagic sediment) is also possible. Lead sources of the massive sulfide deposits in the Moira Sound unit also included an older source region, possibly a Late Proterozoic or Cambrian volcanosedimentary sequence and the massive sulfide deposits in the Wales Group. Preliminary regional comparison of the Pb-isotopic data indicates that the Greens Creek (Admiralty Island, Alaska) and Windy Craggy (northern British Columbia) deposits probably did not share a common lead source with the VMS deposits on Prince of Wales Island. Other sulfide occurrences on Admiralty Island are also more radiogenic than those on Prince of Wales Island. Large differences in 207Pb/204Pb ratio suggest that the lead in the VMS deposits in different parts of the Alexander terrane evolved from sources with heterogeneous U/Pb ratios, resulting from mixing of mantle and crustal components. 

  14. Coupling meteorology, metal concentrations, and Pb isotopes for source attribution in archived precipitation samples.

    PubMed

    Graney, Joseph R; Landis, Matthew S

    2013-03-15

    A technique that couples lead (Pb) isotopes and multi-element concentrations with meteorological analysis was used to assess source contributions to precipitation samples at the Bondville, Illinois USA National Trends Network (NTN) site. Precipitation samples collected over a 16month period (July 1994-October 1995) at Bondville were parsed into six unique meteorological flow regimes using a minimum variance clustering technique on back trajectory endpoints. Pb isotope ratios and multi-element concentrations were measured using high resolution inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) on the archived precipitation samples. Bondville is located in central Illinois, ~250km downwind from smelters in southeast Missouri. The Mississippi Valley Type ore deposits in Missouri provided a unique multi-element and Pb isotope fingerprint for smelter emissions which could be contrasted to industrial emissions from the Chicago and Indianapolis urban areas (~125km north and east, of Bondville respectively) and regional emissions from electric utility facilities. Differences in Pb isotopes and element concentrations in precipitation corresponded to flow regime. Industrial sources from urban areas, and thorogenic Pb from coal use, could be differentiated from smelter emissions from Missouri by coupling Pb isotopes with variations in element ratios and relative mass factors. Using a three endmember mixing model based on Pb isotope ratio differences, industrial processes in urban airsheds contributed 56±19%, smelters in southeast Missouri 26±13%, and coal combustion 18±7%, of the Pb in precipitation collected in Bondville in the mid-1990s. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Using isotopic dilution to assess chemical extraction of labile Ni, Cu, Zn, Cd and Pb in soils.

    PubMed

    Garforth, J M; Bailey, E H; Tye, A M; Young, S D; Lofts, S

    2016-07-01

    Chemical extractants used to measure labile soil metal must ideally select for and solubilise the labile fraction, with minimal solubilisation of non-labile metal. We assessed four extractants (0.43 M HNO3, 0.43 M CH3COOH, 0.05 M Na2H2EDTA and 1 M CaCl2) against these requirements. For soils contaminated by contrasting sources, we compared isotopically exchangeable Ni, Cu, Zn, Cd and Pb (EValue, mg kg(-1)), with the concentrations of metal solubilised by the chemical extractants (MExt, mg kg(-1)). Crucially, we also determined isotopically exchangeable metal in the soil-extractant systems (EExt, mg kg(-1)). Thus 'EExt - EValue' quantifies the concentration of mobilised non-labile metal, while 'EExt - MExt' represents adsorbed labile metal in the presence of the extractant. Extraction with CaCl2 consistently underestimated EValue for Ni, Cu, Zn and Pb, while providing a reasonable estimate of EValue for Cd. In contrast, extraction with HNO3 both consistently mobilised non-labile metal and overestimated the EValue. Extraction with CH3COOH appeared to provide a good estimate of EValue for Cd; however, this was the net outcome of incomplete solubilisation of labile metal, and concurrent mobilisation of non-labile metal by the extractant (MExtEValue). The Na2H2EDTA extractant mobilised some non-labile metal in three of the four soils, but consistently solubilised the entire labile fraction for all soil-metal combinations (MExt ≈ EExt). Comparison of EValue, MExt and EExt provides a rigorous means of assessing the underlying action of soil chemical extraction methods and could be used to refine long-standing soil extraction methodologies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Data Reduction of Laser Ablation Split-Stream (LASS) Analyses Using Newly Developed Features Within Iolite: With Applications to Lu-Hf + U-Pb in Detrital Zircon and Sm-Nd +U-Pb in Igneous Monazite

    NASA Astrophysics Data System (ADS)

    Fisher, Christopher M.; Paton, Chad; Pearson, D. Graham; Sarkar, Chiranjeeb; Luo, Yan; Tersmette, Daniel B.; Chacko, Thomas

    2017-12-01

    A robust platform to view and integrate multiple data sets collected simultaneously is required to realize the utility and potential of the Laser Ablation Split-Stream (LASS) method. This capability, until now, has been unavailable and practitioners have had to laboriously process each data set separately, making it challenging to take full advantage of the benefits of LASS. We describe a new program for handling multiple mass spectrometric data sets collected simultaneously, designed specifically for the LASS technique, by which a laser aerosol is been split into two or more separate "streams" to be measured on separate mass spectrometers. New features within Iolite (https://iolite-software.com) enable the capability of loading, synchronizing, viewing, and reducing two or more data sets acquired simultaneously, as multiple DRSs (data reduction schemes) can be run concurrently. While this version of Iolite accommodates any combination of simultaneously collected mass spectrometer data, we demonstrate the utility using case studies where U-Pb and Lu-Hf isotope composition of zircon, and U-Pb and Sm-Nd isotope composition of monazite were analyzed simultaneously, in crystals showing complex isotopic zonation. These studies demonstrate the importance of being able to view and integrate simultaneously acquired data sets, especially for samples with complicated zoning and decoupled isotope systematics, in order to extract accurate and geologically meaningful isotopic and compositional data. This contribution provides instructions and examples for handling simultaneously collected laser ablation data. An instructional video is also provided. The updated Iolite software will help to fully develop the applications of both LASS and multi-instrument mass spectrometric measurement capabilities.

  17. Parent zonation in thermochronometers - resolving complexity revealed by ID-TIMS U-Pb dates and implications for the application of decay-based thermochronometers

    NASA Astrophysics Data System (ADS)

    Navin Paul, Andre; Spikings, Richard; Chew, David; Daly, J. Stephen; Ulyanov, Alexey

    2017-04-01

    High temperature (>350℃) U-Pb thermochronometers primarily use accessory minerals such as apatite, titanite and rutile, and assume that daughter isotopes are lost by thermally activated volume diffusion while the parent remains immobile. Studies exploiting such behaviour have been successfully used to reconstruct thermal histories spanning several hundred million years (e.g. Cochrane et al., 2014). However, outliers in date (ID-TIMS) vs diffusion length space are frequently observed, and grains are frequently found to be either too young or too old for expected thermal history solutions using the diffusion data of Cherniak et al. (2010). These deviations of single grain apatite U-Pb dates from expected behaviour could be caused by a combination of i) metamorphic (over-)growth, ii) fluid-aided Pb mobilisation during alteration/recrystallization, iii) parent isotope zonation, iv) metamictisation, and v) changes in diffusion length with time (e.g. fracturing). We present a large data set from the northern Andes of South America, where we compare apatite U-Pb ID-TIMS-(TEA) data with LA-ICP-MS element maps and in-situ apatite U-Pb LA-(MC)-ICP-MS dates. These are combined with U-Pb zircon and 40Ar/39Ar (muscovite) data to attempt to distinguish between thermally activated volume diffusion and secondary overgrowth/recrystallization. We demonstrate that in young (e.g. Phanerozoic) apatites that have not recrystallized or experienced metasomatic overgrowths, U-Pb dates are dominantly controlled by volume diffusion and intra-crystal uranium zonation. This implies that ID-TIMS analyses of apatites with zoned parent isotope distributions will not usually recover accurate thermal history solutions, and an in-situ dating method is required. Recovering the uranium distribution during in-situ analysis provides a means to account for parent zonation, substantially increasing the accuracy of the modelled t-T-paths. We present in-situ data from apatites where scatter in date v

  18. Hercynian Pb-Zn mineralization types in the Alcudia Valley mining district (Spain) and their reflect in Pb isotopic signatures

    NASA Astrophysics Data System (ADS)

    García de Madinabeitia, S.; Santos Zalduegui, J. F.; Palero, F.; Gil Ibarguchi, J. I.; Carracedo, M.

    2003-04-01

    More than 450 ore deposits indexed within the Alcudia Valley of the Central-Iberian Zone (Spain) may be grouped by their tectonic and lithologic characteristics (1,2) as follows: type A of rare stratabound mineralizations, and types B, C, D and E represented by abundant Hercynian veins (post-Namurian). 86 new Pb isotope analyses of galenas from the four vein types reveal that types B and C have similar isotopic ratios with values of μ_2 = 10.07, ω_2 = 40.6 and a mean model age of 564 Ma. Types D and E have μ_2 and ω_2 values of 9.79 and 38.5, respectively, but differ each other with respect to their model ages, 600 Ma (type D) and 335 Ma (type E). The observed variations appear to be related to the geochemical features of the metasedimentary host-rocks of the mineralizations where two distinct types of Pb isotopic ratios have been reported (3): one with μ_2 and ω_2 comparable to those of the D and E types and another with a more radiogenic composition, close to those of the B and C types of galenas. Nägler et al. have suggested partial rehomogeneization of Pb isotopic composition within the metasediments at ca. 330 Ma, that is, prior to the mineralization events, but the extent of this process and its effects on the ore bodies isotopic features is not evident. The origin of the more abundant E type ore bodies has been related to the Hercynian granitic rocks in the area (2, and references therein). Other plutons within this sector of the Central Iberian Zone (e.g., Linares, etc.; cf. accompanying Abstract) associate ore bodies whose Pb isotopic composition is very similar to that of the E type galenas from the Alcudia Valley. The isotopic data obtained thus point to a related or common source material for the various types of granites within the area studied. Yet, the Pb isotopic composition of other mineralizations (B, C, D), likewise located in Hercynian veins, allow to consider different types of Pb-Zn ore bodies and point therefore to different sources of

  19. Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products.

    PubMed

    Boulyga, Sergei F; Heilmann, Jens; Heumann, Klaus G

    2005-08-01

    Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different 34S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured 34S/32S isotope ratio of the isotope-diluted sample remained constant-a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 microg g(-1) ('sulfur-free' premium gasoline) to 10.4 mg g(-1) (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 microg g(-1) and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level.

  20. 40 Ma of hydrothermal W mineralization during the Variscan orogenic evolution of the French Massif Central revealed by U-Pb dating of wolframite

    NASA Astrophysics Data System (ADS)

    Harlaux, Matthieu; Romer, Rolf L.; Mercadier, Julien; Morlot, Christophe; Marignac, Christian; Cuney, Michel

    2018-01-01

    We present U-Pb thermal ionization mass spectrometer (TIMS) ages of wolframite from several granite-related hydrothermal W±Sn deposits in the French Massif Central (FMC) located in the internal zone of the Variscan belt. The studied wolframite samples are characterized by variable U and Pb contents (typically <10 ppm) and show significant variations in their radiogenic Pb isotopic compositions. The obtained U-Pb ages define three distinct geochronological groups related to three contrasting geodynamic settings: (i) Visean to Namurian mineralization (333-327 Ma) coeval with syn-orogenic compression and emplacement of large peraluminous leucogranites (ca. 335-325 Ma), (ii) Namurian to Westphalian mineralization (317-315 Ma) synchronous with the onset of late-orogenic extension and emplacement of syn-tectonic granites (ca. 315-310 Ma) and (iii) Stephanian to Permian mineralization (298-274 Ma) formed during post-orogenic extension contemporaneous with the Permian volcanism in the entire Variscan belt. The youngest ages (276-274 Ma) likely reflect the reopening of the U-Pb isotopic system after wolframite crystallization and may correspond to late hydrothermal alteration (e.g. ferberitization). Our results demonstrate that W(±Sn) mineralization in the FMC formed during at least three distinct hydrothermal events in different tectono-metamorphic settings over a time range of 40 Ma.

  1. Tracing Cd, Zn and Pb pollution sources in bivalves using isotopes

    NASA Astrophysics Data System (ADS)

    Shiel, A. E.; Weis, D. A.; Orians, K. J.

    2010-12-01

    In a multi-tracer study, Cd, Zn and Pb isotopes (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are evaluated as tools to distinguish between natural and anthropogenic sources of these metals in bivalves from western Canada (British Columbia), the eastern USA, Hawaii and France. High Cd concentrations found in BC oysters have elicited economic and health concerns. The source of these high Cd levels is unknown but thought to be largely natural. High Cd levels in BC oysters are largely attributed to the natural upwelling of Cd-rich intermediate waters in the North Pacific as the δ114/110Cd (-0.69 to -0.09‰) and δ66/64Zn (0.28 to 0.36‰) values of BC oysters fall within the range reported for North Pacific seawater. Different contributions from anthropogenic sources account for the variability of Cd isotopic compositions of BC oysters; the lightest of these oysters are from the BC mainland. These oysters also have Pb isotopic compositions that reflect primarily anthropogenic sources (e.g., leaded and unleaded automotive gasoline and smelting of Pb ores, potentially historical). On the contrary, USA East Coast bivalves exhibit relatively light Cd isotopic compositions (δ114/110Cd = -1.20 to -0.54‰; lighter than reported for North Atlantic seawater) due to the high prevalence of industry on this coast. The Pb isotopic compositions of these bivalves indicate contributions from the combustion of coal. The large variability of environmental health among coastal areas in France is reflected in the broad range of Cd isotopic compositions exhibited by French bivalves (δ114/110Cd = -1.08 to -0.20‰). Oysters and mussels from the Marennes-Oléron basin and Gironde estuary have the lightest Cd isotopic compositions of the French oysters consistent with significant historical Cd emissions from the now-closed proximal Zn smelter. In these bivalves, significant declines in the Cd levels between 1984/7 and 2004/5 are not accompanied by a significant shift in the Cd

  2. 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

  3. U-Pb ages of secondary silica at Yucca Mountain, Nevada: Implications for the paleohydrology of the unsaturated zone

    USGS Publications Warehouse

    Neymark, L.A.; Amelin, Y.; Paces, J.B.; Peterman, Z.E.

    2002-01-01

    Uranium, Th and Pb isotopes were analyzed in layers of opal and chalcedony from individual mm- to cm-thick calcite and silica coatings at Yucca Mountain, Nevada, USA, a site that is being evaluated for a potential high-level nuclear waste repository. These calcite and silica coatings on fractures and in lithophysal cavities in Miocene-age tuffs in the unsaturated zone (UZ) precipitated from descending water and record a long history of percolation through the UZ. Opal and chalcedony have high concentrations of U (10 to 780 ppm) and low concentrations of common Pb as indicated by large values of 206Pb/204Pb (up to 53,806), thus making them suitable for U-Pb age determinations. Interpretations of U-Pb isotope systems in opal samples at Yucca Mountain are complicated by the incorporation of excess 234U at the time of mineral formation, resulting in reverse discordance of U-Pb ages. However, the 207PB/235U ages are much less affected by deviation from initial secular equilibrium and provide reliable ages of most silica deposits between 0.6 and 9.8 Ma. For chalcedony subsamples showing normal age discordance, these ages may represent minimum times of deposition. Typically, 207Pb/235U ages are consistent with the microstratigraphy in the mineral coating samples, such that the youngest ages are for subsamples from outer layers, intermediate ages are from inner layers, and oldest ages are from innermost layers. 234U and 230Th in most silica layers deeper in the coatings are in secular equilibrium with 238U, which is consistent with their old age and closed system behavior during the past -0.5 Ma. The ages for subsamples of silica layers from different microstratigraphic positions in individual calcite and silica coating samples collected from lithophysal cavities in the welded part of the Topopah Spring Tuff yield slow long-term average growth rates of 1 to 5 mm/Ma. These data imply that the deeper parts of the UZ at Yucca Mountain maintained long-term hydrologic stability

  4. 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.

  5. Effects of Simple Leaching of Crushed and Powdered Materials on High-precision Pb Isotope Analyses

    NASA Astrophysics Data System (ADS)

    Todd, E.; Stracke, A.

    2013-12-01

    We present new results of simple leaching experiments on the Pb isotope composition of USGS standard reference material powders and on ocean island basalt whole rock splits and powders. Rock samples were leached with 6N HCl in two steps, first hot and then in an ultrasonic bath, and washed with ultrapure H2O before conventional sample digestion and chromatographic purification of Pb. Pb isotope analyses were determined with Tl-doped MC-ICP-MS. Intra- and inter-session analytical reproducibility of repeated analyses of both synthetic Pb solutions and Pb from single digests of chemically processed natural samples were generally < 100 ppm (2 S.D.). The comparison of leached and unleached samples shows that leaching reliably removes variable amounts of different contaminants for different starting materials. For repeated digests of a single sample, the leached samples reproduce better than the unleached ones, showing that leaching effectively removes heterogeneously distributed extraneous Pb. However, the reproducibility of repeated digests of variably contaminated natural samples is up to an order of magnitude worse than the analytical reproducibility of ca. 100 ppm. More complex leaching methods (e.g., Nobre Silva et al., 2009) yield Pb isotope ratios within error of and with similar reproducibility to our method, showing that the simple leaching method is reliable. The remaining Pb isotope heterogeneity of natural samples, which typically exceeds 100 ppm, is thus attributed to inherent isotopic sample heterogeneity. Tl-doped MC-ICP-MS Pb ratio determination is therefore a sufficiently precise method for Pb isotope analyses in natural rocks. More precise Pb double- or triple-spike methods (e.g., Galer, 1999; Thirlwall, 2000), may exploit their full potential only in cases where natural isotopic sample heterogeneity is demonstrably negligible. References: Galer, S., 1999, Chem. Geol. 157, 255-274. Nobre Silva, et al. 2009, Geochemistry Geophysics Geosystems 10, Q08012

  6. U-Pb systematics in coexisting zircon, rutile and titanite from granophyres in the Archean Stillwater Complex: metamictization and the fate of radiogenic Pb

    NASA Astrophysics Data System (ADS)

    Friedman, R. M.; Wall, C. J.; Scoates, J. S.; Meurer, W. P.

    2009-12-01

    Self-irradiation of zircon causes structural damage (metamictization) that can result in the loss of radiogenic Pb during interaction with aqueous solutions. To evaluate this behavior in metamict zircon, and in other U-bearing accessory phases like titanite and rutile, we are examining the U-Pb systematics of granophyric rocks from the ca. 2.7 Ga Stillwater layered intrusion, Montana. Four samples were studied in detail, including a pegmatitic ksp-qtz core to a gabbroic pegmatoid in the Lower Banded Series (N1), an alaskite and an amphibole-rich reaction zone between the alaskite and anorthosite (AN1) in the Middle Banded Series, and an amphibole-bearing granophyre from the Upper Banded Series (GN3). Except in the pegmatite, zircon is variably metamict with amorphous zones characterized by distinctive Ca-enrichment. Single zircon grains were analyzed by ID-TIMS following annealing and chemical abrasion, and multi-grain (n=4-5) fractions of titanite and rutile were analyzed by conventional ID-TIMS; the UBC 233-235U-205Pb isotopic tracer is calibrated against mixed U-Pb gravimetric reference solutions made available through the EarthTime initiative. The U-Pb systematics are coherent only for the pegmatite yielding both a Concordia age of 2709.60 ± 0.80 Ma (2σ, including tracer calibration, decay-constant errors not included) for low-U zircon (76-237 ppm) and concordant titanite results with 207Pb/206Pb ages from 2701-2710 Ma. The results for high-U zircon (up to 1438 ppm) for the other three samples are strongly discordant (9-43%, 85-89%, 28-71%, respectively) with a wide range of 207Pb/206Pb ages (2583-2647 Ma, 2210-2357 Ma, 2345-2499 Ma). Given the extreme incompatibility of Pb2+ in zircon and the highly metamict state of zircon in these granophyres, we are investigating the extent to which radiogenic lead is selectively removed during the chemical abrasion and annealing process from step-wise leaching experiments and image analysis (CL, SEM). In contrast

  7. Generation of syntectonic calc-alkaline, magnesian granites through remelting of pre-tectonic igneous sources - U-Pb zircon ages and Sr, Nd and Pb isotope data from the Donkerhoek granite (southern Damara orogen, Namibia)

    NASA Astrophysics Data System (ADS)

    Schwark, L.; Jung, S.; Hauff, F.; Garbe-Schönberg, D.; Berndt, J.

    2018-06-01

    The 541 ± 4 Ma-old magnesian, weakly peraluminous, calc-alkalic Donkerhoek Onanis granite is part of the ca. 6000 km2 large Donkerhoek batholith in the Southern Zone of the Damara orogen of Namibia. Linear major and trace element variations and decreasing MgO, FeO, Al2O3, CaO, K2O, Na2O, Ba and Sr concentrations with increasing SiO2 indicate that this part of the batholith represent a coherent mass and underwent fractional crystallization processes. The Donkerhoek Onanis granites are isotopically evolved (initial εNd: -4.7 to -12.3, initial 87Sr/86Sr: 0.7099-0.7157) with moderately radiogenic Pb isotope ratios (206Pb/204Pb: 17.26-18.22; 207Pb/204Pb: 15.59-15.67; 208Pb/204Pb: 37.60-38.06). Beside heterogeneities imparted by the sources, an evaluation of LREE fractionation and Nd isotope data suggests that AFC processes also modified some samples. Based on the chemical and isotope data, the Donkerhoek Onanis granites cannot be derived by partial melting of Al- and Fe-rich metasedimentary rocks of the Kuiseb formation in which they intruded. Instead, melting of meta-igneous crustal sources with Proterozoic crustal residence ages is more likely. Three igneous to meta-igneous rock suites from the area (Matchless amphibolites, Proterozoic mafic to felsic gneisses from the southern Kalahari craton basement, syn-tectonic Salem granodiorites to granites) are potential sources. An evaluation of chemical and isotope data suggests that remelting of early syn-orogenic Salem-type granites is the most likely process which would also explain the existence of ca. 563 ± 4 Ma-old zircon in the Donkerhoek Onanis granites. Comparison of the Donkerhoek Onanis granites with experimentally derived melt compositions from an intermediate igneous parent indicates temperatures between 800 and 850 °C. It is suggested that the Pan-African igneous activity in this part of the Damara Belt was a moderate-temperature intra-crustal event. Although there are some compositional similarities with

  8. Sr, Nd, and Pb Isotopic Geochemistry of Rhyolites from the Eastern Rhodopes, Bulgaria

    NASA Astrophysics Data System (ADS)

    Ivanova, R.; Kamenov, G. D.; Yanev, Y.

    2002-12-01

    Paleogene Eastern Rhodopes Volcanic Area (ERVA) is part of a more than 2000 km long magmatic belt in SE Europe extending from the Inner Dinarids (West Bosnia-Herzegovina) to Western Anatolia (European Turkey). Volcanic activity occurred during the Late Eocene-Early Oligocene and was spatially related to extensional Paleogene shallow marine basins underlain by a high-grade metamorphic basement. The volcanism is bimodal in character, with minor mafic (basalts) and major intermediate (mainly andesites) to acid (mainly rhyolites) volcanics present in similar volumes. This work focuses on Maritsa volcanic group (36-32 Ma) located in the NE part of the ERVA, S Bulgaria. The volcanic group comprises Lozen volcano composed of dacites, rhyodacites, and rhyolites, St Marina rhyolite dome, and Sheinovets rhyolite dome-cluster located within a caldera with the same name. Measured present day 87Sr/86Sr of the rhyolites range from 0.7075 to 0.7180, however on a plot 87Rb/86Sr vs 87Sr/86Sr the data form an errorchron (MSWD=21) with 30.5 +/-3.6Ma age and 87Sr/86Sr initial equal to 0.7074. Pb isotopic compositions in all of the volcanoes show similar values ranging from 18.712 to 18.768 in 206Pb/204Pb, 15.643 to 15.687 in 207Pb/204Pb, and 38.790 to 38.922 in 208Pb/204Pb. Nd isotopes show also little variations with 143Nd/144Nd ranging from 0.51242 to 0.51249. The similarity in the isotopic compositions between the volcanoes suggests common, homogeneous magmatic source. Crustal origin of the rhyolites as a result of melting of the metamorphic basement is not plausible because the rhyolites have different Sr and Nd isotopic compositions from the gneisses in the ERVA. Sr and Nd isotopic data for the rhyolites differ also from the basalts (i.e. possible mantle melts) in the Eastern Rhodopes region. Rhyolites have higher 87Sr/86Sr and lower 143Nd/144Nd ratios compared to the basalts, thus suggesting involvement of crustal component in the magma generation, most probably the metamorphic

  9. Laser Ablation in situ (U-Th-Sm)/He and U-Pb Double-Dating of Apatite and Zircon: Techniques and Applications

    NASA Astrophysics Data System (ADS)

    McInnes, B.; Danišík, M.; Evans, N.; McDonald, B.; Becker, T.; Vermeesch, P.

    2015-12-01

    We present a new laser-based technique for rapid, quantitative and automated in situ microanalysis of U, Th, Sm, Pb and He for applications in geochronology, thermochronometry and geochemistry (Evans et al., 2015). This novel capability permits a detailed interrogation of the time-temperature history of rocks containing apatite, zircon and other accessory phases by providing both (U-Th-Sm)/He and U-Pb ages (+trace element analysis) on single crystals. In situ laser microanalysis offers several advantages over conventional bulk crystal methods in terms of safety, cost, productivity and spatial resolution. We developed and integrated a suite of analytical instruments including a 193 nm ArF excimer laser system (RESOlution M-50A-LR), a quadrupole ICP-MS (Agilent 7700s), an Alphachron helium mass spectrometry system and swappable flow-through and ultra-high vacuum analytical chambers. The analytical protocols include the following steps: mounting/polishing in PFA Teflon using methods similar to those adopted for fission track etching; laser He extraction and analysis using a 2 s ablation at 5 Hz and 2-3 J/cm2fluence; He pit volume measurement using atomic force microscopy, and U-Th-Sm-Pb (plus optional trace element) analysis using traditional laser ablation methods. The major analytical challenges for apatite include the low U, Th and He contents relative to zircon and the elevated common Pb content. On the other hand, apatite typically has less extreme and less complex zoning of parent isotopes (primarily U and Th). A freeware application has been developed for determining (U-Th-Sm)/He ages from the raw analytical data and Iolite software was used for U-Pb age and trace element determination. In situ double-dating has successfully replicated conventional U-Pb and (U-Th)/He age variations in xenocrystic zircon from the diamondiferous Ellendale lamproite pipe, Western Australia and increased zircon analytical throughput by a factor of 50 over conventional methods

  10. Lead (Pb) isotopic fingerprinting and its applications in lead pollution studies in China: a review.

    PubMed

    Cheng, Hefa; Hu, Yuanan

    2010-05-01

    As the most widely scattered toxic metal in the world, the sources of lead (Pb) observed in contamination investigation are often difficult to identify. This review presents an overview of the principles, analysis, and applications of Pb isotopic fingerprinting in tracing the origins and transport pathways of Pb in the environment. It also summarizes the history and current status of lead pollution in China, and illustrates the power of Pb isotopic fingerprinting with examples of its recent applications in investigating the effectiveness of leaded gasoline phase-out on atmospheric lead pollution, and the sources of Pb found in various environmental media (plants, sediments, and aquatic organisms) in China. The limitations of Pb isotopic fingerprinting technique are discussed and a perspective on its development is also presented. Further methodological developments and more widespread instrument availability are expected to make isotopic fingerprinting one of the key tools in lead pollution investigation. Copyright 2009 Elsevier Ltd. All rights reserved.

  11. Radiogenic Isotopes As Paleoceanographic Tracers in Deep-Sea Corals: Advances in TIMS Measurements of Pb Isotopes and Application to Southern Ocean Corals

    NASA Astrophysics Data System (ADS)

    Wilson, D. J.; van de Flierdt, T.; Bridgestock, L. J.; Paul, M.; Rehkamper, M.; Robinson, L. F.; Adkins, J. F.

    2014-12-01

    Deep-sea corals have emerged as a valuable archive of deep ocean paleoceanographic change, with uranium-series dating providing absolute ages and the potential for centennial resolution. In combination with measurements of radiocarbon, neodymium isotopes and clumped isotopes, this archive has recently been exploited to reconstruct changes in ventilation, water mass sourcing and temperature in relation to millennial climate change. Lead (Pb) isotopes in both corals and seawater have also been used to track anthropogenic inputs through space and time and to trace transport pathways within the oceans. Better understanding of the oceanic Pb cycle is emerging from the GEOTRACES programme. However, while Pb isotopes have been widely used in environmental studies, their full potential as a (pre-anthropogenic) paleoceanographic tracer remains to be exploited. In deep-sea corals, challenges exist from low Pb concentrations in aragonite in comparison to secondary coatings, the potential for contamination, and the efficient elemental separation required for measurement by thermal ionisation mass spectrometry (TIMS). Here we discuss progress in measuring Pb isotopes in coral aragonite using a 207Pb-204Pb double spike on a ThermoFinnigan Triton TIMS. For a 2 ng NIST-981 Pb standard, the long term reproducibility (using 1011 Ω resistors) is ~1000 ppm (2 s.d.) on 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios. We now show that using a new 1012 Ω resistor to measure the small 204Pb beam improves the internal precision on these ratios from ~500 ppm (2 s.e.) to ~250 ppm (2 s.e.) and we envisage a potential improvement in the long term reproducibility as a consequence. We further assess the internal precision and external reproducibility of our method using a BCR-2 rock standard and an in-house coral standard. Preliminary evidence on the application of this method to natural samples is derived from cleaning experiments and replication tests on deep-sea corals from the Southern

  12. Search for extinct natural radioactivity of Pb205 via thallium-isotope anomalies in chondrites and lunar soil.

    NASA Technical Reports Server (NTRS)

    Huey, J. M.; Kohman, T. P.

    1972-01-01

    Thallium and Pb204 contents were determined by stable-isotope-dilution analysis in 16 chondrites, one achondrite, and Apollo 11 and 12 lunar fines. Meteoritic thallium contents vary over a large range, 0.02 to 100 ppb, corresponding to the fact that thallium is a highly fractionated volatile element. Lunar thallium contents are less than 5 ppb. The Tl205/Tl203 ratio was determined in most of the samples, with precision ranging from 0.03% to several percent depending mainly on the amount of thallium present. No variations from the terrestrial ratio were observed. The chondritic isochron slope for Pb205 (13.8-m.y. half-life) is less than or equal to 0.00009 (99% confidence level), corresponding to an interval of at least 60 m.y. and possibly exceeding 120 m.y. between the termination of s-process nucleosynthesis and the lead-thallium fractionations.

  13. The Ellsworth terrane, coastal Maine: Geochronology, geochemistry, and Nd-Pb isotopic composition - Implications for the rifting of Ganderia

    USGS Publications Warehouse

    Schulz, K.J.; Stewart, D.B.; Tucker, R.D.; Pollock, J.C.; Ayuso, R.A.

    2008-01-01

    The Ellsworth terrane is one of a number of fault-bounded blocks that occur along the eastern margin of Ganderia, the western-most of the peri-Gondwanan domains in the northern Appalachians that were accreted to Laurentia in the Paleozoic. Geologic relations, detrital zircon ages, and basalt geochemistry suggest that the Ellsworth terrane is part of Ganderia and not an exotic terrane. In the Penobscot Bay area of coastal Maine, the Ellsworth terrane is dominantly composed of bimodal basalt-rhyolite volcanic sequences of the Ellsworth Schist and unconformably overlying Castine Volcanics. We use new U-Pb zircon geochronology, geochemistry, and Nd and Pb isotopes for these volcanic sequences to constrain the petrogenetic history and paleotectonic setting of the Ellsworth terrane and its relationship with Ganderia. U-Pb zircon geochronology for rhyolites indicates that both the Ellsworth Schist (508.6 ?? 0.8 Ma) and overlying Castine Volcanics (503.5 ?? 2.5 Ma) are Middle Cambrian in age. Two tholefitic basalt types are recognized. Type Tb-1 basalt, present as pillowed and massive lava flows and as sills in both units, has depleted La and Ce ([La/Nd]N = 0.53-0.87) values, flat heavy rare earth element (REE) values, and no positive Th or negative Ta anomalies on primitive mantle-normalized diagrams. In contrast, type Th-2 basalt, present only in the Castine Volcanics, has stightly enriched LREE ([La/Yb]N = 1.42-2.92) values and no Th or Th anomalies. Both basalt types have strongly positive ??Nd (500) values (Th-1 = +7.9-+8.6; Th-2 = +5.6-+7.0) and relatively enriched Pb isotopic compositions (206Ph/204Pb = 18.037-19.784; 207/204Pb = 15.531-15.660; 2088Pb/204Pb = 37.810-38.817). The basalts have compositions transitional between recent normal and enriched mid-ocean-ridge basalt, and they were probably derived by partial melting of compositionatly heterogeneous asthenosphenc mantle. Two types of rhyolite also are present. Type R-1 rhyolite, which mostly occurs as tuffs

  14. 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.

  15. 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

  16. 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.

  17. Linking Barbados Mineral Dust Aerosols to North African Sources Using Elemental Composition and Radiogenic Sr, Nd, and Pb Isotope Signatures

    NASA Astrophysics Data System (ADS)

    Bozlaker, Ayse; Prospero, Joseph M.; Price, Jim; Chellam, Shankararaman

    2018-01-01

    Large quantities of African dust are carried across the Atlantic to the Caribbean Basin and southern United States where it plays an important role in the biogeochemistry of soils and waters and in air quality. Dusts' elemental and isotopic composition was comprehensively characterized in Barbados during the summers of 2013 and 2014, the season of maximum dust transport. Although total suspended insoluble particulate matter (TSIP) mass concentrations varied significantly daily and between the two summers, the abundances (μg element/g TSIP) of 50 elements during "high-dust days" (HDD) were similar. Aerosols were regularly enriched in Na, Cu, Zn, As, Se, Mo, Cd, Sn, Sb, and W relative to the upper continental crust. Enrichment of these elements, many of which are anthropogenically emitted, was significantly reduced during HDD, attributed to mixing and dilution with desert dust over source regions. Generally, Ti/Al, Si/Al, Ca/Al, Ti/Fe, Si/Fe, and Ca/Fe ratios during HDD differed from their respective values in hypothesized North African source regions. Nd isotope composition was relatively invariant for "low-dust days" (LDD) and HDD. In contrast, HDD-aerosols were more radiogenic exhibiting higher 87Sr/86Sr, 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios compared to LDD. Generally, Barbados aerosols' composition ranged within narrow limits and was much more homogeneous than that of hypothesized African source soils. Our results suggest that summertime Barbados aerosols are dominated by a mixture of particles originating from sources in the Sahara-Sahel regions. The Bodélé Depression, long suspected as a major source, appears to be an insignificant contributor of summertime western Atlantic dust.

  18. 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.

  19. Intra-grain Common Pb Correction and Detrital Apatite U-Pb Dating via LA-ICPMS Depth Profiling

    NASA Astrophysics Data System (ADS)

    Boyd, P. D.; Galster, F.; Stockli, D. F.

    2017-12-01

    Apatite is a common accessory phase in igneous and sedimentary rocks. While apatite is widely employed as a low-temperature thermochronometric tool, it has been increasingly utilized to constrain moderate temperature cooling histories by U-Pb dating. Apatite U-Pb is characterized by a thermal sensitivity window of 375-550°C. This unique temperature window recorded by the apatite U-Pb system, and the near-ubiquitous presence of apatite in igneous and clastic sedimentary rocks makes it a powerful tool able to illuminate mid-crustal tectono-thermal processes. However, as apatite incorporates only modest amounts of U and Th (1-10s of ppm) the significant amounts of non-radiogenic "common" Pb incorporated during its formation presents a major hurdle for apatite U-Pb dating. In bedrock samples common Pb in apatite can be corrected for by the measurement of Pb in a cogenetic mineral phase, such as feldspar, that does not incorporate U or from determination of a common Pb composition from multiple analyses in Tera-Wasserburg space. While these methods for common Pb correction in apatite can work for igneous samples, they cannot be applied to detrital apatite in sedimentary rocks with variable common Pb compositions. The obstacle of common Pb in apatite has hindered the application of detrital apatite U-Pb dating in provenance studies, despite the fact that it would be a powerful tool. This study presents a new method for the in situ correction of common Pb in apatite through the utilization of novel LA-ICP-MS depth profiling, which can recover U-Pb ratios at micron-scale spatial resolution during ablation of a grain. Due to the intra-grain U variability in apatite, a mixing line for a single grain can be generated in Tera-Wasserburg Concordia space. As a case study, apatite from a Variscan alpine granite were analyzed using both the single and multi-grain method, with both methods giving identical results. As a second case study the intra-grain method was then performed

  20. Reverse isotope dilution method for determining benzene and metabolites in tissues

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

    Bechtold, W.E.; Sabourin, P.J.; Henderson, R.F.

    1988-07-01

    A method utilizing reverse isotope dilution for the analysis of benzene and its organic soluble metabolites in tissues of rats and mice is presented. Tissues from rats and mice that had been exposed to radiolabeled benzene were extracted with ethyl acetate containing known, excess quantities of unlabeled benzene and metabolites. Butylated hydroxytoluene was added as an antioxidant. The ethyl acetate extracts were analyzed with semipreparative reversed-phase HPLC. Isolated peaks were collected and analyzed for radioactivity (by liquid scintillation spectrometry) and for mass (by UV absorption). The total amount of each compound present was calculated from the mass dilution of themore » radiolabeled isotope. This method has the advantages of high sensitivity, because of the high specific activity of benzene, and relative stability of the analyses, because of the addition of large amounts of unlabeled carrier analogue.« less

  1. Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

    PubMed

    Chew, Gina; Walczyk, Thomas

    2013-04-02

    Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

  2. 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

  3. 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.

  4. A Modern Analog to the Depositional Age Problem: Zircon and Apatite Fission Track and U-Pb Age Distributions by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Donelick, H. M.; Donelick, M. B.; Donelick, R. A.

    2012-12-01

    Sand from three river systems in North Idaho (Snake River near Lewiston, Clearwater River near Lewiston and the Salmon River near White Bird) and two regional ash fall events (Mt. Mazama and Mt. St. Helens) were collected for zircon U-Pb detrital age analysis. Up to 120 grains of zircon per sample were ablated using a Resonetics M-50 193 nm ArF Excimer laser ablation (LA) system and the Pb, Th, and U isotopic signals were quantified using an Agilent 7700x quadrupole inductively coupled plasma-mass spectrometer (ICP-MS). Isotopic signals for major, minor, and trace elements, including all REEs, were also monitored. The youngest zircon U-Pb ages from the river samples were approximately 44 Ma; Cenozoic Idaho Batholith and Precambrian Belt Supergroup ages were well represented. Significant common Pb contamination of the Clearwater River sample (e.g., placer native Cu was observed in the sample) precluded detailed analysis of the zircon U-Pb ages but no interpretable ages <44 Ma were observed. Interestingly, not one of the river samples yielded zircon U-Pb ages near 0 Ma, despite all three catchment areas having received significant ash from Mt. St. Helens in 1980, and Mount Mazama 7,700 years ago, and no doubt other events during the Quaternary. Work currently in progress seeks to address bias against near 0 Ma ages in the catchment areas due to: a) small, local ash fall grain sizes and b) overwhelming number of older grains relative to the ash fall grains. Data from Mt. St. Helens ash from several localities near the mountain (Toutle River and Maple Flats, WA) and several far from the mountain (Spokane, WA; Princeton, ID; Kalispell, MT) and Mt. Mazama ash fall deposits near Lewiston, ID and Spokane, WA will be presented to address these possibilities. Additionally, fission track and U-Pb ages from apatites collected from these river and ash fall samples will also be shown to help constrain the problem.

  5. 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.

  6. U-Pb ID-TIMS zircon ages of TTG gneisses of the Aravalli Craton of India

    NASA Astrophysics Data System (ADS)

    Chauhan, Hiredya; Saikia, Ashima; Kaulina, Tatiana; Bayanova, Tamara; Ahmad, Talat

    2015-04-01

    The crystalline basement of the Aravalli Craton is a heterogeneous assemblage dominated by granitic gneisses and granites with sporadic occurrences of amphibolites and dismembered sedimentary enclaves (Upadhyaya et al., 1992). This assemblage is known to have experienced multiple deformation and metamorphic events followed by emplacement of voluminous granites and basaltic dykes. Based on Sm-Nd whole rock data on the basement Mewar orthogneisses of Jhamarkotra region (Gopalan et al., 1990) and Pb/Pb ages of zircon from Gingla Granites which intrudes the basement (Wiedenbeck et al., 1996), it has been inferred that the whole magmatic episode leading to the formation of the basement spanned from 3300 to 2400 Ma and that the Aravalli cratonic block had broadly stabilized by 2500 Ma on which the younger Aravalli and Delhi Supergroup unconformably deposited. However, no comprehensive age data on the basement gneisses from the study area spanning the entire magmatic episode is available. This work attempts to provide a time frame work for evolution of the basement gneisses of the Aravalli Craton. We present here U-Pb zircon ages from the Precambrian basement TTG gneisses of the Aravalli Craton of north western India. Pb and U were measured on multicollector Finnigan-MAT 262 mass spectrometer. The temperatures of measurements were 1300°C for Pb and 1500°C for U. Pb isotope ratios were corrected for mass fractionation with a factor of 0.10% per amu, based on repeat analyses of the standard NBS SRM 982. The U analyses were corrected for mass fractionation with a factor of 0.003% per amu, based on repeat analyses of the NBS U 500 standard. Reproducibility of the U-Pb ratios was determined from the repeated analysis of standard zircon IGFM-87 (Ukraine) and taken as 0.5% for 207Pb/235U and 206Pb/238U ratios, respectively, at 95% confidence level. All calculations were done using the programs PBDAT and ISOPLOT (Ludwig 1991, 2008). Four zircon fractions corresponding to four

  7. Mesozoic magmatism and timing of epigenetic Pb-Zn-Ag mineralization in the western Fortymile mining district, east-central Alaska: Zircon U-Pb geochronology, whole-rock geochemistry, and Pb isotopes

    USGS Publications Warehouse

    Dusel-Bacon, Cynthia; Aleinkoff, J.N.; Day, W.C.; Mortensen, J.K.

    2015-01-01

    Epigenetic Pb-Zn-Ag ± Cu prospects in the western Fortymile district are spatially associated with splays of the northeast-trending Kechumstuk sinistral-normal fault zone and with ca. 68-66 Ma felsic intrusions and dikes. The similarity between Pb isotope compositions of feldspars from the Late Cretaceous igneous bodies and sulfides from the epithermal prospects suggests a Late Cretaceous age for most of the mineralization. Fluid flow along the faults undoubtedly played a major role in mineralization. We interpret displacement on the northeast-trending faults to be a far-field effect of dextral translation along Late Cretaceous plate-scale boundaries and faults that were roughly parallel to the subsequently developed Denali and Tintina fault systems, which currently bound the region.

  8. Uranium 238U/235U isotope ratios as indicators of reduction: Results from an in situ biostimulation experiment at Rifle, Colorado, USA

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

    Bopp IV, C.J.; Lundstrom, C.C.; Johnson, T.M.

    2010-02-01

    The attenuation of groundwater contamination via chemical reaction is traditionally evaluated by monitoring contaminant concentration through time. However, this method can be confounded by common transport processes (e.g. dilution, sorption). Isotopic techniques bypass the limits of concentration methods, and so may provide improved accuracy in determining the extent of reaction. We apply measurements of {sup 238}U/{sup 235}U to a U bioremediation field experiment at the Rifle Integrated Field Research Challenge Site in Rifle, Colorado (USA). An array of monitoring and injection wells was installed on a 100 m{sup 2} plot where U(VI) contamination was present in the groundwater. Acetate-amended groundwatermore » was injected along an up-gradient gallery to encourage the growth of dissimilatory metal reducing bacteria (e.g. Geobacter species). During amendment, U concentration dropped by an order of magnitude in the experiment plot. We measured {sup 238}U/{sup 235}U in samples from one monitoring well by MC-ICP-MS using a double isotope tracer method. A significant {approx}1.00{per_thousand} decrease in {sup 238}U/{sup 235}U occurred in the groundwater as U(VI) concentration decreased. The relationship between {sup 238}U/{sup 235}U and concentration corresponds approximately to a Rayleigh distillation curve with an effective fractionation factor ({alpha}) of 1.00046. We attribute the observed U isotope fractionation to a nuclear field shift effect during enzymatic reduction of U(VI){sub (aq)} to U(IV){sub (s)}.« less

  9. Enhanced Continental Weathering on Antarctica During the Mid Miocene Climatic Optima Based on Pb Isotopes

    NASA Astrophysics Data System (ADS)

    Martin, E. E.; Fenn, C.; Basak, C.

    2012-12-01

    Feedbacks between climate and continental weathering can be monitored over geologic time scales using Pb isotopes preserved in marine sediments. During chemical weathering, radiogenic Pb is preferentially released to the dissolved phase, producing weathering solutions with more radiogenic isotopic values than the parent rock. The offset between the composition of the solution and rock tend to increase with the intensity of incongruent weathering (von Blanckenburg and Nägler, 2001; Harlavan and Erel, 2002). The seawater isotopic signal extracted from Fe-Mn oxides on bulk marine sediments is interpreted to represent the composition of local dissolved weathering inputs. For example, increasing seawater Pb isotopes observed during the most recent deglaciation are believed to reflect enhanced weathering of newly exposed glacial rock flour under warm conditions (Foster and Vance, 2006; Kurzweil et al., 2010). For this study we evaluated Nd and Pb isotopes from both the seawater fraction (extracted from Fe-Mn oxides) and parent rock (the detrital fraction of marine sediment) during the Mid-Miocene Climatic Optimum (MMCO) and subsequent cooling and East Antarctic Ice Sheet (EAIS) expansion (18 to 8 Ma) from Ocean Drilling Program site 744 on Kerguelen Plateau (2300 m; Indian sector) and sites 689 and 690 on Maud Rise (2080 m and 2914 m; Atlantic sector). The absolute value of seawater 206Pb/204Pb and separation between values for seawater and detrital fractions increased during the MMCO, suggesting enhanced weathering in proglacial and deglaciated areas exposed by ice sheet meltback during the warm interval. During the ensuing cooling, seawater values and the offset between the two archives decreased. Similar trends are displayed by 207Pb/204Pb and 208Pb/204Pb, although 207Pb/204Pb detrital values tend to be higher than seawater values. Reconstructions of atmospheric pCO2 in the Miocene have suggested both 1) decoupling between pCO2 and climate with consistently low

  10. U-Pb Geochronology and Hf-isotope constrains on Formation of Archaean Crust From the Lewisian of NW Scotland, Great Britain

    NASA Astrophysics Data System (ADS)

    Crowley, Q. G.; Noble, S. R.; Key, R.

    2006-12-01

    The Lewisian complex of NW Scotland is dominantly composed of Archaean tonalitic to granodioritic gneisses, ultramafic bodies and minor metasedimentary components. Although the area is internationally well known and has been much studied for over a century, the precise timing of crustal forming events has proven difficult to ascertain. We present data from both in-situ laser ablation (LA) ICP-MS and an adaptation of a new U-Pb chemical abrasion ID-TIMS technique (Mattinson 2006) applied to multi-age component zircons from the Assynt block of this region. The new data reveal a previously unrecognised complexity and provide the first unequivocal proof of an Archean metamorphic event in the area. In a wider context the data also elucidate some of the processes involved in early global crust formation and plate tectonic events. In-situ LA-ICPMS U-Pb dating has indicated a ca 2.8Ga protolith age for a tonalite gneiss with evidence for a ca. 3.6Ga xenocrystic component (the oldest discovered in the UK). Non-conventional U-Pb ID-TIMS utilising a combination of high-temperature annealing followed by multi-step incremental dissolution on single grains has dated zircon growth at ca 2.7Ga (Badcallian) and 2.5Ga (Inverian) with later Pb-loss occurring at ca 1.9Ga and ca 1.7Ga (early and late Laxfordian respectively). This latter method combines a pseudo-spatial resolution normally associated with an in-situ technique but benefits from the high-precision analysis of ID-TIMS. Zircon Hf isotopes indicate that some rocks from the Assynt area are typical of Archaean continental crust (epsilon Hf ca -1. The tonalite gneisses however have strongly negative epsilon Hf values of -7 to -10 indicating a more complex history of derivation through partial melting of ancient crust with residual garnet as a long- lived control on Hf. Archaean events at ca. 3.6Ga, ca 2.8Ga and ca 2.7Ga have also been recorded in west Greenland (e.g. Mojzsis & Harrison 1999, Richards and Appel, 1987

  11. Emeishan volcanism and the end-Guadalupian extinction: New U-Pb TIMS ages

    NASA Astrophysics Data System (ADS)

    Mundil, Roland; Denyszyn, Steve; He, Bin; Metcalfe, Ian; Yigang, Xu

    2010-05-01

    High-resolution geochronology with an age resolution at the permil level is instrumental in testing proposed causal links between continental-scale, short-term volcanic events and environmental crises that affect life globally. Synchroneity with large-scale volcanic events has been shown for three of the five most severe extinctions, namely the end-Permian extinction coinciding with Siberian Trapp volcanism, the end-Triassic extinction with Central Atlantic Magmatic Province) volcanism and the end-Cretaceous with Deccan Trapp volcanism. Recent studies also show that the magnitude of the extinction is not solely a function of the size (volume) of the volcanic event but more importantly of the eruption rate and also the nature of the host rock that is intruded, and the resulting reactions and release of gases that can affect climate. The end-Guadalupian (end Middle Permian, ca 260 Ma) biotic crisis has traditionally not been included in the 'big five' mass extinctions, possibly because of its close proximity in time to the end-Permian event, although its magnitude (in terms of total extinction rate) is comparable to the three most severe extinctions (end-Ordovician, end-Permian, end-Cretaceous). As a result, research of the end-Guadalupian event has so far been neglected and its timing as well as the temporal relation to the Emeishan volcanic province in western China is as yet not fully studied. Geochronological data are so far mostly based on ambiguous 40Ar/39Ar analyses of commonly altered basaltic products and U-Pb zircon analyses on felsic products using micro-beam techniques that typically result in radio-isotopic ages with percent-level uncertainty, and thus insufficient for high-resolution correlations of events. In addition, no precise and accurate radio-isotopic data exist from this time period so that evolutionary events (extinction and recovery) on land and in the ocean are notoriously difficult to correlate though biostratigraphic records are available

  12. 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

  13. Multiple enrichment of the Carpathian-Pannonian mantle: Pb-Sr-Nd isotope and trace element constraints

    NASA Astrophysics Data System (ADS)

    Rosenbaum, Jeffrey M.; Wilson, Marjorie; Downes, Hilary

    1997-07-01

    Pb isotope compositions of acid-leached clinopyroxene and amphibole mineral separates from spinel peridotite mantle xenoliths entrained in Tertiary-Quaternary alkali basalts from the Carpathian-Pannonian Region of eastern Europe provide important constraints on the processes of metasomatic enrichment of the mantle lithosphere in an extensional tectonic setting associated with recent subduction. Principal component analysis of Pb-Sr-Nd isotope and rare earth element compositions of the pyroxenes is used to identify the geochemical characteristics of the original lithospheric mantle protolith and a spectrum of infiltrating metasomatic agents including subduction-related aqueous fluids and silicate melts derived from a subduction-modified mantle wedge which contains a St. Helena-type (HIMU) plume component. The mantle protolith is highly depleted relative to mid-ocean ridge basalt-source mantle with Pb-Nd-Sr isotope compositions consistent with an ancient depletion event. Silicate melt infiltration into the protolith accounts for the primary variance in the Pb-Sr-Nd isotope compositions of the xenoliths and has locally generated metasomatic amphibole. Infiltration of aqueous fluids has introduced radiogenic Pb and Sr without significantly perturbing the rare earth element signature of the protolith. The Pb isotope compositions of the fluid-modified xenoliths suggest that they reacted with aqueous fluids released from a subduction zone which had equilibrated with sediment derived from an ancient basement terrain. We propose a model for mantle lithosphere evolution consistent with available textural and geochemical data for the xenolith population. The Pb-Sr-Nd isotope compositions of both alkaline mafic magmas and rare, subduction-related, calc-alkaline basaltic andesites from the region provide important constraints for the nature of the asthenospheric mantle wedge and confirm the presence of a HIMU plume component. These silicate melts contribute to the metasomatism

  14. U-Th-Pb systematics of the Estherville mesosiderite

    NASA Technical Reports Server (NTRS)

    Brouxel, M.; Tatsumoto, M.

    1990-01-01

    Results are presented on a detailed U-Th-Pb systematics of the Estherville mososiderite, which was performed in a study involving stepwise leaching experiments. The Pb-Pb internal 'isochrons' for Estherville yielded ages of 4556 + or - 35 Ma, 4506 + or - 75 Ma, and 4422 + or - 50 Ma, indicating that the silicate fraction of the Estherville mesosiderite is very heterogeneous and was formed early in the solar system history. Results clearly identifies the Pb-Pb isochron as a mixing line. The U-Pb lower-intercept ages could be divided into two groups: (1) around 3 Ga, and likely related to the 3.6 Ga heating event, and (2) close to 0 Ma and to 62 Ma.

  15. 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

  16. Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region.

    PubMed

    Sharpe, Ashley E; Kamenov, George D; Gilli, Adrian; Hodell, David A; Emery, Kitty F; Brenner, Mark; Krigbaum, John

    2016-01-01

    We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region.

  17. Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region

    PubMed Central

    Kamenov, George D.; Gilli, Adrian; Hodell, David A.; Emery, Kitty F.; Brenner, Mark; Krigbaum, John

    2016-01-01

    We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region. PMID:27806065

  18. Seawater and Detrital Marine Pb Isotopes as Monitors of Antarctic Weathering Following Ice Sheet Development

    NASA Astrophysics Data System (ADS)

    Fenn, C.; Martin, E. E.; Basak, C.

    2011-12-01

    Comparisons of seawater and detrital Pb isotopes from sites proximal to Antarctica at the Eocene/Oligocene transition (EOT) are being used to understand variations in continental weathering associated with the development of the East Antarctic Ice Sheet (EAIS). Previous work has shown that seawater and detrital archives yield similar isotopic values during Eocene warmth, which is interpreted to record congruent chemical weathering of the continent. In contrast, distinct isotopic values for the two phases at the EOT represents increased incongruent mechanical weathering during growth of the ice sheet. For this study we expanded beyond the initial glaciation at the EOT to determine whether less dramatic changes in ice volume and climate also produce variations in weathering and intensity that are recorded by seawater and detrital Pb isotopes. We collected Nd and Pb isotope data from extractions of Fe-Mn oxide coatings of bulk decarbonated marine sediments, which preserve seawater isotopic values, and from complete dissolutions of the remaining silicate fraction for Ocean Drilling Program Site 748 on Kerguelen Plateau (1300 m modern water depth). The data spans an interval of deglaciation from ~23.5-27 Ma documented by δ18O that has been equated to a ~30% decrease in ice volume on Antarctica (Pekar and Christie-Blick, 2008, Palaeogeogr., Palaeoclim., Palaeoecol.). Initial results from Site 748 include the first ɛNd values for intermediate waters in the Oligocene Southern Ocean and reveal a value of ~-8 over the entire 3.5 my interval, which is consistent with values reported for deep Indian Ocean sites at this time and similar to deeper Southern Ocean sites. Corresponding detrital ɛNd values are less radiogenic and decrease from -9 to -13 during the study interval. Detrital 206Pb/204Pb values also decrease during the warming interval, while seawater 206Pb/204Pb values increase. The decrease in detrital values indicates the composition of source materials entering

  19. Quantitative assessment of Pb sources in isotopic mixtures using a Bayesian mixing model.

    PubMed

    Longman, Jack; Veres, Daniel; Ersek, Vasile; Phillips, Donald L; Chauvel, Catherine; Tamas, Calin G

    2018-04-18

    Lead (Pb) isotopes provide valuable insights into the origin of Pb within a sample, typically allowing for reliable fingerprinting of their source. This is useful for a variety of applications, from tracing sources of pollution-related Pb, to the origins of Pb in archaeological artefacts. However, current approaches investigate source proportions via graphical means, or simple mixing models. As such, an approach, which quantitatively assesses source proportions and fingerprints the signature of analysed Pb, especially for larger numbers of sources, would be valuable. Here we use an advanced Bayesian isotope mixing model for three such applications: tracing dust sources in pre-anthropogenic environmental samples, tracking changing ore exploitation during the Roman period, and identifying the source of Pb in a Roman-age mining artefact. These examples indicate this approach can understand changing Pb sources deposited during both pre-anthropogenic times, when natural cycling of Pb dominated, and the Roman period, one marked by significant anthropogenic pollution. Our archaeometric investigation indicates clear input of Pb from Romanian ores previously speculated, but not proven, to have been the Pb source. Our approach can be applied to a range of disciplines, providing a new method for robustly tracing sources of Pb observed within a variety of environments.

  20. Precise U-Pb Zircon Constraints on the Earliest Magmatic History of the Carolina Terrane.

    PubMed

    Wortman; Samson; Hibbard

    2000-05-01

    The early magmatic and tectonic history of the Carolina terrane and its possible affinities with other Neoproterozoic circum-Atlantic arc terranes have been poorly understood, in large part because of a lack of reliable geochronological data. Precise U-Pb zircon dates for the Virgilina sequence, the oldest exposed part, constrain the timing of the earliest known stage of magmatism in the terrane and of the Virgilina orogeny. A flow-banded rhyolite sampled from a metavolcanic sequence near Chapel Hill, North Carolina, yielded a U-Pb zircon date of 632.9 +2.6/-1.9 Ma. A granitic unit of the Chapel Hill pluton, which intrudes the metavolcanic sequence, yielded a nearly identical U-Pb zircon date of 633 +2/-1.5 Ma, interpreted as its crystallization age. A felsic gneiss and a dacitic tuff from the Hyco Formation yielded U-Pb zircon dates of 619.9 +4.5/-3 Ma and 615.7 +3.7/-1.9 Ma, respectively. Diorite and granite of the Flat River complex have indistinguishable U-Pb upper-intercept dates of 613.9 +1.6/-1.5 Ma and 613.4 +2.8/-2 Ma. The Osmond biotite-granite gneiss, which intruded the Hyco Formation before the Virgilina orogeny, crystallized at 612.4 +5.2/-1.7 Ma. Granite of the Roxboro pluton, an intrusion that postdated the Virgilina orogeny, yielded a U-Pb upper intercept date of 546.5 +3.0/-2.4 Ma, interpreted as the time of its crystallization. These new dates both provide the first reliable estimates of the age of the Virgilina sequence and document that the earliest known stage of magmatism in the Carolina terrane had begun by 633 +2/-1.5 Ma and continued at least until 612.4 +5.2/-1.7 Ma, an interval of approximately 25 m.yr. Timing of the Virgilina orogeny is bracketed between 612.4 +5.2/-1.7 Ma and 586+/-10 Ma (reported age of the upper Uwharrie Formation). The U-Pb systematics of all units studied in the Virgilina sequence are simple and lack any evidence of an older xenocrystic zircon component, which would indicate the presence of a continental

  1. Coupled Hf-Nd-Pb isotope co-variations of HIMU oceanic island basalts from Mangaia, Cook-Austral islands, suggest an Archean source component in the mantle transition zone

    NASA Astrophysics Data System (ADS)

    Nebel, Oliver; Arculus, Richard J.; van Westrenen, Wim; Woodhead, Jon D.; Jenner, Frances E.; Nebel-Jacobsen, Yona J.; Wille, Martin; Eggins, Stephen M.

