LA-ICP-MS Pb-U Dating of Young Zircons from the Kos-Nisyros Volcanic Centre, SE Aegean Arc (Greece)

NASA Astrophysics Data System (ADS)

Guillong, M.; Von Quadt, A.; Peytcheva, I.; Bachmann, O.

2014-12-01

Zircon Pb-U dating has become a key technique for answering many important questions in geosciences. This paper describes a new LA-ICP-MS approach. We show, using previously dated samples of a large quaternary rhyolitic eruption in the Kos-Nisyros volcanic centre (the 161 ka Kos Plateau Tuff), that the precision of our LA-ICP-MS method is as good as via SHRIMP, while ID-TIMS measurements confirm the accuracy. Gradational age distribution over >140 ka of the Kos zircons and the near-absence of inherited cores indicate near-continuous crystallisation in a growing magma reservoir with little input from wall rocks. Previously undated silicic eruptions from Nisyros volcano (Lower Pumice, Nikia Flow, Upper Pumice), which are stratigraphically constrained to have happened after the Kos Plateau Tuff, are dated to be younger than respectively 124 ± 35 ka, 111 ± 42 ka and 70 ± 24 ka. Samples younger than 1 Ma were corrected for initial thorium disequilibrium using a new formula that also accounts for disequilibrium in 230Th decay. Guillong, M. et al., 2014, JAAS, 29, p. 963-967; doi: 10.1039/c4ja00009a.

In situ detrital zircon (U-Th)/He thermochronology

NASA Astrophysics Data System (ADS)

Tripathy, A.; Monteleone, B. D.; van Soest, M. C.; Hodges, K.; Hourigan, J. K.

2010-12-01

situ method, utilizing SIMS to determine the U-Th concentrations. The major mode is the same as the conventional dataset, with only single outliers missing from the in situ dataset. The in situ method is described as follows: Zircons are polished and imaged using cathodoluminesence to guide laser spot placement. Then, each grain is ablated with a 193nm ArF Excimer laser using 20-35µm beam sizes and depths of 10-17µm. After purification, 4He is analyzed on a ThermoScientific Helix Split Flight Tube mass spectrometer. U-Th concentrations are measured on the polished mount using a Cameca IMS 6f by placing a 60µm diameter beam directly over the He laser pit to cover the surface area contributing to the measured He. In theory, using LA-ICP-MS to obtain U-Th concentrations could be a faster, cheaper, but possibly less precise, technique. However, using laser ablation would allow pit sizes that average the U-Th concentration over the volume of material available that contributes to the measured He, thus accounting for intracrystalline α-recoil effects. Preliminary data on slabs of Sri Lankan zircon suggest this could be a viable method, but will require further exploration and refinement.

Single-Shot Laser Ablation Split-Stream (SS-LASS) Analysis Depth Profiling

NASA Astrophysics Data System (ADS)

Kylander-Clark, A. R.; Stearns, M. A.; Viete, D. R.; Cottle, J. M.; Hacker, B. R.

2014-12-01

Laser ablation depth profiling of geochronometers—such as zircon, monazite, titanite and rutile—has become popular in recent years as a tool to both determine date vs. depth or trace-element (TE) composition vs. depth; the former allows the dating of thin rims and, potentially, inversion of Pb-loss profiles for thermal histories, whereas the latter can yield insight into changes in PTX or mineral parageneses and inversion of trace-element profiles for thermal histories. In this study, we combine both techniques, enabling simultaneous acquisition of U-Th/Pb isotopic ratios and trace-element compositions, by joining a 193 nm excimer laser to a multi-collector ICP-MS and single-collector ICP-MS. The simultaneous acquisition allows direct shot-by-shot linkage between time and petrology, expanding our ability to understand the evolution of complex geologic systems. We construct each depth profile by capturing the analyte with a succession of individual laser pulses (each ~100 nm deep) . This has two main advantages over a typical time-dependent analysis of a multi-shot routine composed of tens to hundreds of shots and a several μm deep hole. 1) The reference material is analyzed between each shot for a more-accurate standardization of each aliquot of ablated material. 2) There is no mixing of material ablated from successive laser pulses during transmission to the ICP. The method is limited by count rate, which depends on spot size, excavation rate, instrument sensitivity, etc., and, for single-collector ICP, the switching time, which limits the number of elements that can be analyzed and their total counts. We explore the latter theoretically and experimentally to provide insight on both the ideal number of elements to measure and the dwell time in any given sample. Examples of the utility of SS-LASS include the comparison of apparent Pb loss to diffusion profiles of trace elements in rims of metamorphic rutile and titanite, as well as the determination of the

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Laser-ablation ICP-MS as a tool for whole rock trace element analyses on fused powders

NASA Astrophysics Data System (ADS)

Girard, G.; Rooney, T. O.

2013-12-01

Here we present an accurate and precise technique for routine trace element analysis of geologic materials by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We focus on rock powders previously prepared for X-ray fluorescence by fusion in a Li2B4O7 flux, and subsequently quenched in a Pt mold to form a glass disk. Our method allows for the analysis up to 30 trace elements by LA-ICP-MS using a Photon-Machines Analyte G2 193 nm excimer laser coupled to a Thermo-Fisher Scientific ICAP Q quadrupole ICP-MS. Analyses are run as scans on the surface of the disks. Laser ablation conditions for which trace element fractionation effects are minimal have been empirically determined to be ~ 4 J m-2 fluence, at 10 Hz , and 10 μm s-1 scan speed, using a 110 μm laser beam size. Ablated material is carried into the ICP-MS by a He carrier at a rate of 0.75 L min-1. Following pre-ablation to remove surface particles, samples are ablated for 200 s, of which 140 s are used for data acquisition. At the end of each scan, a gas blank is collected for 30 s. Dwell times for each element vary between 15 and 60 μs, depending on abundance and instrument sensitivity, allowing 120 readings of each element during the data acquisition time window. To correct for variations in the total volume of material extracted by the laser, three internal standards are used, Ca, Fe and Zr. These elements are routinely analyzed by X-ray fluorescence by the Geoanalytical laboratory at Michigan State University with precision and accuracy of <5%. The availability of several internal standards allows for better correction of possible persisting laser ablation fractionation effects; for a particular trace element, we correct using the internal standard that best reproduces its ablation behavior. Our calibration is based on a combination of fused powders of US Geological Survey and Geological Survey of Japan rock standards, NIST SRM 612 glass, and US Geological Survey natural and

Characteristics of zircon suitable for REE extraction

NASA Astrophysics Data System (ADS)

Watanabe, Y.; Hoshino, M.

2011-12-01

Zircons (ZrSiO4) from Naegi and Ohro granitic pegmatites, Japan and from Saigon alkaline basalt, Vietnam, were mineralogically characterized by inductively couples plasma mass spectrometry (ICP-MS), electron-microprobe analysis (EMPA), X-ray powder diffraction, micro-Raman spectroscopy and leaching experiment. The powder XRD and Raman spectra analyses show that the degree of crystallinity decreases from Saigon, to Ohro and Naegi zircons. Quantitative analytical results by the EMPA indicate that the Naegi and Ohro zircon samples contain a large amount of REE2O3, while REE contents in Saigon zircon are below detection limit. The leaching experiments for the present zircons under the condition of a solvent 1M-HCl, at a room temperature to 250 °C and retention time of 30h resulted in about 100 %, 50 % and 1 % recoveries of REE from the Naegi, Ohro and Saigon zircons, respectively. Leaching experiments for the Naegi zircon under the condition of a solvent 1N-HCl, heating temperature of 50 °C, 100 °C, 150 °C and 200 °C, and retention time 30h, showed that a significant amount of REE was leached out at a temperature above 150 °C. However, the leaching experiments of the Naegi and Ohro zircons at room temperature (about 25 °C) show that REE were hard to be leached. These results indicates that both low crystallinity of zircon and higher leaching temperature are requisite for effective leaching of REE from zircon.

Proterozoic to Mesozoic evolution of North-West Africa and Peri-Gondwana microplates: Detrital zircon ages from Morocco and Canada

NASA Astrophysics Data System (ADS)

Marzoli, Andrea; Davies, Joshua H. F. L.; Youbi, Nasrrddine; Merle, Renaud; Dal Corso, Jacopo; Dunkley, Daniel J.; Fioretti, Anna Maria; Bellieni, Giuliano; Medina, Fida; Wotzlaw, Jörn-Frederik; McHone, Greg; Font, Eric; Bensalah, Mohamed Khalil

2017-05-01

The complex history of assemblage and disruption of continental plates surrounding the Atlantic Ocean is in part recorded by the distribution of detrital zircon ages entrained in continental sedimentary strata from Morocco (Central High Atlas and Argana basins) and Canada (Grand Manan Island, New Brunswick). Here we investigate detrital zircon from the latest Triassic (ca. 202 Ma) sedimentary strata directly underlying lava flows of the Central Atlantic magmatic province or interlayered within them. SHRIMP (Sensitive High-Resolution Ion MicroProbe) and LA-ICP-MS (Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry) U-Pb ages for zircon range from Paleozoic to Archean with a dominant Neoproterozoic peak, and significant amounts of ca. 2 Ga zircon. These ages suggest a prevailing West African (Gondwanan) provenance at all sampling sites. Notably, the Paleoproterozoic zircon population is particularly abundant in central Morocco, north of the High Atlas chain, suggesting the presence of Eburnean-aged rocks in this part of the country, which is consistent with recent geochronologic data from outcropping rocks. Minor amounts of late Mesoproterozoic and early Neoproterozoic zircon ages (ca. 1.1-0.9 Ga) in Moroccan samples are more difficult to interpret. A provenance from Avalonia or Amazonia, as proposed by previous studies is not supported by the age distributions observed here. An involvement of more distal source regions, possibly located in north-eastern Africa (Arabian Nubian Shield) would instead be possible. Paleozoic zircon ages are abundant in the Canadian sample, pointing to a significant contribution from Hercynian aged source rocks. Such a signal is nearly absent in the Moroccan samples, suggesting that zircon-bearing Hercynian granitic rocks of the Moroccan Meseta block were not yet outcropping at ca. 200 Ma. The only Moroccan samples that yield Paleozoic zircon ages are those interlayered within the CAMP lavas, suggesting an increased dismantling

Analysis of Trace Siderophile Elements at High Spatial Resolution Using Laser Ablation ICP-MS

NASA Astrophysics Data System (ADS)

Campbell, A. J.; Humayun, M.

2006-05-01

Laser ablation inductively coupled plasma mass spectometry is an increasingly important method of performing spatially resolved trace element analyses. Over the last several years we have applied this technique to measure siderophile element distributions at the ppm level in a variety of natural and synthetic samples, especially metallic phases in meteorites and experimental run products intended for trace element partitioning studies. These samples frequently require trace element analyses to be made at a finer spatial resolution (25 microns or better) than is frequently attained using LA-ICP-MS. In this presentation we review analytical protocols that were developed to optimize the LA-ICP-MS measurements for high spatial resolution. Particular attention is paid to the trade-offs involving sensitivity, ablation pit depth and diameter, background levels, and number of elements measured. To maximize signal/background ratios and avoid difficulties associated with ablating to depths greater than the ablation pit diameter, measurement involved integration of rapidly varying, transient but well-behaved signals. The abundances of platinum group elements and other siderophile elements in ferrous metals were calibrated against well-characterized standards, including iron meteorites and NIST certified steels. The calibrations can be set against the known abundance of an independently determined element, but normalization to 100 percent can also be employed, and was more useful in many circumstances. Evaluation of uncertainties incorporated counting statistics as well as a measure of instrumental uncertainty, determined by replicate analyses of the standards. These methods have led to a number of insights into the formation and chemical processing of metal in the early solar system.

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.

The pre-orogenic detrital zircon record of the Variscan orogeny: Preliminary results

NASA Astrophysics Data System (ADS)

Stephan, Tobias; Kroner, Uwe

2017-04-01

To test plate-tectonic constellations in consideration of the long-term development of sedimentary transport paths, temporally and spatially highly resolved records of provenance analysis are mandatory. The interpretation of existing studies focus on small-scale areas within an orogen thereby neglecting the differing distribution of provenance data in the entire orogenic system. This study reviews a large data set of compiled geochronological data to document the development of pre-orogenic tectonic units on the example of the Variscan orogeny. Constrained by tectonic and geological models, the temporal distribution of U-Pb detrital zircon ages, used as a proxy for sedimentary provenance, shows that some minima and maxima of zircon abundance are nearly synchronous for thousands of kilometres along the orogeny. Age spectra of Precambrian to Lower Palaeozoic samples were constructed on the basis of 38729 U-Pb ages from 685 samples that were compiled from 102 publications. The age compilation combines thermal ionization mass spectrometry (TIMS), laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS), sensitive high-resolution ion microprobe (SHRIMP), and secondary ion mass spectrometry (SIMS) analyses. The data was re-processed using a common age calculation and concordance filter to ensure comparability. The concordance of each zircon grain was calculated from 206Pb/238U and 207Pb/235U ages to guarantee that only concordant grains, i.e., with <10% normal and <5% reverse discordance, were included in the age compilation. In order to ignore a metamorphic overprint and hence a blur of the younger age spectra, the compilation is constrained to age data older than 400 Ma only. If a precise sample age is not documented by the author, the weighted-mean age of the youngest zircon population (n > 3) is used for the maximum age of deposition. In addition to the location of >600 samples, the precise depositional ages result in a spatially and temporally high

The India and South China cratons at the margin of Rodinia — Synchronous Neoproterozoic magmatism revealed by LA-ICP-MS zircon analyses

NASA Astrophysics Data System (ADS)

Hofmann, M.; Linnemann, U.; Rai, V.; Becker, S.; Gärtner, A.; Sagawe, A.

2011-04-01

The palaeogeographic position of South China in relation to India in the Neoproterozoic is controversial. Resolution of this controversy constrains the reconstruction of Rodinia during its breakup and contributes to our understanding of Snowball Earth. This work compares the Neoproterozoic histories of the Lesser Himalaya in northern India and the Yangtze block in southern China. We present U-Pb LA-ICP-MS ages of detrital zircon grains from six Indian and three Chinese siliciclastic sedimentary rocks, such as sandstones or diamictites/tillites. In total, 1148 grains were analysed from which 833 measurements gave ages with a degree of concordance between 90 and 110%. The correlation of the Indian and the Chinese sections is possible using the tillites of both areas purportedly deposited during the Snowball Earth time interval: the Blaini tillite from India and the Nantuo tillite from China. The U-Pb ages confirm the Marinoan age of the Chinese Liantuo tillite. Although the youngest zircon age for the Indian Blaini tillite is about 678 Ma, the Marinoan age is indicated by the presence of a typical Marinoan white to bright yellowish overlying cap carbonate. In addition to the tillites, representative detrital zircon ages from over- and underlying clastic rocks were determined. The Chinese samples are dominated by zircons with Neoproterozoic ages with a main peak between ca. 750 Ma and ca. 950 Ma and are characterised by the absence of Archaean ages. The Indian samples contain abundant Neoproterozoic zircon grains, but also contain Mesoproterozoic to Archaean zircons. For all samples, a local source area that provided the Neoproterozoic zircons is likely. A synchronous Neoproterozoic magmatic event in both cratons probably reflects the breakup of the supercontinent Rodinia and therefore the same tectono-magmatic event. Our results indicate a similar history for India and South China which both underwent at least one synchronous episode of crustal growth during the

He, U, and Th Depth Profiling of Apatite and Zircon Using Laser Ablation Noble Gas Mass Spectrometry and SIMS

NASA Astrophysics Data System (ADS)

Monteleone, B. D.; van Soest, M. C.; Hodges, K. V.; Hervig, R.; Boyce, J. W.

2008-12-01

Conventional (U-Th)/He thermochronology utilizes single or multiple grain analyses of U- and Th-bearing minerals such as apatite and zircon and does not allow for assessment of spatial variation in concentration of He, U, or Th within individual crystals. As such, age calculation and interpretation require assumptions regarding 4He loss through alpha ejection, diffusive redistribution of 4He, and U and Th distribution as an initial condition for these processes. Although models have been developed to predict 4He diffusion parameters, correct for the effect of alpha ejection on calculated cooling ages, and account for the effect of U and Th zonation within apatite and zircon, measurements of 4He, U, and Th distribution have not been combined within a single crystal. We apply ArF excimer laser ablation, combined with noble gas mass spectrometry, to obtain depth profiles within apatite and zircon crystals in order to assess variations in 4He concentration with depth. Our initial results from pre-cut, pre-heated slabs of Durango apatite, each subjected to different T-t schedules, suggest a general agreement of 4He profiles with those predicted by theoretical diffusion models (Farley, 2000). Depth profiles through unpolished grains give reproducible alpha ejection profiles in Durango apatite that deviate from alpha ejection profiles predicted for ideal, homogenous crystals. SIMS depth profiling utilizes an O2 primary beam capable of sputtering tens of microns and measuring sub-micron resolution variation in [U], [Th], and [Sm]. Preliminary results suggest that sufficient [U] and [Th] zonation is present in Durango apatite to influence the form of the 4He alpha ejection profile. Future work will assess the influence of measured [U] and [Th] zonation on previously measured 4He depth profiles. Farley, K.A., 2000. Helium diffusion from apatite; general behavior as illustrated by Durango fluorapatite. J. Geophys. Res., B Solid Earth Planets 105 (2), 2903-2914.

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

U-Pb detrital zircon dates and provenance data from the Beaufort Group (Karoo Supergroup) reflect sedimentary recycling and air-fall tuff deposition in the Permo-Triassic Karoo foreland basin

NASA Astrophysics Data System (ADS)

Viglietti, Pia A.; Frei, Dirk; Rubidge, Bruce S.; Smith, Roger M. H.

2018-07-01

Detrital zircon U-Pb age dating was used for provenance determination and maximum age of deposition for the Upper Permian (upper Teekloof and Balfour formations) and Lower Triassic (Katberg Formation) lithostratigraphic subdivisions of the Beaufort Group of South Africa's Karoo Basin. Ten samples were analysed using laser ablation - single collector - magnetic sectorfield - inductively coupled plasma - mass spectrometry (LA-SF-ICP-MS). The results reveal a dominant Late Carboniferous-Late Permian population (250 ± 5 Ma - 339 ± 5 Ma), a secondary Cambrian-Neoproterozoic (489 ± 5 Ma to 878 ± 24 Ma) population, a minor Mesoproterozoic (908 ± 24 Ma to 1308 ± 23) population, and minor occurrences of Devonian, Ordovician, Proterozoic and Archean zircon grains. Multiple lines of evidence (e.g. roundness and fragmentary nature of zircons, palaeo-current directions, and previous work), suggest the older zircon populations are related to sedimentary recycling in the Gondwanide Orogeny. The youngest and dominant population contain elongate euhedral grains interpreted to be directly derived from their protolith. Since zircons form in felsic igneous rocks, and no igneous rocks of Late Permian age occur in the Karoo Basin, these findings suggest significant input of volcanic material by ash falls. These results support sedimentological and palaeontological data for a Lopingian (Late Permian) age for the upper Beaufort Group, but contradict previous workers who retrieved Early Triassic dates from zircons in ashes for the Beaufort and Ecca Groups. Pb-loss not revealed by resolvable discordance on the concordia diagram, and metamictization of natural zircons are not factored into the conclusions of earlier workers.

North Qinling Terrain as a provenance of Kuanping Group: LA-ICP-MS U-Pb Geochronology of detrital zircons

NASA Astrophysics Data System (ADS)

Hu, B.; Li, S.; Zhai, M.; Wu, J.; Jia, X.

2017-12-01

Though some Neoproterozoic S-type granites in the North Qinling Terrain (NQT), China indicate the collision between the NQT and an unknown block, there are still controversial. The LA-ICP-MS U-Pb ages of detrital zircons of meta-sandstones from the Kuanping Group in Luonan area, NQT, provide sedimentology evidence to prove that the NQT and an unknown block from Rodinia supercontinent have been collided during Meso-Neoproterozoic. The U-Pb ages of detrital zircons from the Kuanping Group show that the main age peaks are at 2.58 Ga, 2.46 Ga, 2.0 Ga, 1.78 Ga, 1.6 Ga, 1.45 Ga and 1.27 Ga. The youngest age of 880 Ma indicates that the sedimentary age of the Kuanping Group is less than 880 Ma. The provenances, which provide 1.45 - 0.88 Ga sediments may come from NQT, which magmatic and metamorphic rocks during this period outcropped. Whereas provenances providing 2.6- 1.6 Ga sediments may come from an unknown block. This indicates that the Kuangping Group received both NQT and the unknown block materials. Therefore, the NQT and the unknown block may have collided before 880 Ma. 889 - 848 Ma A-type granites distributing the NQT was considered forming under a post-collisional tectonics. According the youngest detrital zircon ages of 880 Ma, it is inferred that the Kuanping Basin may also form in the same tectonic environments. Neoproterozoic Kuanping basin and 889 - 848 Ma A-type granites may be a result which NQT broken off a block of Rodinia supercontinent. Acknowledgments: This research is supported by National Key Research and Development Plan of China (2016YFC0601002), Special Fund for Basic Scientific Research of Central Colleges, Chang'an University (310827172201, 0009-2014G1271067) and National Nature Science Foundation of China (41402042).

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.

Zircon/fluid trace element partition coefficients measured by recrystallization of Mud Tank zircon at 1.5 GPa and 800-1000 °C

NASA Astrophysics Data System (ADS)

Ayers, John C.; Peters, Timothy J.

2018-02-01

Hydrothermal zircon grains have trace element characteristics such as low Th/U, high U, and high rare earth element (REE) concentrations that distinguish them from magmatic, metamorphic, and altered zircon grains, but it is unclear whether these characteristics result from distinctive fluid compositions or zircon/fluid fractionation effects. New experiments aimed at measuring zircon/fluid trace element partition coefficients Dz/f involved recrystallizing natural Mud Tank zircon with low trace element concentrations in the presence of H2O, 1 m NaOH, or 1 m HCl doped with ∼1000 ppm of rare earth elements (REE), Y, U and Th and ∼500 ppm of Li, B, P, Nb, Ba, Hf, and Ta. Experiments were run for 168 h at 1.5 GPa, 800-1000 °C, and fO2 = NNO in a piston cylinder apparatus using the double capsule method. LA-ICP-MS analysis shows that run product zircon crystals have much higher trace element concentrations than in Mud Tank zircon starting material. Dz/f values were estimated from run product zircon analyses and bulk composition using mass balance. Most elements behave incompatibly, with median Dz/f being highest for Hf = 8 and lowest for B = 0.02. Addition of NaOH or HCl had little influence on Dz/f values. Dz/f for LREE are anomalously high, likely due to contamination of run product zircon with quenched solutes enriched in incompatible elements, so DLREE were estimated using lattice strain theory. Brice curves for +3 ions yield zircon/fluid DLu/DLa of ∼800-5000. A Brice curve fit to +4 ions yielded DCe4+ values. Estimated concentrations of Ce3+ and Ce4+ show that the average Ce4+/Ce3+ in zircon of 27 is much higher than in fluid of 0.02. Th and U show little fractionation, with median DTh/DU = 0.7, indicating that the low Th/U in natural hydrothermal zircon is inherited from the fluid. Natural fluid compositions estimated from measured Dz/f and published compositions of hydrothermal zircon grains from aplite and eclogite reflect the mineralogy of the host rock, e

Trace element study in scallop shells by laser ablation ICP-MS: the example of Ba/Ca ratios

NASA Astrophysics Data System (ADS)

Lorrain, A.; Pécheyran, C.; Paulet, Y.-M.; Chauvaud, L.; Amouroux, D.; Krupp, E.; Donard, O.

2003-04-01

As scallop shells grow incrementally at a rate of one line per day, environmental changes could then be evidenced on a daily basis. As an example for trace element incorporation studies, barium is a geochemical tracer that can be directly related to oceanic primary productivity. Hence, monitoring Ba/Ca variations in a scallop shell should give information about phytoplanktonic events encountered day by day during its life. The very high spatial resolution (typically 40 - 200 µm) and the high elemental sensitivity required can only be achieved by the combination of laser ablation coupled to inductively coupled plasma mass spectrometry. This study demonstrates that Laser ablation coupled to ICP-MS determination is a relevant tool for high resolution distribution measurement of trace elements in calcite matrix. The ablation strategy related to single line rastering and calcium normalisation were found to be the best analytical conditions in terms of reproducibility and sensitivity. The knowledge of P. maximus growth rings periodicity (daily), combined with LA-ICP-MS micro analysis allows the acquisition of time dated profiles with high spatial and thus temporal resolution. This resolution makes P. maximus a potential tool for environmental reconstruction and especially for accurate calibration of proxies. However, the relations among Ba/Ca peaks and phytoplanktonic events differed according to the animals and some inter-annual discrepancies complexify the interpretation.

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.

HAFNIAN ZIRCONS

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

von Knorring, O.; Hornung, G.

1961-06-17

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

[Progress in the application of laser ablation ICP-MS to surface microanalysis in material science].

PubMed

Zhang, Yong; Jia, Yun-hai; Chen, Ji-wen; Shen, Xue-jing; Liu, Ying; Zhao, Leiz; Li, Dong-ling; Hang, Peng-cheng; Zhao, Zhen; Fan, Wan-lun; Wang, Hai-zhou

2014-08-01

In the present paper, apparatus and theory of surface analysis is introduced, and the progress in the application of laser ablation ICP-MS to microanalysis in ferrous, nonferrous and semiconductor field is reviewed in detail. Compared with traditional surface analytical tools, such as SEM/EDS (scanning electron microscopy/energy dispersive spectrum), EPMA (electron probe microanalysis analysis), AES (auger energy spectrum), etc. the advantage is little or no sample preparation, adjustable spatial resolution according to analytical demand, multi-element analysis and high sensitivity. It is now a powerful complementary method to traditional surface analytical tool. With the development of LA-ICP-MS technology maturing, more and more analytical workers will use this powerful tool in the future, and LA-ICP-MS will be a super star in elemental analysis field just like LIBS (Laser-induced breakdown spectroscopy).

Crustal melting and recycling: geochronology and sources of Variscan syn-kinematic anatectic granitoids of the Tormes Dome (Central Iberian Zone). A U-Pb LA-ICP-MS study

NASA Astrophysics Data System (ADS)

López-Moro, F. J.; López-Plaza, M.; Gutiérrez-Alonso, G.; Fernández-Suárez, J.; López-Carmona, A.; Hofmann, M.; Romer, R. L.

2018-04-01

In this study, we report U-Pb Laser Ablation ICP-MS zircon and ID-TIMS monazite ages for peraluminous granitoid plutons (biotite ± muscovite ± cordierite ± sillimanite) in the Tormes Dome, one of the gneiss-cored domes located in the Central Iberian Zone of the Variscan belt of northern Spain. Textural domains in zircon, interpreted to represent the magmatic crystallization of the granitoids (and one monazite fraction in the Ledesma pluton) yielded ages around 320 Ma, in agreement with other geochronological studies in the region. This age is interpreted to date the timing of decompression crustal melting driven by the extensional collapse of the orogenic belt in this domain of the Variscan chain of western Europe. In addition, there are several populations of inherited (xenocrystic) zircon: (1) Carboniferous zircon crystals (ca. 345 Ma) as well as one of the monazite fractions in the coarse-grained facies of the Ledesma pluton that also yielded an age of ca. 343 Ma. (2) Devonian-Silurian zircon xenocrysts with scattered ages between ca. 390 and 432 Ma. (3) Middle Cambrian-Ordovician (ca. 450-511 Ma). (4) Ediacaran-Cryogenian zircon ages (ca. 540-840 Ma). (5) Mesoproterozoic to Archaean zircon (900-2700 Ma). The abundance of Carboniferous-inherited zircon shows that crustal recycling/cannibalization may often happen at a fast pace in orogenic scenarios with only short lapses of quiescence. In our case study, it seems plausible that a "crustal layer" of ca. 340 Ma granitoids/migmatites was recycled, partially or totally, only 15-20 My after its emplacement.

Analysis on ultrashort-pulse laser ablation for nanoscale film of ceramics

NASA Astrophysics Data System (ADS)

Ho, C. Y.; Tsai, Y. H.; Chiou, Y. J.

2017-06-01

This paper uses the dual-phase-lag model to study the ablation characteristics of femtosecond laser processing for nanometer-sized ceramic films. In ultrafast process and ultrasmall size where the two lags occur, a dual-phase-lag can be applied to analyse the ablation characteristics of femtosecond laser processing for materials. In this work, the ablation rates of nanometer-sized lead zirconate titanate (PZT) ceramics are investigated using a dual-phase-lag and the model is solved by Laplace transform method. The results obtained from this work are validated by the available experimental data. The effects of material thermal properties on the ablation characteristics of femtosecond laser processing for ceramics are also discussed.

Laser ablation ICP-MS profiling and semiquantitative determination of trace element concentrations in desert tortoise shells: documenting the uptake of elemental toxicants.

PubMed

Seltzer, Michaeld; Berry, Kristinh

2005-03-01

The outer keratin layer (scute) of desert tortoise shells consists of incrementally grown laminae in which various bioaccumulated trace elements are sequestered during scute deposition. Laser ablation ICP-MS examination of laminae in scutes of dead tortoises revealed patterns of trace elemental distribution from which the chronology of elemental uptake can be inferred. These patterns may be of pathologic significance in the case of elemental toxicants such as arsenic, which has been linked to both shell and respiratory diseases. Laser ablation transects, performed along the lateral surfaces of sectioned scutes, offered the most successful means of avoiding exogenous contamination that was present on the scute exterior. Semiquantitative determination of elemental concentrations was achieved using sulfur, a keratin matrix element, as an internal standard. The results presented here highlight the potential of laser ablation ICP-MS as a diagnostic tool for investigating toxic element uptake as it pertains to tortoise morbidity and mortality.

Laser ablation ICP-MS profiling and semiquantitative determination of trace element concentrations in desert tortoise shells: Documenting the uptake of elemental toxicants

USGS Publications Warehouse

Seltzer, M.D.; Berry, K.H.

2005-01-01

The outer keratin layer (scute) of desert tortoise shells consists of incrementally grown laminae in which various bioaccumulated trace elements are sequestered during scute deposition. Laser ablation ICP-MS examination of laminae in scutes of dead tortoises revealed patterns of trace elemental distribution from which the chronology of elemental uptake can be inferred. These patterns may be of pathologic significance in the case of elemental toxicants such as arsenic, which has been linked to both shell and respiratory diseases. Laser ablation transects, performed along the lateral surfaces of sectioned scutes, offered the most successful means of avoiding exogenous contamination that was present on the scute exterior. Semiquantitative determination of elemental concentrations was achieved using sulfur, a keratin matrix element, as an internal standard. The results presented here highlight the potential of laser ablation ICP-MS as a diagnostic tool for investigating toxic element uptake as it pertains to tortoise morbidity and mortality.

Geochronology of Zircon in Eclogite Reveals Imbrication of the Ultrahigh-Pressure Western Gneiss Region of Norway.

NASA Astrophysics Data System (ADS)

Young, D. J.; Kylander-Clark, A. R.; Root, D. B.

2014-12-01

Eclogite provides the only record of kinematic events at the deepest levels of orogens. Integrating the U-Pb geochronology and trace element chemistry of zircon in eclogite reveals the most complete view of the PTt history, yet low concentrations of uranium and zirconium and drier compositions that hinder zircon growth at peak conditions render it a challenging rocktype for this approach. The iconic Western Gneiss Region (WGR) in Norway is one of the largest terranes of deeply subducted continental rocks in the world, and contains many indicators of ultrahigh-pressure metamorphic conditions (P>2.8 GPa) that developed during the Siluro-Devonian Caledonian Orogeny. A metamorphic transition from amphibolite-facies to ultrahigh-pressure eclogite facies broadly coincides with a km-scale shear zone that underlies the majority of the WGR. A critical unknown is the timing of movement on this feature, which emplaced allochthonous units above the Baltica basement, but might also have accommodated late-orogenic exhumation of the WGR from mantle depths. We carried out laser ablation split-stream ICPMS (LASS) and selected multigrain TIMS analyses of zircons from eleven eclogites across the southern WGR, of which eight are located within or above the shear zone. LASS spots on polished grains mostly yield weakly discordant Proterozoic intrusive ages, and often minimal indication of a Caledonian (U)HP metamorphic overprint. Direct ablation into unpolished zircon reveals thin rims of Caledonian age in some cases. Overall, the dataset shows that all samples began zircon growth at approximately the same time (ca. 430-420 Ma). Eclogite from lower levels of the shear zone does not contain any dates younger than ca. 410 Ma, however, while eclogite from higher levels continued growth until ca. 400 Ma. We interpret this to result from thrusting of the WGR above cooler basement after 410 Ma, terminating new zircon crystallization within the shear zone but allowing limited further growth in

The performance and the characterization of laser ablation aerosol particle time-of-flight mass spectrometry (LAAP-ToF-MS)

NASA Astrophysics Data System (ADS)

Gemayel, Rachel; Hellebust, Stig; Temime-Roussel, Brice; Hayeck, Nathalie; Van Elteren, Johannes T.; Wortham, Henri; Gligorovski, Sasho

2016-05-01

Hyphenated laser ablation-mass spectrometry instruments have been recognized as useful analytical tools for the detection and chemical characterization of aerosol particles. Here we describe the performances of a laser ablation aerosol particle time-of-flight mass spectrometer (LAAP-ToF-MS) which was designed for aerodynamic particle sizing using two 405 nm scattering lasers and characterization of the chemical composition of single aerosol particle via ablation/ionization by a 193 nm excimer laser and detection in a bipolar time-of-flight mass spectrometer with a mass resolving power of m/Δm > 600.

We describe a laboratory based optimization strategy for the development of an analytical methodology for characterization of atmospheric particles using the LAAP-ToF-MS instrument in combination with a particle generator, a differential mobility analyzer and an optical particle counter. We investigated the influence of particle number concentration, particle size and particle composition on the detection efficiency. The detection efficiency is a product of the scattering efficiency of the laser diodes and the ionization efficiency or hit rate of the excimer laser. The scattering efficiency was found to vary between 0.6 and 1.9 % with an average of 1.1 %; the relative standard deviation (RSD) was 17.0 %. The hit rate exhibited good repeatability with an average value of 63 % and an RSD of 18 %. In addition to laboratory tests, the LAAP-ToF-MS was used to sample ambient air during a period of 6 days at the campus of Aix-Marseille University, situated in the city center of Marseille, France. The optimized LAAP-ToF-MS methodology enables high temporal resolution measurements of the chemical composition of ambient particles, provides new insights into environmental science, and a new investigative tool for atmospheric chemistry and physics, aerosol science and health impact studies.

Allanite age-dating: Non-matrix-matched standardization in quadrupole LA-ICP-MS

NASA Astrophysics Data System (ADS)

Burn, M.; Lanari, P.; Pettke, T.; Engi, M.

2014-12-01

Allanite Th-U-Pb age-dating has recently been found to be powerful in unraveling the timing of geological processes such as the metamorphic dynamics in subduction zones and crystallization velocity of magmas. However, inconsistencies among analytical techniques have raised doubts about the accuracy of allanite age data. Spot analysis techniques such as LA-ICP-MS are claimed to be crucially dependent on matrix-matched standards, the quality of which is variable. We present a new approach in LA-ICP-MS data reduction that allows non-matrix-matched standardization via well constrained zircon reference materials as primary standards. Our data were obtained using a GeoLas Pro 193 nm ArF excimer laser ablation system coupled to an ELAN DRC-e quadrupole ICP-MS. We use 32 μm and 24 μm spot sizes; laser operating conditions of 9 Hz repetition rate and 2.5 J/cm2 fluence have proven advantageous. Matrix dependent downhole fractionation evolution is empirically determined by analyzing 208Pb/232Th and 206Pb/238U and applied prior to standardization. The new data reduction technique was tested on three magmatic allanite reference materials (SISSb, CAPb, TARA); within error these show the same downhole fractionation evolution for all allanite types and in different analytical sessions, provided measurement conditions remain the same. Although the downhole evolution of allanite and zircon differs significantly, a link between zircon and allanite matrix is established by assuming CAPb and TARA to be fixed at the corresponding reference ages. Our weighted mean 208Pb/232Th ages are 30.06 ± 0.22 (2σ) for SISSb, 275.4 ± 1.3 (2σ) for CAPb, and 409.9 ± 1.8 (2σ) for TARA. Precision of single spot age data varies between 1.5 and 8 % (2σ), dependent on spot size and common lead concentrations. Quadrupole LA-ICP-MS allanite age-dating has thus similar uncertainties as do other spot analysis techniques. The new data reduction technique is much less dependent on quality and homogeneity

Tracing the depositional history of Kalimantan diamonds by zircon provenance and diamond morphology studies

NASA Astrophysics Data System (ADS)

Kueter, Nico; Soesilo, Joko; Fedortchouk, Yana; Nestola, Fabrizio; Belluco, Lorenzo; Troch, Juliana; Wälle, Markus; Guillong, Marcel; Von Quadt, Albrecht; Driesner, Thomas

2016-11-01

Diamonds in alluvial deposits in Southeast Asia are not accompanied by indicator minerals suggesting primary kimberlite or lamproite sources. The Meratus Mountains in Southeast Borneo (Province Kalimantan Selatan, Indonesia) provide the largest known deposit of these so-called "headless" diamond deposits. Proposals for the origin of Kalimantan diamonds include the adjacent Meratus ophiolite complex, ultra-high pressure (UHP) metamorphic terranes, obducted subcontinental lithospheric mantle and undiscovered kimberlite-type sources. Here we report results from detailed sediment provenance analysis of diamond-bearing Quaternary river channel material and from representative outcrops of the oldest known formations within the Alino Group, including the diamond-bearing Campanian-Maastrichtian Manunggul Formation. Optical examination of surfaces of diamonds collected from artisanal miners in the Meratus area (247 stones) and in West Borneo (Sanggau Area, Province Kalimantan Barat; 85 stones) points toward a classical kimberlite-type source for the majority of these diamonds. Some of the diamonds host mineral inclusions suitable for deep single-crystal X-ray diffraction investigation. We determined the depth of formation of two olivines, one coesite and one peridotitic garnet inclusion. Pressure of formation estimates for the peridotitic garnet at independently derived temperatures of 930-1250 °C are between 4.8 and 6.0 GPa. Sediment provenance analysis includes petrography coupled to analyses of detrital garnet and glaucophane. The compositions of these key minerals do not indicate kimberlite-derived material. By analyzing almost 1400 zircons for trace element concentrations with laser ablation ICP-MS (LA-ICP-MS) we tested the mineral's potential as an alternative kimberlite indicator. The screening ultimately resulted in a small subset of ten zircons with a kimberlitic affinity. Subsequent U-Pb dating resulting in Cretaceous ages plus a detailed chemical reflection make

Usefulness of laser ablation ICP-MS for analysis of metallic particles released to oral mucosa after insertion of dental implants.

PubMed

Sajnóg, Adam; Hanć, Anetta; Koczorowski, Ryszard; Makuch, Krzysztof; Barałkiewicz, Danuta

2018-03-01

Despite the fact that titanium is considered highly biocompatible, its presence in the oral cavity (an environment of frequently changing pH and temperature) may result in the release of titanium from intraosseous implants into the oral mucosa, causing a range of reactions from the human body. Fragments of oral mucosa collected from patients after dental implant insertion were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The study revealed an elevated content of elements (Ti, Al, V) which are components of the metal implants and temporary cover screws. Dynamic ablation of the tissue surface was used in order to obtain maps of the content and distribution of analyzed elements. The material consisted of 30 oral mucosa tissue fragments collected 3-5 months after implantation and 10 samples collected before implantation (control group). The application of optical microscope allowed for indication and confirmation of the location of metal particles prior to LA-ICP-MS analysis. The so-obtained map permitted location of regions containing metal particles. LA-ICP-MS analysis revealed groups of samples with similar properties of metal particles, thus confirming that those metal particles were the main source of the elevated content of metals (Ti, Al, V) in the tissue after implantation. A calibration strategy based on matrix matched solid standards with powdered egg white proteins as matrix material was applied with 34 S as an internal standard. The accuracy of the analytical method was verified by ablating pellets of certified reference material ERM-BB422 Fish muscle. Copyright © 2017 Elsevier GmbH. All rights reserved.

Ambient infrared laser ablation mass spectrometry (AIRLAB-MS) of live plant tissue with plume capture by continuous flow solvent probe.

PubMed

O'Brien, Jeremy T; Williams, Evan R; Holman, Hoi-Ying N

2015-03-03

A new experimental setup for spatially resolved ambient infrared laser ablation-mass spectrometry (AIRLAB-MS) that uses an infrared microscope with an infinity-corrected reflective objective and a continuous flow solvent probe coupled to a Fourier transform ion cyclotron resonance mass spectrometer is described. The efficiency of material transfer from the sample to the electrospray ionization emitter was determined using glycerol/methanol droplets containing 1 mM nicotine and is ∼50%. This transfer efficiency is significantly higher than values reported for similar techniques. Laser desorption does not induce fragmentation of biomolecules in droplets containing bradykinin, leucine enkephalin and myoglobin, but loss of the heme group from myoglobin occurs as a result of the denaturing solution used. An application of AIRLAB-MS to biological materials is demonstrated for tobacco leaves. Chemical components are identified from the spatially resolved mass spectra of the ablated plant material, including nicotine and uridine. The reproducibility of measurements made using AIRLAB-MS on plant material was demonstrated by the ablation of six closely spaced areas (within 2 × 2 mm) on a young tobacco leaf, and the results indicate a standard deviation of <10% in the uridine signal obtained for each area. The spatial distribution of nicotine was measured for selected leaf areas and variation in the relative nicotine levels (15-100%) was observed. Comparative analysis of the nicotine distribution was demonstrated for two tobacco plant varieties, a genetically modified plant and its corresponding wild-type, indicating generally higher nicotine levels in the mutant.

Crustal Zircons from the Podiform Chromitites in Luobusa Ophiolite, Tibet

NASA Astrophysics Data System (ADS)

Yamamoto, S.; Komiya, T.; Maruyama, S.

2004-12-01

For the past decade, diamonds and unusual mineral asemblages were reported in podiform chromitites of the Luobusa ophiolite, southern Tibet, China (Bai 1993, Bai 2000, Yan 2001) by heavy mineral separation. These include (1) native elements, (2) alloys, (3) carbide, (4) platinium group elements (PGE) and arsenides, (5) silicates (6) oxide, (7) carbonates, (8) minerals with unusual compositons. Despite many questions as to these minerals above still remain open, these mineral inclusions would provide us the important infomation on the formation of the podiform chromitites. In this study, over 100 zircons were discovered by heavy mineral separation of podiform chromitite in Luobusa ophiolite. The discovery of accessory zircons in chromitites allowed us to date the formation of the chromitite and history of tectonic evolutions. Here we report the U-Pb age and mineral inclusions of zircons and discuss with unusually old age zircons. 20 zircon grains in chromitites from No. 1 site were analyzed. Zircons from the chromitites in Luobusa ophiolite are usually euhedral-subhedral and some are rounded. Cathodoluminescence images of these zircons indicate that some zircons have clear oscillatory zoning, whereas other zircons show apparent homogeneous overgrowth. U-Pb dating of these zircons by LA-ICP-MS yielded two different ages. One group has relatively younger age, 107-534Ma, which plots nearly on a concordia line. Another group has older age 1460-1822Ma, which plots off the concordia line. There is insignificant difference of apparent ages within a single zircon grain. For example, a zircon has 1650 Ma in the core, whereas does 1654 Ma in the rim. We identified several mineral inclusions, quartz, feldspar, mica, apatite, within both yonger and older zircons using laser-Raman spectrometry and EPMA. No high-pressure minerals or mantle minerals were identified. This means that these unusually old zircons were formed in low-pressure crustal emvironment. Where did the zircons

Analysis of rare earth elements in coal fly ash using laser ablation inductively coupled plasma mass spectrometry and scanning electron microscopy

NASA Astrophysics Data System (ADS)

Thompson, Robert L.; Bank, Tracy; Montross, Scott; Roth, Elliot; Howard, Bret; Verba, Circe; Granite, Evan

2018-05-01

Reference standard NIST SRM 1633b and FA 345, a fly ash sample from an eastern U.S. coal power plant, were analyzed to determine and quantify the mineralogical association of rare earth elements (REE). These analyses were completed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and a scanning electron microscope, equipped with an energy-dispersive X-ray spectrometer (SEM-EDS). Internal standardization was avoided by quantifying elemental concentrations by normalizing to 100% oxides. Mineral grains containing elevated REE concentrations were found in diverse chemical environments, but were most commonly found in regions where Al and Si were predominant. Dividing the spot analyses into time segments yielded plots that showed the REE content changing over time as individual mineral grains were being ablated. SEM-EDS images of FA 345 confirmed the trends that were found in the LA-ICP-MS results. Small grains of apatite, monazite, or zircon were frequently observed as free mineral grains or embedded in amorphous aluminosilicate glass and were not associated with ferrous particles. This finding is consistent with previous reports that magnetic enrichment may be an effective way of concentrating non-magnetic REE phases. Furthermore, aggressive mechanical and chemical-based separation schemes will be required to separate and recover REE from aluminosilicate glass.

Trace elemental analysis of glass and paint samples of forensic interest by ICP-MS using laser ablation solid sample introduction

NASA Astrophysics Data System (ADS)

Almirall, Jose R.; Trejos, Tatiana; Hobbs, Andria; Furton, Kenneth G.

2003-09-01

The importance of small amounts of glass and paint evidence as a means to associate a crime event to a suspect or a suspect to another individual has been demonstrated in many cases. Glass is a fragile material that is often found at the scenes of crimes such as burglaries, hit-and-run accidents and violent crime offenses. Previous work has demonstrated the utility of elemental analysis by solution ICP-MS of small amounts of glass for the comparison between a fragment found at a crime scene to a possible source of the glass. The multi-element capability and the sensitivity of ICP-MS combined with the simplified sample introduction of laser ablation prior to ion detection provides for an excellent and relatively non-destructive technique for elemental analysis of glass fragments. The direct solid sample introduction technique of laser ablation (LA) is reported as an alternative to the solution method. Direct solid sampling provides several advantages over solution methods and shows great potential for a number of solid sample analyses in forensic science. The advantages of laser ablation include the simplification of sample preparation, thereby reducing the time and complexity of the analysis, the elimination of handling acid dissolution reagents such as HF and the reduction of sources of interferences in the ionization plasma. Direct sampling also provides for essentially "non-destructive" sampling due to the removal of very small amounts of sample needed for analysis. The discrimination potential of LA-ICP-MS is compared with previously reported solution ICP-MS methods using external calibration with internal standardization and a newly reported solution isotope dilution (ID) method. A total of ninety-one different glass samples were used for the comparison study using the techniques mentioned. One set consisted of forty-five headlamps taken from a variety of automobiles representing a range of twenty years of manufacturing dates. A second set consisted of forty

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

QEMSCAN+LA-ICP-MS: a 'big data' generator for sedimentary provenance analysis

NASA Astrophysics Data System (ADS)

Vermeesch, Pieter; Rittner, Martin; Garzanti, Eduardo

2017-04-01

Sedimentary provenance may be traced by 'fingerprinting' sediments with chemical, mineralogical or isotopic means. Normally, each of these provenance proxies is characterised on a separate aliquot of the same sample. For example, the chemical composition of the bulk sample may be analysed by X-ray fluorescence (XRF) on one aliquot, framework petrography on another, heavy mineral analysis on a density separate of a third split, and zircon U-Pb dating on a further density separate of the heavy mineral fraction. The labour intensity of this procedure holds back the widespread application of multi-method provenance studies. We here present a new method to solve this problem and avoid mineral separation by coupling a QEMSCAN electron microscope to an LA-ICP-MS instrument and thereby generate all four aforementioned provenance datasets as part of the same workflow. Given a polished hand specimen, a petrographic thin section, or a grain mount, the QEMSCAN+LA-ICP-MS method produces chemical and mineralogical maps from which the X-Y coordinates of the datable mineral are extracted. These coordinates are subsequently passed on to the laser ablation system for isotopic and, hence, geochronological analysis. In the process of finding all the zircons in a sediment grain mount, the QEMSCAN yields the compositional and mineralogical compositions as byproducts. We have applied the new QEMSCAN+LA-ICP-MS instrument suite to over 100 samples from three large sediment routing systems: (1) the Tigris-Euphrates river catchments and Rub' Al Khali desert in Arabia; (2) the Nile catchment in northeast Africa and (3) desert and beach sands between the Orange and Congo rivers in southwest Africa. These studies reveal (1) that Rub' Al Khali sand is predominantly derived from the Arabian Shield and not from Mesopotamia; (2) that the Blue Nile is the principal source of Nile sand; and (3) that Orange River sand is carried northward by longshore drift nearly 1,800km from South Africa to southern

Bioimaging of metallothioneins in ocular tissue sections by laser ablation-ICP-MS using bioconjugated gold nanoclusters as specific tags.

PubMed

Cruz-Alonso, María; Fernandez, Beatriz; Álvarez, Lydia; González-Iglesias, Héctor; Traub, Heike; Jakubowski, Norbert; Pereiro, Rosario

2017-12-18

An immunohistochemical method is described to visualize the distribution of metallothioneins 1/2 (MT 1/2) and metallothionein 3 (MT 3) in human ocular tissue. It is making use of (a) antibodies conjugated to gold nanoclusters (AuNCs) acting as labels, and (b) laser ablation (LA) coupled to inductively coupled plasma - mass spectrometry (ICP-MS). Water-soluble fluorescent AuNCs (with an average size of 2.7 nm) were synthesized and then conjugated to antibody by carbodiimide coupling. The surface of the modified AuNCs was then blocked with hydroxylamine to avoid nonspecific interactions with biological tissue. Immunoassays for MT 1/2 and MT 3 in ocular tissue sections (5 μm thick) from two post mortem human donors were performed. Imaging studies were then performed by fluorescence using confocal microscopy, and LA-ICP-MS was performed in the retina to measure the signal for gold. Signal amplification by the >500 gold atoms in each nanocluster allowed the antigens (MT 1/2 and MT 3) to be imaged by LA-ICP-MS using a laser spot size as small as 4 μm. The image patterns found in retina are in good agreement with those obtained by conventional fluorescence immunohistochemistry which was used as an established reference method. Graphical abstract Gold nanoclusters (AuNCs) conjugated to a primary specific antibody serve as a label for amplified bioimaging of metallothioneins (MTs) by laser ablation coupled to inductively coupled plasma - mass spectrometry (ICP-MS) in human ocular tissue sections.

Zircon U-Pb age of the Pescadero felsite: A late Cretaceous igneous event in the forearc, west-central California Coast Ranges

USGS Publications Warehouse

Ernst, W.G.; Martens, U.C.; McLaughlin, R.J.; Clark, J.C.; Moore, Diane E.

2011-01-01

Weathered felsite is associated with the late Campanian-Maastrichtian Pigeon Point Formation near Pescadero, California. Poorly exposed, its age and correlation are uncertain. Is it part of the Pigeon Point section west of the San Gregorio-Hosgri fault? Does it rest on Nacimiento block basement? Is it dextrally offset from the Oligocene Cambria Felsite, ~185 km to the southeast? Why is a calc-alkaline hypabyssal igneous rock intrusive into the outboard accretionary prism? To address these questions, we analyzed 43 oscillatory-zoned zircon crystals from three incipiently recrystallized pumpellyite ?? prehnite ?? laumontite-bearing Pescadero felsite samples by sensitive high-resolution ion microprobe-reverse geometry (SHRIMPRG) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) techniques. Thirty-three zircons gave late Mesozoic U-Pb ages, with single-grain values ranging from 81 to 167 Ma; ten have pre-Mesozoic, chiefl y Proterozoic ages. A group of the four youngest Pescadero zircons yielded an apparent maximum igneous age of ca. 86-90 Ma. Refl ecting broad age scatter and presence of partly digested sandstone inclusions, we interpret the rest of the zircons (perhaps all) as xenocrysts. Twenty-three zircons were separated and analyzed from two samples of the similar Cambria Felsite, yielding a unimodal 27 Ma U-Pb age. Clearly, the origin of the Upper Oligocene Cambria Felsite is different from that of the Upper Cretaceous Pescadero felsite; these rocks are not correlated, and do not constrain displacement along the San Gregorio-Hosgri fault. Peak ages differ slightly, but relative probability curves for Mesozoic and pre-Mesozoic Pescadero zircons compare well, for example, with abundant U-Pb age data for detrital zircons from Franciscan metaclastic strata ~100 km to the east in the Diablo Range- San Francisco Bay area, San Joaquin Great Valley Group turbidites, Upper Cretaceous Nacimiento block Franciscan strata, and Upper Cretaceous

Detrital zircon provenance from three turbidite depocenters of the Middle-Upper Triassic Songpan-Ganzi complex, central China: Record of collisional tectonics, erosional exhumation, and sediment production

USGS Publications Warehouse

Weislogel, A.L.; Graham, S.A.; Chang, E.Z.; Wooden, J.L.; Gehrels, G.E.

2010-01-01

To test the idea that the voluminous upper Middle to Upper Triassic turbidite strata in the Songpan-Ganzi complex of central China archive a detrital record of Dabie ultrahigh-pressure (UHP) terrane unroofing, we report 2080 single detrital U-Pb zircon ages by sensitive high-resolution ion microprobe-reverse geometry (SHRIMP-RG) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis from 29 eastern Songpan-Ganzi complex sandstone samples. Low (<0.07) Th/U zircons, consistent with crystallization under UHP conditions, are rare in eastern Songpan-Ganzi complex zircon, and U-Pb ages of low Th/U zircons are incompatible with a Dabie terrane source. An unweighted pair group method with arithmetic mean nearest-neighbor analysis of Kolmogorov-Smirnov two-sample test results reveals that the eastern Songpan-Ganzi complex is not a single contiguous turbidite system but is instead composed of three subsidiary depocenters, each associated with distinct sediment sources. The northeastern depocenter contains zircon ages characterized by Paleozoic and bimodally distributed Precambrian zircon populations, which, together with south-to southeast-directed paleocurrent data, indicate derivation from the retro-side of the Qinling-Dabie (Q-D) collisional orogen wedge. In the central depocenter, the dominantly Paleozoic detrital zircon signature and south-to southwest-oriented paleocurrent indicators reflect a profusion of Paleozoic zircon grains. These data are interpreted to reflect an influx of material derived from erosion of Paleozoic supra-UHP rocks of the Dabie terrane in the eastern Qinling-Dabie orogen, which we speculate may have been enhanced by development of a monsoonal climate. This suggests that erosional unroofing played a significant role in the initial phase of UHP exhumation and likely influenced the petrotectonic and structural evolution of the Qinling-Dabie orogen, as evidenced by compressed Triassic isotherms/grads reported in the

Spark ablation-inductively coupled plasma spectrometry for analysis of geologic materials

USGS Publications Warehouse

Golightly, D.W.; Montaser, A.; Smith, B.L.; Dorrzapf, A.F.

1989-01-01

Spark ablation-inductively coupled plasma (SA-ICP) spectrometry is applied to the measurement of hafnium-zirconium ratios in zircons and to the determination of cerium, cobalt, iron, lead, nickel and phosphorus in ferromanganese nodules. Six operating parameters used for the high-voltage spark and argon-ICP combination are established by sequential simplex optimization of both signal-to-background ratio and signal-to-noise ratio. The time-dependences of the atomic emission signals of analytes and matrix elements ablated from a finely pulverized sample embedded in a pressed disk of copper demonstrate selective sampling by the spark. Concentration ratios of hafnium to zirconium in zircons are measured with a precision of 4% (relative standard deviation, RSD). For ferromanganese nodules, spectral measurements based on intensity ratios of analyte line to the Mn(II) 257.610 nm line provide precisions of analysis in the range from 7 to 14% RSD. The accuracy of analysis depends on use of standard additions of the reference material USGS Nod P-1, and an independent measurement of the Mn concentration. ?? 1989.

Ambient infrared laser ablation mass spectrometry (AIRLAB-MS) with plume capture by continuous flow solvent probe

DOEpatents

O'Brien, Jeremy T.; Williams, Evan R.; Holman, Hoi-Ying N.

2017-10-31

A new experimental setup for spatially resolved ambient infrared laser ablation mass spectrometry (AIRLAB-MS) that uses an infrared microscope with an infinity-corrected reflective objective and a continuous flow solvent probe coupled to a Fourier transform ion cyclotron resonance mass spectrometer is described. The efficiency of material transfer from the sample to the electrospray ionization emitter was determined using glycerol/methanol droplets containing 1 mM nicotine and is .about.50%. This transfer efficiency is significantly higher than values reported for similar techniques.

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

USGS Publications Warehouse

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

2007-01-01

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

Evaluating the utility of detrital thermochronometric studies: detrital laser ablation (U-Th)/He dating and conventional bedrock zircon (U-Th)/He analyses from the eastern Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Horne, A.; Hodges, K. V.; Van Soest, M. C.

2016-12-01

Recent applications of the newly developed `laser ablation double dating' (LADD) technique, an integrated laser microprobe U/Pb and (U-Th)/He dating method, have showcased the potential utility of LADD for detrital thermochronologic studies. However, detrital thermochronologic techniques rely on confidence that detrital data adequately represent the full range of bedrock cooling ages within a catchment. To test this primary assumption, we compare (U-Th)/He zircon ages from age-elevation transects to LADD (U-Th)/He zircon ages from modern fluvial detritus collected at the range front in the eastern Sierra Nevada, California. Terminated by a normal fault escarpment, the small, steep catchments along the eastern side of the Sierra Nevada batholith are apropos locations for comparing the ability of detrital data to deduce the exhumation history of a source terrain with standard age-elevation transects. Additionally, the exhumation of the Sierra Nevada batholith is also intriguing, as past evaluations of the post-emplacement exhumation history of the range have yielded discrepant results. Thus far, analyses from the southern extent of the eastern Sierra Nevada show narrow ranges of cooling ages consistent with simple, relatively rapid exhumation. Ongoing analyses will expand the dataset such that we can fully compare bedrock and detrital age ranges as well as characterize the exhumation history of the range with a thermochronometer that has not been used to date the batholith.