    2013-07-01

    Although it is widely accepted that oceanic island basalts (OIB) sample geochemically distinct mantle reservoirs including recycled oceanic crust, the composition, age, and locus of these reservoirs remain uncertain. OIB with highly radiogenic Pb isotope signatures are grouped as HIMU (high-μ, with μ = 238U/204Pb), and exhibit unique Hf-Nd isotopic characteristics, defined as ΔɛHf, deviant from a terrestrial igneous rock array that includes all other OIB types. Here we combine new Hf isotope data with previous Nd-Pb isotope measurements to assess the coupled, time-integrated Hf-Nd-Pb isotope evolution of the most extreme HIMU location (Mangaia, French Polynesia). In comparison with global MORB and other OIB types, Mangaia samples define a unique trend in coupled Hf-Nd-Pb isotope co-variations (expressed in 207Pb/206Pb vs. ΔɛHf). In a model employing subducted, dehydrated oceanic crust, mixing between present-day depleted MORB mantle (DMM) and small proportions (˜5%) of a HIMU mantle endmember can re-produce the Hf-Nd-Pb isotope systematics of global HIMU basalts (sensu stricto; i.e., without EM-1/EM-2/FOZO components). An age range of 3.5 to <2 Ga is required for HIMU endmember(s) that mix with DMM to account for the observed present-day HIMU isotope compositions, suggesting a range of age distributions rather than a single component in the mantle. Our data suggest that mixing of HIMU mantle endmembers and DMM occurs in the mantle transition zone by entrainment in secondary plumes that rise at the edge of the Pacific Large Low Seismic Velocity Zone (LLSVP). These create either pure HIMU (sensu stricto) or HIMU affected by other enriched mantle endmembers (sensu lato). If correct, this requires isolation of parts of the mantle transition zone for >3 Gyr and implies that OIB chemistry can be used to test geodynamic models.

  2. Reference measurements for total mercury and methyl mercury content in marine biota samples using direct or species-specific isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Krata, Agnieszka; Vassileva, Emilia; Bulska, Ewa

    2016-11-01

    The analytical procedures for reference measurements of the total Hg and methyl mercury (MeHg) mass fractions at various concentration levels in marine biota samples, candidates for certified reference materials (oyster and clam Gafrarium tumidum), were evaluated. Two modes of application of isotope dilution inductively coupled plasma mass spectrometry method (ID ICP-MS), namely direct isotope dilution and species-specific isotope dilution analysis with the use of two different quantification mass spectrometry techniques were compared. The entire ID ICP-MS measurement procedure was described by mathematical modelling and the combined uncertainty of measurement results was estimated. All factors influencing the final results as well as isotopic equilibrium were systematically investigated. This included the procedural blank, the moisture content in the biota samples and all factors affecting the blend ratio measurements (instrumental background, spectral interferences, dead time and mass discrimination effects as well as the repeatability of measured isotopic ratios). Modelling of the entire measurement procedures and the use of appropriate certified reference materials enable to assure the traceability of obtained values to the International System of Units (SI): the mole or the kilogram. The total mass fraction of mercury in oyster and clam biota samples, after correction for moisture contents, was found to be: 21.1 (1.1) 10(-9) kg kg(-1) (U =5.1% relative, k=2) and 390.0 (9.4) 10(-9) kg kg(-1) (U=2.4% relative, k=2), respectively. For the determination of mercury being present as methyl mercury, the non-chromatographic separation on anion-exchange resin AG1-X8 of the blended samples was applied. The content of MeHg (as Hg) in oyster sample was found: 4.81 (24) 10(-9)kgkg(-1) (U=5.0%, k=2) and 4.84 (21) 10(-9)kgkg(-1) (U=4.3%, k=2) with the use of quadrupole (ICP QMS) or sector field (ICP SFMS) inductively coupled plasma mass spectrometers, respectively. In the

  3. A novel technique to determine cobalt exchangeability in soils using isotope dilution.

    PubMed

    Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

    2008-01-01

    The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.

  4. Using Pb isotopes in surface media to distinguish anthropogenic sources from undercover uranium sources

    NASA Astrophysics Data System (ADS)

    Kyser, Kurt; Lahusen, Larry; Drever, Garth; Dunn, Colin; Leduc, Evelyne; Chipley, Don

    2015-09-01

    The response in elemental concentrations and Pb isotopes in various surface media from the Cigar West unconformity-type uranium deposit located at a depth of 450 m were measured to ascertain if element migration from the deposit can be detected at the surface. The media included clay-size fractions separated from the A2, B and C soil horizons, and tree cores and twigs from black spruce (Picea mariana) and jack pine (Pinus banksiana) trees. Lead isotopes were used to trace any effect on the surface media from the deposit at depth because the 207Pb/206Pb ratios in the ore are < 0.1, whereas the background values in the basin are > 0.7 and modern anthropogenic Pb from aerosols are near 0.9. The tree cores record their lowest and therefore most radiogenic 207Pb/206Pb ratios of < 0.7 near the surface projection of the deposit and associated structures, particularly in tree rings that predate any exploration and drilling activity in the area. The median 207Pb/206Pb ratios increase in the order C, B soil horizon clays, tree cores, A2 soil clays and twigs because of the increasing contribution of common Pb with high ratios from anthropogenic sources that affect the shallowest media the most. Although this anthropogenic Pb as well as that from the background dominates the composition of all media at the surface and the contribution from the deposit at depth is diminished toward the surface, ore-related Pb is still present as a few percent of the composition of pathfinder elements and Pb isotopes.

  5. Quantitative Mass Spectrometry by Isotope Dilution and Multiple Reaction Monitoring (MRM).

    PubMed

    Russo, Paul; Hood, Brian L; Bateman, Nicholas W; Conrads, Thomas P

    2017-01-01

    Selected reaction monitoring (SRM) is used in molecular profiling to detect and quantify specific known proteins in complex mixtures. Using isotope dilution (Barnidge et al., Anal Chem 75(3):445-451, 2003) methodologies, peptides can be quantified without the need for an antibody-based method. Selected reaction monitoring assays employ electrospray ionization mass spectrometry (ESI-MS) followed by two stages of mass selection: a first stage where the mass of the peptide ion is selected and, after fragmentation by collision-induced dissociation (CID), a second stage (tandem MS) where either a single (e.g., SRM) or multiple (multiple reaction monitoring, MRM) specific peptide fragment ions are transmitted for detection. The MRM experiment is accomplished by specifying the parent masses of the selected endogenous and isotope-labeled peptides for MS/MS fragmentation and then monitoring fragment ions of interest, using their intensities/abundances and relative ratios to quantify the parent protein of interest. In this example protocol, we will utilize isotope dilution MRM-MS to quantify in absolute terms the total levels of the protein of interest, ataxia telangiectasia mutated (ATM) serine/threonine protein kinase. Ataxia telangiectasia mutated (ATM) phosphorylates several key proteins that initiate activation of the DNA damage checkpoint leading to cell cycle arrest.

  6. On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials.

    PubMed

    Fernández, Beatriz; Rodríguez-González, Pablo; García Alonso, J Ignacio; Malherbe, Julien; García-Fonseca, Sergio; Pereiro, Rosario; Sanz-Medel, Alfredo

    2014-12-03

    We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6-21% for pressed pellets and 3-21% for fused solids were obtained from n=3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Isotopic evidence of spatial magnitude of the Pb deposition near a lead smelter

    NASA Astrophysics Data System (ADS)

    Flament, P.; Franssens, M.; Debout, K.; Weis, D.

    2003-05-01

    In order to détermine the dry deposition of lead around a Pb-Zn refinery, two cross-sectional sampling experiments, using deposition plates, have been performed on a daiiy basis, ucder representative meteorological situations (north-easterly and south-westerly winds). The amount of lead deposited as well as its isotopic composition (expressed by the ^{206}Pb/^{207}Pb ratio) are systematically measured. For a daily production of approximately 670 metric tons of (Pb+Zn) the dry fallout, greater than 1000 μg Pb.h^{-1}.m^{-2} on the edge of the plant, falls to about 100 μg Pb.h^{-1}.m^{-2}, four kilometres away from the refinery. This value is still ten times higher than th urban background (<10 μg Pb.h^{-1}.m^{-2}). The spatial extension of the dry deposition plume is evidenced by the evolution of the isotopic signature of the refinery (1.10<^{206}Pb/^{207}), clearly distinct from the urban backgrounde signature (1.15<^{206}Pb/^{207}Pb<1.16). As a first estimate, the extension of the deposition plume seems not to be linked to the wind speed. At the opposite, diffuse emissions from slag heaps are related to this parameter.

  8. U-Th-Pb, Sm-Nd, Rb-Sr, and Lu-Hf systematics of returned Mars samples

    NASA Technical Reports Server (NTRS)

    Tatsumoto, M.; Premo, W. R.

    1988-01-01

    The advantage of studying returned planetary samples cannot be overstated. A wider range of analytical techniques with higher sensitivities and accuracies can be applied to returned samples. Measurement of U-Th-Pb, Sm-Nd, Rb-Sr, and Lu-Hf isotopic systematics for chronology and isotopic tracer studies of planetary specimens cannot be done in situ with desirable precision. Returned Mars samples will be examined using all the physical, chemical, and geologic methods necessary to gain information on the origin and evolution of Mars. A returned Martian sample would provide ample information regarding the accretionary and evolutionary history of the Martian planetary body and possibly other planets of our solar system.

  9. 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.

  10. 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.

  11. Fluid/rock Interaction History of a Faulted Rhyolite-Granite Contact Determined by Sr- Pb-Isotopes, Th/U-Disequilibria and Elemental Distributions (Eastern Rhine Graben Shoulder, SW-Germany)

    NASA Astrophysics Data System (ADS)

    Marbach, T.; Mangini, A.; Kober, B.; Schleicher, A.; Warr, L. N.

    2003-04-01

    Major and trace element analyses allow to obtain information concerning the chemical changes induced by alteration. Differences are partly petrographic because the profile crosses the granite-rhyolite contact, but they are also due to different alteration levels induced by fluid circulation along the fault system which has drained the alteration processes. The granite-rhyolite contact constitutes the primary structure. Only the most incompatible elements (Si, Al, Zr, Hf) retain their original signatures and reflect a mixing between typical granite and rhyolite lithologies across the altered zones (cataclasite). The more mobile elements show a different composition within the altered zones (cataclasite) notably a high leaching of cations. The geochemical tracers also suggest at least one strong hydrothermal event with reducing conditions in the altered zones. The isotopic analyses delivered qualitative and temporal information. The use of several isotopic systems, Rb/Sr-, U/Pb-isotopes and Th/U disequilibria, reveals a complex history of polyphase fluid/rock interaction following the Permian volcanic extrusion, showing notable disturbances during the late Jurassic hydrothermal activities, the Tertiary rifting of the Rhine Graben and more recent Quaternary alteration. The granite zone of the sampling profile has underwent an event which set up a new Rb-Sr isotopic composition and reset the Rb/Sr system which originatly corresponded to the Carboniferous intrusion ages. The Rb-Sr data of the granite samples produce a whole rock isochron of 152 ± 5,7 Ma (2σ error) in good agreement with the well-known late Jurassic hydrothermal event (135--160 Ma). The rocks evolution lines for Pb support a Tertiary hydrothermal event (54 Ma ± 16; 1σ error), potentially connected with the development of the Rhine Graben. The profile samples have undergone uranium and thorium redistribution processes which have occurred within the last ˜10^6 years. The samples of the altered zones

  12. Trace elements and Pb isotopes in soils and sediments impacted by uranium mining.

    PubMed

    Cuvier, A; Pourcelot, L; Probst, A; Prunier, J; Le Roux, G

    2016-10-01

    The purpose of this study is to evaluate the contamination in As, Ba, Co, Cu, Mn, Ni, Sr, V, Zn and REE, in a high uranium activity (up to 21,000Bq∙kg(-1)) area, downstream of a former uranium mine. Different geochemical proxies like enrichment factor and fractions from a sequential extraction procedure are used to evaluate the level of contamination, the mobility and the availability of the potential contaminants. Pb isotope ratios are determined in the total samples and in the sequential leachates to identify the sources of the contaminants and to determine the mobility of radiogenic Pb in the context of uranium mining. In spite of the large uranium contamination measured in the soils and the sediments (EF≫40), trace element contamination is low to moderate (2Pb enrichment is highlighted, the Pb isotopic signature of the contaminated soils is strongly radiogenic. Measurements performed on the sequential leachates reveal inputs of radiogenic Pb in the most mobile fractions of the contaminated soil. Inputs of low-mobile radiogenic Pb from mining activities may also contribute to the Pb signature recorded in the residual phase of the contaminated samples. We demonstrate that Pb isotopes are efficient tools to trace the origin and the mobility of the contaminants in environments affected by uranium mining. Copyright © 2016. Published by Elsevier B.V.

  13. Lead exposure in raptors from Japan and source identification using Pb stable isotope ratios.

    PubMed

    Ishii, Chihiro; Nakayama, Shouta M M; Ikenaka, Yoshinori; Nakata, Hokuto; Saito, Keisuke; Watanabe, Yukiko; Mizukawa, Hazuki; Tanabe, Shinsuke; Nomiyama, Kei; Hayashi, Terutake; Ishizuka, Mayumi

    2017-11-01

    Lead (Pb) poisoning is widespread among raptors and water birds. In Japan, fragments of Pb ammunition are still found in endangered eagles although more than 10 years have passed since legislation regarding use of Pb ammunition was introduced. This study was performed to investigate Pb exposure in raptors from various locations in Japan. We measured hepatic and renal Pb concentrations and hepatic Pb isotope ratios of Steller's sea eagles (Haliaeetus pelagicus), white-tailed sea eagles (Haliaeetus albicilla), golden eagles (Aquila chrysaetos), and 13 other species (total 177 individuals) that were found dead, as well as blood samples from three eagles found in a weakened state during 1993-2015 from Hokkaido (northern part), Honshu (the main island), and Shikoku (a southern island) of Japan. In the present study in Hokkaido, one quarter of the sea eagles showed a high Pb concentration, suggesting exposure to abnormally high Pb levels and Pb poisoning. Pb isotope ratios indicated that endangered Steller's sea eagle and white-tailed sea eagle were poisoned by Pb ammunition that was used illegally in Hokkaido. In other areas of Japan, both surveillance and regulations were less extensive than in Hokkaido, but Pb poisoning in raptors was also noted. Therefore, Pb poisoning is still a serious problem in raptors in various areas of Japan due to accidental ingestion of materials containing Pb, especially Pb ammunition. Copyright © 2017. Published by Elsevier Ltd.

  14. The isotopic composition of uranium and lead in Allende inclusions and meteoritic phosphates

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Wasserburg, G. J.

    1981-01-01

    The isotopic compositions of uranium and lead in Ca-Al-rich inclusions from the Allende chondrite and in whitlockite from the St. Severin chondrite and the Angra dos Reis achondrite are reported. Isoptopic analysis of acid soluble fractions of the Allende inclusions and the meteoritic whitlockite, which show isotopic anomalies in other elements, reveals U-235/U-238 ratios from 1/137.6 to 1/138.3, within 20 per mil of normal terrestrial U abundances. The Pb isotopic compositions of five coarse-grained Allende inclusions give a mean Pb-207/Pb-206 model age of 4.559 + or - 0.015 AE, in agreement with the U results. Pb isotope ratios of two fine-grained inclusions and a coarse-grained inclusion with strong mass fractionation and some nonlinear isotopic anomalies indicate that the U-Pb systems of these inclusions have evolved differently from the rest of Allende. Th/U abundance ratios in the Allende inclusions and meteoritic phosphate are found to range from 3.8 to 96, presumably indicating an optimal case for Cm/U fractionation, although the normal U concentrations do not support claims of abundant live Cm-247 or Cm-247/U-238 fractionation at the time of meteorite formation, in contrast to previous results. A limiting Cm-247/U-235 ratio of 0.004 at the time of meteorite formation is calculated which implies that the last major r process contribution at the protosolar nebula was approximately 100 million years prior to Al-26 formation and injection.

  15. Heavy metals pollution and pb isotopic signatures in surface sediments collected from Bohai Bay, North China.

    PubMed

    Gao, Bo; Lu, Jin; Hao, Hong; Yin, Shuhua; Yu, Xiao; Wang, Qiwen; Sun, Ke

    2014-01-01

    To investigate the characteristics and potential sources of heavy metals pollution, surface sediments collected from Bohai Bay, North China, were analyzed for the selected metals (Cd, Cr, Cu, Ni, Pb, and Zn). The Geoaccumulation Index was used to assess the level of heavy metal pollution. Pb isotopic compositions in sediments were also measured to effectively identify the potential Pb sources. The results showed that the average concentrations of Cd, Cr, Cu, Ni, Pb, and Zn were 0.15, 79.73, 28.70, 36.56, 25.63, and 72.83 mg/kg, respectively. The mean concentrations of the studied metals were slightly higher than the background values. However, the heavy metals concentrations in surface sediments in Bohai Bay were below the other important bays or estuaries in China. The assessment by Geoaccumulation Index indicated that Cr, Zn, and Cd were classified as "the unpolluted" level, while Ni, Cu, and Pb were ranked as "unpolluted to moderately polluted" level. The order of pollution level of heavy metals was: Pb > Ni > Cu > Cr > Zn > Cd. The Pb isotopic ratios in surface sediments varied from 1.159 to 1.185 for (206)Pb/(207)Pb and from 2.456 to 2.482 for (208)Pb/(207)Pb. Compared with Pb isotopic radios in other sources, Pb contaminations in the surface sediments of Bohai Bay may be controlled by the mix process of coal combustion, aerosol particles deposition, and natural sources.

  16. Pb-Pb systematics of lunar rocks: differentiation, magmatic and impact history of the Moon

    NASA Astrophysics Data System (ADS)

    Nemchin, A.; Martin, W.; Norman, M. D.; Snape, J.; Bellucci, J. J.; Grange, M.

    2016-12-01

    Two independent decay chains in U-Pb system allow the determination of both ages and initial isotope compositions by analyzing only Pb in the samples. A typical Pb analysis represents a mixture of radiogenic Pb produced from the in situ U decay, initial Pb and laboratory contamination. Utilizing the ability of ion probes to analyse 10-30 micrometer-sized spots in the samples while avoiding fractures and other imperfections that commonly host contamination, permits extraction of pure lunar Pb compositions from the three component mixtures. This results in both accurate and precise ages of the rocks and their initial compositions. Lunar Mare and KREEP basalts postdating the major lunar bombardment are likely to represent such three component mixtures and are therefore appropriate for this approach, also giving an opportunity to investigate Pb evolution in their sources. A source evolution model constrained using available data indicates a major differentiation on the Moon at 4376±18 Ma and very radiogenic lunar mantle at this time. This age is likely to reflect the mean time of KREEP formation during the last stage of Magma Ocean differentiation. Rocks older than about 3.9 Ga are more complex than basalts and may include an extra Pb component, if modified by impacts. An example of this is presented by Pb-Pb data obtained for the anorthosite sample 62236, where the age of the rock is determined as 4367±29 Ma from analyses of CPx lamellae inside the large Opx grains: however large plagioclase crystals do not contain Pb in quantities sufficient for ion probe analysis, precluding determination of the initial Pb composition of the sample. Most of Pb is found in the brecciated parts of the anorthosite between the large grains. The composition of this Pb is similar to the initial Pb of 3909±17 Ma Apollo 16 breccia 66095, suggesting that is was injected into the anorthosite during a 3.9 Ga impact. Similar ca 3.9 Ga ages were determined for 1-2 millimeter size feldspathic

  17. Sr, Nd, and Pb isotopes of ultramafic xenoliths in volcanic rocks of Eastern China: enriched components EMI and EMII in subcontinental lithosphere

    USGS Publications Warehouse

    Tatsumoto, M.; Basu, A.R.; Wankang, H.; Junwen, W.; Guanghong, X.

    1992-01-01

    The UThPb, SmNd, and RbSr isotopic systematics of mafic and ultramafic xenolithic rocks and associated megacrystic inclusions of aluminous augite and garnet, that occur in three alkalic volcanic suites: Kuandian in eastern Liaoning Province, Hanluoba in Hebei Province, and Minxi in western Fujian Province, China are described. In various isotopic data plots, the inclusion data invariably fall outside the isotopic ranges displayed by the host volcanic rocks, testifying to the true xenolithic nature of the inclusions. The major element partitioning data on Ca, Mg, Fe, and Al among the coexisting silicate minerals of the xenoliths establish their growth at ambient mantle temperatures of 1000-1100??C and possible depths of 70-80 km in the subcontinental lithosphere. Although the partitioning of these elements reflects equilibrium between coexisting minerals, equilibria of the Pb, Nd, and Sr isotopic systems among the minerals were not preserved. The disequilibria are most notable with respect to the 206Pb 204Pb ratios of the minerals. On a NdSr isotopic diagram, the inclusion data plot in a wider area than that for oceanic basalts from a distinctly more depleted component than MORB with higher 143Nd 144Nd and a much broader range of 87Sr 86Sr values, paralleling the theoretical trajectory of a sea-water altered lithosphere in NdSr space. The garnets consistently show lower ?? and ?? values than the pyroxenes and pyroxenites, whereas a phlogopite shows the highest ?? and ?? values among all the minerals and rocks studied. In a plot of ??207 and ??208, the host basalts for all three areas show lower ??207 and higher ??208 values than do the xenoliths, indicating derivation of basalts from Th-rich (relative to U) sources and xenoliths from U-rich sources. The xenolith data trends toward the enriched mantle components, EMI and EMII-like, characterized by high 87Sr 86Sr and ??207 values but with slightly higher 143Nd 144Nd. The EMI trend is shown more distinctly by the host

  18. 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.

  19. 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

  20. ^2^3^8U/^2^3^5U Ratios of Anagrams: Angrites and Granites

    NASA Astrophysics Data System (ADS)

    Tissot, F. L. H.; Dauphas, N.

    2012-03-01

    We report ^2^3^8U/^2^3^5U ratios of five angrites and give the corresponding Pb-Pb ages of D'Orbigny and Angra Dos Reis. The U-isotopic composition of terrestrial granites (I, S, and A types) is also assessed to determine the influence of the protolith.

  1. Pb-Sr-Nd-O isotopic characterization of Mesozoic rocks throughout the northern end of the Peninsular Ranges batholith: Isotopic evidence for the magmatic evolution of oceanic arc–continental margin accretion during the Late Cretaceous of southern California

    USGS Publications Warehouse

    Kistler, Ronald W.; Wooden, Joseph L.; Premo, Wayne R.; Morton, Douglas M.

    2014-01-01

    Within the duration of the U.S. Geological Survey (USGS)–based Southern California Areal Mapping Project (SCAMP), many samples from the northern Peninsular Ranges batholith were studied for their whole-rock radioisotopic systematics (rubidium-strontium [Rb-Sr], uranium-thorium-lead [U-Th-Pb], and samarium-neodymium [Sm-Nd]), as well as oxygen (O), a stable isotope. The results of three main studies are presented separately, but here we combine them (>400 analyses) to produce a very complete Pb-Sr-Nd-O isotopic profile of an arc-continent collisional zone—perhaps the most complete in the world. In addition, because many of these samples have U-Pb zircon as well as argon mineral age determinations, we have good control of the timing for Pb-Sr-Nd-O isotopic variations.The ages and isotopic variations help to delineate at least four zones across the batholith from west to east—an older western zone (126–108 Ma), a transitional zone (111–93 Ma), an eastern zone (94–91 Ma), and a much younger allochthonous thrust sheet (ca. 84 Ma), which is the upper plate of the Eastern Peninsular Ranges mylonite zone. Average initial 87Sr/86 Sr (Sri), initial 206Pb/204Pb (206 Pbi), initial 208Pb/204Pb (average 208Pbi), initial epsilon Nd (average εNdi), and δ18O signatures range from 0.704, 18.787, 38.445, +3.1, and 4.0‰–9.0‰, respectively, in the westernmost zone, to 0.7071, 19.199, 38.777, −5, and 9‰–12‰, respectively, in the easternmost zone. The older western zone is therefore the more chemically and isotopically juvenile, characterized mostly by values that are slightly displaced from a mantle array at ca. 115 Ma, and similar to some modern island-arc signatures. In contrast, the isotopic signatures in the eastern zones indicate significant amounts of crustal involvement in the magmatic plumbing of those plutons. These isotopic signatures confirm previously published results that interpreted the Peninsular Ranges batholith as a progressively

  2. Geochemical and isotopic (Nd-Pb-Sr-O) variations bearing on the genesis of volcanic rocks from Vesuvius, Italy

    USGS Publications Warehouse

    Ayuso, R.A.; de Vivo, B.; Rolandi, G.; Seal, R.R.; Paone, A.

    1998-01-01

    Alkaline volcanism produced by Monte Somma-Vesuvius volcano includes explosive plinian and subplinian activity in addition to effusive lava flows. Pumice, scoria, and lava (150 samples) exhibit major- and trace-element gradients as a function of SiO2 (58.9-47.2 wt%) and MgO (0-7.8 wt%); Mg value are ???50. Internally gradational chemical groups or cycles are distinguished by age: (1) 25 000 to 14 000 yr B.P.; (2) 8000 yr B.P. to A.D. 79; and (3) A.D. 79 to 1944. A small number of lavas, dikes and scora were also analysed from the Somma formation (~ 35 000 to 25 000 yr B.P.). Within each group, contents of Na2O + K2O increas with decreasing MgO along distinct rocks. Nb/Y values are variable from 0.66 to 3.14 (at SiO2 ??? 50 wt%) generally in the range of alkaline and ultra-alkaline rocks. Variations in contents of some majro elements (e.g., P and Ti), and trace elements (e.g., Th, Nb, Ta, Zr, Hf, Pb, La, and Sc), as well as contrasting trends in ratios of various elements (e.g., Ta/Yb, Hf/U, Th/Ta, Th/Hf, Th/Yb, etc.) are also generally consistent with the group subdivisions. For example, Th/Hf increases from ??? 5 to ??? 10 with decreasing age for the Vesuvius system as a whole, yielding similar compositions in the least evolved rocks (low-silica, high-MgO, imcompatible element-poor) erupted at the end of each cycle. Internal variations within individual eruptions also systematically changed generally towards a common mafic composition at the end of each cycle, thus reflecting the dominanit volume in the magma chamber. At the start of a new eruptive cycle, the rocks are relatively enriched in incompatible elements; younger groups also contain higher abundances than other groups. N-MORB-normalized multielement diagrams exhibit selective enrichments of Sr, K, Rb, Th, and the light rare-earth elements; deep Nb and Ta negative anomalies commonly seen in rocks generated at orogenic margins are absent in the light rare-earth elements; deep Nb and Ta netgative anomalies

  3. Evolution of mare basalts - The complexity of the U-Th-Pb system

    NASA Technical Reports Server (NTRS)

    Unruh, D. M.; Tatsumoto, M.

    1977-01-01

    An attempt has been made to gain more insight into mare-basalt evolution by performing a very detailed leaching and mineral-separation U-Th-Pb systematics study on mare basalt 15085. It is found that about 20-50% of the U, Th, and Pb reside on the grain boundaries or in the mesostasis and that the Pb-207/Pb-206 ratios of the grain boundaries and crystal interiors are distinctly different. These distinct trends appear to represent either continuous or episodic postcrystallizational disturbances to the U-Th-Pb system of this rock. Using U and Pb partition coefficients, it is concluded that existing two- and three-stage U-Pb evolution models do not accurately describe mare-basalt genesis. An alternative two-stage + KREEP mixing model is proposed as a simple approximation to U-Pb evolution in lunar rocks. Most Rb-Sr and Sm-Nd data are compatible with this model.

  4. Geochemistry, Nd-Pb Isotopes, and Pb-Pb Ages of the Mesoproterozoic Pea Ridge Iron Oxide-Apatite–Rare Earth Element Deposit, Southeast Missouri

    USGS Publications Warehouse

    Ayuso, Robert A.; Slack, John F.; Day, Warren C.; McCafferty, Anne E.

    2016-01-01

    Iron oxide-apatite and iron oxide-copper-gold deposits occur within ~1.48 to 1.47 Ga volcanic rocks of the St. Francois Mountains terrane near a regional boundary separating crustal blocks having contrasting depleted-mantle Sm-Nd model ages (TDM). Major and trace element analyses and Nd and Pb isotope data were obtained to characterize the Pea Ridge deposit, improve identification of exploration targets, and better understand the regional distribution of mineralization with respect to crustal blocks. The Pea Ridge deposit is spatially associated with felsic volcanic rocks and plutons. Mafic to intermediate-composition rocks are volumetrically minor. Data for major element variations are commonly scattered and strongly suggest element mobility. Ratios of relatively immobile elements indicate that the felsic rocks are evolved subalkaline dacite and rhyolite; the mafic rocks are basalt to basaltic andesite. Granites and rhyolites display geochemical features typical of rocks produced by subduction. Rare earth element (REE) variations for the rhyolites are diagnostic of rocks affected by hydrothermal alteration and associated REE mineralization. The magnetite-rich rocks and REE-rich breccias show similar REE and mantle-normalized trace element patterns.Nd isotope compositions (age corrected) show that: (1) host rhyolites have ɛNd from 3.44 to 4.25 and TDM from 1.51 to 1.59 Ga; (2) magnetite ore and specular hematite rocks display ɛNd from 3.04 to 4.21 and TDM from 1.6 to 1.51 Ga, and ɛNd from 2.23 to 2.81, respectively; (3) REE-rich breccias have ɛNd from 3.04 to 4.11 and TDM from 1.6 to 1.51 Ga; and (4) mafic to intermediate-composition rocks range in ɛNd from 2.35 to 3.66 and in TDM from 1.66 to 1.56. The ɛNd values of the magnetite and specular hematite samples show that the REE mineralization is magmatic; no evidence exists for major overprinting by younger, crustal meteoric fluids, or by externally derived Nd. Host rocks, breccias, and

  5. 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

  6. The lead (Pb) isotope signature, behaviour and fate of traffic-related lead pollution in roadside soils in The Netherlands.

    PubMed

    Walraven, N; van Os, B J H; Klaver, G Th; Middelburg, J J; Davies, G R

    2014-02-15

    In this study the origin, behaviour and fate of anthropogenic Pb in sandy roadside soils were assessed by measuring soil characteristics, Pb isotope composition and content. In 1991 and 2003 samples were taken at different depth intervals at approximately 8 and 75 m from two highways in The Netherlands. The Pb isotope composition of the litter layer ((206)Pb/(207)Pb=1.12-1.14) differs from the deeper soil samples ((206)Pb/(207)Pb=1.20-1.21). Based on a mixing model it is concluded that the samples contain two Pb sources: natural Pb and anthropogenic Pb, the latter mainly derived from gasoline. (206)Pb/(207)Pb ratios demonstrate that the roadside soils were polluted to a depth of ~15 cm. Within this depth interval, anthropogenic Pb content is associated with organic matter. Although Pb pollution only reached a depth of ~15 cm, this does not mean that the topsoils retain all anthropogenic Pb. Due to the low pH and negligible binding capacity of soils at depths >15 cm, anthropogenic Pb migrated towards groundwater after reaching depths of >15 cm. The Pb isotope composition of the groundwater ((206)Pb/(207)Pb=1.135-1.185) establishes that groundwater is polluted with anthropogenic Pb. The contribution of anthropogenic Pb to the groundwater varies between ~30 and 100%. Based on the difference in soil Pb content and Pb isotope compositions over a period of 12 years, downward Pb migration is calculated to vary from 72 ± 95 to 324 ± 279 mg m(-2)y(-1). Assuming that the downward Pb flux is constant over time, it is calculated that 35-90% of the atmospherically delivered Pb has migrated to the groundwater. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. 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

  8. Hawaiian hot spot dynamics as inferred from the Hf and Pb isotope evolution of Mauna Kea volcano

    NASA Astrophysics Data System (ADS)

    Blichert-Toft, Janne; Weis, Dominique; Maerschalk, Claude; Agranier, Arnaud; Albarède, Francis

    2003-02-01

    The present work reports multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements of the isotopic compositions of Hf and Pb in the first 3 km of the deep core retrieved by the Hawaii Scientific Drilling Project. The measurements cover all the samples from the standard geochemical reference set, glasses from the deep hole, and replicates from the pilot hole. Both Hf and Pb are less radiogenic in Mauna Loa compared to Mauna Kea. The transition between Mauna Kea and Mauna Loa lavas in the deep core is progressive for ɛHf and 208Pb/204Pb, but a sharp discontinuity is observed for 208Pb*/206Pb*. There is no correlation between the alkalinity of the samples and isotopic composition. In detail, the Hf isotope compositions of samples from the pilot hole are not all identical to those of the HSDP-2 core for samples retrieved from a similar depth, suggesting that steep topography existed at the time of emplacement or that a different eruptive sequence was recorded. The strong correlation between 208Pb*/206Pb* and 3He/4He (He data from M. D. Kurz et al. (Rapid helium isotopic variability in Mauna Kea shield lavas from the Hawaiian Scientific Drilling Project, submitted to Geochemistry Geophysics Geosystems, 2002)) requires the episodic incorporation of a component that resembles the basalts erupted by either Kilauea or the Loihi eruptive centers (this component is referred to as K/L). The data suggest that some 500 kyr ago, Mauna Kea was tapping a mantle source similar to that tapped by Kilauea today. Isotopic variability of Pb and He cannot be accounted for by radiogenic ingrowth in a closed system, but requires the mixing of mantle source components with distinct outgassing histories. The time series of isotopic and concentration data in Mauna Kea samples spanning about 350,000 years of age indicate the recurrence of geochemical patterns in the melting column. Ignoring the most recent alkalic samples, we find that the dominant fluctuations

  9. Radiogenic Isotopes in Weathering and Hydrology

    NASA Astrophysics Data System (ADS)

    Blum, J. D.; Erel, Y.

    2003-12-01

    as on the observation that radiogenic isotopes are sometimes preferentially released compared to nonradiogenic isotopes of the same element during acid leaching of rocks ( Hart and Tilton, 1966; Silver et al., 1984; Erel et al., 1991). A major finding of these investigations was that weathering often results in anomalously young Rb-Sr isochron ages, and discordant Pb-Pb ages. Rubidium is generally retained relative to strontium in whole-rock samples, and in some cases radiogenic strontium and lead are lost preferentially to common strontium and lead from weathered minerals.The most widely utilized of these isotopic systems is Rb-Sr, followed by U-Pb. The K-Ar system is not directly applicable to most studies of rock-water interaction, because argon is a noble gas, and upon release during mineral weathering mixes with atmospheric argon, limiting its usefulness as a tracer in most weathering applications. Argon and other noble gas isotopes have, however, found important applications in hydrology (see Chapter 5.15). Three other isotopic systems commonly used in geochronology and petrology include Sm-Nd, Lu-Hf, and Re-Os. These parent and daughter elements are in very low abundance and concentrated in trace mineral phases. Sm-Nd, Lu-Hf, and Re-Os have been used in a few weathering studies but have not been utilized extensively in investigations of weathering and hydrology.The decay of 87Rb to 87Sr has a half-life of 48.8 Gyr, and this radioactive decay results in natural variability in the 87Sr/86Sr ratio in rubidium-bearing minerals (e.g., Blum, 1995). The trace elements rubidium and strontium are geochemically similar to the major elements potassium and calcium, respectively. Therefore, minerals with high K/Ca ratios develop high 87Sr/86Sr ratios over geologic timescales. Once released into the hydrosphere, strontium retains its isotopic composition without significant fractionation by geochemical or biological processes, and is therefore a good tracer for sources and

  10. ISOTOPIC EVALUATION OF PB OCCURRENCES IN THE RIVERINE ECOSYSTEMS OF THE KANKAKEE WATERSHED, ILLINOIS-INDIANA.

    EPA Science Inventory

    Environmental background levels of Pb were measured in ponds, river waters, sediments, suspended sediments, rocks, and air particulates within the Kankakee watershed during the period of 1995 to 1999. Stable isotopic Pb distinguised airborne Pb and its incorporation into riverin...

  11. Origin and tectonic implications of the Zhaxikang Pb-Zn-Sb-Ag deposit in northern Himalaya: evidence from structures, Re-Os-Pb-S isotopes, and fluid inclusions

    NASA Astrophysics Data System (ADS)

    Zhou, Qing; Li, Wenchang; Qing, Chengshi; Lai, Yang; Li, Yingxu; Liao, Zhenwen; Wu, Jianyang; Wang, Shengwei; Dong, Lei; Tian, Enyuan

    2018-04-01

    The Zhaxikang Pb-Zn-Sb-Ag-(Au) deposits, located in the eastern part of northern Himalaya, totally contain more than 1.146 million tonnes (Mt) of Pb, 1.407 Mt of Zn, 0.345 Mt of Sb, and 3 kilotonnes (kt) of Ag. Our field observations suggest that these deposits are controlled by N-S trending and west- and steep-dipping normal faults, suggesting a hydrothermal rather than a syngenetic sedimentary origin. The Pb-Zn-Sb-Ag-(Cu-Au) mineralization formed in the Eocene as indicated by a Re-Os isochron age of 43.1 ± 2.5 Ma. Sulfide minerals have varying initial Pb isotopic compositions, with (206Pb/204Pb)i of 19.04-19.68, (207Pb/204Pb)i of 15.75-15.88, and (208Pb/204Pb)i of 39.66-40.31. Sulfur isotopic values display a narrow δ34S interval of +7.8-+12.2‰. These Pb-S isotopic data suggest that the Zhaxikang sources of Pb and S should be mainly from the coeval felsic magmas and partly from the surrounding Mesozoic strata including metasedimentary rocks and layered felsic volcanic rocks. Fluid inclusion studies indicate that the hydrothermal fluids have medium temperatures (200-336 °C) but varying salinities (1.40-18.25 wt.% NaCl equiv.) with densities of 0.75-0.95 g/cm3, possibly suggesting an evolution mixing between a high salinity fluid, perhaps of magmatic origin, with meteoric water.

  12. Constraining the Flux of Impactors Postdating Heavy Bombardment Using U-Pb Ages of Impact Glasses

    NASA Technical Reports Server (NTRS)

    Nemchin, A. A.; Norman, M. L.; Ziegler, R. A.; Grange, M. L.

    2013-01-01

    Spherules of glass varying in size from a few micrometres to a few millimetres are common in the lunar regolith. While some of these glass beads are products of pyroclastic fire fountains others originate as impact melt ejected from the target that breaks into small droplets and solidifies as spherical particles while raining back to the lunar surface. These glasses preserve information about the chemical composition of the target and often contain sufficient amount of radioactive nuclides such as 40K to enable Ar-40-Ar-39 dating of individual beads. Studies measuring the age of glass beads have been used in attempts to establish variations in the flux of impactors hitting the Moon, particularly during the period that postdates the formation of major impact basins [1,2]. These studies proposed a possibility of spike in the impact flux about 800 Ma [2] and over the last 400 Ma [1]. More recently U-Th-Pb isotopic systems have been also utilized to determine the age of impact glasses from the Apollo 17 regolith [3]. Our aim is to extend the application of the U-Pb system in impact glasses to spherules isolated from Apollo 14 soil 14163 in an attempt to further investigate the applicability of this isotopic system to the chronology of impact glass beads and gain additional information on the impact flux in the inner Solar system.

  13. Monzonitoid magmatism of the copper-porphyritic Lazurnoe deposit (South Primor'e): U-Pb and K-Ar geochronology and peculiarities of ore-bearing magma genesis by the data of isotopic-geochemical studies

    NASA Astrophysics Data System (ADS)

    Sakhno, V. G.; Kovalenko, S. V.; Alenicheva, A. A.

    2011-05-01

    Magmatic rocks from the copper-porphyritic Lazurnoe deposit (Central Primor'e) have been studied. It has been found that rocks from the Lazurnyi massif are referred to gabbro-monzodiorites, monzodiorites, and monzo-granodiorites formed during two magmatic phases of different ages. The earlier phase is represented by gabbro-monzodiorites and diorites of the North Stock, and the later one, by gabbro-monzodiorites and monzo-grano-diorites of the South Stock. On the basis of isotopic dating by the U-Pb (SHRIMP) method for zircon and by the K-Ar method for hornblendes and biotites, the age of magmatic rocks is determined at 110 ± 4 for the earlier phase and at 103.5 ± 1.5 for the later one. Examination of the isotopic composition for Nd, Sr, Pb, Hf, δ18O, and REE spectra has shown that melts of the first phase are contaminated with crustal rocks and they are typical for a high degree of secondary alterations. Potassiumfeldspar, biotite, propylitic alterations, and sulfidization are manifested in these rocks. The rocks of the later stage of magmatism are characteristic for a primitive composition of isotopes and the absence of secondary alterations. They carry the features of adakite specifics that allows us to consider them derivatives of mantle generation under high fluid pressure. The intrusion of fluid-saturated melts of the second phase into the magmatic source of the first phase caused both an alteration pattern of rocks and copper-porphyritic mineralization. Isotopes of sulfur and oxygen allow us to consider the ore component to be of magmatic origin.

  14. Metallic elements and isotope of Pb in wet precipitation in urban area, South America

    NASA Astrophysics Data System (ADS)

    Migliavacca, Daniela Montanari; Teixeira, Elba Calesso; Gervasoni, Fernanda; Conceição, Rommulo Vieira; Raya Rodriguez, Maria Teresa

    2012-04-01

    The atmosphere of urban areas has been the subject of many studies to show the atmospheric pollution in large urban centers. By quantifying wet precipitation through the analysis of metallic elements (ICP/AES) and Pb isotopes, the wet precipitation of the Metropolitan Area of the Porto Alegre (MAPA), Brazil, was characterized. The samples were collected between July 2005 and December 2007. Zn, Fe and Mn showed the highest concentration in studied sites. Sapucaia do Sul showed the highest average for Zn, due to influence by the steel plant located near the sampling site. The contribution of anthropogenic emissions from vehicular activity and steel plants in wet precipitation and suspended particulate matter in the MAPA was identified by the isotopic signatures of 208Pb/207Pb and 206Pb/207Pb. Moreover the analyses of the metallic elements allowed also to identify the contribution of other anthropic sources, such as steel plants and oil refinery.

  15. Reconstruction of historical lead contamination and sources in Lake Hailing, Eastern China: a Pb isotope study.

    PubMed

    Zhang, Rui; Guan, Minglei; Shu, Yujie; Shen, Liya; Chen, Xixi; Zhang, Fan; Li, Tiegang; Jiang, Tingchen

    2016-05-01

    The history records of lead and its stable isotopic ratios were determined in a sediment core to receive anthropogenic impacts on the Lake Hailing in eastern China. The sediment core was dated based on (210)Pb, (137)Cs, and (239+240)Pu. The historical changes of Pb/Al and Pb isotope ratios showed increasing trend upward throughout the core, suggesting changes in energy usage and correlating closely with the experience of a rapid economic and industrial development of the catchment, Linyi City, in eastern China. Based on the mixing end member model of Pb isotope ratios, coal combustion emission dominated anthropogenic Pb sources in the half part of the century contributing 13 to 43 % of total Pb in sediment. Moreover, contributions of chemical and organic fertilizer were 1-13 and 5-14 %, respectively. In contrast, the contribution of leaded gasoline was low than 8 %. The results indicated that historical records of Pb contamination predominantly sourced from coal combustion and chemical and organic fertilizer in the catchment. In addition, an increase of coal combustion source and fertilizers was found throughout the sediment core, whereas the contribution of leaded gasoline had declined after 2000s, which is attributed to the phaseout of leaded gasoline in China.

  16. Major, trace element and isotope geochemistry (Sr-Nd-Pb) of interplinian magmas from Mt. Somma-Vesuvius (Southern Italy)

    USGS Publications Warehouse

    Somma, R.; Ayuso, R.A.; de Vivo, B.; Rolandi, G.

    2001-01-01

    Major, trace element and isotopic (Sr, Nd, Pb) data are reported for representative samples of interplinian (Protohistoric, Ancient Historic and Medieval Formations) activity of Mt. Somma-Vesuvius volcano during the last 3500 years. Tephra and lavas exhibit significant major, trace element and isotopic variations. Integration of these data with those obtained by previous studies on the older Somma suites and on the latest activity, allows to better trace a complete petrological and geochemical evolution of the Mt. Somma-Vesuvius magmatism. Three main groups of rocks are recognized. A first group is older than 12.000 yrs, and includes effusive-explosive activity of Mt. Somma. The second group (8000-2700 yrs B.P.) includes the products emitted by the Ottaviano (8000 yrs. B.P.) and Avellino (3550 yrs B.P.) plinian eruptions and the interplinian activity associated with the Protohistoric Formation. Ancient Historic Formation (79-472 A.D.), Medieval Formation (472-1139 A.D.) and Recent interplinian activity (1631-1944 A.D.) belong to the third group of activity (79-1944 A.D.). The three groups of rocks display distinct positive trends of alkalis vs. silica, which become increasingly steeper with age. In the first group there is an increase in silica and alkalis with time, whereas an opposite tendency is observed in the two younger groups. Systematic variations are also evident among the incompatible (Pb, Zr, Hf, Ta, Th, U, Nb, Rb, Cs, Ba) and compatible elements (Sr, Co, Cr). REE document variable degrees of fractionation, with recent activity displaying higher La/Yb ratios than Medieval and Ancient Historic products with the same degree of evolution. N-MORB normalized multi-element diagrams for interplinian rocks show enrichment in Rb, Th, Nb, Zr and Sm (> *10 N-MORB). Sr isotope ratios are variable, with Protohistoric rocks displaying 87Sr/86Sr= 0.70711-0.70810, Ancient Historic 87Sr/86Sr=0.70665-0.70729, and Medieval 87Sr/86Sr=0.70685-0.70803. Neodymium isotopic

  17. Field isotopic study of lead fate and compartmentalization in earthworm-soil-metal particle systems for highly polluted soil near Pb recycling factory.

    PubMed

    Goix, Sylvaine; Mombo, Stéphane; Schreck, Eva; Pierart, Antoine; Lévêque, Thibaut; Deola, Frédéric; Dumat, Camille

    2015-11-01

    Earthworms are important organisms in soil macrofauna and play a key role in soil functionality, and consequently in terrestrial ecotoxicological risk assessments. Because they are frequently observed in soils strongly polluted by metals, the influence of earthworm bioturbation on Pb fate could therefore be studied through the use of Pb isotopes. Total Pb concentrations and isotopic composition ((206)Pb, (207)Pb and (208)Pb) were then measured in earthworms, casts and bulk soils sampled at different distance from a lead recycling factory. Results showed decreasing Pb concentrations with the distance from the factory whatever the considered matrix (bulk soils, earthworm bodies or cast samples) with higher concentrations in bulk soils than in cast samples. The bivariate plot (208)Pb/(206)Pb ratios versus (206)Pb/(207)Pb ratios showed that all samples can be considered as a linear mixing between metallic process particulate matter (PM) and geochemical Pb background. Calculated anthropogenic fraction of Pb varied between approximately 84% and 100%. Based on Pb isotopic signatures, the comparison between casts, earthworms and bulk soils allowed to conclude that earthworms preferentially ingest the anthropogenic lead fraction associated with coarse soil organic matter. Actually, soil organic matter was better correlated with Pb isotopic ratios than with Pb content in soils. The proposed hypothesis is therefore a decrease of soil organic matter turnover due to Pb pollution with consequences on Pb distribution in soils and earthworm exposure. Finally, Pb isotopes analysis constitutes an efficient tool to study the influence of earthworm bioturbation on Pb cycle in polluted soils. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. 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.

  19. Nd, Pb, Sr, and O isotopic characterization of Saudi Arabian Shield terranes

    USGS Publications Warehouse

    Stoeser, D.B.; Frost, C.D.

    2006-01-01

    New Nd, Sr and O isotopic data for granitoid rocks of the Saudi Arabian Shield are presented together with published Nd, Pb, Sr and O isotopic data and all available geologic and geochronologic information to re-evaluate the terranes defined for the Saudi Arabian part of the Arabian-Nubian Shield. Three groups of terranes are identified: 1) the western arc terranes, 2) the eastern arc terranes, and 3) the Khida terrane. The Khida terrane is the only terrane composed of pre-Neoproterozoic continental crust. The western arc terranes are of oceanic arc affinity, and have the least radiogenic Pb and Sr and most radiogenic Nd isotopic compositions and some of the lowest ??18O values of any rocks of the Saudi Arabian Shield. Although some previous studies have characterized the eastern arc terranes as of continental affinity, this study shows that they too are composed of Neoproterozoic oceanic arcs, although their sources have slightly elevated 208Pb/204Pb, Nd, Sri, and ??18O values compared to the western arc terranes. These data suggest that either the isotopic composition of the mantle source for the western arc terranes is more depleted than that of the eastern arc terranes or the eastern arc terranes have been mixed with a small amount of cratonic source material, or both. We further elaborate on the Hulayfah-Ad Dafinah fault zone as a major boundary within the Saudi Arabian portion of the East African Orogen. With further study, its northern extension may be shown to pass through what has been defined as the Hail terrane, and its southern extension appears to lie under cover east of the Tathlith-Malahah terrane and extend into Yemen. It may represent the collision zone between East and West Gondwana, and at the very least it is an important suture between groups of arc terranes of contrasting isotopic composition caught between two converging continents.

  20. Direct high-precision U-Pb geochronology of the end-Cretaceous extinction and calibration of Paleocene astronomical timescales

    NASA Astrophysics Data System (ADS)

    Clyde, William C.; Ramezani, Jahandar; Johnson, Kirk R.; Bowring, Samuel A.; Jones, Matthew M.

    2016-10-01

    The Cretaceous-Paleogene (K-Pg) boundary is the best known and most widely recognized global time horizon in Earth history and coincides with one of the two largest known mass extinctions. We present a series of new high-precision uranium-lead (U-Pb) age determinations by the chemical abrasion isotope dilution thermal ionization mass spectrometry (CA-ID-TIMS) method from volcanic ash deposits within a tightly constrained magnetobiostratigraphic framework across the K-Pg boundary in the Denver Basin, Colorado, USA. This new timeline provides a precise interpolated absolute age for the K-Pg boundary of 66.021 ± 0.024 / 0.039 / 0.081 Ma, constrains the ages of magnetic polarity Chrons C28 to C30, and offers a direct and independent test of early Paleogene astronomical and 40Ar/39Ar based timescales. Temporal calibration of paleontological and palynological data from the same deposits shows that the interval between the extinction of the dinosaurs and the appearance of earliest Cenozoic mammals in the Denver Basin lasted ∼185 ky (and no more than 570 ky) and the 'fern spike' lasted ∼1 ky (and no more than 71 ky) after the K-Pg boundary layer was deposited, indicating rapid rates of biotic extinction and initial recovery in the Denver Basin during this event.

  1. Trace determination of zinc by substoichiometric isotope dilution analysis

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

    Sandhya, D.; Priya, S.; Subramanian, M.O.S.

    1996-09-01

    A radiometric method based on substoichiometric isotope dilution analysis using 1,10-phenanthroline and a substoichiometric amount of eosin was developed for determining trace amounts of zinc. Evaluation of various metal ion interferences shows that as little as 0.2 {mu}g Zn could be determined in an aqueous-phase volume of 60 mL. The method has been successfully applied to the determination of Zn in city waste incineration ash, cadmium metal, Fourts-B tablets, Boro-plus ointment, and magnesium alloy samples. 12 refs., 3 figs., 3 tabs.

  2. Isotopic separation of acetaldehyde and methanol from their deuterated isotopologues on a porous layer open tubular column allows quantification by stable isotope dilution without mass spectrometric detection.

    PubMed

    Schmarr, Hans-Georg; Wacker, Michael; Mathes, Maximilian

    2017-01-20

    An isotopic separation of acetaldehyde and acetaldehyde-2,2,2-d3 was achieved in a temperature programmed run on a porous layer open tubular (PLOT) capillary column coated with particles of divinylbenzene ethylene glycol/dimethylacrylate (Rt ® -U-BOND). This is the prerequisite for the development of quantitative analytical methods based on a stable isotope dilution assay (SIDA) without a mass spectrometric detection (non-MS SIDA). For routine analysis a flame ionization detector (FID) can thus be applied as a robust and low-cost alternative. In a preliminary study, static headspace extraction and gas chromatographic separation (HS-GC-FID) of acetaldehyde in aqueous solutions was shown as an application. Good linearity was obtained in a calibration range from 0.4 to 40mgL -1 , with peak integration benefitting from the inverse isotope effect encountered on the specific porous polymer. Furthermore, separation of methanol and deuterated methanol (d3) could also be achieved under the same chromatographic conditions. The achieved isotopic separation of these important volatile compounds now allows non-MS SIDA-based methods that are still to be developed. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Geochronology, geochemistry and Sr-Nd-Pb-Hf isotopes of the Early Jurassic granodiorite from the Sankuanggou intrusion, Heilongjiang Province, Northeastern China: Petrogenesis and geodynamic implications

    NASA Astrophysics Data System (ADS)

    Deng, Ke; Li, Qiugen; Chen, Yanjing; Zhang, Cheng; Zhu, Xuefeng; Xu, Qiangwei

    2018-01-01

    Mesozoic granitoid rocks represent a volumetrically component of the Northeastern (NE) China and preserve useful information about the tectonomagmatic history of this region. The Sankuanggou intrusion associated with skarn Fe-Cu deposit in the Duobaoshan ore field within NE China primarily consists of granodiorite with minor alkali-feldspar granite and diorite, which intrudes the Ordovician Duobaoshan Formation in the region. Zircon LA-ICP-MS U-Pb geochronology and whole-rock geochemistry, and Sr-Nd-Pb-Hf isotope analysis were performed on the Sankuanggou intrusion to investigate the petrogenesis and geodynamic implications. Zircon U-Pb dating of magmatic zircons from the granodiorite rock suggests that the intrusion was emplaced in the Early Jurassic (177 ± 1 Ma). Geochemically, it belongs to the metaluminous to slightly peraluminous high-K calc-alkaline I-type granitoids with a narrow range of SiO2 concentration (65.73-67.33 wt.%), high Ba, Sr, LREE and LILE contents and low abundance of Rb, Y, HREE and HFSE. All of these studied samples have homogeneous initial isotope traits with (87Sr/86Sr)i ranging from 0.70415 to 0.70423, εNd(t) of + 3.6 to + 4.0, (206Pb/204Pb)i = 17.933-18.458, (207Pb/204Pb)i = 15.520-15.587 and (208Pb/204Pb)i = 37.523-38.087, and zircon εHf(t) values varying from + 4.8 to + 9.9. These results, combined with the previous data, demonstrate that the Sankuanggou granitoids were formed by partial melting of the pre-existing juvenile crust in an extensional regime related to the post-collisional setting following the closure of the CAOB rather than previously proposed continental arc setting related to Paleo-Pacific or the Mongol-Okhotsk subduction, although their potential influence should not be dismissed.

  4. Lead isotopes and trace metal ratios of aerosols as tracers of Pb pollution sources in Kanpur, India

    NASA Astrophysics Data System (ADS)

    Sen, Indra; Bizimis, Michael; Tripathi, Sachchida; Paul, Debajyoti; Tyagi, Swati; Sengupta, Deep

    2015-04-01

    The anthropogenic flux of Pb in the Earth's surface is almost an order of magnitude higher than its corresponding natural flux [1]. Identifying the sources and pathways of anthropogenic Pb in environment is important because Pb toxicity is known to have adverse effects on human health. Pb pollution sources for America, Europe, and China are well documented. However, sources of atmospheric Pb are unknown in India, particularly after leaded gasoline was phased out in 2000. India has a developing economy with a rapidly emerging automobile and high temperature industry, and anthropogenic Pb emission is expected to rise in the next decade. In this study, we report on the Pb- isotope compositions and trace metal ratios of airborne particulates collected in Kanpur, an industrial city in northern India. The Pb concentration in the airborne particulate matter varies between 14-216 ng/m3, while the other heavy metals vary by factor of 10 or less, e.g. Cd=0.3-3 ng/m3, As=0.4-3.5 ng/m3, Zn=36-161 ng/m3, and Cu=3-22 ng/m3. The 206Pb/207Pb, 208Pb/206Pb, and 208Pb/207Pb vary between 1.112 - 1.129, 2.123-2.141, and 2.409-2.424 respectively, and are highly correlated with each other (R2>0.9). Pb isotopes and trace metal data reveals that coal combustion is the major source of anthropogenic Pb in the atmosphere, with limited contribution from mining and smelting processes. We further conclude that combination of Pb isotope ratios and V/Pb ratios are powerful tracers for Pb source apportionment studies, which is otherwise difficult to differentiate based only on Pb systematics [1] Sen and Peucker-Ehrenbrink (2012), Environ. Sci. Technol.(46), 8601-8609

  5. New data for paleoprotherozoic PGE-bearing anorthosite of Kandalaksha massif (Baltic shield): U-Pb and Sm-Nd ages

    NASA Astrophysics Data System (ADS)

    Steshenko, Ekaterina; Bayanova, Tamara; Serov, Pavel

    2015-04-01

    The aims of this researches were to study the isotope U-Pb age of zircon and rutile and Sm-Nd (rock forming and sulphide minerals) on Kandalaksha anorthosite massif due to study of polimetamorphic history. In marginal zone firstly have been obtained the presence of sulphide mineralization with PGE (Chashchin, Petrov , 2013). Kandalaksha massif is located in the N-E part of Baltic shield and consists of three parts. 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 polymetamorphism. Two fractions of single grains from anorthosite of the massif gave precise U-Pb age, which is equal to 2450± 3 Ma. Leucocratic gabbro-norite were dated by U-Pb method, with age up to 2230 ± 10 Ma. This age reflects the time of granulite metamorphism according to data of (Mitrofanov, Nirovich, 2003). Two fractions of rutile have been analyzed by U-Pb method and reflect age of 1700 ± 10 Ma. It is known that the closure temperature of U-Pb system rutile is 400-450 ° C (Mezger et.al., 1989), thus cooling processes of massif rocks to these temperatures was about 1.7 Ga. These data reflect one of the stages of metamorphic alteration of the massif. Three stages of metamorphism are distinguished by Sm-Nd method. Isotope Sm-Nd dating on Cpx-WR line gives the age of 2311 Ma which suggested of high pressure granulite metamorphism. Moreover Cpx-Pl line reflect the age 1908 Ma of low pressure granulite metamorphism. Also two-points (Grt-Rt) Sm-Nd isochrone yield the age 1687 Ma of the last metamorphic alterations in Kandalaksha anorthosite massif. Model Sm-Nd age of the leucocratic gabbro-norite is 2796 Ma with positive ɛNd (+0.32). It means that the source of gabbro-norite was mantle reservoir. All investigations are devoted to memory of academician PAS F. MItrofanov which was a leader of scientific school for

  6. In situ Pb-Pb dating of rutile from slowly cooled granulites by LA-MC-ICP-MS: confirmation of the high closure temperature (>=600°C) for Pb diffusion in rutile

    NASA Astrophysics Data System (ADS)

    Vry, J.; Baker, J.; Waight, T.

    2003-04-01

    We have analysed Pb isotopes in natural rutile crystals by laser ablation MC-ICP-MS to assess the potential of rapid Pb-Pb dating of rutile with this method. The rutile samples are from granulite-facies Mg- and Al-rich rocks from the Reynolds Range, Northern Territory, Australia. This metamorphic terrane has a well-constrained high-T cooling history (ca. 3^oC/Myr) defined by previous U-Pb dating of monazite and zircon (peak metamorphism at 1584 Ma), which we have supplemented with additional Rb-Sr dates of phlogopite, biotite and muscovite. The dated rutiles vary in size from 3 to 0.05 mm, have Pb concentrations of ca. 20 ppm, and were analysed with a 266 nm laser coupled to an AXIOM MC-ICP-MS (spot size of 200-50 μm). Individual larger crystals (>= 200 μm) exhibit sufficient Pb isotopic heterogeneity (206Pb/204Pb = 10000-80000) to perform isochron calculations on several short analyses of a single grain (30-60 s). The largest rutiles yielded Pb-Pb isochron ages of 1540-1555 Ma with typical uncertainties of ± 1 to 10 Ma. 207Pb/206Pb ages are typically within 1% of the Pb-Pb isochron ages testifying to the radiogenic nature of Pb in the rutile. A mean age for all the analysed rutiles was 1548.4 ± 9.1 Ma (n = 33). Comparable 207Pb/206Pb ages were also obtained from individual smaller crystals (50 μm) where the 204Pb ion beam could not be measured precisely. The results demonstrate that even small rutile crystals are extremely resistant to isotopic resetting, and that this mineral is a high-T chronometer. Phlogopite and muscovite Rb-Sr ages are <1454 and 1400-1480 Ma, respectively, with some of the phlogopite and biotite micas having been partially reset by later thermal events younger than 400 Ma. All the mica ages are considerably younger (100-70 My) than the rutile ages, which approach U-Pb ages for monazite and zircon overgrowths, even though the mica closure temperatures (350-500^oC) are comparable or slightly higher than earlier geological estimates [1] of

  7. Isotopic (U-Pb, Nd) and geochemical constraints on the origins of the Aileu and Gondwana sequences of Timor

    NASA Astrophysics Data System (ADS)

    Boger, S. D.; Spelbrink, L. G.; Lee, R. I.; Sandiford, M.; Maas, R.; Woodhead, J. D.

    2017-02-01

    Detrital zircon U-Pb age data collected from the argillitic sedimentary rocks of the Timorese Aileu Complex and Gondwana Sequence indicate that both units were derived from a common source containing 200-600 Ma, 900-1250 Ma and 1450-1900 Ma zircon. The modally most significant age population within this range of ages dates to c. 260 Ma. The observed spectrum of ages can be traced to the eastern active margin of Pangaea and its immediate foreland, which today is best exposed along the northeast coast of Australia. Compared to the relative homogeneity of the detrital zircon age data, geochemical and Nd isotopic data show that the mudstones of the Aileu Complex are on average more siliceous, have higher K2O/Na2O, Rb/Sr, Th/Sc and yield notably older Nd TDM model ages when compared to those from the Gondwana Sequence. These data are interpreted to suggest that, although both sequences share a common east Pangaea provenance, they were eroded from different sections of this active margin and deposited in spatially separated basins. The present proximity of these units is a result of their tectonic juxtaposition during the Pliocene to Recent collision between the northern edge of the Indo-Australia plate and the Banda Arc.

  8. 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.

  9. Reference measurement procedure for total glycerides by isotope dilution GC-MS.

    PubMed

    Edwards, Selvin H; Stribling, Shelton L; Pyatt, Susan D; Kimberly, Mary M

    2012-04-01

    The CDC's Lipid Standardization Program established the chromotropic acid (CA) reference measurement procedure (RMP) as the accuracy base for standardization and metrological traceability for triglyceride testing. The CA RMP has several disadvantages, including lack of ruggedness. It uses obsolete instrumentation and hazardous reagents. To overcome these problems the CDC developed an isotope dilution GC-MS (ID-GC-MS) RMP for total glycerides in serum. We diluted serum samples with Tris-HCl buffer solution and spiked 200-μL aliquots with [(13)C(3)]-glycerol. These samples were incubated and hydrolyzed under basic conditions. The samples were dried, derivatized with acetic anhydride and pyridine, extracted with ethyl acetate, and analyzed by ID-GC-MS. Linearity, imprecision, and accuracy were evaluated by analyzing calibrator solutions, 10 serum pools, and a standard reference material (SRM 1951b). The calibration response was linear for the range of calibrator concentrations examined (0-1.24 mmol/L) with a slope and intercept of 0.717 (95% CI, 0.7123-0.7225) and 0.3122 (95% CI, 0.3096-0.3140), respectively. The limit of detection was 14.8 μmol/L. The mean %CV for the sample set (serum pools and SRM) was 1.2%. The mean %bias from NIST isotope dilution MS values for SRM 1951b was 0.7%. This ID-GC-MS RMP has the specificity and ruggedness to accurately quantify total glycerides in the serum pools used in the CDC's Lipid Standardization Program and demonstrates sufficiently acceptable agreement with the NIST primary RMP for total glyceride measurement.

  10. Sr-Nd-Pb isotope variability across and along the Ecuadorian volcanic arc

    NASA Astrophysics Data System (ADS)

    Ancellin, Marie-Anne; Samaniego, Pablo; Vlastélic, Ivan; Nauret, François; Gannoun, Mouhcine; Hidalgo, Silvana

    2016-04-01

    Determining the contribution of different potential sources in arc magma genesis is of paramount importance for discriminating the role of deep-seated processes at work in the slab and mantle wedge, as well as the process occurring during the magma ascent through the arc crust. The Ecuadorian volcanic arc (2°S - 1°N) results from the subduction of the oceanic Nazca plate below the continental south-American plate. This volcanic province, developed in front of the subducting Carnegie ridge, is characterized by at least 50-60 volcanic centres of Pleistocene-Holocene age, which are distributed along the Western and Eastern Cordilleras and in the back-arc region. Previous studies on this province focused on two main issues: (1) the role of the deep-seated process occurring at the level of the subducting slab and the mantle wedge ([1], [2]), and (2) the role of crustal process ([3]). In this work, we use existing and new (57 samples from 36 volcanoes of the whole Ecuadorian arc) major-trace element and Sr-Nd-Pb isotope data to resolve precisely magma compositional changes occurring across and along the volcanic arc and to precise the role of the heterogeneous crust underlying this arc segment. In the 207Pb/204Pb vs. 206Pb/204Pb diagram, most of Western Cordillera volcanic centres and Back arc volcanoes display a flat trend characterized by a large variation in 206Pb/204Pb (18.5 - 19.15), with little variation in 207Pb/204Pb (15.54-15.62). Along this trend, back arc volcanoes tend towards unradiogenic compositions with Reventador as end-member whereas western cordilleras volcanoes generally show more radiogenic compositions (Pilavo, Imbabura). In contrast, the Eastern cordillera volcanoes display more radiogenic 207Pb/204Pb (15.60 - 15.70) or 208Pb/204Pb (38.7 - 39) at a given 206Pb/204Pb compared to the Western cordillera with similar variation in 206Pb/204Pb (18.85 - 19.05). Extreme compositions are observed at Tungurahua and Antisana volcanoes. Several volcanoes of

  11. Direct determination of halogens in powdered geological and environmental samples using isotope dilution laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Boulyga, Sergei F.; Heumann, Klaus G.

    2005-04-01

    Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) with a special laser ablation system for bulk analyses (LINA-Spark(TM)-Atomiser) was applied for direct determinations of chlorine, bromine, and iodine in rock and sediment samples. Special attention was focused on possible inter-halogen fractionations and analyte/spike isotope fractionations by using LA-ICP-MS and LA-ICP-IDMS, respectively. A variation of Br/Cl and I/Cl element intensity ratios by a factor of 1.3-3 was observed when changing the nebulizer gas flow rate in the range of 0.84-1.0 L min-1 and the laser power density in the range of 2-10 GW cm-2, respectively. When using an internal standard for halogen quantification in LA-ICP-MS, this inter-element fractionation can cause systematic errors, which can be avoided by applying the isotope dilution technique. However, at high laser power densities (>5.7 GW cm-2 for iodine and >4.0 GW cm-2 for bromine and chlorine) the corresponding measured isotope ratio of the isotope-diluted sample deviates significantly from the target value. Under optimised conditions concentrations in the range of 30 [mu]g g-1-16 × 103 [mu]g g-1 for chlorine, <2-140 [mu]g g-1 for bromine, and <0.1-31 [mu]g g-1 for iodine were determined by LA-ICP-IDMS in two sediment reference materials (SRM 1646, SRM 2704) and three rock reference samples (GS-N, Granite; BX-N, Bauxite; DT-N, Disthene), which have not been certified for these halogens. The sediment results agree well within the given uncertainties with indicative values by different methods and the results of the rock samples with those obtained by negative thermal ionisation isotope dilution mass spectrometry. The detection limits of LA-ICP-IDMS are 8 [mu]g g-1 for chlorine, 1.7 [mu]g g-1 for bromine, and 0.1 [mu]g g-1 for iodine.

  12. Uranium disequilibrium in groundwater: An isotope dilution approach in hydrologic investigations

    USGS Publications Warehouse

    Osmond, J.K.; Rydell, H.S.; Kaufman, M.I.

    1968-01-01

    The distribution and environmental disequilibrium patterns of naturally occurring uranium isotopes (U234 and U238) in waters of the Floridan aquifer suggest that variations in the ratios of isotopic activity and concentrations can be used quantitatively to evaluate mixing proportions of waters from differing sources. Uranium is probably unique in its potential for this approach, which seems to have general usefulness in hydrologic investigations.

  13. 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

  14. The evolution of Gondwana: U-Pb, Sm-Nd, Pb-Pb and geochemical data from Neoproterozoic to Early Palaeozoic successions of the Kango Inlier (Saldania Belt, South Africa)

    NASA Astrophysics Data System (ADS)

    Naidoo, Thanusha; Zimmermann, Udo; Chemale, Farid

    2013-08-01

    The provenance of Neoproterozoic to Early Palaeozoic rocks at the southern margin of the Kalahari craton reveals a depositional setting and evolution with a significant position in the formation of Gondwana. The sedimentary record shows a progression from immature, moderately altered rocks in the Ediacaran Cango Caves Group; to mature, strongly altered rocks in the Early Palaeozoic Kansa Group and overlying formations; culminating below very immature quartzarenites of Ordovician age. Petrographic and geochemical observations suggest the evolution of a small restricted basin with little recycling space towards a larger continental margin where substantial turbidite deposition is observed. For the southern Kalahari craton, a tectonic evolution comparable to supracrustal rocks in southern South America, Patagonia and Antarctica is supported by similarities in U-Pb ages of detrital zircons (Mesoproterozoic, Ediacaran and Ordovician grain populations); Sm-Nd isotopes (TDM: 1.2-1.8 Ga); and Pb-Pb isotopes. The maximum depositional age of the Huis Rivier Formation (upper Cango Caves Group) is determined at 644 Ma, but a younger age is still possible due to the limited zircon yield. The Cango Caves Group developed in a retro-arc foreland basin syntectonically to the Terra Australis Orogeny, which fringed Gondwana. The Kansa Group and overlying Schoemanspoort Formation are related to an active continental margin developed after the Terra Australis Orogen, with Patagonia being the ‘missing link’ between the Central South American arc and Antarctica during the Ordovician. This explains the occurrence of Ordovician detritus in these rocks, as a source rock of this age has not been discovered in South Africa. The absence of arc characteristics defines a position distal to the active continental margin, in a retro-arc foreland basin. The similarity of isotope proxies to major tectonic provinces in Antarctica and Patagonia, with those on the margins of the Kalahari craton

  15. Determination of 90Sr / 238U ratio by double isotope dilution inductively coupled plasma mass spectrometer with multiple collection in spent nuclear fuel samples with in situ 90Sr / 90Zr separation in a collision-reaction cell

    NASA Astrophysics Data System (ADS)

    Isnard, H.; Aubert, M.; Blanchet, P.; Brennetot, R.; Chartier, F.; Geertsen, V.; Manuguerra, F.

    2006-02-01

    Strontium-90 is one of the most important fission products generated in nuclear industry. In the research field concerning nuclear waste disposal in deep geological environment, it is necessary to quantify accurately and precisely its concentration (or the 90Sr / 238U atomic ratio) in irradiated fuels. To obtain accurate analysis of radioactive 90Sr, mass spectrometry associated with isotope dilution is the most appropriated method. But, in nuclear fuel samples the interference with 90Zr must be previously eliminated. An inductively coupled plasma mass spectrometer with multiple collection, equipped with an hexapole collision cell, has been used to eliminate the 90Sr / 90Zr interference by addition of oxygen in the collision cell as a reactant gas. Zr + ions are converted into ZrO +, whereas Sr + ions are not reactive. A mixed solution, prepared from a solution of enriched 84Sr and a solution of enriched 235U was then used to quantify the 90Sr / 238U ratio in spent fuel sample solutions using the double isotope dilution method. This paper shows the results, the reproducibility and the uncertainties that can be obtained with this method to quantify the 90Sr / 238U atomic ratio in an UOX (uranium oxide) and a MOX (mixed oxide) spent fuel samples using the collision cell of an inductively coupled plasma mass spectrometer with multiple collection to perform the 90Sr / 90Zr separation. A comparison with the results obtained by inductively coupled plasma mass spectrometer with multiple collection after a chemical separation of strontium from zirconium using a Sr spec resin (Eichrom) has been performed. Finally, to validate the analytical procedure developed, measurements of the same samples have been performed by thermal ionization mass spectrometry, used as an independent technique, after chemical separation of Sr.

  16. Evidencing lead deposition at the urban scale using "short-lived" isotopic signatures of the source term (Pb-Zn refinery)

    NASA Astrophysics Data System (ADS)

    Franssens, Matthias; Flament, Pascal; Deboudt, Karine; Weis, Dominique; Perdrix, Espéranza

    2004-09-01

    To demonstrate the ability of the lead isotope signature technique to evidence the spatial extent of an industrial Pb deposition plume at a local scale, dry deposition of lead in the urban environment of a Pb-Zn refinery was investigated, as a study case, using transient ("short-lived") isotopic signatures of the industrial source. Sampling campaigns were achieved in representative weather conditions, on an 8-h basis. Dry deposition rates measured downwind from refinery emissions (≈102-103 μg Pb m-2 h-1), cross-sectionally in a 3-5 km radius area around the plant, represent 10-100 times the urban background dry fallout, measured upwind, as well as fallout measured near other potential sources of anthropogenic Pb. The Pb-Zn refinery isotopic signature (approx. 1.100<206Pb/207Pb<1.135) is made identifiable, using the same set of Pb and Zn ores for 2 days before sampling and during field experiments, by agreement with the executive staff of the plant. This source signature is less radiogenic than signatures of urban background Pb aerosols (1.155<206Pb/207Pb<1.165) and minor sources of Pb aerosols (1.147<206Pb/207Pb<1.165). By a simple binary mixing model calculation, we established the extension of the industrial Pb deposition plume. Fifty to eighty percents of total lead settled by the dry deposition mode, 3-4 km away from the refinery, still have an industrial origin. That represents from 40 to 80 μg Pb m-2 h-1, in an area where the blood lead level exceeds 100 μg Pb l-1 for 30% of men and 12% of women living there. We demonstrate here that stable Pb isotope analysis is able to evidence the Pb dry deposition plume in stabilised aerodynamic conditions, using a short-lived source term, suggesting that this methodology is able to furnish valuable data to validate industrial Pb aerosols dispersion models, at the urban scale.

  17. Origin and fate of sulfide liquids in hotspot volcanism (La Réunion): Pb isotope constraints from residual Fe-Cu oxides

    NASA Astrophysics Data System (ADS)

    Vlastélic, I.; Gannoun, A.; Di Muro, A.; Gurioli, L.; Bachèlery, P.; Henot, J. M.

    2016-12-01

    Immiscible sulfide liquids in basaltic magmas play an important role in trace metal transport and the sulfur budget of volcanic eruptions. However, sulfides are transient phases, whose origin and fate are poorly constrained. We address these issues by analyzing sulfide destabilization products preserved in lavas from La Réunion Island. Iron oxide globules and coatings, typically 20-80 μm in size, were found to occur in vesicles of differentiated lavas from Piton des Neiges, and recent pumice samples from Piton de la Fournaise. Field and mineralogical evidence indicates that the iron oxides are syn-eruptive phases not resulting from hydrothermal processes. Samples were first studied by Scanning Electron Microscopy. The globules were separated, whereas the smaller spherules and coatings were concentrated by magnetic sorting and acid leaching, and samples were processed through wet chemistry. The Fe oxide phases comprise 49-74 wt.% Fe, 26-40 wt.% O, and up to 6 wt.% Cu, 811 ppm Ni, 140 ppm Bi, and 8.5 ppm Pb. Compared to the host lava, Cu, Ni, and Bi are enriched by a factor of 101-103. Systematic Pb isotope disequilibrium (between 500 ppm and 2.9% for 206Pb/204Pb) exists between Fe oxides and host rocks, with Fe oxides generally displaying less radiogenic ratios. Unradiogenic Pb is a typical signature of sulfide, which tends to concentrate Pb, but not its parent elements U and Th. Thus, both the chemical and isotopic compositions of the vesicle-hosted Fe oxides suggest that they are more or less direct products of the destabilization of immiscible sulfide liquids. Although Pb dominantly partitions into the gas phase during sulfide breakdown, the original Pb isotope signature of sulfide is preserved in the residual oxide. The composition estimated for the parent sulfides (206Pb/204Pb = 18.20-18.77, 207Pb/204Pb = 15.575, and 208Pb/204Pb = 38.2-38.8) precludes a genetic link with the La Réunion plume, and suggests a lithospheric or crustal origin. It is estimated

  18. Cooling rates and the depth of detachment faulting at oceanic core complexes: Evidence from zircon Pb/U and (U-Th)/He ages

    USGS Publications Warehouse

    Grimes, Craig B.; Cheadle, Michael J.; John, Barbara E.; Reiners, P.W.; Wooden, J.L.

    2011-01-01

    Oceanic detachment faulting represents a distinct mode of seafloor spreading at slow spreading mid-ocean ridges, but many questions persist about the thermal evolution and depth of faulting. We present new Pb/U and (U-Th)/He zircon ages and combine them with magnetic anomaly ages to define the cooling histories of gabbroic crust exposed by oceanic detachment faults at three sites along the Mid-Atlantic Ridge (Ocean Drilling Program (ODP) holes 1270D and 1275D near the 15??20???N Transform, and Atlantis Massif at 30??N). Closure temperatures for the Pb/U (???800??C-850??C) and (U-Th)/He (???210??C) isotopic systems in zircon bracket acquisition of magnetic remanence, collectively providing a temperature-time history during faulting. Results indicate cooling to ???200??C in 0.3-0.5 Myr after zircon crystallization, recording time-averaged cooling rates of ???1000??C- 2000??C/Myr. Assuming the footwalls were denuded along single continuous faults, differences in Pb/U and (U-Th)/He zircon ages together with independently determined slip rates allow the distance between the ???850??C and ???200??C isotherms along the fault plane to be estimated. Calculated distances are 8.4 ?? 4.2 km and 5.0 2.1 km from holes 1275D and 1270D and 8.4 ?? 1.4 km at Atlantis Massif. Estimating an initial subsurface fault dip of 50 and a depth of 1.5 km to the 200??C isotherm leads to the prediction that the ???850??C isotherm lies ???5-7 km below seafloor at the time of faulting. These depth estimates for active fault systems are consistent with depths of microseismicity observed beneath the hypothesized detachment fault at the TAG hydrothermal field and high-temperature fault rocks recovered from many oceanic detachment faults. Copyright 2011 by the American Geophysical Union.

  19. HFS and isotope shift in the atomic spectrum of205Pb

    NASA Astrophysics Data System (ADS)

    Barboza-Flores, M.; Redi, O.; Schönberger, P.; Stroke, H. H.; Naumann, R. A.

    1987-06-01

    The hfs of205Pb in the 283.3-nm resonance line and its isotope shift (IS) have been measured in absorption with the use of dispersive spectroscopy. A new method for calibration and analysis, when internal standards are not available is described. The results are: hfs interaction constants A=70.3(5)×10-3 cm-1, B=-0.6(1.1)×10-3 cm-1,205Pb-208Pb IS=-123.9(2.0)×10-3 cm-1. The derived nuclear magnetic dipole moment, μ=0.704(5) μ N is in good agreement with values calculated with a nuclear configuration mixing model.

  20. Effects of soil dilution and amendments (mussel shell, cow bone, and biochar) on Pb availability and phytotoxicity in military shooting range soil.

    PubMed

    Ahmad, Mahtab; Soo Lee, Sang; Yang, Jae E; Ro, Hee-Myong; Han Lee, Young; Sik Ok, Yong

    2012-05-01

    Bioavailability and bioaccessibility determine the level of metal toxicity in the soils. Inorganic soil amendments may decrease metal bioavailability and enhance soil quality. This study used mussel shell, cow bone, and biochar to reduce lead (Pb) toxicity in the highly contaminated military shooting range soil in Korea. Water-soluble and 1-M ammonium nitrate extractions, and a modified physiologically based extraction test (PBET) were performed to determine Pb bioavailability and bioaccessibility in the soil, respectively. Active C in the soil was also measured to evaluate the effects of the amendments on biological soil quality. The Pb contaminated soil was diluted in serial with uncontaminated soil for the bioassays. Seed germination and root elongation tests using lettuce (Lactuca sativa) showed increases in germination percentage and root length in soil treated with the amendments. Biochar was most effective and increased seed germination by 360% and root length by 189% compared to the unamended soil. Up to 20% soil dilution resulted in more than 50% seed germination. Bioavailability and bioaccessibility of Pb in the soils were decreased by 92.5% and 48.5% with mussel shell, by 84.8% and 34.5% with cow bone, and by 75.8% and 12.5% with biochar, respectively, compared to the unamended soil. We found that the Pb availability in the military shooting range soil can be reduced effectively by the tested amendments or soil dilution alternately, thereby decreasing the risk of ecotoxicity. Furthermore, the increasing active C from the amendments revitalized the soil contaminated with Pb. Copyright © 2012 Elsevier Inc. All rights reserved.

  1. SHRIMP-RG U-Pb ages of provenance and metamorphism from detrital zircon populations and Pb-Sr-Nd signatures of prebatholithic metasedimentary rocks at Searl Ridge, northern Peninsular Ranges batholith, southern California: Implications for their age, origin, and tectonic setting

    USGS Publications Warehouse

    Premo, Wayne R.; Morton, Douglas M.

    2014-01-01

    Twenty-four samples were collected from prebatholithic metasedimentary rocks along Searl Ridge, the north rim of the Diamond Valley Reservoir, Domenigoni Valley, centrally located in the northern Peninsular Ranges of southern California. These rocks exhibit progressive metamorphism from west to east across fundamental structural discontinuities now referred to as a “transition zone.” Documented structural and mineralogical changes occur across this metamorphic gradient. Sensitive high-resolution ion microprobe–reverse geometry (SHRIMP-RG) U-Pb ages were obtained from detrital zircons from metasedimentary rocks through the transition zone. To the west, metapelitic and minor metasandstone units yielded numerous concordant 206Pb/238U ages between 210 and 240 Ma, and concordant 207Pb/206Pb ages at 1075–1125 Ma, 1375–1430 Ma, and 1615–1735 Ma, although distinct differences in provenance were noted between units. A few older 207Pb/206Pb ages obtained were ca. 2250 Ma and ca. 2800 Ma. Rocks of the eastern part of the transition zone include high-grade paragneisses that yielded numerous concordant 206Pb/238U ages between 103 and 123 Ma and between 200 and 255 Ma, and concordant 207Pb/206Pb ages at 1060–1150 Ma, 1375–1435 Ma, and 1595–1710 Ma. Some zircon results from these high-grade gneisses are marked by distinct Pb-loss discordia with lower-intercept ages of ca. 215 Ma and Paleoproterozoic upper-intercept ages. Younger ages between 100 and 105 Ma are mainly obtained from rims of some zircon grains that are characterized by low Th/U values (<0.1) and high U contents (>1000 ppm), indicating the likelihood of metamorphic zircon growth at that time. The similarity of zircon age populations between western and eastern units through the transition zone indicates that this fundamental structure probably dissects sediments of the same basin. This supposition is further supported by initial whole-rock Pb-Sr-Nd isotopic data that show similar average

  2. U-Pb Geochronology of Devonian Granites in the Meguma Terrane of Nova Scotia, Canada: Evidence for Hotspot Melting of a Neoproterozoic Source.

    PubMed

    Keppie; Krogh

    1999-09-01

    U-Pb isotopic analyses of monazite and zircon from six granitic plutons in the Meguma Terrane yield nearly concordant ages of 373+/-3 Ma, interpreted as the time of intrusion. U-Pb analyses of euhedral zircons with thick rims overgrowing cores, which were abraded to remove all or most of the rim, plot on chords between 370+/-3 and 628+/-33 Ma (Larrys River and Halfway Cove plutons), 372+/-3 and approximately 660 Ma (Shelburne pluton), and 373+/-2 and approximately 732 Ma (Barrington Passage pluton). The upper intercepts are interpreted as the age of magma source, correlatives of which are present in the Avalon Composite Terrane to the north. This basement may be either in depositional or tectonic contact with the overlying Cambro-Ordovician Meguma Group. Other zircons in the granites are generally irregular-euhedral with thin rims, and most U-Pb isotopic analyses fall between two chords from 373-2040 and 373-2300 Ma, with a few lying outside this field. These zircons are probably derived from the country rock (Goldenville Formation), which a previous study has shown contains detrital zircons with concordant U-Pb ages of 3000, 2000, and 600 Ma, and numerous intermediate discordant ages. These new ages, along with published data, document a relatively short (5-10 m.yr.) but voluminous period of magmatism. This age is approximately synchronous with intrusion of mafic rocks and lamprophyre dikes and regional low-pressure metamorphism and was followed by rapid denudation of 5-12 km. These observations may be interpreted in terms of shallowly dipping subduction and overriding of a mantle plume that eventually penetrates through the subducting plate to melt the overriding continental plate. Subsequent northward migration of the plume could explain both the approximately 360 Ma magmatism in the Cobequid Highlands (Avalon Composite Terrane) and the mid-Carboniferous plume-related intrusions around the Magdalen Basin.

  3. Li-Zn-Pb multi isotopic characterization of the Loire River Basin, France

    NASA Astrophysics Data System (ADS)

    Millot, R.; Desaulty, A.; Widory, D.; Bourrain, X.

    2013-12-01

    The Loire River in France is approximately 1010 km long and drains an area of 117 800 km2. Upstream, the Loire River flows following a south to north direction from the Massif Central down to the city of Orléans, 650 km from its source. The Loire River is one of the main European riverine inputs to the Atlantic Ocean. Over time, its basin has been exposed to numerous sources of anthropogenic metal pollutions, such as metal mining, industry, agriculture and domestic inputs. The Loire River basin is thus an excellent study site to develop new isotope systematics for tracking anthropogenic sources of metal pollutions (Zn and Pb) and also to investigate Li isotope tracing that can provide key information on the nature of weathering processes at the Loire River Basin scale. Preliminary data show that Li-Zn-Pb concentrations and isotopic compositions span a wide range in river waters of the Loire River main stream and the main tributaries. There is a clear contrast between the headwaters upstream and rivers located downstream in the lowlands. In addition, one of the major tributaries within the Massif Central (the Allier River) is clearly influenced by inputs resulting from mineralizations and thermomineral waters. The results showed that, on their own, each of these isotope systematics reveals important information about the geogenic or anthropogenic origin Li-Zn-Pb. Considered together, they are however providing a more integrated understanding of the overall budgets of these elements at the scale of the Loire River Basin.

  4. U-Pb dating of uranium deposits in collapse breccia pipes of the Grand Canyon region

    USGS Publications Warehouse

    Ludwig, K. R.; Simmons, K.R.

    1992-01-01

    Two major periods of uranium mineralization are indicated by U-Pb isotope dating of uranium ores from collapse breccia pipes in the Grand Canyon region, northern Arizona. The Hack 2 and 3, Kanab North, and EZ 1 and 2 orebodies apparently formed in the interval of 200 ?? 20 Ma, similar to ages inferred for strata-bound, Late Triassic-hosted uranium deposits in southern Utah and northern Arizona. Samples from the Grand Canyon and Pine Nut pipes, however, indicate a distinctly older age of about 260 Ma. The clustering in ages for a variety of uranium deposits at about the age of the lower part of the Chinle Formation (Late Triassic) suggests that uranium in these deposits may have been derived by leaching from volcanic ash in the Chinle and mobilized by ground-water movement. Pb isotope ratios of galenas in mineralized pipes are more radiogenic than those of sulfides from either uranium-poor pipes or occurrences away from pipes. Fluids which passed through the pipes had interacted with the Proterozoic basement, possibly through the vertical fractures which influenced the location and evolution of the pipes themselves. -from Authors

  5. Earth Processes: Reading the Isotopic Code

    NASA Astrophysics Data System (ADS)

    Basu, Asish; Hart, Stan

    Publication of this monograph will coincide, to a precision of a few per mil, with the centenary of Henri Becquerel's discovery of "radiations actives" (C. R. Acad. Sci., Feb. 24, 1896). In 1896 the Earth was only 40 million years old according to Lord Kelvin. Eleven years later, Boltwood had pushed the Earth's age past 2000 million years, based on the first U/Pb chemical dating results. In exciting progression came discovery of isotopes by J. J. Thomson in 1912, invention of the mass spectrometer by Dempster (1918) and Aston (1919), the first measurement of the isotopic composition of Pb (Aston, 1927) and the final approach, using Pb-Pb isotopic dating, to the correct age of the Earth: close—2.9 Ga (Gerling, 1942), closer—3.0 Ga (Holmes, 1949) and closest—4.50 Ga (Patterson, Tilton and Inghram, 1953).

  6. U, Th, Pb and REE abundances and Pb 207/Pb 206 ages of individual minerals in returned lunar material by ion microprobe mass analysis.

    NASA Technical Reports Server (NTRS)

    Andersen, C. A.; Hinthorne, J. R.

    1972-01-01

    Results of ion microprobe analyses of Apollo 11, 12 and 14 material, showing that U, Th, Pb and REE are concentrated in accessory minerals such as apatite, whitlockite, zircon, baddeleyite, zirkelite, and tranquillityite. Th/U ratios are found to vary by over a factor of 40 in these minerals. K, Ba, Rb and Sr have been localized in a K rich, U and Th poor glass phase that is commonly associated with the U and Th bearing accessory minerals. Li is observed to be fairly evenly distributed between the various accessory phases. The phosphates have been found to have REE abundance patterns (normalized to the chondrite abundances) that are fairly flat, while the Zr bearing minerals have patterns that rise steeply, by factors of ten or more, from La to Gd. All the accessory minerals have large negative Eu anomalies. Radiometric age dates (Pb 207/Pb 206) of the individual U and Th bearing minerals compare favorably with the Pb 207/Pb 206 age of the bulk rocks.

  7. 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.

  8. The Nd-, Sr- and Pb-isotopic character of lavas from Taal, Laguna de Bay and Arayat volcanoes, southwestern Luzon, Philippines: Implications for arc magma petrogenesis

    USGS Publications Warehouse

    Mukasa, S.B.; Flower, M.F.J.; Miklius, Asta

    1994-01-01

    Following the amalgamation of a collage of pre-Neogene terranes largely by strike-slip and convergence mechanisms to form the Philippine islands, volcanic chains, related to oppositely dipping subduction zones, developed along the eastern and western margins of the archipelago. There is ample field evidence that this volcanic activity, predominantly calc-alkaline in chemical character, had commenced by the Oligocene. Volcanoes resulting from subduction along the Manila-Negros trench in the west (e.g. Taal, Laguna de Bay and Arayat) form a high-angle linear array, trending away from the MORE field on Pb-isotopic covariation diagrams; have the highest Sr- and lowest Nd-isotopic compositions, of the two chains (but nevertheless plotting above bulk earth on the 87Sr/86Sr versus 143Nd/144Nd covariation diagram); and exhibit Sm/Nd and Rb/Sr values that are lower and higher, respectively, than the estimated values for bulk earth. While the Sm/Nd and Rb/Sr characteristics are common to both chains, volcanoes associated with the Philippine-East Luzon trench have Pb-isotopic compositions that fall in the Indian Ocean MORB field and that require time-integrated evolution in a high Th/U environment. They also have higher Nd- and lower Sr-isotopic ratios. The source materials of Philippine volcanoes, therefore, have undergone varied recent enrichments in LILE, as indicated by the decoupling of isotopic and elemental ratios. These enrichments, particularly for the western volcanoes, cannot be entirely due to small degrees of partial melting in the mantle wedge, considering that they were accompanied by elevations in radiogenic Pb. Elevated Pb ratios are best explained by the introduction of subducted, continentally derived sediments. The sedimentary component in the western volcanoes is probably the South China Sea sediments derived largely from Eurasia. That this component is not available in the Philippine-East Luzon trench is reflected by the fact that the eastern volcanoes

  9. Quantitative Analysis by Isotopic Dilution Using Mass Spectroscopy: The Determination of Caffeine by GC-MS.

    ERIC Educational Resources Information Center

    Hill, Devon W.; And Others

    1988-01-01

    Describes a laboratory technique for quantitative analysis of caffeine by an isotopic dilution method for coupled gas chromatography-mass spectroscopy. Discusses caffeine analysis and experimental methodology. Lists sample caffeine concentrations found in common products. (MVL)

  10. Characteristics of Heavy Metals and Pb Isotopic Composition in Sediments Collected from the Tributaries in Three Gorges Reservoir, China

    PubMed Central

    Gao, Bo; Zhou, Huaidong; Huang, Yong; Wang, Yuchun; Gao, Jijun; Liu, Xiaobo

    2014-01-01

    The concentrations, distribution, accumulation, and potential ecological risk of heavy metals (Cr, Cu, Zn, Ni, As, Pb, Cd, and Hg) in sediments from the Three Gorges Reservoir (TGR) tributaries were determined and studied. Pb isotopic compositions in sediments were also measured to effectively identify the potential Pb sources. The results showed that the average concentrations of heavy metals in sediment of TGR tributaries were higher than the local background values of soils and sediments in China. The assessment by Geoaccumulation Index indicated that Cu, Ni, and Hg were at the “slightly polluted” level and Cd was ranked as the “moderately polluted” level in tributary sediments of TGR. The assessment by Potential Ecological Risk Index showed that Hg and Cd were the predominant elements in tributary sediments in TGR. The Pb isotopic ratios in sediments varied from 1.171 to 1.202 for 206Pb/207Pb and from 2.459 to 2.482 for 208Pb/207Pb in TGR. All Pb isotopic ratios in sediments were similar to those from coal combustion, lead ores (the mining activities and smelting process), and cement material, indicating that these anthropogenic inputs may be the main sources for Pb pollution in sediments of TGR tributaries. PMID:24624045

  11. Pb, Sr, and Nd isotopes in seamount basalts from the Juan de Fuca Ridge and Kodiak-Bowie seamount chain, northeast Pacific

    USGS Publications Warehouse

    Hegner, E.; Tatsumoto, M.

    1989-01-01

    Pb, Sr, and Nd isotopic ratios and their parent/daughter element concentrations for 28 basalts from 10 hotspot and nonhotspot seamounts are reported. Nd and Sr isotopic compositions (143Nd/144Nd = 0.51325-0.51304; 87Sr/86Sr = 0.70237-0.70275) plot in the envelope for Juan de Fuca-Gorda ridge basalts with tholeiitic basalts showing more depleted sources and a better negative correlation than transitional to alkalic basalts. Pb isotopic ratios in tholeiitic and alkalic basalts overlap (206Pb/204Pb = 18.29-19.44) and display a trend toward more radiogenic Pb in alkalic basalts. The isotopic data for hotspot and nonhotspot basalts are indistinguishable and correlate broadly with rock composition, implying that they are controlled by partial melting. The isotopic variation in the seamount basalts is about 60% (Nd-Sr) to 100% (Pb) of that in East Pacific Rise basalts and is interpreted as a lower limit for the magnitude of mantle heterogeneity in the northeast Pacific. The data indicate absence of a chemically distinct plume component in the linear seamount chains and strongly suggest an origin from mid-ocean ridge basalt-like east Pacific mantle. -Authors

  12. Quantifying the signature of the industrial revolution from Pb and Cd isotopes in the Susquehanna Shale Hills Critical Zone Observatory

    NASA Astrophysics Data System (ADS)

    Ma, L.; Herndon, E.; Jin, L.; Sanchez, D.; Brantley, S. L.

    2013-12-01

    Anthropogenic forcings have dominated metal cycling in many environments. During the period of the industrial revolution, mining and smelting of ores and combustion of fossil fuels released non-negligible amounts of potentially toxic metals such as Pb, Cd, Mn, and Zn into the environment. The extent and fate of these metal depositions in soils during that period however, have not been adequately evaluated. Here, we combine Pb isotopes with Cd isotopes to trace the sources of metal pollutants in a small temperate watershed (Shale Hills) in Pennsylvania. Previous work has shown that Mn additions to soils in central PA was caused by early iron production, as well as coal burning and steel making upwind. Comparison of the Pb and Cd concentrations in the bedrock and soils from this watershed show that Pb and Cd in soils at Shale Hills are best characterized by addition profiles, consistent with atmospheric additions. Three soil profiles at Shale Hills on the same hillslope have very similar anthropogenic Pb inventories. Pb isotope results further reveal that the extensive use of local coals during iron production in early 19th century in Pennsylvania is most likely the anthropogenic Pb source for the surface soils at Shale Hills. Pb concentrations and isotope ratios were used to calculate mass balance and diffusive transport models in soil profiles. The model results further reveal that during the 1850s to 1920s, coal burning in local iron blasting furnaces significantly increased the Pb deposition rates to 8-14 μg cm-2 yr-1, even more than modern Pb deposition rates derived from the use of leaded gasoline in the 1940s to 1980s. Furthermore, Cd has a low boiling point (~760 °C) and easily evaporates and condenses. The evaporation and condensation processes could generate systematic mass-dependent isotope fractionation between Cd in coal burning products and the naturally occurring Cd in the sulfide minerals of coals. This fractionation indicates that Cd isotopes can

  13. Isotope Dilution-Based Targeted and Nontargeted Carbonyl Neurosteroid/Steroid Profiling.

    PubMed

    Sharp, Sheila; Mitchell, Scott J; Vallée, Monique; Kuzmanova, Elena; Cooper, Michelle; Belelli, Delia; Lambert, Jeremy J; Huang, Jeffrey T-J

    2018-04-17

    Neurosteroids are brain-derived steroids, capable of rapidly modulating neuronal excitability in a nongenomic manner. Dysregulation of their synthesis or metabolism has been implicated in many pathological conditions. Here, we describe an isotope dilution based targeted and nontargeted (ID-TNT) profiling of carbonyl neurosteroids/steroids. The method combines stable isotope dilution, hydroxylamine derivatization, high-resolution MS scanning, and data-dependent MS/MS analysis, allowing absolute quantification of pregnenolone, progesterone, 5α-dihydroprogesterone, 3α,5α-tetrahydroprogesterone, and 3β,5α-tetrahydroprogesterone, and relative quantification of other carbonyl containing steroids. The utility and validity of this approach was tested in an acute stress mouse model and via pharmacological manipulation of the steroid metabolic pathway with finasteride. We report that brain levels of 3α,5α-tetrahydroprogesterone, a potent enhancer of GABA A receptor (GABA A R-mediated inhibitory function, from control mice is in the 5-40 pmol/g range, a value greater than previously reported. The approach allows the use of data from targeted analysis to guide the normalization strategy for nontargeted data. Furthermore, novel findings, including a striking increase of brain pregnenolone following finasteride administration were discovered in this study. Collectively, our results indicate that this approach has distinct advantages for examining targeted and nontargeted neurosteroid/steroid pathways in animal models and could facilitate a better understanding of the physiological and pathological roles of neurosteroids as modulators of brain excitability.

  14. ISOTOPIC COMPOSITION OF THE COMMON LEAD OF JAPAN

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

    Sakai, H.; Sato, K.

    1958-11-01

    Lead tetramethyl was synthesized from lead iodide isolated from 14 galenas, 2 anglesites, and 6 pyromorphites of Japan. The mass spectrometric analysis was carried out for the peaks of lead and lead hydride ions. The isotopic compositions of leads from these minerais lie wiyhn a narrow range. The average values for gnlanas are 18.51 O 0.05 for Pb/sup 238//Pb/sup 204/ 15.60 plus or minus 0.05 for Pb/sup 207//Pb/sup 204/8.76 plus or minus 0.15 forPb/ sup 208//Pb/sup 204/ For lead of secondary minerals they are 18.52 plus or minus 0.05, 15.62 plus or minus 0.05, and 38.78 plus or minus 0.15,more » respectively. No detectabla difference was observed between the isotopic compositions of primary and secondary lead ores. The ratios, U/sub 238/Pb/sup 204, and Th/sup 232/ U/sup 238/, in the source magma are estimated from the lead abundances. They are« less

  15. Comprehensive Pb-Sr-Nd-Hf isotopic, trace element, and mineralogical characterization of mafic to ultramafic rock reference materials

    NASA Astrophysics Data System (ADS)

    Fourny, Anaïs.; Weis, Dominique; Scoates, James S.

    2016-03-01

    Controlling the accuracy and precision of geochemical analyses requires the use of characterized reference materials with matrices similar to those of the unknown samples being analyzed. We report a comprehensive Pb-Sr-Nd-Hf isotopic and trace element concentration data set, combined with quantitative phase analysis by XRD Rietveld refinement, for a wide range of mafic to ultramafic rock reference materials analyzed at the Pacific Centre for Isotopic and Geochemical Research, University of British Columbia. The samples include a pyroxenite (NIM-P), five basalts (BHVO-2, BIR-1a, JB-3, BE-N, GSR-3), a diabase (W-2), a dolerite (DNC-1), a norite (NIM-N), and an anorthosite (AN-G); results from a leucogabbro (Stillwater) are also reported. Individual isotopic ratios determined by MC-ICP-MS and TIMS, and multielement analyses by HR-ICP-MS are reported with 4-12 complete analytical duplicates for each sample. The basaltic reference materials have coherent Sr and Nd isotopic ratios with external precision below 50 ppm (2SD) and below 100 ppm for Hf isotopes (except BIR-1a). For Pb isotopic reproducibility, several of the basalts (JB-3, BHVO-2) require acid leaching prior to dissolution. The plutonic reference materials also have coherent Sr and Nd isotopic ratios (<50 ppm), however, obtaining good reproducibility for Pb and Hf isotopic ratios is more challenging for NIM-P, NIM-N, and AN-G due to a variety of factors, including postcrystallization Pb mobility and the presence of accessory zircon. Collectively, these results form a comprehensive new database that can be used by the geochemical community for evaluating the radiogenic isotope and trace element compositions of volcanic and plutonic mafic-ultramafic rocks.

  16. Application of isotope-dilution laser ablation ICP-MS for direct determination of Pu concentrations in soils at pg g(-1) levels.

    PubMed

    Boulyga, Sergei F; Tibi, Markus; Heumann, Klaus G

    2004-01-01

    The methods available for determination of environmental contamination by plutonium at ultra-trace levels require labor-consuming sample preparation including matrix removal and plutonium extraction in both nuclear spectroscopy and mass spectrometry. In this work, laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for direct analysis of Pu in soil and sediment samples. Application of a LINA-Spark-Atomizer system (a modified laser ablation system providing high ablation rates) coupled with a sector-field ICP-MS resulted in detection limits as low as 3x10(-13) g g(-1) for Pu isotopes in soil samples containing uranium at a concentration of a few microg g(-1). The isotope dilution (ID) technique was used for quantification, which compensated for matrix effects in LA-ICP-MS. Interferences by UH+ and PbO2+ ions and by the peak tail of 238U+ ions were reduced or separated by use of dry plasma conditions and a mass resolution of 4000, respectively. No other effects affecting measurement accuracy, except sample inhomogeneity, were revealed. Comparison of results obtained for three contaminated soil samples by use of alpha-spectrometry, ICP-MS with sample decomposition, and LA-ICP-IDMS showed, in general, satisfactory agreement of the different methods. The specific activity of (239+240)Pu (9.8 +/- 3.0 mBq g(-1)) calculated from LA-ICP-IDMS analysis of SRM NIST 4357 coincided well with the certified value of 10.4 +/- 0.2 mBq g(-1). However, the precision of LA-ICP-MS for determination of plutonium in inhomogeneous samples, i.e. if "hot" particles are present, is limited. As far as we are aware this paper reports the lowest detection limits and element concentrations yet measured in direct LA-ICP-MS analysis of environmental samples.

  17. Calibrating Late Cretaceous Terrestrial Cyclostratigraphy with High-precision U-Pb Zircon Geochronology: Qingshankou Formation of the Songliao Basin, China

    NASA Astrophysics Data System (ADS)

    Wang, T.; Ramezani, J.; Wang, C.

    2015-12-01

    A continuous succession of Late Cretaceous lacustrine strata has been recovered from the SK-I south (SK-Is) and SKI north (SK-In) boreholes in the long-lived Cretaceous Songliao Basin in Northeast China. Establishing a high-resolution chronostratigraphic framework is a prerequisite for integrating the Songliao record with the global marine Cretaceous. We present high-precision U-Pb zircon geochronology by the chemical abrasion isotope dilution thermal-ionization mass spectrometry method from multiple bentonite core samples from the Late Cretaceous Qingshankou Formation in order to assess the astrochronological model for the Songliao Basin cyclostratigraphy. Our results from the SK-Is core present major improvements in precision and accuracy over the previously published geochronology and allow a cycle-level calibration of the cyclostratigraphy. The resulting choronostratigraphy suggest a good first-order agreement between the radioisotope geochronology and the established astrochronological time scale over the corresponding interval. The dated bentonite beds near the 1780 m depth straddle a prominent oil shale layer of the Qingshankou Formation, which records a basin-wide lake anoxic event (LAE1), providing a direct age constraint for the LAE1. The latter appears to coincide in time with the Late Cretaceous (Turonian) global sea level change event Tu4 presently constrained at 91.8 Ma.

  18. Hydrothermal titanite from the Chengchao iron skarn deposit: temporal constraints on iron mineralization, and its potential as a reference material for titanite U-Pb dating

    NASA Astrophysics Data System (ADS)

    Hu, Hao; Li, Jian-Wei; McFarlane, Christopher R. M.

    2017-09-01

    Uranium-lead isotopes and trace elements of titanite from the Chengchao iron skarn deposit (Daye district, Eastern China), located along the contact zones between Triassic marine carbonates and an early Cretaceous intrusive complex consisting of granite and quartz diorite, were analyzed using laser ablation inductively coupled plasma mass spectrometry to provide temporal constraints on iron mineralization and to evaluate its potential as a reference material for titanite U-Pb geochronology. Titanite grains from mineralized endoskarn have simple growth zoning patterns, exhibit intergrowth with magnetite, diopside, K-feldspar, albite and actinolite, and typically contain abundant primary two-phase fluid inclusions. These paragenetic and textural features suggest that these titanite grains are of hydrothermal origin. Hydrothermal titanite is distinct from the magmatic variety from the ore-related granitic intrusion in that it contains unusually high concentrations of U (up to 2995 ppm), low levels of Th (12.5-453 ppm), and virtually no common Pb. The REE concentrations are much lower, as are the Th/U and Lu/Hf ratios. The hydrothermal titanite grains yield reproducible uncorrected U-Pb ages ranging from 129.7 ± 0.7 to 132.1 ± 2.7 Ma (2σ), with a weighted mean of 131.2 ± 0.2 Ma [mean standard weighted deviation (MSWD) = 1.7] that is interpreted as the timing of iron skarn mineralization. This age closely corresponds to the zircon U-Pb age of 130.9 ± 0.7 Ma (MSWD = 0.7) determined for the quartz diorite, and the U-Pb ages for zircon and titanite (130.1 ± 1.0 Ma and 131.3 ± 0.3 Ma) in the granite, confirming a close temporal and likely genetic relationship between granitic magmatism and iron mineralization. Different hydrothermal titanite grains have virtually identical uncorrected U-Pb ratios suggestive of negligible common Pb in the mineral. The homogeneous textures and U-Pb characteristics of Chengchao hydrothermal titanite suggest that the mineral might be a

  19. 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.

  20. Pb-isotopic compositions of volcanic rocks in the West and East Philippine island arcs: presence of the Dupal isotopic anomaly

    NASA Astrophysics Data System (ADS)

    Mukasa, Samuel B.; McCabe, Robert; Gill, James B.

    1987-07-01

    The Philippine islands are situated between two oppositely dipping zones of seismicity. With the exception of a few areas, such as in the west central Philippines where the North Palawan continental terrane (NPCT) has collided with the archipelago, these seismic zones are well defined to depths of 200 km. Active volcanic chains overlay segments in each of these zones, suggesting that subduction is presently taking place both east and west of the islands. Lavas we have studied are thus divided between what has been termed the West Philippine arc and the East Philippine arc. West Philippine arc volcanic rocks which were extruded before the Philippine archipelago collided with the NPCT, or which are younger than the collision but crop out hundreds of kilometers from the collision zone, and all but one of the rocks from the East Philippine arc fall in the MORB field on 207Pb/ 204Pb versus 206Pb/ 204Pb covariation diagrams. This is surprising considering the frequency with which arc materials have 207Pb/ 204Pb ratios higher than those of MORB, the highBa/REE and Sr/REE ratios in the lavas and the possibility of sediment subduction given the small accretionary prisms. All of these rocks have high 208Pb/ 204Pb ratios with respect to Pacific and Atlantic Ocean MORB, but are similar to Indian Ocean MORB and IOB. Thus the Philippines consist of island arcs with the peculiar Dupal isotopic anomaly documented between 0° and 60°S in the southern hemisphere and particularly in the Indian Ocean region. This demonstrates that the Dupal isotopic anomaly is not restricted to the southern hemisphere, or to MORB and OIB. Post-collision rocks cropping out near the NPCT, in the West Philippine arc, have elevated 208Pb/ 204Pb and 207Pb/ 204Pb ratios that could be attributed to assimilation of the newly introduced continental crust (NPCT) by mantle-derived magmas or to the addition of a sedimentary component to mantle-derived magmas.

  1. Lead isotopes in trade wind aerosols at Barbados - The influence of European emissions over the North Atlantic

    NASA Technical Reports Server (NTRS)

    Hamelin, B.; Grousset, F. E.; Biscaye, P. E.; Zindler, A.; Prospero, J. M.

    1989-01-01

    Previous studies have shown that Pb can be used as a transient tracer in the atmosphere and the ocean because of strong time-variability of industrial inputs and because Pb isotopic composition can be used to identify contributions from different sources. Pb isotopic measurements on aerosols collected from the North Atlantic Ocean in the trade wind belt are presented. Aerosols sampled at Barbados during the 1969-1985 period have a Pb isotopic composition different from that observed by previous investigators in Bermuda corals and Sargasso Sea waters. Barbados aerosols appear to contain significant amounts of relatively unradiogenic industrial and automotive Pb that is derived from Europe and carried to Barbados by the trade winds. In contrast, Bermuda corals and Sargasso sea waters are influenced mainly by U.S.-derived emissions, which contain more radiogenic Pb originating from Missouri-type ores. This difference generates a strong latitudinal Europe-U.S.A. isotopic gradient, thus allowing study of trans-Atlantic atmospheric transport and ocean mixing processes.

  2. Reaction paths and host phases of uranium isotopes (235U; 238U), Saanich Inlet

    NASA Astrophysics Data System (ADS)

    Amini, M.; Holmden, C. E.; Francois, R. H.

    2009-12-01

    In recent times, Uranium has become increasingly the focus of stable isotope fractionation studies. Variations in 238U/235U have been reported as a result of redox reactions [1,2] from the nuclear field shift effect [3], and a mass-dependent, microbially-mediated, kinetic isotope effect [4]. The 238U/235U variability caused by changes in environmental redox conditions leads to an increase in the 238U/235U ratios of the reduced U species sequestered into marine sediments. This points to U isotope variability as a new tool to study ancient ocean redox changes. However, the process by which reduced sediments become enriched in the heavy isotopes of U is not yet known, and hence the utility of 238U/235U as a redox tracer remains to be demonstrated. In order to further constrain sedimentary U enrichment and related isotope effect, we are investigating U isotopic compositions of water samples and fresh surface sediment grab samples over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. U was sequentially extracted from sediments in order to characterize specific fractions for their isotopic composition. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10‰ (2sd). Fifteeen analyses of seawater yielded δ238U of -0.42±0.08‰ (2sd). The results for the water samples indicate a homogenous δ238U value throughout the Saanich Inlet water column that matches the global seawater signature. All of the water samples from above and below average -0.42±0.05‰ (2sd). In contrast, a plankton net sample yielded a distinctly different, (about 0.5‰ lighter) isotope value. Bacterial reduction experiments [4] have also shown isotope enrichment factors of about -0.3‰. In addition, metal isotope fractionation occurs during adsorption with the light isotope being

  3. Determination of 241Am in sediments by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS).

    PubMed

    Agarande, M; Benzoubir, S; Bouisset, P; Calmet, D

    2001-08-01

    Trace levels (pg kg(-1)) of 241Am in sediments were determined by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS) using a microconcentric nebulizer. 241Am was isolated from major elements like Ca and Fe by different selective precipitations. In further steps. Am was first separated from other transuranic elements and purified by anion exchange and extraction chromatography prior to the mass spectrometric measurements. The ID HR ICP-MS results are compared with isotope dilution alpha spectrometry.

  4. Spatio-temporal distribution and sources of Pb identified by stable isotopic ratios in sediments from the Yangtze River Estuary and adjacent areas.

    PubMed

    Chen, Bin; Liu, Jian; Hu, Limin; Liu, Ming; Wang, Liang; Zhang, Xilin; Fan, Dejiang

    2017-02-15

    To understand the spatio-temporal distribution and sources of Pb in the sediments of the Yangtze River Estuary and its adjacent areas, 25 surface sediments and 1 sediment core were collected from the study areas. The concentrations of Al and Pb of these sediments exhibit a decreasing trend from the nearshore towards the offshore, with higher concentrations in the coastal areas of the East China Sea (ECS) and southwest of Jeju Island. According to the stable isotopic ratios of Pb, in combination with the elemental ratios and clay mineral data, it is inferred that sedimentary Pb in the surface sediments of the coastal areas of the ECS may come primarily from the Yangtze River, while the Pb southwest of Jeju Island is probably derived from both the Yangtze and Yellow Rivers. The particulate Pb derived from the Yangtze River was possibly dispersed along two paths: the path southward along the coastline of the ECS and the path eastward associated with the Changjiang Diluted Water (CDW), which crosses the shelf of the ECS towards the area southeast of Jeju Island. Although the Yangtze River Basin witnessed rapid economic development during the period from the late 1970s to the middle 1990s, the influence of human activity on Pb concentration remained weak in the Yangtze River Estuary. Since the early 2000s, however, sedimentary Pb has been significantly increasing in the coastal mud areas of the ECS due to the increasing influence of human activity, such as the increase in atmospheric emission of anthropogenic Pb in China, construction of the Three Gorges Dam (TGD), and the construction of smaller dams in the upper reaches of the Yangtze River. Coal combustion and the smelting of non-ferrous metals are possible anthropogenic sources for the sedimentary Pb in the Yangtze River Estuary. Copyright © 2016. Published by Elsevier B.V.

  5. In-situ Pb isotope analysis of Fe-Ni-Cu sulphides by laser ablation multi-collector ICPMS: New insights into ore formation in the Sudbury impact melt sheet

    NASA Astrophysics Data System (ADS)

    Darling, J. R.; Storey, C. D.; Hawkesworth, C. J.; Lightfoot, P. C.

    2012-12-01

    Laser-ablation (LA) multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) is ideally suited to in situ determination of isotope ratios in sulphide minerals. Using samples of magmatic sulphide ore from the Sudbury impact structure, we test LA-MC-ICPMS analytical protocols that aim to meet a range of analytical challenges in the analysis of Pb isotopes. These include: potential matrix sensitive isotopic fractionation; interferences on Pb isotopes; low melting points of many sulphide minerals; the availability of standards. Magmatic sulphides of wide ranging mineralogy (pyrrhotite, pentlandite, chalcopyrite, pyrite and sphalerite) were analysed for Pb isotopic composition, using the silicate glass NIST SRM 610 as an external standard to correct for instrumental mass-fractionation. Despite matrix sensitive melting and re-deposition around ablation pits, several lines of evidence indicate that all analyses are accurate, within typical analytical uncertainties of 0.003-2% (2σ), and that the defined approach is insensitive to compositional diversity in sample matrix: (a) laser ablation and dissolution based measurements of sulphide powders are in agreement; (b) analyses from each sample define isochron ages within uncertainty of the known crystallization age (1850 Ma); (c) the results of sulphide measurements by laser ablation are consistent with age-corrected feldspar analyses from the same samples. The results have important implications for ore formation in Sudbury. The Pb isotope data regressions are consistent with age corrected feldspar analyses from each respective sample, which together with time integrated Th/U ratios that match whole rock values (3.1, 4.0 and 6.1 for the Worthington, Copper Cliff and Parkin Offset Dykes, respectively) indicate chemical equilibrium between the silicate and sulphide systems during ore formation. The sulphides within each respective sample have indistinguishable model initial Pb isotope ratios (207Pb/204Pbm

  6. Tracing of ca 800 yr old mining activity in peat bog using Pb elemental concentrations and isotope compositions.

    NASA Astrophysics Data System (ADS)

    Baron, S.; Carignan, J.; Ploquin, A.

    2003-04-01

    Sixty sites of slags have been documented on the Mont-Lozère in southern France. The petrographic analysis shows that slags are metallurgical wastes (800 to 850 yr BP) which certainly result from smelting activity for lead and silver extraction (Ploquin et al., 2001). The aims of this study are: 1) to trace the source of Pb ores which supplied the smelting sites, by using the Pb isotopic composition of several surrounding Pb deposits, 2) to evaluate the actual pollution caused by these slags, by using elemental and isotopic compositions of soils, water and vegetation, and 3) to document the pollution history of the region, by using elemental and isotopic compositions of peat bog cores collected in the neighbourhood of the historical smelting sites. The lead isotopic composition of galena collected in most surrounding ores is very similar to that of different slag samples. On the other hand, the high precision of the results allowed us to select the mineralised areas which were probably the ore sources. The Pb isotopic composition of slags is even more homogeneous: 208/206 Pb: 2.092±0.002; 206/207 Pb: 1.179±0.001; 208/204 Pb: 38.663±0.025; 207/204 Pb: 15.665±0.006; 206/204 Pb: 18.476±0.023, and will allow source tracing in the environment. The "Narses Mortes" peat bog, around which two smelting sites have been reported, is strongly minerotrophic and contains 8 to 60% ash. A 1.40 m core have been retrieved and divided into 58 individual samples. Minerotrophic peat bog records both atmospheric deposition, soils leaching and the grounwater influence. The measured metal concentrations are normalised to Al contents of peat bog samples and the metal/Al ratios are compared to that of the Mont-Lozère granite: relative excess in metal concentrations are found in peat bog samples. An increasing excess of most metals (Pb, Zn, Cd...) was measured for surface samples, from 55 cm depth to the top of the core (23 cm depth). This profil might be attributed to atmospheric

  7. Contribution to the certification of B, Cd, Cu, Mg and Pb in a synthetic water sample, by use of isotope-dilution ICP-MS, for Comparison 12 of the International Measurement Evaluation Programme.