Evidence for Archean inheritance in the pre-Panafrican crust of Central Cameroon: Insight from zircon internal structure and LA-MC-ICP-MS Usbnd Pb ages

NASA Astrophysics Data System (ADS)

Ganwa, Alembert Alexandre; Klötzli, Urs Stephan; Hauzenberger, Christoph

2016-08-01

The main geological feature of Central Cameroon is the wide spread occurrence of granitoids emplaced in close association with transcurrent regional shear zones. The basement of this vast domain is a Paleoproterozoic ortho-and para-derivative formation, which has been intensely reworked, together with subsequent intrusions and sediments, during the Panafrican orogenesis in the Neoproterozoic. As consequence, the area underwent pervasive metamorphism and intense deformation. This makes it difficult to distinguish between Panafrican metasediments or syntectonic plutonites and their respective basement. Our study presents zircon features (CL-BSE-SE) and in-situ U-Th-Pb LA-MC-ICP-MS geochronology of a meta-sedimentary pyroxene-amphibole-bearing gneiss of the Méiganga area in Central Cameroon. Based on the Internal structures of the zircon four characteristic zonation patterns can be deciphered: 1) cores with magmatic oscillatory zonation 2) zircons with oscillatory or sector zonation, 3) zircons with sector zoning or blurred zoning, and 4) narrow bright un-zoned rims. These groups suggest that the rock experienced a number of geological events. Considering this zircon characteristic, the U-Th-Pb data allow to distinguish four ages: 2116 ± 57 Ma, consistent with ages from the Paleoproterozoic West Central African Belt; 2551 ± 33 Ma which marks a late Neoarchean magmatic event; 2721 ± 27 Ma related to a Neoarchean magmatic even in Central Cameroon, similar to one found in the Congo Craton. A zircon core gives ages around 2925 Ma which provides some evidence of the presence of the Mesoarchean basement prior to the Neoarchean magmatism. A weighted average of lower intercepts ages gives a value of 821 ± 50 Ma, representing the age of later metamorphism event. The various characteristic group and related ages reflect not only the complexity of the history of the pyroxene amphibole gneiss, but also show that the meta-sediment has at least three zircon contributing

Temporal and Spatial Fluctuations in Ancestral Northern Cascade Arc Magmatism from New LA-ICP-MS U-Pb Zircon Dating

NASA Astrophysics Data System (ADS)

McCallum, I. S.; Mullen, E.; Jean-Louis, P.; Tepper, J. H.

2015-12-01

Mt. Baker and the adjacent Chilliwack batholith (MBC focus) in NW Washington preserve the longest magmatic record in the Cascade Arc, providing an excellent natural laboratory for examining the spatial, temporal and geochemical evolution of Cascade magmatism and links to tectonic processes. We present new U-Pb zircon LA-ICP-MS ages for 14 samples from MBC and neighboring regions of the north Cascades. The new results are up to 8 Myr different from previous K-Ar ages, illustrating the need for new age determinations in the Cascades. A maximum age of 34.74±0.24 Ma (2σ) (Post Creek stock) is consistent with 35-40 Ma ages for arc inception in the southern Cascades. The most voluminous MBC plutons cluster at 32-29 Ma, consistent with an early flare-up that also coincides with intrusion of the Index batholith farther south (2 samples at 33.26±0.19, 33.53±0.15 Ma). This flare-up is absent in the northernmost Cascades where the oldest pluton (Fall Creek stock) is 6.646±0.046 Ma, 4 Myr younger than previously cited. Earliest Cascade magmatism is progressively younger to the north of MBC, possibly tracing the northerly passage of the slab edge. MBC activity was continuous to 22.75±0.17 Ma (Whatcom Arm), marking the initiation of an 11 Myr hiatus. Magmatism resumed at 11.33±0.08 Ma (Indian Creek) and continued to the modern Mt. Baker cone, defining a pattern of southwesterly migration over ~55 km that may be attributable to slab rollback and arc rotation (e.g. Wells & McCaffrey 2013). Uniformity of the rate and direction of migration implies that rollback and rotation began at least 11 Myr ago. Post-hiatus magmas show distinct geochemical and petrologic characteristics including a major Pb isotopic shift. The 2.430±0.016 Ma Lake Ann stock contains 4.2 Ma zircon antecrysts, recording prolonged activity in that area. The 1.165±0.013 Ma Kulshan caldera ignimbrite contains ~200 Ma inherited zircons that may provide the first direct record of Wrangellian basement beneath

Tandem Laser Induced Breakdown Spectroscopy (LIBS), Laser Ablation Inductively Coupled Plasma Mass Spectroscopy (LA-ICP-MS) and/or Laser Ablation Inductively Coupled Plasma Optical Emission Spectroscopy (LA-ICP-OES) for the analysis of samples of geological interest

NASA Astrophysics Data System (ADS)

Oropeza, D.

2016-12-01

A highly innovative laser ablation sampling instrument (J200 Tandem LA - LIBS) that combines the capabilities and analytical benefits of LIBS, LA-ICP-MS and LA-ICP-OES was used for micrometer-scale, spatially-resolved, elemental analysis of a wide variety of samples of geological interest. Data collected using ablation systems consisted of nanosecond (Nd:YAG operated 266nm) and femtosecond lasers (1030 and 343nm). An ICCD LIBS detector and Quadrupole based mass spectrometer were selected for LIBS and ICP-MS detection, respectively. This tandem instrument allows simultaneous determination of major and minor elements (for example, Si, Ca, Na, and Al, and trace elements such as Li, Ce, Cr, Sr, Y, Zn, Zr among others). The research also focused on elemental mapping and calibration strategies, specifically the use of emission and mass spectra for multivariate data analysis. Partial Least Square Regression (PLSR) is shown to minimize and compensate for matrix effects in the emission and mass spectra improving quantitative analysis by LIBS and LA-ICP-MS, respectively. The study provides a benchmark to evaluate analytical results for more complex geological sample matrices.

High resolution analysis of trace elements in corals by laser ablation ICP-MS

NASA Astrophysics Data System (ADS)

Sinclair, Daniel J.; Kinsley, Leslie P. J.; McCulloch, Malcolm T.

1998-06-01

A method has been developed using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for rapid high resolution analysis of B, Mg, Sr, Ba, and U in corals. Corals represent a challenge for a microbeam technique due to their compositional and structural heterogeneity, their nonsilicate matrix, and their unusual range of trace element compositions relative to available standards. The method employs an argon-fluoride excimer laser (λ = 193 nm), masked to produce a beam 600 μm wide by 20 μm across to average ablation sampling over a range of structural features. Coral sections are scanned at a constant rate beneath the laser to produce a continuous sampling of the coral surface. Sensitivity drift is controlled by careful preconditioning of the ICP-MS to carbonate material, and standardisation is carried out by bracketing each traverse down the coral sample by analyses of a CaSiO 3 glass synthesised from coral powder. The method demonstrates excellent reproducibility of both the shape and magnitude of coralline trace element profiles, with typical precisions of between 1.0 and 3.7% based on analysis of the synthetic standard. Accuracy varies between 3.8% for B and 31% for U. Discrepancies are attributed to heterogeneities in the synthetic standard, and matrix differences between the silicate standard and carbonate sample. The method is demonstrated by analysis of a coral collected from Australia's Great Barrier Reef near a weather station recording in-situ sea-surface-temperature (SST). The elements B, Mg, Sr, and U show seasonal compositional cycles, and tentative calibrations against SST have been derived. Using independent ICP-MS solution estimates of the coral composition to correct for standardisation uncertainties, the following calibrations have been derived: B/Ca (μmol/mol)= 1000 (±20)- 20.6 (±0.8)× SSTMg/Ca (mmol/mol)= 0.0 (±0.3)+ 0.16 (±0.01)× SSTSr/Ca (mmol/mol)= 10.8 (±0.1)- 0.070 (±0.004)× SSTU/Ca (μmol/mol)= 2.24 (±0

The influence of laser pulse duration and energy on ICP-MS signal intensity, elemental fractionation, and particle size distribution in NIR fs-LA-ICP-MS

PubMed Central

Diwakar, Prasoon K.; Harilal, Sivanandan S.; LaHaye, Nicole L.; Hassanein, Ahmed; Kulkarni, Pramod

2015-01-01

Laser parameters, typically wavelength, pulse width, irradiance, repetition rate, and pulse energy, are critical parameters which influence the laser ablation process and thereby influence the LA-ICP-MS signal. In recent times, femtosecond laser ablation has gained popularity owing to the reduction in fractionation related issues and improved analytical performance which can provide matrix-independent sampling. The advantage offered by fs-LA is due to shorter pulse duration of the laser as compared to the phonon relaxation time and heat diffusion time. Hence the thermal effects are minimized in fs-LA. Recently, fs-LA-ICP-MS demonstrated improved analytical performance as compared to ns-LA-ICP-MS, but detailed mechanisms and processes are still not clearly understood. Improvement of fs-LA-ICP-MS over ns-LA-ICP-MS elucidates the importance of laser pulse duration and related effects on the ablation process. In this study, we have investigated the influence of laser pulse width (40 fs to 0.3 ns) and energy on LA-ICP-MS signal intensity and repeatability using a brass sample. Experiments were performed in single spot ablation mode as well as rastering ablation mode to monitor the Cu/Zn ratio. The recorded ICP-MS signal was correlated with total particle counts generated during laser ablation as well as particle size distribution. Our results show the importance of pulse width effects in the fs regime that becomes more pronounced when moving from femtosecond to picosecond and nanosecond regimes. PMID:26664120

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

PubMed Central

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

2016-01-01

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

Siderophile Element Profile Measurements in Iron Meteorites Using Laser Ablation ICP-MS

NASA Technical Reports Server (NTRS)

Watson, H. C.; Watson, E. B.; McDonough, W. F.

2005-01-01

Understanding the behaviour of siderophile elements during cooling of iron meteorites can lead to insight into the general thermal histories of the meteorites as well as their respective parent bodies. Traditionally trace element analyses in meteorites have been done using techniques that only measure the average concentration in each phase. With these methods, all of the spatial information with respect to the distribution of an element within one phase is lost. Measuring concentration profiles of trace elements in meteorites is now possible, with the advent of high-resolution analytical techniques such as laser ablation, inductively coupled plasma mass spectrometry (LA-ICP-MS) with spatial resolution <20 microns. [e.g. 1,2] and secondary ion mass spectrometry [3]. These profiles can give more insight into both the partitioning and diffusive behavior of siderophile elements in metal systems relevant to iron meteorites, as well as parent body cooling rates.

Top-down mass spectrometry imaging of intact proteins by laser ablation ESI FT-ICR MS.

PubMed

Kiss, András; Smith, Donald F; Reschke, Brent R; Powell, Matthew J; Heeren, Ron M A

2014-05-01

Laser ablation ESI (LAESI) is a recent development in MS imaging. It has been shown that lipids and small metabolites can be imaged in various samples such as plant material, tissue sections or bacterial colonies without any sample pretreatment. Further, LAESI has been shown to produce multiply charged protein ions from liquids or solid surfaces. This presents a means to address one of the biggest challenges in MS imaging; the identification of proteins directly from biological tissue surfaces. Such identification is hindered by the lack of multiply charged proteins in common MALDI ion sources and the difficulty of performing tandem MS on such large, singly charged ions. We present here top-down identification of intact proteins from tissue with a LAESI ion source combined with a hybrid ion-trap FT-ICR mass spectrometer. The performance of the system was first tested with a standard protein with electron capture dissociation and infrared multiphoton dissociation fragmentation to prove the viability of LAESI FT-ICR for top-down proteomics. Finally, the imaging of a tissue section was performed, where a number of intact proteins were measured and the hemoglobin α chain was identified directly from tissue using CID and infrared multiphoton dissociation fragmentation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Prospects for Practical Laser Ablation U/Pb and (U-Th)/He Double-Dating (LADD) of Detrital Apatite

NASA Astrophysics Data System (ADS)

Horne, A.; Hodges, K. V.; Van Soest, M. C.

2017-12-01

A laser ablation micro-analytical technique for (U-Th)/He dating has been shown to be an effective approach to the thermochronologic study of detrital zircons (Tripathy-Lang et al., J. Geophys. Res., 2013), while Evans et al. (J. Anal. At. Spectrom., 2015) and Horne et al. (Geochim. Cosmochim. Acta, 2016) demonstrated how the technique could be modified to enable laser ablation U/Pb and (U-Th)/He double-dating (LADD) of detrital zircon and titanite. These successes beg the question of whether or not LADD is viable for another commonly encountered detrital mineral: apatite. Exploratory LADD studies in Arizona State University's Group 18 Laboratories - using Durango fluorapatite, apatite from the Fish Canyon tuff, and detrital apatite from modern fluvial sediments in the eastern Sierra Nevada of California - illustrate that the method is indeed viable for detrital apatite. However, the method may not be appropriate for all detrital samples. For example, many apatite grains encountered in detrital samples from young orogenic settings have low concentrations of U and Th and small crystal sizes. This can lead to imprecise laser ablation (U-Th)/He dates, especially for very young grains potentially obscuring or inhibiting relevant interpretations of the data set.

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.

Detrital zircon geochronology and provenance of the Chubut Group in the northeast of Patagonia, Argentina

NASA Astrophysics Data System (ADS)

Navarro, Edgardo L.; Astini, Ricardo A.; Belousova, Elena; Guler, M. Verónica; Gehrels, George

2015-11-01

The Chubut Group constitutes the most widespread sedimentary unit in NE Patagonia, characterized by variable-energy fluvial deposits. U-Pb analysis of detrital zircons from two sections of the Chubut Group constraint the age of the oldest sedimentary rocks in the northeast of the Somuncurá - Cañadón Asfalto Basin. In the Cañadón Williams area, at San Jorge section, 20 km NW of Telsen locality, dating of 56 detrital zircons from a medium to coarse sandstone indicated a maximum depositional age of 109 ± 1 Ma (n = 4). These sandstones were interpreted to represent shallow channels, associated with a lacustrine system. In the Telsen locality, a laser ablation analysis of 115 detrital zircons from a medium to coarse-grained sandstone, from fluvial channel facies, yielded a maximum depositional age of ca. 106 ± 1 Ma (n = 8). Both ages are consistent with volcanic events of the Barremian to Albian age in the central Patagonian Andes Region. Cathodoluminescence images of zircons from the San Jorge sample suggest an igneous origin, which is further supported by Th/U values above 0.5 in most of the grains. The distribution of the statistical modes of the main age populations of detrital zircons for the two samples [182, 185 and 189 Ma for Telsen sample (T2S) and 181 ± 1 Ma for San Jorge sample (SJS)] matches the age of the volcanic Marifil Formation. The rocks of the Marifil Formation of these ages are exposed NE to SE of the study area. The abundance of zircons of similar Jurassic ages (n = 52 for SJS and n = 105 for T2S) and the external morphology of the zircons in the sample SJS, implies a close proximity of the source area. Suggestion that the Marifil Formation was the main provenance source is also supported by northeast-southeasterly paleocurrents measured at the San Jorge and Telsen sections.

Imaging of Selenium by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in 2-D Electrophoresis Gels and Biological Tissues.

PubMed

Cruz, Elisa Castañeda Santa; Susanne Becker, J; Sabine Becker, J; Sussulini, Alessandra

2018-01-01

Selenium and selenoproteins are important components of living organisms that play a role in different biological processes. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a powerful analytical technique that has been employed to obtain distribution maps of selenium in biological tissues in a direct manner, as well as in selenoproteins, previously separated by their molecular masses and isoelectric points using two-dimensional polyacrylamide gel electrophoresis (2-D PAGE). In this chapter, we present the protocols to perform LA-ICP-MS imaging experiments, allowing the distribution visualization and determination of selenium and/or selenoproteins in biological systems.

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

NASA Astrophysics Data System (ADS)

Fisher, Christopher M.; Vervoort, Jeffrey D.

2018-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Pre-Variscan evolution of the Western Tatra Mountains: new insights from U-Pb zircon dating.

PubMed

Burda, Jolanta; Klötzli, Urs

In situ LA-MC-ICP-MS U-Pb zircon geochronology combined with cathodoluminescence imaging were carried out to determine protolith and metamorphic ages of orthogneisses from the Western Tatra Mountains (Central Western Carpathians). The metamorphic complex is subdivided into two units (the Lower Unit and the Upper Unit). Orthogneisses of the Lower Unit are mostly banded, fine- to medium-grained rocks while in the Upper Unit varieties with augen structures predominate. Orthogneisses show a dynamically recrystallised mineral assemblage of Qz + Pl + Bt ± Grt with accessory zircon and apatite. They are peraluminous (ASI = 1.20-1.27) and interpreted to belong to a high-K calc-alkaline suite of a VAG-type tectonic setting. LA-MC-ICP-MS U-Pb zircon data from samples from both units, from crystals with oscillatory zoning and Th/U > 0.1, yield similar concordia ages of ca. 534 Ma. This is interpreted to reflect the magmatic crystallization age of igneous precursors. These oldest meta-magmatics so far dated in the Western Tatra Mountains could be linked to the fragmentation of the northern margin of Gondwana. In zircons from a gneiss from the Upper Unit, cores with well-developed oscillatory zoning are surrounded by weakly luminescent, low contrast rims (Th/U < 0.1). These yield a concordia age of ca. 387 Ma corresponding to a subsequent, Eo-Variscan, high-grade metamorphic event, connected with the formation of crustal-scale nappe structures and collision-related magmatism.

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

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

Developments in Laser-Ablation Split-Stream Petrochronology

NASA Astrophysics Data System (ADS)

Kylander-Clark, Andrew R.

2017-04-01

One of the biggest challenges in assessing the timing and rates of petrogenesis and deformation is having the ability to match the age of a dated mineral to the conditions at which that mineral grew. This is especially challenging for high-temperature chonometers that can grow and remain stable over a wide range of pressures and temperatures. The development of the laser-ablation split-stream method has afforded the ability to rapidly aquire chemical and chronologic data that are directly linked; as such, timing and rates of processes are better constrained than before. Several examples are given within: 1) Zircon and monazite from a single, coesite-bearing sample from the Western Gneiss Region in western Norway record the entire 30+ Myr history of metamorphism during Caledonian orogenesis, from intial burial, through ultrahigh-pressure (UHP) conditions, and back to crustal levels. Early monazite ( 425 Ma) contains low concentrations of Sr and HREE, consistent with plagioclase and garnet stability during prograde metamorphism. 420-400 Ma ages from monazite (high Sr, increased Eu/Eu*, low HREE) and zircon (increased Eu/Eu*, low HREE) indicate the timing of HP conditions, and monazite with low Sr and high HREE indicates the breakdown of omphacite and garnet at 390 Ma. 2) Titanite is becoming more widely used as chronometer, primarly because laser ablation has made analysis more feasible. Nevertheless, dates produced from titanite can be difficult to interpret because titanite may alter more easily than zircon and monazite. LASS analyses of titanite, combined with X-ray maps and backscattered electron images provide insight into processes involved in growth, recrystallization and dissolution/reprecipitation, and allow us to better interpret ages and the geologic process that they represent. This study presents recrystallized titanite from metamorphic terranes as well as ocillatory-zoned titanite from igneous rocks, and suggests some possible processes that explain the

Ti-in-zircon thermometry: applications and limitations

NASA Astrophysics Data System (ADS)

Fu, Bin; Page, F. Zeb; Cavosie, Aaron J.; Fournelle, John; Kita, Noriko T.; Lackey, Jade Star; Wilde, Simon A.; Valley, John W.

2008-08-01

The titanium concentrations of 484 zircons with U-Pb ages of ˜1 Ma to 4.4 Ga were measured by ion microprobe. Samples come from 45 different igneous rocks (365 zircons), as well as zircon megacrysts (84) from kimberlite, Early Archean detrital zircons (32), and zircon reference materials (3). Samples were chosen to represent a large range of igneous rock compositions. Most of the zircons contain less than 20 ppm Ti. Apparent temperatures for zircon crystallization were calculated using the Ti-in-zircon thermometer (Watson et al. 2006, Contrib Mineral Petrol 151:413-433) without making corrections for reduced oxide activities (e.g., TiO2 or SiO2), or variable pressure. Average apparent Ti-in-zircon temperatures range from 500° to 850°C, and are lower than either zircon saturation temperatures (for granitic rocks) or predicted crystallization temperatures of evolved melts (˜15% melt residue for mafic rocks). Temperatures average: 653 ± 124°C (2 standard deviations, 60 zircons) for felsic to intermediate igneous rocks, 758 ± 111°C (261 zircons) for mafic rocks, and 758 ± 98°C (84 zircons) for mantle megacrysts from kimberlite. Individually, the effects of reduced a_{TiO2} or a_{SiO2}, variable pressure, deviations from Henry’s Law, and subsolidus Ti exchange are insufficient to explain the seemingly low temperatures for zircon crystallization in igneous rocks. MELTs calculations show that mafic magmas can evolve to hydrous melts with significantly lower crystallization temperature for the last 10-15% melt residue than that of the main rock. While some magmatic zircons surely form in such late hydrous melts, low apparent temperatures are found in zircons that are included within phenocrysts or glass showing that those zircons are not from evolved residue melts. Intracrystalline variability in Ti concentration, in excess of analytical precision, is observed for nearly all zircons that were analyzed more than once. However, there is no systematic change in Ti

Laser ablation ICP-MS applications using the timescales of geologic and biologic processes

NASA Astrophysics Data System (ADS)

Ridley, W. I.

2003-04-01

Geochemists commonly examine geologic processes on timescales of 10^4--10^9 years, and accept that often age relations, e.g., chemical zoning in minerals, can only be measured in a relative sense. The progression of a geologic process that involves geochemical changes may be assessed using trace element microbeam techniques, because the textural, and therefore spatial context, of the analytical scheme can be preserved. However, quantification requires appropriate calibration standards. Laser ablation ICP-MS (LA-ICP-MS) is proving particularly useful now that appropriate standards are becoming available. For instance, trace element zoning patterns in primary sulfides (e.g., pyrite, sphalerite, chalcopyrite, galena) and secondary phases can be inverted to examine relative changes in fluid composition during cycles of hydrothermal mineralization. In turn such information provides insights into fluid sources, migration pathways and depositional processes. These studies have only become possible with the development of appropriate sulfide calibration standards. Another example, made possible with the development of appropriate silicate calibration standards, is the quantitative spatial mapping of REE variations in amphibolite-grade garnets. The recognition that the trace and major elements are decoupled provides a better understanding of the various sources of elements during metamorphic re-equilibration. There is also a growing realization that LA-ICP-MS has potential in biochemical studies, and geochemists have begun to turn their attention in this direction, working closely with biologists. Unlike many geologic processes, the timescales of biologic processes are measured in years to centuries and are frequently amenable to absolute dating. Examples that can be cited where LA-ICP-MS has been applied include annual trace metal variations in tree rings, corals, teeth, bones, bird feathers and various animal vibrissae (sea lion, walrus, wolf). The aim of such studies is

High sensitivity in-situ analysis of light lithophile (Li, Be, B) and alkali (Rb, Cs) elements by laser ablation magnetic sector ICP-MS: application to back arc basin magmatism

NASA Astrophysics Data System (ADS)

Kent, A. J.; Ungerer, C. A.

2003-12-01

Light lithophile (B, Be, Li) and alkali elements (Rb, Cs) provide many constraints on the origin and evolution of primitive magmatic rocks. However these elements are often present at low abundances, requiring large sample volumes, and may be strongly effected by alteration or sample contamination. We have developed a technique for rapid, in-situ, analysis of B, Be, Li, Rb and Cs abundances in glasses, glass inclusions and minerals using laser ablation microsampling and analysis by magnetic sector ICP-MS. By coupling the high sensitivity, dynamic range and low backgrounds of the ICP-MS with the speed and minimal sample preparation requirements of laser ablation, we can analyze these elements with detection limits that rival many solution-based techniques in ~60 s and using << 200 ng of material. Analyses are conducted using a NewWave DUV 193 nm ArF Excimer laser system, with He carrier gas. Samples were ablated at energies of 10-12 mJ/cm2 with pulse rates between 2-5 hz, and by either translating a 50 μ m laser spot over the surface at a rate of 5 μ m/s or by maintaining a stationary 50-70 μ m spot. Ablated material was analyzed with a VG Axiom single collector ICP-MS using a high-sensitivity sampler cone. All peaks were checked at high mass resolving power for molecular interferences, and analyses were conducted at low resolving power to maximize transmission. Careful monitoring of backgrounds was required for low-abundance measurements. Calculated detection limits are 1-2 ppb (Cs, Be), 5-10 ppb (Li) and 15-20 ppb (B, Rb). Surface contamination was removed with a pre-analysis ablation pass, and the small size of the laser spot allowed us to avoid altered and devitrified areas. Analysis of standard glasses showed excellent agreement with accepted values and repeat analyses suggest external errors are typically < 5-10%. Glasses from the Lau Basin show strong enrichments in B, Rb and Cs that correlate with a slab-fluid signature. B, Be Rb and Cs contents are very

Coordinated U–Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

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

Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

Here, we present the results of a coordinated SIMS U–Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ~4.33 Ga, however they differ in thatmore » only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ≤300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb– 206Pb ages of 4.33 Ga. These grains are our best

Coordinated U-Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

NASA Astrophysics Data System (ADS)

Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

2017-04-01

We present the results of a coordinated SIMS U-Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ∼4.33 Ga, however they differ in that only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ⩽300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb-206Pb ages of 4.33 Ga. These grains are our best constraints on

Coordinated U–Pb geochronology, trace element, Ti-in-zircon thermometry and microstructural analysis of Apollo zircons

DOE PAGES

Crow, Carolyn A.; McKeegan, Kevin D.; Moser, Desmond E.

2016-12-28

Here, we present the results of a coordinated SIMS U–Pb, trace element, Ti-in-zircon thermometry, and microstructural study of 155 lunar zircons separated from Apollo 14, 15, and 17 breccia and soil samples that help resolve discrepancies between the zircon data, the lunar whole rock history and lunar magma ocean crystallization models. The majority of lunar grains are detrital fragments, some nearly 1 mm in length, of large parent crystals suggesting that they crystallized in highly enriched KREEP magmas. The zircon age distributions for all three landing sites exhibit an abundance of ages at ~4.33 Ga, however they differ in thatmore » only Apollo 14 samples have a population of zircons with ages between 4.1 and 3.9 Ga. These younger grains comprise only 10% of all dated lunar zircons and are usually small and highly shocked making them more susceptible to Pb-loss. These observations suggest that the majority of zircons crystallized before 4.1 Ga and that KREEP magmatism had predominantly ceased by this time. We also observed that trace element analyses are easily affected by contributions from inclusions (typically injected impact melt) within SIMS analyses spots. After filtering for these effects, rare-earth element (REE) abundances of pristine zircon are consistent with one pattern characterized by a negative Eu anomaly and no positive Ce anomaly, implying that the zircons formed in a reducing environment. This inference is consistent with crystallization temperatures based on measured Ti concentrations and new estimates of oxide activities which imply temperatures ranging between 958 ± 57 and 1321 ± 100 °C, suggesting that zircon parent magmas were anhydrous. Together, the lunar zircon ages and trace elements are consistent with a ≤300 My duration of KREEP magmatism under anhydrous, reducing conditions. We also report two granular texture zircons that contain baddeleyite cores, which both yield 207Pb– 206Pb ages of 4.33 Ga. These grains are our best

Experimental evidence for use of aluminum in zircon as a new tracer to distinguish peraluminous and metaluminous melts

NASA Astrophysics Data System (ADS)

Wang, Y.; Trail, D.

2017-12-01

Aluminum (Al) is the third most abundant rock-forming element in Earth's crust. It also substitutes into the zircon lattice as trace impurity. For zircons that lack parent rock information, e.g. Hadean zircon (>4.0 Ga), Al in zircon could be a potentially useful tool to investigate the formation and evolution of the parental magma. Aluminum saturation index (ASI; molar ratio of Al2O3/(CaO+Na2O+K2O)) is widely used to distinguish peraluminous rocks (ASI>1) from metaluminous rocks (ASI<1). We grew zircons in piston cylinder from granitic melts, with different ASI values but same temperature, pressure and water content. Synthetic zircons with variable sizes, as large as 20 µm, were observed under SEM and analyzed using LA-ICP-MS. Our analyses reveal that the Al content of zircons that crystalized from a peraluminous melt (ASI=1.25) is, on average, one magnitude higher than crystals from peralkaline melt (ASI=0.5), e.g., 100s of ppm, vs. 10s of ppm. This indicates that aluminum solubility in zircon is related to the ASI value of parental melt. This experimental result agrees with studies of natural zircons, where Al contents of peraluminous zircons ( 10 ppm) are an order of magnitude higher than zircons from metaluminous rocks ( 1.3 ppm) (Trail et al., 2017). We suggest that melts with ASI>1 can result in an elevated alumina activity, which leads to zircons with elevated Al contents. The notably higher Al concentration in experimental zircons (10s to 100s ppm), compared with natural zircons (1 to 10 ppm), could be explained by the much higher crystallization temperature, e.g., >1100°C vs. <900°C. Both field and experimental studies support the notion that a relationship exists between the Al content in zircon and the melt ASI value. This conclusion has several meaningful applications: 1) it may be used to infer source rock characteristics of Hadean zircons, and to shed light on the formation and evolution of the earliest crust; 2) it may provide additional

Subcellular analysis by laser ablation electrospray ionization mass spectrometry

DOEpatents

Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh

2014-12-02

In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

Discrete prepotential as an indicator of successful ablation in patients with coronary cusp ventricular arrhythmia.

PubMed

Hachiya, Hitoshi; Yamauchi, Yasuteru; Iesaka, Yoshito; Yagishita, Atsuhiko; Sasaki, Takeshi; Higuchi, Koji; Kawabata, Mihoko; Sugiyama, Koji; Tanaka, Yasuaki; Kusa, Shigeki; Nakamura, Hiroaki; Miyazaki, Shinsuke; Taniguchi, Hiroshi; Isobe, Mitsuaki; Hirao, Kenzo

2013-10-01

Although coronary cusp (CC) ventricular arrhythmia (VA) can be treated by catheter ablation, reliable indicators of successful ablation sites have not been fully identified. This study comprised 392 patients undergoing radiofrequency catheter ablation for outflow tract-VA at 3 institutions from January 2007 to August 2012. The successful ablation site was on the left CC or right CC in 35 (8.9%) of the 392 patients. In 9 (26%) of these 35 patients, a discrete prepotential was recognized, 5 of whom had left CC-VAs and 4 of whom had right CC-VAs. Radiofrequency catheter ablation was successful at the site of the prepotential in all 9 of these patients. The duration of the isoelectric line between the end of the discrete prepotential and the onset of the ventricular electrogram was 27±13 ms. The time from onset of the discrete prepotential at the successful ablation site on the CC to the QRS onset (activation time) was 69±20 ms (range, 50-98 ms). Pace mapping was graded as excellent at the successful ablation site in only 1 patient. No discrete prepotential was recorded in any successful right outflow tract-VA ablation case in this study. A discrete prepotential was seen in 9 (26%) of 35 patients with CC-VA. In left and right CC-VA, the site of a discrete prepotential with ≥50 ms activation time may indicate a successful ablation site.