    PubMed

    Diemer, J; Quétel, C R; Taylor, P D P

    2002-09-01

    The contribution of the Institute for Reference Materials and Measurements to the certification of the B, Cd, Cu, Mg, and Pb content of a synthetic water sample used in Comparison 12 of the International Measurement Evaluation Programme (IMEP-12) is described. The aim of the IMEP programme is to demonstrate objectively the degree of equivalence and quality of chemical measurements of individual laboratories on the international scene by comparing them with reference ranges traceable to the SI (Système International d'Unités). IMEP is organized in support of European Union policies and helps to improve the traceability of values produced by field chemical measurement laboratories. The analytical procedure used to establish the reference values for the B, Cd, Cu, Mg, and Pb content of the IMEP-12 sample is based on inductively coupled plasma-isotope-dilution mass spectrometry (ICP-IDMS) applied as a primary method of measurement. The measurements performed for the IMEP-12 study are described in detail. Focus is on the element boron, which is particularly difficult to analyze by ICP-MS because of potential problems of low sensitivity, high mass discrimination, memory effects, and abundance sensitivity. For each of the certified amount contents presented here a total uncertainty budget was calculated using the method of propagation of uncertainties according to ISO (International Organization for Standardization) and Eurachem guidelines. For all investigated elements with concentrations in the low micro g kg(-1) and mg kg(-1) range (corresponding to pmol kg(-1) to the high micro mol kg(-1) level), SI-traceable reference values with relative expanded uncertainties ( k=2) of less than 2 % were obtained.

  8. Inherited Pb isotopic records in olivine antecryst-hosted melt inclusions from Hawaiian lavas

    NASA Astrophysics Data System (ADS)

    Sakyi, Patrick Asamoah; Tanaka, Ryoji; Kobayashi, Katsura; Nakamura, Eizo

    2012-10-01

    Dislocation textures of olivine grains and Pb isotopic compositions (207Pb/206Pb and 208Pb/206Pb) of olivine-hosted melt inclusions in basaltic lavas from three Hawaiian volcanoes (Kilauea, Mauna Loa, and Koolau) were examined. More than 70% of the blocky olivine grains in the studied samples have a regular-shaped dislocation texture with their dislocation densities exceeding 106 cm-2, and can be considered as deformed olivine. The size distribution of blocky olivine grains shows that more than 99% of blocky olivines coarser than 1.2 mm are identified as deformed olivine. These deformed olivine grains are identified as antecrysts, which originally crystallized from previous stages of magmatism in the same shield, followed by plastic deformation prior to entrainment in the erupted host magmas. This study revealed that entrainment of mantle-derived crystallization products by younger batches of magma is an important part of the evolution of magnesium-rich Hawaiian magma. Lead isotopic compositions of melt inclusions hosted in the olivine antecrysts provide information of the evolutionary history of Hawaiian volcanoes which could not have been accessed if only whole rock analyses were carried out. Antecryst-hosted melt inclusions in Kilauea and Koolau lavas demonstrate that the source components in the melting region changed during shield formation. In particular, evidence of interaction of plume-derived melts and upper mantle was observed in the earliest stage of Koolau magmatism.

  9. Slab-derived components in the subcontinental lithospheric mantle beneath Chilean Patagonia: Geochemistry and Sr-Nd-Pb isotopes of mantle xenoliths and host basalt

    NASA Astrophysics Data System (ADS)

    Jalowitzki, Tiago; Gervasoni, Fernanda; Conceição, Rommulo V.; Orihashi, Yuji; Bertotto, Gustavo W.; Sumino, Hirochika; Schilling, Manuel E.; Nagao, Keisuke; Morata, Diego; Sylvester, Paul

    2017-11-01

    In subduction zones, ultramafic xenoliths hosted in alkaline basalts can yield significant information about the role of potential slab-derived components in the subcontinental lithospheric mantle (SCLM). Chemical and isotopic heterogeneities in such xenoliths are usually interpreted to reflect melt extraction followed by metasomatic re-enrichment. Here we report new whole-rock major, trace element and isotopic (Sr-Nd-Pb) data for a Proterozoic suite of 17 anhydrous spinel-lherzolites and Eocene (new K-Ar data) host alkaline basalt found near Coyhaique ( 46°S), Aysén Region, Chile. These Patagonian nodules are located in a current back-arc position, 100 km east of the present day volcanic arc and 320 km from the Chile Trench. The mantle xenoliths consist of coarse- to medium-grained spinel-lherzolites with trace element compositions characteristic of a subduction zone setting, such as pronounced negative Nb, Ta and Ti anomalies coupled with significant enrichment of LILEs (e.g., U) and chalcophile elements (W, Pb and Sn). Most of them are characterized by flat to depleted light-rare earth element (LREE) patterns (Ce/YbN = 0.6-1.1) coupled with less radiogenic Sr-Pb (87Sr/86Sr = 0.702422-0.703479; 206Pb/204Pb = 18.212-18.539) and more radiogenic Nd isotopic compositions (143Nd/144Nd = 0.512994-0.513242), similar to the depleted mantle component (DMM or PREMA). In contrast, samples with slight LREE enrichment (Ce/YbN = 1.3-1.8) show more radiogenic Sr-Pb (87Sr/86Sr = 0.703791-0.704239; 206Pb/204Pb = 18.572-18.703) and less radiogenic Nd isotopic compositions (143Nd/144Nd = 0.512859-0.512934), similar to the EM-2 reservoir. These new geochemical and isotope data suggest that the Coyhaique spinel-lherzolites are derived from a heterogeneous SCLM resulting from mixing between a depleted mantle component and up to 10% of slab-derived components. The enriched component added to the SCLM represents variable extents of melts of both subducted Chile Trench sediments and

  10. Pb isotopic constrains and environmental risk assessment of the Domizio Flegreo and Agro Aversano area (Campania region, Italy).

    NASA Astrophysics Data System (ADS)

    Rezza, Carmela; Albanese, Stefano; Ayuso, Robert; Lima, Annamaria; Sorvari, Jaana; De Vivo, Benedetto

    2016-04-01

    contribution. These studies were done at the Radiogenic Isotope Laboratory of the U.S. Geological Survey (Reston, VA, USA) following standard isotopic separations in Class 100 laboratories. The samples were analyzed using an HR-ICP-MS and a FinniganMat (Spectromat) spectrometers. Notably, the Pb isotopic compositions of human hair generally matched the Pb isotopic values that were previously shown by others to represent the composition of aerosol (2) (Tommasini et al., 2000), implying that Pb originates from the anthropogenic activities in the area. Further studies will include the determination of risks to human health caused by the elevated concentrations of the key elements in the environment and food items.To start with, apreliminary conceptual model will be created that serves as a basis for a detailed regional risk assessments.The results will enable us to define specific risk management actions needed for the protection of human health in the study area. (1)Hakanson et al., 1980.An ecological risk index for aquatic pollution control. A sedimentological approach. Water Research. 14, 975 -100. (2)Tommasini et al., 2000.Lead isotopic composition of three ring as biogeochemical tracers of heavy metal pollution: a reconnaisance study from Firenze. Italy. Appl. Geochm. 15, 891-900.

  11. Characteristics of lead geochemistry and the mobility of Pb isotopes in the system of pedogenic rock-pedosphere-irrigated riverwater-cereal-atmosphere from the Yangtze River delta region, China.

    PubMed

    Wang, Cheng; Wang, Jianhua; Yang, Zhongfang; Mao, Changping; Ji, Junfeng

    2013-11-01

    Knowledge of the characteristics of Pb and its isotopic transfer in different compartments is scant, especially for the mobility of Pb isotopes in the geochemical cycle. The present study characterizes differential Pb transport mechanism and the mobility of Pb isotopes in the pedogenic parent rock-pedosphere-irrigated riverwater-cereal-atmosphere system in the Yangtze River delta region, by determining Pb concentration and Pb isotopic ratios of pedogenic parent rocks, fluvial suspended particle matter, tillage soils, soil profiles, irrigated riverwater, fertilizer, Pb ore, cereal roots and grains. The results show that Pb isotopes in the geochemical cycle generally follow the equation of (208)Pb/(206)Pb=-1.157×(206)Pb/(207)Pb+3.46 (r(2)=0.941). However, Pb isotopes have different mobility in different environmental matrixes. Whereas in the pedosphere, the heavier Pb ((208)Pb) usually shows stronger mobility relative to the lighter Pb, and is more likely to transfer into soil exchangeable Pb fraction and carbonates phase. The lighter Pb shows stronger transfer ability from soil to cereal grain via root compared to the heavier Pb. However, the cereal grains have lower (206)Pb/(207)Pb and higher (208)Pb/(206)Pb ratios than root and tillage soil, similar to the airborne Pb and anthropogenic Pb, implying that a considerable amount of Pb in cereal grains comes from the atmosphere. The estimate model shows that 16.7-52.6% (average: 33.5%) of Pb in rice grain is the airborne Pb. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. The plumbotectonic model for Pb isotopic systematics among major terrestrial reservoirs - A case for bi-directional transport

    NASA Astrophysics Data System (ADS)

    Zartman, Robert E.; Haines, Sara M.

    1988-06-01

    Version IV of plumbotectonics expands and refines the original model of DOE and ZARTMAN (1979) and ZARTMAN and DOE (1981) for explaining Pb (Sr, and Nd) isotopic systematics among major terrestrial reservoirs. A case for bi-directional transport among reservoirs is based on the observed isotopic compositions for different tectonic settings, and finds a rationale in the kinetics of plate tectonics. Chemical fractionation and radioactive decay create isotopic differences during periods of isolation of one reservoir from another, whereas dynamic processes allowing mixing between reservoirs tend to reduce these differences. Observed isotopic characteristics reflect a balance between these opposing tendencies and provide constraints on the extent and timing of fractionation and mixing processes. Plumbotectonics does not require interaction with a lower mantle or core reservoir over most of the Earth's lifetime, and, in fact, achieves a material balance consistent with no such exchange of material. Important evidence of the amount and timing of crustal recycling, and of the residence times of mantle heterogeneities lies in the coupled 207Pb /204Pb- 206 Pb 204Pb systematics. We believe that examination of the published data base fully supports our contention of significant bi-directional transport of material among terrestrial reservoirs. Plumbotectonics allows us to explore many aspects of reservoir interaction, and to identify parameters that provide meaningful constraints on mantle-crust differentiation. We put forth a compromise fit to many of the model variables in version IV, which can serve as a reference for future work.

  13. 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

  14. Microwave-assisted deuterium exchange: the convenient preparation of isotopically labelled analogues for stable isotope dilution analysis of volatile wine phenols.

    PubMed

    Crump, Anna M; Sefton, Mark A; Wilkinson, Kerry L

    2014-11-01

    This study reports the convenient, low cost, one-step synthesis of labelled analogues of six volatile phenols, guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-ethylphenol, eugenol and vanillin, using microwave-assisted deuterium exchange, for use as internal standards for stable isotope dilution analysis. The current method improves on previous strategies in that it enables incorporation of deuterium atoms on the aromatic ring, thereby ensuring retention of the isotope label during mass spectrometry fragmentation. When used as standards for SIDA, these labelled volatile phenols will improve the accuracy and reproducibility of quantitative food and beverage analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. High-precision Temporal Calibration of the Early Cambrian Biotic and Paleoenvironmental Records: New U-Pb Geochronology from Eastern Yunnan, China.

    NASA Astrophysics Data System (ADS)

    Tsukui, K.; Ramezani, J.; Zhu, M.; Maloof, A. C.; Porter, S.; Moore, J.; Eddy, M. P.; Bowring, S. A.

    2016-12-01

    The Terreneuvian Epoch of the early Cambrian marks the global diversification of early animal life, as well as major perturbations to Earth's geochemical cycles. Understanding possible links between biotic evolution (e.g., emergence of skeletal animals) and the recognized changes in ocean chemistry requires a high fidelity chronostratigraphic framework for the early Cambrian records. One such chronostratigraphy was built by mapping local early Cambrian carbon isotope profiles onto a U-Pb age-calibrated marine carbonate δ13C record from Morocco, assuming global synchroneity of the observed δ13C trends. Here we present a direct test of this assumption using high-precision U-Pb geochronology (CA-ID-TIMS method) of ash beds from key lower Cambrian horizons throughout eastern Yunnan Province in South China. Preliminary age results from ash beds near the top of the Dengying Formation (Fm.) and the basal Daibu Member (Mb.) of the Zhujiaqing Fm. in multiple sections place the basal Cambrian negative δ13C excursion (BACE) in China at ca. 540.7-539.6 Ma. Our new U-Pb dates from the overlying Zhongyicun Mb. at the Meishucun and nearby sections improve significantly upon previous in situ U-Pb geochronology and constrain the onset of high-frequency δ13C oscillations in some sections to between 533.5 and 532.9 Ma. Most importantly, a new U-Pb date of ca. 526 Ma from the basal Shiyantou Fm. in the Xiaotan Section marks the termination of a >1 million year-long period of consistently positive (≥+4‰) δ13C values (ZHUCE) that is characteristic of many early Cambrian records worldwide. This date establishes a robust time correlation between ZHUCE in South China and its equivalent 5p excursion in Morocco and Siberia, and constrains the timing and duration of the largest positive δ13C anomalies in the Cambrian.

  16. Modelling the isotopic evolution of the Earth.

    PubMed

    Paul, Debajyoti; White, William M; Turcotte, Donald L

    2002-11-15

    We present a flexible multi-reservoir (primitive lower mantle, depleted upper mantle, upper continental crust, lower continental crust and atmosphere) forward-transport model of the Earth, incorporating the Sm-Nd, Rb-Sr, U-Th-Pb-He and K-Ar isotope-decay systematics. Mathematically, the model consists of a series of differential equations, describing the changing abundance of each nuclide in each reservoir, which are solved repeatedly over the history of the Earth. Fluxes between reservoirs are keyed to heat production and further constrained by estimates of present-day fluxes (e.g. subduction, plume flux) and current sizes of reservoirs. Elemental transport is tied to these fluxes through 'enrichment factors', which allow for fractionation between species. A principal goal of the model is to reproduce the Pb-isotope systematics of the depleted upper mantle, which has not been done in earlier models. At present, the depleted upper mantle has low (238)U/(204)Pb (mu) and (232)Th/(238)U (kappa) ratios, but Pb-isotope ratios reflect high time-integrated values of these ratios. These features are reproduced in the model and are a consequence of preferential subduction of U and of radiogenic Pb from the upper continental crust into the depleted upper mantle. At the same time, the model reproduces the observed Sr-, Nd-, Ar- and He-isotope ratios of the atmosphere, continental crust and mantle. We show that both steady-state and time-variant concentrations of incompatible-element concentrations and ratios in the continental crust and upper mantle are possible. Indeed, in some cases, incompatible-element concentrations and ratios increase with time in the depleted mantle. Hence, assumptions of a progressively depleting or steady-state upper mantle are not justified. A ubiquitous feature of this model, as well as other evolutionary models, is early rapid depletion of the upper mantle in highly incompatible elements; hence, a near-chondritic Th/U ratio in the upper mantle

  17. Uranium isotope ratios of Muonionalusta troilite and complications for the absolute age of the IVA iron meteorite core

    NASA Astrophysics Data System (ADS)

    Brennecka, Gregory A.; Amelin, Yuri; Kleine, Thorsten

    2018-05-01

    The crystallization ages of planetary crustal material (given by basaltic meteorites) and planetary cores (given by iron meteorites) provide fiducial marks for the progress of planetary formation, and thus, the absolute ages of these objects fundamentally direct our knowledge and understanding of planet formation and evolution. The lone precise absolute age of planetary core material was previously obtained on troilite inclusions from the IVA iron meteorite Muonionalusta. This previously reported Pb-Pb age of 4565.3 ± 0.1 Ma-assuming a 238U/235U =137.88-only post-dated the start of the Solar System by approximately 2-3 million years, and mandated fast cooling of planetary core material. Since an accurate Pb-Pb age requires a known 238U/235U of the sample, we have measured both 238U/235U and Pb isotopic compositions of troilite inclusions from Muonionalusta. The measured 238U/235U of the samples range from ∼137.84 to as low as ∼137.22, however based on Pb and U systematics, terrestrial contamination appears pervasive and has affected samples to various extents for Pb and U. The cause of the relative 235U excess in one sample does not appear to be from terrestrial contamination or the decay of short-lived 247Cm, but is more likely from fractionation of U isotopes during metal-silicate separation during core formation, exacerbated by the extreme U depletion in the planetary core. Due to limited Pb isotopic variation and terrestrial disturbance, no samples of this study produced useful age information; however the clear divergence from the previously assumed 238U/235U of any troilite in Muonionalusta introduces substantial uncertainty to the previously reported absolute age of the sample without knowledge of the 238U/235U of the sample. Uncertainties associated with U isotope heterogeneity do not allow for definition of a robust age of solidification and cooling for the IVA core. However, one sample of this work-paired with previous work using short

  18. Quaternary climate modulation of Pb isotopes in the deep Indian Ocean linked to the Himalayan chemical weathering

    NASA Astrophysics Data System (ADS)

    Wilson, David J.; Galy, Albert; Piotrowski, Alexander M.; Banakar, Virupaxa K.

    2015-08-01

    We use reductive sediment leaching to extract lead (Pb) from the authigenic fraction of marine sediments and reconstruct the Pb isotope evolution of the deep central Indian Ocean over the past 250 thousand years at ∼3 kyr resolution. Temporal variations define a binary mixing line that is consistent with data from ferromanganese nodules and which records mixing between two well-defined endmembers through time. The unradiogenic endmember appears to represent a widely-distributed Pb source, from mid-ocean ridges or possibly volcanic aerosols, while the radiogenic endmember coincides with the composition of Ganges-Brahmaputra river sediments that are indicative of the Himalayan weathering inputs. Glacial-interglacial Pb isotope variations are striking and can be explained by an enhancement of Himalayan contributions by two to three times during interglacial periods, indicating that climate modulates the supply of dissolved elements to the ocean. While these changes could accurately record variations in the continental chemical weathering flux in response to warmer and wetter conditions during interglacials, the relative proportions of Pb derived from the Ganges and Brahmaputra appear to have been constant through time. This observation may point towards particulate-dissolved interactions in the estuary or pro-delta as a buffer of short timescale variability in the composition (and potentially flux) of the fluvial inputs. In addition, the changes are recorded at 3800 m water depth, and with the lack of deep water formation in the Bay of Bengal, a mechanism to transfer such a signature into the deep ocean could either be reversible scavenging of dissolved Pb inputs and/or boundary exchange on the deep sea fan. Unless the mechanism transferring the Pb isotope signature into the deep ocean was itself highly sensitive to global climate cycles, and with the absence of a precessional signal in our Pb isotope data, we suggest that the Indian climate and its influence on

  19. Comparison of TIMS and MC-ICP-MS Analyses of Pb Isotopic Compositions on Prehistoric Mauna Loa Basalts: Implications for Plume Source Components

    NASA Astrophysics Data System (ADS)

    De Jong, J.; Weis, D.; Maerschalk, C.; Rhodes, J. M.

    2001-12-01

    Recent isotopic studies on Hawaiian lavas have shown the necessity of constraining fractionation for Pb isotopes. This isotopic system presents systematic variations reflecting the presence of different plume components in the source of Hawaiian basalts. We have analyzed a series of 23 tholeiitic Mauna Loa basalts ranging in age from 36,780 to 140 y for their Pb isotopic compositions by TIMS (Micromass Sector 54) and MC-ICP-MS (Nu Plasma) to directly compare results from the same, carefully leached, samples. These analyses indicate an internal precision better than 120 ppm for the MC-ICP-MS Pb ratios, while for the TIMS ratios, it is in the per mil range. This results in a more coherent dataset for the MC-ICP-MS analyses, with the range of 207Pb/204Pb variations decreasing by a factor of 3 and of 208Pb/204Pb ratios by a factor of 1.5. The co-variations between the Pb isotopic data and other geochemical parameters for the Hawaiian lavas are now much stronger and better defined. There are clearly two groups amongst the prehistoric Mauna Loa basalts: one group with higher 87Sr/86Sr (>0.7038) and low 206Pb/204Pb (<18.15) that covers the entire range of Nb/Y (0.31 to 0.51) observed in this volcano, and the other group with low 87Sr/86Sr (<0.7038) and higher 206Pb/204Pb with Nb/Y<0.4. The second group is only present in basalts younger than 3,000 y or older than 24,000 y. The high 87Sr/86Sr group was not sampled in the HSDP I drill core, which covers an age range of 100,000 y. This either reflects a sampling bias, as the upper flow units (<10,000 y) were not sampled for geochemistry, or variations in magma supply. Altogether, Mauna Loa lava flows that are younger than 20,000 y show much more isotopic variation than older flows and there is a nearly continuous transition away from the Kilauea component. This may indicate that the transition between the Mauna Loa and Mauna Kea trends is not as sharp as previously documented. This study shows the importance of reducing the

  20. Investigating Uranium Mobility Using Stable Isotope Partitioning of 238U/235U and a Reactive Transport Model

    NASA Astrophysics Data System (ADS)

    Bizjack, M.; Johnson, T. M.; Druhan, J. L.; Shiel, A. E.

    2015-12-01

    We report a numerical reactive transport model which explicitly incorporates the effectively stable isotopes of uranium (U) and the factors that influence their partitioning in bioactive systems. The model reproduces trends observed in U isotope ratios and concentration measurements from a field experiment, thereby improving interpretations of U isotope ratios as a tracer for U reactive transport. A major factor contributing to U storage and transport is its redox state, which is commonly influenced by the availability of organic carbon to support metal-reducing microbial communities. Both laboratory and field experiments have demonstrated that biogenic reduction of U(VI) fractionates the stable isotope ratio 238U/235U, producing an isotopically heavy solid U(IV) product. It has also been shown that other common reactive transport processes involving U do not fractionate isotopes to a consistently measurable level, which suggests the capacity to quantify the extent of bioreduction occurring in groundwater containing U using 238U/235U ratios. A recent study of a U bioremediation experiment at the Rifle IFRC site (Colorado, USA) applied Rayleigh distillation models to quantify U stable isotope fractionation observed during acetate amendment. The application of these simplified models were fit to the observations only by invoking a "memory-effect," or a constant source of low-concentration, unfractionated U(VI). In order to more accurately interpret the measured U isotope ratios, we present a multi-component reactive transport model using the CrunchTope software. This approach is capable of quantifying the cycling and partitioning of individual U isotopes through a realistic network of transport and reaction pathways including reduction, oxidation, and microbial growth. The model incorporates physical heterogeneity of the aquifer sediments through zones of decreased permeability, which replicate the observed bromide tracer, major ion chemistry, U concentration, and U

  1. Detrital zircon U-Pb and (U-Th)/He double-dating of Upper Cretaceous-Cenozoic Zagros foreland basin strata in the Kurdistan Region of northern Iraq

    NASA Astrophysics Data System (ADS)

    Barber, D. E.; Stockli, D. F.; Koshnaw, R. I.; Horton, B. K.; Tamar-Agha, M. Y.; Kendall, J. J.

    2014-12-01

    The NW Zagros orogen is the result of the multistage collisional history associated with Late Cretaceous-Cenozoic convergence of the Arabian and Eurasian continents and final closure of Neotethys. Siliciclastic strata preserved within a ~400 km segment of the NW Zagros fold-thrust belt and foreland basin in the Iraqi Kurdistan Region (IKR) provide a widespread record of exhumation and sedimentation. As a means of assessing NW Zagros foreland basin evolution and chronostratigraphy, we present coupled detrital zircon (DZ) U-Pb and (U-Th)/He geo-thermochronometric data of Upper Cretaceous to Pliocene siliciclastic strata from the Duhok, Erbil, and Suleimaniyah provinces of IKR. LA-ICP-MS U-Pb age analyses reveal that the foreland basin fill in IKR in general was dominantly derived from Pan-African/Arabian-Nubian, Peri-Gondwandan, Eurasian, and Cretaceous volcanic arc terrenes. However, the provenance of these strata varies systematically along strike and through time, with an overall increase in complexity upsection. DZ age distribution of Paleocene-Eocene strata is dominated by a ~95 Ma grain age population, likely sourced from the Late Cretaceous Hassanbag-Bitlis volcanic arc complex along the northern margin of Arabia. In contrast, DZ U-Pb age distributions of Neogene strata show a major contribution derived from various Eurasian (e.g., Iranian, Tauride, Pontide; ~45, 150, 300 Ma) and Pan-African (~550, 950 Ma) sources. The introduction of Eurasian DZ ages at the Paleogene-Neogene transition likely records the onset of Arabian-Eurasian collision. Along strike to the southeast, the DZ U-Pb spectra of Neogene strata show a decreased percentage of Pan-African, Peri-Gondwandan, Tauride, and Ordovician ages, coupled with a dramatic increase in 40-50 Ma DZ ages that correspond to Urumieh-Dokhtar magmatic rocks in Iran. Combined with paleocurrent data, this suggests that Neogene sediments were transported longitudinally southeastward through an unbroken foreland basin

  2. Reductive amination derivatization for the quantification of garlic components by isotope dilution analysis.

    PubMed

    Lin, Yi-Reng; Huang, Mei-Fang; Wu, You-Ying; Liu, Meng-Chieh; Huang, Jing-Heng; Chen, Ziyu; Shiue, Yow-Ling; Wu, Chia-En; Liang, Shih-Shin

    2017-09-01

    In this work, we synthesized internal standards for four garlic organosulfur compounds (OSCs) by reductive amination with 13 C, D 2 -formaldehyde, and developed an isotope dilution analysis method to quantitate these organosulfur components in garlic samples. Internal standards were synthesized for internal absolute quantification of S-allylcysteine (SAC), S-allylcysteine sulfoxide (alliin), S-methylcysteine (SMC), and S-ethylcysteine (SEC). We used a multiple reaction monitoring (MRM) to detect 13 C, D 2 -formaldehyde-modified OSCs by ultrahigh-performance liquid phase chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and obtained MS spectra showing different ratios of 13 C, D 2 -formaldehyde-modified and H 2 -formaldehyde-modified compounds. The resulting labeled and unlabeled OSCs were exhibited correlation coefficient (R 2 ) ranged from 0.9989 to 0.9994, respectively. The average recoveries for four OSCs at three concentration levels ranged from 89% to 105%. By 13 C, D 2 -formaldehyde and sodium cyanoborohydride, the reductive amination-based method can be utilized to generate novel internal standard for isotope dilution and to extend the quantitative application. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Evolution of Nd and Pb isotopes in Central Pacific seawater from ferromanganese crusts

    USGS Publications Warehouse

    Ling, H.F.; Burton, K.W.; O'Nions, R. K.; Kamber, B.S.; Von Blanckenburg, F.; Gibb, A.J.; Hein, J.R.

    1997-01-01

    Hydrogenetic ferromanganese crusts incorporate elements from ambient seawater during their growth on seamounts. By analysing Nd, Pb and Be isotope profiles within crusts it is possible to reconstruct seawater tracer histories. Depth profiles of 10Be/9Be ratios in three Pacific ferromanganese crusts have been used to obtain growth rates which are between 1.4 and 3.8 mm/Ma. Nd and Pb isotopes provide intact records of isotopic variations in Pacific seawater over the last 20 Ma or more. There were only small changes in Pb isotope composition in the last 20 Ma. This indicates a constant Pb composition for the erosional sources and suggests further that erosional Nd inputs may have been uniform too. ??ND values vary considerably with time and most probably reflect changes in ocean circulation. The ??ND values of the crusts not only vary as a function of age but also as a function of water depth. From 25 to 0 Ma, crust VA13/2 from 4.8 km water depth has a similar pattern of ??ND variation to the two shallower crusts from 1.8 and 2.3 km, but about 1.0 to 1.5 units more negative. This suggests that ??ND stratification in Pacific seawater, as demonstrated for the present day, has been maintained for at least 20 Ma. Each crust shows a decrease in ??ND from 3-5 Ma to the present, which is interpreted in terms of an increase in the NADW component present in the Pacific. From 10 to 3-5 Ma ago the crusts show an increase in ??ND. This suggests a decreasing role for a deep water source with ??ND less than circum-Pacific sources. In this regard the Panamanian gateway restriction from ???10 Ma with final closure at 3-5 Ma may have played an important role in reducing access of Atlantic-derived Nd to the Pacific.

  4. In-Situ U-Pb Dating of Apatite by Hiroshima-SHRIMP: Contributions to Earth and Planetary Science.

    PubMed

    Terada, Kentaro; Sano, Yuji

    2012-01-01

    The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U-Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U-Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years.

  5. Lead isotopes in trade wind aerosols at Barbados: the influence of European emissions over the North Atlantic

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

    Hamelin, B.; Grousset, F.E.; Biscaye, P.E.

    1989-11-15

    Previous studies have shown that Pb can be used as a transient tracer in the atmosphere and the ocean because of strong time-variability of industrial inputs and because Pb isotopic composition can be used to identify contribution from different sources. We present Pb isotopic measurements on aerosols collected from the North Atlantic Ocean in the trade wind belt. Aerosols sampled at Barbados during the 1969--1985 period have a Pb isotopic compositions different from that observed by previous investigators in Bermuda corals and Sargasso Sea waters. Barbados aerosols appear to contain significant amounts of relatively unradiogenic industrial and automotive Pb thatmore » is derived from Europe and carried to Barbados by the trade winds. In contrast, Bermuda corals and Sargasso sea waters are influenced mainly by U.S.-derived emissions, which contain more radiogenic Pb originating from Missouri-type ores. This difference generates a strong latitudinal Europe-U.S.A. isotopic gradient, thus allowing study of trans-Atlantic atmospheric transport and ocean mixing processes. {copyright} American Geophysical Union 1989« less

  6. Apportioning atmospheric pollution to Canadian and American sources in Kejimkujik National Park, Nova Scotia, using Pb isotopes in precipitation

    NASA Astrophysics Data System (ADS)

    DesJardins, Michelle J.; Telmer, Kevin; Beauchamp, S.

    Precipitation samples were collected from July 2001 through June 2002 to determine sources of anthropogenic heavy metal pollutants to Kejimkujik National Park, Nova Scotia using Pb isotope ratios. Generally, Mean annual Pb concentrations (0.116 μg l -1) and depositional fluxes (151 μg m -2) are lower than other reported mid-Atlantic coastal regions. Pb isotope compositions may be explained by binary mixing of anthropogenic emissions from US and Canadian sources, indicating long-range atmospheric transport of pollutants from populated and industrial regions of northeastern US and southeastern Canada. The 206Pb/ 207Pb ratios in precipitation ranged from 1.165 to 1.201, with an annual weighted mean 206Pb/ 207Pb ratio of 1.181, indicating that on an annual basis, US and Canadian sources contribute 61% and 39%, respectively, of the anthropogenic Pb (and likely other similarly behaved metal pollutants) reaching Kejimkujik Park. These results differ from those estimated by using epiphytic lichens due to one or a combination of the following possibilities: (1) some of the Pb in the lichens reflects more radiogenic local bedrock sources; (2) there has been an overall increase in the proportion of Canadian inputs since the early 1990s; (3) there was an unusually higher proportion of Pb inputs from Canadian sources during the study period; or (4) possible shifts in the isotopic composition of the Canadian and US sources that may have occurred due to increased international trade in lead and a lesser dependency on national production. As well, seasonal variations in the sources were observed, with summer and fall months having a lower mean 206Pb/ 207Pb ratio of 1.178 (more Canadian) than the winter and spring months with 206Pb/ 207Pb of 1.185 (more American).

  7. "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

  8. Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

    NASA Astrophysics Data System (ADS)

    Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

    2016-04-01

    Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet

  9. Short communication: milk output in llamas (Lama glama) in relation to energy intake and water turnover measured by an isotope dilution technique.

    PubMed

    Riek, A; Klinkert, A; Gerken, M; Hummel, J; Moors, E; Südekum, K-H

    2013-03-01

    Despite the fact that llamas have become increasingly popular as companion and farm animals in both Europe and North America, scientific knowledge on their nutrient requirements is scarce. Compared with other livestock species, relatively little is known especially about the nutrient and energy requirements for lactating llamas. Therefore, we aimed to measure milk output in llama dams using an isotope dilution technique and relate it to energy intakes at different stages of lactation. We also validated the dilution technique by measuring total water turnover (TWT) directly and comparing it with values estimated by the isotope dilution technique. Our study involved 5 lactating llama dams and their suckling young. Milk output and TWT were measured at 4 stages of lactation (wk 3, 10, 18, and 26 postpartum). The method involved the application of the stable hydrogen isotope deuterium ((2)H) to the lactating dam. Drinking water intake and TWT decreased significantly with lactation stage, whether estimated by the isotope dilution technique or calculated from drinking water and water ingested from feeds. In contrast, lactation stage had no effect on dry matter intake, metabolizable energy (ME) intake, or the milk water fraction (i.e., the ratio between milk water excreted and TWT). The ratios between TWT measured and TWT estimated (by isotope dilution) did not differ with lactation stage and were close to 100% in all measurement weeks, indicating that the D(2)O dilution technique estimated TWT with high accuracy and only small variations. Calculating the required ME intakes for lactation from milk output data and gross energy content of milk revealed that, with increasing lactation stage, ME requirements per day for lactation decreased but remained constant per kilogram of milk output. Total measured ME intakes at different stages of lactation were similar to calculated ME intakes from published recommendation models for llamas. Copyright © 2013 American Dairy Science

  10. Determination of Glyphosate, its Degradation Product Aminomethylphosphonic Acid, and Glufosinate, in Water by Isotope Dilution and Online Solid-Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry

    USGS Publications Warehouse

    Meyer, Michael T.; Loftin, Keith A.; Lee, Edward A.; Hinshaw, Gary H.; Dietze, Julie E.; Scribner, Elisabeth A.

    2009-01-01

    The U.S. Geological Survey method (0-2141-09) presented is approved for the determination of glyphosate, its degradation product aminomethylphosphonic acid (AMPA), and glufosinate in water. It was was validated to demonstrate the method detection levels (MDL), compare isotope dilution to standard addition, and evaluate method and compound stability. The original method USGS analytical method 0-2136-01 was developed using liquid chromatography/mass spectrometry and quantitation by standard addition. Lower method detection levels and increased specificity were achieved in the modified method, 0-2141-09, by using liquid chromatography/tandem mass spectrometry (LC/MS/MS). The use of isotope dilution for glyphosate and AMPA and pseudo isotope dilution of glufosinate in place of standard addition was evaluated. Stable-isotope labeled AMPA and glyphosate were used as the isotope dilution standards. In addition, the stability of glyphosate and AMPA was studied in raw filtered and derivatized water samples. The stable-isotope labeled glyphosate and AMPA standards were added to each water sample and the samples then derivatized with 9-fluorenylmethylchloroformate. After derivatization, samples were concentrated using automated online solid-phase extraction (SPE) followed by elution in-line with the LC mobile phase; the compounds separated and then were analyzed by LC/MS/MS using electrospray ionization in negative-ion mode with multiple-reaction monitoring. The deprotonated derivatized parent molecule and two daughter-ion transition pairs were identified and optimized for glyphosate, AMPA, glufosinate, and the glyphosate and AMPA stable-isotope labeled internal standards. Quantitative comparison between standard addition and isotope dilution was conducted using 473 samples analyzed between April 2004 and June 2006. The mean percent difference and relative standard deviation between the two quantitation methods was 7.6 plus or minus 6.30 (n = 179), AMPA 9.6 plus or minus 8

  11. U-Pb geochronology documents out-of-sequence emplacement of ultramafic layers in the Bushveld Igneous Complex of South Africa.

    PubMed

    Mungall, James E; Kamo, Sandra L; McQuade, Stewart

    2016-11-14

    Layered intrusions represent part of the plumbing systems that deliver vast quantities of magma through the Earth's crust during the formation of large igneous provinces, which disrupt global ecosystems and host most of the Earth's endowment of Pt, Ni and Cr deposits. The Rustenburg Layered Suite of the enormous Bushveld Igneous Complex of South Africa has been presumed to have formed by deposition of crystals at the floor of a subterranean sea of magma several km deep and hundreds of km wide called a magma chamber. Here we show, using U-Pb isotopic dating of zircon and baddeleyite, that individual chromitite layers of the Rustenburg Layered Suite formed within a stack of discrete sheet-like intrusions emplaced and solidified as separate bodies beneath older layers. Our U-Pb ages and modelling necessitate reassessment of the genesis of layered intrusions and their ore deposits, and challenge even the venerable concept of the magma chamber itself.

  12. Lead isotope database of unpublished results from sulfide mineral occurrences-California, Idaho, Oregon, and Washington

    USGS Publications Warehouse

    Church, S.E.

    2010-01-01

    The Pb isotope database for sulfide deposits and occurrences in the Western United States was funded by the Mineral Resources Program, U.S. Geological Survey (USGS). Reports on Pb isotope data from Alaska were published in Church and others (1987a) and Gaccetta and Church (1989). The primary objectives of the project were three-fold: * To utilize Pb isotope signatures, in conjunction with the regional mapping, to assess the relative ages and to categorize the types of deposits studied, * To relate the Pb isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and * To use the Pb isotope data to correlate lithotectonic terranes within the northern Cordillera. The report by Church and others (1987b) shows how this fingerprinting methodology can be applied to trace the offset of lithostratigraphic terranes

  13. Total synthesis of isotopically enriched Si-29 silica NPs as potential spikes for isotope dilution quantification of natural silica NPs.

    PubMed

    Pálmai, Marcell; Szalay, Roland; Bartczak, Dorota; Varga, Zoltán; Nagy, Lívia Naszályi; Gollwitzer, Christian; Krumrey, Michael; Goenaga-Infante, Heidi

    2015-05-01

    A new method was developed for the preparation of highly monodisperse isotopically enriched Si-29 silica nanoparticles ((29)Si-silica NPs) with the purpose of using them as spikes for isotope dilution mass spectrometry (IDMS) quantification of silica NPs with natural isotopic distribution. Si-29 tetraethyl orthosilicate ((29)Si-TEOS), the silica precursor was prepared in two steps starting from elementary silicon-29 pellets. In the first step Si-29 silicon tetrachloride ((29)SiCl4) was prepared by heating elementary silicon-29 in chlorine gas stream. By using a multistep cooling system and the dilution of the volatile and moisture-sensitive (29)SiCl4 in carbon tetrachloride as inert medium we managed to reduce product loss caused by evaporation. (29)Si-TEOS was obtained by treating (29)SiCl4 with absolute ethanol. Structural characterisation of (29)Si-TEOS was performed by using (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopy and Fourier-transform infrared (FTIR) spectroscopy. For the NP preparation, a basic amino acid catalysis route was used and the resulting NPs were analysed using transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential measurements. Finally, the feasibility of using enriched NPs for on-line field-flow fractionation coupled with multi-angle light scattering and inductively coupled plasma mass spectrometry (FFF/MALS/ICP-MS) has been demonstrated. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. High-precision Pb isotopic measurements of teeth and environmental samples from Sofia (Bulgaria): insights for regional lead sources and possible pathways to the human body

    NASA Astrophysics Data System (ADS)

    Kamenov, George D.

    2008-08-01

    High-precision Pb isotopic measurements on teeth and possible sources in a given area can provide important insights for the lead (Pb) sources and pathways in the human body. Pb isotopic analyses on soils from the area of Sofia, Bulgaria show that Pb is contributed by three end-members represented by two natural sources and leaded gasoline. Sequential leaching experiments reveal that the alumosilicate fraction of the soils is mainly controlled by natural Pb derived from two mountain massifs bordering the city. Around 1/3 to a half of the Pb in the soil leachates, however, can be explained by contamination from leaded gasoline. Contemporary teeth from Sofia residents show very similar Pb isotopic compositions to the soil leachates, also indicating that around 1/3 to a half of the Pb can be explained by derivation from leaded gasoline. The remarkable isotopic similarities between the teeth and the most labile fractions of the local soils suggest that the lead can be derived from the latter. Pb incorporation in the human body via soil-plant-human or soil-plant-animal-human chains is unlikely due to the fact that no significant farming occurs in the city area. The isotopic compositions of the local soil labile fractions can be used as approximation of the bioaccessible lead for humans. Considering all possible scenarios it appears that soil and/or soil-born dust inhalation and/or ingestion is the most probable pathway for incorporation of local soil lead in the local population. The high-precision Pb isotope data presented in this work indicate that apparently the local soil is what plays major role in the human Pb exposure.

  15. Quantitation of Rotundone in Grapefruit (Citrus paradisi) Peel and Juice by Stable Isotope Dilution Assay.

    PubMed

    Nakanishi, Akira; Fukushima, Yusuke; Miyazawa, Norio; Yoshikawa, Keisuke; Maeda, Tomoko; Kurobayashi, Yoshiko

    2017-06-21

    Aroma extract dilution analyses of the aromas of peels and juices of white and pink grapefruits revealed that rotundone, responsible for peppery, spicy, and woody odors, was detected for the first time at high flavor dilution factors of 256-1024. In both juices, rotundone was detected at the highest flavor dilution factor of 1024. Rotundone in grapefruits was quantitated by a stable isotope dilution assay with a newly synthesized deuterium-labeled internal standard, rotundone-d 2,3 : its levels were 2180 and 1920 ng/kg in white and pink grapefruit peels and 29.6 and 49.8 ng/kg in white and pink grapefruit juices, respectively. On the basis of these results, sensory analysis was performed to assess the effects of rotundone on a white grapefruit juice aroma reconstitute. This sensory analysis revealed that rotundone does not impart a woody odor or affect any of the existing attributes, but increases various attributes, thus confirming that rotundone is indispensable for the aroma of grapefruit juice.

  16. The trace and Pb isotope chemistry of the Jan Mayen Fracture Zone and the extinct Aegir Ridge

    NASA Astrophysics Data System (ADS)

    Sayit, K.; Hanan, B. B.; Ito, G.; Howell, S. M.; Vogt, P. R.; Breivik, A. J.; Mjelde, R.; Pedersen, R.

    2012-12-01

    The extinct Aegir Ridge (AR) was active during the early opening of the N-Atlantic, 54 to 25 Ma, when spreading jumped to the Kolbeinsey Ridge. Crustal thickness produced by the AR is low (3.5 to 6 km), and the magmatically starved Norway Basin appears as a hole in the surrounding excess volcanism of the Iceland hotspot. Two possible alternatives are; either the lithospheric structure of the Jan Mayen micro-continent (JMMC) blocked the plume flow to the AR, and/or Iceland plume material reaching the ridge experienced a previous melt extraction, leading to relatively low melt production. We report the trace element and Pb isotope systematics of the mafic rocks dredged from the AR ~64-69° N and adjacent Jan Mayen FZ. On the basis of the immobile trace element chemistry, several groups are identified, with a large range of Zr/Nb (2.7-60.7). A very-depleted group ([Ce/Yb]N = 0.3) was found in the Jan Mayen FZ, while the most enriched, OIB-like group ([Ce/Yb]N = 12.4) was recovered from the ridge flank scarps. A notable feature of the Aegir samples is variable Th enrichment relative Nb (Th/Nb = 0.07-0.49), similar to subduction zone signatures. In terms of Pb isotopes, the samples show significant variations that correlate with trace element chemistry (206Pb/204Pb: 207Pb/204Pb: 208Pb/204Pb = 16.63-18.81:15.16-15.55:36.67-38.62). The Pb systematics of the Aegir rocks are compatible with a three-component mixing model with mixing trends between the C-like Iceland plume component and a mixture that is composed of EM-1-type material and depleted MORB asthenosphere. The presence of the C-like isotope compositions in the Aegir samples from the Jan Mayen FZ and ridge flank scarps suggests that Iceland plume material has been tapped. However, the very-depleted trace element signatures indicate that the plume component was previously melt depleted. Apparently, the JMMC impeaded flow of enriched plume material to the AR. The Aegir rocks Pb isotope signature may represent

  17. Assessing of distribution, mobility and bioavailability of exogenous Pb in agricultural soils using isotopic labeling method coupled with BCR approach.

    PubMed

    Huang, Zhi-Yong; Xie, Hong; Cao, Ying-Lan; Cai, Chao; Zhang, Zhi

    2014-02-15

    The contamination of Pb in agricultural soils is one of the most important ecological problems, which potentially results in serious health risk on human health through food chain. Hence, the fate of exogenous Pb contaminated in agricultural soils is needed to be deeply explored. By spiking soils with the stable enriched isotopes of (206)Pb, the contamination of exogenous Pb(2+) ions in three agricultural soils sampled from the estuary areas of Jiulong River, China was simulated in the present study, and the distribution, mobility and bioavailability of exogenous Pb in the soils were investigated using the isotopic labeling method coupled with a four-stage BCR (European Community Bureau of Reference) sequential extraction procedure. Results showed that about 60-85% of exogenous Pb was found to distribute in reducible fractions, while the exogenous Pb in acid-extractable fractions was less than 1.0%. After planting, the amounts of exogenous Pb presenting in acid-extractable, reducible and oxidizable fractions in rhizospheric soils decreased by 60-66%, in which partial exogenous Pb was assimilated by plants while most of the metal might transfer downward due to daily watering and applying fertilizer. The results show that the isotopic labeling technique coupled with sequential extraction procedures enables us to explore the distribution, mobility and bioavailability of exogenous Pb contaminated in soils, which may be useful for the further soil remediation. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. U-Pb Geochronology of Grandite Skarn Garnet: Case Studies From Jurassic Skarns of California

    NASA Astrophysics Data System (ADS)

    Gevedon, M. L.; Seman, S.; Barnes, J.; Stockli, D. F.; Lackey, J. S.

    2016-12-01

    We present 3 case studies using a new method for U-Pb dating grossular-andradite (grandite) skarn garnet via LA-ICP-MS (Seman et al., in prep). Grandite is commonly rich in U, with high Fe3+ contents generally correlating with higher U concentrations. Micron-scale non-radiogenic Pb heterogeneities allow for regression of age data using Tera-Wasserberg concordia. Although others have dated accessory skarn minerals, garnet U-Pb ages are powerful because garnet grows early and is nearly ubiquitous in skarns, resists alteration, and provides a formation age independent of that of the causative pluton. The Darwin stock (Argus range, eastern CA) was likely a short-lived, single pulse of magmatism, genetically related to the Darwin skarn. A robust skarn garnet U-Pb age of 176.8 ± 1.3 Ma agrees well with the pluton U-Pb zircon age of 175 Ma (Chen and Moore, 1982). Furthermore, zircon separated from, and in textural equilibrium with, exoskarn garnetite yields a U-Pb age of 176.8 ± 1 Ma. Such agreement between plutonic and skarn zircon ages with a skarn garnet age in a geologically simple field area is the ideal scenario for establishing grandite U-Pb as a viable tool for directly dating skarns. The Black Rock skarn (BRS; eastern CA) is more complex: multiple plutons and ambiguous field relations complicate determination of a causative pluton. A skarn garnet U-Pb age of 172.0 ± 3 Ma confirms a middle Jurassic BRS formation age. Investigation of 4 local plutons yield zircon U-Pb ages of 222 ± 3 Ma, 213 ± 4 Ma, 207 ± 4 Ma and 176.2 ± 2 Ma. Comparison of the skarn garnet U-Pb and pluton ages suggest the BRS is genetically related to the youngest pluton, providing basis for further field and geochemical investigation. The Whitehorse skarn (WS; Mojave Desert, CA) lies in an important region for studying the changing tectono-magmatic regime of the Jurassic North American Cordillera; basin fill suggests a tectonically-controlled oscillating regional shoreline (Busby, 2012

  19. U-Pb Dating of Zircons and Phosphates in Lunar Meteorites, Acapulcoites and Angrites

    NASA Technical Reports Server (NTRS)

    Zhou, Q.; Zeigler, R. A.; Yin, Q. Z.; Korotev, R. L.; Joliff, B. L.; Amelin, Y.; Marti, K.; Wu, F. Y.; Li, X. H.; Li, Q. L.; hide

    2012-01-01

    Zircon U-Pb geochronology has made a great contribution to the timing of magmatism in the early Solar System [1-3]. Ca phosphates are another group of common accessory minerals in meteorites with great potential for U-Pb geochronology. Compared to zircons, the lower closure temperatures of the U-Pb system for apatite and merrillite (the most common phosphates in achondrites) makes them susceptible to resetting during thermal metamorphism. The different closure temperatures of the U-Pb system for zircon and apatite provide us an opportunity to discover the evolutionary history of meteoritic parent bodies, such as the crystallization ages of magmatism, as well as later impact events and thermal metamorphism. We have developed techniques using the Cameca IMS-1280 ion microprobe to date both zircon and phosphate grains in meteorites. Here we report U-Pb dating results for zircons and phosphates from lunar meteorites Dhofar 1442 and SaU 169. To test and verify the reliability of the newly developed phosphate dating technique, two additional meteorites, Acapulco, obtained from Acapulco consortium, and angrite NWA 4590 were also selected for this study as both have precisely known phosphate U-Pb ages by TIMS [4,5]. Both meteorites are from very fast cooled parent bodies with no sign of resetting [4,5], satisfying a necessity for precise dating.

  20. Analysis of U.S. soil lead (Pb) studies from 1970 to 2012.

    PubMed

    Datko-Williams, Laura; Wilkie, Adrien; Richmond-Bryant, Jennifer

    2014-01-15

    Although lead (Pb) emissions to the air have substantially decreased in the United States since the phase-out of leaded gasoline by 1995, amounts of lead in some soils remain elevated. Lead concentrations in residential and recreational soils are of concern because health effects have been associated with Pb exposure. Elevated soil Pb is especially harmful to young children due to their higher likelihood of soil ingestion. The purpose of this study is to create a comprehensive compilation of U.S. soil Pb data published from 1970 through 2012 as well as to analyze the collected data to reveal spatial and/or temporal soil Pb trends in the U.S. over the past 40 years. A total of 84 soil Pb studies across 62 U.S. cities were evaluated. Median soil Pb values from the studies were analyzed with respect to year of sampling, residential location type (e.g., urban, suburban), and population density. In aggregate, there was no statistically significant correlation between year and median soil Pb; however, within single cities, soil Pb generally declined over time. Our analysis shows that soil Pb quantities in city centers were generally highest and declined towards the suburbs and exurbs of the city. In addition, there was a statistically significant, positive relationship between median soil Pb and population density. In general, the trends examined here align with previously reported conclusions that soil Pb levels are higher in larger urban areas and Pb tends to remain in soil for long periods of time. © 2013.

  1. 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.

  2. Isotopic composition of Pb in ore deposits of the Betic Cordillera, Spain; origin and relationship to other European deposits

    USGS Publications Warehouse

    Arribas , Antonio; Tosdal, Richard M.

    1994-01-01

    The Betic Cordillera in southern Spain is a complex Alpine fold belt that resulted from the Cretaceous through Cenozoic collision of Africa with Europe. The region is illustrative of one of the characteristics of the Alpine-Mediterranean orogen: the occurrence over a limited area of mineral deposits with a wide variety of host rocks, mineralization ages, and styles. The metamorphic basement in the Betic zone is characterized by a nappe structure of superimposed tectonostratigraphic units and consists of lower Paleozoic to Lower Triassic clastic metasedimentary rocks. This is overlain by Middle to Upper Triassic platform carbonate rocks with abundant strata-bound F-Pb-Zn-(Ba) deposits (e.g., Sierra de Gador, Sierra Alhamilla). Cretaceous to Paleogene subduction-related compression in southeastern Spain was followed by Miocene postcollisional extension and resulted in the formation of the Almeria-Cartagena volcanic belt and widespread hydrothermal activity and associated polymetallic mineralization. Typical Miocene hydrothermal deposits include volcanic-hosted Au (e.g., Rodalquilar) and Ag-rich base metal (e.g., Cabo de Gata, Mazarron) deposits as well as complex polymetallic veins, mantos, and irregular replacement bodies which are hosted by Paleozoic and Mesozoic metamorphic rocks and Neogene sedimentary and volcanic rocks (e.g., Cartagena, Sierra Almagrera, Sierra del Aguilon, Loma de Bas).Lead isotope compositions were measured on sulfide samples from nine ore districts and from representative fresh samples of volcanic and basement rock types of the region. The results have been used to evaluate ore-forming processes in southeastern Spain with emphasis on the sources of metals. During a Late Triassic mineralizing event, Pb was leached from Paleozoic clastic metasedimentary rocks and incorporated in galena in strata-bound F-Pb-Zn-(Ba) deposits ( 206 Pb/ 204 Pb = 18.332 + or - 12, 207Pb/ 204 Pb = 15.672 + or - 12, 208 Pb/ 204 Pb = 38.523 + or - 46). The second

  3. 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

  4. Quantifying time in sedimentary successions by radio-isotopic dating of ash beds

    NASA Astrophysics Data System (ADS)

    Schaltegger, Urs

    2014-05-01

    Sedimentary rock sequences are an accurate record of geological, chemical and biological processes throughout the history of our planet. If we want to know more about the duration or the rates of some of these processes, we can apply methods of absolute age determination, i.e. of radio-isotopic dating. Data of highest precision and accuracy, and therefore of highest degree of confidence, are obtained by chemical abrasion, isotope-dilution, thermal ionization mass spectrometry (CA-ID-TIMS) 238U-206Pb dating techniques, applied to magmatic zircon from ash beds that are interbedded with the sediments. This techniques allows high-precision estimates of age at the 0.1% uncertainty for single analyses, and down to 0.03% uncertainty for groups of statistically equivalent 206Pb/238U dates. Such high precision is needed, since we would like the precision to be approximately equivalent or better than the (interpolated) duration of ammonoid zones in the Mesozoic (e.g., Ovtcharova et al. 2006), or to match short feedback rates of biological, climatic, or geochemical cycles after giant volcanic eruptions in large igneous provinces (LIP's), e.g., at the Permian/Triassic or the Triassic/Jurassic boundaries. We also wish to establish as precisely as possible temporal coincidence between the sedimentary record and short-lived volcanic events within the LIP's. Precision and accuracy of the U-Pb data has to be traceable and quantifiable in absolute terms, achieved by direct reference to the international kilogram, via an absolute calibration of the standard and isotopic tracer solutions. Only with a perfect control on precision and accuracy of radio-isotopic data, we can confidently determine whether two ages of geological events are really different, and avoid mistaking interlaboratory or interchronometer biases for age difference. The development of unprecedented precision of CA-ID-TIMS 238U-206Pb dates led to the recognition of protracted growth of zircon in a magmatic liquid (see

  5. Kondo Effect of U Impurities in Dilute (YU)2Zn17

    NASA Astrophysics Data System (ADS)

    Takagi, Shigeru; Suzuki, Hiroyuki; Anzai, Kousuke

    2001-10-01

    Extending previous work on single-site properties of U ions in (LaU)2Zn17, we have investigated, from ρ(T), χ(T) and Cp(T) on single crystals, (Y1-xUx)2Zn17 with x=0.025 and 0.050, which has almost the same unit-cell volume as an antiferromagnetic heavy-electron compound U2Zn17. Remarkable features in the dilute-impurity limit have been clarified, which include Kondo behavior of ρ(T), large and almost isotropic χimp(T), and strongly enhanced Cimp(T)/T with gigantic γimp=2.02 2.05 J/K2·mole-U as T→0 due to a low characteristic energy-scale of the system. It is shown that gross features of the data are explained in terms of the conventional Kondo effect in the presence of the crystal field with the U3+ \\varGamma6 doublet ground state. It is also shown that the variation of γ with the unit-cell volume in related systems is not explained as a volume effect on TK and that even the behavior of fictitious “paramagnetic” U2Zn17 is not described as a collection of U impurities in dilute (YU)2Zn17.

  6. The double-edged sword of high-precision U-Pb geochronology or be careful what you wish for. (Invited)

    NASA Astrophysics Data System (ADS)

    Bowring, S. A.

    2010-12-01

    Over the past two decades, U-Pb geochronology by ID-TIMS has been refined to achieve internal (analytical) uncertainties on a single grain analysis of ± ~ 0.1-0.2%, and 0.05% or better on weighted mean dates. This level of precision enables unprecedented evaluation of the rates and durations of geological processes, from magma chamber evolution to mass extinctions and recoveries. The increased precision, however, exposes complexity in magmatic/volcanic systems and highlights the importance of corrections related to disequilibrium partitioning of intermediate daughter products, and raises questions as to how best to interpret the complex spectrum of dates characteristic of many volcanic rocks. In addition, the increased precision requires renewed emphasis on the accuracy of U decay constants, the isotopic composition of U, the calibration of isotopic tracers, and the accurate propagation of uncertainties It is now commonplace in the high precision dating of volcanic ash-beds to analyze 5-20 single grains of zircon in an attempt to resolve the eruption/depositional age. Data sets with dispersion far in excess of analytical uncertainties are interpreted to reflect Pb-loss, inheritance, and protracted crystallization, often supported with zircon chemistry. In most cases, a weighted mean of the youngest reproducible dates is interpreted as the time of eruption/deposition. Crystallization histories of silicic magmatic systems recovered from plutonic rocks may also be protracted, though may not be directly applicable to silicic eruptions; each sample must be evaluated independently. A key to robust interpretations is the integration high-spatial resolution zircon trace element geochemistry with high-precision ID-TIMS analyses. The EARTHTIME initiative has focused on many of these issues, and the larger subject of constructing a timeline for earth history using both U-Pb and Ar-Ar chronometers. Despite continuing improvements in both, comparing dates for the same rock

  7. 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

  8. Profiling of new psychoactive substances (NPS) by using stable isotope ratio mass spectrometry (IRMS): study on the synthetic cannabinoid 5F-PB-22.

    PubMed

    Münster-Müller, S; Scheid, N; Holdermann, T; Schneiders, S; Pütz, M

    2018-05-21

    In this paper results of a pilot study on the profiling of the synthetic cannabinoid receptor agonist 5F-PB-22 (5F-QUPIC, pentylfluoro-1H-indole-3-carboxylic acid-8-quinolinyl ester) via isotope ratio mass spectrometry are presented. It is focused on δ 13 C, δ 15 N and δ 2 H isotope ratios, which are determined using elemental analyser (EA) and high temperature elemental analyser (TC/EA) coupled to an isotope ratio mass spectrometer (IRMS). By means of a sample of pure material of 5F-PB-22 it is shown that the extraction of 5F-PB-22 from herbal material, a rapid clean-up procedure, or preparative column chromatography had no influences on the isotope ratios. Furthermore, 5F-PB-22 was extracted from fourteen different herbal blend samples ("Spice products" from police seizures) and analysed via IRMS, yielding three clusters containing seven, five and two samples, distinguishable through their isotopic composition, respectively. It is assumed that herbal blends in each cluster have been manufactured from individual batches of 5F-PB-22. This article is protected by copyright. All rights reserved.

  9. Modeling the Lead(Pb) concentrations in corals in the Singapore Straits

    NASA Astrophysics Data System (ADS)

    Chen, M.; Lee, J.; Nurhati, I. S.; Switzer, A. D.; Boyle, E. A.

    2012-12-01

    The leaded gasoline has dominated the global Pb emission and has imposed serious health problems in the past 50 years. While countries in North America and Western Europe phased out leaded gasoline in 1970s and early 1980s, many fast developing Asian countries have been using it until recently. In order to monitor anthropogenic Pb variations in marine environments, the history of seawater Pb in the Singapore Strait -- one of the world's busiest shipping lanes has been reconstructed from a 50 year-long coral core (Lee et al., unpublished record). A 50-year-long coral Pb/Ca record from the Singapore Strait was measured using isotope dilution ICPMS (for Pb) and FAAS (for Ca). Here, we propose a statistical model to correlate lead measured in the Singapore coral (Pb/Ca) and the possible Pb sources in the region. The measurement reveals that the Pb in coral is only weakly correlated with Pb the gasoline emission from the neighboring countries (i.e. Singapore, Malaysia, and Batam Indonesia). Such weak correlation implies that either the gasoline may not be a dominating source to Singapore Strait or the transport process of the Pb (either atmospheric or oceanographic) in this region complicates the interpretation. In this case, we tested a number of statistical correlations to understand the possible roles of leaded gasoline emission, rainfall, sediment flux and the residence time of the Pb inferred by the Pb210 data. From our current tests, a relatively high correlation appeared between the Pb in coral and the local annual precipitation, with a lag time of 2 years. The 2 year lag is somewhat surprising and we expect to elaborate further by correlating the Pb in coral with the Pb isotope signatures in an attempt to identify possible sources.;

  10. U-Pb ages of uraniferous opals and implications for the history of beryllium, fluorine, and uranium mineralization at Spor Mountain, Utah

    USGS Publications Warehouse

    Ludwig, K. R.; Lindsey, D.A.; Zielinski, R.A.; Simmons, K.R.

    1980-01-01

    The U-Pb isotope systematics of uraniferous opals from Spor Mountain, Utah, were investigated to determine the suitability of such material for geochronologic purposes, and to estimate the timing of uranium and associated beryllium and fluorine mineralization. The results indicate that uraniferous opals can approximate a closed system for uranium and uranium daughters, so that dating samples as young as ???1 m.y. should be possible. In addition, the expected lack of initial 230Th and 231Pa in opals permits valuable information on the initial 234U/238U to be obtained on suitable samples of ???10 m.y. age. The oldest 207Pb/235U apparent age observed, 20.8 ?? 1 m.y., was that of the opal-fluorite core of a nodule from a beryllium deposit in the Spor Mountain Formation. This age is indistinguishable from that of fission-track and K-Ar ages from the host rhyolite, and links the mineralization to the first episode of alkali rhyolite magmatism and related hydrothermal activity at Spor Mountain. Successively younger ages of 13 m.y. and 8-9 m.y. on concentric outer zones of the same nodule indicate that opal formed either episodically or continuously for over 10 m.y. Several samples of both fracture-filling and massive-nodule opal associated with beryllium deposits gave 207Pb/235U apparent ages of 13-16 m.y., which may reflect a restricted period of mineralization or perhaps an averaging of 21- and <13-m.y. periods of opal growth. Several samples of fracture-filling opal in volcanic rocks as young as 6 m.y. gave 207Pb/235U ages of 3.4-4.8 m.y. These ages may reflect hot-spring activity after the last major eruption of alkali rhyolite. ?? 1980.

  11. High-precision Pb Isotopes Reveal Two Small Magma Bodies Beneath the Summit of Kilauea Volcano

    NASA Astrophysics Data System (ADS)

    Pietruszka, A. J.; Heaton, D. E.; Marske, J. P.; Garcia, M. O.

    2013-12-01

    The summit magma storage reservoir of Kilauea Volcano is one of the most important components of the volcano's magmatic plumbing system, but its geometry is poorly known. High-precision Pb isotopic analyses of Kilauea summit lavas (1959-1982) define the minimum number of magma bodies within the summit reservoir and their volumes. The 206Pb/204Pb ratios of these lavas display a temporal decrease due to changes in the composition of the parental magma delivered to the volcano. Analyses of multiple lavas from some individual eruptions reveal small but significant differences in 206Pb/204Pb. The extra-caldera lavas from Aug. 1971 and Jul. 1974 display lower Pb isotope ratios and higher MgO contents (10 wt. %) than the intra-caldera lavas (MgO ~7-8 wt. %) from each eruption. From 1971 to 1982, the 206Pb/204Pb ratios of the lavas define two separate decreasing temporal trends. The intra-caldera lavas from 1971, 1974, 1975, Apr. 1982 and the lower MgO lavas from Sep. 1982 have higher 206Pb/204Pb ratios at a given time (compared to the extra-caldera lavas and the higher MgO lavas from Sep. 1982). These trends require that the intra- and extra-caldera lavas (and the Sep. 1982 lavas) were supplied from two separate, partially isolated magma bodies. Numerous studies (Fiske and Kinoshita, 1969; Klein et al., 1987) have long identified the locus of Kilauea's summit reservoir ~2 km southeast of Halemaumau (HMM) at a depth of ~2-7 km, but more recent investigations have discovered a second magma body located <1 km below the east rim of HMM (Battaglia et al., 2003; Johnson et al., 2010). The association between the vent locations of the extra-caldera lavas near the southeast rim of the caldera and their higher MgO contents suggests that these lavas tapped the deeper magma body. In contrast, the lower MgO intra-caldera lavas were likely derived from the shallow magma body beneath HMM. Residence time modeling based on the Pb isotope ratios of the lavas suggests that the magma volume

  12. Exploring the U-Pb systematics of titanite from the Archean Stillwater Complex

    NASA Astrophysics Data System (ADS)

    Friedman, R. M.; Wall, C. J.; Scoates, J. S.; Weis, D. A.; Meurer, W. P.

    2011-12-01

    The Stillwater Complex is a large mafic-ultramafic layered intrusion in the Beartooth Mountains of Montana (USA) and host to the world-class J-M Reef platinum group element deposit. The size and geologic/economic importance of this igneous complex make it an important target for high-precision U-Pb dating. As a part of a comprehensive U-Pb study of the Stillwater Complex, we present ID-TIMS U-Pb titanite data, including new single grain results produced using the EARTHTIME ET535 spike, for very low-volume, relatively felsic granophyric and pegmatitic rocks associated with Stillwater layered rocks. Four samples studied include a pegmatitic ksp-qtz core to a gabbroic pegmatoid in the Lower Banded Series (N1), an alaskite (quartz diorite) and an amphibole-rich reaction zone between the alaskite and anorthosite (AN1) in the Middle Banded Series, and an amphibole-bearing granophyre from the Upper Banded Series (GN3). CA-TIMS U-Pb dating of zircon from these samples yielded concordant results only for the pegmatitic rock (weighted 207Pb/206Pb: 2709.65 ± 0.80 Ma, n = 5), which agrees with new zircon ages from Stillwater layered rocks. Results for high-U (up to 1438 ppm) metamict zircon that occurs in the other three rocks were highly discordant and did not yield precise ages. Titanite U-Pb results for the pegmatite are about -1% to +1% discordant with two groupings of 207Pb/206Pb dates: one with a weighted average of 2708.1 ± 2.0 Ma (n = 2), which overlaps in age with zircon from the same sample and the crystallization age of the Stillwater Complex, and a second, younger grouping of 2701.1 ± 1.3 Ma (n = 5). Younger dates record an early Pb-loss event, possibly related to intrusion of cross-cutting quartz monzonites. The alaskite data also shows two groupings of 207Pb/206Pb dates, although more subtle: a weighted average of 2709.3 ± 1.8 Ma (n = 3) and a single result of 2706.5 ± 1.7 Ma. Titanite from the other two samples has undergone significant Pb-loss. Results for

  13. High accuracy method for the application of isotope dilution to gas chromatography/mass spectrometric analysis of gases.

    PubMed

    Milton, Martin J T; Wang, Jian

    2003-01-01

    A new isotope dilution mass spectrometry (IDMS) method for high-accuracy quantitative analysis of gases has been developed and validated by the analysis of standard mixtures of carbon dioxide in nitrogen. The method does not require certified isotopic reference materials and does not require direct measurements of the highly enriched spike. The relative uncertainty of the method is shown to be 0.2%. Reproduced with the permission of Her Majesty's Stationery Office. Copyright Crown copyright 2003.

  14. The White Nile as a source for Nile sediments: Assessment using U-Pb geochronology of detrital rutile and monazite

    NASA Astrophysics Data System (ADS)

    Be'eri-Shlevin, Yaron; Avigad, Dov; Gerdes, Axel

    2018-04-01

    Basement terranes exposed at the headwaters of the White Nile include Archean-Paleoproterozoic rocks of the Congo Craton, whose northern sectors were severely reworked during Neoproterozoic orogeny. New U-Pb analyses of detrital rutile and monazite from early Quaternary to Recent coastal quartz sands of Israel, at the northeast extension of the Nile sedimentary system, yield mostly late Neoproterozoic ages, with a dominant peak at ca. 600 Ma. While derivation from the reworked sectors of the Craton cannot be negated, the absence of pre-Neoproterozoic rutile and monazite indicates that the detrital contribution from the Congo cratonic nuclei into the main Nile was insignificant. The near absence of White Nile basement-derived heavy minerals from the Nile sands arriving at the Eastern Mediterranean may be explained by a number of factors such as relatively minor erosion of the Cratonic basement nuclei during the Quaternary, late connection of the White Nile to the main Nile system with a possibility that northern segments connected prior to more southerly ones, and a long-term effective sediment blockage mechanism at the mouth of White Nile. Likewise, our previous study demonstrated that Nile sands display a detrital zircon U-Pb-Hf pattern consistent with significant recycling of NE African Paleozoic sediments. It is thus plausible that any detrital contribution from White Nile basement rocks was thoroughly diluted by eroded Paleozoic sediments, or their recycled products, which were likely the greatest sand reservoir in the region. This study adds to previous studies showing the advantage of a multi mineral U-Pb geochronology strategy in constraining sediment provenance patterns.

  15. Pb evolution in the Martian mantle

    NASA Astrophysics Data System (ADS)

    Bellucci, J. J.; Nemchin, A. A.; Whitehouse, M. J.; Snape, J. F.; Bland, P.; Benedix, G. K.; Roszjar, J.

    2018-03-01

    The initial Pb compositions of one enriched shergottite, one intermediate shergottite, two depleted shergottites, and Nakhla have been measured by Secondary Ion Mass Spectrometry (SIMS). These values, in addition to data from previous studies using an identical analytical method performed on three enriched shergottites, ALH 84001, and Chassigny, are used to construct a unified and internally consistent model for the differentiation history of the Martian mantle and crystallization ages for Martian meteorites. The differentiation history of the shergottites and Nakhla/Chassigny are fundamentally different, which is in agreement with short-lived radiogenic isotope systematics. The initial Pb compositions of Nakhla/Chassigny are best explained by the late addition of a Pb-enriched component with a primitive, non-radiogenic composition. In contrast, the Pb isotopic compositions of the shergottite group indicate a relatively simple evolutionary history of the Martian mantle that can be modeled based on recent results from the Sm-Nd system. The shergottites have been linked to a single mantle differentiation event at 4504 Ma. Thus, the shergottite Pb isotopic model here reflects a two-stage history 1) pre-silicate differentiation (4504 Ma) and 2) post-silicate differentiation to the age of eruption (as determined by concordant radiogenic isochron ages). The μ-values (238U/204Pb) obtained for these two different stages of Pb growth are μ1 of 1.8 and a range of μ2 from 1.4-4.7, respectively. The μ1-value of 1.8 is in broad agreement with enstatite and ordinary chondrites and that proposed for proto Earth, suggesting this is the initial μ-value for inner Solar System bodies. When plotted against other source radiogenic isotopic variables (Sri, γ187Os, ε143Nd, and ε176Hf), the second stage mantle evolution range in observed mantle μ-values display excellent linear correlations (r2 > 0.85) and represent a spectrum of Martian mantle mixing-end members (depleted

  16. Open system models of isotopic evolution in Earth's silicate reservoirs: Implications for crustal growth and mantle heterogeneity

    NASA Astrophysics Data System (ADS)

    Kumari, Seema; Paul, Debajyoti; Stracke, Andreas

    2016-12-01

    An open system evolutionary model of the Earth, comprising continental crust (CC), upper and lower mantle (UM, LM), and an additional isolated reservoir (IR) has been developed to study the isotopic evolution of the silicate Earth. The model is solved numerically at 1 Myr time steps over 4.55 Gyr of Earth history to reproduce both the present-day concentrations and isotope ratios of key radioactive decay systems (Rb-Sr, Sm-Nd, and U-Th-Pb) in these terrestrial reservoirs. Various crustal growth scenarios - continuous versus episodic and early versus late crustal growth - and their effect on the evolution of Sr-Nd-Pb isotope systematics in the silicate reservoirs have been evaluated. Modeling results where the present-day UM is ∼60% of the total mantle mass and a lower mantle that is non-primitive reproduce the estimated geochemical composition and isotope ratios in Earth's silicate reservoirs. The isotopic evolution of the silicate Earth is strongly affected by the mode of crustal growth; only an exponential crustal growth pattern with crustal growth since the early Archean satisfactorily explains the chemical and isotopic evolution of the crust-mantle system and accounts for the so-called Pb paradoxes. Assuming that the OIB source is located in the deeper mantle, our model could, however, not reproduce its target ɛNd of +4.6 for the UM, which has been estimated from the average isotope ratios of 32 individual ocean island localities. Hence, either mantle plumes sample the LM in a non-representative way, or the simplified model set-up does not capture the full complexity of Earth's lower mantle (Nd isotope) evolution. Compared to the results obtained for a 4.55 Ga Earth, a model assuming a protracted U-Pb evolution of silicate Earth by ca. 100 Myr reproduces a slightly better fit for the Pb isotope ratios in Earth's silicate reservoirs. One notable feature of successful models is the early depletion of incompatible elements (as well as rapid decrease in Th/U) in

  17. Zircon Zoning, Trace Elements and U-Pb Dates Reveal Crustal Foundering Beneath the Pamir

    NASA Astrophysics Data System (ADS)

    Hacker, B. R.; Shaffer, M. E. F.; Ratschbacher, L.; Kylander-Clark, A. R.

    2017-12-01

    Xenoliths that erupted in the SE Pamir of Tajikistan at 11.2 Ma from 1000-1050°C and 90 km depth illuminate what happens when crust founders into the mantle. The xenoliths are a broad range of crustal rock types and contain abundant xenoliths whose U-Pb isotopic ratios and trace-element contents were examined by laser-ablation split stream inductively coupled plasma mass spectrometry. Cathodoluminescence imaging of the grains shows igneous cores with oscillatory zoning overprinted by substantial recrystallization. The bulk of the U-Pb dates are concordant and range from 160 Ma to 11 Ma. The range of dates suggest that the xenoliths were likely derived from the Jurassic-Cretaceous Andean-style magmatic arc and its Proterozoic-Mesozoic host rocks along the southern margin of Asia. The zircons show distinct changes in Eu anomaly, Lu/Gd ratio, and Ti concentrations that are interpreted to indicate garnet growth and minimal heating at 22-20 Ma, and then 200-300°C of heating, 25 km of burial, and alkali-carbonate melt injection at 14-11 Ma. These changes are interpreted to coincide with: i) heat input due to Indian slab breakoff at 22‒20 Ma; ii) rapid thickening and foundering of the Pamir lithosphere at 14‒11 Ma, prior to and synchronous with collision between deep Indian and Asian lithospheres beneath the Pamir.

  18. Uranium-lead isotope systematics of Mars inferred from the basaltic shergottite QUE 94201

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

    Gaffney, A M; Borg, L E; Connelly, J N

    2006-12-22

    Uranium-lead ratios (commonly represented as {sup 238}U/{sup 204}Pb = {mu}) calculated for the sources of martian basalts preserve a record of petrogenetic processes that operated during early planetary differentiation and formation of martian geochemical reservoirs. To better define the range of {mu} values represented by the source regions of martian basalts, we completed U-Pb elemental and isotopic analyses on whole rock, mineral and leachate fractions from the martian meteorite Queen Alexandra Range 94201 (QUE 94201). The whole rock and silicate mineral fractions have unradiogenic Pb isotopic compositions that define a narrow range ({sup 206}Pb/{sup 204}Pb = 11.16-11.61). In contrast, themore » Pb isotopic compositions of weak HCl leachates are more variable and radiogenic. The intersection of the QUE 94201 data array with terrestrial Pb in {sup 206}Pb/{sup 204}Pb-{sup 207}Pb/{sup 204}Pb-{sup 208}Pb/{sup 204}Pb compositional space is consistent with varying amounts of terrestrial contamination in these fractions. We calculate that only 1-7% contamination is present in the purified silicate mineral and whole rock fractions, whereas the HCl leachates contain up to 86% terrestrial contamination. Despite the contamination, we are able to use the U-Pb data to determine the initial {sup 206}Pb/{sup 204}Pb of QUE 94201 (11.086 {+-} 0.008) and calculate the {mu} value of the QUE 94201 mantle source to be 1.823 {+-} 0.008. This is the lowest {mu} value calculated for any martian basalt source, and, when compared to the highest values determined for martian basalt sources, indicates that {mu} values in martian source reservoirs vary by at least 100%. The range of source {mu} values further indicates that the {mu} value of bulk silicate Mars is approximately three. The amount of variation in the {mu} values of the mantle sources ({mu} {approx} 2-4) is greater than can be explained by igneous processes involving silicate phases alone. We suggest the possibility that a

  19. Evidence of a connection between the Atlantic and Mediterranean during the Messinian Salinity Crisis from Pb and Nd isotopes

    NASA Astrophysics Data System (ADS)

    Modestou, Sevasti; Gutjahr, Marcus; Fietzke, Jan; Rodés, Ángel; Frank, Martin; Bolhão Muiños, Susana; Ellam, Rob; Flecker, Rachel

    2014-05-01

    Prior to the opening of the Gibraltar Strait at 5.33 Ma, the Betic (southern Spain) and Rifian (northern Morocco) marine palaeocorridors linked the Mediterranean to the Atlantic. Although the central regions of these corridors have been heavily eroded due to uplift, evidence published to date indicates that both closed before the onset of the Messinian Salinity Crisis (MSC; 5.97 to 5.33 Ma [1, 2]). However, pre-MSC corridor closure presents a paradox, as the volume of halite deposited within the Mediterranean basin requires several times the volume of seawater contained in the basin itself. In this regard, radiogenic isotopes such as Sr, Pb, and Nd can provide key information about the timing of exchange through the Betic and Rifian palaeogateways. Due to the resolvable isotopic difference in Nd isotope signatures of outgoing Mediterranean and incoming Atlantic water masses, demonstrated both for the present day as well as the past environment, this isotope system can be used to identify exchange between these two water bodies. Although less well constrained to date, the Pb isotope system can be used in a similar manner due to its short residence time in seawater and interbasin variability. A high resolution Pb isotope record extracted using laser ablation from ferromanganese crust 3514-6 (recovered from the Lion Seamount, NE Atlantic, water depth 690-940 m) indicates a relatively constant Pb isotope signature before, during and after the MSC period. The previously published [3] Nd isotope record of crust 3514-6 corroborates that the crust was deposited in a current distinct from NE Atlantic Deep water or Antarctic Intermediate Water, the principal currents in the region of the Lion Seamount. The combined Pb and Nd isotope evolution suggests that Mediterranean Outflow Water (MOW) was continuously advected into the NE Atlantic during and after the MSC. Furthermore, preliminary Nd isotope records from Late Miocene sediments collected in the Sorbas Basin, Spain

  20. U-Pb Dating of Calcite to Constrain Basinal Brine Flux Events: An Example from the Upper Midwest USA

    NASA Astrophysics Data System (ADS)

    Rasbury, T.; Luczaj, J.

    2017-12-01

    Calcite forms in a variety of settings and can be the product of surface to deep basinal fluids. As such, this mineral can uniquely record details of the fluids responsible for its formation. The forms of calcium carbonates and their stratigraphic relationships from the thin section to the regional scale give important insights on pulses of fluids. A fundamental question is the age of such fluid pulses. While calcite excludes uranium (U) from its crystal structure, some is incorporated and depending on the U/Pb ratio, this provides an opportunity for radiometric dating. Calcite crystals of various sizes and crystal habits are found in Paleozoic carbonate rocks throughout the region from the western Michigan basin to the upper Mississippi valley. These are typically associated with Mississippi Valley-type (MVT) mineralization, including galena, sphalerite, and iron sulfides, but typically post-date the main MVT event. We have analyzed a variety of these calcites and find multiple generations of calcite, separated by tens of millions of years. The initial Pb isotope ratios are similar to the isotope ratios of nearby galena, strongly suggesting a genetic relationship. Our oldest ages are 200 Ma, and we find ages ranging into the Cenozoic. Based on the Paleozoic-hosted galena Pb-isotope isoscapes from the region, the fluids may have been sourced from both the Michigan and Illinois basins. An important and unanswered question is what would cause significant fluid movement out of the basins substantially after Appalachian orogenesis. Noble gas data from brines in the Michigan Basin have a mantle component and have been suggested to be responsible for recognized elevated temperatures across the basin (Ma et al., 2009). Multiple thermal events during the Paleozoic and Mesozoic eras may have an internal heat source related to reactivation of faults of the Keweenawan Rift system below the Michigan Basin. Perhaps a mantle heat source from below episodically fluxes into the

  1. The Pb Isotope Pedigree of Western Samoan Volcanics: New Insights From High-Precision Analysis by NEPTUNE ICP/MS

    NASA Astrophysics Data System (ADS)

    Hart, S. R.; Workman, R. K.; Coetzee, M.; Blusztajn, J. S.; Ball, L.; Johnson, K. T.

    2002-12-01

    The Samoan hotspot has produced a chain of volcanism stretching from the island of Savai'i in the west to the presently active "leading-edge" volcano, Vailulu'u, in the east. An alignment of seamounts and submarine banks extending west of Savai'i is believed to be the earliest expression of the hotspot (Johnson, 1986). In 2001, we sampled the oldest shield exposures on Savai'i and western Upolu; these, and samples from the western banks Lalla Rookh, Combe and Alexa, have been analyzed for Pb isotopes using a new high precision Pb technique developed on the NEPTUNE ICP/Multi-Collector at W.H.O.I. Pb samples were doped with the NBS 997 thallium standard, with Pb/Tl ratios between 4 and 10; mass discrimination was adjusted to 205Tl/203Tl=2.387075 using an exponential fractionation law. Each run consisted of 35 cycles (16 s each) at an uptake rate of 0.13 μl/min (~12 minutes per run). The abundance sensitivity of the NEPTUNE is 2 ppm downmass and 1 ppm upmass; tailing at mass 204 from Tl is therefore ~30 ppm for 204Pb in a Pb/Tl = 4 solution. This can be adequately accounted for by careful selection of off-peak baseline positions. Beyond this effect, there is no dependence of Pb isotope ratios on Pb/Tl, over the range from 4-10. The correction on 204Pb for 204Hg was also minimal (20-30 ppm) and quite stable. Thirty runs of the NBS 981 standard (200 ppb solution, 12 different days over a period of 5 months) produced results very similar to the best TIMS data, with excellent external reproducibility: 206Pb/204Pb=19.9309(90), 207Pb/204Pb=15.4843(98), 208Pb/204Pb=36.6756(112) (in parenthesis, +/- 2σ in ppm). Similar external reproducibility was achieved for the Samoan basalt samples (duplicate runs on different days on solution splits from a single chemistry: +/- 2σ ppm = 101, 89 and 117, respectively). Over this time period, the variability of Tl mass bias was very small (+/- 130 ppm standard deviation). The only significant pitfall we have encountered is a memory

  2. Multi-isotope tracers to investigate processes in the Elbe, Weser and Ems river catchment using B, Mo, Sr, and Pb isotope ratios assessed by MC ICP-MS

    NASA Astrophysics Data System (ADS)

    Irrgeher, Johanna; Reese, Anna; Zimmermann, Tristan; Prohaska, Thomas; Retzmann, Anika; Wieser, Michael E.; Zitek, Andreas; Proefrock, Daniel

    2017-04-01

    Environmental monitoring of complex ecosystems requires reliable sensitive techniques based on sound analytical strategies to identify the source, fate and sink of elements and matter. Isotopic signatures can serve to trace pathways by making use of specific isotopic fingermarks or to distinguish between natural and anthropogenic sources. The presented work shows the potential of using the isotopic variation of Sr, Pb (as well-established isotopic systems), Mo and B (as novel isotopic system) assessed by MC ICP-MS in water and sediment samples to study aquatic ecosystem transport processes. The isotopic variation of Sr, Pb, Mo and B was determined in different marine and estuarine compartments covering the catchment of the German Wadden Sea and its main tributaries, the Elbe, Weser and Ems River. The varying elemental concentrations, the complex matrix and the expected small variations in the isotopic composition required the development and application of reliable analytical measurement approaches as well as suited metrological data evaluation strategies. Aquatic isoscapes were created using ArcGIS® by relating spatial isotopic data with geographical and geological maps. The elemental and isotopic distribution maps show large variation for different parameters and also reflect the numerous impact factors (e.g. geology, anthropogenic sources) influencing the catchment area.

  3. 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

  4. The Hadean upper mantle conundrum: evidence for source depletion and enrichment from Sm-Nd, Re-Os, and Pb isotopic compositions in 3.71 Gy boninite-like metabasalts from the Isua Supracrustal Belt, Greenland

    NASA Astrophysics Data System (ADS)

    Frei, Robert; Polat, Ali; Meibom, Anders

    2004-04-01

    Here we present Sm-Nd, Re-Os, and Pb isotopic data of carefully screened, least altered samples of boninite-like metabasalts from the Isua Supracrustal Belt (ISB, W Greenland)that characterize their mantle source at the time of their formation. The principal observations of this study are that by 3.7-3.8 Ga melt source regions existed in the upper mantle with complicated enrichment/depletion histories. Sm-Nd isotopic data define a correlation line with a slope corresponding to an age of 3.69 ± 0.18 Gy and an initial εNd value of +2.0 ± 4.7. This Sm-Nd age is consistent with indirect (but more precise) U-Pb geochronological estimates for their formation between 3.69-3.71 Ga. Relying on the maximum formation age of 3.71 Gy defined by the external age constraints, we calculate an average εNd [T = 3.71 Ga] value of +2.2 ± 0.9 (n = 18, 1σ) for these samples, which is indicative of a strongly depleted mantle source. This is consistent with the high Os concentrations, falling in the range between 1.9-3.4 ppb, which is similar to the estimated Os concentration for the primitive upper mantle. Re-Os isotopic data (excluding three outliers) yield an isochron defining an age of 3.76 ± 0.09 Gy (with an initial γOs value of 3.9 ± 1.2), within error consistent with the Sm-Nd age and the indirect U-Pb age estimates. An average initial γOs [T = 3.71 Ga] value of + 4.4 ± 1.2 (n = 8; 2σ) is indicative of enrichment of their source region during, or prior to, its melting. Thus, this study provides the first observation of an early Archean upper mantle domain with a distinctly radiogenic Os isotopic signature. This requires a mixing component characterized by time-integrated suprachondritic Re/Os evolution and a Os concentration high enough to strongly affect the Os budget of the mantle source; modern sediments, recycled basaltic crust, or the outer core do not constitute suitable candidates. At this point, the nature of the mantle or crustal component responsible for the

  5. Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

    NASA Astrophysics Data System (ADS)

    Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

    2017-10-01

    Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

  6. Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

    USGS Publications Warehouse

    Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

    1999-01-01

    Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and

  7. 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

  8. 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.

  9. 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.

  10. Rb-Sr whole-rock and mineral ages, K-Ar, 40Ar/39Ar, and U-Pb mineral ages, and strontium, lead, neodymium, and oxygen isotopic compositions for granitic rocks from the Salinian Composite Terrane, California:

    USGS Publications Warehouse

    Kistler, R.W.; Champion, D.E.

    2001-01-01

    This report summarizes new and published age and isotopic data for whole-rocks and minerals from granitic rocks in the Salinian composite terrane, California. Rubidium-strontium whole-rock ages of plutons are in two groups, Early Cretaceous (122 to 100 Ma) and Late Cretaceous (95 to 82 Ma). Early Cretaceous plutons occur in all granitic rock exposures from Bodega Head in the north to those from the Santa Lucia and Gabilan Ranges in the central part of the terrane. Late Cretaceous plutons have been identified in the Point Reyes Peninsula, the Santa Lucia and the Gabilan Ranges, and in the La Panza Range in the southern part of the terrane. Ranges of initial values of isotopic compositions are 87Sr/86Sr, 0.7046-0.7147, δ18O, +8.5 to +12.5 per mil, 206Pb/204Pb, 18.901-19.860, 207Pb/204Pb, 15.618-15.814, 208Pb/204Pb, 38.569- 39.493, and εNd, +0.9 to -8.6. The initial 87Sr/86Sr=0.706 isopleth is identified in the northern Gabilan Range and in the Ben Lomond area of the Santa Cruz Mountains, in Montara Mountain, in Bodega Head, and to the west of the Farallon Islands on the Cordell Bank. This isotopic boundary is offset about 95 miles (160km) by right-lateral displacements along the San Gregorio-Hosgri and San Andreas fault systems.

  11. STATISTICAL ESTIMATES OF VARIANCE FOR 15N ISOTOPE DILUTION MEASUREMENTS OF GROSS RATES OF NITROGEN CYCLE PROCESSES

    EPA Science Inventory

    It has been fifty years since Kirkham and Bartholmew (1954) presented the conceptual framework and derived the mathematical equations that formed the basis of the now commonly employed method of 15N isotope dilution. Although many advances in methodology and analysis have been ma...

  12. Coupling Meteorology, Metal Concentrations, and Pb Isotopes for Source Attribution in Archived Precipitation Samples

    EPA Science Inventory

    A technique that couples lead (Pb) isotopes and multi-element concentrations with meteorological analysis was used to assess source contributions to precipitation samples at the Bondville, Illinois USA National Trends Network (NTN) site. Precipitation samples collected over a 16 ...

  13. 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

    The identification and retrieval of a large population of ancient zircons (>4 Ga; Hadean) is of utmost priority if models of the early evolution of Earth are to be rigorously tested. We have developed a rapid and accurate U-Pb zircon age determination protocol utilizing a fully automated multi-collector ion microprobe, the ANU SHRIMP II, to screen and date these zircons. Unattended data acquisition relies on the calibration of a digitized sample map to the Sensitive High Resolution Ion MicroProbe (SHRIMP) sample-stage co-ordinate system. High precision positioning of individual grains can be produced through optical image processing of a specified mount location. The focal position of the mount can be optimized through a correlation between secondary-ion steering and the spot position on the target. For the Hadean zircon project, sample mounts are photographed and sample locations (normally grain centers) are determined off-line. The sample is loaded, reference points calibrated, and the target positions are then visited sequentially. In SHRIMP II multiple-collector mode, zircons are initially screened (ca. 5 s data acquisition) through their 204Pb corrected 207Pb/206Pb ratio; suitable candidates are then analyzed in a longer routine to obtain better measurement statistics, U/Pb, and concentration data. In SHRIMP I and SHRIMP RG, we have incorporated the automated analysis protocol to single-collector measurements. These routines have been used to analyze over 100,000 zircons from the Jack Hills quartzite. Of these, ca. 7%, have an age greater than 3.8 Ga, the oldest grain being 4372 +/- 6 Ma (2[sigma]), and this age is part of a group of analyses around 4350 Ma which we interpret as the age when continental crust first began to coalesce in this region. In multi-collector mode, the analytical time taken for a single mount with 400 zircons is approximately 6 h; whereas in single-collector mode, the analytical time is ca. 17 h. With this productivity, we can produce

  14. 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

  15. Theoretical implications for the estimation of dinitrogen fixation by large perennial plant species using isotope dilution

    Treesearch

    Dwight D. Baker; Maurice Fried; John A. Parrotta

    1995-01-01

    Estimation of symbiotic N2 fixation associated with large perennial plant species, especially trees, poses special problems because the process must be followed over a potentially long period of time to integrate the total amount of fixation. Estimations using isotope dilution methodology have begun to be used for trees in field studies. Because...

  16. Pb-Sr-Nd isotopes in surficial materials at the Pebble Porphyry Cu-Au-Mo Deposit, Southwestern Alaska: can the mineralizing fingerprint be detected through cover?

    USGS Publications Warehouse

    Ayuso, Robert A.; Kelley, Karen D.; Eppinger, Robert G.; Forni, Francesca

    2013-01-01

    The Cretaceous Pebble porphyry Cu-Au-Mo deposit is covered by tundra and glacigenic sediments. Pb-Sr-Nd measurements were done on sediments and soils to establish baseline conditions prior to the onset of mining operations and contribute to the development of exploration methods for concealed base metal deposits of this type. Pebble rocks have a moderate range for 206Pb/204Pb = 18.574 to 18.874, 207Pb/204Pb = 15.484 to 15.526, and 208,Pb/204Pb = 38.053 to 38.266. Mineralized granodiorite shows a modest spread in 87Sr/86Sr (0.704354–0.707621) and 143Nd/144Nd (0.512639–0.512750). Age-corrected (89 Ma) values for the granodiorite yield relatively unradiogenic Pb (e.g., 207Pb/204Pb 87Sr/86Sr, and positive values of ɛNd (1.00–4.52) that attest to a major contribution of mantle-derived source rocks. Pond sediments and soils have similar Pb isotope signatures and 87Sr/86Sr and 143Nd/144Nd values that resemble the mineralized granodiorites. Glacial events have obscured the recognition of isotope signatures of mineralized rocks in the sediments and soils. Baseline radiogenic isotope compositions, prior to the onset of mining operations, reflect natural erosion, transport and deposition of heterogeneous till sheets that included debris from barren rocks, mineralized granodiorite and sulfides from the Pebble deposit, and other country rocks that pre- and postdate the mineralization events. Isotopic variations suggest that natural weathering of the deposit is generally reflected in these surficial materials. The isotope data provide geochemical constraints to glimpse through the extensive cover and together with other geochemical observations provide a vector to concealed mineralized rocks genetically linked with the Pebble deposit.

  17. The history of a continent from U-Pb ages of zircons from Orinoco River sand and Sm-Nd isotopes in Orinoco basin river sediments

    USGS Publications Warehouse

    Goldstein, S.L.; Arndt, N.T.; Stallard, R.F.

    1997-01-01

    We report SHRIMP U-Pb ages of 49 zircons from a sand sample from the lower Orinoco River, Venezuela, and Nd model ages of the fine sediment load from the main river and tributaries. The U-Pb ages reflect individual magmatic or metamorphic events, the Sm-Nd model ages reflect average crustal-residence ages of the sediment sources. Together they allow delineation of the crust-formation history of the basement precursors of the sediments. The U-Pb ages range from 2.83 to 0.15 Ga, and most are concordant or nearly so. Discrete age groupings occur at ??? 2.8, ??? 2.1, and ??? 1.1 Ga. The oldest group contains only three samples but is isolated from its closest neighbors by a ??? 600 Ma age gap. Larger age groupings at ??? 2.1 and ??? 1.1 Ga make up about a third and a quarter of the total number of analyses, respectively. The remaining analyses scatter along concordia, and most are younger than 1.6 Ga. The ??? 2.8 and ??? 2.1 Ga ages correspond to periods of crust formation of the Imataca and Trans-Amazonian provinces of the Guyana Shield, respectively, and record intervals of short but intensive continental growth. These ages coincide with ??? 2.9 and ??? 2.1 Ga Nd model ages of sediments from tributaries draining the Archean and Proterozoic provinces of the Guyana Shield, respectively, indicating that the U-Pb ages record the geological history of the crystalline basement of the Orinoco basin. Zircons with ages corresponding to the major orogenies of the North Atlantic continents (the Superior at ??? 2.7 Ga and Hudsonian at 1.7-1.9 Ga) were not found in the Orinoco sample. The age distribution may indicate that South and North America were separated throughout their history. Nd model ages of sediments from the lower Orinoco River and Andean tributaries are ??? 1.9 Ga, broadly within the range displayed by major rivers and dusts. This age does not coincide with known thermal events in the region and reflects mixing of sources with different crust-formation ages. The

  18. Sr-Nd-Pb Isotope Geochemistry of Melange Formation: Implications for Identification of Fluid Sources in the Mantle Wedge and the Arc

    NASA Astrophysics Data System (ADS)

    Bebout, G. E.; King, R. L.; Moriguti, T.; Nakamura, E.

    2004-12-01

    Paramount to our ability to decipher the behavior of fluids and melts within the mantle wedge and the overall subduction system are the chemical compositions of rocks adjacent to the slab-mantle interface. Profound metamorphic and metasomatic alteration of pre-subduction lithologies to form melange along the slab-mantle interface may yield rock types inheriting mixed chemical compositions of diverse pre-subduction lithologies. Early work on melange geochemistry indicates competitive effects between mechanical mixing, metasomatism by fluids or melts, and mineral stabilities imposed by the resulting bulk composition. We have explored the Sr-Nd-Pb isotope geochemistry of low- to high-grade melange zones in the Catalina Schist, CA, to address this crucial missing component in studies of subduction-zone mass flux. The Catalina Schist contains lawsonite-albite (LA), lawsonite-blueschist (LB), and amphibolite (AM) facies melange zones, all with mineralogy dominated by talc, chlorite, and Na-Ca amphiboles, with additional minerals such as micas, rutile, zircon, and apatite stabilized based on bulk sample chemistry. Major element compositions vary, from strongly ultramafic in the AM melange, to more crustal-like compositions (i.e., more reminiscent of basaltic to sedimentary protoliths) for LA and LB melange. However, initial Sr and Nd isotope ratios for all grades of melange are essentially indistinguishable, displaying a wide variation from 87Sr/86Sr=0.703-0.709 and ɛ Nd= +15 to -15. Covariations are generally negative, similar to that of the mantle array, but with some samples extending to higher Sr ratios at constant ɛ Nd that probably reflect inheritance of seawater Sr. No clear mixing relationships between 87Sr/86Sr and 1/Sr exist, suggesting either localized buffering of Sr isotope ratios or that mixing relations are obscured by secondary devolatilization. However, a clear mixing trend for Nd indicates two end-members, one a high-concentration, positive ɛ Nd

  19. A Coast Mountains provenance for the Valdez and Orca groups, southern Alaska, based on Nd, Sr, and Pb isotopic evidence

    USGS Publications Warehouse

    Farmer, G.L.; Ayuso, R.; Plafker, G.

    1993-01-01

    Nd, Sr, and Pb isotopic data were obtained for fourteen fine- to coarse-grained samples of accreted flysch of the Late Cretaceous and early Tertiary Valdez and Orca Groups in southern Alaska to determine the flysch provenance. Argillites and greywackes from the Orca Group, as well as compositionally similar but higher metamorphic grade rocks from the Valdez Group, show a restricted range of correlated ??{lunate}Nd ( -0.6 to -3.8) and 87Sr 86Sr (0.7060-0.7080) at the time of sediment deposition ( ??? 50 Ma). Pb isotopic compositions also vary over a narrow range ( 206Pb 204Pb = 19.138-19.395, 207Pb 204Pb = 15.593-15.703, 208Pb 204Pb = 38.677-39.209), and in the Orca Group the samples generally become more radiogenic with decreasing ??{lunate}Nd and increasing 87Sr 86Sr. All samples have similar trace element compositions characterized by moderate light rare earth element enrichments, and low ratios of high field strength elements to large ion lithophile elements. Based on petrographic, geochemical, and isotopic data the sedimentary rocks are interpreted to have been derived largely from a Phanerozoic continental margin arc complex characterized by igneous rocks with ??{lunate}Nd values between 0 and -5. The latter conclusion is supported by the ??{lunate}Nd values of a tonalite clast and a rhyodacite clast in the Orca Group (??{lunate}Nd = -4.9 and -0.9, respectively). However, trondjemitic clasts in the Orca Group have significantly lower ??{lunate}Nd ( ??? -10) and require a derivation of a portion of the flysch from Precambrian crustal sources. The Nd, Sr, and Pb isotopic compositions of both the Valdez and Orca Groups overlap the values determined for intrusive igneous rocks exposed within the northern portion of the Late Cretaceous to early Tertiary Coast Mountains Plutonic Complex in western British Columbia and equivalent rocks in southeastern Alaska. The isotopic data support previous conclusions based on geologic studies which suggest that the flysch was

  20. Thermal and exhumation history of the central Tianshan (NW China): Constraints by U-Pb geochronology and Ar-Ar and (U-Th)/He thermochronology

    NASA Astrophysics Data System (ADS)

    Yin, J.; Chen, W.; Hodges, K. V.; Xiao, W.; Van Soest, M. C.; Cai, K.; Zhang, B.; Mercer, C. M.; Yuan, C.

    2015-12-01

    Geochronology and thermochronology using multiple mineral-isotopic chronometers reveals the thermo-tectonic history of the central Tianshan (NW China) from emplacement to exhumation. Granites from the central Tianshan, which are associated with the southward subduction of the northern Tianshan Ocean, have been dated at 362-354 Ma using the LA-ICP-MS Zircon U-Pb method. A younger diorite sample (282 ± 1 Ma, Zircon U-Pb method by LA-ICP-MS) from northern Tianshan formed during the final closure of the Northern Tianshan Ocean when the Junggar Block collided with the Yili-Central Tianshan Block. 40Ar/39Ar step-wise heating plateau dates (biotite Ar/Ar: 312-293 Ma; Plagioclase Ar/Ar: 270-229 Ma) from the Central Tianshan show rapid post-magmatic cooling during the Late Carboniferous-Early Permian followed by a more modest rate of cooling from the middle Permian to the middle Jurassic. The northern Tianshan diorite (biotite Ar/Ar: 240 ± 1 Ma) also reveals a middle Jurassic cooling. Apatite (U-Th )/He dates from the central Tianshan samples range from ca. 130 Ma to ca. 116 Ma. The Apatite (U-Th )/He date for the northern Tianshan sample is ca. 27 Ma. Previous studies also reported Apatite (U-Th)/He ages of ca. 44 Ma-11 Ma in the Baluntai area of the southern Central Tianshan[1]. Two episodes of cooling are distinguished by thermal history modelling: (1) Mesozoic cooling occurred as the result of the exhumation and tectonic reactivation of the central Tianshan; and (2) The Tianshan orogenic belt has been rapidly exhumed since the Middle Cenozoic. References [1] Lü, H.H., Chang, Y., Wang, W., Zhou, Z.Y., 2013. Rapid exhumation of the Tianshan Mountains since the early Miocene: Evidence from combined apatite fission track and (U-Th)/He thermochronology. Science China: Earth Sciences, 43(12): 1964-1974 (in Chinese).

  1. Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

    DOE PAGES

    Horkley, J. J.; Carney, K. P.; Gantz, E. M.; ...

    2015-03-17

    Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure “spike” solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for “age” determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determinemore » 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution, and the encapsulation of the materials will be described.« less

  2. A Stable U Isotopic Perspective on the U Budget and Global Extent of Modern Anoxia in the Ocean.

    NASA Astrophysics Data System (ADS)

    Tissot, F.; Dauphas, N.

    2015-12-01

    Isotopic fractionation between U4+ and U6+makes U stable isotopes potential tracers of global paleoredox conditions. In this work [1], we put the U-proxy up to a test against a highly constrained system: the modern ocean. We measured a large number of seawater samples from geographically diverse locations and found that the open ocean has a homogenous isotopic composition at δ238USW= -0.392 ± 0.005 ‰ (rel. to CRM-112a). From our measurement of rock samples (n=64) and compilations of literature data (n=380), we then estimated the U isotopic compositions of the various reservoirs involved in the modern oceanic U budget, as well as the fractionation factors associated with U incorporation into those reservoirs. Using a steady-state model, we compared the isotopic composition of the seawater predicted by the four most recent U oceanic budgets [2-5] to the modern seawater value we measured. Three of these budgets [2-4] predict a seawater isotopic composition in very good agreement with the observed δ238USW, which strengthens our confidence in the isotopic fractionation factors associated with each deposition environment and the fact that U is at steady-state in the modern ocean. The U oceanic budget of Henderson and Anderson (2003) does not reproduce the observed seawater composition because the U flux to anoxic/euxinic sediments relative to the total U flux out of the ocean is high in their model, which our analysis shows cannot be correct. The U isotopic composition of seawater is used to constrain the extent of anoxia in the modern ocean (% of seafloor covered by anoxic/euxinic sediments), which is 0.21 ± 0.09 %. This work demonstrates that stable isotopes of U can indeed trace the extent of anoxia in the modern global ocean, thereby validating the application of U isotope measurements to paleoredox reconstructions. Based on the above work, we will present the best estimate of the modern oceanic U budget. [1] Tissot F.L.H., Dauphas N. (2015) Geochim Cosmochim

  3. Isotope geochronology of the Precambrian

    NASA Astrophysics Data System (ADS)

    Levskii, L. K.; Levchenkov, O. A.

    This symposium discusses the use of isotope methods for establishing the geochronology of Precambrian formations, with special consideration given to geochronological studies of the early phases of the earth's core evolution in the Baltic and Vitim-Aldan shields and the Enderby Land (Antarctica). Attention is also given to the Early Archean Vodlozero gneiss complex and its structural-metamorphic evolution, the influence of geological events during the Proterozoic on the state of the U-Pb and Rb-Sr systems in the Archean postkinematic granites of Karelia, the Rb-Sr systems in the andesite basalts of the Suna-Semch' region (Karelia), and the geochronology of the Karelian granite-greenstone region. Also discussed are the petrogenesis and age of the rocks from the Kola ultradeep borehole, the isotope-geochronological evidence for the early Precambrian history of the Aldan-Olekma region, the Rb-Sr systems in metasedimentary rocks of the Khani graben, and the U-Pb ages of zircons from polymetamorphic rocks of the Archean granulite complex of Enderby Land.

  4. Integrated elemental and Sr-Nd-Pb-Hf isotopic studies of Mesozoic mafic dykes from the eastern North China Craton: implications for the dramatic transformation of lithospheric mantle

    NASA Astrophysics Data System (ADS)

    Liu, Shen; Feng, Caixia; Santosh, M.; Feng, Guangying; Coulson, Ian M.; Xu, Mengjing; Guo, Zhuang; Guo, Xiaolei; Peng, Hao; Feng, Qiang

    2018-02-01

    Evolution of the lithospheric mantle beneath the North China Craton (NCC) from its Precambrian cratonic architecture until Paleozoic, and the transformation to an oceanic realm during Mesozoic, with implications on the destruction of cratonic root have attracted global attention. Here we present geochemical and isotopic data on a suite of newly identified Mesozoic mafic dyke swarms from the Longwangmiao, Weijiazhuang, Mengjiazhuang, Jiayou, Huangmi, and Xiahonghe areas (Qianhuai Block) along the eastern NCC with an attempt to gain further insights on the lithospheric evolution of the region. The Longwangmiao dykes are alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 4.3) and EM1-like Sr-Nd-Pb-Hf isotopic signature ((87Sr/86Sr) i > 0.706; ε Nd (t) < -6.3, (206Pb/204Pb) i > 16.6, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.8, ε Hf (t) < -22.4). The Weijiazhuang dykes are sub-alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 3.7), and display similar EM1-like isotopic features ((87Sr/86Sr) i > 0.706; ε Nd (t) < -7.0, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -23.3). The Mengjiazhuang dykes are also sub-alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 2.4) and EM1-like isotopic features((87Sr/86Sr) i > 0.706; ε Nd (t) < -18.4, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -8.6). The Jiayou dykes also display sub-alkaline affinity with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 3.7) and EM1-like Sr-Nd-Pb-Hf isotopic features ((87Sr/86Sr) i > 0.706; ε Nd(t) < -15.3, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -18.4). The Huangmi dykes are alkaline (with Na2O + K2O ranging to more than 5.9 wt.%)) with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 9.3) and EM1-like isotopic composition ((87Sr/86Sr) i > 0.705; ε Nd (t) < -15.1, (206Pb/204Pb) i > 16.9, (207Pb/204Pb) i > 15.5, (208Pb/204Pb) i > 36

  5. U-Th-Pb systematics of selected samples from Apollo 17, Boulder 1, Station 2

    USGS Publications Warehouse

    Nunes, P.D.; Tatsumoto, M.

    1975-01-01

    Nine U-Th-Pb whole-rock analyses of selected brecciated materials from sample 72215 and one analysis of a pigeonite basalt clast from 72275 are presented. Both samples are from Boulder 1, Apollo 17. These data supplement previous Boulder 1 U-Th-Pb analyses of samples 72275 and 72255. U and Th concentrations indicate that most of the samples contain a moderate to large KREEP component. Samples containing the least KREEP are a noritic clast (72255,49; Civet Cat clast) and an anorthositic clast (72275,117). Evidence for the migration of Pb from Pb-rich matrix material into relatively Pb-poor clasts is presented for two clasts. Most of the Boulder 1 data define a linear trend that intersects concordia at ??? 3.9 and 4.4 b.y. when plotted on a U-Pb concordia diagram. The presence of one anorthositic clast distinctly off this trend indicates that a simple two-stage U-Pb evolution history is inadequate to explain all the data. Accordingly physical significance is only attached to the lower concordia intercept age of 3.9-4.0 b.y. The older concordia intercept age of ??? 4.4 b.y. is interpreted to reflect an averaging of events both older and younger than 4.4 b.y. The data suggest that significant differentiation and/or metamorphism occurred ??? 4.2 b.y. ago. The age of this event, however, is not accurately defined by these data. ?? 1975 D. Reidel Publishing Company, Dordrecht-Holland.

  6. Pb isotope systematics in volcanic river system: Constraints about weathering processes

    NASA Astrophysics Data System (ADS)

    Negrel, P. J.; Millot, R.; Petelet-Giraud, E.; Guerrot, C.

    2012-12-01

    We present a series of lead isotopes in soils and sediments developed on volcanic rocks forming a small watershed flowing through the Massif Central (France). The Massif Central volcanic province is a widespread area of Tertiary to Recent continental alkaline volcanism comprising alkali basalts and basanites. The Allanche watershed has an area of 160 km2, a maximum altitude in the watershed of 1400 m (a.s.l.) and the relief between the extreme sampling points of 340 m The river is 29 km long from headwaters to the outlet and from its origin in the Cézallier area to its mouth in the Allagnon river (a tributary of the Allier river), the Allanche river flows through the volcanic terrains of the lava plateau (11 to 2.5 Ma). Main bedrocks are basanites (nepheline or leucitic basalts), with SiO2 around 41-45%, low Na2O + K2O (<5%), and with modal or normative nepheline or leucite and a ground mass of clinopyroxene and plagioclase. Surrounding rocks are feldspatic basalts with SiO2 close to 46-49%, low Na2O + K2O (<5%). The main phase in these basalts is plagioclase with normative nepheline, hyperstene and olivine. Crustal contamination (e.g. by granite, gneiss or metasedimentary granulite, as stated by Downes, 1987, doi: 10.1144/GSL.SP.1987.030.01.25) has occurred in the differentiated magmas of both series, as witnessed by lead isotopic variations in conjunction with Rb/La ratios and lead contents. Using Pb isotope ratios, major and trace elements (from Négrel and Deschamps, 1996, Aquatic Geochemistry, 2, 1-27) we therefore compare sediments and soils evolution over the Allanche river watershed. K and Ca are considered as mobile reference elements and illustrate the weathering state of soils and sediments relative to parent rocks through a large decrease in K and Ca content when compared to Si; the sediments being less depleted than soils. Lead, with regards to Si shows three behaviour with depleted Si content- same lead content that bedrock, depleted Si content- less

  7. Activity disequilibrium between 234U and 238U isotopes in natural environment.

    PubMed

    Boryło, Alicja; Skwarzec, Bogdan

    The aim of this work was to calculate the values of the 234 U/ 238 U activity ratio in natural environment (water, sediments, Baltic organisms and marine birds from various regions of the southern Baltic Sea; river waters (the Vistula and the Oder River); plants and soils collected near phosphogypsum waste heap in Wiślinka (Northern Poland) and deer-like animals from Northern Poland. On the basis of the studies it was found that the most important processes of uranium geochemical migration in the southern Baltic Sea ecosystem are the sedimentation of suspended material and the vertical diffusion from the sediments into the bottom water. Considerable values of the 234 U/ 238 U are characterized for the Vistula and Oder Rivers and its tributaries. The values of the 234 U/ 238 U activity ratio in different tissues and organs of the Baltic organisms, sea birds and wild deer are varied. Such a large variation value of obtained activity ratios indicates different behavior of uranium isotopes in the tissues and organisms of sea birds and wild animals. This value shows that uranium isotopes can be disposed at a slower or faster rate. The values of the 234 U/ 238 U activity ratio in the analyzed plants, soils and mosses collected in the vicinity of phosphogypsum dumps in Wiślinka are close to one and indicate the phosphogypsum origin of the analyzed nuclides. Uranium isotopes 234 U and 238 U are not present in radioactive equilibrium in the aquatic environment, which indicates that their activities are not equal. The inverse relationship is observed in the terrestrial environment, where the value of the of the 234 U/ 238 U activity ratio really oscillates around unity.

  8. The Late Paleozoic magmatic evolution of the Aqishan-Yamansu belt, Eastern Tianshan: Constraints from geochronology, geochemistry and Sr-Nd-Pb-Hf isotopes of igneous rocks

    NASA Astrophysics Data System (ADS)

    Zhao, Liandang; Chen, Huayong; Zhang, Li; Zhang, Weifeng; Yang, Juntao; Yan, Xuelu

    2018-03-01

    The Aqishan-Yamansu belt in the Eastern Tianshan (Xinjiang, NW China) is an important mineralization belt. The belt mainly comprises Carboniferous volcanic, volcaniclastic and clastic rocks, and hosts many intermediate-felsic intrusions and Fe (-Cu) deposits. The biotite diorite, felsic brecciated tuff, granodiorite and syenite from the western Aqishan-Yamansu belt are newly zircon U-Pb dated to be 316.7 ± 1.4 Ma, 315.6 ± 2.6 Ma, 305.8 ± 1.9 Ma and 252.5 ± 1.4 Ma, respectively. The mafic rocks (mafic brecciated tuff and diabase porphyry) are tholeiitic to calc-alkaline series, LILE-rich (e.g., Rb, Ba and Pb), HFSE-depleted (e.g., Nb and Ta), and have high Mg#(44-60), Nb/Ta (15.0-20.0), Ba/La (>30) and Ba/Nb (>57) values/ratios, and low Th/Yb ratios (<1), probably originating from mantle wedge metasomatized by slab-derived fluids. The intermediate-felsic igneous rocks are LILE-rich, HFSE-depleted, with high Sr and Y contents showing typical of normal arc magma affinity. Moreover, the depleted εHf(t) (>2.10) and positive εNd(t) (>5.7), combined with variable Nb/Ta ratios (9.52-21.4), Y/Nb ratios (1.47-39.7) and Pb isotopes (206Pb/204Pb = 16.225-17.640, 207Pb/204Pb = 15.454-15.520, 208Pb/204Pb = 37.097-38.025) suggest that these rocks were magma mixing products between juvenile crustal-derived magmas and minor mantle-derived magmas. Combined published works with our new ages, geochemical and isotopic data, we propose that the Aqishan-Yamansu belt was an Early Carboniferous fore-arc basin during the southward subduction of the Kangguer oceanic slab beneath the Yili-Central Tianshan block. With the continuing southward subduction, the Aqishan-Yamansu fore-arc basin initiated to close, which generated the mafic and intensive intermediate-felsic magmatism associated with regional Fe (-Cu) mineralization.

  9. Development of procedure for measurement of Pb isotope ratios in seawater by application of seaFAST sample pre-treatment system and Sector Field Inductively Coupled Plasma Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Vassileva, Emilia; Wysocka, Irena

    2016-12-01

    Anthropogenic Pb in the oceans, derived from high-temperature industrial processes, fuel combustion and incineration can have an isotopic signature distinct from naturally occurring Pb, supplied by rock weathering. To identify the different pollution sources accurately and to quantify their relative contributions, Pb isotope ratios are widely used. Due to the high salt content (approximately 3.5% of total dissolved solids) and very low levels of Pb (typically from 1 to 100 ng L- 1) in seawater the determination of Pb isotope ratios requires preliminary matrix separation and analyte preconcentration. An analytical protocol for the measurements of Pb isotope ratios in seawater combining seaFAST sample pre-treatment system and Sector Field Inductively Coupled Plasma Mass Spectrometry (SF ICP-MS) was developed. The application of seaFAST system was advantageous, because of its completely closed working cycle and small volumes of chemicals introduced in pre-treatment step, resulting in very low detection limits and procedural blanks. The preconcentration/matrix separation step was also of crucial importance for minimizing the isobaric and matrix interferences, coming from the seawater. In order to differentiate between anthropogenic and natural Pb sources, particular attention was paid to the determination of 204Pb isotope because of its implication in some geological interpretations. The validation of the analytical procedure was effectuated according to the recommendations of the ISO/IEC 17025 standard. The method was validated by processing the common Pb isotope reference material NIST SRM 981. All major sources of uncertainty were identified and propagated together following the ISO/GUM guidelines. The estimation of the total uncertainty associated to each measurement result was fundamental tool for sorting the main sources of possible biases. The developed analytical procedure was applied to the coastal and open seawater samples, collected in different regions of

  10. Fallout isotope chronology of the near-surface sediment record of Lake Bolătău.

    PubMed

    Bihari, Árpád; Karlik, Máté; Mîndrescu, Marcel; Szalai, Zoltán; Grădinaru, Ionela; Kern, Zoltán

    2018-01-01

    Fallout isotope ( 210 Pb ex, 137 Cs and 241 Am) based dating has been carried out on the near-surface sediment core collected from Lake Bolătău-Feredeu (Bukovina, Romania). The motivation was to improve the chronology of this recent section in connection with significant fluctuations observed in sediment accumulation rates, particle size distribution and primordial radioisotope (i.e. 40 K and 232 Th) composition. Previously only an extrapolation of a broad-range OxCal age-depth model, which was based on 8 AMS radiocarbon dates from the deeper part of a parallel sediment sequence and tentatively validated for the upper part using the double peaks of the 137 Cs activity concentration distribution, was available for the studied section (1-24 cm). Parallel to the previous 137 Cs measurement, 210 Pb and 226 Ra (for a more detailed, 210 Pb ex -based chronology), 241 Am (for an additional time-marker), as well as 40 K and 232 Th concentrations have also been determined by gamma-spectrometry. In case of the 210 Pb ex -based chronology, due to a large deviation from a pure exponential distribution, the Constant Flux (CF) model has been used for the calculation of sediment ages and accumulation rates. Although the broad-range OxCal and the CF model were broadly similar down to 22 cm, the 210 Pb ex -based ages are clearly superior in terms of uncertainty in the uppermost 12 cm, while the broad-range model has smaller uncertainty below 20 cm (>150 years). The CF model gave an average mass accumulation rate of (0.08 ± 0.03) g cm -2 yr -1 for sections 0-11 cm, and (0.03 ± 0.01) g cm -2 yr -1 for sections 12-22 cm, respectively. Significant changes have been observed in the depth distribution of both the particle size distribution and the elemental/isotopic composition of the sediment record, most likely related to the variation observable in the intensity and volume of precipitation in the catchment. The obtained high-resolution records of Lake Bolătău, including

  11. Pb-Sr isotopic and geochemical constraints on sources and processes of lead contamination in well waters and soil from former fruit orchards, Pennsylvania, USA: A legacy of anthropogenic activities

    USGS Publications Warehouse

    Ayuso, Robert A.; Foley, Nora K.