Zircon growth in shear zones

NASA Astrophysics Data System (ADS)

Kaulina, Tatiana

2013-04-01

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

LA-ICP-MS zircon U-Pb and muscovite K-Ar ages of basement rocks from the south arm of Sulawesi, Indonesia

NASA Astrophysics Data System (ADS)

Jaya, Asri; Nishikawa, Osamu; Hayasaka, Yasutaka

2017-11-01

The zircon U-Pb and muscovite K-Ar age from the Bantimala, Barru and Biru basement complexes in the South Arm of Sulawesi, Indonesia provide new information regarding the timing of magmatism, metamorphism and sedimentation in this region and have implications for the origin and evolution of the study area. The study area is at the juncture between the southeast margin of Sundaland and Bird's Head-Australia. The age of both the zircon U-Pb of detrital materials in the Bantimala Complex and the muscovite K-Ar of amphibolite in the Biru Complex fall in the Late Early Cretaceous (between 109 and 115 Ma), which is a similar age range to previous data for both the sedimentary and metamorphic rocks. The youngest detrital zircon in the schist samples from the Barru Complex fall into the Triassic in age (between 243 and 247 Ma). These age data indicate that the protolith of all three basement complexes were involved in the subduction system and metamorphosed in the late Early Cretaceous, but there are several differences in their deposition environment under and out of the influence of the late Early Cretaceous magmatism in the Bantimala and Barru Complexes, respectively. Felsic igneous activities are confirmed in the Late Cretaceous and the Eocene by the zircon U-Pb age of igneous rocks intruding or included as detrital fragments in three basement complexes. These dates are similar to those reported from the Meratus Complex of South Kalimantan. The detrital zircon age distributions of the basement rocks in the South Arm of Sulawesi display predominant Mesozoic (Cretaceous and Triassic) and Paleozoic populations with a small population of Proterozoic ages supporting the hypothesis that the West Sulawesi block originated from the region of the circum Bird's Head-Australian, namely the Inner Banda block. The absence of Jurassic zircon age population in the South Arm of Sulawesi suggests the division of the South Arm of Sulawesi from the Inner Banda block in early stage of

In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

PubMed

Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

2017-12-19

Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is <0.3‰ (1s). No significant matrix effects have been identified in calcite with the amplitude of chemical composition variation (i.e., MnO, SrO, MgO, or FeO) up to 2.5 wt %. Two modern corals were investigated using magmatic calcite as the calibration standard, and the average δ 13 C values for both corals are similar to the bulk IRMS values. Moreover, coral exhibits significant heterogeneity in carbon isotope compositions, with differences up to 4.85‰ within an individual coral. This study indicates that LA-MC-ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

Ceramic with zircon coating

NASA Technical Reports Server (NTRS)

Wang, Hongyu (Inventor)

2003-01-01

An article comprises a silicon-containing substrate and a zircon coating. The article can comprise a silicon carbide/silicon (SiC/Si) substrate, a zircon (ZrSiO.sub.4) intermediate coating and an external environmental/thermal barrier coating.

Analysis of metal-binding proteins separated by non-denaturating gel electrophoresis using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

PubMed

Becker, J Susanne; Mounicou, Sandra; Zoriy, Miroslav V; Becker, J Sabine; Lobinski, Ryszard

2008-09-15

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have become established as very efficient and sensitive biopolymer and elemental mass spectrometric techniques for studying metal-binding proteins (metalloproteins) in life sciences. Protein complexes present in rat tissues (liver and kidney) were separated in their native state in the first dimension by blue native gel electrophoresis (BN-PAGE). Essential and toxic metals, such as zinc, copper, iron, nickel, chromium, cadmium and lead, were detected by scanning the gel bands using quadrupole LA-ICP-MS with and without collision cell as a microanalytical technique. Several proteins were identified by using MALDI-TOF-MS together with a database search. For example, on one protein band cut from the BN-PAGE gel and digested with the enzyme trypsin, two different proteins - protein FAM44B and cathepsin B precursor - were identified. By combining biomolecular and elemental mass spectrometry, it was possible to characterize and identify selected metal-binding rat liver and kidney tissue proteins.

Development of a petrochronology laboratory in Russia

NASA Astrophysics Data System (ADS)

Yavryan, M.; Powerman, V.; Nourgaliev, D. K.

2017-12-01

Each year more and more U-Pb detrital zircon studies are coming from Russia. However, the latest developments in zircon studies, namely combining U-Pb age with the measurements of REE concentrations and Lu-Hf isotopy on the same grain, have been unavailable in Russia. Kazan Federal U. has undertaken certain efforts in order to develop Russia's first petrochronology laboratory. The following equipment was recently purchased, installed and put into operation: Neptune Plus HR MC ICPMS, with jet-interface and RPQ filter. iCAP-Qc quadruple ICPMS. 2 x NWR213 laser ablation systems; one of them equipped with the TwoVol2 ablation chamber. Helium gas is used to flush the ablation chamber; 5 ml/min. of nitrogen is mixed downstream before plasma in order to increase the signal. The following methods have been set up at KFU on the Neptune Plus ICPMS: (1) U-Pb geochronology on zircons. A set of standards have been dated (R33, 91500, Plesovice, Mudtank, GJ-1, AS-3); (2) U-Pb geochronology on perovskites. We have collected, separated and analyzed Baikal Tazheran 463 Ma perovskite, previously dated on TIMS (e.g., Ireland et al., 1990; Li et al., 2010), using 91500 zircon as a primary standard. We intend to start using Tazheran perovskite as an in-house standard for dating perovskites. (3) Lu-Hf isotopy on a set of standard zircons. All results will be presented during the poster session. Our next steps will include setting the (a) U-Pb geochronology and (b) REE measurements on the quadruple MS; (c) splitting the ablation stream into two and directing them to Neptune for Lu-Hf measurements and to iCAP for either U-Pb, or REE, or both types of measurements; (d) experimenting with pre-ablation in order to diminish common lead, with (e) rastering during ablation to diminish downhole fractionation, with (f) squid signal smoothing device.

Ti-in-Zircon Thermometer: Preliminary Results

NASA Astrophysics Data System (ADS)

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

2005-12-01

The titanium in zircon thermometer has been applied to 167 zircons from diverse rock types. These rocks include metamorphosed anorthosite and gabbro (1.15 Ga, intrusion age), and unmetamorphosed granitic pegmatite (0.9 Ga) from the Adirondack Highlands; metaluminous and peraluminous granites (114-90 Ma) of the Sierra Nevada Batholith; megacrysts from kimberlite pipes in southern Africa, Brazil, and Siberia; and detrital zircons (4.4-3.9 Ga) of metaconglomerate from Jack Hills, Western Australia. Titanium concentration in zircon was analysed using a CAMECA IMS-1280 ion microprobe (see Page et al., this volume). Spot analyses were correlated to U-Pb SHRIMP pits especially for Adirondack and Jack Hills zircons. The majority of zircons have Ti-content less than 10 ppm. Variability, in excess of analytical precision, within individual zircons is observed in about one-third of crystals. In general, there is no systematic change in Ti from core to rim (identified by cathodoluminescence) of zircons, or with regard to age, U content, Th/U ratio, or U-Pb age concordance for these non-metamict grains. The average temperatures for zircon crystallization in different rock suites using the experimental/empirical calibration of Watson and Harrison (W&H, 2005, Science 308:841), assuming the presence of rutile and quartz, are estimated to be: anorthosite 735±41°C (1SD, n=24; Ti = 10±5 ppm); metagabbro 714±31°C (n=19; Ti = 8±4 ppm); Adirondack pegmatite 500±16°C (n=5; Ti = 0.3±0.1 ppm); metaluminous and peraluminous granites from Sierra Nevada 681±67°C (n=53; Ti = 6±5 ppm) and 613±75°C (n=68; Ti = 3±3 ppm); kimberlite megacrysts 740±64°C (n=169; Ti = 14±13 ppm) (Page et al., this volume); and detrital zircons from Jack Hills metaconglomerate 718±63°C (n=64; Ti = 10±9 ppm). Most of the host rocks contain ilmenite or titanite suggesting that α(TiO2)>0.5, but rutile activity is unknown for megacrysts and detrital zircons. Pegmatite contains no Ti-rich minerals

Laser ablation ICP-MS analysis of the radial distribution of lead in the femur of Alligator mississippiensis.

PubMed

Seltzer, Michael D; Lance, Valentine A; Elsey, Ruth M

2006-06-15

A laser ablation ICP-MS technique has been used to examine the radial distribution of lead in transverse sections of alligator femur. Annual bone growth in the femur results in the deposition of incremental layers of calcified tissue at the periphery of existing bone. Patterns of lead concentration within these layers provide a record of time-dependent accumulation from which exposure history can potentially be deduced. Femur specimens obtained from captive-reared alligators exhibited levels of lead accumulation that were entirely consistent with previously documented clinical signs of lead intoxication. In contrast, femurs obtained from wild alligators contained only minor amounts of lead that were likely accumulated as a result of incidental exposure.

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

NASA Astrophysics Data System (ADS)

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

2004-05-01

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

Imaging of metal bioaccumulation in hay-scented fern (Dennstaedtia punctilobula) rhizomes growing on contaminated soils by laser ablation ICP-MS.

PubMed

Koelmel, Jeremy; Amarasiriwardena, Dulasiri

2012-09-01

Understanding Pb removal from the translocation stream is vital to engineering Pb hyperaccumulation in above ground organs, which would enhance the economic feasibility of Pb phytoextraction technologies. We investigated Cu, Pb, Sb and Zn distributions in Hay-scented fern (Dennstaedtia punctilobula) rhizomes on shooting range soils by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), analyzing digested rhizomes, stems, and fronds using ICP-MS. Nutrients Cu and Zn concentrated in fronds while toxic elements Pb and Sb did not, showing potential Pb and Sb sequestration in the rhizome. Frond and rhizome concentration of Pb was 0.17 ± 0.10% and 0.32 ± 0.21% of dry biomass, respectively. The 208Pb/13C and 121Sb/13C determined by LA-ICP-MS increased from inner sclerotic cortex to the epidermis, while Pb concentrated in the starchy cortex only in contaminated sites. These results suggest that concentration dependent bioaccumulation in the rhizome outer cortex removes Pb from the vascular transport stream. Copyright © 2012 Elsevier Ltd. All rights reserved.

On the origin of extraterrestrial stratospheric particles: Interplanetary dust or meteor ablation debris?. M.S. Thesis

NASA Technical Reports Server (NTRS)

Kyte, F. T.

1977-01-01

Meteor ablation debris was distinguished from unablated interplanetary dust in a collection of extraterrestrial particles collected in the stratosphere using NASA U-2 aircraft. A 62 g sample of the Murchison (C2) meteorite was artificially ablated to characterize ablation debris for comparison with the stratospheric particles. By using proper experimental conditions, artificial ablation debris can be produced that is similar to natural ablation debris. Analyses of natural fusion crusts, artificial fusion crust, and artificial ablation debris of the Murchison meteorite produced criteria for recognizing debris ablated by a primitive meteoroid. Ninety-five percent of the stratospheric particles can be described as either ablation debris from a primitive meteoroid, or as very primitive interplanetary dust.

Age and origin of the Merrimack terrane, southeastern New England: A detrital zircon U-Pb geochronology study

NASA Astrophysics Data System (ADS)

Sorota, Kristin

Metasedimentary rocks of the Merrimack terrane (MT) originated as a thick cover sequence on Ganderia consisting of sandstones, calcareous sandstones, pelitic rocks and turbidites. In order to investigate the age, provenance and stratigraphic order of these rocks and correlations with adjoining terranes, detrital zircon suites from 7 formations across the MT along a NNE-trending transect from east-central Massachusetts to SE New Hampshire were analyzed by U-Pb LA-ICP-MS methods on 90-140 grains per sample. The youngest detrital zircons in the western units, the Worcester, Oakdale and Paxton Formations, are ca. 438 Ma while those in the Kittery, Eliot and Berwick Formations in the northeast are ca. 426 Ma. The Tower Hill Formation previously interpreted to form the easternmost unit of the MT in MA, has a distinctly different zircon distribution with its youngest zircon population in the Cambrian. All samples except for the Tower Hill Formation have detrital zircon age distributions with significant peaks in the mid-to late Ordovician, similar abundances of early Paleozoic and late Neoproterozoic zircons, significant input from ˜1.0 to ˜1.8 Ga sources and limited Archean grains. The similarities in zircon provenance suggest that all units across the terrane, except for the Tower Hill Formation, belong to a single sequence of rocks, with similar sources and with the units in the NE possibly being somewhat younger than those in east-central Massachusetts. The continuous zircon age distributions observed throughout the Mesoproterozoic and late Paleoproterozoic are consistent with an Amazonian source. All samples, except the Tower Hill Formation, show sedimentary input from both Ganderian and Laurentian sources and suggest that Laurentian input increases as the maximum depositional age decreases.

Provenance analysis and detrital zircon geochronology on the onshore Makran accretionary wedge, SE Iran: implication for the geodynamic setting

NASA Astrophysics Data System (ADS)

Mohammadi, Ali; Burg, Jean-Pierre; Winkler, Wilfried; Ruh, Jonas

2014-05-01

The Makran, located in Southeast Iran and South Pakistan, is one of the largest accretionary wedges on Earth. In Iran it comprises turbiditic sediments ranging in age from Late Cretaceous to Holocene. We present a provenance analysis on sandstones, which is aimed at reconstructing the assemblages of source rocks and the tectonic setting from which the clastic material was derived. Sandstone samples collected from different units span the regional stratigraphy from Late Cretaceous to Miocene. Laser ablation ICP-MS resulted in ca 2800 new U-Pb ages of individual detrital zircons from 18 samples collected in onshore Makran. 101 detrital zircons from a Late Cretaceous fine grained sandstone range from 180 to 160 Ma (Middle Jurassic). 478 detrital zircons from mid- to late Eocene sandstones allow differentiating a NE and NW sector of the Makran Basin. Zircon grains in the NE basin belong to two populations peaking at 180 to 160 Ma (late Early to Middle Jurassic) and 50 to 40 Ma (Mid-Eocene), with the noticeable absence of Cretaceous grains. In the NW basin, detrital zircons are 120 to 40 Ma (late Early Cretaceous to Lutetian, Eocene). 587 detrital zircon grains from fine to medium grained Oligocene sandstones collected over the whole area also range from 120 to 40 Ma (late Early Cretaceous to Eocene, Lutetian). 1611 detrital zircons from early Miocene sandstones show again distinctly different ages in the eastern and western parts of the basin. They range from 120 to 40 Ma (late Early Cretaceous to Eocene) in the eastern and from 80 to 40 Ma (Late Cretaceous to Eocene) in the western basin. Hf isotopes analyses were performed on 120 zircon grains from 6 samples. Negative values (-2 to -15) in Middle Jurassic and late Early Cretaceous zircons indicate minor or no influence of mantle reservoirs which implies a rifting setting during crystallization of the zircons. Low negative to positive (-5 to +10) values in Late Cretaceous and Eocene zircons indicate mixed crustal and

Li isotopes in archean zircons

NASA Astrophysics Data System (ADS)

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

2009-12-01

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

Complete zircon and chromite digestion by sintering of granite, rhyolite, andesite and harzburgite rock reference materials for geochronological purposes

NASA Astrophysics Data System (ADS)

Bokhari, Syed Nadeem H.; Meisel, Thomas

2014-05-01

Zircon (ZrSiO4) is a common accessory mineral in nature that occurs in a wide variety of sedimentary, igneous, and metamorphic rocks. Zircon has the ability to retain substantial chemical and isotopic information that are used in range of geochemical and geo- chronological investigations. Sample digestion of such rock types is a limiting factor due to the chemical inertness of zircon (ZrSiO4) tourmaline, chromite, barite, monazite, sphene, xenotime etc. as the accuracy of results relies mainly on recovery of analytes from these minerals. Dissolution by wet acid digestions are often incomplete and high blank and total dissolved solids (TDS) contents with alkali fusions lead to an underestimation of analyte concentrations. Hence an effective analytical procedure, that successfully dissolves refractory minerals such as zircon is needed to be employed for reliable analytical results. Na2O2 digestion [1] was applied in characterisation of granite (G-3), rhyolite (MRH), andesite (MGL-AND) and harzburgite (MUH-1) powdered reference material with solution based ICP-MS analysis. In this study we undertake a systematic evaluation of decomposition time and sample:Na2O2 ratio and test portion size after minimising effect of all other constraints that makes homogeneity ambiguous. In recovering zircon and chromite 100 mg test portion was mixed with different amounts of Na2O2 i.e. 100-600 mg. Impact of decomposition time was observed by systematically increasing heating time from 30-45 minutes to 90-120 minutes at 480°C. Different test portion sizes 100-500 mg of samples were digested to control variance of inhomogeneity. An improved recovery of zirconium in zircon in granite (G-3), rhyolite MRH), andesite (MGL-AND) and chromite in harzburgite (MUH-1) was obtained by increasing heating time (2h) at 480°C and by keeping (1:6) ratio of sample:Na2O2. Through this work it has been established that due to presence of zircon and chromite, decomposition time and sample:Na2O2 ratio has

Hydrogen diffusion in Zircon

NASA Astrophysics Data System (ADS)

Ingrin, Jannick; Zhang, Peipei

2016-04-01

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

Detrital zircons and Earth system evolution

NASA Astrophysics Data System (ADS)

McKenzie, R.

2016-12-01

Zircon is a mineral commonly produced in silicic magmatism. Therefore, due to its resilience and exceedingly long residence times in the continental crust, detrital zircon records can be used to track processes associated with silicic magmatism throughout Earth history. In this contribution I will address the potential role of preservational biases in zircon record, and further discuss how zircon datasets can be used to help better understand the relationship between lithospheric and Earth system evolution. I will use large compilations of zircon data to trace the composition and weatherability of the continental crust, to evaluate temporal rates of crustal recycling, and finally to track spatiotemporal variation in continental arc magmatism and volcanic CO2 outgassing throughout Earth history. These records demonstrate that secular changes in plate tectonic regimes played a prominent role in modulating conditions of the ocean+atmosphere system and long-term climate state for the last 3 billion years.

Sulfur in zircons: A new window into melt chemistry

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Zircon-scale insights into the history of a Supervolcano, Bishop Tuff, Long Valley, California, with implications for the Ti-in-zircon geothermometer

USGS Publications Warehouse

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

2011-01-01

Zircon has the outstanding capacity to record chronological, thermal, and chemical information, including the storage history of zoned silicic magma reservoirs like the one responsible for the Bishop Tuff of eastern California, USA. Our novel ion microprobe approach reveals that Bishop zircon rims with diverse chemical characteristics surround intermediate domains with broadly similar compositions. The highest Y, REE, U, and Th concentrations tend to accompany the largest excesses in Y + REE3+:P beyond what can be explained by xenotime substitution in zircon. Apparent Ti-in-zircon temperatures of <720??C for zircon rims are distinctly lower than most of the range in eruption temperatures, as estimated from FeTi-oxide equilibria and zircon solubility at quench. While permissive of crystallization of zircon at near-solidus conditions, the low Ti-in-zircon temperatures are probably better explained by sources of inaccuracy in the temperature estimates. After apparently nucleating from different melts, zircons from across the Bishop Tuff compositional spectrum may have evolved to broadly similar chemical and thermal conditions and therefore it is possible that there was no significant thermal gradient in the magma reservoir at some stage in its evolution. There is also no compelling evidence for punctuated heat ?? chemical influxes during the intermediate stages of zircon growth. Judging by the zircon record, the main volume of the erupted magma evolved normally by secular cooling but the latest erupted portion is characterized by a reversal in chemistry that appears to indicate perfusion of the magma reservoir by-or zircon entrainment in-a less evolved melt from the one in which the zircons had previously resided. ?? 2010 Springer-Verlag.

Geochemistry of the Spor Mountain rhyolite, western Utah, as revealed by laser ablation ICP-MS, cathodoluminescence, and electron microprobe analysis

NASA Astrophysics Data System (ADS)

Dailey, S. R.; Christiansen, E. H.; Dorais, M.; Fernandez, D. P.

2015-12-01

The Miocene topaz rhyolite at Spor Mountain in western Utah hosts one of the largest beryllium deposits in the world and was responsible for producing 85% of the beryllium mined worldwide in 2010 (Boland, 2012). The Spor Mountain rhyolite is composed primarily of Ca-poor plagioclase (An8), sodic sanidine (Or40), Fe-rich biotite (Fe/(Fe+Mg)>0.95; Al 1.2-1.4 apfu), and Ti-poor quartz, along with several trace-element rich accessory phases including zircon, monazite, thorite, columbite, and allanite. Cathodoluminescence (CL) studies of quartz show oscillatory zoning, with 80% of the examined crystals displaying euhedral edges and slightly darker rims. CL images were used to guide laser ablation (LA) ICP-MS analysis of quartz, along with analyses of plagioclase, sanidine, biotite, and glass. Ti concentrations in quartz are 20±6 ppm; there is no quantifiable variation of Ti from core to rim within the diameter of the laser spot (53 microns). Temperatures, calculated using Ti in quartz (at 2 kb, aTiO2=0.34), vary between 529±10 C (Thomas et al., 2011), 669±13 C (Huang and Audetat, 2012), and 691±13 C (Wark and Watson, 2006). Two feldspar thermometry yield temperatures of 686±33 C (Elkins and Grove, 1990) and 670±41 C (Benisek et al., 2010). Zr saturation temperatures (Watson and Harrison, 1983) average 711±28 C. Analysis of the glass reveal the Spor Mountain rhyolite is greatly enriched in rare elements (i.e. Li, Be, F, Ga, Rb, Nb, Mo, Sn, and Ta) compared to average continental crust (Rudnick and Gao, 2003). Be in the glass can have as much as 100 ppm, nearly 50 times the concentration in continental crust. REE partition coefficients for sanidine are 2 to 3 times higher in the Spor Mountain rhyolite when compared to other silicic magmas (Nash and Crecraft, 1985; Mahood and Hildreth, 1983), although plagioclase tends to have lower partition coefficients; biotite has lower partition coefficients for LREE and higher partition coefficients for HREE. The patterns of

Etching fission tracks in zircons

USGS Publications Warehouse

Naeser, C.W.

1969-01-01

A new technique has been developed whereby fission tracks can be etched in zircon with a solution of sodium hydroxide at 220??C. Etching time varied between 15 minutes and 5 hours. Colored zircon required less etching time than the colorless varieties.

Examination of the Mass Transfer of Additive Elements in Barium Titanate Ceramics during Sintering Process by Laser Ablation ICP-MS.

PubMed

Sakate, Daisuke; Iwazaki, Yoshiki; Kon, Yoshiaki; Yokoyama, Takaomi; Ohata, Masaki

2018-01-01

The mass transfer of additive elements during the sintering of barium titanate (BaTiO 3 ) ceramic was examined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in the present study. An analytical sample consisting of two pellets of BaTiO 3 with different concentrations of additive elements of manganese (Mn) and holmium (Ho) as well as silicon (Si) as a sintering reagent was prepared and measured by LA-ICP-MS with small laser irradiated diameter of 10 μm to evaluate the distributions and concentrations of additive elements in order to examine their mass transfers. As results, enrichments of Mn and Si as an additive element and a sintering reagent, respectively, were observed on the adhesive surface between two BaTiO 3 pellets, even though Ho did not show a similar phenomenon. The mass transfers of additive elements of Mn and Ho were also examined, and Mn seemed to show a larger mass transfer than that of Ho during the sintering process for BaTiO 3 ceramics. The results obtained in this study shows the effectives of LA-ICP-MS for the future improvement of MLCCs.

At what conditions does zircon grow/dissolve during high-T metamorphism? Relating zircon textures to PT-conditions

NASA Astrophysics Data System (ADS)

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

2015-04-01

A key question in ziconology is when and how zircon grows during metamorphism. To shed light on zircon forming processes and the corresponding PT-conditions during high-T metamorphism a case study was undertaken. The Ivrea Zone (N-Italy) exposes a lower continental crustal section in which a continuous metamorphic field gradient from amphibolite to granulite facies is documented. This field gradient is thought to reflect protracted heating during late Paleozoic times, with a probable high-T peak in the Permian. We present first results from a primarily textural study supported by U-Pb ages, Th/U ratios and Ti-in-Zrn thermometry. Four types of zircon were identified based on their overgrowth proportions and the preservation of detrital cores. Zircon grains were thus classified as Type1 - detrital grains with no overgrowth or very narrow rims (300 Ma) and appears to reflect an early dehydration phase. Rim2b has Permian ages (median 275 Ma), is by far the most common overgrowth type, found in a wide PT-range. Its development appears related to biotite breakdown. Rim3 is texturally indicative of magmatic zircon, occurs only in diatexites. Rim4 is the latest overgrowth and is locally found at all metamorphic grades. Textural features suggest late fluid-related recrystallization of existing zircon. At lowest grade (675±35°C, 6±2 kbar) zircons show type1 only, overgrowths are too thin to clearly identify the rim type. Further upgrade (~700°C, 7 kbar) type1 and type2 dominate. Type2 zircons show rim1, rim2a and occasionally rim4. At the Mu-out isograd (750±50°C, 8.2±1.4 kbar) most zircons are of type2, now with rim2b instead of 2a, in addition to rim1 and rim4. Near and in granulite facies (to 800°C, 8±2 kbar) mostly zircon type2 and type4 are present. While rim1 gets more narrow with increasing metamorphic grade, rim2b grows significantly thicker. Occasionally rim2a and rim4 occur. Close to the Bt-out isograd (~860°C, 9.2±1.7 kbar), mostly type3 and type4 are

First application of the revised Ti-in-zircon geothermometer to Paleoproterozoic ultrahigh-temperature granulites of Tuguiwula, Inner Mongolia, North China Craton

NASA Astrophysics Data System (ADS)

Liu, S. J.; Li, J. H.; Santosh, M.

2010-02-01

The revised titanium-in-zircon geothermometer was applied to Paleoproterozoic ultrahigh-temperature (UHT) granulites at Tuguiwula, Inner Mongolia, North China Craton. The Tuguiwula granulites contain diagnostic UHT mineral assemblages such as sapphirine + quartz and high alumina orthopyroxene + sillimanite + quartz, suggesting formation under temperatures of ca. 1,000°C and pressures of up to 10 kbar. Here, we report detailed petrographic studies and ICP-MS data on titanium concentration in zircons associated with the UHT assemblages. The zircons associated with sapphirine-spinel-sillimanite-magnetite assemblages have the highest Ti concentration of up to 57 ppm, yielding a temperature of 941°C, and suggesting that the growth of zircons occurred under ultrahigh-temperature conditions. The maximum temperatures obtained by the revised Ti-in-zircon geothermometer is lower than the equilibrium temperature of sapphirine + quartz, indicating an interval of cooling history of the granulites from UHT condition to ca. 940°C. Many of the zircons have Ti concentrations ranging from 10 to 33 ppm, indicating their growth or recrystallization under lower temperatures of ca. 745-870°C. These zircons are interpreted to have recrystallized during the retrograde stage indicated by microstructures such as cordierite rim or corona between spinel and quartz, and orthopyroxene-cordierite symplectite around garnet. Previous geochronological study on the zircons of the Tuguiwula UHT granulites gave a mean U-Pb SHRIMP age of 1.92 Ga. However, based on the Ti-in-zircon geothermometer results reported in this work, and considering the relatively slow thermal relaxation of these rocks, we infer that the timing of peak UHT metamorphism in the Tuguiwula area could be slightly older than 1.92 Ga.

Detrital zircon and igneous protolith ages of high-grade metamorphic rocks in the Highland and Wanni Complexes, Sri Lanka: Their geochronological correlation with southern India and East Antarctica

NASA Astrophysics Data System (ADS)

Kitano, Ippei; Osanai, Yasuhito; Nakano, Nobuhiko; Adachi, Tatsuro; Fitzsimons, Ian C. W.

2018-05-01

The high-grade metamorphic rocks of Sri Lanka place valuable constraints on the assembly of central parts of the Gondwana supercontinent. They are subdivided into the Wanni Complex (WC), Highland Complex (HC) and Vijayan Complex (VC), but their correlation with neighbouring Gondwana terranes is hindered by a poor understanding of the contact between the HC and WC. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb dating of remnant zircon cores from 45 high-grade metamorphic rocks in Sri Lanka reveals two domains with different age characteristics that correlate with the HC and WC and which help constrain the location of the boundary between them. The HC is dominated by detrital zircon ages of ca. 3500-1500 Ma from garnet-biotite gneiss, garnet-cordierite-biotite gneiss, some samples of garnet-orthopyroxene-biotite gneiss and siliceous gneiss (interpreted as paragneisses) and igneous protolith ages of ca. 2000-1800 Ma from garnet-hornblende-biotite gneiss, other samples of garnet-orthopyroxene-biotite gneiss, garnet-two-pyroxene granulite, two-pyroxene granulite and charnockite (interpreted as orthogneisses). In contrast, the WC is dominated by detrital zircon ages of ca. 1100-700 Ma from paragneisses and igneous protolith ages of ca. 1100-800 Ma from orthogneisses. This clearly suggests the HC and WC have different origins, but some of our results and previous data indicate their spatial distribution does not correspond exactly to the unit boundary proposed in earlier studies using Nd model ages. Detrital zircon and igneous protolith ages in the HC suggest that sedimentary protoliths were eroded from local 2000-1800 Ma igneous rocks and an older Paleoproterozoic to Archean craton. In contrast, the WC sedimentary protoliths were mainly eroded from local late Mesoproterozoic to Neoproterozoic igneous rocks with very minor components from an older 2500-1500 Ma craton, and in the case of the WC precursor sediments there was possibly

Bioimaging of metals in brain tissue by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and metallomics.