    2016-01-01

    Isotopic discrimination can be an effective tool in establishing a direct link between sources of Pb contamination and the presence of anomalously high concentrations of Pb in waters, soils, and organisms. Residential wells supplying water containing up to 1600 ppb Pb to houses built on the former Mohr orchards commercial site, near Allentown, PA, were evaluated to discern anthropogenic from geogenic sources. Pb (n = 144) and Sr (n = 40) isotopic data and REE (n = 29) data were determined for waters from residential wells, test wells (drilled for this study), and surface waters from pond and creeks. Local soils, sediments, bedrock, Zn-Pb mineralization and coal were also analyzed (n = 94), together with locally used Pb-As pesticide (n = 5). Waters from residential and test wells show overlapping values of 206Pb/207Pb, 208Pb/207Pb and 87Sr/86Sr. Larger negative Ce anomalies (Ce/Ce*) distinguish residential wells from test wells. Results show that residential and test well waters, sediments from residential water filters in water tanks, and surface waters display broad linear trends in Pb isotope plots. Pb isotope data for soils, bedrock, and pesticides have contrasting ranges and overlapping trends. Contributions of Pb from soils to residential well waters are limited and implicated primarily in wells having shallow water-bearing zones and carrying high sediment contents. Pb isotope data for residential wells, test wells, and surface waters show substantial overlap with Pb data reflecting anthropogenic actions (e.g., burning fossil fuels, industrial and urban processing activities). Limited contributions of Pb from bedrock, soils, and pesticides are evident. High Pb concentrations in the residential waters are likely related to sediment build up in residential water tanks. Redox reactions, triggered by influx of groundwater via wells into the residential water systems and leading to subtle changes in pH, are implicated in precipitation of Fe oxyhydroxides

  12. Pb, Sr, and Nd isotopic compositions of a suite of Late Archean, igneous rocks, eastern Beartooth Mountains: implications for crust-mantle evolution

    USGS Publications Warehouse

    Wooden, J.L.; Mueller, P.A.

    1988-01-01

    A series of compositionally diverse, Late Archean rocks (2.74-2.79 Ga old) from the eastern Beartooth Mountains, Montana and Wyoming, U.S.A., have the same initial Pb, Sr, and Nd isotopic ratios. Lead and Sr initial ratios are higher and Nd initial ratios lower than would be expected for rocks derived from model mantle sources and strongly indicate the involvement of an older crustal reservoir in the genesis of these rocks. Crustal contamination during emplacement can be ruled out for a variety of reasons. Instead a model involving subduction of continental detritus and contamination of the overlying mantle as is often proposed for modern subduction environments is preferred. This contaminated mantle would have all the isotopic characteristics of mantle enriched by internal mantle metasomatism but would require no long-term growth or changes in parent to daughter element ratios. This contaminated mantle would make a good source for some of the Cenozoic mafic volcanics of the Columbia River, Snake River Plain, and Yellowstone volcanic fields that are proposed to come from ancient, enriched lithospheric mantle. The isotopic characteristics of the 2.70 Ga old Stillwater Complex are a perfect match for the proposed contaminated mantle which provides an alternative to crustal contamination during emplacement. The Pb isotopic characteristics of the Late Archean rocks of the eastern Beartooth Mountains are similar to those of other Late Archean rocks of the Wyoming Province and suggest that Early Archean, upper crustal rocks were common in this terrane. The isotopic signatures of Late Archean rocks in the Wyoming Province are distinctive from those of other Archean cratons in North America which are dominated by a MORB-like, Archean mantle source (Superior Province) and/or a long-term depleted crustal source (Greenland). ?? 1988.

  13. Towards A Modern Calibration Of The 238U/235U Paleoredox Proxy: Apparent Uranium Isotope Fractionation Factor During U(VI)-U(IV) Reduction In The Black Sea

    NASA Astrophysics Data System (ADS)

    Rolison, J. M.; Stirling, C. H.; Middag, R.; Rijkenberg, M. J. A.; De Baar, H. J. W.

    2015-12-01

    The isotopic compositions of redox-sensitive metals, including uranium (U), in marine sediments have recently emerged as powerful diagnostic tracers of the redox state of the ancient ocean-atmosphere system. Interpretation of sedimentary isotopic information requires a thorough understating of the environmental controls on isotopic fractionation in modern anoxic environments before being applied to the paleo-record. In this study, the relationship between ocean anoxia and the isotopic fractionation of U was investigated in the water column and sediments of the Black Sea. The Black Sea is the world's largest anoxic basin and significant removal of U from the water column and high U accumulation rates in modern underlying sediments have been documented. Removal of U from the water column occurs during the redox transition of soluble U(VI) to relatively insoluble U(IV). The primary results of this study are two-fold. First, significant 238U/235U fractionation was observed in the water column of the Black Sea, suggesting the reduction of U induces 238U/235U fractionation with the preferential removal of 238U from the aqueous phase. Second, the 238U/235U of underlying sediments is related to the water column through the isotope fractionation factor of the reduction reaction but is influenced by mass transport processes. These results provide important constraints on the use of 238U/235U as a proxy of the redox state of ancient oceans.

  14. EXAFS Reveals the Mechanism of U Isotope Fractionation During Adsorption to Mn Oxyhydroxide

    NASA Astrophysics Data System (ADS)

    Wasylenki, L. E.; Brennecka, G.; Bargar, J.; Weyer, S.; Anbar, A. D.

    2010-12-01

    Natural variations in the ratio of 238U/235U due to “stable” isotope fractionation have now been reported for a range of geological samples [1-3]. Among the observed variations are a small difference in 238U/235U between seawater and ferromanganese sediments (seawater slightly heavier) and a larger difference, with opposite sense, between seawater and black shales (seawater lighter). These variations suggest that long-term changes in the proportions of oxic and anoxic/sulfidic sinks for U in the ocean over Earth’s history may be recorded as shifts in the isotopic compositions of marine sediments. Thus U isotopes are a potential paleoredox proxy for the oceans, as suggested by [4]. In order to investigate the mechanism behind fractionation of U isotopes in oxidizing marine environments, we previously conducted simple adsorption experiments in which an isotopically known pool of dissolved U partly adsorbed onto synthetic birnessite, a common Mn oxyhydroxide in hydrogenetic ferromanganese crusts. Our experimental result agreed very well with that observed between seawater and natural ferromanganese sediments: δ238U/235U of adsorbed U was 0.2‰ lighter than δ238U/235U of dissolved U [5]. The magnitude of fractionation is constant as a function of experimental duration and fraction of U adsorbed, suggesting an equilibrium isotope effect. Many metal isotope effects are driven by changes in oxidation state for the metal of interest. Because both dissolved and adsorbed U are hexavalent in this system, a redox reaction cannot be causing isotope fractionation. We therefore hypothesized that a difference in uranium’s coordination environment between dissolved and adsorbed U is likely responsible for the isotope effect. We analyzed a sample from our experimental study with extended X-ray absorption fine structure (EXAFS) spectroscopy. Comparison of the EXAFS spectrum of U adsorbed on birnessite with the spectra of aqueous U species (UO22+ and UO2(CO3)34-) reveals

  15. Bioavailability and uptake of smelter emissions in freshwater zooplankton in northeastern Washington, USA lakes using Pb isotope analysis and trace metal concentrations.

    PubMed

    Child, A W; Moore, B C; Vervoort, J D; Beutel, M W

    2018-07-01

    The upper Columbia River and associated valley systems are highly contaminated with metal wastes from nearby smelting operations in Trail, British Columbia, Canada (Teck smelter), and to a lesser extent, Northport, Washington, USA (Le Roi smelter). Previous studies have investigated depositional patterns of airborne emissions from these smelters, and documented the Teck smelter as the primary metal contamination source. However, there is limited research directed at whether these contaminants are bioavailable to aquatic organisms. This study investigates whether smelter derived contaminants are bioavailable to freshwater zooplankton. Trace metal (Zn, Cd, As, Sb, Pb and Hg) concentrations and Pb isotope compositions of zooplankton and sediment were measured in lakes ranging from 17 to 144 km downwind of the Teck smelter. Pb isotopic compositions of historic ores used by both smelters are uniquely less radiogenic than local geologic formations, so when zooplankton assimilate substantial amounts of smelter derived metals their compositions deviate from local baseline compositions toward ore compositions. Sediment metal concentrations and Pb isotope compositions in sediment follow significant (p < 0.001) negative exponential and sigmoidal patterns, respectively, as distance from the Teck smelting operation increases. Zooplankton As, Cd, and Sb contents were related to distance from the Teck smelter (p < 0.05), and zooplankton Pb isotope compositions suggest As, Cd, Sb and Pb from historic and current smelter emissions are biologically available to zooplankton. Zooplankton from lakes within 86 km of the Teck facility display isotopic evidence that legacy ore pollution is biologically available for assimilation. However, without water column data our study is unable to determine if legacy contaminants are remobilized from lake sediments, or erosional pathways from the watershed. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. U-Pb age of the Diana Complex and Adirondack granulite petrogenesis

    USGS Publications Warehouse

    Basu, A.R.; Premo, W.R.

    2001-01-01

    U-Pb isotopic analyses of eight single and multi-grain zircon fractions separated from a syenite of the Diana Complex of the Adirondack Mountains do not define a single linear array, but a scatter along a chord that intersects the Concordia curve at 1145 ?? 29 and 285 ?? 204 Ma. For the most concordant analyses, the 207Pb/206Pb ages range between 1115 and 1150 Ma. Detailed petrographic studies revealed that most grains contained at least two phases of zircon growth, either primary magmatic cores enclosed by variable thickness of metamorphic overgrowths or magmatic portions enclosing presumably older xenocrystic zircon cores. The magmatic portions are characterized by typical dipyramidal prismatic zoning and numerous black inclusions that make them quite distinct from adjacent overgrowths or cores when observed in polarizing light microscopy and in back-scattered electron micrographs. Careful handpicking and analysis of the "best" magmatic grains, devoid of visible overgrowth of core material, produced two nearly concordant points that along with two of the multi-grain analyses yielded an upper-intercept age of 1118 ?? 2.8 Ma and a lower-intercept age of 251 ?? 13 Ma. The older age is interpreted as the crystallization age of the syenite and the younger one is consistent with late stage uplift of the Appalachian region. The 1118 Ma age for the Diana Complex, some 35 Ma younger than previously believed, is now approximately synchronous with the main Adirondack anorthosite intrusion, implying a cogenetic relationship among the various meta-igneous rocks of the Adirondacks. The retention of a high-temperature contact metamorphic aureole around Diana convincingly places the timing of Adirondack regional metamorphism as early as 1118 Ma. This result also implies that the sources of anomalous high-temperature during granulite metamorphism are the syn-metamorphic intrusions, such as the Diana Complex.

  17. Mercury anomalies as a proxy for large igneous province volicanism and effects on the carbon cycle in a U-Pb age-constrained section spanning the end-Triassic mass extinction, Levanto, Peru

    NASA Astrophysics Data System (ADS)

    Yager, J. A.; West, A. J.; Bergquist, B. A.; Thibodeau, A. M.; Corsetti, F. A.; Berelson, W.; Rosas, S.; Bottjer, D. J.

    2017-12-01

    Understanding the causes of the end-Triassic extinction and their potential relationship to Central Atlantic Magmatic Province (CAMP) volcanism necessitates careful correlation of carbon cycle records (largely from marine sections) and volcanism (largely from terrestrial successions) in a robust chronological framework. Here, we report stable carbon isotopes and mercury concentrations and isotopes from the Levanto section in Northern Peru as a putative proxy for CAMP (a large igneous province) in a marine section. Levanto represents deposition well below storm wave base and is lithologically homogenous before, during, and after the end-Triassic extinction interval, making it ideal for detailed chemostratigraphy. Furthermore, abundant intercalated ash beds allow us to correlate mercury concentrations in the marine record directly with CAMP basalt ages, providing a test of the correspondence of mercury anomalies with the eruption of CAMP volcanics. Age dating and C isotope analyses provide an opportunity to explore orbital tuning of the carbon isotope record and ground truth it with existing U-Pb ages from the section, a feature not available in any other marine sections examined to date. The abundance of U-Pb dated ashes in the Levanto section allows us to correlate orbital tuning with other basins, which lack absolute age control, providing a better understanding for the C cycle changes associated with the Triassic-Jurassic boundary.

  18. Reply to Comment on "Zircon U-Th-Pb dating using LA-ICP-MS: Simultaneous U-Pb and U-Th dating on the 0.1 Ma Toya Tephra, Japan"

    NASA Astrophysics Data System (ADS)

    Ito, Hisatoshi

    2015-04-01

    Guillong et al. (2015) mentioned that corrections for abundance sensitivity for 232Th and molecular zirconium sesquioxide ions (Zr2O3+) are critical for reliable determination of 230Th abundances in zircon for LA-ICP-MS analyses. There is no denying that more rigorous treatments are necessary to obtain more reliable ages than those in Ito (2014). However, as shown in Fig. 2 in Guillong et al. (2015), the uncorrected (230Th)/(238U) for reference zircons except for Mud Tank are only 5-20% higher than unity. Since U abundance of Toya Tephra zircons that have U-Pb ages < 1 Ma is in-between that of FCT and Plesovice, the overestimation of 230Th by both abundance sensitivity and molecular interferences is expected to be 5-20% for the Toya Tephra. Moreover Ito (2014) obtained U-Th ages of the Toya Tephra by comparison with Fish Canyon Tuff (FCT) data. Because both the FCT and the Toya Tephra have similar trends of overestimation of 230Th, the effect of overestimation of 230Th to cause overestimation of U-Th age should be cancelled out or negligible. Therefore the pivotal conclusion in Ito (2014) that simultaneous U-Pb and U-Th dating using LA-ICP-MS is possible and useful for Quaternary zircons holds true.

  19. Pb isotopes as an indicator of the Asian contribution to particulate air pollution in urban California.

    PubMed

    Ewing, Stephanie A; Christensen, John N; Brown, Shaun T; Vancuren, Richard A; Cliff, Steven S; Depaolo, Donald J

    2010-12-01

    During the last two decades, expanding industrial activity in east Asia has led to increased production of airborne pollutants that can be transported to North America. Previous efforts to detect this trans-Pacific pollution have relied upon remote sensing and remote sample locations. We tested whether Pb isotope ratios in airborne particles can be used to directly evaluate the Asian contribution to airborne particles of anthropogenic origin in western North America, using a time series of samples from a pair of sites upwind and downwind of the San Francisco Bay Area. Our results for airborne Pb at these sites indicate a median value of 29% Asian origin, based on mixing relations between distinct regional sample groups. This trans-Pacific Pb is present in small quantities but serves as a tracer for airborne particles within the growing Asian industrial plume. We then applied this analysis to archived samples from urban sites in central California. Taken together, our results suggest that the analysis of Pb isotopes can reveal the distribution of airborne particles affected by Asian industrial pollution at urban sites in northern California. Under suitable circumstances, this analysis can improve understanding of the global transport of pollution, independent of transport models.

  20. Pb Isotopes as an Indicator of the Asian Contribution to Particulate Air Pollution in Urban California

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

    Ewing, Stephanie A.; Christensen, John N.; Brown, Shaun T.

    2010-10-25

    During the last two decades, expanding industrial activity in east Asia has led to increased production of airborne pollutants that can be transported to North America. Previous efforts to detect this trans-Pacific pollution have relied upon remote sensing and remote sample locations. We tested whether Pb isotope ratios in airborne particles can be used to directly evaluate the Asian contribution to airborne particles of anthropogenic origin in western North America, using a time series of samples from a pair of sites upwind and downwind of the San Francisco Bay Area. Our results for airborne Pb at these sites indicate amore » median value of 29 Asian origin, based on mixing relations between distinct regional sample groups. This trans-Pacific Pb is present in small quantities but serves as a tracer for airborne particles within the growing Asian industrial plume. We then applied this analysis to archived samples from urban sites in central California. Taken together, our results suggest that the analysis of Pb isotopes can reveal the distribution of airborne particles affected by Asian industrial pollution at urban sites in northern California. Under suitable circumstances, this analysis can improve understanding of the global transport of pollution, independent of transport models.« less

  1. Determination of urea kinetics by isotope dilution with [13C]urea and gas chromatography-isotope ratio mass spectrometry (GC-IRMS) analysis.

    PubMed

    Kloppenburg, W D; Wolthers, B G; Stellaard, F; Elzinga, H; Tepper, T; de Jong, P E; Huisman, R M

    1997-07-01

    1. Stable urea isotopes can be used to study urea kinetics in humans. The use of stable urea isotopes for studying urea kinetic parameters in humans on a large scale is hampered by the high costs of the labelled material. We devised a urea dilution for measurement of the distribution volume, production rate and clearance of urea in healthy subjects and renal failure patients using the inexpensive single labelled [13C]urea isotope with subsequent analysis by headspace chromatography-isotope ratio MS (GC-IRMS) of the [13C]urea enrichment. 2. The method involves measurement of the molar percentage excess of [13C]urea in plasma samples taken over a 4 h period after an intravenous bolus injection of [13C]urea. During the sample processing procedure, the plasma samples together with calibration samples containing a known molar percentage excess of [13C]urea are acidified with phosphoric acid to remove endogenous CO2, and are subsequently incubated with urease to convert the urea present in the plasma samples into CO2. The 13C enrichment of the generated CO2 is analysed by means of GC-IRMS. This method allows measurement of the molar percentage excess of [13C]urea to an accuracy of 0.02%. 3. Reproducibility studies showed that the sample processing procedure [within-run coefficient of variation (CV) < 2.8% and between-run CV < 8.8%] and the GC-IRMS analysis (within-day CV < 1.3% and between-day CV < 1.3%) could be repeated with good reproducibility. 4. In clinical urea kinetic studies in a healthy subject and in a renal failure patient without residual renal function, reproducible values of the distribution volume, production rate and clearance of urea were determined using minimal amounts of [13C]urea (25-50 mg). 5. Because only low [13C]urea enrichments are needed in this urea dilution method using GC-IRMS analysis, the costs of urea kinetic studies are reduced considerably, especially in patients with renal failure.

  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. In-Situ Geochronology: Extending Larims to Pb-Pb Isocrhons

    NASA Astrophysics Data System (ADS)

    Whitaker, Tom; Anderson, Scott; Levine, Jonathan

    2016-04-01

    Introduction: We have previously described development of Laser Ablation Resonance Ionization Mass Spectrometry (LARIMS) for in-situ determination of the radiometric age of rocks using isotope ratios of Rb and Sr [1,2]. LARIMS uses laser resonance excitation of the target elements, which provides elemental selectivity, thus eliminating isobaric interferences with little or no sample preparation and allowing thousands of samples to be measured in significantly shorter periods of time than traditional methods. We have recently begun research that aims to extend the Rb-Sr capability to include Pb-Pb measurements. Preliminary measurements of Standard Reference Material 612 (SRM-612) from the National Institute of Standards and Technology (NIST) demonstrate that resonance ionization of Pb can measure samples with as little as 0.12 ppm total Pb. Background: In-situ LARIMS will enable measurements of 1) isotope geochemistry relevant for chronology and igneous evolution, 2) light isotopes relevant for habitability, life, and climate history, as well as 3) elemental abundances relevant to understanding local and regional geology. In particular, the elemental selectivity of LARIMS makes isotopic geochronology measurements possible that heretofore required extensive sample preparation and were thought to be practically impossible for in-situ measurements. For example, we have used Rb-Sr LARIMS to analyze a piece of the Martian meteorite Zagami and the Duluth Gabbro, a lunar analogue. In these measurements, we obtained isochron ages consistent with the published ages within 200 Ma. Pb-Pb geochronology is well-suited for LARIMS analysis. The use of a single element simplifies the laser system and eliminates inter-element fractionation that can be problematic in Rb-Sr analysis or other multi-element LARIMS measurements. In general, there is less interference at masses corresponding to Pb isotopes than at lighter masses. However, there are potential interferences such as Hg and

  4. New zircon (U-Th)/He and U/Pb eruption age for the Rockland tephra, western USA

    USGS Publications Warehouse

    Coble, Matthew A.; Burgess, Seth; Klemetti, Erik W.

    2017-01-01

    Eruption ages of a number of prominent Quaternary volcanic deposits remain inaccurately and/or imprecisely constrained, despite their importance as regional stratigraphic markers in paleo-environment reconstruction and as evidence of climate-altering eruptions. Accurately dating volcanic deposits presents challenging analytical considerations, including poor radiogenic yield, scarcity of datable minerals, and contamination of crystal populations by magma, eruption, and transport processes. One prominent example is the Rockland tephra, which erupted from the Lassen Volcanic Center in the southern Cascade arc. Despite a range in published eruption ages from 0.40 to 0.63 Ma, the Rockland tephra is extensively used as a marker bed across the western United States. To more accurately and precisely constrain the age of the Rockland tephra-producing eruption, we report U/Pb crystallization dates from the outermost ∼2 μm of zircon crystal faces (surfaces) using secondary ion mass spectrometry (SIMS). Our new weighted mean 238U/206Pb age for Rockland tephra zircon surfaces is 0.598 ± 0.013 Ma (2σ) and MSWD = 1.11 (mean square weighted deviation). As an independent test of the accuracy of this age, we obtained new (U-Th)/He dates from individual zircon grains from the Rockland tephra, which yielded a weighted mean age of 0.599 ± 0.012 Ma (2σ, MSWD = 5.13). We also obtained a (U-Th)/He age of 0.628 ± 0.014 Ma (MSWD = 1.19) for the Lava Creek Tuff member B, which was analyzed as a secondary standard to test the accuracy of the (U-Th)/He technique for Quaternary tephras, and to evaluate assumptions made in the model-age calculation. Concordance of new U/Pb and (U-Th)/He zircon ages reinforces the accuracy of our preferred Rockland tephra eruption age, and confirms that zircon surface dates sample zircon growth up to the time of eruption. We demonstrate the broad applicability of coupled U/Pb zircon-surface and single-grain zircon (U-Th)/He geochronology to

  5. New zircon (U-Th)/He and U/Pb eruption age for the Rockland tephra, western USA

    NASA Astrophysics Data System (ADS)

    Coble, Matthew A.; Burgess, Seth D.; Klemetti, Erik W.

    2017-09-01

    Eruption ages of a number of prominent Quaternary volcanic deposits remain inaccurately and/or imprecisely constrained, despite their importance as regional stratigraphic markers in paleo-environment reconstruction and as evidence of climate-altering eruptions. Accurately dating volcanic deposits presents challenging analytical considerations, including poor radiogenic yield, scarcity of datable minerals, and contamination of crystal populations by magma, eruption, and transport processes. One prominent example is the Rockland tephra, which erupted from the Lassen Volcanic Center in the southern Cascade arc. Despite a range in published eruption ages from 0.40 to 0.63 Ma, the Rockland tephra is extensively used as a marker bed across the western United States. To more accurately and precisely constrain the age of the Rockland tephra-producing eruption, we report U/Pb crystallization dates from the outermost ∼2 μm of zircon crystal faces (surfaces) using secondary ion mass spectrometry (SIMS). Our new weighted mean 238U/206Pb age for Rockland tephra zircon surfaces is 0.598 ± 0.013 Ma (2σ) and MSWD = 1.11 (mean square weighted deviation). As an independent test of the accuracy of this age, we obtained new (U-Th)/He dates from individual zircon grains from the Rockland tephra, which yielded a weighted mean age of 0.599 ± 0.012 Ma (2σ, MSWD = 5.13). We also obtained a (U-Th)/He age of 0.628 ± 0.014 Ma (MSWD = 1.19) for the Lava Creek Tuff member B, which was analyzed as a secondary standard to test the accuracy of the (U-Th)/He technique for Quaternary tephras, and to evaluate assumptions made in the model-age calculation. Concordance of new U/Pb and (U-Th)/He zircon ages reinforces the accuracy of our preferred Rockland tephra eruption age, and confirms that zircon surface dates sample zircon growth up to the time of eruption. We demonstrate the broad applicability of coupled U/Pb zircon-surface and single-grain zircon (U-Th)/He geochronology to accurate

  6. CHRONOLOGICAL CONSTRAINTS ON FLUID CIRCULATION IN MESOZOIC FORMATIONS OF THE EASTERN PART OF THE PARIS BASIN INFERRED FROM U-Pb DATING OF SECONDARY INFILLING CARBONATES

    NASA Astrophysics Data System (ADS)

    Pisapia, C.; Deschamps, P.; Hamelin, B.; Buschaert, S.

    2009-12-01

    equilibrium composition, indicating that the precipitation phase was older than 650 ky. U-Pb measurements were performed on a VG sector Thermal Ionization Mass Spectrometer (TIMS) using a 205Pb-236U-233U-229Th spike. Pb contents are generally very low, between 3 and 20 ppb, while U contents are more variable, leading to μ = 238U/204Pb up to ~600. Sub-samples with high μ show radiogenic 206Pb/204Pb ratio, but at this stage isochrons generally show high scatter. These U-Pb data however are consistent with an Eocene-Oligocene period for the late carbonates precipitation phase. We will discuss the different processes that may be responsible for these errorchrons (i.e. heterogeneities in the initial isotopic composition; multi-stage growth) as well as the chronological constraints that can be drawn from these data.

  7. Siderophile and chalcophile element abundances in oceanic basalts, Pb isotope evolution and growth of the earth's core

    NASA Technical Reports Server (NTRS)

    Newsom, H. E.; White, W. M.; Jochum, K. P.; Hofmann, A. W.

    1986-01-01

    The hypothesis that the mantle Pb isotope ratios reflect continued extraction of Pb into the earth's core over geologic time is evaluated by studying the depeletion of chalcophile and siderophile elements in the mantle. Oceanic basalt samples are analyzed in order to determine the Pb, Sr, and Nd isotropic compositions and the abundances of siderophile and chalcophile elements and incompatible lithophile elements. The data reveal that there is no systematic variation of siderophile or chalcophile element abundances relative to abundances of lithophile elements and the Pb/Ce ratio of the mantle is constant. It is suggested that the crust formation involves nonmagmatic and magmatic processes.

  8. Isotopic studies of the late Archean plutonic rocks of the Wind River Range, Wyoming.

    USGS Publications Warehouse

    Stuckless, J.S.; Hedge, C.E.; Worl, R.G.; Simmons, K.R.; Nkomo, I.T.; Wenner, D.B.

    1985-01-01

    Two late Archaean intrusive events were documented in the Wind River Range by isotopic studies of the Rb-Sr and U-Th-Pb systems in whole-rock samples and the U-Pb systematics for zircon. An age of approx 2630(20) m.y. for the Louis Lake batholith and apparent ages of 2504(40) to 2575(50) m.y. for the Bear Ears pluton were obtained. Post-magmatic hydrothermal events approximately Tertiary in age, lowered delta 18O values and disturbed parent-daughter relationships in most of the isotopic systems investigated. The two intrusive units apparently were derived from different protoliths. Initial isotopic ratios and petrochemistry for the Louis Lake batholith are consistent with an early Archaean trondhjemitic to tonalitic source. The protolith for the Bear Ears pluton must have been subjected to high-grade metamorphism that caused loss of Rb and U prior to magma generation. -L.C.H.

  9. U.S. Department of Energy Isotope Program

    ScienceCinema

    None

    2018-01-16

    The National Isotope Development Center (NIDC) interfaces with the User Community and manages the coordination of isotope production across the facilities and business operations involved in the production, sale, and distribution of isotopes. A virtual center, the NIDC is funded by the Isotope Development and Production for Research and Applications (IDPRA) subprogram of the Office of Nuclear Physics in the U.S. Department of Energy Office of Science. PNNL’s Isotope Program operates in a multi-program category-2 nuclear facility, the Radiochemical Processing Laboratory (RPL), that contains 16 hot cells and 20 gloveboxes. As part of the DOE Isotope Program, the Pacific Northwest National Laboratory dispenses strontium-90, neptunium-237, radium-223, and thorium-227. PNNL’s Isotope Program uses a dedicated hot-cell for strontium-90 dispensing and a dedicated glovebox for radium-223 and thorium-227 dispensing. PNNL’s Isotope Program has access to state of the art analytical equipment in the RPL to support their research and production activities. DOE Isotope Program funded research at PNNL has advanced the application of automated radiochemistry for isotope such as zirconium-89 and astatine-211 in partnership with the University of Washington.

  10. U.S. Department of Energy Isotope Program

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

    None

    The National Isotope Development Center (NIDC) interfaces with the User Community and manages the coordination of isotope production across the facilities and business operations involved in the production, sale, and distribution of isotopes. A virtual center, the NIDC is funded by the Isotope Development and Production for Research and Applications (IDPRA) subprogram of the Office of Nuclear Physics in the U.S. Department of Energy Office of Science. PNNL’s Isotope Program operates in a multi-program category-2 nuclear facility, the Radiochemical Processing Laboratory (RPL), that contains 16 hot cells and 20 gloveboxes. As part of the DOE Isotope Program, the Pacific Northwestmore » National Laboratory dispenses strontium-90, neptunium-237, radium-223, and thorium-227. PNNL’s Isotope Program uses a dedicated hot-cell for strontium-90 dispensing and a dedicated glovebox for radium-223 and thorium-227 dispensing. PNNL’s Isotope Program has access to state of the art analytical equipment in the RPL to support their research and production activities. DOE Isotope Program funded research at PNNL has advanced the application of automated radiochemistry for isotope such as zirconium-89 and astatine-211 in partnership with the University of Washington.« less

  11. Western US Seismic Observations Viewed Through Lead Isotope Maps

    NASA Astrophysics Data System (ADS)

    Bouchet, R. A.; Blichert-Toft, J.; Levander, A.; Reid, M. R.; Albarede, F.

    2013-12-01

    To shed light on the nature and history of the different geological units identified by the seismic models that have come from USArray in the western US, we compiled literature Pb isotope compositions of ores (n=1200), K-feldspars from granites (n=400), and felsic plutonic rocks (n=1300), data that for most part were not in the NAVDAT database. We complemented this compilation by analyzing the Pb isotope compositions of K-feldspars (76) and whole-rocks (6) of felsic xenoliths and felsic plutonic rocks from the Colorado Plateau (CP). The raw Pb isotope abundances for the complete data set were converted into three independent, geologically informative parameters in the form of the model age T (time of last U/Pb fractionation) and the two chemical ratios 238U/204Pb (μ) and 232Th/238U (κ). These parameters were then imaged on isotopic maps of the western US using 0.5°×0.5° grid-cell averaging for μ and κ and a 0.5°×0.5° grid-cell maximum after removing the 2.5% highest values (outliers) for T. Comparing these chemical maps to seismic maps of tomographic anomalies [1] and Moho and LAB depths determined from receiver functions [2] leads to the following observations: (i) Pb model ages: they match geological ages mostly where the continental mantle is cold and the Moho is deep. Elsewhere, Pb model ages are younger than geological ages. We interpret this feature as the chronological expression of a delayed cooling of deep crustal layers below the closure temperature (˜550-700°C) of Pb in K-feldspar, the major host of this element in the crust [3] or of age resetting by orogenic activity. (ii) While U/Pb (μ) does not vary systematically with other geochemical or seismic data, high Th/U (κ) values are usually observed where Vp/Vs is also high, as in the Snake River basin and central Colorado. High kappa values also form a 'ridge' trending south from northwestern Utah through the Basin and Range into the Mojave-Yavapai block. High-κ areas may reflect the

  12. Ore genesis of the Wusihe carbonate-hosted Zn-Pb deposit in the Dadu River Valley district, Yangtze Block, SW China: evidence from ore geology, S-Pb isotopes, and sphalerite Rb-Sr dating

    NASA Astrophysics Data System (ADS)

    Xiong, Suo-Fei; Gong, Yong-Jun; Jiang, Shao-Yong; Zhang, Xiao-Jing; Li, Qian; Zeng, Guo-Ping

    2018-01-01

    The Wusihe carbonate-hosted Zn-Pb deposit (3.7 Mt. Zn + Pb at a grade of 8.6% Zn and 2.0% Pb) is the largest deposit in the Dadu River Valley district of the Sichuan-Yunnan-Guizhou metallogenic province of southwest China. Three types of orebodies occur: (1) stratiform, banded and lamellar, within dolomite of the Neoproterozoic Dengying Formation; (2) vein type; and (3) breccia type. Four stages of mineralization are distinguished: (i) pyrite stage, (ii) pyrite-pyrrhotite-galena-sphalerite-bitumen stage, (iii) sphalerite-galena stage, and (iv) bitumen-calcite stage. Sphalerite and galena from stages II and III show δ34S ranges from +7.1 to +9.7‰ and +9.1 to +13.1‰, respectively. High-precision in situ lead isotope analyses of sulfides show 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios of 37.938 to 38.336, 15.579 to 15.682, and 17.951 to 18.195, respectively, which suggest a mixing of lead from the basement and the host rocks. Rb-Sr isotope analyses for six sphalerite samples of stage II yielded an isochron age of 411 ± 10 Ma (MSWD = 1.4). Combining all available ore geology and geochemical data, together with fluid inclusion data reported previously, we suggest that the Wusihe deposit is a Mississippi Valley-type (MVT) deposit.

  13. High-precision Pb isotopes reveal two small magma bodies beneath the summit of Kilauea Volcano

    NASA Astrophysics Data System (ADS)

    Pietruszka, A. J.; Heaton, D. E.; Marske, J. P.; Garcia, M. O.

    2011-12-01

    The summit magma storage reservoir of Kilauea Volcano is one of the most important components of the volcano's magmatic pluming system, but the geometry (size and shape) of this reservoir is poorly known. Here we use high-precision Pb isotopic analyses of historical Kilauea summit lavas (1823-2010) to define the minimum number of magma bodies within the summit reservoir and their volumes. The 206Pb/204Pb ratios of these lavas display a systematic temporal fluctuation characterized by low values in 1823, a gradual increase to a maximum in 1921, an abrupt drop to relatively constant intermediate values from 1929 to 1959, and a rapid decrease to 2010. These variations indicate that Kilauea's summit reservoir is being supplied by rapidly changing parental magma compositions derived from a mantle source that is heterogeneous on a small scale. Analyses of multiple lavas from several individual eruptions reveal small but significant differences in 206Pb/204Pb ratios (~0.01-0.03). For example, the extra-caldera lavas from Aug. 1971 and Jul. 1974 display significantly lower Pb isotope ratios and higher MgO contents (10 wt. %) than the intra-caldera lavas (MgO ~7-8 wt. %) from each eruption. From 1971 to 1982, the 206Pb/204Pb ratios of the lavas define two separate decreasing temporal trends. The intra-caldera lavas from 1971, 1974, 1975, Apr. 1982 and the lower MgO lavas from Sep. 1982 have consistently higher 206Pb/204Pb ratios at a given time (compared to the extra-caldera lavas and the higher MgO lavas from Sep. 1982). These trends require that the intra- and extra-caldera lavas (and the Sep. 1982 lavas) were supplied from two separate magma bodies. Numerous studies by HVO scientists (e.g., Fiske and Kinoshita, 1969; Klein et al., 1987) have long identified the main locus of Kilauea's summit reservoir ~2 km southeast of Halemaumau (near the caldera rim) at a depth of ~2-7 km, but more recent investigations have discovered a secondary magma body located <1 km below the

  14. Monazite paragenesis and U-Pb systematics in rocks of the eastern Mojave Desert, California, U.S.A.: implications for thermochronometry

    USGS Publications Warehouse

    Kingsbury, J.A.; Miller, C.F.; Wooden, J.L.; Harrison, T.M.

    1993-01-01

    Studies of the paragenesis and U-Pb systematics of monazite in rocks from the eastern Mojave Desert, California, corroborate its potential usefulness as a prograde thermochronometer and in dating granite inheritance. Unmetamorphosed Latham Shale and its equivalents at grades ranging from greenschist to upper amphibolite facies are virtually identical in composition. Monazite is absent in the shale and low-grade schists, but it is abundant in schists at staurolite and higher grades. Lower-grade schists instead include minute Th- and Ce-oxides and unidentified Ce-poor LREE-phosphates that apparently are lower-temperature precursors to monazite. Thus monazite originates when the pelite passes through lower-amphibolite-facies conditions. Monazites from three Upper Cretaceous granites yield ages that are strongly discordant. Upper intercepts of 1.6-1.7 Ga are similar to those defined by U-Pb data for coexisting zircons and coincide with a period of copious magmatism in the Mojave crust. As the host Upper Cretaceous granitic magmas were all above 700??C, effective closure of the restitic monazites to Pb loss must be well in excess of this temperature. U-Pb compositions of monazite from Proterozoic granitoids and schist also indicate high Pb retentivity. Taken together, these studies support the suggestion that monazite can be an effective prograde thermochronometer. At least in pelites, it is not usually retained as a detrital mineral, but rather forms during moderate-temperature metamorphism. Its U-Pb system should not be reset by subsequent higher-grade metamorphism. ?? 1993.

  15. Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

    NASA Technical Reports Server (NTRS)

    Moriwaki, R.; Usui, T.; Simon, J. I.; Jones, J. H.; Yokoyama, T.

    2015-01-01

    Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial µ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial µ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

  16. Uranium Isotope Fractionation during Oxidation of Dissolved U(iv) and Synthetic Solid UO2

    NASA Astrophysics Data System (ADS)

    Wang, X.; Johnson, T. M.; Lundstrom, C. C.

    2013-12-01

    U isotopes (238U/235U) show promise as a tool for environmental monitoring of U contamination as well as a proxy for paleo-redox conditions. However, the isotopic fractionation mechanisms of U are still poorly understood. In groundwater systems, U(VI), a mobile contaminant, can be reduced to immobile U(IV) and thus remediated. Previous work shows that 238U/235U of the remaining U(VI) changes with the extent of reduction. Therefore, U(VI) isotope composition in groundwater can potentially be used to detect and perhaps quantify the extent of reduction. However, knowing if isotopic fractionation occurs during U(IV) oxidation is equally important. First, the reduced U(IV) (either solid or as dissolved organic complexes) potentially can be reoxidized to U(VI). If isotope fractionation occurs during oxidation, it would complicate the use of U isotope composition as a monitoring technique. Further, in natural weathering processes, U(IV) minerals are oxidized to form dissolved U(VI), which is carried to rivers and eventually to the ocean and deposited in marine sediments. The weathering cycle is thus sensitive to redox conditions, meaning the sedimentary U isotope record may serve as a paleoredox indicator, provided U isotope fractionation during oxidation and reduction are well known. We conducted experiments oxidizing 2 different U(IV) species by O2 and measuring isotopic fractionation factors. In one experiment, dissolved U(IV) in 0.1 N HCl (pH 1) was oxidized by entrained air. As oxidation proceeds at pH 1, the remaining dissolved U(IV) becomes progressively enriched in 238U in a linear trend, while the product U(VI) paralleled, but was offset to 1.0‰ lighter in 238U/235U. This linear progression of both remaining reactant and product suggests equilibrium fractionation during oxidation of dissolved U(IV) by O2. A second experiment oxidized synthetic, solid UO2 (in 20 mM NaHCO3, pH 7) with entrained air. The oxidative fractionation is very weak in this case with

  17. Reconstructing the evolution of the submarine Monterey Canyon System from Os, Nd, and Pb isotopes in hydrogenetic Fe-Mn crusts

    USGS Publications Warehouse

    Conrad, T.A.; Nielsen, S.G.; Peucker-Ehrenbrink, Bernhard; Blusztajn, J.; Winslow, D.; Hein, James; Paytan, A.

    2017-01-01

    The sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187Os/188Os, Nd, and Pb isotopes in hydrogenetic ferromanganese crusts from three seamounts along the central and southern California margin. From 6.8 to 4.5 (± 0.5) Ma, all three isotope systems show more radiogenic values at Davidson Seamount, located near the base of the Monterey Canyon System, than in Fe-Mn crusts from the more remote Taney and Hoss seamounts. At the Taney seamounts, approximately 225 km farther offshore from Davidson Seamount, 187Os/188Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve towards more radiogenic values from 6.8 to 4.5 (± 0.5) Ma. However, none of the isotope systems in Fe-Mn crusts deviate from seawater at Hoss Seamount located approximately 450 km to the south. The regional gradients in isotope ratios indicate that substantial input of dissolved and particulate terrestrial material into the Monterey Canyon System is responsible for the local deviations in the seawater Nd, Pb, and Os isotope compositions from 6.8 to 4.5 (± 0.5) Ma. The isotope ratios recorded in Fe-Mn crusts are consistent with a southern Sierra Nevada or western Basin and Range provenance of the terrestrial material which was delivered by rivers to the canyon. The exhumation of the modern Monterey Canyon must have begun between 10 and 6.8 ± 0.5 Ma, as indicated by our data, the age of incised strata, and paleo-location of the Monterey Canyon relative to the paleo-coastline.

  18. Reconstructing the Evolution of the Submarine Monterey Canyon System From Os, Nd, and Pb Isotopes in Hydrogenetic Fe-Mn Crusts

    NASA Astrophysics Data System (ADS)

    Conrad, T. A.; Nielsen, S. G.; Peucker-Ehrenbrink, B.; Blusztajn, J.; Winslow, D.; Hein, J. R.; Paytan, A.

    2017-11-01

    The sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187Os/188Os, Nd, and Pb isotopes in hydrogenetic ferromanganese crusts from three seamounts along the central and southern California margin. From 6.8 to 4.5 (±0.5) Ma, all three isotope systems show more radiogenic values at Davidson Seamount, located near the base of the Monterey Canyon System, than in Fe-Mn crusts from the more remote Taney and Hoss Seamounts. At the Taney Seamounts, approximately 225 km farther offshore from Davidson Seamount, 187Os/188Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve toward more radiogenic values from 6.8 to 4.5 (±0.5) Ma. However, none of the isotope systems in Fe-Mn crusts deviate from seawater at Hoss Seamount located approximately 450 km to the south. The regional gradients in isotope ratios indicate that substantial input of dissolved and particulate terrestrial material into the Monterey Canyon System is responsible for the local deviations in the seawater Nd, Pb, and Os isotope compositions from 6.8 to 4.5 (±0.5) Ma. The isotope ratios recorded in Fe-Mn crusts are consistent with a southern Sierra Nevada or western Basin and Range provenance of the terrestrial material which was delivered by rivers to the canyon. The exhumation of the modern Monterey Canyon must have begun between 10 and 6.8 ± 0.5 Ma, as indicated by our data, the age of incised strata, and paleo-location of the Monterey Canyon relative to the paleo-coastline.

  19. DUPAL anomaly in the Sea of Japan: Pb, Nd, and Sr isotopic variations at the eastern Eurasian continental margin

    USGS Publications Warehouse

    Tatsumoto, M.; Nakamura, Y.

    1991-01-01

    Volcanic rocks from the eastern Eurasian plate margin (southwestern Japan, the Sea of Japan, and northeastern China) show enriched (EMI) component signatures. Volcanic rocks from the Ulreung and Dog Islands in the Sea of Japan show typical DUPAL anomaly characteristics with extremely high ??208/204 Pb (up to 143) and enriched Nd and Sr isotopic compositions (??{lunate}Nd = -3 to -5, 87Sr 86Sr = ~0.705). The ??208/204 Pb values are similar to those associated with the DUPAL anomaly (up to 140) in the southern hemisphere. Because the EMI characteristics of basalts from the Sea of Japan are more extreme than those of southwestern Japan and inland China basalts, we propose that old mantle lithosphere was metasomatized early (prior to the Proterozoic) with subduction-related fluids (not present subduction system) so that it has been slightly enriched in incompatible elements and has had a high Th/U for a long time. The results of this study support the idea that the old subcontinental mantle lithosphere is the source for EMI of oceanic basalts, and that EMI does not need to be stored at the core/ mantle boundary layer for a long time. Dredged samples from seamounts and knolls from the Yamato Basin Ridge in the Sea of Japan show similar isotopic characteristics to basalts from the Mariana arc, supporting the idea that the Yamato Basin Ridge is a spreading center causing separation of the northeast Japan Arc from Eurasia. ?? 1991.

  20. Mid-Neoproterozoic intraplate magmatism in the northern margin of the Southern Granulite Terrane, India: Constraints from geochemistry, zircon U-Pb geochronology and Lu-Hf isotopes

    NASA Astrophysics Data System (ADS)

    Deeju, T. R.; Santosh, M.; Yang, Qiong-Yan; Pradeepkumar, A. P.; Shaji, E.

    2016-11-01

    The northern margin of the Southern Granulite Terrane in India hosts a number of mafic, felsic and alkaline magmatic suites proximal to major shear/paleo-suture zones and mostly represents magmatism in rift-settings. Here we investigate a suite of gabbros and granite together with intermediate (dioritic) units generated through mixing and mingling of a bimodal magmatic suite. The massive gabbro exposures represent the cumulate fraction of a basic magma whereas the granitoids represent the product of crystallization in felsic magma chambers generated through crustal melting. Diorites and dioritic gabbros mostly occur as enclaves and lenses within host granitoids resembling mafic magmatic enclaves. Geochemistry of the felsic units shows volcanic arc granite and syn-collisional granite affinity. The gabbro samples show mixed E-MORB signature and the magma might have been generated in a rift setting. The trace and REE features of the rocks show variable features of subduction zone enrichment, crustal contamination and within plate enrichment, typical of intraplate magmatism involving the melting of source components derived from both depleted mantle sources and crustal components derived from older subduction events. The zircons in all the rock types show magmatic crystallization features and high Th/U values. Their U-Pb data are concordant with no major Pb loss. The gabbroic suite yields 206Pb/238U weighted mean ages in the range of 715 ± 4-832.5 ± 5 Ma marking a major phase of mid Neoproterozoic magmatism. The diorites crystallized during 206Pb/238U weighted mean age of 724 ± 6-830 ± 2 Ma. Zircons in the granite yield 206Pb/238U weighted mean age of 823 ± 4 Ma. The age data show broadly similar age ranges for the mafic, intermediate and felsic rocks and indicate a major phase of bi-modal magmatism during mid Neoproterozoic. The zircons studied show both positive and negative εHf(t) values for the gabbros (-6.4 to 12.4), and negative values for the diorites (-7

  1. Congener-specific determination of ultratrace levels of chlorinated and brominated polycyclic aromatic hydrocarbons in atmosphere and industrial stack gas by isotopic dilution gas chromatography/high resolution mass spectrometry method.

    PubMed

    Jin, Rong; Liu, Guorui; Zheng, Minghui; Fiedler, Heidelore; Jiang, Xiaoxu; Yang, Lili; Wu, Xiaolin; Xu, Yang

    2017-08-04

    Isotopic dilution gas chromatography combined with high resolution mass spectrometry (GC/HRMS) has overwhelming advantages with respect to the accuracy of congener-specific ultratrace analysis of complex persistent organic pollutants (POPs) in environmental matrices. However, an isotopic dilution GC/HRMS method for analysis of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) using 13 C-labelled congeners as internal standards has not been established. In this study, a method for identification and quantification of 38 congeners of Cl-PAHs and Br-PAHs in atmosphere and stack gas samples from waste incinerators was developed using the isotopic dilution GC/HRMS technique. The instrumental detection limits of the GC/HRMS method ranged from 0.2pg to 1.8pg for Cl-PAH congeners, and 0.7pg to 2.7pg for Br-PAH congeners, which were about three orders of magnitude lower than those of the GC/quadrupole MS method. This new method developed was also the first to enable determination of Cl-PAH and Br-PAH homologs comprising congeners with the same molecular skeleton and chlorine or bromine substitution numbers. Among the detected congeners, seven Cl-PAH congeners and thirteen Br-PAH congeners that were abundant in the atmosphere and stack gases released from waste incinerators were firstly detected in real samples and reported using the established isotopic dilution GC/HRMS method. The developed isotopic dilution GC/HRMS is significant and needed for better studying the environmental behavior and health risk of Cl-PAHs and Br-PAHs. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Determining provenance of marine metal pollution in French bivalves using Cd, Zn and Pb isotopes

    NASA Astrophysics Data System (ADS)

    Shiel, Alyssa E.; Weis, Dominique; Cossa, Daniel; Orians, Kristin J.

    2013-11-01

    Cadmium, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) have been used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from the coastlines of France (English Channel, Atlantic and Mediterranean coasts). The Cd isotopic signatures (δ114Cd = -1.08‰ to -0.52‰) exhibited by bivalves from the coastlines of France, excluding those from NE France, are within the range of those exhibited by bivalves from the USA East coast (δ114Cd = -1.20‰ to -0.54‰). This indicates the high prevalence of industry, as well as the low natural contributions of Cd from North Atlantic waters in both regions. Thus, the significance of anthropogenic Cd sources is similar. These significant anthropogenic contributions are identified for bivalves with a large range in tissue Cd concentrations. Importantly, French bivalves from the Gironde estuary and Marennes-Oléron basin (regions of historic and modern importance for oyster farming, respectively) exhibited the highest Cd levels of the study. Their Cd isotopic signatures indicate historical smelting emissions remain the primary Cd source despite the cessation of local smelting activities in 1986 and subsequent remedial efforts. No significant variability is observed in the δ66Zn values of the French bivalves (∼0.53‰), with the exception of the much heavier compositions exhibited by oysters from the polluted Gironde estuary (1.19-1.27‰). Lead isotopes do not fractionate during processing like Cd and Zn. They can, therefore, be used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as metal sources to French bivalves. Cadmium and Zn isotopes are successfully used here as tracers of anthropogenic processing emissions and are combined with Pb isotope "fingerprinting" techniques to identify metal sources.

  3. Integrated Laser Ablation U/Pb and (U-Th)/He Dating of Detrital Accessory Minerals from the Naryani River, Central Nepal

    NASA Astrophysics Data System (ADS)

    Horne, A.; Hodges, K. V.; Van Soest, M. C.

    2015-12-01

    The newly developed 'laser ablation double dating' (LADD) technique, an integrated laser microprobe U/Pb and (U-Th)/He dating method, could be an exceptionally valuable tool in detrital thermochronology for identifying sedimentary provenance and evaluating the exhumation history of a source region. A recent proof-of-concept study has used LADD to successfully date both zircon and titanite crystals from the well-characterized Fish Canyon tuff, but we also believe that another accessory mineral, rutile, could be amenable to dating via the LADD technique. To continue the development of the method, we present an application of LADD to detrital zircon, titanite, and rutile from a sample collected on the lower Naryani River of central Nepal. Preliminary analyses of the sample have yielded zircon U/Pb dates ranging from 31.4 to 2405 Ma; zircon (U-Th)/He from 1.8 to 15.4 Ma; titanite U/Pb between 18 and 110 Ma; titanite (U-Th)/He between 1 and 16 Ma; rutile U/Pb from 6 to 45 Ma; and rutile (U-Th)/He from 2 to 25 Ma. In addition to the initial data, we can use Ti-in-zircon, Zr-in-titanite, and Zr-in-rutile thermometers to determine the range of possible long-term cooling rates from grains with U/Pb ages younger than collision. Thus far our results from zircon analyses imply a cooling rate of approximately 15°C/Myr; titanite analyses imply between 10 and 67°C/Myr; and rutile between 9 and 267°C/Myr. This spread in potential cooling rates, especially in the order of magnitude differences of cooling rates calculated from the rutile grains, suggests that the hinterland source regions of the Naryani river experienced dramatically different exhumation histories during Himalayan orogenisis. Ongoing analyses will expand the dataset such that we can more adequately characterize the range of possibilities represented in the sample.

  4. 236U measurement with accelerator mass spectrometry at CIAE

    NASA Astrophysics Data System (ADS)

    Wang, Xianggao; Jiang, Shan; He, Ming; Dong, Kejun; Wang, Wei; Li, Chaoli; He, Guozhu; Li, Shizhuo; Gong, Jie; Lu, Liyuan; Wu, Shaoyong

    2010-07-01

    236U is a long-lived radioactive isotope which is produced principally by thermal neutron capture on 235U. 236U may be potentially applied in geological research and nuclear safeguards. Accelerator mass spectrometry is presently the most sensitive technique for the measurement of 236U and a measurement method for long-lived heavy ion 236U has been developed. The set-up uses a dedicated injector and the newly proposed 208Pb 16O2- molecular ions for the simulation of 236U ion transport. A sensitivity of lower than 10 -10 has been achieved for the isotopic ratio 236U/ 238U in present work.

  5. The Eocene Thermal Maximum 2 (ETM-2) in a terrestrial section of the High Arctic: identification by U-Pb zircon ages of volcanic ashes and carbon isotope records of coal and amber (Stenkul Fiord, Ellesmere Island, Canada)

    NASA Astrophysics Data System (ADS)

    Reinhardt, Lutz; von Gosen, Werner; Piepjohn, Karsten; Lückge, Andreas; Schmitz, Mark

    2017-04-01

    The Stenkul Fiord section on southern Ellesmere Island reveals largely fluvial clastic sediments with intercalated coal seams of the Margaret Formation of Late Paleocene/Early Eocene age according to palynology and vertebrate remains. Field studies in recent years and interpretative mapping of a high-resolution satellite image of the area southeast of Stenkul Fiord revealed that the clastic deposits consist of at least four sedimentary units (Units 1 to 4) separated by unconformities. Several centimeter-thin volcanic ash layers, recognized within coal layers and preserved as crandallite group minerals (Ca-bearing goyazite), suggest an intense volcanic ash fall activity. Based on new U-Pb zircon ages (ID-TIMS) of three ash layers, the volcanic ash fall took place at 53.7 Ma in the Early Eocene, i.e. within the Eocene Thermal Maximum 2 (ETM-2) hyperthermal. The ETM-2 is bracketed further by discrete negative excursions of carbon isotope records of both bulk coal and amber droplets collected from individual coal layers of the section. The identification of the ETM-2 hyperthermal provides a stratigraphic tie-point in the terrestrial Margaret Formation sediments enabling assignment of the lowermost sedimentary Unit 1 to the Late Paleocene-earliest Eocene, Unit 2 to the Early Eocene, whereas Unit 3 and 4 might be Early to Middle Eocene in age. Thus the timing of syn-sedimentary movements of the Eurekan deformation causal for the observed unconformities in the section can be studied and the positions of further hyperthermals like the PETM or the ETM-3 in the section can be identified in the future. The integration of structural studies, new U-Pb zircon ages, and different carbon isotope records provides a new stratigraphic framework for further examination of the unique Early Eocene flora and fauna preserved in this high-latitude outcrop.

  6. 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

  7. The composition and distribution of the rejuvenated component across the Hawaiian plume: Hf-Nd-Sr-Pb isotope systematics of Kaula lavas and pyroxenite xenoliths

    NASA Astrophysics Data System (ADS)

    Bizimis, Michael; Salters, Vincent J. M.; Garcia, Michael O.; Norman, Marc D.

    2013-10-01

    Rejuvenated volcanism refers to the reemergence of volcanism after a hiatus of 0.5-2 Ma following the voluminous shield building stage of Hawaiian volcanoes. The composition of the rejuvenated source and its distribution relative to the center of the plume provide important constraints on the origin of rejuvenated volcanism. Near-contemporaneous lavas from the Kaula-Niihau-Kauai ridge and the North Arch volcanic field that are aligned approximately orthogonally to the plume track can constrain the lateral geochemical heterogeneity and distribution of the rejuvenated source across the volcanic chain. Nephelinites, phonolites and pyroxenite xenoliths from Kaula Island have radiogenic Hf, Nd and unradiogenic Sr isotope compositions consistent with a time-integrated depleted mantle source. The pyroxenites and nephelinites extend to the lowest 208Pb/204Pb reported in Hawaiian rocks. These data, along with new Pb isotope data from pyroxenites from the Salt Lake Crater (Oahu) redefine the composition of the depleted end-member of the Hawaiian rejuvenated source at 208Pb/204Pb=37.35±0.05, 206Pb/204Pb = 17.75±0.03, ɛNd = 9-10, ɛHf ˜16-17 and 87Sr/88Sr <0.70305. The revised isotope composition also suggests that this depleted component may contribute to LOA and KEA trend shield stage Hawaiian lavas, consistent with the rejuvenated source being part of the Hawaiian plume and not entrained upper mantle. The isotope systematics of rejuvenated magmas along the Kaula-Niihau-Kauai-North Arch transect are consistent with a larger proportion of the rejuvenated depleted component in the periphery of the plume track rather than along its axis.

  8. 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

  9. Pb-Pb geochronologic study on the carbonaceous rocks in the Krai area, Altai, Russia: V-C boundary or Snowball Earth event?

    NASA Astrophysics Data System (ADS)

    Nohda, S.; Uchio, Y.; Kani, T.; Isozaki, Y.; Maruyama, S.

    2003-12-01

    We have analyzed the limestones occurred in the Kurai area, Altai district, Russia to define Pb-Pb isochron age and examine their variation of Sr isotopic compositions through time. The limestones are inferred to have deposited at the boundary of the Vendian-Cambrian from stratigraphic analyses. In this study, We have newly collected samples for the purpose of the present Pb isotopic study on the basis of the reinvestigated stratigraphic map. Samples are also available from various horizons to examine isotopic variation of Sr through time. We made a minor modification on the method of Pb extraction process from the samples to maintain a stable and higher yield, which made it possible to obtain reliable Pb isotopic data. At present, we have obtained an isochron age of 598 + - 25 Ma (MSWD=1.06) for 9 samples. The present age is evidently older than the boundary of the Vendian-Cambrian, and seems to be correlated with the snowball Earth event. Sr isotopes show substantial variation from 0.7059 to 0.7077 which is interpreted in terms of environmental change during the snowball Earth event. Besides the Pb isotopic age, homogenous 208Pb/204Pb ratios of the samples are suggestive that Th/Pb ratio had been uniform within the seawater or through the formation process of the limestone.

  10. Target analyte quantification by isotope dilution LC-MS/MS directly referring to internal standard concentrations--validation for serum cortisol measurement.

    PubMed

    Maier, Barbara; Vogeser, Michael

    2013-04-01

    Isotope dilution LC-MS/MS methods used in the clinical laboratory typically involve multi-point external calibration in each analytical series. Our aim was to test the hypothesis that determination of target analyte concentrations directly derived from the relation of the target analyte peak area to the peak area of a corresponding stable isotope labelled internal standard compound [direct isotope dilution analysis (DIDA)] may be not inferior to conventional external calibration with respect to accuracy and reproducibility. Quality control samples and human serum pools were analysed in a comparative validation protocol for cortisol as an exemplary analyte by LC-MS/MS. Accuracy and reproducibility were compared between quantification either involving a six-point external calibration function, or a result calculation merely based on peak area ratios of unlabelled and labelled analyte. Both quantification approaches resulted in similar accuracy and reproducibility. For specified analytes, reliable analyte quantification directly derived from the ratio of peak areas of labelled and unlabelled analyte without the need for a time consuming multi-point calibration series is possible. This DIDA approach is of considerable practical importance for the application of LC-MS/MS in the clinical laboratory where short turnaround times often have high priority.

  11. High Pb/Ce reservoir in depleted, altered mantle peridotites

    NASA Astrophysics Data System (ADS)

    Godard, M.; Kelemen, P.; Hart, S.; Jackson, M.; Hanghoj, K.