PubMed

Becker, J Sabine; Matusch, Andreas; Palm, Christoph; Salber, Dagmar; Morton, Kathryn A; Becker, J Susanne

2010-02-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been developed and established as an emerging technique in the generation of quantitative images of metal distributions in thin tissue sections of brain samples (such as human, rat and mouse brain), with applications in research related to neurodegenerative disorders. A new analytical protocol is described which includes sample preparation by cryo-cutting of thin tissue sections and matrix-matched laboratory standards, mass spectrometric measurements, data acquisition, and quantitative analysis. Specific examples of the bioimaging of metal distributions in normal rodent brains are provided. Differences to the normal were assessed in a Parkinson's disease and a stroke brain model. Furthermore, changes during normal aging were studied. Powerful analytical techniques are also required for the determination and characterization of metal-containing proteins within a large pool of proteins, e.g., after denaturing or non-denaturing electrophoretic separation of proteins in one-dimensional and two-dimensional gels. LA-ICP-MS can be employed to detect metalloproteins in protein bands or spots separated after gel electrophoresis. MALDI-MS can then be used to identify specific metal-containing proteins in these bands or spots. The combination of these techniques is described in the second section.

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.

Zircon age-temperature-compositional spectra in plutonic rocks

DOE PAGES

Samperton, Kyle M.; Bell, Elizabeth A.; Barboni, Mélanie; ...

2017-08-23

We present that geochronology can resolve dispersed zircon dates in plutonic rocks when magma cooling time scales exceed the temporal precision of individual U-Pb analyses; such age heterogeneity may indicate protracted crystallization between the temperatures of zircon saturation (T sat) and rock solidification (T solid). Diffusive growth models predict asymmetric distributions of zircon dates and crystallization temperatures in a cooling magma, with volumetrically abundant old, hot crystallization at T sat decreasing continuously to volumetrically minor young, cold crystallization at T solid. We present integrated geochronological and geochemical data from Bergell Intrusion tonalites (Central Alps, Europe) that document zircon compositional changemore » over hundreds of thousands of years at the hand-sample scale, indicating melt compositional evolution during solidification. Ti-in-zircon thermometry, crystallization simulation using MELTS software, and U-Pb dates produce zircon mass-temperature-time distributions that are in excellent agreement with zircon growth models. In conclusion, these findings provide the first quantitative validation of longstanding expectations from zircon saturation theory by direct geochronological investigation, underscoring zircon’s capacity to quantify supersolidus cooling rates in magmas and resolve dynamic differentiation histories in the plutonic rock record.« less

Zircon age-temperature-compositional spectra in plutonic rocks

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

Samperton, Kyle M.; Bell, Elizabeth A.; Barboni, Mélanie

We present that geochronology can resolve dispersed zircon dates in plutonic rocks when magma cooling time scales exceed the temporal precision of individual U-Pb analyses; such age heterogeneity may indicate protracted crystallization between the temperatures of zircon saturation (T sat) and rock solidification (T solid). Diffusive growth models predict asymmetric distributions of zircon dates and crystallization temperatures in a cooling magma, with volumetrically abundant old, hot crystallization at T sat decreasing continuously to volumetrically minor young, cold crystallization at T solid. We present integrated geochronological and geochemical data from Bergell Intrusion tonalites (Central Alps, Europe) that document zircon compositional changemore » over hundreds of thousands of years at the hand-sample scale, indicating melt compositional evolution during solidification. Ti-in-zircon thermometry, crystallization simulation using MELTS software, and U-Pb dates produce zircon mass-temperature-time distributions that are in excellent agreement with zircon growth models. In conclusion, these findings provide the first quantitative validation of longstanding expectations from zircon saturation theory by direct geochronological investigation, underscoring zircon’s capacity to quantify supersolidus cooling rates in magmas and resolve dynamic differentiation histories in the plutonic rock record.« less

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

Electrophysiological markers predicting impeding AV-block during ablation of atrioventricular nodal reentry tachycardia.

PubMed

Fragakis, Nikolaos; Krexi, Lydia; Kyriakou, Panagiota; Sotiriadou, Melani; Lazaridis, Charalambos; Karamanolis, Athanasios; Dalampyras, Panagiotis; Tsakiroglou, Stelios; Skeberis, Vassilios; Tsalikakis, Dimitrios; Vassilikos, Vassilios

2018-01-01

Radiofrequency (RF) ablation of the slow pathway (SP) in atrioventricular nodal reentry tachycardia (AVNRT) is occasionally complicated with atrioventricular block (AVB) often predicted by junctional beats (JB) with loss of ventriculo-atrial (VA) conduction. We analyzed retrospectively 153 patients undergoing ablation of SP for typical AVNRT. Patients were divided into two age groups: 127 ≤ 70 years and 26 > 70 years. We analyzed the interval between the atrial electrogram in the His-bundle position and the distal ablation catheter [A(H)-A(RFd)] and between the distal ablation catheter and the proximal coronary sinus catheter [A(RFd)-A(CS)] before RF applications with and without JB. We evaluated if these intervals can be used as predictors of JB incidence and also of JB with loss of VA conduction. We also assessed if age influences the risk of loss of VA conduction. The A(H)-A(RFd) and A(RFd)-A(CS) intervals were significantly shorter in RF applications causing JB than those without JB (33 ± 11 ms vs 39 ± 9 ms, P < 0.001, 14 ± 9 ms vs 20 ± 7 ms, P < 0.001, respectively). The A(H)-A(RFd) and A(RFd)-A(CS) intervals were also significantly shorter in RFs causing JB with VA block than those with VA conduction (29 ± 11 ms vs 35 ± 11 ms, P < 0.001, 8 ± 8 ms vs 17 ± 8 ms, P < 0.001, respectively). Patients > 70 years had shorter intervals (36 ± 11 ms vs 29 ± 8 ms, P  =  0.012, 17 ± 8 ms vs 13 ± 7 ms, P  =  0.027, respectively), while VA block was more common in this age group. The A(H)-A(RFd) and A(RFd)-A(CS) intervals can be used as markers for predicting JB occurrence as well as impending AVB. JB with loss of VA conduction occur more often in older patients possibly due to a higher position of SP. © 2017 Wiley Periodicals, Inc.

The Effect of Element Substitution on Ti-in-Zircon Geothermometry in Volcanic Zircons from Mount Pinatubo, Philippines

NASA Astrophysics Data System (ADS)

Lee, S. L.; Hattori, K.

2017-12-01

Despite the extensive application of the Ti-in-zircon geothermometer, its accuracy in natural systems remains uncertain. In order to investigate the parameters contributing to Ti in zircon, we examined zircons from dacitic eruption products of Mount Pinatubo, Philippines, from the Pliocene (>2.5-2.7 Ma), 35000BP and 1991AD. All samples are unaltered and quenched from magmas at 790-825°C (Fe-Ti-oxide thermometry). Furthermore, the magma conditions of 1991 samples are well characterized: 780°C (cummingtonite rims on hornblende, Fe-Ti-oxide thermometry), 2 kbar pressure, 5.5-6.5 wt.% H2O and fO2 of NNO+1.6. Calculated zircon saturation temperatures are 760, 744 and 738°C (oldest to youngest). Zircon Ti concentrations are low (2.0-8.8 ppm), show positive covariation with U (35.6-639 ppm), Th (18.7-696 ppm), ∑REE (237-1310 ppm) and Y (247-1770 ppm), and negative covariation with Hf (7610-12000 ppm). The Ti-in-zircon geothermometer by Ferry and Watson (2007) yields mean temperatures of 690, 666 and 663°C (oldest to youngest), using TiO2 activity=0.6, SiO2 activity=1 and -40°C pressure correction. Therefore, temperatures calculated using this method are underestimated by >100°C. We suggest that elements in the Zr site impact the substitution of Ti in the Si site of zircon. Ti shows a positive covariation with Zr/Hf (37.0-57.3, r2=0.551). The ionic radius of Hf4+ is smaller than Zr4+, whereas cations like U4+, Th4+, REE3+ and Y3+ are larger. The departure from the ideal crystal configuration is evaluated using the parameter Zr/(Hf-x), whereby x=U4+, Th4+, ∑REE and Y3+. Ti contents are more strongly correlated with the parameter than Zr/Hf (r2=0.559, 0.565, 0.608, 0.616; respectively). This suggests that large cations replacing Zr strain the lattice, reducing the amount of Ti incorporated into zircon. This further suggests that ZrSiO4 activity is less than 1 in natural rocks, resulting in the systematic underestimation of Ti-in-zircon temperatures.

Geochemical signatures and magmatic stability of terrestrial impact produced zircon

NASA Astrophysics Data System (ADS)

Wielicki, Matthew M.; Harrison, T. Mark; Schmitt, Axel K.

2012-03-01

Understanding the role of impacts on early Earth has major implications to near surface conditions, but the apparent lack of preserved terrestrial craters > 2 Ga does not allow a direct sampling of such events. Ion microprobe U-Pb ages, REE abundances and Ti-in-zircon thermometry for impact produced zircon are reported here. These results from terrestrial impactites, ranging in age from ~ 35 Ma to ~ 2 Ga, are compared with the detrital Hadean zircon population from Western Australia. Such comparisons may provide the only terrestrial constraints on the role of impacts during the Hadean and early Archean, a time predicted to have a high bolide flux. Ti-in-zircon thermometry indicates an average of 773 °C for impact-produced zircon, ~ 100 °C higher than the average for Hadean zircon crystals. The agreement between whole-rock based zircon saturation temperatures for impactites and Ti-in-zircon thermometry (at aTiO2 = 1) implies that Ti-in-zircon thermometry record actual crystallization temperatures for impact melts. Zircon saturation modeling of Archean crustal rock compositions undergoing thermal excursions associated with the Late Heavy Bombardment predicts equally high zircon crystallization temperatures. The lack of such thermal signatures in the Hadean zircon record implies that impacts were not a dominant mechanism of producing the preserved Hadean detrital zircon record.

Transformations to granular zircon revealed: Twinning, reidite, and ZrO2 in shocked zircon from Meteor Crater (Arizona, USA)

USGS Publications Warehouse

Cavosie, Aaron; Timms, Nicholas E.; Erickson, Timmons M.; Hagerty, Justin J.; Hörz, Friedrich

2016-01-01

Granular zircon in impact environments has long been recognized but remains poorly understood due to lack of experimental data to identify mechanisms involved in its genesis. Meteor Crater in Arizona (United States) contains abundant evidence of shock metamorphism, including shocked quartz, the high pressure polymorphs coesite and stishovite, diaplectic SiO2 glass, and lechatelierite (fused SiO2). Here we report the presence of granular zircon, a new shocked mineral discovery at Meteor Crater, that preserve critical orientation evidence of specific transformations that occurred during its formation at extreme impact conditions. The zircon grains occur as aggregates of sub-µm neoblasts in highly shocked Coconino Formation Sandstone (CFS) comprised of lechatelierite. Electron backscatter diffraction shows that each grain consists of multiple domains, some with boundaries disoriented by 65°, a known {112} shock-twin orientation. Other domains have crystallographic c-axes in alignment with {110} of neighboring domains, consistent with the former presence of the high pressure ZrSiO4 polymorph reidite. Additionally, nearly all zircon preserve ZrO2 + SiO2, providing evidence of partial dissociation. The genesis of CFS granular zircon started with detrital zircon that experienced shock-twinning and reidite formation from 20 to 30 GPa, ultimately yielding a phase that retained crystallographic memory; this phase subsequently recrystallized to systematically oriented zircon neoblasts, and in some areas partially dissociated to ZrO2. The lechatelierite matrix, experimentally constrained to form at >2000 °C, provided an ultra high-temperature environment for zircon dissociation (~1670 °C) and neoblast formation. The capacity of granular zircon to preserve a cumulative P-T record has not been recognized previously, and provides a new method for retrieving histories of impact-related mineral transformations in the crust at conditions far beyond which most rocks melt.

(De)coupled zircon metamictization, radiation damage, and He diffusivity

NASA Astrophysics Data System (ADS)

Ault, A. K.; Guenthner, W.; Reiners, P. W.; Moser, A. C.; Miller, G. H.; Refsnider, K. A.

2017-12-01

We develop and apply a new protocol for targeting crystals for the zircon (U-Th)/He (He) thermochronometry to maximize effective U (eU) and corresponding closure temperature variability to develop zircon He date-eU correlations observed in some datasets. Our approach exploits visual proxies for radiation damage accumulation (metamictization) during zircon selection. We show that by purposefully targeting a spectrum of zircon textures from pristine to metamict grains, it is possible to generate broad eU variation in suites of zircon from a single sample and zircon He date-eU-metamictization trends that can be exploited to resolve increasingly complex thermal histories. We present plane light photographs, eU concentration, and zircon He results from 59 individual zircons from nine crystalline rock samples. Six of the nine samples come from exposed Proterozoic granitoids on SE Baffin Island, Canada; Boulder Creek, CO; Sandia Mountains, NM; and Mecca Hills, CA. We report data from three Archean Baffin samples to compare with the Proterozoic Baffin sample date-eU-metamictization trend. In each Proterozoic sample, target zircons display a spectrum of metamictization from pristine, transparent crystals to purple-brown, translucent grains. Progressive loss of transparency and increase in discoloration consistently corresponds to an increase in eU in all samples. Individual zircon eU varies from 89-1885 ppm and, within each sample, the total eU spread is 538 ppm to 1374 ppm. For any given eU value, the Archean zircon appear comparatively more metamict than the Proterozoic Baffin grains and samples collectively define a 1681 ppm range in eU, with more restrictive intrasample eU spreads (199-1120 ppm). Proterozoic samples from Baffin, Sandia, and Front Range yield negative zircon He date-eU correlations with intrasample date ranges of 90-783 Ma. Increasing eU and younger dates correspond with increasing metamictization. In contrast, all three Proterozoic Mecca Hills samples

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

Role of zircon in tracing crustal growth and recycling

NASA Astrophysics Data System (ADS)

Compston, W.; Williams, I. S.; Armstrong, R. A.; Claoue-Long, J. C.; Kinny, P. D.; Foster, J. J.; Kroener, A.; Pidgeon, R. T.; Myers, J. S.

Single crystal ion probe ages of zircons is discussed, which allow much better time resolution compared to other geochronological methods, although the technique is not without problems. Rocks from two areas that contain composite zircon populations, including true magmatic zircons as well as a variety of xenocrystic types are described. It is often difficult to distinguish these; xenocrystic zircons, for example, cannot always be identified on the basis of morphology alone. Additional evidence is needed before making age interpretations. Evidence is also presented of zircon growth long after the original time of crystallization, in some cases apparently at temperatures less than 300 C. The spectacular discovery of 4.1 to 4.2 Ga detrital zircons in metaquartzites from the Mount Narryer area of Western Australia is described. Similar zircons with ages as old as 4276 Ma have been found in the nearby Jack Hills area. The source areas or parent lithologies of these zircons have not yet been determined, but the author expects that they may be unrecognized or buried antecedents of the K rich Narryer gneisses. U or Th concentrations of zircon cannot be used to discriminate between felsic and mafic source rocks.

Role of zircon in tracing crustal growth and recycling

NASA Technical Reports Server (NTRS)

Compston, W.; Williams, I. S.; Armstrong, R. A.; Claoue-Long, J. C.; Kinny, P. D.; Foster, J. J.; Kroener, A.; Pidgeon, R. T.; Myers, J. S.

1988-01-01

Single crystal ion probe ages of zircons is discussed, which allow much better time resolution compared to other geochronological methods, although the technique is not without problems. Rocks from two areas that contain composite zircon populations, including true magmatic zircons as well as a variety of xenocrystic types are described. It is often difficult to distinguish these; xenocrystic zircons, for example, cannot always be identified on the basis of morphology alone. Additional evidence is needed before making age interpretations. Evidence is also presented of zircon growth long after the original time of crystallization, in some cases apparently at temperatures less than 300 C. The spectacular discovery of 4.1 to 4.2 Ga detrital zircons in metaquartzites from the Mount Narryer area of Western Australia is described. Similar zircons with ages as old as 4276 Ma have been found in the nearby Jack Hills area. The source areas or parent lithologies of these zircons have not yet been determined, but the author expects that they may be unrecognized or buried antecedents of the K rich Narryer gneisses. U or Th concentrations of zircon cannot be used to discriminate between felsic and mafic source rocks.

Using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to characterize copper, zinc and mercury along grizzly bear hair providing estimate of diet.

PubMed

Noël, Marie; Christensen, Jennie R; Spence, Jody; Robbins, Charles T

2015-10-01

We enhanced an existing technique, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to function as a non-lethal tool in the temporal characterization of trace element exposure in wild mammals. Mercury (Hg), copper (Cu), cadmium (Cd), lead (Pb), iron (Fe) and zinc (Zn) were analyzed along the hair of captive and wild grizzly bears (Ursus arctos horribilis). Laser parameters were optimized (consecutive 2000 μm line scans along the middle line of the hair at a speed of 50 μm/s; spot size=30 μm) for consistent ablation of the hair. A pressed pellet of reference material DOLT-2 and sulfur were used as external and internal standards, respectively. Our newly adapted method passed the quality control tests with strong correlations between trace element concentrations obtained using LA-ICP-MS and those obtained with regular solution-ICP-MS (r(2)=0.92, 0.98, 0.63, 0.57, 0.99 and 0.90 for Hg, Fe, Cu, Zn, Cd and Pb, respectively). Cross-correlation analyses revealed good reproducibility between trace element patterns obtained from hair collected from the same bear. One exception was Cd for which external contamination was observed resulting in poor reproducibility. In order to validate the method, we used LA-ICP-MS on the hair of five captive grizzly bears fed known and varying amounts of cutthroat trout over a period of 33 days. Trace element patterns along the hair revealed strong Hg, Cu and Zn signals coinciding with fish consumption. Accordingly, significant correlations between Hg, Cu, and Zn in the hair and Hg, Cu, and Zn intake were evident and we were able to develop accumulation models for each of these elements. While the use of LA-ICP-MS for the monitoring of trace elements in wildlife is in its infancy, this study highlights the robustness and applicability of this newly adapted method. Copyright © 2015 Elsevier B.V. All rights reserved.

Provenance of sediments from Sumatra, Indonesia - Insights from detrital U-Pb zircon geochronology, heavy mineral analyses and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Liebermann, C.; Hall, R.; Gough, A.

2017-12-01

The island of Sumatra is situated at the southwestern margin of the Indonesian archipelago. Although it is the sixth largest island in the world, the geology of the Sumatra sedimentary basins and their underlying basement is relatively poorly understood in terms of their provenance. This work is a multi-proxy provenance study utilizing U-Pb detrital zircon dating by LA-ICP-MS combined with optical and Raman spectroscopy-based heavy mineral analysis. It will help to unravel the stratigraphy of Sumatra, contribute to paleogeographic reconstruction of western SE Asia, and aid a wider understanding of Sumatran petroleum plays. Thin section analyses, heavy mineral assemblages, and >3500 concordant U-Pb zircon ages, from samples acquired during two fieldwork seasons indicate a mixed provenance for Cenozoic sedimentary formations, including both local igneous sources and mature basement rocks. Characteristic Precambrian zircon age spectra are found in all analysed Cenozoic sedimentary strata. These can be correlated with zircon age populations found in Sumatran basement rocks; Neoproterozoic and Mesoproterozoic age groups are dominant (c. 500-600 Ma, c. 850-1000 Ma, c. 1050-1200 Ma). Paleoproterozoic to Archaean zircons occur as minor populations. The Phanerozoic age spectra of the Cenozoic formations are characterised by distinct Carboniferous, Permo-Triassic, and Jurassic-Cretaceous zircon populations. Permo-Triassic zircons are interpreted to come from granitoids in the Malay peninsula or Sumatra itself. Eocene to Lower Miocene strata are characterised by ultrastable heavy minerals such as zircon, tourmaline, and rutile, which together with garnet, suggest the principal sources were igneous and metamorphic basement rocks. Cenozoic zircons appear only from the Middle Miocene onwards. This change is interpreted to indicate a new contribution from a local volcanic arc, and is supported by the occurrence of unstable heavy minerals such as apatite and clinopyroxene, and the

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

NASA Astrophysics Data System (ADS)

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

2004-05-01

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

Zircon U-Pb dating of eclogite from the Qiangtang terrane, north-central Tibet: a case of metamorphic zircon with magmatic geochemical features

NASA Astrophysics Data System (ADS)

Zhai, Qing-guo; Jahn, Bor-ming; Li, Xian-hua; Zhang, Ru-yuan; Li, Qiu-li; Yang, Ya-nan; Wang, Jun; Liu, Tong; Hu, Pei-yuan; Tang, Suo-han

2017-06-01

Zircon is probably the most important mineral used in the dating formation of high-pressure (HP) and ultrahigh-pressure (UHP) metamorphic rocks. The origin of zircon, i.e., magmatic or metamorphic, is commonly assessed by its external morphology, internal structure, mineral inclusions, Th/U ratios and trace element composition. In this study, we present an unusual case of metamorphic zircon from the Qiangtang eclogite, north-central Tibet. The zircon grains contain numerous eclogite-facies mineral inclusions, including omphacite, phengite, garnet and rutile; hence, they are clearly of metamorphic origin. However, they display features similar to common magmatic zircon, including euhedral crystal habit, high Th/U ratios and enriched heavy rare earth elements pattern. We suggest that these zircon grains formed from a different reservoir from that for garnet where no trace elements was present and trace element equilibrium between zircon and garnet was achieved. U-Pb dating of zircon gave an age of 232-237 Ma for the eclogite, and that of rutile yielded a slightly younger age of ca. 217 Ma. These ages are consistent with the reported Lu-Hf mineral isochron and phengite Ar-Ar ages. The zircon U-Pb and mineral Lu-Hf isochron ages are interpreted as the time of the peak eclogite-facies metamorphism, whereas the rutile U-Pb and phengite Ar-Ar ages represent the time of exhumation to the middle crust. Thus, the distinction between metamorphic and magmatic zircons cannot be made using only Th/U ratios and heavy REE compositions for HP-UHP metamorphic rocks of oceanic derivation.

Low pressure laser ablation coupled to inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Fliegel, Daniel; Günther, Detlef

2006-07-01

The particle size distribution in laser ablation inductively coupled plasma mass spectrometry is known to be a critical parameter for complete vaporization of particles. Any strategy to reduce the particle size distribution of laser generated aerosols has the potential to increase the ion signal intensity and to reduce fractionation effects. Due to the fact that vapor generation, nucleation, condensation, and agglomeration take place within an extremely short period of time, ablation under atmospheric pressure might not allow influencing these processes while under reduced pressure condition the cooling of the aerosol and therefore the condensation is expected to be slower. In this study, a low pressure laser ablation cell for the generation of laser aerosols was coupled to an ICP-MS. In contrast to the previously developed trapped ablation mode, the newly designed cell allows the adjustment of the pressure in the ablation cell between 20 and 1400 mbar prior to the ablation. Ablation experiments carried out using this configuration showed a dependence of the aerosol properties (size distribution and particle structure) on the ablation cell pressure. The intensity ratio U/Th measured as a figure of merit for complete vaporization within the ICP indicated a change in the aerosol structure at approximately 500 mbar toward smaller particle size. A significant difference between low pressure and at ambient pressure ablated aerosol was observed. The intensity ratios (U/Th) of the ablated sample moves closer to the bulk composition at lower pressures at the expense of sensitivity. Therefore the decrease in the ICP-MS signal intensity in the low pressure cell can be attributed to vapor deposition within the ablation cell walls. Moreover, scanning electron microscope images of aerosols collected on filters after the low pressure ablation cell suggest the possibility of a slower cooling velocity of the aerosol, which was observed in the condensed material on the surface of

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Geochronology and Geochemistry of Zircons from the IODP Site U1437 in the Rear of the Izu-Bonin Volcanic Arc

NASA Astrophysics Data System (ADS)

Andrews, G. D.; Schmitt, A. K.; Busby, C. J.; Brown, S. R.

2015-12-01

Zircons recovered from International Ocean Discovery Program Expedition 350 Site U1437 (31°47.390'N, 139°01.580'E) in the Izu-Bonin arc were analyzed by SIMS to constrain their age (U/Pb geochronology) and geochemistry (trace elements, δ18O); LA-ICP-MS ɛHf analyses are pending. Seven intervals were dated successfully: six tuffs and lapilli-tuffs between 680.99 and 1722.46 m below sea floor (mbsf) and a single peperitic rhyolitic intrusion at 1388.86 - 1390.07 mbsf. Thirty-two intervals which underwent mineral separation lacked zircon, or yielded zircon much older than age expectations for U1437. Geochronology results from separated zircons confirm and extend the shipboard age model to 1360.77 mbsf where Late Miocene (Tortonian) submarine volcanic rocks (11.3 ±0.7 Ma; n = 17) were sampled. In-situ measurement of zircons associated with magnetite crystals in the rhyolite intrusion yield an age of 13.6 ±1.7 Ma (n = 9). Zircon U contents are low (typically <300 ppm), with trace element ratios characteristic of oceanic lithosphere and near-mantle δ18O values (4-6 ‰). Individual Miocene zircon crystals are difficult to distinguish by age alone from those in the drilling mud (sepiolite) used during Expedition 350; the sepiolite is quarried by IMV Nevada in the Amargosa Valley. Our analysis of thirty-three zircons from the sepiolite finds that they have a broad and varied age distribution (2 - 2033 Ma) with a prominent peak at 12-14 Ma, bimodal δ18O values (peaks at 5-5.5 and 6.5-7.5 ‰), and dominantly continental trace element signatures. Three zircons from U1437 are tentatively identified as sepiolite-derived, but a single Eocene grain (51.7 ±2.4 Ma) recovered from 1722.46 mbsf has an age unlike those in the sepiolite, and potentially is genuinely xenocrystic. The majority of U1437 zircons thus crystallized from evolved melts lacking continental characteristics, although thermal and compositional conditions conducive for zircon crystallization appear to have

U-Pb zircon and biostratigraphic data of high-pressure/low-temperature metamorphic rocks of the Talea Ori: tracking the Paleotethys suture in central Crete, Greece

NASA Astrophysics Data System (ADS)

Zulauf, G.; Dörr, W.; Krahl, J.; Lahaye, Y.; Chatzaras, V.; Xypolias, P.

2016-10-01

Inherited deformation microfabrics of detrital quartz grains and U-Pb (Laser ablation (LA)-ICPMS and ID TIMS) ages of detrital zircons separated from the Phyllite-Quartzite Unit s.l. of the Talea Ori, central Crete, suggest strikingly different source rocks. Albite gneiss of the lower Rogdia Beds includes Cambrian and Neoproterozoic rounded zircons with main U-Pb age peaks at 628 and 988 Ma. These and minor Paleoproterozoic and Archean peaks, together with the lack of Variscan-aged and Mesoproterozoic zircons, are similar to the age spectra obtained from the Phyllite-Quartzite Unit s.str. of the Peloponnesus and eastern Crete and from the Taurides. All of these zircons should be derived from the northeastern passive margin of Gondwana (Cimmeria). Metatuffites of the uppermost Rogdia Beds and metasandstone of Bali beach, on the other hand, include euhedral detrital zircons displaying a Variscan U-Pb age spectra at ca. 300 Ma with concordia ages at 291 ± 3, 300 ± 1 Ma (Rogdia) and 286 ± 3, 300 ± 3, 313 ± 2 Ma (Bali). Both types of metasediments and their zircons are similar to those of the pre-Alpine basement and overlying Tyros Beds of eastern Crete, revealing a provenance at the southern active margin of Laurasia. Thus, in central Crete the Paleotethys suture should be situated inside the Rogdia Beds. Magmatic zircons separated from a rhyolite boulder of the lower Achlada Beds yielded a concordant U-Pb zircon age at 242 ± 2 Ma placing a maximum age for the deposition of the (meta)conglomerate from which the boulder was collected. This age is compatible with an Olenekian-early Anisian age of the underlying Vasilikon marble suggested by new findings of the foraminifera Meandrospira aff. pusilla. Both the Achlada Beds and the Vasilikon marble can be attributed to the lower Tyros Beds of eastern Crete. The Alpine deformation led to a pervasive mylonitic foliation, which is affecting most of the studied rocks. This foliation results from D2 top

Detrital zircon analysis of Mesoproterozoic and neoproterozoic metasedimentary rocks of northcentral idaho: Implications for development of the Belt-Purcell basin

USGS Publications Warehouse

Lewis, R.S.; Vervoort, J.D.; Burmester, R.F.; Oswald, P.J.

2010-01-01

The authors analyzed detrital zircon grains from 10 metasedimentary rock samples of the Priest River complex and three other amphibolite-facies metamorphic sequences in north-central Idaho to test the previous assignment of these rocks to the Mesoproterozoic Belt-Purcell Supergroup. Zircon grains from two samples of the Prichard Formation (lower Belt) and one sample of Cambrian quartzite were also analyzed as controls with known depositional ages. U-Pb zircon analysis by laser ablation - inductively coupled plasma - mass spectrometry reveals that 6 of the 10 samples contain multiple age populations between 1900 and 1400 Ma and a scatter of older ages, similar to results reported from the Belt- Purcell Supergroup to the north and east. Results from the Priest River metamorphic complex confirm previous correlations with the Prichard Formation. Samples from the Golden and Elk City sequences have significant numbers of 1500-1380 Ma grains, which indicates that they do not predate the Belt. Rather, they are probably from a relatively young, southwestern part of the Belt Supergroup (Lemhi subbasin). Non-North American (1610-1490 Ma) grains are rare in these rocks. Three samples of quartzite from the Syringa metamorphic sequence northwest of the Idaho batholith contain zircon grains younger than the Belt Supergroup and support a Neoproterozoic age. A single Cambrian sample has abundant 1780 Ma grains and none younger than ~1750 Ma. These results indicate that the likely protoliths of many high-grade metamorphic rocks in northern Idaho were strata of the Belt-Purcell Supergroup or overlying rocks of the Neoproterozoic Windermere Supergroup and not basement rocks.

Fission track dating of kimberlitic zircons

USGS Publications Warehouse

Haggerty, S.E.; Raber, E.; Naeser, C.W.

1983-01-01

The only reliable method for dating kimberlites at present is the lengthy and specialized hydrothermal procedure that extracts 206Pb and 238U from low-uranium zircons. This paper describes a second successful method by fission track dating of large single-crystal zircons, 1.0-1.5 cm in dimension. The use of large crystals overcomes the limitations imposed in conventional fission track analysis which utilizes crushed fragments. Low track densities, optical track dispersion, and the random orientation of polished surfaces in the etch and irradiation cycle are effectively overcome. Fission track ages of zircons from five African kimberlites are reported, from the Kimberley Pool (90.3 ?? 6.5 m.y.), Orapa (87.4 ?? 5.7 and 92.4 ?? 6.1 m.y.), Nzega (51.1 ?? 3.8 m.y.), Koffiefontein (90.0 ?? 8.2 m.y.), and Val do Queve (133.4 ?? 11.5 m.y.). In addition we report the first radiometric ages (707.9 ?? 59.6 and 705.5 ?? 61.0 m.y.) of crustal zircons from kimberlites in northwest Liberia. The fission track ages agree well with earlier age estimates. Most of the zircons examined in this study are zoned with respect to uranium but linear correlations are established (by regression analysis) between zones of variable uranium content, and within zones of constant uranium content (by analysis of variance). Concordance between the fission track method and the U/Pb technique is established and we concluded that track fading from thermal annealing has not taken place. Kimberlitic zircons dated in this study, therefore, record the time of eruption. ?? 1983.

Testing the reliability of information extracted from ancient zircon

NASA Astrophysics Data System (ADS)

Kielman, Ross; Whitehouse, Martin; Nemchin, Alexander

2015-04-01

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

Preliminary study on multi-element profile mapping of crustal and mantle zircons by using Synchrotron Radiation X-ray Fluorescence (SR-XRF)

NASA Astrophysics Data System (ADS)

Hasözbek, Altug; Shyam, Badri; Siebel, Wolfgang; Schmitt, Axel; Akay, Erhan; Skinner, Lawrie

2013-04-01

Zircon (ZrSiO4) is a mineral of singular importance in the geosciences. Zircon microanalysis has greatly contributed to our understanding of key events in earth's history as certain radioactive heavy elements and their daughter products are well-preserved within the exceptionally stable inorganic matrix of the mineral. A prevailing notion in this field is that zircon, as a mineral, is predominantly a crustal mineral; this has been contested in the last few years with more reports of mantle-derived zircons (Siebel et al., 2009). Zircons enriched from different parts of the upper mantle to lower crust from Turkey (Hasozbek et al. 2010) and Germany (Siebel et al., 2009) will be presented in this study using SR-XRF mapping carried out at beamline 2-IDE at the Advanced Photon Source synchrotron facility (Argonne National Laboratory, USA). The high-resolution (5-10 µm) elemental maps were obtained with collimated and linearly polarized synchrotron radiation (10 to 17 keV) and possess the advantage of being a completely non-destructive technique. Elemental maps of various trace and rare-earth elements along the cross-section of the zircons reveal a zonation-related distribution, which may be used to reveal factors affecting the growth history and dynamics of the crystal formation. Further, abrupt changes in elemental distribution or concentration were found to correspond to faults or inclusions within the zircon crystal. If such observations are found to be applicable for a wide range of samples, elemental mapping with this technique may serve as an important qualitative diagnostic to locating µ-meter inclusions that may be challenging to identify using other techniques (ICP-MS LA, SHRIMP,…) Through these preliminary elemental profile mapping studies of crustal and mantle zircons using SR-XRF methods, we aim to highlight a relatively quick and promising analytical method that may be used to study various geological problems.

Hydrogen incorporation and charge balance in natural zircon

NASA Astrophysics Data System (ADS)

De Hoog, J. C. M.; Lissenberg, C. J.; Brooker, R. A.; Hinton, R.; Trail, D.; Hellebrand, E.

2014-09-01

The water and trace element contents of natural igneous zircons were determined to constrain the mechanism of hydrogen incorporation. The low radiation-damage zircons were derived from Fe-Ti oxide gabbros from the Vema Fracture Zone (11°N, Mid-Atlantic Ridge). They contain up to 1212 ppmw H2O, 1.9 wt.% Y2O3 and 0.6 wt.% P2O5 and are generally strongly zoned. REE + Y are partially charge-balanced by P (Y, REE3+ + P5+ = Zr4+ + Si4+), but a large REE excess is present. On an atomic basis, this excess is closely approximated by the amount of H present in the zircons. We therefore conclude that H is incorporated by a charge-balance mechanism (H+ + REE3+ = Zr4+). This interpretation is consistent with FTIR data of the Vema zircons, which shows a strongly polarised main absorption band at ca. 3100 cm-1, similar to experimentally grown Lu-doped hydrous zircon. The size of this 3100 cm-1 band scales with H and REE contents. Apart from a small overlapping band at 3200 cm-1, no other absorption bands are visible, indicating that a hydrogrossular-type exchange mechanism does not appear to be operating in these zircons. Because of charge-balanced uptake of H, P and REE in zircon, the partitioning of these elements into zircon is dependent on each of their concentrations. For instance, DREEzrc/melt increases with increasing H and P contents of the melt, whereas DHzrc/melt increases with increasing REE content but decreases with increasing P content. In addition, H-P-REE systematics of sector zoning indicate kinetic effects may play an important role. Hence, using H in zircon to determine the water content of melts is problematic, and REE partitioning studies need to take into account P and H2O contents of the melt.

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.

Fission track dating of kimberlitic zircons

NASA Astrophysics Data System (ADS)

Haggerty, Stephen E.; Raber, Ellen; Naeser, Charles W.

1983-04-01

The only reliable method for dating kimberlites at present is the lengthy and specialized hydrothermal procedure that extracts 206Pb and 238U from low-uranium zircons. This paper describes a second successful method by fission track dating of large single-crystal zircons, 1.0-1.5 cm in dimension. The use of large crystals overcomes the limitations imposed in conventional fission track analysis which utilizes crushed fragments. Low track densities, optical track dispersion, and the random orientation of polished surfaces in the etch and irradiation cycle are effectively overcome. Fission track ages of zircons from five African kimberlites are reported, from the Kimberley Pool (90.3 ± 6.5 m.y.), Orapa (87.4 ± 5.7 and 92.4 ± 6.1 m.y.), Nzega (51.1 ± 3.8 m.y.), Koffiefontein (90.0 ± 8.2 m.y.), and Val do Queve (133.4 ± 11.5 m.y.). In addition we report the first radiometric ages (707.9 ± 59.6 and 705.5 ± 61.0 m.y.) of crustal zircons from kimberlites in northwest Liberia. The fission track ages agree well with earlier age estimates. Most of the zircons examined in this study are zoned with respect to uranium but linear correlations are established (by regression analysis) between zones of variable uranium content, and within zones of constant uranium content (by analysis of variance). Concordance between the fission track method and the U/Pb technique is established and we concluded that track fading from thermal annealing has not taken place. Kimberlitic zircons dated in this study, therefore, record the time of eruption.

Deposition and element fractionation processes during atmospheric pressure laser sampling for analysis by ICP-MS

NASA Astrophysics Data System (ADS)

Eggins, S. M.; Kinsley, L. P. J.; Shelley, J. M. G.

1998-05-01

We have used an ArF excimer laser coupled to a quadrupole inductively coupled plasma mass spectrometry (ICP-MS) for the measurement of a range of elements during excavation of a deepening ablation pit in a synthetic glass (NIST 612). Analyte behaviour shows progressive volatile element enrichment at shallow hole depths, with a change to refractory element enrichment as the ablation pit deepens further. Examination of ablation pit morphology and the surface condensate deposited around the ablation site reveals the importance of sequential condensation of refractory, then volatile phases from the cooling plasma plume after the end of the laser pulse. We interpret the observed element fractionation behaviour to reflect a change in ablation processes from photothermal dominated to plasma dominated mechanisms. The development of the surface deposit is greatly reduced by ablating in an ambient atmosphere of He instead of Ar and is accompanied by a two- to four-fold increase in ICP-MS sensitivity.

Gap detection threshold in the rat before and after auditory cortex ablation.

PubMed

Syka, J; Rybalko, N; Mazelová, J; Druga, R

2002-10-01

Gap detection threshold (GDT) was measured in adult female pigmented rats (strain Long-Evans) by an operant conditioning technique with food reinforcement, before and after bilateral ablation of the auditory cortex. GDT was dependent on the frequency spectrum and intensity of the continuously present noise in which the gaps were embedded. The mean values of GDT for gaps embedded in white noise or low-frequency noise (upper cutoff frequency 3 kHz) at 70 dB sound pressure level (SPL) were 1.57+/-0.07 ms and 2.9+/-0.34 ms, respectively. Decreasing noise intensity from 80 dB SPL to 20 dB SPL produced a significant increase in GDT. The increase in GDT was relatively small in the range of 80-50 dB SPL for white noise and in the range of 80-60 dB for low-frequency noise. The minimal intensity level of the noise that enabled GDT measurement was 20 dB SPL for white noise and 30 dB SPL for low-frequency noise. Mean GDT values at these intensities were 10.6+/-3.9 ms and 31.3+/-4.2 ms, respectively. Bilateral ablation of the primary auditory cortex (complete destruction of the Te1 and partial destruction of the Te2 and Te3 areas) resulted in an increase in GDT values. The fifth day after surgery, the rats were able to detect gaps in the noise. The values of GDT observed at this time were 4.2+/-1.1 ms for white noise and 7.4+/-3.1 ms for low-frequency noise at 70 dB SPL. During the first month after cortical ablation, recovery of GDT was observed. However, 1 month after cortical ablation GDT still remained slightly higher than in controls (1.8+/-0.18 for white noise, 3.22+/-0.15 for low-frequency noise, P<0.05). A decrease in GDT values during the subsequent months was not observed.

Oxygen diffusion in zircon

NASA Astrophysics Data System (ADS)

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

1997-05-01

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

Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

USGS Publications Warehouse

Pribil, Michael; Ridley, William I.; Emsbo, Poul

2015-01-01

Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

Radiation Damage Study in Natural Zircon Using Neutrons Irradiation

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

Lwin, Maung Tin Moe; Amin, Yusoff Mohd.; Kassim, Hasan Abu

2011-03-30

Changes of atomic displacements in crystalline structure of natural zircon (ZrSiO{sub 4}) can be studied by using neutron irradiation on the surface of zircon and compared the data from XRD measurements before and after irradiation. The results of neutron irradiation on natural zircon using Pneumatic Transfer System (PTS) at PUSPATI TRIGA Research Reactor in the Malaysian Nuclear Agency are discussed in this work. The reactor produces maximum thermal power output of 1 MWatt and the neutron flux of up to 1x10{sup 13} ncm{sup -2}s{sup -1}. From serial decay processes of uranium and thorium radionuclides in zircon crystalline structure, the emissionmore » of alpha particles can produce damage in terms of atomic displacements in zircon. Hence, zircon has been extensively studied as a possible candidate for immobilization of fission products and actinides.« less

Are there impact-formed zircons in the Hadean record?

NASA Astrophysics Data System (ADS)

Wielicki, M. M.; Lu, X.; Bell, E. A.; Schmitt, A. K.; Harrison, T. M.

2008-12-01

Detrital Hadean zircons from the Jack Hills, Western Australia, show a remarkable cluster of crystallization temperatures at 680±25°C. This is particularly surprising as a simple model relating rock composition and Zr concentration predicts that a very broad spectrum of crystallization temperatures (ca. 650°C to 1000°C) with a median value of 780°C, would result from impact melting of the Earth's surface. Magmatic fractionation would tend to increase the aforementioned values. Given the predicted high rate of impacts during the Hadean, the absence of such a population in the Jack Hills zircons could signal a profound sampling problem, a hint of a history much different than previously supposed, or our lack of understanding of zircon formation due to impact related processes. We have begun to examine the latter issue by investigating the crystallization temperatures of zircons formed in melt sheets preserved in the geologic record. The Sudbury Igneous Complex, formed at 1850±3 Ma within the second largest impact crater on Earth, includes two igneous units termed the Black and Felsic Norites. Examination of zircons from each by SIMS confirms their crystallization age at 1847.3±2.2 Ma and yields Ti-in-zircon temperatures of 720°C and 750°C, respectively. This is consistent with that predicted from zircon saturation systematics. A statistical test indicates that the combined norite population is distinct from the Hadean temperature distribution. Thus the question arises: where are the Hadean zircons expected to have formed at >780°C via impact processes? Similar analysis is being pursued for zircons from the Vredefort Impact Structure, South Africa, which should provide further information on impact-formed zircon temperature spectra.

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.

Small-Volume U-Pb Zircon Geochronology by Laser Ablation-Multicollector-ICP-MS

DTIC Science & Technology

2008-11-03

Ecstall pluton in the Coast Mountains of British Columbia: Evidence for local deformation rather than large-scale transport. Journal of Geophysical...Journal of Metamorphic Geology 18, 719–735. Kalsbeek, F., Jepsen, H.F., Nutman, A.P., 2001. From source migmatites to plutons : tracking the origin of

Substrate-Mediated Laser Ablation under Ambient Conditions for Spatially-Resolved Tissue Proteomics

PubMed Central

Fatou, Benoit; Wisztorski, Maxence; Focsa, Cristian; Salzet, Michel; Ziskind, Michael; Fournier, Isabelle

2015-01-01

Numerous applications of ambient Mass Spectrometry (MS) have been demonstrated over the past decade. They promoted the emergence of various micro-sampling techniques such as Laser Ablation/Droplet Capture (LADC). LADC consists in the ablation of analytes from a surface and their subsequent capture in a solvent droplet which can then be analyzed by MS. LADC is thus generally performed in the UV or IR range, using a wavelength at which analytes or the matrix absorb. In this work, we explore the potential of visible range LADC (532 nm) as a micro-sampling technology for large-scale proteomics analyses. We demonstrate that biomolecule analyses using 532 nm LADC are possible, despite the low absorbance of biomolecules at this wavelength. This is due to the preponderance of an indirect substrate-mediated ablation mechanism at low laser energy which contrasts with the conventional direct ablation driven by sample absorption. Using our custom LADC system and taking advantage of this substrate-mediated ablation mechanism, we were able to perform large-scale proteomic analyses of micro-sampled tissue sections and demonstrated the possible identification of proteins with relevant biological functions. Consequently, the 532 nm LADC technique offers a new tool for biological and clinical applications. PMID:26674367

Deformation-related microstructures in magmatic zircon and implications for diffusion

NASA Astrophysics Data System (ADS)

Reddy, Steven Michael; Timms, Nicholas E.; Hamilton, Patrick Joseph; Smyth, Helen R.

2009-02-01

An undeformed glomeroporphyritic andesite from the Sunda Arc of Java, Indonesia, contains zoned plagioclase and amphibole glomerocrysts in a fine-grained groundmass and records a complex history of adcumulate formation and subsequent magmatic disaggregation. A suite of xenocrystic zircon records Proterozoic and Archaean dates whilst a discrete population of zoned, euhedral, igneous zircon yields a SHRIMP U-Pb crystallisation age of 9.3 ± 0.2 Ma. Quantitative microstructural analysis of zircon by electron backscatter diffraction (EBSD) shows no deformation in the inherited xenocrysts, but intragrain orientation variations of up to 30° in 80% of the young zircon population. These variations are typically accommodated by both progressive crystallographic bending and discrete low angle boundaries that overprint compositional growth zoning. Dispersion of crystallographic orientations are dominantly by rotation about an axis parallel to the zircon c-axis [001], which is coincident with the dominant orientation of misorientation axes of adjacent analysis points in EBSD maps. Less common <100> misorientation axes account for minor components of crystallographic dispersion. These observations are consistent with zircon deformation by dislocation creep and the formation of tilt and twist boundaries associated with the operation of <001>{100} and <100>{010} slip systems. The restriction of deformation microstructures to large glomerocrysts and the young magmatic zircon population, and the absence of deformation within the host igneous rock and inherited zircon grains, indicate that zircon deformation took place within a low-melt fraction (<5% melt), mid-lower crustal cumulate prior to fragmentation during magmatic disaggregation and entrainment of xenocrystic zircons during magmatic decompression. Tectonic stresses within the compressional Sunda Arc at the time of magmatism are considered to be the probable driver for low-strain deformation of the cumulate in the late

Effectiveness of atrial fibrillation rotor ablation is dependent on conduction velocity: An in-silico 3-dimensional modeling study

PubMed Central

Lim, Byounghyun; Hwang, Minki; Song, Jun-Seop; Ryu, Ah-Jin; Joung, Boyoung; Shim, Eun Bo; Ryu, Hyungon

2017-01-01

Background We previously reported that stable rotors are observed in in-silico human atrial fibrillation (AF) models, and are well represented by a dominant frequency (DF). In the current study, we hypothesized that the outcome of DF ablation is affected by conduction velocity (CV) conditions and examined this hypothesis using in-silico 3D-AF modeling. Methods We integrated 3D CT images of left atrium obtained from 10 patients with persistent AF (80% male, 61.8±13.5 years old) into in-silico AF model. We compared AF maintenance durations (max 300s), spatiotemporal stabilities of DF, phase singularity (PS) number, life-span of PS, and AF termination or defragmentation rates after virtual DF ablation with 5 different CV conditions (0.2, 0.3, 0.4, 0.5, and 0.6m/s). Results 1. AF maintenance duration (p<0.001), spatiotemporal mean variance of DF (p<0.001), and the number of PS (p = 0.023) showed CV dependent bimodal patterns (highest at CV0.4m/s and lowest at CV0.6m/s) consistently. 2. After 10% highest DF ablation, AF defragmentation rates were the lowest at CV0.4m/s (37.8%), but highest at CV0.5 and 0.6m/s (all 100%, p<0.001). 3. In the episodes with AF termination or defragmentation followed by 10% highest DF ablation, baseline AF maintenance duration was shorter (p<0.001), spatiotemporal mean variance of DF was lower (p = 0.014), and the number of PS was lower (p = 0.004) than those with failed AF defragmentation after DF ablation. Conclusion Virtual ablation of DF, which may indicate AF driver, was more likely to terminate or defragment AF with spatiotemporally stable DF, but not likely to do so in long-lasting and sustained AF conditions, depending on CV. PMID:29287119

Zircon-Based Ceramics Composite Coating for Environmental Barrier Coating

NASA Astrophysics Data System (ADS)

Suzuki, M.; Sodeoka, S.; Inoue, T.

2008-09-01

Studies on plasma spraying of zircon (ZrSiO4) have been carried out by the authors as one of the candidates for an environmental barrier coating (EBC) application, and had reported that substrate temperature is one of the most important factors to obtain crack-free and highly adhesive coating. In this study, several amounts of yttria were added to zircon powder, and the effect of the yttria addition on the structure and properties of the coatings were evaluated to improve the stability of the zircon coating structure at elevated temperature. The coatings obtained were composed of yttria-stabilized zirconia (YSZ), glassy silica, whereas the one prepared from monolithic zircon powder was composed of the metastable high temperature tetragonal phase of zirconia and glassy silica. After the heat treatment over 1200 °C, silica and zirconia formed zircon in all coatings. However, coatings with higher amounts of yttria exhibited lower amounts of zircon. This resulted in the less open porosity of the coating at elevated temperature. These yttria-added coatings also showed good adhesion even after the heat treatment, while monolithic zircon coating pealed off.

Isotopic Composition of Oxygen in Lunar Zircons

NASA Technical Reports Server (NTRS)

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

2005-01-01

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

A Proof of Concept to Bridge the Gap between Mass Spectrometry Imaging, Protein Identification and Relative Quantitation: MSI~LC-MS/MS-LF.

PubMed

Théron, Laëtitia; Centeno, Delphine; Coudy-Gandilhon, Cécile; Pujos-Guillot, Estelle; Astruc, Thierry; Rémond, Didier; Barthelemy, Jean-Claude; Roche, Frédéric; Feasson, Léonard; Hébraud, Michel; Béchet, Daniel; Chambon, Christophe

2016-10-26

Mass spectrometry imaging (MSI) is a powerful tool to visualize the spatial distribution of molecules on a tissue section. The main limitation of MALDI-MSI of proteins is the lack of direct identification. Therefore, this study focuses on a MSI~LC-MS/MS-LF workflow to link the results from MALDI-MSI with potential peak identification and label-free quantitation, using only one tissue section. At first, we studied the impact of matrix deposition and laser ablation on protein extraction from the tissue section. Then, we did a back-correlation of the m / z of the proteins detected by MALDI-MSI to those identified by label-free quantitation. This allowed us to compare the label-free quantitation of proteins obtained in LC-MS/MS with the peak intensities observed in MALDI-MSI. We managed to link identification to nine peaks observed by MALDI-MSI. The results showed that the MSI~LC-MS/MS-LF workflow (i) allowed us to study a representative muscle proteome compared to a classical bottom-up workflow; and (ii) was sparsely impacted by matrix deposition and laser ablation. This workflow, performed as a proof-of-concept, suggests that a single tissue section can be used to perform MALDI-MSI and protein extraction, identification, and relative quantitation.

A Proof of Concept to Bridge the Gap between Mass Spectrometry Imaging, Protein Identification and Relative Quantitation: MSI~LC-MS/MS-LF

PubMed Central

Théron, Laëtitia; Centeno, Delphine; Coudy-Gandilhon, Cécile; Pujos-Guillot, Estelle; Astruc, Thierry; Rémond, Didier; Barthelemy, Jean-Claude; Roche, Frédéric; Feasson, Léonard; Hébraud, Michel; Béchet, Daniel; Chambon, Christophe

2016-01-01

Mass spectrometry imaging (MSI) is a powerful tool to visualize the spatial distribution of molecules on a tissue section. The main limitation of MALDI-MSI of proteins is the lack of direct identification. Therefore, this study focuses on a MSI~LC-MS/MS-LF workflow to link the results from MALDI-MSI with potential peak identification and label-free quantitation, using only one tissue section. At first, we studied the impact of matrix deposition and laser ablation on protein extraction from the tissue section. Then, we did a back-correlation of the m/z of the proteins detected by MALDI-MSI to those identified by label-free quantitation. This allowed us to compare the label-free quantitation of proteins obtained in LC-MS/MS with the peak intensities observed in MALDI-MSI. We managed to link identification to nine peaks observed by MALDI-MSI. The results showed that the MSI~LC-MS/MS-LF workflow (i) allowed us to study a representative muscle proteome compared to a classical bottom-up workflow; and (ii) was sparsely impacted by matrix deposition and laser ablation. This workflow, performed as a proof-of-concept, suggests that a single tissue section can be used to perform MALDI-MSI and protein extraction, identification, and relative quantitation. PMID:28248242

Significance of zircon U-Pb ages from the Pescadero felsite, west-central California coast ranges

USGS Publications Warehouse

McLaughlin, Robert J.; Moore, Diane E.; ,; Martens, UWE C.; Clark, J.C.

2011-01-01

Weathered felsite is associated with the late Campanian–Maastrichtian Pigeon Point Formation near Pescadero, California. Poorly exposed, its age and correlation are uncertain. Is it part of the Pigeon Point section west of the San Gregorio–Hosgri fault? Does it rest on Nacimiento block basement? Is it dextrally offset from the Oligocene Cambria Felsite, ∼185 km to the southeast? Why is a calc-alkaline hypabyssal igneous rock intrusive into the outboard accretionary prism? To address these questions, we analyzed 43 oscillatory-zoned zircon crystals from three incipiently recrystallized pumpellyite ± prehnite ± laumontite-bearing Pescadero felsite samples by sensitive high-resolution ion microprobe–reverse geometry (SHRIMP-RG) and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) techniques. Thirty-three zircons gave late Mesozoic U-Pb ages, with single-grain values ranging from 81 to 167 Ma; ten have pre-Mesozoic, chiefly Proterozoic ages. A group of the four youngest Pescadero zircons yielded an apparent maximum igneous age of ca. 86–90 Ma. Reflecting broad age scatter and presence of partly digested sandstone inclusions, we interpret the rest of the zircons (perhaps all) as xenocrysts. Twenty-three zircons were separated and analyzed from two samples of the similar Cambria Felsite, yielding a unimodal 27 Ma U-Pb age. Clearly, the origin of the Upper Oligocene Cambria Felsite is different from that of the Upper Cretaceous Pescadero felsite; these rocks are not correlated, and do not constrain displacement along the San Gregorio–Hosgri fault. Peak ages differ slightly, but relative probability curves for Mesozoic and pre-Mesozoic Pescadero zircons compare well, for example, with abundant U-Pb age data for detrital zircons from Franciscan metaclastic strata ∼100 km to the east in the Diablo Range–San Francisco Bay area, San Joaquin Great Valley Group turbidites, Upper Cretaceous Nacimiento block Franciscan strata, and Upper

Provenance and metamorphic PT conditions of Cryogenian-Ediacaran metasediments from the Kid metamorphic complex, Sinai, NE Arabian-Nubian Shield: Insights from detrital zircon geochemistry and mineral chemistry

NASA Astrophysics Data System (ADS)

El-Bialy, Mohammed Z.; Ali, Kamal A.; Abu El-Enen, Mahrous M.; Ahmed, Ahmed H.

2015-12-01

The Malhaq and Um Zariq formations occupy the northern part of the Neoproterozoic Kid metamorphic complex of SE Sinai, NE Arabian-Nubian Shield. This study presents new mineral chemistry data and LA-ICP-MS analyses of the trace element concentrations on zircons separated from metapelites from these formations. The detrital zircons of Um Zariq Formation are more enriched in ΣREE, whereas Malhaq Formation zircons are markedly HREE-enriched with strongly fractionated HREE patterns. The quite differences in the overall slope and size of the Eu and Ce anomalies between REE patterns of the two zircon suites provide a robust indication of different sources. The Ti-in-zircon thermometer has revealed that the zircons separated from Malhaq Formation were crystallized within the 916-1018 °C range, while those from Um Zariq Formation exhibit higher range of crystallization temperatures (1084-1154 °C). The detrital zircons of Malhaq Formation were derived mainly from mafic source rocks (basalt and dolerite), whereas Um Zariq Formation zircons have varied and more evolved parent rocks. Most of the investigated zircons from both formations are concluded to be unaltered magmatic that were lately crystallized from a high LREE/HREE melt. All the studied detrital zircon grains show typical trace elements features of crustal-derived zircons. All of the Um Zariq Formation and most of Malhaq Formation detrital zircons are geochemically discriminated as continental zircons. Both formation metapelites record similar, overlapping peak metamorphic temperatures (537-602 °C and 550-579 °C, respectively), and pressures (3.83-4.93 kbar and 3.69-4.07 kbar, respectively). The geothermal gradient, at the peak metamorphic conditions, was quite high (37-41 °C/km) corresponding to metamorphism at burial depth of 14-16 km. The peak regional metamorphism of Um Zariq and Malhaq formations is concluded to be generated during extensional regime and thinning of the lithosphere in an island arc

Radiofrequency catheter ablation of idiopathic ventricular arrhythmias originating from intramural foci in the left ventricular outflow tract: efficacy of sequential versus simultaneous unipolar catheter ablation.

PubMed

Yamada, Takumi; Maddox, William R; McElderry, H Thomas; Doppalapudi, Harish; Plumb, Vance J; Kay, G Neal

2015-04-01

Idiopathic ventricular arrhythmias (VAs) originating from the left ventricular outflow tract (LVOT) sometimes require catheter ablation from the endocardial and epicardial sides for their elimination, suggesting the presence of intramural VA foci. This study investigated the efficacy of sequential and simultaneous unipolar radiofrequency catheter ablation from the endocardial and epicardial sides in treating intramural LVOT VAs. Fourteen consecutive LVOT VAs, which required sequential or simultaneous irrigated unipolar radiofrequency ablation from the endocardial and epicardial sides for their elimination, were studied. The first ablation was performed at the site with the earliest local ventricular activation and best pace map on the endocardial or epicardial side. When the first ablation was unsuccessful, the second ablation was delivered on the other surface. If this sequential unipolar ablation failed, simultaneous unipolar ablation from both sides was performed. The first ablation was performed on the epicardial side in 9 VAs and endocardial side in 5 VAs. The intramural LVOT VAs were successfully eliminated by the sequential (n=9) or simultaneous (n=5) unipolar catheter ablation. Simultaneous ablation was most likely to be required for the elimination of the VAs when the distance between the endocardial and epicardial ablation sites was >8 mm and the earliest local ventricular activation time relative to the QRS onset during the VAs of <-30 ms was recorded at those ablation sites. LVOT VAs originating from intramural foci could usually be eliminated by sequential unipolar radiofrequency ablation and sometimes required simultaneous ablation from both the endocardial and epicardial sides. © 2015 American Heart Association, Inc.

Cardiac memory in patients with Wolff-Parkinson-White syndrome: noninvasive imaging of activation and repolarization before and after catheter ablation.