    2005-12-01

    We find consistent, high Pb/Ce in ICP-MS data for residual peridotites from the Mid-Atlantic Ridge (MAR, from ODP Leg 209), mid-ocean ridges (MOR) worldwide [1], Oman, Josephine and Trinity ophiolites, and the Jurassic Talkeetna arc. (MAR and Oman data from Montpellier; Josephine, Trinity and Talkeetna from WSU; some Pb concentrations checked by ID at WHOI). These samples have average Pb/Ce 10x primitive mantle (PM), with only 3 of 180 samples < PM. REE patterns and Ce concentration < PM in 165 of 180 samples are consistent with depletion via melt extraction, plus some magmatic refertilization. High Pb (average 3x PM, median 0.5x PM), could be due to (a) retention of Pb in residual sulfide, (b) addition of Pb in sulfide and plagioclase during `impregnation' by crystallizing melt, and/or (c) addition of Pb in sulfide and carbonate during alteration. Pb/Ce is correlated negatively with Ce concentration, suggesting a role for (a). Pb concentration is strongly correlated with Th and Nb. These elements are considered immobile during hydrothermal alteration, their correlations with Pb are positive, and Pb is > PM in many samples, all suggesting a complementary role for (b) and a limited role for (c). All samples except Talkeetna have Th/Pb < PM. All samples except some MOR peridotites also have U/Pb < PM. DRILLED MAR peridotites show U/Pb > PM in shallow, oxidized samples and < PM in downhole, reduced samples. Thus, high U/Pb in DREDGED MOR peridotites [1] is attributed to seafloor weathering. Given that oxidized weathering only extends tens of meters below the seafloor, we infer that most MOR peridotites have Th/Pb and U/Pb < PM. If they form with Pb isotope ratios similar to MORB, these rocks will evolve to values less radiogenic than the geochron. The effect of subduction modification on Th/Pb and U/Pb is unclear. For example, if elevated Pb is common in unaltered residual peridotites, subduction modification is likely to be minor. The size of the high Pb/Ce, low Th/Pb

  12. Late Quaternary loess in northeastern Colorado: Part II - Pb isotopic evidence for the variability of loess sources

    USGS Publications Warehouse

    Aleinikoff, J.N.; Muhs, D.R.; Sauer, R.R.; Fanning, C.M.

    1999-01-01

    A new application of the Pb isotopic tracer technique has been used to determine the relative importance of different silt sources for late Wisconsin loess in the central Great Plains of eastern Colorado. Samples of the Peoria Loess collected throughout the study area contain K-feldspar derived from two isotopically and genetically distinct sources: (1) glaciogenic material from Early and Middle Proterozoic crystalline rocks of the Colorado province, and (2) volcaniclastic material from the Tertiary White River Group exposed on the northern Great Plains. Pb isotopic compositions of K-feldspar in loess from two dated vertical sections (at Beecher Island and Last Chance, Colorado) vary systematically, implying climatic control of source availability. We propose a model whereby relatively cold conditions promoted the advance of Front Range valley glaciers discharging relatively little glaciogenic silt, but strong winds caused eolian erosion of White River Group silt due to a decrease in vegetation cover. During warmer periods, valley glaciers receded and discharged abundant glaciogenic silt, while surfaces underlain by the White River Group were stabilized by vegetation. Isotopic data from eastern Colorado loess sections record two warm-cold-warm cycles during late Wisconsin time between about 21 000 and 11 000 radiocarbon yr B.P., similar to results from other studies in the United States and Greenland.

  13. Lead Isotope Characteristics of the Mindyak Gold Deposit, Southern Urals: Evidence for the Source of Metals

    NASA Astrophysics Data System (ADS)

    Chugaev, A. V.; Znamensky, S. E.

    2018-01-01

    The isotopic composition of Pb in pyrite of the Mindyak orogenic gold deposit located in the Main Ural Fault Zone, the Southern Urals, has been studied by the high-precision MC-ICP-MS method. Orebodies at the deposit are composed of early pyrite and late polysulfide-carbonate-quartz mineral assemblages. The orebodies are localized in olistostrome with carbonaceous clayey-cherty cement. Pyrites from early and late mineral assemblages are close in Pb isotope ratios. For early pyrite 206Pb/204Pb = 18.250-18.336, 207Pb/204Pb = 15.645-15.653, 208Pb/204Pb = 38.179-38.461; while for late pyrite 206Pb/204Pb = 18.102-18.378, 207Pb/204Pb = 15.635-15.646, 208Pb/204Pb = 38.149-38.320. The model parameters μ2 (238U/204Pb = 9.91 ± 2), ω2 (232Th/204Pb = 38.5 ± 4), and 232Th/238U = 3.88 ± 3 indicate that an upper crustal Pb source played a leading role in ore formation. Carbonaceous shale as an olistostrome cement and syngenetic sulfide mineralization are considered to be the main Pb sources of both early and late mineral assemblages. An additional recept in apparently magmatic lead is suggested for the late veinlet mineralization. The involvement of lead from several sources in ore formation is consistent with the genetic model, which assumes a two-stage formation of orebodies at the Mindyak deposit.

  14. Distribution and Source Identification of Pb Contamination in industrial soil

    NASA Astrophysics Data System (ADS)

    Ko, M. S.

    2017-12-01

    INTRODUCTION Lead (Pb) is toxic element that induce neurotoxic effect to human, because competition of Pb and Ca in nerve system. Lead is classified as a chalophile element and galena (PbS) is the major mineral. Although the Pb is not an abundant element in nature, various anthropogenic source has been enhanced Pb enrichment in the environment after the Industrial Revolution. The representative anthropogenic sources are batteries, paint, mining, smelting, and combustion of fossil fuel. Isotope analysis widely used to identify the Pb contamination source. The Pb has four stable isotopes that are 208Pb, 207Pb, 206Pb, and 204Pb in natural. The Pb is stable isotope and the ratios maintain during physical and chemical fractionation. Therefore, variations of Pb isotope abundance and relative ratios could imply the certain Pb contamination source. In this study, distributions and isotope ratios of Pb in industrial soil were used to identify the Pb contamination source and dispersion pathways. MATERIALS AND METHODS Soil samples were collected at depth 0­-6 m from an industrial area in Korea. The collected soil samples were dried and sieved under 2 mm. Soil pH, aqua-regia digestion and TCLP carried out using sieved soil sample. The isotope analysis was carried out to determine the abundance of Pb isotope. RESULTS AND DISCUSSION The study area was developed land for promotion of industrial facilities. The study area was forest in 1980, and the satellite image show the alterations of land use with time. The variations of land use imply the possibilities of bringing in external contaminated soil. The Pb concentrations in core samples revealed higher in lower soil compare with top soil. Especially, 4 m soil sample show highest Pb concentrations that are approximately 1500 mg/kg. This result indicated that certain Pb source existed at 4 m depth. CONCLUSIONS This study investigated the distribution and source identification of Pb in industrial soil. The land use and Pb

  15. An isotope-dilution standard GC/MS/MS method for steroid hormones in water

    USGS Publications Warehouse

    Foreman, William T.; Gray, James L.; ReVello, Rhiannon C.; Lindley, Chris E.; Losche, Scott A.

    2013-01-01

    An isotope-dilution quantification method was developed for 20 natural and synthetic steroid hormones and additional compounds in filtered and unfiltered water. Deuterium- or carbon-13-labeled isotope-dilution standards (IDSs) are added to the water sample, which is passed through an octadecylsilyl solid-phase extraction (SPE) disk. Following extract cleanup using Florisil SPE, method compounds are converted to trimethylsilyl derivatives and analyzed by gas chromatography with tandem mass spectrometry. Validation matrices included reagent water, wastewater-affected surface water, and primary (no biological treatment) and secondary wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100%; with overall relative standard deviation of 28%. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples analyzed in 2009–2010 ranged from 84–104%, with relative standard deviations of 6–36%. Detection levels estimated using ASTM International’s D6091–07 procedure range from 0.4 to 4 ng/L for 17 analytes. Higher censoring levels of 100 ng/L for bisphenol A and 200 ng/L for cholesterol and 3-beta-coprostanol are used to prevent bias and false positives associated with the presence of these analytes in blanks. Absolute method recoveries of the IDSs provide sample-specific performance information and guide data reporting. Careful selection of labeled compounds for use as IDSs is important because both inexact IDS-analyte matches and deuterium label loss affect an IDS’s ability to emulate analyte performance. Six IDS compounds initially tested and applied in this method exhibited deuterium loss and are not used in the final method.

  16. 238U and 235U isotope fractionation upon oxidation of uranium-bearing rocks by fracture waters

    NASA Astrophysics Data System (ADS)

    Chernyshev, I. V.; Golubev, V. N.; Chugaev, A. V.; Mandzhieva, G. V.

    2016-10-01

    The variations in 238U/235U values accompanying mobilization of U by fracture waters from uranium-bearing rocks, in which U occurs as a fine impregnation of oxides and silicates, were studied by the high-precision (±0.07‰) MC-ICP-MS method. Transition of U into the aqueous phase in the oxidized state U(VI) is accompanied by its isotope fractionation with enrichment of dissolved U(VI) in the heavy isotope 238U up to 0.32‰ in relation to the composition of the solid phases. According to the sign, this effect is consistent with the tendency of the behavior of 238U and 235U upon interaction of river waters with rocks of the catchment areas [11] and with the effect observed during oxidation of uraninite by the oxygen-bearing NaHCO3 solution [12].

  17. Zircon U-Pb ages and Hf isotopes for the Diablillos Intrusive Complex, Southern Puna, Argentina: Crustal evolution of the Lower Paleozoic Orogen, Southwestern Gondwana margin

    NASA Astrophysics Data System (ADS)

    Ortiz, Agustín; Hauser, Natalia; Becchio, Raúl; Suzaño, Néstor; Nieves, Alexis; Sola, Alfonso; Pimentel, Marcio; Reimold, Wolf

    2017-12-01

    The evolution of the rocks of the Lower Paleozoic Orogen in Puna, at the Southwestern Gondwana margin, has been widely debated. In particular, the scarce amount of geological and geochemical data available for the Diablillos Intrusive Complex, Eastern Magmatic Belt, Southern Puna, require a further study for new evidence towards the understanding of sources, magmatic processes and emplacement of magmas, in order to better comprehend the crustal evolution in this setting. We present new combined U-Pb and Hf isotope analyses on zircon by LA-MC-ICP-MS from monzogranite, granodiorite and diorite rocks of the Diablillos Intrusive Complex. We obtained 206Pb/238U concordant weighted average ages of 517 ± 3 Ma and 515 ± 6 Ma for the monzogranite and diorite, respectively, and a concordant age of 521 ± 4 Ma for the granodiorite. These ages permit to constrain the climax of magmatic activity in the Diablillos Complex around ∼515-520 Ma, while the emplacement of the complex took place between ∼540 Ma and 490 Ma (representing a ca. 50 Ma magmatic event). Major and trace element data, initial 87Sr/86Sr values varying from 0.70446 to 0.71278, positive and negative ɛNd(t) values between +2.5 and -4, as well as ɛHf(t) for zircon data between + 3 and -3 indicate that the analyzed samples represent contaminated magmas. The ɛHf(t) and the ɛNd(t) values for this complex specify that these rocks are derived from interaction of a dominant Mesoproterozoic crystalline and/or a metasedimentary source and juvenile mantle-derived magmas, with a TDM model age range of ∼1.2-1.5 Ga, with later reworking during lower Paleozoic times. The combined data obtained in this contribution together with previous data, allow us to suggest that the formation of the Eastern Magmatic Belt of the Puna was part of a long-lived magmatic event during Early Paleozoic times. Whereby the granitoids of the Eastern Magmatic Belt formed through intra-crustal recycling at an active continental margin, with

  18. Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals) in coal samples.

    PubMed

    Boulyga, Sergei F; Heilmann, Jens; Prohaska, Thomas; Heumann, Klaus G

    2007-10-01

    A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for (35)Cl+ to more than 6 x 10(5) cps for (238)U+ for 1 microg of trace element per gram of coal sample. Detection limits vary from 450 ng g(-1) for chlorine and 18 ng g(-1) for sulfur to 9.5 pg g(-1) for mercury and 0.3 pg g(-1) for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis.

  19. Sources of granite magmatism in the Embu Terrane (Ribeira Belt, Brazil): Neoproterozoic crust recycling constrained by elemental and isotope (Sr-Nd-Pb) geochemistry

    NASA Astrophysics Data System (ADS)

    Alves, Adriana; Janasi, Valdecir de Assis; Campos Neto, Mario da Costa

    2016-07-01

    Whole rock elemental and Sr-Nd isotope geochemistry and in situ K-feldspar Pb isotope geochemistry were used to identify the sources involved in the genesis of Neoproterozoic granites from the Embu Terrane, Ribeira Belt, SE Brazil. Granite magmatism spanned over 200 Ma (810-580 Ma), and is dominated by crust-derived relatively low-T (850-750 °C, zircon saturation) biotite granites to biotite-muscovite granites. Two Cryogenian plutons show the least negative εNdt (-8 to -10) and highest mg# (30-40) of the whole set. Their compositions are strongly contrasted, implying distinct sources for the peraluminous (ASI ∼ 1.2) ∼660 Ma Serra do Quebra-Cangalha batholith (metasedimentary rocks from relatively young upper crust with high Rb/Sr and low Th/U) and the metaluminous (ASI = 0.96-1.00) ∼ 630 Ma Santa Catarina Granite. Although not typical, the geochemical signature of these granites may reflect a continental margin arc environment, and they could be products of a prolonged period of oceanic plate consumption started at ∼810 Ma. The predominant Ediacaran (595-580 Ma) plutons have a spread of compositions from biotite granites with SiO2 as low as ∼65% (e.g., Itapeti, Mauá, Sabaúna and Lagoinha granites) to fractionated muscovite granites (Mogi das Cruzes, Santa Branca and Guacuri granites; up to ∼75% SiO2). εNdT are characteristically negative (-12 to -18), with corresponding Nd TDM indicating sources with Paleoproterozoic mean crustal ages (2.0-2.5 Ga). The Guacuri and Santa Branca muscovite granites have the more negative εNdt, highest 87Sr/86Srt (0.714-0.717) and lowest 208Pb/206Pb and 207Pb/206Pb, consistent with an old metasedimentary source with low time-integrated Rb/Sr. However, a positive Nd-Sr isotope correlation is suggested by data from the other granites, and would be consistent with mixing between an older source predominant in the Mauá granite and a younger, high Rb/Sr source that is more abundant in the Lagoinha granite sample. The

  20. All possible tripartitions of {}(236) 236U isotope in collinear configuration

    NASA Astrophysics Data System (ADS)

    Santhosh, K. P.; Krishnan, Sreejith; Joseph, Jayesh George

    2018-07-01

    Using the recently proposed unified ternary fission model (UTFM), the tripartition of ^{236}U isotope was studied for all possible fragmentations, in which the interacting potential barrier is taken as the sum of the Coulomb and proximity potentials with fragments in collinear configuration. The highest yield is obtained for the fragmentation ^{48}Ca{+}^{58}Ti{+}^{130}Sn and next highest yield is found for ^{58}Cr{+}^{46}Ar{+}^{132}Sn, which stress the importance of doubly magic or near doubly magic nuclei in the tripartition of ^{236}U isotope. The formation of ^{68}Ni and ^{70}Ni as the edge fragments linking the doubly magic nucleus ^{132}Sn by the isotope of Si is in good agreement with experimental and theoretical studies, in the collinear cluster tripartition of ^{236}U isotope which reveals the reliability of our model (UTFM) in ternary fission.

  1. 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).

  2. Leaching behavior of U, Mn, Sr, and Pb from different particle-size fractions of uranium mill tailings.

    PubMed

    Liu, Bo; Peng, Tongjiang; Sun, Hongjuan

    2017-06-01

    Pollution by the release of heavy metals from tailings constitutes a potential threat to the environment. To characterize the processes governing the release of Mn, Sr, Pb, and U from the uranium mill tailings, a dynamic leaching test was applied for different size of uranium mill tailings samples. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) were performed to determine the content of Mn, Sr, Pb, and U in the leachates. The release of mobile Mn, Sr, Pb, and U fraction was slow, being faster in the initial stage and then attained a near steady-state condition. The experimental results demonstrate that the release of Mn, Sr, Pb, and U from uranium mill tailings with different size fractions is controlled by a variety of mechanisms. Surface wash-off is the release mechanism for Mn. The main release mechanism of Sr and Pb is the dissolution in the initial leaching stage. For U, a mixed process of wash-off and diffusion is the controlling mechanism.

  3. Recalibration of the Palaeocene-Eocene boundary (P-E) using high precision U-Pb and Ar-Ar isotopic dating

    NASA Astrophysics Data System (ADS)

    Chambers, L.; Pringle, M.; Fitton, G.; Larsen, L. M.; Pedersen, A. K.; Parrish, R.

    2003-04-01

    In the current time scales (Cande and Kent, 95; Berggren et al, 95) the P-E Boundary is positioned at 55 Ma based primarily on the age of the -17 ash layer in Denmark. In the absence of a global stratigraphic section and point the boundary is an interval of 1 m.y. from 55.5 to 54.5 Ma that includes all of the different means of calibrating the boundary tie point, including the NP9/NP10 calcareous nannofossil zonal boundary, the planktonic foraminiferal P5/P6a zonal boundary, preliminary ages for the -17 and +19 ash layers (unpub.), the base of the London Clay Formation, and the δ13C spike. Here we present new Ar-Ar ages for the -17 and +19 ash layers in Denmark and combine this study with a calibration of the Ar-Ar with the U-Pb method. As Ar-Ar ages are relative to the known age of a standard or monitor, U-Pb ages on zircons from the same rocks from the British Tertiary Igneous Province provide an absolute age calibration for all of our Ar-Ar ages (including the monitors). An additional complication arises because the time scale is currently being revised (J. Ogg, Pers. Comm.). In the new time scale the P-E boundary will stay at 55 Ma and the K-T boundary will move by 0.5 m.y. to 65.5 Ma. Our results have a direct impact on the positioning of the P-E Boundary relative to the K-T boundary as definitive K-T tektite is used as one of our Ar-Ar standards. Ar-Ar ages and U-Pb ages for the same sample from the BTIP are indistinguishable when the ages used for the Ar-Ar monitor minerals are those recommended in Renne et al (98). This means that the K-T tektite is 65.78 ± 0.03 Ma, the -17 ash is 54.52 ± 0.05Ma, and the +19 ash is 54.04 ± 0.14 Ma. If the P-E boundary is taken to be between the -17 and +19 ash layers, as in DSDP Hole 550 (the ashes bracket the planktonic foraminiferal P5/P6a zonal boundary) then the current position at 55 Ma is too old. We therefore suggest that if the K-T boundary moves to 65.5 Ma, then the P-E boundary should not stay at 55 Ma, but

  4. Petrology, geochemistry and U-Pb geochronology of magmatic rocks from the high-sulfidation epithermal Au-Cu Chelopech deposit, Srednogorie zone, Bulgaria

    NASA Astrophysics Data System (ADS)

    Chambefort, Isabelle; Moritz, Robert; von Quadt, Albrecht

    2007-10-01

    The Chelopech deposit is one of the largest European gold deposits and is located 60 km east of Sofia, within the northern part of the Panagyurishte mineral district. It lies within the Banat-Srednegorie metallogenic belt, which extends from Romania through Serbia to Bulgaria. The magmatic rocks define a typical calc-alkaline suite. The magmatic rocks surrounding the Chelopech deposit have been affected by propylitic, quartz-sericite, and advanced argillic alteration, but the igneous textures have been preserved. Alteration processes have resulted in leaching of Na2O, CaO, P2O5, and Sr and enrichment in K2O and Rb. Trace element variation diagrams are typical of subduction-related volcanism, with negative anomalies in high field strength elements (HFSE) and light element, lithophile elements. HFSE and rare earth elements were relatively immobile during the hydrothermal alteration related to ore formation. Based on immobile element classification diagrams, the magmatic rocks are andesitic to dacitic in compositions. Single zircon grains, from three different magmatic rocks spanning the time of the Chelopech magmatism, were dated by high-precision U-Pb geochronology. Zircons of an altered andesitic body, which has been thrust over the deposit, yield a concordant 206Pb/238U age of 92.21 ± 0.21 Ma. This age is interpreted as the crystallization age and the maximum age for magmatism at Chelopech. Zircon analyses of a dacitic dome-like body, which crops out to the north of the Chelopech deposit, give a mean 206Pb/238U age of 91.95 ± 0.28 Ma. Zircons of the andesitic hypabyssal body hosting the high-sulfidation mineralization and overprinted by hydrothermal alteration give a concordant 206Pb/238U age of 91.45 ± 0.15 Ma. This age is interpreted as the intrusion age of the andesite and as the maximum age of the Chelopech epithermal high-sulfidation deposit. 176Hf/177Hf isotope ratios of zircons from the Chelopech magmatic rocks, together with published data on the

  5. Evolving Pb isotope signatures of London airborne particulate matter (PM 10)-constraints from on-filter and solution-mode MC-ICP-MS.

    PubMed

    Noble, Stephen R; Horstwood, Matthew S A; Davy, Pamela; Pashley, Vanessa; Spiro, Baruch; Smith, Steve

    2008-07-01

    Pb isotope compositions of biologically significant PM(10) atmospheric particulates from a busy roadside location in London UK were measured using solution- and laser ablation-mode MC-ICP-MS. The solution-mode data for PM(10) sampled between 1998-2001 document a dramatic shift to increasingly radiogenic compositions as leaded petrol was phased out. LA-MC-ICP-MS isotope analysis, piloted on a subset of the available samples, is shown to be a potential reconnaissance analytical technique. PM(10) particles trapped on quartz filters were liberated from the filter surface, without ablating the filter substrate, using a 266 nm UV laser and a dynamic, large diameter, low-fluence ablation protocol. The Pb isotope evolution noted in the London data set obtained by both analytical protocols is similar to that observed elsewhere in Western Europe following leaded petrol elimination. The data therefore provide important baseline isotope composition information useful for continued UK atmospheric monitoring through the early 21(st) century.

  6. High-precision ID-TIMS zircon U-Pb geochronology using new 1013 Ohm resistors

    NASA Astrophysics Data System (ADS)

    Von Quadt, A.; Buret, Y.; Large, S.; Peytcheva, I.; Trinquier, A.; Wotzlaw, J. F.

    2015-12-01

    Faraday cups equipped with high gain amplifiers provide a means to measure small ion beams in static mode without the limited linear range of ion counting systems. We tested the application of newly available 1013 Ohm resistors to ID-TIMS zircon U-Pb geochronology using a range of natural and synthetic reference materials. The TritonPlus-RPQ at the Institute of Geochemistry and Petrology, ETH Zurich, is equipped with five new 1013 Ohm resistors and one MasCom secondary electron multiplier, allowing to measure the 202-204-205-206-207-208Pb masses in static mode. U is measured subsequently as U-oxide (265-267-270UO2) during a second step, also in static Faraday mode. The gain calibration of the 1013 Ohm resistors was performed using the procedure of Trinquier (2014), with 144Nd-146Nd being measured using 1011 Ohm resistor and 142-143-145-148-150Nd being measured using 1013 Ohm resitors (Trinquier, 2014; Koornneef et al., 2014). Standard deviations of the noise in all five new 1013 Ohm resistors are lower than 5.0 x 10-6 over a 6 month period, with no shift occurring over this time interval. This new detector set-up was tested by analyzing natural zircon standard materials and synthetic U/Pb solutions (www.earthime.org), ranging in age from ~2 Ma to ~600 Ma. All natural zircon standards were chemically abraded (Mattinson, 2005) and all samples were spiked with the ET2535 tracer solution. U-Pb dates obtained using the static measurement routine are compared to measurements employing dynamic peak jumping routines on the MasCom multiplier. This study illustrates the benefits and current limitations of using high gain amplifiers to measure small ion beams for zircon U-Pb geochronology compared to conventional dynamic ion counting techniques. Mattinson, J.M. (2005) Chemical Geology 220:47-66; Trinquier, A. (2014) Application Note 30281; Koornneef, J. et al (2014) Analytica Chimica Acta 819:49-55.

  7. Sr and Pb isotopic geochemistry of feldspars and implications for the growth of megacrysts in plutonic settings.

    NASA Astrophysics Data System (ADS)

    Munnikhuis, J.; Glazner, A. F.; Coleman, D. S.; Mills, R. D.

    2015-12-01

    Why megacrystic textures develop in silicic igneous rocks is still unknown. One hypothesis is that these crystals nucleate early in a magma chamber with a high liquid content. A supportive observation of this hypothesis is areas in plutons with high concentrations of megacrysts suggesting flow sorting. Another group of hypotheses suggest megacrystic textures form during protracted late-stage coarsening in a low-melt, interlocked matrix due to either thermal oscillations from incremental pluton emplacement, or Ostwald ripening. Isotopic analyses of large, euhedral K-feldspar megacrysts from the Cretaceous intrusive suites of the Sierra Nevada batholith (SNB) provide new insight into their origin. Megacrysts from the SNB reach the decimeter scale, are Or rich (85-90%), are perthitic, and host mineral inclusions of nearly all phases in the host rock. In-situ micro-drilling of transects, from core to rim, of the alkali feldspars provides material for Sr and Pb isotopic analyses by thermal ionization mass spectrometry (TIMS). Preliminary 87Sr/86Sr(i) isotopic data from samples from the Cathedral Peak Granodiorite, of the Tuolumne Intrusive Suite range from 0.706337 to 0.706452 (~1.6ɛSr) near the cores, whereas a sawtooth pattern with larger variability, 0.706179 to 0.706533 (~5ɛSr), occurs nears the rims. We interpret these preliminary data to indicate that the late portion of growth (i.e. crystal rim) was dominated by either cannibalism of small K-feldspar crystals with isotopic variability, or by addition of isotopically diverse late components to the magma. By comparing the Sr and Pb isotopic stratigraphy of megacrysts from a variety of rock matrices and different granitoids in the SNB isotopic trends can be evaluated to determine if crystals sizes are dependent on disequilibrium processes or grow at a steady state.

  8. Lead isotopic evidence for mixed sources of Proterozoic granites and pegmatites, Black Hills, South Dakota, USA

    NASA Astrophysics Data System (ADS)

    Krogstad, Eirik J.; Walker, Richard J.; Nabelek, Peter I.; Russ-Nabelek, Carol

    1993-10-01

    The lead isotopic compositions of K-feldspars separated from the ca. 1700 Ma Harney Peak Granite complex and spatially associated granitic pegmatites indicate that these rocks were derived from at least two sources. It has been reported previously that the core of the Harney Peak Granite complex is dominated by relatively lower/ gd18O (avg. 11.5 %.) granites, whereas higher / gd18O (avg. 13.2%.) granites occur around the periphery of the complex. The higher δ 18O granites and one simple pegmatite have low values of 207Pb /204Pb for their 206Pb /204Pb Thus, they likely were derived from a source with a short crustal residence time. This source may have been the pelitic schists into which the Harney Peak Granite complex and pegmatites were intruded. Feldspars from granites with lower / gd18O values have significantly higher 207Pb /204Pb for their 206Pb /204Pb . The data define a linear array with a slope equivalent to an age of ca. 2.6 Ga with t 2 defined to be 1.7 Ga. Such a slope could represent a mixing array or a secondary isochron for the source. These low δ18O granites could have been derived from a source with a high U/ Pb and with a crustal residence beginning before the Proterozoic. The source (s) of these granites may have been a sediment derived from late Archean continental crust. The highly evolved Tin Mountain pegmatite has lead isotopic systematics intermediate between those of the two granite groups, suggesting either a mixed source or contamination. Two late Archean granites, the Little Elk Granite and the Bear Mountain Granite, had precursors with high U/Pb and low Th/U histories. The Th/U history of the Bear Mountain Granite is too low for this rock to have been an important component of the source of the Proterozoic granites. However, crustal rocks with lead isotopic compositions similar to those of the Little Elk Granite were an important source of lead for some of the Proterozoic granitic rocks.

  9. Effective LA-ICP-MS dating of common-Pb bearing accessory minerals with new data reduction schemes in Iolite

    NASA Astrophysics Data System (ADS)

    Kamber, Balz S.; Chew, David M.; Petrus, Joseph A.

    2014-05-01

    Compared to non-destructive geochemical analyses, LA-ICP-MS consumes ca. 0.1 μm of material per ablation pulse. It is therefore to be expected that the combined analyses of ca. 200 pulses will encounter geochemical and isotopic complexities in all but the most perfect minerals. Experienced LA-ICP-MS analysts spot down-hole complexities and choose signal integration areas accordingly. In U-Pb geochronology, the task of signal integration choice is complex as the analyst wants to avoid areas of common Pb and Pb-loss and separate true (concordant) age complexity. Petrus and Kamber (2012) developed VizualAge as a tool for reducing and visualising, in real time, U-Pb geochronology data obtained by LA-ICP-MS as an add-on for the freely available U-Pb geochronology data reduction scheme of Paton et al. (2010) in Iolite. The most important feature of VizualAge is its ability to display a live concordia diagram, allowing users to inspect the data of a signal on a concordia diagram as the integration area it is being adjusted, thus providing immediate visual feedback regarding discordance, uncertainty, and common lead for different regions of the signal. It can also be used to construct histograms and probability distributions, standard and Tera-Wasserburg style concordia diagrams, as well as 3D U-Th-Pb and total U-Pb concordia diagrams. More recently, Chew et al. (2014) presented a new data reduction scheme (VizualAge_UcomPbine) with much improved common Pb correction functionality. Common Pb is a problem for many U-bearing accessory minerals and an under-appreciated difficulty is the potential presence of (possibly unevenly distributed) common Pb in calibration standards, introducing systematic inaccuracy into entire datasets. One key feature of the new method is that it can correct for variable amounts of common Pb in any U-Pb accessory mineral standard as long as the standard is concordant in the U/Pb (and Th/Pb) systems after common Pb correction. Common Pb correction

  10. Zircon U-Pb age, Hf isotopic compositions and geochemistry of the Silurian Fengdingshan I-type granite Pluton and Taoyuan mafic-felsic Complex at the southeastern margin of the Yangtze Block

    NASA Astrophysics Data System (ADS)

    Zhong, Yufang; Ma, Changqian; Zhang, Chao; Wang, Shiming; She, Zhenbing; Liu, Lei; Xu, Haijin

    2013-09-01

    This work presents an integrated study of zircon U-Pb ages and Hf isotope along with whole-rock geochemistry on Silurian Fengdingshan I-type granites and Taoyuan mafic-felsic intrusive Complex located at the southeastern margin of the Yangtze Block, filling in a gap in understanding of Paleozoic I-type granites and mafic-intermediate igneous rocks in the eastern South China Craton (SCC). The Fengdingshan granite and Taoyuan hornblende gabbro are dated at 436 ± 5 Ma and 409 ± 2 Ma, respectively. The Fengdingshan granites display characteristics of calc-alkaline I-type granite with high initial 87Sr/86Sr ratios of 0.7093-0.7127, low ɛNd(t) values ranging from -5.6 to -5.4 and corresponding Nd model ages (T2DM) of 1.6 Ga. Their zircon grains have ɛHf(t) values ranging from -2.7 to 2.6 and model ages of 951-1164 Ma. The Taoyuan mafic rocks exhibit typical arc-like geochemistry, with enrichment in Rb, Th, U and Pb and depletion in Nb, Ta. They have initial 87Sr/86Sr ratios of 0.7053-0.7058, ɛNd(t) values of 0.2-1.6 and corresponding T2DM of 1.0-1.1 Ga. Their zircon grains have ɛHf(t) values ranging from 3.2 to 6.1 and model ages of 774-911 Ma. Diorite and granodiorite from the Taoyuan Complex have initial 87Sr/86Sr ratios of 0.7065-0.7117, ɛNd(t) values from -5.7 to -1.9 and Nd model ages of 1.3-1.6 Ga. The petrographic and geochemical characteristics indicate that the Fengdingshan granites probably formed by reworking of Neoproterozoic basalts with very little of juvenile mantle-derived magma. The Taoyuan Complex formed by magma mixing and mingling, in which the mafic member originated from a metasomatized lithospheric mantle. Both the Fengdingshan and Taoyuan Plutons formed in a post-orogenic collapse stage in an intracontinental tectonic regime. Besides the Paleozoic Fengdingshan granites and Taoyuan hornblende gabbro, other Neoproterozoic and Indosinian igneous rocks located along the southeastern and western margin of the Yangtze Block also exhibit decoupled

  11. Application and validation of isotope dilution method (IDM) for predicting bioavailability of hydrophobic organic contaminants in soil.

    PubMed

    Wang, Jie; Taylor, Allison; Schlenk, Daniel; Gan, Jay

    2018-05-01

    Risk assessment of hydrophobic organic contaminants (HOCs) using the total chemical concentration following exhaustive extraction may overestimate the actual availability of HOCs to non-target organisms. Existing methods for estimating HOC bioavailability in soil have various operational limitations. In this study, we explored the application of isotope dilution method (IDM) to quantify the accessible fraction (E) of DDTs and PCBs in both historically-contaminated and freshly-spiked soils. After addition of 13 C or deuterated analogues to a soil sample, the phase distribution of isotope-labeled and native chemicals reached an apparent equilibrium within 48 h of mixing. The derived E values in the three soils ranged from 0.19 to 0.82, depending on the soil properties and also the contact time of HOCs (i.e., aging). The isotope dilution method consistently predicted greater accumulation into earthworm (Eisenia fetida) than that by polyethylene (PE) or solid phase microextraction (SPME) sampler, likely because desorption in the gut enhanced bioavailability of soil-borne HOCs. A highly significant linear regression (R 2  = 0.91) was found between IDM and 24-h Tenax desorption, with a slope statistically identical to 1. The IDM-derived accessible concentration (C e ) was further shown to accurately predict tissue residues in earthworm exposed in the same soils. Given the relatively short duration and simple steps, IDM has the potential to be readily adopted for measuring HOC bioaccessibility in soil and for improving risk assessment and evaluation of remediation efficiency. Copyright © 2018 Elsevier Ltd. All rights reserved.

  12. Bioaccessibility of U, Th and Pb in particulate matter from an abandoned uranium mine

    NASA Astrophysics Data System (ADS)

    Millward, Geoffrey; Foulkes, Michael; Henderson, Sam; Blake, William

    2016-04-01

    Currently, there are approximately 150 uranium mines in Europe at various stages of either operation, development, decommissioning, restoration or abandonment (wise-uranium.com). The particulate matter comprising the mounds of waste rock and mill tailings poses a risk to human health through the inadvertent ingestion of particles contaminated with uranium and thorium, and their decay products, which exposes recipients to the dual toxicity of heavy elements and their radioactive emissions. We investigated the bioaccessibility of 238U, 232Th and 206,214,210Pb in particulate samples taken from a contaminated, abandoned uranium mine in South West England. Sampling included a mine shaft, dressing floor and waste heap, as well as soils from a field used for grazing. The contaminants were extracted using the in-vitro Unified Bioaccessibility Research Group of Europe Method (UBM) in order to mimic the digestion processes in the human stomach (STOM) and the combined stomach and gastrointestinal tract (STOM+INT). Analyses of concentrations of U, Th and Pb in the extracts were by ICP-MS and the activity concentrations of radionuclides were determined on the same particles, before and after extraction, using gamma spectroscopy. 'Total' concentrations of U, Th and Pb for all samples were in the range 57 to 16,200, 0.28 to 3.8 and 69 to 4750 mg kg-1, respectively. For U and Pb the concentrations in the STOM fraction were lower than the total and STOM+INT fractions were even lower. However, for Th the STOM+INT fractions were higher than the STOM due to the presence of Th carbonate species within the gastrointestinal fluid. Activity concentrations for 214Pb and 210Pb, including total, STOM and STOM+INT, were in the range 180 to <1 Bq g-1 for the dressing floor and waste heap and 18 to <1 Bq g-1 for the grazing land. Estimates of the bioaccessible fractions (BAFs) of 238U in the most contaminated samples were 39% and 8% in the STOM and STOM+INT, respectively, whereas the respective

  13. Geochronology, fluid inclusions and isotopic characteristics of the Chaganbulagen Pb-Zn-Ag deposit, Inner Mongolia, China

    NASA Astrophysics Data System (ADS)

    Li, Tiegang; Wu, Guang; Liu, Jun; Wang, Guorui; Hu, Yanqing; Zhang, Yunfu; Luo, Dafeng; Mao, Zhihao; Xu, Bei

    2016-09-01

    The large Chaganbulagen Pb-Zn-Ag deposit is located in the Derbugan metallogenic belt of the northern Great Xing'an Range. The vein-style orebodies of the deposit occur in the NWW-trending fault zones. The ore-forming process at the deposit can be divided into three stages: an early quartz-pyrite-arsenopyrite-pyrrhotite-sphalerite-galena-chalcopyrite stage, a middle quartz-carbonate-pyrite-sphalerite-galena-silver-bearing minerals stage, and a late quartz-carbonate-pyrite stage. The sericite sample yielded a 40Ar -39Ar plateau age of 138 ± 1 Ma and an isochron age of 137 ± 3 Ma, and the zircon LA-ICP-MS U-Pb age of monzogranite porphyry was 143 ± 2 Ma, indicating that the ages of mineralization and monzogranite porphyry in the Chaganbulagen deposit should be the Early Cretaceous, and that the mineralization should be slightly later than the intrusion of monzogranite porphyry. There are only liquid inclusions in quartz veins of the Chaganbulagen deposit. Homogenization temperatures, densities, and salinities of the fluid inclusions from the early stage are 261-340 °C, 0.65-0.81 g/cm3, and 0.7-6.3 wt.% NaCl eqv., respectively. Fluid inclusions of the middle stage have homogenization temperatures, densities, and salinities of 209-265 °C, 0.75-0.86 g/cm3, and 0.5-5.7 wt.% NaCl eqv., respectively. For fluid inclusions of the late stage, their homogenization temperatures, densities, and salinities are 173-219 °C, 0.85-0.91 g/cm3, and 0.4-2.7 wt.% NaCl eqv., respectively. The ore-forming fluids of the deposit are generally characterized by moderate temperature and low salinity and density, and belong to an H2O-NaCl ± CO2 ± CH4 system. The δ18Owater values calculated for ore-bearing quartz vary from - 17.9‰ to - 10.8‰, and the δDV-SMOW values from bulk extraction of fluid inclusion waters vary from - 166‰ to - 127‰, suggesting that the ore-forming fluids consist dominantly of meteoric water. The δ34SV-CDT values range from 1.4‰ to 4.1‰. The 206Pb/204

  14. Determination of the alkylpyrazine composition of coffee using stable isotope dilution-gas chromatography-mass spectrometry (SIDA-GC-MS).

    PubMed

    Pickard, Stephanie; Becker, Irina; Merz, Karl-Heinz; Richling, Elke

    2013-07-03

    A stable isotope dilution analysis based on gas chromatography-mass spectrometry analysis (SIDA-GC-MS) was developed for the quantitative analysis of 12 alkylpyrazines found in commercially available coffee samples. These compounds contribute to coffee flavor. The accuracy of this method was tested by analyzing model mixtures of alkylpyrazines. Comparisons of alkylpyrazine-concentrations suggested that water as extraction solvent was superior to dichloromethane. The distribution patterns of alkylpyrazines in different roasted coffees were quite similar. The most abundant alkylpyrazine in each coffee sample was 2-methylpyrazine, followed by 2,6-dimethylpyrazine, 2,5-dimethylpyrazine, 2-ethylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-5-methylpyrazine, and 2,3,5-trimethylpyrazine, respectively. Among the alkylpyrazines tested, 2,3-dimethylpyrazine, 2-ethyl-3-methylpyrazine, 2-ethyl-3,6-dimethylpyrazine, and 2-ethyl-3,5-dimethylpyrazine revealed the lowest concentrations in roasted coffee. By the use of isotope dilution analysis, the total concentrations of alkylpyrazines in commercially available ground coffee ranged between 82.1 and 211.6 mg/kg, respectively. Decaffeinated coffee samples were found to contain lower amounts of alkylpyrazines than regular coffee samples by a factor of 0.3-0.7, which might be a result of the decaffeination procedure.

  15. Mineral chemistry and shrimp U-Pb Geochronology of mesoproterozoic polycrase-titanite veins in the sullivan Pb-Zn-Ag Deposit, British Columbia

    USGS Publications Warehouse

    Slack, J.F.; Aleinikoff, J.N.; Belkin, H.E.; Fanning, C.M.; Ransom, P.W.

    2008-01-01

    Small polycrase-titanite veins 0.1-2 mm thick cut the tourmalinite feeder zone in the deep footwall of the Sullivan Pb-Zn-Ag deposit, southeastern British Columbia. Unaltered, euhedral crystals of polycrase and titanite 50-100 ??m in diameter are variably replaced by a finer-grained alteration-induced assemblage composed of anhedral polycrase and titanite with local calcite, albite, epidote, allanite, and thorite or uranothorite (or both). Average compositions of the unaltered and altered polycrase, as determined by electron-microprobe analysis, are (Y0.38 REE0.49 Th0.10 Ca0.04 Pb0.03 Fe0.01U0.01) (Ti1.48 Nb0.54 W0.04 Ta0.02)O6 and (Y0.42 REE0.32 Th0.15 U0.06 Ca0.04 Pb0.01 Fe0.01) (Ti1.57 Nb0.44 W0.04 Ta0.02)O6, respectively. The unaltered titanite has, in some areas, appreciable F (to 0.15 apfu), Y (to 0.40 apfu), and Nb (to 0.13 apfu). SHRIMP U-Pb geochronology of eight grains of unaltered polycrase yields a weighted 207Pb/206Pb age of 1413 ?? 4 Ma (2??) that is interpreted to be the age of vein formation. This age is 50-60 m.y. younger than the ca. 1470 Ma age of synsedimentary Pb-Zn-Ag mineralization in the Sullivan deposit, which is based on combined geological and geochronological data. SHRIMP ages for altered polycrase and titanite suggest later growth of minerals during the ???1370-1320 Ma East Kootenay and ???1150-1050 Ma Grenvillian orogenies. The 1413 ?? 4 Ma age for the unaltered polycrase in the veins records a previously unrecognized post-ore (1370 Ma) mineralizing event in the Sullivan deposit and vicinity. The SHRIMP U-Pb age of the polycrase and high concentrations of REE, Y, Ti, Nb, and Th in the veins, together with elevated F in titanite and the absence of associated sulfides, suggest transport of these high-field-strength elements (HFSE) by F-rich and S-poor hydrothermal fluids unrelated to the fluids that formed the older Fe-Pb-Zn-Ag sulfide ores of the Sullivan deposit. Fluids containing abundant REE, HFSE, and F may have been derived from a

  16. Temporal geochemical variations in lavas from Kīlauea's Pu`u `Ō`ō eruption (1983-2010): Cyclic variations from melting of source heterogeneities

    NASA Astrophysics Data System (ADS)

    Greene, Andrew R.; Garcia, Michael O.; Pietruszka, Aaron J.; Weis, Dominique; Marske, Jared P.; Vollinger, Michael J.; Eiler, John

    2013-11-01

    Geochemical time series analysis of lavas from Kīlauea's ongoing Pu`u `Ō`ō eruption chronicle mantle and crustal processes during a single, prolonged (1983 to present) magmatic event, which has shown nearly two-fold variation in lava effusion rates. Here we present an update of our ongoing monitoring of the geochemical variations of Pu`u `Ō`ō lavas for the entire eruption through 2010. Oxygen isotope measurements on Pu`u `Ō`ō lavas show a remarkable range (δ18O values of 4.6-5.6‰), which are interpreted to reflect moderate levels of oxygen isotope exchange with or crustal contamination by hydrothermally altered Kīlauea lavas, probably in the shallow reservoir under the Pu`u `Ō`ō vent. This process has not measurably affected ratios of radiogenic isotope or incompatible trace elements, which are thought to vary due to mantle-derived changes in the composition of the parental magma delivered to the volcano. High-precision Pb and Sr isotopic measurements were performed on lavas erupted at ˜6 month intervals since 1983 to provide insights about melting dynamics and the compositional structure of the Hawaiian plume. The new results show systematic variations of Pb and Sr isotope ratios that continued the long-term compositional trend for Kīlauea until ˜1990. Afterward, Pb isotope ratios show two cycles with ˜10 year periods, whereas the Sr isotope ratios continued to increase until ˜2003 and then shifted toward slightly less radiogenic values. The short-term periodicity of Pb isotope ratios may reflect melt extraction from mantle with a fine-scale pattern of repeating source heterogeneities or strands, which are about 1-3 km in diameter. Over the last 30 years, Pu`u `Ō`ō lavas show 15% and 25% of the known isotopic variation for Kīlauea and Mauna Kea, respectively. This observation illustrates that the dominant time scale of mantle-derived compositional variation for Hawaiian lavas is years to decades.

  17. Lead Isotopes and Temporal Records of Atmospheric Aerosol and Pollutants in Lichens

    NASA Astrophysics Data System (ADS)

    Getty, S. R.; Nash, T.; Asmerom, Y.

    2001-05-01

    Lichens are useful receptors of atmospheric particulate matter (PM) and pollutants due to their retention of body parts (unlike plants), slow growth rates, fairly uniform morphologies, lack of a vascular system, and sessile character over decades to centuries. Lichen biomonitoring has been used widely to map patterns of aerosol deposition, yet few studies have tested whether lichens can preserve a temporal record of airborne PM and pollutants. We show with U-Pb data that epilithic lichens (rock as host) can retain in their porous structure an integrated, decadal-scale history of changing aerosol inputs to desert ecosystems. Three lichens resided along an 80-km transect from a copper smelter (Douglas, AZ) closed in early 1987, to the ENE into adjacent New Mexico. For the radially growing lichen (Xanthoparmelia sp.), U-Pb data were obtained along cm-scale transects in the growth direction on a single thallus. Profiles from lichen rim to interior show increasing [Pb] and [U], or net accumulation with thallus age. Total lead contents are highest near the smelter. In contrast, each lead isotope profile (206Pb/207Pb) is flat during smelter operation, showing low ratios near the smelter (1.152) and high ratios (1.175) 80 km away. This suggests comparable mixtures of crust and smelter lead per locality over decades. Since smelter closure, lichens 80 km from the smelter show a sharp upturn in lead ratio in the recently grown lichen rim, indicating that smelter lead is either dispersed by aeolian recycling, or suppressed in desert soils. The amplitude and position of the isotope signal suggests a soil recovery "half-life" of about 13 yrs, a radial growth rate of 0.57+/-0.1 mm/yr, and a total lichen age of 105+/-18 yrs. Lichens near the smelter have no upturn in isotope ratio, indicating continued aeolian recylcing of lead from soils about 11 yrs after closure. Results at a far-removed desert site (c. New Mexico) also argue that isotope profiles reflect aerosol deposition

  18. Is the Macquarie Arc (Lachlan Orogen) An Exotic Terrane or Formed on the Gondwanan Margin? Reappraisal by SHRIMP U-Pb Dating of Volcano-Sedimentary Rocks

    NASA Astrophysics Data System (ADS)

    Buckman, S.; Zhang, Q.; Nutman, A. P.

    2017-12-01

    A fundamental question concerning the Ordovician Macquarie Arc rocks is did they form within the palaeo-Pacific Ocean and are entirely juvenile, or did they evolve on the periphery of Gondwana? This is a key issue to ongoing debates concerning the growth of the eastern Gondwanan margin throughout the Palaeozoic. This problem is complicated by the arc now occurs as several slices, in post-arc tectonic contact with the eastern Gondwanan Ordovician Adaminaby Group. The dispersal of the arc as tectonic slices means that the temporal correlation of lithologies across the extent of the arc's exposure needs to be verified via U-Pb zircon geochronology. Our zircon U-Pb geochronology reveals that samples with the oldest zircons of Palaeozoic volcanic origin do not contain any Gondwanan-sourced zircons (particularly Cambrian and Neoproteorzoic). These samples, particularly some ascribed to the Weemalla Formation and Mitchell Formation have unimodal zircon populations of 450.5 Ma and 479.8 Ma. On the other hand, some samples with somewhat younger volcanic populations of 415 Ma and 458 Ma contain some Gondwanan-sourced older detrital zircons as well. Some of these latter samples are derived from outcrops that have previously consigned to the Yarrimbah Formation, should be older than, or equivalent to, the samples with the unimodal volcanic zircon populations of 480 Ma. This shows clearly that the consignment of some Macquarie Arc units to particular formations needs to be revised. The geochemical and radiogenic isotopic characteristics of the Macquarie Arc indicate that it is dominated by products of an intra-oceanic island arc that developed contemporaneously but spatially separated from Adaminaby Group passive margin sedimentation along eastern Gondwana. However, because our new U-Pb zircon data reveals that only samples with the youngest volcanic zircons also contain Gondwanan zircons, it shows that before the death of the arc, it was proximal to the Gondwanan margin

  19. Mineralogy, geochemistry, and Sr-Pb isotopic geochemistry of hydrothermal massive sulfides from the 15.2°S hydrothermal field, Mid-Atlantic Ridge

    NASA Astrophysics Data System (ADS)

    Wang, Hao; Li, Xiaohu; Chu, Fengyou; Li, Zhenggang; Wang, Jianqiang; Yu, Xing; Bi, Dongwei

    2018-04-01

    The 15.2°S hydrothermal field is located at 15.2°S, 13.4°W within the Mid-Atlantic Ridge (MAR) and was initially discovered during Cruise DY125-22 by the Chinese expedition during R/V Dayangyihao in 2011. Here, we provide detailed mineralogical, bulk geochemical, and Sr-Pb isotopic data for massive sulfides and basalts from the 15.2°S hydrothermal field to improve our understanding of the mineral compositions, geochemical characteristics, type of hydrothermal field, and the source of metals present at this vent site. The samples include 14 massive sulfides and a single basalt. The massive sulfides are dominated by pyrite with minor amounts of sphalerite and chalcopyrite, although a few samples also contain minor amounts of gordaite, a sulfate mineral. The sulfides have bulk compositions that contain low concentrations of Cu + Zn (mean 7.84 wt%), Co (mean 183 ppm), Ni (mean 3 ppm), and Ba (mean 16 ppm), similar to the Normal Mid-Ocean Ridge Basalt (N-MORB) type deposits along the MAR but different to the compositions of the Enriched-MORB (E-MORB) and ultramafic type deposits along this spreading ridge. Sulfides from the study area have Pb isotopic compositions (206Pb/204Pb = 18.4502-18.4538, 207Pb/204Pb = 15.4903-15.4936, 208Pb/204Pb = 37.8936-37.9176) that are similar to those of the basalt sample (206Pb/204Pb = 18.3381, 207Pb/204Pb = 15.5041, 208Pb/204Pb = 37.9411), indicating that the metals within the sulfides were derived from leaching of the surrounding basaltic rocks. The sulfides also have 87Sr/86Sr ratios (0.708200-0.709049) that are much higher than typical MAR hydrothermal fluids (0.7028-0.7046), suggesting that the hydrothermal fluids mixed with a significant amount of seawater during massive sulfide precipitation.

  20. Trace-element and Sr, Nd, Pb, and O isotopic composition of Pliocene and Quaternary alkali basalts of the Patagonian Plateau lavas of southernmost South America

    USGS Publications Warehouse

    Stern, C.R.; Frey, F.A.; Futa, K.; Zartman, R.E.; Peng, Z.; Kurtis, Kyser T.

    1990-01-01

    The Pliocene and Quaternary Patagonian alkali basalts of southernmost South America can be divided into two groups. The "cratonic" basalts erupted in areas of Cenozoic plateau volcanism and continental sedimentation and show considerable variation in 87Sr/86Sr (0.70316 to 0.70512), 143Nd/144Nd (e{open}Nd) and 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios (18.26 to 19.38, 15.53 to 15.68, and 38.30 to 39.23, respectively). These isotopic values are within the range of oceanic island basalts, as are the Ba/La, Ba/Nb, La/Nb, K/Rb, and Cs/Rb ratios of the "cratonic" basalts. In contrast, the "transitional" basalts, erupted along the western edge of the outcrop belt of the Pliocene and Quaternary plateau lavas in areas that were the locus of earlier Cenozoic Andean orogenic arc colcanism, have a much more restricted range of isotopic composition which can be approximated by 87Sr/86Sr=0.7039??0.0004, e{open}Nd, 206Pb/204Pb=18.60??0.08, 207Pb/204Pb=15.60??0.01, and 208Pb/204Pb=38.50??0.10. These isotopic values are similar to those of Andean orogenic are basalts and, compared to the "cratonic" basalts, are displaced to higher 87Sr/86Sr at a given 143Nd/144Nd and to higher 207Pb/204Pb at a given 208Pb/204Pb. The "transitional" basalts also have Ba/La, Ba/Nb, La/Nb, and Cs/Rb ratios higher than the "cratonic" and oceanic island basalts, although not as high as Andean orogenic are basalts. In contrast to the radiogenic isotopes, ??18O values for both groups of the Patagonian alkali basalts are indistinguishable and are more restricted than the range reported for Andean orogenic are basalts. Whole rock ??18O values calculated from mineral separates for both groups range from 5.3 to 6.5, while measured whole rock ??18O values range from 5.1 to 7.8. The trace element and isotopic data suggest that decreasing degrees of partial melting in association with lessened significance of subducted slabderived components are fundamental factors in the west to east transition from arc

  1. Determination of 238u/235u, 236u/238u and uranium concentration in urine using sf-icp-ms and mc-icp-ms: an interlaboratory comparison.

    PubMed

    Parrish, Randall R; Thirlwall, Matthew F; Pickford, Chris; Horstwood, Matthew; Gerdes, Axel; Anderson, James; Coggon, David

    2006-02-01

    Accidental exposure to depleted or enriched uranium may occur in a variety of circumstances. There is a need to quantify such exposure, with the possibility that the testing may post-date exposure by months or years. Therefore, it is important to develop a very sensitive test to measure precisely the isotopic composition of uranium in urine at low levels of concentration. The results of an interlaboratory comparison using sector field (SF)-inductively coupled plasma-mass spectrometry (ICP-MS) and multiple collector (MC)-ICP-MS for the measurement of uranium concentration and U/U and U/U isotopic ratios of human urine samples are presented. Three urine samples were verified to contain uranium at 1-5 ng L and shown to have natural uranium isotopic composition. Portions of these urine batches were doped with depleted uranium (DU) containing small quantities of U, and the solutions were split into 100 mL and 400 mL aliquots that were subsequently measured blind by three laboratories. All methods investigated were able to measure accurately U/U with precisions of approximately 0.5% to approximately 4%, but only selected MC-ICP-MS methods were capable of consistently analyzing U/U to reasonable precision at the approximately 20 fg L level of U abundance. Isotope dilution using a U tracer demonstrates the ability to measure concentrations to better than +/-4% with the MC-ICP-MS method, though sample heterogeneity in urine samples was shown to be problematic in some cases. MC-ICP-MS outperformed SF-ICP-MS methods, as was expected. The MC-ICP-MS methodology described is capable of measuring to approximately 1% precision the U/U of any sample of human urine over the entire range of uranium abundance down to <1 ng L, and detecting very small amounts of DU contained therein.

  2. Anthropogenic versus natural control on trace element and Sr-Nd-Pb isotope stratigraphy in peat sediments of southeast Florida (USA), ˜1500 AD to present

    NASA Astrophysics Data System (ADS)

    Kamenov, George D.; Brenner, Mark; Tucker, Jaimie L.

    2009-06-01

    is oil combustion. The decline in V accumulation after 1970 in the BCM peat corresponds to the introduction of low-sulfur fuels and the change from heavy to distilled oils since the 1970s. After the 1920s, Pb distribution in the peat follows closely the history of alkyl lead consumption in the US, which peaked in the 1970s. Pb isotopes support this inference and furthermore, record changes in the ore sources used to produce leaded gasoline. Idaho ores dominated the peat Pb isotope record until the 1960s, followed by Pb from Mississippi Valley Type deposits from the 1960s to the 1980s. Enhanced fluxes of Cu, Zn, Cd, Sn, Sb, Bi, and to some extent Ni during the last century are likely also related to fossil fuel combustion. Local agricultural activities may also have influenced the geochemical cycles of Cu and Zn. The peat record shows enhanced U accumulation during the last century, possibly related to phosphate mining in western Florida. Sr isotopes in the peat core also reflect anthropogenic influence. The 87Sr/ 86Sr ratio decreases from natural background values in the basal part of the core to lower values in the upper part of the core. The Sr isotope shift is probably related to quarrying operations in Florida, and marks the first time an anthropogenic signal has been detected using the Sr isotope record in a peat core.

  3. Signatures of mountain building: Detrital zircon U/Pb ages from northeast Tibet

    USGS Publications Warehouse

    Lease, Richard O.; Burbank, Douglas W.; Gehrels, George E.; Wang, Zhicai; Yuan, Daoyang

    2007-01-01

    Although detrital zircon has proven to be a powerful tool for determining provenance, past work has focused primarily on delimiting regional source terranes. Here we explore the limits of spatial resolution and stratigraphic sensitivity of detrital zircon in ascertaining provenance, and we demonstrate its ability to detect source changes for terranes separated by only a few tens of kilometers. For such an analysis to succeed for a given mountain, discrete intrarange source terranes must have unique U/Pb zircon age signatures and sediments eroded from the range must have well-defined depositional ages. Here we use ∼1400 single-grain U/Pb zircon ages from northeastern Tibet to identify and analyze an area that satisfies these conditions. This analysis shows that the edges of intermontane basins are stratigraphically sensitive to discrete, punctuated changes in local source terranes. By tracking eroding rock units chronologically through the stratigraphic record, this sensitivity permits the detection of the differential rock uplift and progressive erosion that began ca. 8 Ma in the Laji Shan, a 10-25-km-wide range in northeastern Tibet with a unique U/Pb age signature.

  4. Odorant Screening and Quantitation of Thiols in Carmenere Red Wine by Gas Chromatography-Olfactometry and Stable Isotope Dilution Assays.

    PubMed

    Pavez, Carolina; Agosin, Eduardo; Steinhaus, Martin

    2016-05-04

    The sensory impact of thiols in Vitis vinifera 'Carmenere' red wines was evaluated. For this purpose, aroma extract dilution analysis was applied to the thiols isolated from a Carmenere red wine by affinity chromatography with a mercurated agarose gel. Results revealed the presence of four odorants, identified as 2-furanylmethanethiol, 3-sulfanylhexyl acetate, 3-sulfanyl-1-hexanol, and 2-methyl-3-sulfanyl-1-butanol, with the latter being described here for the first time in Carmenere red wines. Quantitation of the four thiols in the Carmenere wine screened by aroma extract dilution analysis and in three additional Carmenere wines by stable isotope dilution assays resulted in concentrations above the respective orthonasal odor detection threshold values. Triangle tests applied to wine model solutions with and without the addition of the four thiols showed significant differences, thus suggesting that the compounds do have the potential to influence the overall aroma of red wine.

  5. Problems of geological and isotopic age of the Okhotsk-Chukotsk Volcanogenic Belt (OCVB)

    NASA Astrophysics Data System (ADS)

    Belyi, V. F.