PubMed

Ghosh, Subham; Rhee, Edward K; Avari, Jennifer N; Woodard, Pamela K; Rudy, Yoram

2008-08-26

Cardiac memory refers to a change in ventricular repolarization induced by and persisting for minutes to months after cessation of a period of altered ventricular activation (eg, resulting from pacing or preexcitation in patients with Wolff-Parkinson-White syndrome). ECG imaging (ECGI) is a novel imaging modality for noninvasive electroanatomic mapping of epicardial activation and repolarization. Fourteen pediatric patients with Wolff-Parkinson-White syndrome and no other congenital disease, were imaged with ECGI a day before and 45 minutes, 1 week, and 1 month after successful catheter ablation. ECGI determined that preexcitation sites were consistent with sites of successful ablation in all cases to within a 1-hour arc of each atrioventricular annulus. In the preexcited rhythm, activation-recovery interval (ARI) was the longest (349+/-6 ms) in the area of preexcitation leading to high average base-to-apex ARI dispersion of 95+/-9 ms (normal is approximately 40 ms). The ARI dispersion remained the same 45 minutes after ablation, although the activation sequence was restored to normal. ARI dispersion was still high (79+/-9 ms) 1 week later and returned to normal (45+/-6 ms) 1 month after ablation. The study demonstrates that ECGI can noninvasively localize ventricular insertion sites of accessory pathways to guide ablation and evaluate its outcome in pediatric patients with Wolff-Parkinson-White syndrome. Wolff-Parkinson-White is associated with high ARI dispersion in the preexcited rhythm that persists after ablation and gradually returns to normal over a period of 1 month, demonstrating the presence of cardiac memory. The 1-month time course is consistent with transcriptional reprogramming and remodeling of ion channels.

Provenance from zircon U-Pb age distributions in crustally contaminated granitoids

NASA Astrophysics Data System (ADS)

Bahlburg, Heinrich; Berndt, Jasper

2016-05-01

The basement of sedimentary basins is often entirely covered by a potentially multi-stage basin fill and therefore removed from direct observation and sampling. Melts intruding through the basin stratigraphy at a subsequent stage in the geological evolution of a region may assimilate significant volumes of country rocks. This component may be preserved in the intrusive body either as xenoliths or it may be reflected only by the age spectrum of incorporated zircons. Here we present the case of an Ordovician calc-alkaline intrusive belt in NW Argentina named the "Faja Eruptiva de la Puna Oriental" (Faja Eruptiva), which in the course of intrusion sampled the unexposed and unknown basement of the Ordovician basin in this region, and parts of the basin stratigraphy. We present new LA-ICP-MS U-Pb ages on zircons from 9 granodiorites and granites of the Faja Eruptiva. The main part of the Faja Eruptiva intruded c. 445 Ma in the Late Ordovician. The zircon ages obtained from the intrusive rocks have a large spread between 2683.5 ± 21.6 and 440.0 ± 4.9 Ma and reflect the underlying crust and may be interpreted in several ways. The inherited zircons may have been derived from the oldest known unit in the region, the thick siliciclastic turbidite successions of the upper Neoproterozoic-lower Cambrian Puncoviscana Formation, which is inferred to represent the basement of the NW Argentina. The basement to the Puncoviscana Formation is not known. Alternatively, the inherited zircons may reflect the geochronological structure of the entire unexposed Early Paleozoic crust underlying this region of which the Puncoviscana Formation was only one component. This crust likely contained rocks pertaining to and detritus derived from earlier orogenic cycles of the southwestern Amazonia craton, including sources of Early Meso- and Paleoproterozoic age. Detritus derived, in turn, from the Faja Eruptiva intrusive belt reflects the origin of the granitoids as well as the inherited

Continental crustal history in SE Asia: Insights from zircon geochronology

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

PubMed

Konegger-Kappel, Stefanie; Prohaska, Thomas

2016-01-01

Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from

Elemental Analysis of Zircon by High Mass Resolution USGS-Stanford SHRIMP-RG: Measuring and Evaluating Ti-in-zircon Temperatures and Compositional Characteristics

NASA Astrophysics Data System (ADS)

Wooden, J. L.; Mazdab, F. K.; Claiborne, L. L.; Miller, C. F.; Barth, A. P.

2006-12-01

High mass resolution of SHRIMP-RG permits measurement of a large set of trace elements for zircon, including 48Ti, Sc, and Nb (requiring better than 9,000 MR) and Be, B, F, P, 49Ti, V, Y, all the REE, Hf, Th, and U (Mazdab and Wooden 2006). A 15-20 micron spot allows analysis of numerous discrete CL zones from single zircons with minimal contributions from unknown material below the exposed surface. Data from suites of zircons from more than 20 individual granitoid samples suggest several general observations: (1) Temperatures calculated by Ti-in-zircon (Watson et al 2006) are entirely compatible with petrologic constraints; uncertainty in a(TiO2) introduces uncertainty in calculated T, but for reasonable values between 0.5 and 0.8 T's consistently fall between 650 and 900 C, mostly in the lower half of the range; (2) T can vary by 150-200 C within suites of zircons from individual samples and even in single zircons, where zonation may be normal (high to low, core to rim), reverse (low to high) or fluctuating; (3) Hf concentrations increase with decreasing T because of Zr/Hf fractionation between zircon and melt (Claiborne et al in press); (4) Many elements and element ratios show a co-variation with T and Hf concentration e.g., Th/U and MREE/HREE decrease with increasing Hf and decreasing T. Hf concentrations can continue to increase after a minimum T is reached, indicating continuing zircon growth from remaining (near eutectic?) melt. Yb/Gd (steepness of the HREE pattern) is an excellent monitor of fractionation, particularly at lower T (below 750 C) where the ratio increases rapidly. This trend may result from co-fractionation of accessory minerals and/or be driven by the thermodynamics of crystal growth, and/or may involve other factors and processes as yet poorly understood. Magmatic zircons commonly have a negative Eu anomaly of about 0.5 or lower which may change little or become more pronounced with falling T; anomalies probably reflect feldspar

Geochemistry, thermometry and isotope ratios on the same zircon crystals: the tandem use of quadrupole LA-ICPMS and CA-TIMS

NASA Astrophysics Data System (ADS)

Olin, P. H.; Schmitz, M. D.; Crowley, J. L.

2011-12-01

Current trends in igneous petrology include the extraction of diverse geochemical information from smaller sample targets by ever more efficient and cost effective means. Igneous zircons are repositories of several types of petrogenetic information, such as magmatic crystallization ages obtained using U-Pb geochronology, magmatic temperatures using Ti-in-zircon geothermometry, and magmatic differentiation and/or mixing trends using trace element contents. Here we demonstrate a tandem quadrupole LA-ICPMS and CA-TIMS approach on single zircon crystals and within domains in single crystals, which extracts all of these data from a single laser spot analysis and then guides the acquisition of CA-TIMS ages at precisions relevant to magmatic histories. We present data from zircon-bearing intrusive and extrusive rocks spanning the compositional spectrum, and highlight results from silicic volcanic rocks with different affinities. The utility of our approach is illustrated in zircons from the Temora diorite, a commonly used standard material which we analysed using 25-μm ablation spots placed on dozens of grains which had been previously annealed and chemically abraded prior to mounting in epoxy. Our LA-ICPMS results illustrate a 3- to 5-fold variation in trace element concentrations and trace element ratios over >150 degrees of cooling as estimated from Ti-in-zircon thermometry. Some geochemical parameters (e.g., Nb/Ta variations and Eu anomalies) are consistent with crystal fractionation during progressive crystallization, while others are bimodal (e.g., Hf and U contents), suggesting the mixing of crystal/magma batches prior to final solidification. LA-ICPMS U-Pb spot ages reproduce the accepted CA-TIMS age within 2% precision and accuracy, while our CA-TIMS results on the same grains constrain the development of the observed geochemical variability to within 100 ka. Other zircon standard materials to be presented include Plesovich syenite, FC1 gabbro, and R33 diorite

Gold in Accessory Zircon (the Kozhim Massif, Subpolar Urals)

NASA Astrophysics Data System (ADS)

Denisova, Yuliya; Pystin, Aleksandr

2017-12-01

The crystals of zircon due to their resistance to external impact of various processes can reveal information about the environment of their formation and the inclusions observed of them. Zircon contains different mineral inclusions: biotite, plagioclase, quartz, apatite, etc. However, there is no information about gold inclusions in the zircons from granites of the Sudpolar Urals. The study results of the inclusions of gold in accessory zircon of the Kozhim granitic massif are presented in this paper. The studied mineral is a dark-brown translucent short-prismatic crystal containing the inclusion of gold and the allocations of quartz. According to studies, the inclusion of gold formed during the growth of zircon and it is the gold covered with a thin film of oxide gold. It was confirmed that the crystallization of the studied zircon occurred at a temperature of 800°C and above on the stage of formation of granites of Kozhim massif. The assumption is made about the additional temperature in the course of which was caused by decreasing of temperature up to 700° C and below during postmagmatic stage.

Improved zircon iron corals for the 1990s

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

Decker, C.

1992-03-01

CIBA-GEIGY/Drakenfeld Colors is dedicated to the research and development of consistent and cost-effective ceramic stains for the whitewares industry. After identifying the trends in color for the 1990s. CIBA-GEIGY/Drakenfeld Colors initiated an extensive R D project to improve zircon ion corals for the whitewares industry. These color trends indicated a need for stronger and cleaner zircon iron corals. This paper discusses the chemistry and crystal structure of zircon iron corals. A historical review of Drakenfeld corals will also be presented. The most recent development in Drakenfeld corals will then be compared to other commercially available zircon iron corals. Taking intomore » consideration these comparisons, conclusions will be drawn suggesting the coral of choice for the 1990s.« less

Twinning in Zircon: Not a High-Pressure Phenomenon

NASA Astrophysics Data System (ADS)

Jones, G. A.; Moser, D.; Shieh, S. R.; Barker, I.

2017-12-01

Microtwins in zircon are commonly found in shocked terrestrial and extraterrestrial samples and are potentially important for shock history and crater reconstruction. Twinning is easily observed with both the optical microscope and variety of electron beam techniques. Twinning as a deformation mechanism is consistent with the high strain rates generated during impact. No constitutive relationships, or even general limits on the physical conditions required for twinning in zircon are known, however. Present speculation on the critical quantity for twin formation, i.e. 10s of GPa of shock pressure (Moser et al. 2011, Timms et al., 2012), has no basis in the underlying mechanisms of twin nucleation, which are related to the motion of dislocations. This erroneous value is due to conflation of twinning sensu stricto with a phase transformation to reidite. Reidite occurs as twin-like lamellae occupying the {112} planes which are thought to be a mirror plane for twinning. We review the crystallographic theory of twinning in zircon. We then evaulate several theories on the nucleation of twins along with their necessary stresses involved. Our aim is to show that shock microtwins in zircon can be a `low pressure' shock phenomenon. This 'low pressure' hypothesis is supported by natural samples. These zircons are from the lower crust nearly 80 km from the centre of the Vredefort impact structure—the most distal zircon shock microstructures yet found in the lithosphere. Twins are present in 10% of the zircon grains greater than 50 µm in diameter. As an extensive, 'low pressure' phenomenon, twins are an easily recognized and potentially widespread record of Earth's impact history.Moser, D.E., Cupelli, C. L., Barker, I., Flowers, R. M., Mowman, J. R., Wooden, J. and Hart, R. (2011) New zircon shock phenomena and their use for dating and […] analysis of the Vredefort dome, Canadian Journal of Earth Sciences 48(2), 117-139.Timms, N.E., Reddy, S. M., Healy, D., Nemchin, A. A

Pre-Alpine evolution of the Seckau Complex (Austroalpine basement/Eastern Alps): Constraints from in-situ LA-ICP-MS Usbnd Pb zircon geochronology

NASA Astrophysics Data System (ADS)

Mandl, Magdalena; Kurz, Walter; Hauzenberger, Christoph; Fritz, Harald; Klötzli, Urs; Schuster, Ralf

2018-01-01

The Variscan European Belt is a complex orogen with its southern margin partly obscured by Alpine tectonics and metamorphism. We present a study of one of the units, the Seckau Complex, that constitute the southern part of the Variscan European Belt in the Eastern Alps in order to clarify its origin, age and lithostratigraphy. The magmatic and geochronological evolution of this Complex in the northwestern part of the Seckau Nappe (as part of the Austroalpine Silvretta-Seckau Nappe System) was investigated by zircon Usbnd Pb dating of paragneisses and metagranitoids coupled with petrological and geochemical data. This reveals the distinction of three newly defined lithostratigraphic/lithodemic sub-units: (1) Glaneck Metamorphic Suite, (2) Hochreichart Plutonic Suite and (3) Hintertal Plutonic Suite. The Glaneck Metamorphic Suite is mainly composed of fine-grained paragneisses that yield Usbnd Pb zircon ages in the range between 2.7 Ga and 2.0 Ga, as well as concordia ages from 572 ± 7 Ma to 559 ± 11 Ma. All of these ages are interpreted as detrital zircon ages originating from an igneous source. The paragneisses are the host rock for the large volumes of metagranitoids of the Hochreichart Plutonic Suite and the Hintertal Plutonic Suite. The Hochreichart Plutonic Suite comprises highly fractionated melts with mainly S-type characteristics and late Cambrian to Early Ordovician Usbnd Pb zircon ages (508 ± 9 Ma to 486 ± 9 Ma), interpreted as magmatic protolith ages. The Hintertal Plutonic Suite is composed of metagranitoids with Late Devonian to early Carboniferous (365 ± 11 Ma and 331 ± 10 Ma) protolith ages, that intruded during an early phase of the Variscan tectonometamorphic event. The metagranitoids of the Hintertal Plutonic Suites define a magmatic fractionation trend, seen in variable Rb/Sr ratios. On this base they can be further subdivided into (a) the Griessstein Pluton characterized by S-type metagranitoids and (b) the Pletzen Pluton distinguished by

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.

Measurement of longitudinal sulfur isotopic variations by laser ablation MC-ICP-MS in single human hair strands.

PubMed

Santamaria-Fernandez, Rebeca; Giner Martínez-Sierra, Justo; Marchante-Gayón, J M; García-Alonso, J Ignacio; Hearn, Ruth

2009-05-01

A new method for the measurement of longitudinal variations of sulfur isotope amount ratios in single hair strands using a laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) is reported here for the first time. Ablation parameters have been optimized for the measurement of sulfur isotope ratios in scalp human hair strands of 80-120-microm thickness and different washing procedures have been evaluated. The repeatability of the method has been tested and the ability to measure sulfur isotopic variations in 1,000-microm-long hair segments has been evaluated. A horse hair sample previously characterized for carbon and nitrogen isotope ratios in an interlaboratory study has been characterized by LA-MC-ICP-MS to be used as an in-house standard for the bracketing of human hair strands. (34)S/(32)S isotope amount ratios have been measured and corrected for instrumental mass bias adopting the external standardization approach using National Institute of Standards and Technology (NIST) RM8553 and full uncertainty budgets have been calculated using the Kragten approach. Results are reported as both (34)S/(32)S isotope amount ratios and deltaS(V-CDT) values (sulfur isotopic differences relative to a reference sample expressed in the Vienna Canyon Diablo Troilite (V-CDT) scale) calculated using NIST RM8553, NIST RM8554, and NIST RM8556 to anchor results to the V-CDT scale. The main advantage of the new method versus conventional gas source isotope ratio mass spectrometry measurements is that longitudinal variations in sulfur isotope amount ratios can be resolved. Proof of concept is shown with human scalp hair strands from three individuals, two UK residents and one traveler (long periods of time abroad). The method enables monitoring of longitudinal isotope ratio variations in single hair strands. Absolute ratios are reported and delta(34)S(V-CDT) values are plotted for comparison. Slight variations of <1.2 per

Creation of a continent recorded in zircon zoning

USGS Publications Warehouse

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

2008-01-01

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

Quantitative analysis of major and trace elements in NH4HF2-modified silicate rock powders by laser ablation - inductively coupled plasma mass spectrometry.

PubMed

Zhang, Wen; Hu, Zhaochu; Liu, Yongsheng; Yang, Wenwu; Chen, Haihong; Hu, Shenghong; Xiao, Hongyan

2017-08-29

In this paper, we described a NH 4 HF 2 digestion method as sample preparation for the rapid determination of major and trace elements in silicate rocks using laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). Sample powders digested by NH 4 HF 2 at 230 °C for 3 h form ultrafine powders with a typical grain size d 80  < 8.5 μm, and various silicate rocks have a consistent grain morphology and size, allowing us to produce pressed powder pellets that have excellent cohesion and homogeneity suitable for laser ablation micro-analysis without the addition of binder. The influences of the digestion parameters were investigated and optimized, including the evaporation stage of removing residual NH 4 HF 2 , sample homogenization, selection of the digestion vessel and calibration strategy of quantitative analysis. The optimized NH 4 HF 2 digestion method was applied to dissolve six silicate rock reference materials (BCR-2, BHVO-2, AGV-2, RGM-2, GSP-2, GSR-1) covering a wide range of rock types. Ten major elements and thirty-five trace elements were simultaneously analyzed by LA-ICP-MS. The analytical results of the six reference materials generally agreed with the recommended values, with discrepancies of less than 10% for most elements. The analytical precision is within 5% for most major elements and within 10% for most trace elements. Compared with previous methods of LA-ICP-MS bulk analysis, our method enables the complete dissolution of refractory minerals, such as zircon, in intermediate-acidic intrusive rocks and limits contamination as well as the loss of volatile elements. Moreover, there are many advantages for the new technique, including reducing matrix effects between reference materials and samples, spiking the internal standard simply and feasibly and sample batch processing. The applicability filed of the new technique in this study was focused on the whole-rock analysis of igneous rock samples, which are from basic rocks to acid

Zircon dating and mineralogy of the Mokong Pan-African magmatic epidote-bearing granite (North Cameroon)

NASA Astrophysics Data System (ADS)

Tchameni, R.; Sun, F.; Dawaï, D.; Danra, G.; Tékoum, L.; Nomo Negue, E.; Vanderhaeghe, O.; Nzolang, C.; Dagwaï, Nguihdama

2016-09-01

We present the mineralogy and age of the magmatic epidote-bearing granite composing most of the Mokong pluton, in the Central Africa orogenic belt (North Cameroon). This pluton intrudes Neoproterozoic (~830 to 700 Ma) low- to high-grade schists and gneisses (Poli-Maroua group), and is crosscut or interleaved with bodies of biotite granite of various sizes. The pluton is weakly deformed in its interior, but solid-state deformation increases toward its margins marked by narrow mylonitic bands trending NNE-SSW. The magmatic epidote granitic rocks are classified as quartz monzodiorite, granodiorite, monzogranite, and syenogranite. They are medium- to coarse-grained and composed of K-feldspar + plagioclase + biotite + amphibole + epidote + magnetite + titanite + zircon + apatite. In these granites, the pistacite component [atomic Fe+3/(Fe3+ + Al)] in epidote ranges from 16 to 29 %. High oxygen fugacity (log ƒO2 - 14 to -11) and the preservation of epidote suggest that the magma was oxidized. Al-in hornblende barometry and hornblende-plagioclase thermometry indicate hornblende crystallization between 0.53 and 0.78 GPa at a temperature ranging from 633 to 779 °C. Zircon saturation thermometry gives temperature estimates ranging from 504 to 916 °C, the latter being obtained on samples containing inherited zircons. U/Pb geochronology by LA-ICP-MS on zircon grains characterized by magmatic zoning yields a concordia age of 668 ± 11 Ma (2 σ). The Mokong granite is the only known occurrence magmatic epidote in Cameroon, and is an important milestone for the comparison of the Central Africa orogenic belt with the Brasiliano Fold Belt, where such granites are much more abundant.

Constraints on the age and provenance of the Chugach accretionary complex from detrital zircons in the Sitka Graywacke near Sitka, Alaska

USGS Publications Warehouse

Haeussler, Peter J.; Gehrels, George E.; Karl, Susan M.

2006-01-01

The Sitka Graywacke is the westernmost and youngest unit of the Chugach accretionary complex in southeastern Alaska. Using laser-ablation inductively coupled plasma mass spectroscopy, we obtained 492 detrital-zircon ages on seven typical samples of Sitka Graywacke turbidites, which were collected in a transect across much of the unit near Sitka, Alaska. Individual grains range in age from 66 to 1,802 m.y. The youngest peak ages on relative-probability plots of the western four samples (74, 72, 74, and 74 m.y., from west to east) are distinctly younger than the youngest peak ages of the eastern three samples (105, 103, and 97 m.y., from west to east). These youngest peak ages set maximum depositional ages for each sample. We suggest that these peak ages are not significantly older (within ~5 m.y.) than the depositional age of the Sitka Graywacke because the deposits accumulated in a trench along a convergent margin, where magmatic sources likely continuously introduced juvenile zircons. The differences in the youngest cluster of detrital-zircon ages between the eastern and western sample localities is likely due to both a change in provenance and a fault. The similarity of the youngest peak ages in the Sitka Graywacke to fossil ages in the Valdez Group, in Prince William Sound, implies that the western part of the Sitka Graywacke is correlative with the Valdez Group, as previously inferred. However, the eastern part of the Sitka Graywacke has youngest detrital-zircon ages older than fossil ages in the Valdez Group and younger than fossil ages in the McHugh Complex, which in south-central Alaska is the oldest part of the accretionary complex. The age distribution of zircons in the older, eastern sequence suggests sources along the British Columbia margin. The detrital-zircon ages in the younger, western sequence are similar to igneous ages from south-central Alaska to southern British Columbia. Right-lateral strike slip on various fault systems inboard of the Sitka

Comparison of laser ablation and dried solution aerosol as sampling systems in inductively coupled plasma mass spectrometry.

PubMed

Coedo, A G; Padilla, I; Dorado, M T

2004-12-01

This paper describes a study designed to determine the possibility of using a dried aerosol solution for calibration in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The relative sensitivities of tested materials mobilized by laser ablation and by aqueous nebulization were established, and the experimentally determined relative sensitivity factors (RSFs) were used in conjunction with aqueous calibration for the analysis of solid steel samples. To such a purpose a set of CRM carbon steel samples (SS-451/1 to SS-460/1) were sampled into an ICP-MS instrument by solution nebulization using a microconcentric nebulizer with membrane desolvating (D-MCN) and by laser ablation (LA). Both systems were applied with the same ICP-MS operating parameters and the analyte signals were compared. The RSF (desolvated aerosol response/ablated solid response) values were close to 1 for the analytes Cr, Ni, Co, V, and W, about 1.3 for Mo, and 1.7 for As, P, and Mn. Complementary tests were carried out using CRM SS-455/1 as a solid standard for one-point calibration, applying LAMTRACE software for data reduction and quantification. The analytical results are in good agreement with the certified values in all cases, showing that the applicability of dried aerosol solutions is a good alternative calibration system for laser ablation sampling.

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

NASA Astrophysics Data System (ADS)

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

2013-02-01

Zircons from two Myanmar jadeitite samples were separated for texture, mineral inclusion, U-Pb dating and trace element composition analyses. Three types of zircons, with respect to U-Pb isotope system, were recognized. Type I zircons are inherited ones, yielding an igneous protolith age of 160 ± 1 Ma; Type II zircons are metasomatic/hydrothermal ones, giving a (minimum) jadeitite formation age of 77 ± 3 Ma; and Type III zircons are incompletely recrystallized ones, with non-coherent and geologically meaningless ages from 153 to 105 Ma. These Myanmar jadeitites would therefore have formed through whole-sale metasomatic replacement processes. Compared with Type I zircons, Type II zircons show typical metasomatic/hydrothermal geochemical signatures, with low Th/U ratio (< 0.1), small Ce anomaly (Ce/Ce* = < 5) and low ΣREE content (40-115 ppm). Type III zircons, however, commonly have the above geochemical signatures straddle in between Type I and Type II zircons. It is shown that the resetting rates of various trace element compositions and U-Pb isotope system of inherited zircons are not coupled "in phase" in response to zircon recrystallization during jadeitite formation. The observed abnormally low Th/U ratio and small Ce anomaly of some Type I zircons, as well as the lack of negative Eu anomaly of all Type I zircons, should be suspected to be of secondary origin. In extreme cases, incompletely recrystallized zircons may show typical metasomatic/hydrothermal geochemical signatures, but leave U-Pb isotope system partially reset or even largely unchanged. Such zircons easily lead to incorrect age interpretation, and hence erroneous geological implication. The Myanmar jadeitites, based on the present study, might have formed during the Late Cretaceous subduction before the beginning of India-Asia continental collision at Paleocene. Previously proposed Late Jurassic ages for Myanmar jadeitites are suggested as results rooted on data retrieved from incompletely

Sands of West Gondwana: An archive of secular magmatism and plate interactions — A case study from the Cambro-Ordovician section of the Tassili Ouan Ahaggar (Algerian Sahara) using U-Pb-LA-ICP-MS detrital zircon ages

NASA Astrophysics Data System (ADS)

Linnemann, Ulf; Ouzegane, Khadidja; Drareni, Amar; Hofmann, Mandy; Becker, Sindy; Gärtner, Andreas; Sagawe, Anja

2011-04-01

Enormous masses of highly mature quartz sands were deposited in Western Gondwana during the Cambrian-Ordovician time, and provide a wide range of information concerning magmatic events through time, provenance, paleoclimate, and basin history. We present a provenance study based on 630 U-Pb (LA-ICP-MS) ages of detrital zircon from the latest Cambrian to Ordovician siliciclastic rocks of the Tassili Ouan Ahaggar basin situated in the Algerian Sahara. Most authors suggest local sources only for the sandstones. Instead, we demonstrate that the detritus is derived from different cratons and terranes which contributed to the deposition of a Cambrian-Ordovician overstep sequence covering western and northern Africa. Most zircon ages (61.0%) fall in the range of ~ 540 to 740 Ma and are interpreted to have been derived from Pan-African orogenic belts such as the Trans-Saharan Belt of NW Africa and previously from the Brazila belt of South America. Other potential sources for this zircon population are terranes of Cadomian affinity situated marginal to West Africa. The second-largest zircon population (20.2%) is 2.0 to 2.2 Ga, and is attributed to sources in the West African craton, such as the Birimian basement and the Eburnean orogenic belt, with possible partial input from the Amazonian craton. A zircon population of 7.1% yields Mesoproterozoic and early Paleoproterozoic ages in the range of ~ 1.3 to ~ 1.8 Ga and was probably derived from source rocks outside of the West African basement, the Tuareg shield and other adjoining areas. The Amazonian craton is a potential source region. A population of 6.7% of all zircon ages scatter from ~ 750 Ma to ~ 980 Ma and may reflect input from latest stages of the formation of Rodinia and its subsequent dispersal. A smaller population (3.2%) of zircon ages lie between ~ 2.3 and 2.65 Ga, and may be derived from late Paleoproterozoic to early Archaean rocks from the West African craton and possibly from Amazonia. Less than 1% of all

Determination of uranium in zircon

USGS Publications Warehouse

Cuttitta, F.; Daniels, G.J.

1959-01-01

A routine fluorimetric procedure is described for the determination of trace amounts of uranium in zircon. It employs the direct extraction of uranyl nitrate with ethyl acetate using phosphate as a retainer for zirconium. Submicrogram amounts or uranium are separated in the presence of 100,000 times the amount of zirconium. The modified procedure has been worked out using synthetic mixtures of known composition and zircon. Results of analyses have an accuracy of 97-98% of the contained uranium and a standard deviation of less than 2.5%. ?? 1959.

Applications of biotite inclusion composition to zircon provenance determination

NASA Astrophysics Data System (ADS)

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

2017-09-01

Detrital zircons are the only confirmed surviving remnants of >4.03 Ga crust while younger detrital zircons provide a parallel record of more recent crustal evolution to that preserved in crystalline rocks. Zircons often preserve inclusions that may provide clues as to the origins of out-of-context grains in the sedimentary record. Previous studies have established that inclusions of biotite in magmatic zircon are compositionally well-matched to biotite in the source rock matrix, although a direct application to ancient detrital zircons has not been made. A number of studies have documented variations in the Fe, Mg, and Al contents of magmatic biotite from different source rocks and tectonic settings, suggesting that biotite inclusions may indeed serve as provenance indicators for detrital zircons. Consistent with earlier studies, we find that the FeO*/MgO ratio of magmatic biotite from continental arcs, collisional, and within-plate settings varies with relative oxidation state as well as whole-rock FeO*/MgO, while its Al2O3/(FeO* + MgO) varies with whole-rock A/CNK (molar Al/(2 ṡ Ca + Na + K)). Biotite from oxidized metaluminous and reduced S-type granitoids can be readily distinguished from each other using FeO*/MgO and Al2O3/(FeO* + MgO), while biotite from reduced I-type and oxidized peraluminous granites may in some cases be more ambiguous. Biotite from peralkaline and reduced A-type granites are also distinguishable from all other categories by Al2O3/(FeO* + MgO) and FeO*/MgO, respectively. Biotite inclusions in Hadean zircons from Jack Hills, Western Australia indicate a mixture of metaluminous and reduced S-type host rocks, while inclusions in 3.6-3.8 Ga detrital zircons from the Nuvvuagittuq Supracrustal Belt indicate more oxidized peraluminous magmas. These results highlight the diversity of felsic materials on the early Earth and suggest that biotite inclusions are applicable to zircon provenance throughout the sedimentary record.

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

NASA Astrophysics Data System (ADS)

Bell, E. A.

2017-12-01

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

Response of zircon to melting and metamorphism in deep arc crust, Fiordland (New Zealand): implications for zircon inheritance in cordilleran granites

NASA Astrophysics Data System (ADS)

Bhattacharya, Shrema; Kemp, A. I. S.; Collins, W. J.