    2008-12-01

    The working stratigraphic chart accepted for the Okhotsk-Chukotsk Volcanogenic Belt (OCVB) at the 3rd Interdepartmental Regional Stratigraphic Conference (IRSC) integrated data of the medium-scale geological survey, the established succession of endemic floras of the developing volcanic highland, and the results of palynological and magnetostratigraphic study ( Resolutions of the 3rd…, 2003). The OCVB was formed during the middle Albian-Santonian (and initial Campanian probably). Sequences of the belt are attributed to the Buor-Kemyus (early-middle Albian), Arman (late Albian), Amka (Cenomanian), and Arkagala (Turonian-Santonian) phytostratigraphic horizons. The lack of data on relations between the horizons and fauna-bearing marine deposits is a serious obstacle for correlation of regional subdivisions with the general stratigraphic scale. The problem can be solved using geological methods of palynological and tephrochronological research. Isotopic ages of the OCVB rocks were determined applying the K-Ar and Rb-Sr isotopic dating in the early period and the Ar-Ar and U-Pb (SHRIMP) methods in recent years. The subdivision scheme of the OCVB volcanics based on the K-Ar relict and Rb-Sr isochron dates, which is accepted as addendum to the working stratigraphic chart, confirms in general the geological inferences concerning the OCVB age. The Ar-Ar and U-Pb dates (less than 100 determinations in total) obtained for the Okhotsk, Central Chukotsk, and Anadyr sectors of the OCVB external zone provoked opinions that the belt age should be radically revised. Analysis of new isotopic dates showed that they contradict in variable extent to geological data on the Okhotsk and Central Chukotsk sectors, whereas there is no significant discordance between isotopic and geological data on the Anadyr sector. Consequently, it can be empirically concluded that geological factors influenced the isotopic systems (“clock”). There is also a considerable discordance between the Ar

  6. Isotope age of the rare metal pegmatite formation in the Kolmozero-Voron'ya greenstone belt (Kola region of the Fennoscandian shield): U-Pb (TIMS) microlite and tourmaline dating

    NASA Astrophysics Data System (ADS)

    Kudryashov, Nikolay; Lyalina, Ludmila; Mokrushin, Artem; Zozulya, Dmitry; Groshev, Nikolay; Steshenko, Ekaterina; Kunakkuzin, Evgeniy

    2016-04-01

    The Kolmozero-Voron'ya greenstone belt is located in the central suture zone, which separates the Murmansk block from the Central-Kola and the Keivy blocks. The belt is represented by volcano-sedimentary rocks of Archaean age of 2.9-2.5 Ga. Rare metal pegmatites (Li, Cs with accessory Nb, Ta, and Be) occur among amphibolite and gabbroid intrusions in the northwestern and southeastern parts of the belt. According to the Rb-Sr data, the age of pegmatites was considered to be 2.7 Ga. Until recently there was no generally accepted point of view on the origin of pegmatites. Now we have isotopic data for a range of rock complexes that could pretend to be parental granites for the rare metal pegmatites. These are granodiorites with the zircon age of 2733±Ma, and microcline and tourmaline granites, which Pb-Pb isochronal age on tourmaline from the tourmaline granite located near the deposit is estimated to be 2520±70 Ma. The pegmatite field of the Vasin Myl'k deposit with the lepidolite--albite--microcline--spodumene--pollucite association is located among amphibolites in the northwestern part of the belt. The deposit is represented by subparallel low-angle zoned veins up to 220 m long and 5 m thick dipping in the southeastern direction at an angle of 10° too 30°. The minerals of the columbite--tonalite group from Vasin Myl'k deposit include microlite, simpsonite, and torolite, and are the oldest among different minerals represented by several generations in pegmatites under consideration. Zircons from the pegmatites are mostly represented by crystals with the structure affected by the action of fluids that put certain restrictions on its use as a geochronometer of the crystallization process. Microlite from the pegmatite taken from the dump of a prospecting drill hole was used for U--Pb (TIMS). The mineral is represented by 0.5--1.0 mm long euhedral octahedral crystals. It is brown in color, and transparent. The microlite crystals were preliminarily cleaned from

  7. Precise and accurate in situ Pb-Pb dating of apatite, monazite, and sphene by laser ablation multiple-collector ICP-MS

    NASA Astrophysics Data System (ADS)

    Willigers, B. J. A.; Baker, J. A.; Krogstad, E. J.; Peate, D. W.

    2002-03-01

    To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the 204Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (≪1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ

  8. Apatite U-Pb thermochronolgy applied to complex geological settings - insights from geo/thermochronology and geochemistry

    NASA Astrophysics Data System (ADS)

    Paul, Andre; Spikings, Richard; Ulyanov, Alexey; Chew, David

    2016-04-01

    Application of high temperature (>350oC) thermochronology is limited to the U-Pb system of accessory minerals, such as apatite, under the assumption that radiogenic lead is lost to thermally activated volume diffusion into an infinite reservoir. Cochrane et al. (2015) have demonstrated a working example from the northern Andes of South America. Predictions from volume diffusion theory were compared with measured single grain U-Pb date correlated to shortest diffusion radius and in-situ profiles measured by LA-ICP-MS. Results from both techniques were found to be in agreement with predictions from thermally activated, volume diffusion. However, outliers from the ID-TIMS data suggested some complexity, as grains were found to be too young relative to their diffusion radius. Interaction of multiple processes can be responsible for the alteration of apatite U-Pb dates such as: (1) metamorphic (over)growth, (2) fluid aided alteration/recrystallization and (3) metamictization and fracturing of the grain. Further, predictions from volume diffusion rely on the input parameters: (a) diffusivity, (b) activation energy and (c) shortest diffusion radius. Diffusivity and activation energy are potentially influenced by the chemical composition and subsequent changes in crystal structure. Currently there is one value for diffusion parameter and activation energy established for (Durango) apatite (Cherniak et al., 1991). Correlation between diffusivity/activation energy and composition has not been established. We investigate if correlations exist between diffusivity/activation energy and composition by obtaining single grain apatite U-Pb date and chemical compostion and correlating these to their diffusion radius. We test the consistency of apatite closure temperature, by comparing the apatite U-Pb dates with lower temperature thermochronometers such as white mica and K-feldspar Ar/Ar and by petrographic observations. We test if chemical information can be a proxy to identify

  9. SrNdPb isotopic and trace element evidence for crustal contamination of plume-derived flood basalts: Oligocene flood volcanism in western Yemen

    NASA Astrophysics Data System (ADS)

    Baker, J. A.; Thirlwall, M. F.; Menzies, M. A.

    1996-07-01

    Oligocene flood basalts from western Yemen have a relatively limited range in initial isotopic composition compared with other continental flood basalts: 87Sr/86Sr = 0.70365-0.70555 ; 143Nd/144Nd = 0.5129-0.51248 ( ɛNd = +6.0 to -2.4) ; 206pb/204Pb = 17.9-19.3 . Most compositions lie outside the isotopic ranges of temporally and spatially appropriate mantle source compositions observed in this area, i.e., Red Sea/Gulf of Aden MORB mantle, the Afar plume, and Pan-African lithospheric mantle Correlations between indices of fractionation, silica, and isotope ratios suggest that crustal contamination has substantially modified the primary isotopic and incompatible trace element characteristics of the flood basalts. However, significant scatter in these correlations was produced by: (a) the heterogeneous isotopic composition of Pan-African crust; (b) the difference in susceptibility of magmas to contamination as a result of variable incompatible trace element contents in primary melts produced by differing degrees of partial melting; (c) the presence or absence of plagioclase as a fractionating phase generating complex contamination trajectories for Sr; (d) sampling over a wide area not representing a single coherent magmatic system; and (e) variation in contamination mechanisms from assimilation associated with fractionation (AFC) to assimilation by hot mafic magmas with little concomitant fractionation. The presence of plagioclase as a fractionating phase in some suites that were undergoing AFC requires assimilation to have taken place within the crust and, coupled with the limited LREE-enrichment accompanying isotopic variations, excludes the possibility that an AFC-type process took place during magma transfer through the lithospheric mantle. Isotopic compositions of some of the inferred crustal assimilants are similar to those postulated by other workers for an enriched lithospheric mantle source of many flood basalts in southwestern Yemen, Ethiopia, and Djibouti

  10. Analysis of hydrazine in drinking water by isotope dilution gas chromatography/tandem mass spectrometry with derivatization and liquid-liquid extraction.

    PubMed

    Davis, William E; Li, Yongtao

    2008-07-15

    A new isotope dilution gas chromatography/chemical ionization/tandem mass spectrometric method was developed for the analysis of carcinogenic hydrazine in drinking water. The sample preparation was performed by using the optimized derivatization and multiple liquid-liquid extraction techniques. Using the direct aqueous-phase derivatization with acetone, hydrazine and isotopically labeled hydrazine-(15)N2 used as the surrogate standard formed acetone azine and acetone azine-(15)N2, respectively. These derivatives were then extracted with dichloromethane. Prior to analysis using methanol as the chemical ionization reagent gas, the extract was dried with anhydrous sodium sulfate, concentrated through evaporation, and then fortified with isotopically labeled N-nitrosodimethylamine-d6 used as the internal standard to quantify the extracted acetone azine-(15)N2. The extracted acetone azine was quantified against the extracted acetone azine-(15)N2. The isotope dilution standard calibration curve resulted in a linear regression correlation coefficient (R) of 0.999. The obtained method detection limit was 0.70 ng/L for hydrazine in reagent water samples, fortified at a concentration of 1.0 ng/L. For reagent water samples fortified at a concentration of 20.0 ng/L, the mean recoveries were 102% with a relative standard deviation of 13.7% for hydrazine and 106% with a relative standard deviation of 12.5% for hydrazine-(15)N2. Hydrazine at 0.5-2.6 ng/L was detected in 7 out of 13 chloraminated drinking water samples but was not detected in the rest of the chloraminated drinking water samples and the studied chlorinated drinking water sample.

  11. Stable isotope dilution microquantification of creatine metabolites in plasma, whole blood and dried blood spots for pharmacological studies in mouse models of creatine deficiency.

    PubMed

    Tran, C; Yazdanpanah, M; Kyriakopoulou, L; Levandovskiy, V; Zahid, H; Naufer, A; Isbrandt, D; Schulze, A

    2014-09-25

    To develop an accurate stable isotope dilution assay for simultaneous quantification of creatine metabolites ornithine, arginine, creatine, creatinine, and guanidinoacetate in very small blood sample volumes to study creatine metabolism in mice. Liquid-chromatography (C18) tandem mass spectrometry with butylation was performed in positive ionization mode. Stable isotope dilution assay with external calibration was applied to three different specimen types, plasma, whole blood and dried blood spot (DBS). Analytical separation, sensitivity, accuracy, and linearity of the assay were adequate. The stable isotope dilution assay in plasma revealed no significant bias to gold standard methods for the respective analytes. Compared to plasma, we observed an overestimate of creatine and creatinine (2- to 5-fold and 1.2- to 2-fold, respectively) in whole-blood and DBS, and an underestimate of arginine (2.5-fold) in DBS. Validation of the assay in mouse models of creatine deficiency revealed plasma creatine metabolite pattern in good accordance with those observed in human GAMT and AGAT deficiency. Single dose intraperitoneal application of ornithine in wild-type mice lead to fast ornithine uptake (Tmax ≤ 10 min) and elimination (T1/2=24 min), and a decline of guanidinoacetate. The assay is fast and reliable to study creatine metabolism and pharmacokinetics in mouse models of creatine deficiency. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Trace- and rare-earth element geochemistry and Pb-Pb dating of black shales and intercalated Ni-Mo-PGE-Au sulfide ores in Lower Cambrian strata, Yangtze Platform, South China

    NASA Astrophysics Data System (ADS)

    Jiang, Shao-Yong; Chen, Yong-Quan; Ling, Hong-Fei; Yang, Jing-Hong; Feng, Hong-Zhen; Ni, Pei

    2006-08-01

    The Lower Cambrian black shale sequence of the Niutitang Formation in the Yangtze Platform, South China, hosts an extreme metal-enriched sulfide ore bed that shows >10,000 times enrichment in Mo, Ni, Se, Re, Os, As, Hg, and Sb and >1,000 times enrichment in Ag, Au, Pt, and Pd, when compared to average upper continental crust. We report in this paper trace- and rare-earth-element concentrations and Pb-Pb isotope dating for the Ni-Mo-PGE-Au sulfide ores and their host black shales. Both the sulfide ores and their host black shales show similar trace-element distribution patterns with pronounced depletion in Th, Nb, Hf, Zr, and Ti, and extreme enrichment in U, Ni, Mo, and V compared to average upper crust. The high-field-strength elements, such as Zr, Hf, Nb, Ta, Sc, Th, rare-earth elements, Rb, and Ga, show significant inter-element correlations and may have been derived mainly from terrigenous sources. The redox sensitive elements, such as V, Ni, Mo, U, and Mn; base metals, such as Cu, Zn, and Pb; and Sr and Ba may have been derived from mixing of seawater and venting hydrothermal sources. The chondrite-normalized REE patterns, positive Eu and Y anomalies, and high Y/Ho ratios for the Ni-Mo-PGE-Au sulfide ores are also suggestive for their submarine hydrothermal-exhalative origin. A stepwise acid-leaching Pb-Pb isotope analytical technique has been employed for the Niutitang black shales and the Ni-Mo-PGE-Au sulfide ores, and two Pb-Pb isochron ages have been obtained for the black shales (531±24 Ma) and for the Ni-Mo-PGE-Au sulfide ores (521±54 Ma), respectively, which are identical and overlap within uncertainty, and are in good agreement with previously obtained ages for presumed age-equivalent strata.

  13. The geochemical and Sr-Nd-Pb-He isotopic characterization of the mantle source of Rungwe Volcanic Province: comparison with the Afar mantle domain

    NASA Astrophysics Data System (ADS)

    Castillo, P. R.; Hilton, D. R.; Halldorsson, S. A.; Wang, R.

    2012-12-01

    The ultimate source of heat and magmatism associated with continental rifting in the East African Rift System (EARS) is generally viewed to be the African Superplume, but there is continuing debate on the surface expression of this large anomalous feature, which originates in the lower mantle. Previous studies have demonstrated an insignificant role for crustal contamination thereby identifying a single mantle plume signature in Quaternary basalts from the Main Ethiopian Rift in the northern EARS. This is designated to be the Afar plume and is characterized by, e.g., 3He/4He >15 RA, 206Pb/204Pb = 19.5 and 87Sr/86Sr = 0.7035 [Rooney et al., J. Pet. 53, 2012]. In contrast, the signature of plume(s) in the southern EARS is less constrained. Rogers et al. [EPSL 176, 2000] proposed a plume in the sub-lithospheric Kenyan mantle with characteristically lower 43Nd/144Nd than the Afar plume whereas Furman [JAES 48, 2007] advocated a high μ [HIMU] plume based primarily on the high 206Pb/204Pb ratios of lavas in all areas within and south of the Turkana Depression: both models assume a 3He/4He lower than the Afar plume. Here we report the trace element and Sr-Nd-Pb isotopic composition of basaltic lavas from the Rungwe Volcanic Province (RVP) in the southern extreme of the Western Rift previously identified as a high 3He/4He locality (~15 RA; [Hilton et al., GRL 38, 2011]). Trace element analyses are within the previously reported range of lava compositions that include a relatively large lithospheric component. More importantly, we identify correlations among incompatible trace element and isotopic ratios (e.g., 3He/4He vs 206Pb/204Pb, Rb/Sr, Nb/Ta; 87Sr/86Sr vs 208Pb/204Pb). Our new results suggest the presence of a distinct, high 3He/4He mantle source beneath RVP that is more radiogenic (e.g., 206Pb/204Pb up to ~19.8; 87Sr/86Sr up to 0.7055) than the Afar mantle plume. There is also very little or no HIMU signature in RPV basalts based on their high Sr and low Nd isotopic

  14. A salt diapir-related Mississippi Valley-type deposit: the Bou Jaber Pb-Zn-Ba-F deposit, Tunisia: fluid inclusion and isotope study

    NASA Astrophysics Data System (ADS)

    Bouhlel, Salah; Leach, David L.; Johnson, Craig A.; Marsh, Erin; Salmi-Laouar, Sihem; Banks, David A.

    2016-08-01

    evaporation of seawater to halite saturation and requires a dilution of more than two times by meteoric water. The higher K/Na values in fluid inclusions from barite suggest that the brines interacted with K-rich rocks in the basement or siliciclastic sediments in the basin. Carbonate gangue minerals (ankerite and calcite) have δ13C and δ18O values that are close to the carbonate host rock and indicate fluid equilibrium between carbonate host rocks and hydrothermal brines. The δ34S values for sphalerite and galena fall within a narrow range (1 to 10 ‰) with a bulk value of 7.5 ‰, indicating a homogeneous source of sulfur. The δ34S values of barite are also relatively homogeneous (22 ‰), with 6 ‰ higher than the δ34S of local and regional Triassic evaporites (15 ‰). The latter are believed to be the source of sulfate. Temperature of deposition together with sulfur isotope data indicate that the reduced sulfur in sulfides was derived through thermochemical sulfate reduction of Triassic sulfate via hydrocarbons produced probably from Late Cretaceous source rocks. The 87Sr/86Sr ratio in the Bou Jaber barite (0.709821 to 0.711408) together with the lead isotope values of Bou Jaber galena (206Pb/204Pb = 18.699 to 18.737; 207Pb/204Pb = 15.635 to 15.708 and 208Pb/204Pb = 38.321 to 38.947) show that metals were extracted from homogeneous crustal source(s). The tectonic setting of the Bou Jaber ore deposit, the carbonate nature of the host rocks, the epigenetic style of the mineralization and the mineral associations, together with sulfur and oxygen isotope data and fluid inclusion data show that the Bou Jaber lead-zinc mineralization has the major characteristics of a salt diapir-related Mississippi Valley-type (MVT) deposit with superimposed events of fluorite and of barite deposition. Field relations are consistent with mineral deposition during the Eocene-Miocene Alpine orogeny from multiple hydrothermal events: (1) Zn-Pb sulfides formed by mixing of two fluids: one

  15. Did the Kiruna iron ores form as a result of a metasomatic or igneous process? New U-Pb and Nd data for the iron oxide apatite ores and their host rocks in the Norrbotten region of northern Sweden

    NASA Astrophysics Data System (ADS)

    Westhues, A.; Hanchar, J. M.; Whitehouse, M. J.; Fisher, C. M.

    2012-12-01

    A number of iron deposits near Kiruna in the Norrbotten region of northern Sweden are of the iron oxide apatite (IOA) type of deposits; also referred to as Kiruna-type deposits. They are commonly considered a subgroup or end-member of iron oxide copper gold (IOCG) deposits, containing no economic grades of copper or gold. Both IOCG and IOA deposits are characterized by abundant low-Ti Fe oxides, an enrichment in REE, and intense sodium and potassium wall-rock alteration adjacent to the ores. Deposits of these types are of a great economic importance, not only for iron, but also for other elements such as rare earth elements (REE) or uranium. Kiruna, the type locality of the IOA type of mineral deposits, is the focus of this study. Despite a century-long mining history and 2500 Mt of iron ore produced in the region to date (with grades of 30 to 70 wt.% Fe), the genesis of these deposits is poorly understood: theories of a magmatic vs. a hydrothermal or metasomatic origin have been debated, and the timing of mineralization of the ores in the Norbotten region has never been directly dated. The results anticipated from this study will provide a better understanding of the nature of the IOA type of mineral deposits and their relation to IOCG deposits such as Olympic Dam in Australia. An array of geochemical methods is used in order to gain insights on the emplacement history of the host rocks, their subsequent alteration, and the ore genesis of these deposits. This includes in situ U/Pb geochronology of zircon, monazite, and titanite to constrain the timing between host rock emplacement, alteration and mineralization. Isotopic data from whole rocks and in situ at mineral scale will provide constraints on the involvement of hydrothermal fluids and their possible sources, as well as on the sources of Fe, U, and the REE. Newly obtained Sm-Nd isotopic data points to distinct source differences between host rocks, ore and alteration related samples. Preliminary in situ U-Pb

  16. Isotopic and geochemical tracers for U(VI) reduction and U mobility at an in situ recovery U mine

    DOE PAGES

    Basu, Anirban; Brown, Shaun T.; Christensen, John N.; ...

    2015-05-19

    In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Post-mining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers ²³⁸U/²³⁵U (δ²³⁸U), ²³⁴U/²³⁸U activity ratio, and ³⁴S/³²S (δ³⁴S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility atmore » an ISR mining site at Rosita, TX, USA. The δ²³⁸U in Rosita groundwater varies from 0.61‰ to -2.49‰, with a trend toward lower δ²³⁸U in downgradient wells. The concurrent decrease in U(VI) concentration and δ²³⁸U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic ²³⁴U/²³⁸U activity ratio and δ³⁴S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.« less

  17. Isotopic and geochemical tracers for U(VI) reduction and U mobility at an in situ recovery U mine

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

    Basu, Anirban; Brown, Shaun T.; Christensen, John N.

    In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Post-mining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers ²³⁸U/²³⁵U (δ²³⁸U), ²³⁴U/²³⁸U activity ratio, and ³⁴S/³²S (δ³⁴S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility atmore » an ISR mining site at Rosita, TX, USA. The δ²³⁸U in Rosita groundwater varies from 0.61‰ to -2.49‰, with a trend toward lower δ²³⁸U in downgradient wells. The concurrent decrease in U(VI) concentration and δ²³⁸U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic ²³⁴U/²³⁸U activity ratio and δ³⁴S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.« less

  18. Provenance of Modern Soils and Limestone and Chert Bedrock of Middle Tennessee Assessed Using Detrital Zircon U-Pb Geochronology

    NASA Astrophysics Data System (ADS)

    Ayers, J. C.; Katsiaficas, N. J.; Wang, X.

    2014-12-01

    Relatively thick soils mantle limestone bedrock throughout much of middle TN. Detrital zircon U-Pb geochronology was used to test two hypotheses: 1) That soil formed by accumulation of insoluble residue during chemical weathering of "dirty" limestone bedrock. 2) That an exotic component, perhaps wind-blown loess, was deposited and weathered to form soil. Samples of soil and underlying bedrock were collected from flat surfaces at the tops of cliffs. At Site 1 the Mississippian cherty limestone of the Fort Payne Formation was collected along with the B1 and B2 horizons of the overlying ultisol. At Site 2 a composite sample of A and B horizons of an alfisol and a sample of the underlying Ordovician limestone of the Hermitage Formation were collected. Zircon was recovered from soil and limestone samples, imaged using cathodoluminescence, and analyzed for trace elements and U-Pb isotopes using a 193 nm laser and quadrupole ICP-MS. Discordant analyses were discarded and 206Pb/238U ages are reported. Trace element concentrations and ratios in zircon seem to not be useful as provenance indicators. However, comparison of U-Pb age spectra showed that soils at both sites predominantly formed by weathering of limestone, with a small exotic component. The Hermitage has significant age peaks at ~1330, 1043, 955 and 439 Ma, and its overlying soil has age peaks at 1410, 1235, 1036 and 442 Ma. The age spectra are significantly different (Kolmogorov-Smirnov probability P = 0.01 < 0.05 significance). The Fort Payne has age peaks at ~1253, 967 and 417 Ma, while the B1 has age peaks at 1440, 1182, 1012 and 450 Ma (K-S P = 0.051) and the B2 at 1240, 941, 362, 81 and 33 Ma (K-S P = 0.073). The young ages in B2 require an exotic component that may account for ~25% of the measured ages. The source of the exotic material has not yet been identified, but its zircon age spectrum does not match previously published age spectra for the regional Pleistocene Peoria loess. Bedrock age peaks

  19. Transport and magnetic properties of dilute rare-earth-PbSe alloys

    NASA Astrophysics Data System (ADS)

    Jovovic, V.; Joottu-Thiagarajan, S.; West, J.; Heremans, J. P.; Story, T.; Golacki, Z.; Paszkowicz, W.; Osinniy, V.

    2007-03-01

    An increase in the density of states is predicted [1] to increase the thermoelectric (TE) figure of merit, and could be induced by doping TE materials with rare-earth elements. This was attempted here: the galvanomagnetic and thermomagnetic properties of dilute alloys of PbSe and Ce, Pr, Nd, Eu, Gd and Yb were measured from 80 to 380K; magnetic susceptibilities were measured from 4 to 120K. The density of states effective mass, the relaxation time, and the carrier density and mobility are calculated from measurements of the electrical conductivity and the Hall, Seebeck and transverse Nernst-Ettingshausen coefficients. The Eu, Gd, Nd and Yb-alloyed samples are paramagnetic; the concentrations of rare-earth atoms are determined from fitting a Curie-Weiss law. The magnetic behavior of the Ce and Pr-alloyed samples is different. Ce, Pr, Nd, Gd and Yb act as donors with efficiencies that will be reported. Alloying with divalent Eu does not affect carrier density but increases the energy gap. This work suggests that the 4f orbitals preserve their atomic-like localized character and exhibit only weak sp-f hybridization. 1 G. D. Mahan and J. O. Sofo, Proc. Natl. Acad. Sci. USA 93 7436 (1996)

  20. 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.

  1. Nd and Pb isotopic Mediterranean overflow water signature in the Gulf of Cadiz over the Mio-Pliocene boundary.

    NASA Astrophysics Data System (ADS)

    van der Schee, Marlies; Gutjahr, Marcus; Sierro, Francisco Javier; Flecker, Rachel; Jiménez Espejo, Francisco; Hodell, David; Abel Flores, Jose

    2014-05-01

    Marine gateways play a major role in ocean circulation and therefore climate. Currently, it is thought that there was no significant Mediterranean Overflow Water (MOW) in the Gulf of Cadiz during the Messinian Salinity Crisis (MSC) in the Late Miocene. However, a connection has supplied the Mediterranean with enough salt to precipitate the extensive evaporates preserved across the basin. After the MSC, the Mediterranean overflow was re-established through the Straits of Gibraltar. Today, MOW follows the continental slope of the Iberian Peninsula at a depth of 500-800 m in the Gulf of Cadiz northwards. In this study, lead and neodymium isotopes are used as water mass tracers for Mio-Pliocene MOW and NE Atlantic water in the Gulf of Cadiz. Complementary biostratigraphic data, carbon and oxygen isotopes and trace elements are presented alongside to corroborate our findings. Here we present a detailed authigenic Fe-Mn oxyhydroxide-derived Pb and Nd isotope records extracted from ~5.85 - 4.0 million year old bulk sediments recovered in IODP Core U1387C in the Gulf of Cadiz (current water depth 559 m). MOW and NE Atlantic waters have different Nd and Pb isotopic characteristics allowing for the identification of bottom water mass provenance changes and mixing proportions at the core site. The properties of the water bodies during the given time period are defined by Fe-Mn crust and marine sediment signatures. We also examine the natural variability within a single precession cycle. In order to confirm that the bulk sediment data indeed reliably reflects the primary composition of the bottom water masses, several bulk sediment samples are compared to foraminifera-derived Nd isotopic compositions. Results from the Messinian show a trend from isotope compositions that are more typical for MOW towards compositions more typical for the NE Atlantic. Subsequently, this trend reverses. After this, around 5.6 Ma an abrupt shift from MOW to more NE Atlantic characteristics is

  2. Plume versus plate origin for the Shatsky Rise oceanic plateau (NW Pacific): Insights from Nd, Pb and Hf isotopes

    NASA Astrophysics Data System (ADS)

    Heydolph, Ken; Murphy, David T.; Geldmacher, Jörg; Romanova, Irina V.; Greene, Andrew; Hoernle, Kaj; Weis, Dominique; Mahoney, John

    2014-07-01

    Shatsky Rise, an early Cretaceous igneous oceanic plateau in the NW Pacific, comprises characteristics that could be attributed to either formation by shallow, plate tectonic-controlled processes or to an origin by a mantle plume (head). The plateau was drilled during Integrated Ocean Drilling Program (IODP) Expedition 324. Complementary to a recent trace element study (Sano et al., 2012) this work presents Nd, Pb and Hf isotope data of recovered lava samples cored from the three major volcanic edifices of the Shatsky Rise. Whereas lavas from the oldest edifice yield fairly uniform compositions, a wider isotopic spread is found for lavas erupted on the younger parts of the plateau, suggesting that the Shatsky magma source became more heterogeneous with time. At least three isotopically distinct components can be identified in the magma source: 1) a volumetrically and spatially most common, moderately depleted component of similar composition to modern East Pacific Ridge basalt but with low 3He/4He, 2) an isotopically very depleted component which could represent local, early Cretaceous (entrained) depleted upper mantle, and 3) an isotopically enriched component, indicating the presence of (recycled) continental material in the magma source. The majority of analyzed Shatsky lavas, however, possess Nd-Hf-Pb isotope compositions consistent with a derivation from an early depleted, non-chondritic reservoir. By comparing these results with petrological and trace element data of mafic volcanic rock samples from all three massifs (Tamu, Ori, Shirshov), we discuss the origin of Shatsky Rise magmatism and evaluate the possible involvement of a mantle plume (head).

  3. Liquid chromatography/electrospray ionization/isotopic dilution mass spectrometry analysis of n-(phosphonomethyl) glycine and mass spectrometry analysis of aminomethyl phosphonic acid in environmental water and vegetation matrixes.

    PubMed

    Grey, L; Nguyen, B; Yang, P

    2001-01-01

    A liquid chromatography/electrospray/mass spectrometry (LC/ES/MS) method was developed for the analysis of glyphosate (n-phosphonomethyl glycine) and its metabolite, aminomethyl phosphonic acid (AMPA) using isotope-labelled glyphosate as a method surrogate. Optimized parameters were achieved to derivatize glyphosate and AMPA using 9-fluorenylmethyl chloroformate (FMOC-Cl) in borate buffer prior to a reversed-phase LC analysis. Method spike recovery data obtained using laboratory and real world sample matrixes indicated an excellent correlation between the recovery of the native and isotope-labelled glyphosate. Hence, the first performance-based, isotope dilution MS method with superior precision, accuracy, and data quality was developed for the analysis of glyphosate. There was, however, no observable correlation between the isotope-labelled glyphosate and AMPA. Thus, the use of this procedure for the accurate analysis of AMPA was not supported. Method detection limits established using standard U.S. Environmental Protection Agency protocol were 0.06 and 0.30 microg/L, respectively, for glyphosate and AMPA in water matrixes and 0.11 and 0.53 microg/g, respectively, in vegetation matrixes. Problems, solutions, and the method performance data related to the analysis of chlorine-treated drinking water samples are discussed. Applying this method to other environmental matrixes, e.g., soil, with minimum modifications is possible, assuring accurate, multimedia studies of glyphosate concentration in the environment and the delivery of useful multimedia information for regulatory applications.

  4. Petrogenesis of Tertiary continental intra-plate lavas between Siebengebirge and Westerwald, Germany: Constraints from trace element systematics and Nd, Sr and Pb isotopes

    NASA Astrophysics Data System (ADS)

    Schubert, S.; Jung, S.; Pfänder, J. A.; Hauff, F.; Garbe-Schönberg, D.

    2015-10-01

    New 39Ar/40Ar ages and major- and trace-element and radiogenic isotope data are presented for basanites and alkali basalts from the transition area between the Westerwald and Siebengebirge volcanic fields (Germany) that belongs to the Central European Volcanic Province (CEVP). The 39Ar/40Ar ages indicate ages of c. 24 and c. 5 Ma which are fully compatible with previous K/Ar ages indicating that the evolution of this volcanic field belongs to the Westerwald area (28-22 Ma and 5 Ma) rather than to the Siebengebirge area (26-23 Ma). Based on the occurrence of > 30 isolated volcanic plugs with a simple igneous history, this volcanic field can be viewed as a monogenetic volcanic field. Compositions of some basanites are primitive, whereas others and the alkali basalts show decreasing Cr and Ni contents and CaO/Al2O3 ratios. However, increasing TiO2, Al2O3 and incompatible elements (Sr, Zr, Y, Hf, Ta) concentrations with decreasing MgO indicating fractionation of mainly olivine with minor amounts of clinopyroxene and spinel can be noticed. Rare earth element systematics suggest that most of the alkaline rocks are generated by different degrees of melting (5%-10%) of a garnet-bearing peridotite containing some residual amphibole. Negative anomalies of Rb and K in primitive mantle-normalized diagrams and a lack of Ba/Rb fractionation suggest that amphibole was the major OH-bearing mineral phase in the mantle. The alkaline rocks have a restricted range in 87Sr/86Sr and 143Nd/144Nd ratios ranging from 0.7033 to 0.7044 and from 0.51275 to 0.51285, respectively. Lead isotope compositions (206Pb/204Pb: 19.21-19.65; 207Pb/204Pb: 15.62-15.67; 208Pb/204Pb: 39.10-39.46) of the alkaline rocks are within the range of most OIB in which the higher values approach the composition of the European Asthenospheric Reservoir (EAR). The correlation between Sr and Nd isotopes and trace element constraints (Ce/Pb; Nb/U) indicates that for some samples interaction with crustal rocks during

  5. 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

  6. Monitoring steel bridge renovation using lead isotopic tracing.

    PubMed

    Salome, Fred; Gulson, Brian; Chiaradia, Massimo; Davis, Jeffrey; Morris, Howard

    2017-05-01

    Monitoring removal of lead (Pb) paint from steel structures usually involves analysis of environmental samples for total lead and determination of blood Pb levels of employees involved in the Pb paint removal. We used high precision Pb isotopic tracing for a bridge undergoing Pb paint removal to determine if Pb in the environmental and blood samples originated from the bridge paint. The paint system on the bridge consisted of an anti-corrosive red Pb primer top-coated with a Micaceous Iron Oxide (MIO) alkyd. Analysis of the red Pb primer gave uniform isotopic ratios indicative of Pb from the geologically-ancient Broken Hill mines in western New South Wales, Australia. Likewise waste abrasive material, as anticipated, had the same isotopic composition as the paint. The isotopic ratios for other samples lay on 2 separate linear arrays on a 207 Pb/ 204 Pb versus 206 Pb/ 204 Pb diagram, one largely defined by gasoline and the majority of the ambient air data, and the other by data for one sample each of gasoline and ambient air and underwater sediments. Isotopic ratios in background ambient air samples for the project were characteristic of leaded gasoline. Air sampling during paint removal showed a contribution of paint Pb ranging from about 20 to 40%. Isotopic ratios in the blood of 8 employees prior to the commencement of work showed that 6 of these had been previously exposed to the Broken Hill Pb possibly from earlier bridge paint removal projects. One subject appeared to have increased exposure to Pb probably from the paint renovations. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. The End of Monterey Submarine Canyon Incision and Potential River Source Areas-Os, Nd, and Pb Isotope Constraints from Hydrogenetic Fe-Mn Crusts

    NASA Astrophysics Data System (ADS)

    Conrad, T. A.; Nielsen, S.; Ehrenbrink, B. P. E.; Blusztajn, J.; Hein, J. R.; Paytan, A.

    2015-12-01

    The Monterey Canyon off central California is the largest submarine canyon off North America and is comparable in scale to the Grand Canyon. The age and history of the Monterey Canyon are poorly constrained due to thick sediment cover and sediment disruption from turbidity currents. To address this deficit we analyzed isotopic proxies (Os, Pb, Nd) from hydrogenetic ferromanganese (Fe-Mn) crusts, which grow over millions of years on elevated rock surfaces by precipitation of metals from seawater. Fe-Mn crusts were studied from Davidson Seamount near the base of the Monterey submarine fan, the Taney Seamount Chain, and from Hoss Seamount, which serves as a regional control (Fig.). Fe-Mn crusts were dated using Os isotope ratios compared to those that define the Cenozoic Os isotope seawater curve. Four Fe-Mn crust samples from Davidson and Taney Seamounts deviate from the Os isotopic seawater curve towards radiogenic values after 4.5±1 Ma. Osmium is well mixed in the global ocean and is not subject to significant diffusive reequilibration in Fe-Mn crusts. We therefore attribute deviations from the Os isotope seawater curve to large-scale terrestrial input that ended about 4.5±1 Ma. The two Davidson samples also show more radiogenic Nd isotope values from about 4.5±1 Ma. Lead isotopes in one Davidson Seamount crust, measured by LA-ICPMS, deviate from regional values after 4.5±1 Ma for about 500 ka towards terrestrial sources. The Taney Seamount Fe-Mn crust does not deviate from regional Nd nor Pb isotope values due to its greater distance from Monterey Canyon and the shorter marine residence times of Nd and Pb. Isotope plots of our crust data and compiled data for potential source rocks indicate that the river that carved Monterey Canyon carried sediment with values closer to the Sierra Nevada than to a Colorado Plateau source, with cessation of major riverine input occurring approximately 4.5±1 Ma, an age that we interpret as the end of the Monterey Canyon

  8. Sr-Nd-Pb isotopic constraints on the nature of the mantle sources involved in the genesis of the high-Ti tholeiites from northern Paraná Continental Flood Basalts (Brazil)

    NASA Astrophysics Data System (ADS)

    Rocha-Júnior, Eduardo R. V.; Marques, Leila S.; Babinski, Marly; Nardy, Antônio J. R.; Figueiredo, Ana M. G.; Machado, Fábio B.

    2013-10-01

    There has been little research on geochemistry and isotopic compositions in tholeiites of the Northern region from the Paraná Continental Flood Basalts (PCFB), one of the largest continental provinces of the world. In order to examine the mantle sources involved in the high-Ti (Pitanga and Paranapanema) basalt genesis, we studied Sr, Nd, and Pb isotopic systematics, and major, minor and incompatible trace element abundances. The REE patterns of the investigated samples (Pitanga and Paranapanema magma type) are similar (parallel to) to those of Island Arc Basalts' REE patterns. The high-Ti basalts investigated in this study have initial (133 Ma) 87Sr/86Sr ratios of 0.70538-0.70642, 143Nd/144Nd of 0.51233-0.51218, 206Pb/204Pb of 17.74-18.25, 207Pb/204Pb of 15.51-15.57, and 208Pb/204Pb of 38.18-38.45. These isotopic compositions do not display any correlation with Nb/Th, Nb/La or P2O5/K2O ratios, which also reflect that these rocks were not significantly affected by low-pressure crustal contamination. The incompatible trace element ratios and Sr-Nd-Pb isotopic compositions of the PCFB tholeiites are different to those found in Tristan da Cunha ocean island rocks, showing that this plume did not play a substantial role in the PCFB genesis. This interpretation is corroborated by previously published osmium isotopic data (initial γOs values range from +1.0 to +2.0 for high-Ti basalts), which also preclude basalt generation by melting of ancient subcontinental lithospheric mantle. The geochemical composition of the northern PCFB may be explained through the involvement of fluids and/or small volume melts related to metasomatic processes. In this context, we propose that the source of these magmas is a mixture of sublithospheric peridotite veined and/or interlayered with mafic components (e.g., pyroxenites or eclogites). The sublithospheric mantle (dominating the osmium isotopic compositions) was very probably enriched by fluids and/or magmas related to the

  9. Modification of a commercial gas chromatography isotope ratio mass spectrometer for on-line carbon isotope dilution: Evaluation of its analytical characteristics for the quantification of organic compounds.

    PubMed

    Alonso Sobrado, Laura; Robledo Fernández, Mario; Cueto Díaz, Sergio; Ruiz Encinar, Jorge; García Alonso, J Ignacio

    2015-11-06

    We describe the instrumental modification of a commercial gas chromatography isotope ratio mass spectrometer (GC-IRMS) and its application for on-line carbon isotope dilution. The main modification consisted in the addition of a constant flow of enriched (13)CO2 diluted in helium after the chromatographic column through the splitter holder located inside the chromatographic oven of the instrument. In addition, and in contrast to the conventional mode of operation of GC-IRMS instruments where the signal at m/z 45 is amplified 100-fold with respect to the signal at m/z 44, the same signal amplification was used in both Faraday cups at m/z 44 and 45. Under these conditions isotope ratio precision for the ratio 44/45 was around 0.05% RSD (n=50). The evaluation of the instrument was performed with mixtures of organic compounds including 11 n-alkanes, 16 PAHs, 12 PCBs and 3 benzothiophenes. It was observed that compounds of very different boiling points could be analysed without discrimination in the injector when a Programmable Temperature Vaporizer (PTV) injector was employed. Moreover, the presence of heteroatoms (Cl or S) in the structure of the organic compounds did not affect their combustion efficiency and therefore the trueness of the results. Quantitative results obtained for all the analytes assayed were excellent in terms of precision (<3% RSD) and accuracy (average relative error≤4%) and what is more important using a single and simple generic internal standard for quantification. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Early history of the moon: Implications of U-Th-Pb and Rb-Sr systematics

    NASA Technical Reports Server (NTRS)

    Tatsumoto, M.; Numes, P. D.; Unruh, D. M.

    1977-01-01

    Anorthosite 60015 contains the lowest initial Sr-87/Sr-86 ratio yet reported for a lunar sample. The initial ratio is equal to that of the achondrite Angra dos Reis and slightly higher than the lowest measured Sr-87/Sr-86 ratio for an inclusion in the C3 carbonaceous chondrite Allende. The Pb-Pb ages of both Angra does Reis and Allende are 4.62 X 10 to the ninth power yr. Thus, the initial Sr/87/Sr-86 ratio found in lunar anorthosite 60015 strongly supports the hypothesis that the age of the Moon is about 4.65 b.y. The U-238/Pb-204 value estimated for the source of the excess lead in "orange soil" 74220 is approximately 35 and lower than the values estimated for the sources of KREEP (600-1000), high-K (300-600), and low-K (100-300) basalts. From these and other physical, chemical and petrographic results it was hypothesized that (1) the moon formed approximately 4.65 b.y. ago; (2) a global-scale gravitational differentiation occurred at the beginning of lunar history; and (3) the differentiation resulted in a radical chemical and mineralogical zoning in which the U-238/Pb-204 ratios increased toward the surface, with the exception of the low U-238/Pb-204 surficial anorthositic layer which "floated" at the beginning of the differentiation relative to the denser pyroxene-rich material.

  11. U-Pb Data On Apatites With Common Lead Correction : Exemples From The Scottish Caledonides

    NASA Astrophysics Data System (ADS)

    Jewison, E.; Deloule, E.; Villeneuve, J.; Bellahsen, N.; Labrousse, L.; Rosenberg, C.; Pik, R.; Chew, D.

    2017-12-01

    Apatite is a widely used mineral in low-temperature thermochronology (U-Th/He and AFT). The use of apatite in U-Pb geochronology has a great potential, given its closure temperature around 450°C, for orogen thermostructural evolution studies. However, since apatite can accumulate significant amount of initial Pb in its structure, its use can be hindered by the lack of 204 Pb estimations. To work around this, two options are commonly used : either use a ploting sytem that does not require corrected ratios, or use a proxy to estimate 204Pb and use it to correct the ratios. In this study we use a SIMS to mesure 204Pb in order to compare Tera-Wasserburg diagram and corrected ages to examine the cooling pattern in the northern Highlands of Scotland. The Highlands is an extensively studied caledonian collision wedge which results from the closure of the Iapétus Ocean during the Orodivician-Silurian. Two orogenic events are related to this closing, the grampian event (480-460Ma) and the scandian event (435-415 Ma) that culminated in the stacking of major ductile thrusts. The thermal history of thoses nappes are hence complex and the cooling pattern poorly constrained. Corrected apatite U-Pb ages provide new constrains on ductile wedge building and improve our understanding of mid to lower-crustal deformation and orogenic exhumation. Thoses corrected ages yield equivalent errors and mean ages from the classic method. Those data suggest a global cooling younger than previously thought and a sequence departing from a simple forward sequence. We thus present a refined thermal evolution and conceptualize a model of ductile wedge evolution.

  12. On the origin of cratonic `high-mu' isotopic signatures

    NASA Astrophysics Data System (ADS)

    Reimink, J. R.; Carlson, R.; Shirey, S. B.; Pearson, D. G.; Kamber, B. S.

    2017-12-01

    Some Archean cratons (i.e. Slave, Wyoming) contain Neoarchean granitoids with initial Pb isotopic compositions indicative of derivation from sources characterized by high time-integrated U/Pb ratios (high-mu [1]). Single-stage high-m precursor source reservoir separation from the depleted mantle occurred no later than 3.9 Ga [2]. However, multi-stage separation could have occurred in the Hadean, suggesting that recycling or reworking of Eoarchean/Hadean crust played a significant role in the generation of Neoarchean granitic crust in many cratons. The Sm-Nd system is similar to the U-Pb system in that it has a short-lived parent-daughter pair (146Sm-142Nd) that is sensitive to very early differentiation events, as well as a long-lived parent-daughter pair (147Sm-143Nd) that is sensitive to differentiation throughout all of Earth history. The 103 Ma half-life of 146Sm makes it sensitive only to Sm/Nd fractionation that occurred in the Hadean, providing a useful tracker for very early differentiation events. Indeed, evidence for Neoarchean remelting of ancient crust in another craton has come from analyses of the paired Sm-Nd isotope systems from the Hudson Bay terrane of the northeastern Superior Province. These results indicate that the source of 2.7 Ga Hudson Bay terrane granitoids was Hadean mafic crust, and not Eoarchean felsic crust [3]. Here, we present new data from Neoarchean granites located in the Slave and Wyoming cratons, along with modeling of the dual paired-isotope systems of U-Pb and Sm-Nd to achieve a tighter constraint on the composition of the precursors and the timing of their melting. Combining our newly collected 142Nd data with the high-m signature of these Neoarchean rocks, we evaluate precursor source separation ages along with the source Sm/Nd and U/Pb compositions. In the simplest end-member scenarios, use of the 142Nd system allows us to test whether the cratonic high-mu signature was created by melting of Hadean mafic crust or Eoarchean

  13. Simultaneous determination of creatinine and creatine in human serum by double-spike isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-MS).

    PubMed

    Fernández-Fernández, Mario; Rodríguez-González, Pablo; Añón Álvarez, M Elena; Rodríguez, Felix; Menéndez, Francisco V Álvarez; García Alonso, J Ignacio

    2015-04-07

    This work describes the first multiple spiking isotope dilution procedure for organic compounds using (13)C labeling. A double-spiking isotope dilution method capable of correcting and quantifying the creatine-creatinine interconversion occurring during the analytical determination of both compounds in human serum is presented. The determination of serum creatinine may be affected by the interconversion between creatine and creatinine during sample preparation or by inefficient chemical separation of those compounds by solid phase extraction (SPE). The methodology is based on the use differently labeled (13)C analogues ((13)C1-creatinine and (13)C2-creatine), the measurement of the isotopic distribution of creatine and creatinine by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and the application of multiple linear regression. Five different lyophilized serum-based controls and two certified human serum reference materials (ERM-DA252a and ERM-DA253a) were analyzed to evaluate the accuracy and precision of the proposed double-spike LC-MS/MS method. The methodology was applied to study the creatine-creatinine interconversion during LC-MS/MS and gas chromatography-mass spectrometry (GC-MS) analyses and the separation efficiency of the SPE step required in the traditional gas chromatography-isotope dilution mass spectrometry (GC-IDMS) reference methods employed for the determination of serum creatinine. The analysis of real serum samples by GC-MS showed that creatine-creatinine separation by SPE can be a nonquantitative step that may induce creatinine overestimations up to 28% in samples containing high amounts of creatine. Also, a detectable conversion of creatine into creatinine was observed during sample preparation for LC-MS/MS. The developed double-spike LC-MS/MS improves the current state of the art for the determination of creatinine in human serum by isotope dilution mass spectrometry (IDMS), because corrections are made for all the possible errors

  14. Advantages of conducting in-situ U-Pb age dating of multiple U-bearing minerals from a single complex: Case in point - the Oka Carbonatite Complex

    NASA Astrophysics Data System (ADS)

    Chen, W.; Simonetti, A.

    2012-12-01

    A detailed radiometric investigation is currently underway focusing on U-bearing accessory minerals apatite, perovskite, and niocalite from the Oka Carbonatite Complex (Canada). One of the main objectives is to obtain a comparative chronology of melt crystallization for the complex. Unlike other commonly adopted U-bearing minerals (e.g., zircon, monazite) for in-situ dating investigations, apatite, perovskite, and niocalite contain relatively high contents of common Pb. Hence, careful assessment of the proportion and composition of the common Pb, and usage of appropriate matrix-matched external standards are imperative. The Madagascar apatite was utilized as the external standard for apatite dating, and the Emerald Lake and Durango apatites were adopted as secondary standards; the latter yield ages of 92.6 ±1.8 and 32.2 ±1.1 Ma, respectively, and these are identical to their accepted ages. Pb/U ages for apatite from Oka were obtained for different rock types, including 8 carbonatites, 4 okaites, 3 ijolites and 3 alnoites, and these define a range of ages between ~105 and ~135 Ma; this result suggests a protracted crystallization history. In total, 266 individual analyses define two peaks at ~115 and ~125Ma. For perovskite dating, the Ice River perovskite standard was utilized as the external standard. The perovskites from one okaite sample yield an age of 112.2 ±1.9 Ma, and is much younger than the previously reported U-Pb perovskite age of 131 ±7 Ma. Hence, the combined U-Pb perovskite ages also suggest a rather prolonged time of melt crystallization. Niocalite is a rare, accessory silicate mineral that occurs within the carbonatites at Oka. The international zircon standard BR266 was selected for use as the external standard and rastering was employed to minimize the Pb-U fractionation. Two niocalite samples give young ages at 110.6 ±1.2 and 115.0 ±1.9 Ma, and are identical to their respective apatite ages (given associated uncertainties) from the same

  15. In situ LA-ICPMS U–Pb dating of cassiterite without a known-age matrix-matched reference material: Examples from worldwide tin deposits spanning the Proterozoic to the Tertiary

    USGS Publications Warehouse

    Neymark, Leonid; Holm-Denoma, Christopher S.; Moscati, Richard J.

    2018-01-01

    Cassiterite (SnO2), a main ore mineral in tin deposits, is suitable for U–Pb isotopic dating because of its relatively high U/Pb ratios and typically low common Pb. We report a LA-ICPMS analytical procedure for U–Pb dating of this mineral with no need for an independently dated matrix-matched cassiterite standard. LA-ICPMS U-Th-Pb data were acquired while using NIST 612 glass as a primary non-matrix-matched standard. Raw data are reduced using a combination of Iolite™ and other off-line data reduction methods. Cassiterite is extremely difficult to digest, so traditional approaches in LA-ICPMS U-Pb geochronology that utilize well-characterized matrix-matched reference materials (e.g., age values determined by ID-TIMS) cannot be easily implemented. We propose a new approach for in situ LA-ICPMS dating of cassiterite, which benefits from the unique chemistry of cassiterite with extremely low Th concentrations (Th/U ratio of 10−4 or lower) in some cassiterite samples. Accordingly, it is assumed that 208Pb measured in cassiterite is mostly of non-radiogenic origin—it was initially incorporated in cassiterite during mineral formation, and can be used as a proxy for common Pb. Using 208Pb as a common Pb proxy instead of 204Pb is preferred as 204Pb is much less abundant and is also compromised by 204Hg interference during the LA-ICPMS analyses.Our procedure relies on 208Pb/206Pb vs 207Pb/206Pb (Pb-Pb) and Tera-Wasserburg 207Pb/206Pb vs 238U/206Pb (U-Pb) isochron dates that are calculated for a ~1.54 Ga low-Th cassiterite reference material with varying amounts of common Pb that we assume remained a closed U-Pb system. The difference between the NIST 612 glass normalized biased U-Pb date and the Pb-Pb age of the reference material is used to calculate a correction factor (F) for instrumental U-Pb fractionation. The correction factor (F) is then applied to measured U/Pb ratios and Tera-Wasserburg isochron dates are obtained for the unknown

  16. In situ U-Th-Pb ages of the Miaoya carbonatite complex in the South Qinling orogenic belt, central China

    NASA Astrophysics Data System (ADS)

    Ying, Yuancan; Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Yang, Yueheng

    2017-10-01

    The Miaoya carbonatite complex in the South Qinling orogenic belt hosts one of the largest rare earth element (REE)-Nb deposits in China that is composed of carbonatite and syenite. The emplacement age of the complex and the geochronological relationship between the carbonatite and syenite have long been debated. In this study, in situ U-Th-Pb ages have been obtained for the constituent minerals zircon, monazite and columbite from carbonatite and syenite of the Miaoya complex, together with their chemical and isotopic compositions. In situ trace element compositions for zircon from carbonatite and syenite are highly variable. The zircon displays slightly heavy REE (HREE)-enriched chondrite-normalized patterns with no Eu anomaly and various light REE (LREE) contents. In situ Th-Pb dating for zircon from the Miaoya complex by laser ablation ICP-MS yields ages of 442.6 ± 4.0 Ma (n = 53) for syenite and 426.5 ± 8.0 Ma (n = 23) for carbonatite. Monazite from carbonatite and syenite shows similar chondrite-normalized REE patterns and yields a consistent Th-Pb age of 240 Ma. Based on petrographic and chemical composition, columbite from the carbonatite can be identified into two groups. The columbite dispersed within carbonatite is characterized by slightly LREE-enriched chondrite-normalized REE patterns, whereas columbite associated with apatite is characterized by LREE-depleted trends. Columbite has been further determined to have a weighted mean 206Pb/238U age of 232.8 ± 4.5 Ma (n = 9) using LA-ICP-MS. Detailed geochronological and chemical investigations suggest that there were two major episodes of magmatic/metasomatic activities in the formational history of the Miaoya carbonatite complex. The early alkaline magmatism emplaced in the Silurian was related to the opening of the Mianlue Ocean, whereas the late metasomatism or hydrothermal overprint occurred during the Triassic South Qinling orogeny. The latter serves as the major ore formation period for both REE (e

  17. Isotope geochemistry of early Kilauea magmas from the submarine Hilina bench: The nature of the Hilina mantle component

    USGS Publications Warehouse

    Kimura, Jun-Ichi; Sisson, Thomas W.; Nakano, Natsuko; Coombs, Michelle L.; Lipman, Peter W.

    2006-01-01

    Submarine lavas recovered from the Hilina bench region, offshore Kilauea, Hawaii Island provide information on ancient Kilauea volcano and the geochemical components of the Hawaiian hotspot. Alkalic lavas, including nephelinite, basanite, hawaiite, and alkali basalt, dominate the earliest stage of Kilauea magmatism. Transitional basalt pillow lavas are an intermediate phase, preceding development of the voluminous tholeiitic subaerial shield and submarine Puna Ridge. Most alkalic through transitional lavas are quite uniform in Sr–Nd–Pb isotopes, supporting the interpretation that variable extent partial melting of a relatively homogeneous source was responsible for much of the geochemical diversity of early Kilauea magmas (Sisson et al., 2002). These samples are among the highest 206Pb/204Pb known from Hawaii and may represent melts from a distinct geochemical and isotopic end-member involved in the generation of most Hawaiian tholeiites. This end-member is similar to the postulated literature Kea component, but we propose that it should be renamed Hilina, to avoid confusion with the geographically defined Kea-trend volcanoes. Isotopic compositions of some shield-stage Kilauea tholeiites overlap the Hilina end-member but most deviate far into the interior of the isotopic field defined by magmas from other Hawaiian volcanoes, reflecting the introduction of melt contributions from both “Koolau” (high 87Sr/86Sr, low 206Pb/204Pb) and depleted (low 87Sr/86Sr, intermediate 206Pb/204Pb) source materials. This shift in isotopic character from nearly uniform, end-member, and alkalic, to diverse and tholeiitic corresponds with the major increase in Kilauea's magmatic productivity. Two popular geodynamic models can account for these relations: (1) The upwelling mantle source could be concentrically zoned in both chemical/isotopic composition, and in speed/extent of upwelling, with Hilina (and Loihi) components situated in the weakly ascending margins and the

  18. Sharpening the U-Th Chronometer: Progress and Outlook

    NASA Astrophysics Data System (ADS)

    McLean, N. M.; Condon, D. J.; Henderson, G. M.; Richards, D. A.; Noble, S.; Mason, A.

    2013-12-01

    Uranium is incorporated into a variety of natural materials when they form, including carbonates like speleothems and corals. The two most abundant naturally occurring uranium isotopes, 238U and 235U, decay to 206Pb and 207Pb over long timescales with half-lives of 4.5 and 0.7 billion years respectively, but transition through several intermediate daughter isotopes with shorter half-lives first. Fractionation between these daughter isotopes, including 234U, 230Th, and 231Pa, and their parent isotopes, followed by their time-dependent return to secular equilibrium over the course of up to ~800 kyr, forms the basis for U-series geochronology, and allows speleothems and corals to be precisely dated. These carbonates often additionally incorporate chemical and isotopic signatures (e.g., trace elements, δ18O and δ13C) from the environment in which they form, and thus are some of the best dated paleoclimate archives, offering clues about past and future conditions for life on Earth. Over the past decade, the analytical precision of U-series isotope measurements has improved dramatically, largely due to the steadily increasing sensitivity of multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Analytical uncertainties in U-Th dates now approach or are better than 0.1% (2σ), for instance ×100 years for a speleothem or coral that is 130 kyr old (Cheng et al., 2013). However, the accuracy of U-series dates also depends on the accuracy of tracer calibrations, reference solutions and data reduction protocols, which has not kept pace in many laboratories. This means that dates measured in different labs, while impressively precise, may not be directly comparable. To address issues of inter-laboratory bias and improve the accuracy and inter-comparability of U-Th dates, we have instigated work in three related directions. First, we report on the mixing of three synthetic U-Th age solutions, created by combining high-purity mono-isotopic solutions to

  19. Sediment transport time measured with U-Series isotopes: Resultsfrom ODP North Atlantic Drill Site 984

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

    DePaolo, Donald J.; Maher, Kate; Christensen, John N.

    High precision uranium isotope measurements of marineclastic sediments are used to measure the transport and storage time ofsediment from source to site of deposition. The approach is demonstratedon fine-grained, late Pleistocene deep-sea sediments from Ocean DrillingProgram Site 984A on the Bjorn Drift in the North Atlantic. The sedimentsare siliciclastic with up to 30 percent carbonate, and dated by sigma 18Oof benthic foraminifera. Nd and Sr isotopes indicate that provenance hasoscillated between a proximal source during the last three interglacialperiods volcanic rocks from Iceland and a distal continental sourceduring glacial periods. An unexpected finding is that the 234U/238Uratios of the silicatemore » portion of the sediment, isolated by leaching withhydrochloric acid, are significantly less than the secular equilibriumvalue and show large and systematic variations that are correlated withglacial cycles and sediment provenance. The 234U depletions are inferredto be due to alpha-recoil loss of234Th, and are used to calculate"comminution ages" of the sediment -- the time elapsed between thegeneration of the small (<_ 50 mu-m) sediment grains in the sourceareas by comminution of bedrock, and the time of deposition on theseafloor. Transport times, the difference between comminution ages anddepositional ages, vary from less than 10 ky to about 300 to 400 ky forthe Site 984A sediments. Long transport times may reflect prior storagein soils, on continental shelves, or elsewhere on the seafloor. Transporttime may also be a measure of bottom current strength. During the mostrecent interglacial periods the detritus from distal continental sourcesis diluted with sediment from Iceland that is rapidly transported to thesite of deposition. The comminution age approach could be used to dateQuaternary non-marine sediments, soils, and atmospheric dust, and may beenhanced by concomitant measurement of 226Ra/230Th, 230Th/234U, andcosmogenic nuclides.« less

  20. 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