2018-04-01

The Cretaceous Mount Daniel Complex (MDC) in northern Fiordland, New Zealand was emplaced as a 50 m-thick dyke and sheet complex into an active shear zone at the base of a Cordilleran magmatic arc. It was emplaced below the 20-25 km-thick, 125.3 ± 1.3 Ma old Western Fiordland Orthogneiss (WFO) and is characterized by metre-scale sheets of sodic, low and high Sr/Y diorites and granites. 119.3 ± 1.2 Ma old, pre-MDC lattice dykes and 117.4 ± 3.1 Ma late-MDC lattice dykes constrain the age of the MDC itself. Most dykes were isoclinally folded as they intruded, but crystallised within this deep-crustal, magma-transfer zone as the terrain cooled and was buried from 25 to 50 km (9-14 kbar), based on published P-T estimated from the surrounding country rocks. Zircon grains formed under these magmatic/granulite facies metamorphic conditions were initially characterized by conservatively assigning zircons with oscillatory zoning as igneous and featureless rims as metamorphic, representing 54% of the analysed grains. Further petrological assignment involved additional parameters such as age, morphology, Th/U ratios, REE patterns and Ti-in-zircon temperature estimates. Using this integrative approach, assignment of analysed grains to metamorphic or igneous groupings improved to 98%. A striking feature of the MDC is that only 2% of all igneous zircon grains reflect emplacement, so that the zircon cargo was almost entirely inherited, even in dioritic magmas. Metamorphic zircons of MDC show a cooler temperature range of 740-640 °C, reflects the moderate ambient temperature of the lower crust during MDC emplacement. The MDC also provides a cautionary tale: in the absence of robust field and microstructural relations, the igneous-zoned zircon population at 122.1 ± 1.3 Ma, derived mostly from inherited zircons of the WFO, would be meaningless in terms of actual magmatic emplacement age of MDC, where the latter is further obscured by younger (ca. 114 Ma) metamorphic overgrowths

Assessment of Alternative [U] and [Th] Zircon Standards for SIMS

NASA Astrophysics Data System (ADS)

Monteleone, B. D.; van Soest, M. C.; Hodges, K.; Moore, G. M.; Boyce, J. W.; Hervig, R. L.

2009-12-01

The quality of in situ (U-Th)/He zircon dates is dependent upon the accuracy and precision of spatially distributed [U] and [Th] measurements on often complexly zoned zircon crystals. Natural zircon standards for SIMS traditionally have been used to obtain precise U-Pb ages rather than precise U and Th concentration. [U] and [Th] distributions within even the most homogeneous U-Pb age standards are not sufficient to make good microbeam standards (i.e., yield good precision: 2σ < 5%) for (U-Th)/He dates. In the absence of sufficiently homogeneous natural zircon crystals, we evaluate the use of the NIST 610 glass standard and a synthetic polycrystalline solid “zircon synrock” made by powdering and pressing natural zircon crystals at 2 GPa and 1100°C within a 13 mm piston cylinder for 24 hours. SIMS energy spectra and multiple spot analyses help assess the matrix-dependence of secondary ion emission and [U] and [Th] homogeneity of these materials. Although spot analyses on NIST 610 glass yielded spatially consistent ratios of 238U/30Si and 232Th/30Si (2σ = 2%, n = 14), comparison of energy spectra collected on glass and zircon reveal significant differences in U, UO, Th, and ThO ion intensities over the range of initial kinetic energies commonly used for trace element analyses. Computing [U] and [Th] in zircon using NIST glass yields concentrations that vary by more than 10% for [U] and [Th], depending on the initial kinetic energy and ion mass (elemental, oxide, or sum of elemental and oxide) used for the analysis. The observed effect of chemistry on secondary ion energy spectra suggests that NIST glass cannot be used as a standard for trace [U] and [Th] in zircon without a correction factor (presently unknown). Energy spectra of the zircon synrock are similar to those of natural zircon, suggesting matrix compatibility and therefore potential for accurate standardization. Spot analyses on the zircon powder pellets, however, show that adequate homogeneity of [U

Time-resolved imaging of gas phase nanoparticle synthesis by laser ablation

NASA Astrophysics Data System (ADS)

Geohegan, David B.; Puretzky, Alex A.; Duscher, Gerd; Pennycook, Stephen J.

1998-06-01

The dynamics of nanoparticle formation, transport, and deposition by pulsed laser ablation of c-Si into 1-10 Torr He and Ar gases are revealed by imaging laser-induced photoluminescence and Rayleigh-scattered light from gas-suspended 1-10 nm SiOx particles. Two sets of dynamic phenomena are presented for times up to 15 s after KrF-laser ablation. Ablation of Si into heavier Ar results in a uniform, stationary plume of nanoparticles, while Si ablation into lighter He results in a turbulent ring of particles which propagates forward at 10 m/s. Nanoparticles unambiguously formed in the gas phase were collected on transmission electron microscope grids for Z-contrast imaging and electron energy loss spectroscopy analysis. The effects of gas flow on nanoparticle formation, photoluminescence, and collection are described.

Laser ablation U-Th-Sm/He dating of detrital apatite

NASA Astrophysics Data System (ADS)

Guest, B.; Pickering, J. E.; Matthews, W.; Hamilton, B.; Sykes, C.

2016-12-01

Detrital apatite U-Th-Sm/He thermochronology has the potential to be a powerful tool for conducting basin thermal history analyses as well as complementing the well-established detrital zircon U-Pb approach in source to sink studies. A critical roadblock that prevents the routine application of detrital apatite U-Th-Sm/He thermochronology to solving geological problems is the costly and difficult whole grain approach that is generally used to obtain apatite U-Th-Sm/He data. We present a new analytical method for laser ablation thermochronology on apatite. Samples are ablated using a Resonetics™ 193 nm excimer laser and liberated 4He is measured using an ASI (Australian Scientific Instruments) Alphachron™ quadrupole mass spectrometer system; collectively known as the Resochron™. The ablated sites are imaged using a Zygo ZescopeTM optical profilometer and ablated pit volume measured using PitVol, a custom MatLabTM algorithm. The accuracy and precision of the method presented here was confirmed using well-characterized Durango apatite and Fish Canyon Tuff (FCT) apatite reference materials, with Durango apatite used as a primary reference and FCT apatite used as a secondary reference. The weighted average of our laser ablation Durango ages (30.5±0.35 Ma) compare well with ages obtained using conventional whole grain degassing and dissolution U-Th-Sm/He methods (32.56±0.43 Ma) (Jonckheere et.al., 1 993; Farley, 2000; McDowell et.al., 2005) for chips of the same Durango crystal. These Durango ages were used to produce a K-value to correct the secondary references and unknown samples. After correction, FCT apatite has a weighted average age of 28.37 ± 0.96 Ma, which agrees well with published ages. As a further test of this new method we have conducted a case study on a set of samples from the British Mountains of the Yukon Territory in NW Canada. Sandstone samples collected across the British Mountains were analyzed using conventional U-Th-Sm/He whole grain

The formation and rejuvenation of continental crust in the central North China Craton: Evidence from zircon U-Pb geochronology and Hf isotope

NASA Astrophysics Data System (ADS)

Li, Qing; Santosh, M.; Li, Sheng-Rong; Guo, Pu

2014-12-01

The Trans-North China Orogen (TNCO) along the central part of the North China Craton (NCC) is considered as a Paleoproterozoic suture along which the Eastern and Western Blocks of the NCC were amalgamated. Here we investigate the Precambrian crustal evolution history in the Fuping segment of the TNCO and the subsequent reactivation associated with extensive craton destruction during Mesozoic. We present zircon LA-ICP-MS U-Pb and Lu-Hf data on TTG (tonalite-trondhjemite-granodiorite) gneiss, felsic orthogneiss, amphibolite and granite from the Paleoproterozoic suite which show magmatic ages in the range of 2450-1900 Ma suggesting a long-lived convergent margin. The εHf(t) values of these zircons range from -11.9 to 12 and their model ages suggest magma derivation from both juvenile components and reworked Archean crust. The Mesozoic magmatic units in the Fuping area includes granite, diorite and mafic microgranular enclaves, the zircons from which define a tight range of 120-130 Ma ages suggesting a prominent Early Cretaceous magmatic event. However, the εHf(t) values of these zircons show wide a range from -30.3 to 0.2, indicating that the magmatic activity involved extensive rejuvenation of the older continental crust.

Quantitative mapping of elements in basil leaves (Ocimum basilicum) based on cesium concentration and growth period using laser ablation ICP-MS.

PubMed

Ko, Jung Aa; Furuta, Naoki; Lim, Heung Bin

2018-01-01

Quantitative elemental mapping of metallic pollutants in sweet basil was studied by laser ablation (LA)-ICP-MS. For this, the sweet basil was cultivated in Hoagland nutrient solution spiked with 100 and 1000 ng mL -1 of Cs for 10-60 days. Then, the Cs distribution in collected leaves was determined by LA-ICP-MS using lab-synthesized standard pellets based on NIST 1573a tomato leaves. For comparison, S, Ca, and K were also simultaneously determined in this measurement with a 13 C + signal from the leaves as an internal standard. The obtained calibration curves showed linear coefficient of determination (R 2 ) of 0.991 for K and 0.999 for Cs. The concentration of Cs measured in the basil leaves increased with growth period and pollutant concentration, and accumulation followed the order of leaf margin, petiole, midrib, and veins. Although no visible symptom was detected, significant suppression of the growth rate was observed due to the presence of high-concentration Cs. The experimental model demonstrated herein showed potential for studying the influence of radioactive pollutants on plants and other organisms in the food chain. Copyright © 2017 Elsevier Ltd. All rights reserved.

Zircons as a Probe of Early Luanr History

NASA Astrophysics Data System (ADS)

Crow, C. A.; McKeegan, K. D.; Gilmour, J. D.; Crowther, S. A.; Talor, D. J.

2013-09-01

Zircons are ideal for investigating the early lunar bombardment because we can measure both U-Pb crystallization ages and fissiongenic Xe degassing ages for the same crystal. We report U-Pb, Pb-Pb and U-Xe ages for three lunar zircons.

Long-term outcome of catheter ablation in atrial fibrillation patients with coexistent metabolic syndrome and obstructive sleep apnea: impact of repeat procedures versus lifestyle changes.

PubMed

Mohanty, Sanghamitra; Mohanty, Prasant; DI Biase, Luigi; Bai, Rong; Trivedi, Chintan; Santangeli, Pasquale; Santoro, Francesco; Hongo, Richard; Hao, Steven; Beheiry, Salwa; Burkhardt, David; Gallinghouse, Joseph G; Horton, Rodney; Sanchez, Javier E; Bailey, Shane; Hranitzky, Patrick M; Zagrodzky, Jason; Natale, Andrea

2014-09-01

Metabolic syndrome (MS) and obstructive sleep apnea (OSA) are well-known independent risk factors for atrial fibrillation (AF) recurrence. This study evaluated ablation outcome in AF patients with coexistent MS and OSA and influence of lifestyle modifications (LSM) on arrhythmia recurrence. We included 1,257 AF patients undergoing first catheter ablation (30% paroxysmal AF). Patients having MS + OSA were classified into Group 1 (n = 126; 64 ± 8 years; 76% male). Group 2 (n = 1,131; 62 ± 11 years; 72% male) included those with either MS (n = 431) or OSA (n = 112; no CPAP users) or neither of these comorbidities (n = 588). Patients experiencing recurrence after first procedure were divided into 2 subgroups; those having sporadic events (frequency < 2 months) remained on previously ineffective antiarrhythmic drugs (AAD) and aggressive LSM, while those with persistent arrhythmia (incessant or ≥2 months) underwent repeat ablation. After 34 ± 8 months of first procedure, 66 (52%) in Group 1 and 386 (34%) in Group 2 had recurrence (P < 0.001). Recurrence rate in only-MS, only-OSA, and without MS/OSA groups were 40%, 38%, and 29%, respectively. Patients with MS + OSA experienced substantially higher recurrence compared to those with lone MS or OSA (52% vs. 40% vs. 38%; P = 0.036). Of the 452 patients having recurrence, 250 underwent redo-ablation and 194 remained on AAD and LSM. At 20 ± 6 months, 76% of the redo group remained arrhythmia-free off AAD whereas 74% of the LSM group were free from recurrence (P = 0.71), 33% of which were off AAD. MS and OSA have additive negative effect on arrhythmia recurrence following single procedure. Repeat ablation or compliant LSM increase freedom from recurrent AF. © 2014 Wiley Periodicals, Inc.

High Pressure Behavior of Zircon at Room Temperature

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Rocholl, A.

2016-12-01

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

Infrared Laser Ablation with Vacuum Capture for Fingermark Sampling

NASA Astrophysics Data System (ADS)

Donnarumma, Fabrizio; Camp, Eden E.; Cao, Fan; Murray, Kermit K.

2017-09-01

Infrared laser ablation coupled to vacuum capture was employed to collect material from fingermarks deposited on surfaces of different porosity and roughness. Laser ablation at 3 μm was performed in reflection mode with subsequent capture of the ejecta with a filter connected to vacuum. Ablation and capture of standards from fingermarks was demonstrated on glass, plastic, aluminum, and cardboard surfaces. Using matrix assisted laser desorption ionization (MALDI), it was possible to detect caffeine after spiking with amounts as low as 1 ng. MALDI detection of condom lubricants and detection of antibacterial peptides from an antiseptic cream was demonstrated. Detection of explosives from fingermarks left on plastic surfaces as well as from direct deposition on the same surface using gas chromatography mass spectrometry (GC-MS) was shown. [Figure not available: see fulltext.

Infrared Laser Ablation with Vacuum Capture for Fingermark Sampling.

PubMed

Donnarumma, Fabrizio; Camp, Eden E; Cao, Fan; Murray, Kermit K

2017-09-01

Infrared laser ablation coupled to vacuum capture was employed to collect material from fingermarks deposited on surfaces of different porosity and roughness. Laser ablation at 3 μm was performed in reflection mode with subsequent capture of the ejecta with a filter connected to vacuum. Ablation and capture of standards from fingermarks was demonstrated on glass, plastic, aluminum, and cardboard surfaces. Using matrix assisted laser desorption ionization (MALDI), it was possible to detect caffeine after spiking with amounts as low as 1 ng. MALDI detection of condom lubricants and detection of antibacterial peptides from an antiseptic cream was demonstrated. Detection of explosives from fingermarks left on plastic surfaces as well as from direct deposition on the same surface using gas chromatography mass spectrometry (GC-MS) was shown. Graphical Abstract ᅟ.

Detrital Zircons Split Sibumasu in East Gondwana

NASA Astrophysics Data System (ADS)

Zhang, X.; Chung, S. L.

2017-12-01

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

Melting depths associated with Jack Hills zircons crystallization as revealed by in situ trace element measurements

NASA Astrophysics Data System (ADS)

Profeta, L.; Ducea, M. N.; Gehrels, G. E.

2016-12-01

The Jack Hills zircons hosted within the Narryer Gneiss Complex, Yilgarn craton have ages from 4.4 Ga up to Mesoarchean. These zircons crystallized from low temperature granitoid magmas (Harrison, 2009). Here, we use trace element measurements obtained simultaneously with U-Pb ages using LA-ICP-MS on 276 Jack Hills zircons in order to estimate the depth of melting. La/Yb are converted to whole rock equivalent values using newly determined REE -whole rock partition coefficients (Chapman et al., 2016). La/Yb are subsequently transformed into depth estimates using the correlation between whole rock La/Yb and crustal thickness put forward in Profeta et al. (2015) for modern arcs. Our data pertains to 4.2 to 3.2 Ga zircons, which are supplemented with previously published data on 4.4.-4.3 Ga zircons (Peck et al. 2001). Depth estimates are averaged over 100 Ma bins, revealing a remarkably constant trend throughout the investigated period with values around 50 ± 10 km. We interpret that these depths may not be the result of a thick continental crust, as is the case for modern arcs, but rather the existence of different melting conditions during the Hadean and Paleoarchean due to elevated thermal regimes within the mantle. The high La/Yb whole rock ratios (with computed values greater than 10) coupled with elevated mantle temperatures point towards granitoid generation from partial melting of hydrated basalts (e.g. Martin et al., 2014). [1] Harrison, T.M., Annu. Rev. Earth Planet. Sci. 37, 479-505 (2009). [2] Chapman, J. B. et al., Chem. Geol. 439, 59-70 (2016). doi: 10.1016/j.chemgeo.2016.06.014. [3] Profeta, L. et al., Sci. Rep. 5, 17786 (2015). doi: 10.1038/srep17786 [4] Peck, W. et al., Cosmochim. Acta 65, 4215-4229 (2001). doi: 10.1016/S0016-7037(01)00711-6 [5] Martin, H. et al. Lithos 198, 1-13 (2014). doi: 10.1016/j.lithos.2014.02.017

New Possibilities for the Accurate in Situ Determination of Chalcophile and Siderophile Trace Elements by Laser Ablation Collision and Reaction Cell ICP-MS

NASA Astrophysics Data System (ADS)

Mason, P. R.

2004-05-01

Our knowledge of how chalcophile and siderophile elements partition in minerals is limited, mainly due to the lack of suitable techniques for their accurate in situ determination. Host minerals (e.g. sulphides) are typically of small size (<30 μ m) and highly heterogeneous in composition, requiring analysis of high spatial resolution. Concentrations of chalcophile elements in silicates and oxides are low (sub μ gg-1) and thus challenging to measure. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), offering high sensitivity and good spatial resolution (10-100 μ m) is thus highly suited for this purpose. Unfortunately, the widespread use of this technique has been limited by enhanced problems specific to chalcophile and siderophile elements. These include inaccuracy due to the presence of spectral interferences, elemental fractionation during ablation/ionization and the lack of suitable calibration standards. Polyatomic spectral interferences, present either as a background component (e.g. O2+, ArAr+) or based around the recombination of matrix elements with argon (e.g. ArS+, ArNi+) hinder accurate analysis. These depend upon the relative concentrations of major matrix components and trace elements to be measured and are significant in many relevant minerals (e.g. sulphides). The use of a collision and reaction cells in ICP-MS is a new method for selective interference attenuation, significantly improving detection limits for elements such as Fe, S and Se by between 1 and 4 orders of magnitude. ArNi+ and ArCu+ interferences in sulphides can be attenuated by at least an order of magnitude leading to improved accuracy for the measurement of the Platinum Group elements Rh and Ru. Sulphur isotopes can be measured interference-free at m/z=32 and 34 by eliminating background O2+. These improvements open up new possibilities for the use of LA-ICP-MS in trace element and isotopic studies at the lowest concentration levels or where sample

Silicic melt evolution in the early Izu-Bonin arc recorded in detrital zircons: Zircon U-Pb geochronology and trace element geochemistry for Site U1438, Amami Sankaku Basin

NASA Astrophysics Data System (ADS)

Barth, A. P.; Tani, K.; Meffre, S.; Wooden, J. L.; Coble, M. A.

2016-12-01

Understanding the petrologic evolution of oceanic arc magmas through time is important because these arcs reveal the processes of formation and the early evolution of juvenile continental crust. The Izu-Bonin (IB) arc system has been targeted because it is one of several western Pacific intraoceanic arcs initiated at 50 Ma and because of its prominent spatial asymmetry, with widespread development of relatively enriched rear arc lavas. We examined Pb/U and trace element compositions in zircons recovered at IODP Site 351-U1438 and compared them to regional and global zircon suites. These new arc zircon data indicate that detrital zircons will yield new insights into the generation of IB silicic melts and form a set of useful geochemical proxies for interpreting ancient arc detrital zircon provenance. Project IBM drilling target IBM1 was explored by Expedition 351 at Site U1438, located in the proximal back-arc of the northern Kyushu-Palau Ridge (KPR) at 27.3°N. A 1.2 km thick section of Paleogene volcaniclastic rocks, increasingly lithified and hydrothermally altered with depth, constitutes a proximal rear arc sedimentary record of IB arc initiation and early arc evolution. The ages and compositions of U1438 zircons are compatible with provenance in one or more edifices of the northern KPR and are incompatible with drilling contamination. Melt zircon saturation temperatures and Ti-in-zircon thermometry suggest a provenance in relatively cool and silicic KPR melts. The abundances of selected trace elements with high native concentrations provide insight into the petrogenesis of U1438 detrital zircon host melts, and may be useful indicators of both short and long-term variations in melt compositions in arc settings. The U1438 zircons are slightly enriched in U and LREE and are depleted in Nb compared to zircons from mid-ocean ridges and the Parece-Vela Basin, as predicted for melts in a primitive oceanic arc setting with magmas derived from a highly depleted mantle

The mineralogical and chronological evidences of subducted continent material in deep mantle: diamond, zircon and rutile separated from the Horoman peridotite of Japan

NASA Astrophysics Data System (ADS)

Li, Y.; Yang, J.; Nida, K.; Yamamoto, S.; Lin, Y.; Li, Q.; Tian, M.; Kon, Y.; Komiya, T.; Maruyama, S.

2017-12-01

The Horoman peridotite complex is an Alpine-type orogenic lherzolite massif of upper-mantle in the Hidaka metamorphic belt, Hokkaido, Japan. The peridotite complex is composed of dunite, harzburgite, spinel lherzolite and plagioclase lherzolite, exhibits a conspicuous layered structure, which is a product of a Cretaceous to early Paleogene arc-trench system formed by westward subduction of an oceanic plate between the paleo-Eurasian and paleo-North American Plates. Various combinations of diamond, corundum, moissanite, zircon, monazite, rutile, and kyanite have been separated from spinel harzburgite (700 kg) and lherzolite (500 kg), respectively. The carbon isotopes analyses of diamond grains by Nano-SIMS yielded significant light carbon isotopes feature as δ13 CPDB values ranging from -29.2 ‰ to -17.2 ‰, with an average of -22.8±0.32 ‰. Zircon grains occur as sub-angular to round in morphological characteristics, similar to zircons of crustal sedimentary rocks. Many zircons contain small inclusions, comprise of quartz, apatite, rutile and muscovite. The U-Pb age of zircon grains analyzed using LA-ICP-MS and SIMS gave a wide age range, from the Jurassic to Archean (ca 159 - 3131 Ma). In the zircon age histogram, four age groups were identified; the age peaks are 2385 Ma, 1890 Ma, 1618 Ma and 1212 Ma, respectively. On the other hand, U-Pb ages of rutile grains analyzed using SIMS gave a peak of 370 Ma in age histogram. The mineralogical and chronological evidences of numerous crustal minerals in peridotite of Horoman suggest that the ancient continent material was subducted in deep mantle and recycled through the upper mantle by multicycle subduction processes.

Pan-Africa/Pan-Brazilian detrital zircons in Lower Palaeozoic schists of SW Norway - enigmatic detrital zircon U-Pb ages

NASA Astrophysics Data System (ADS)

Zimmermann, Udo; Bjørheim, Maren; Clark, Chris

2013-04-01

We present Sensitive High Resolution Ion Microprobe (SHRIMP) U-Pb zircon age data from metasedimentary rocks (schists and quartzites) located in the town of Stavanger (SW Norway). The metasedimentary sequence is composed of schists, medium grained quartz-rich metawackes and quartzites. Quartzites and meta-quartz-wackes exhibit a mylonitic fabric with newly grown fine-grained muscovite defining the fabric. Accessory minerals are zircon, allanite, detrital apatite, monazite, ilmenite, rutile and zircon. The schists are dark and dominated by quartz and feldspar in a fine chloritic and silica-rich matrix and represent the dominant lithology of the region. While quartzites and metawackes show typical geochemical characteristics for strongly reworked rocks, the schists have very low Zr/Sc and Th/Sc ratios below 0.9 and point together with other trace element ratios (La/Sc, Ti/Zr) to the strong influence of less fractionated, mafic, sources in the detritus, possibly arc derived. U-Pb ages of detrital zircon from quartzites range between 740 to 1800 Ma. There is a defined population at 1135 and 1010 Ma tentatively correlated with the Sveconorwegian orogeny. A second population at ~1450 Ma that can be related to a tectono-magmatic event during the Earliest Mesoproterozoic, also recorded in Oslo, southern Sweden and Bornholm, mapped along the proposed southern margin of Baltica. Other detrital zircons record ages between 1586 - 1664 Ma that are not related to the latter event. The oldest U-Pb detrital zircon grain age was 1796 Ma and is potentially associated with the terminal phase of the Svecofennian orogeny. Detrital zircons from the associated schists do show a similar abundance of main age clusters but the oldest found zircons dates to 2013 Ma while the maximum depositional age could be determined by grains of Cambrian to even Ordovician ages with a large 1 sigma error, as such that we rather propose a Cambrian maximum depositional age. It is possible to speculate that

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

PubMed

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

2017-04-07

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

In-Situ Apatite Laser Ablation U-Th-Sm/He Dating, Methods and Challenges

NASA Astrophysics Data System (ADS)

Pickering, J. E.; Matthews, W.; Guest, B.; Hamilton, B.; Sykes, C.

2015-12-01

In-situ, laser ablation U-Th-Sm/He dating is an emerging technique in thermochronology that has been proven as a means to date zircon and monzonite1-5. In-situ U-Th-Sm/He thermochronology eliminates many of the problems and inconveniences associated with traditional, whole grain methods, including; reducing bias in grain selection based on size, shape and clarity; allowing for the use of broken grains and grains with inclusions; avoiding bad neighbour effects; and eliminating safety hazards associated with dissolution. In-situ apatite laser ablation is challenging due to low concentrations of U and Th and thus a low abundance of radiogenic He. For apatite laser ablation to be effective the ultra-high-vacuum (UHV) line must have very low and consistent background levels of He. To reduce He background, samples are mounted in a UHV stable medium. Our mounting process uses a MicroHePP (Microscope Mounted Heated Platen Press) to press samples into FEP (fluorinated ethylene propylene) bonded to an aluminum backing plate. Samples are ablated using a Resonetics 193 nm excimer laser and liberated He is measured using a quadrupole mass spectrometer on the ASI Alphachron noble gas line; collectively this system is known as the Resochron. The ablated sites are imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol, a custom MatLab algorithm developed to enable precise and unbiased measurement of the ablated pit geometry. We use the well-characterized Durango apatite to demonstrate the accuracy and precision of the method. He liberated from forty-two pits, having volumes between 1700 and 9000 um3, were measured using the Resochron. The ablated sites were imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol. U, Th and Sm concentrations were measured by laser ablation and the U-Th-Sm/He age calculated by standard age equation. An age of 33.8±0.31 Ma was determined and compares well with conventional

Magmatic oxygen fugacity estimated using zircon-melt partitioning of cerium

NASA Astrophysics Data System (ADS)

Smythe, Duane J.; Brenan, James M.

2016-11-01

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

Characterization of inclusions in terrestrial impact formed zircon: Constraining the formation conditions of Hadean zircon from Jack Hills, Western Australia

NASA Astrophysics Data System (ADS)

Faltys, J. P.; Wielicki, M. M.; Sizemore, T. M.

2017-12-01

Due to the discovery and subsequent geochemical analysis of Hadean terrestrial material (e.g. detrital zircon from Jack Hills, Western Australia), a dramatic paradigm shift has occurred in the hypothesized near surface conditions of the first 500 million years of Earth's evolution. From a hellish setting riddled with impactors and not fit for life to a much milder environment that may have been uniquely suitable for the origin of life. Geochemical analyses of these ancient materials have been used to suggest the presence of water at or near the surface as well as the existence of continental crust during the Hadean, both of which have been suggested as necessary for the origin of life. However, the intensity of extraterrestrial bombardment during the Hadean and the effects of such events on the origin of life remains poorly understood. Clearly, as evidenced by Phanerozoic impact events, extraterrestrial impactors have the potential to dramatically effect the environment, particularly the biosphere. Early Earth likely experienced multiple large impact events, as evidenced by the lunar record, however whether those impacts were sufficient to frustrate the origin of life remains an open question. Although multiple lines of evidence, including the inclusion population, suggest the formation of Hadean zircon from Jack Hills as crystallizing in an under-thrust environment from S-type magmas, a recent study has suggested their formation in an impact melt environment analogous to a portion of the Sudbury Igneous Complex at the Sudbury impact structure. To determine between these two formation scenarios we have under-taken an inclusion study of terrestrial impact formed zircon from four of the largest terrestrial impact structures (Sudbury, Canada; Manicouagan, Canada; Vredefort, South Africa; Morokweng, South Africa), to compare to the vast inclusion dataset that exists for Jack Hills zircon. Preliminary data suggests a different inclusion population, from Hadean zircon

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

Do Jack Hills Detrital Zircons Contain Records of the Early Geodynamo?

NASA Astrophysics Data System (ADS)

Weiss, B. P.; Maloof, A. C.; Tailby, N. D.; Ramezani, J.; Fu, R. R.; Glenn, D. R.; Kehayias, P.; Walsworth, R. L.; Hanus, V.; Trail, D.; Watson, E. B.; Harrison, T. M.; Bowring, S. A.; Kirschvink, J. L.; Swanson-Hysell, N.; Coe, R. S.; Einsle, J. F.; Harrison, R. J.

2015-12-01

It is unknown when Earth's dynamo magnetic field originated. With crystallization ages ranging from 3.0-4.38 Ga, detrital zircon crystals found in the Jack Hills of Western Australia might preserve a record of the missing first billion years of Earth's magnetic field history. Recently, Tarduno et al. (2015) argued that magnetization in Jack Hills zircons provides evidence for a substantial geomagnetic field dating back to their U/Pb formation ages (3.3 and 4.2 Ga). However, the identification of such ancient field records requires establishing that the zircons have avoided remagnetization since their formation. At a minimum, it should be demonstrated that they have not been remagnetized since being deposited at ~3.0 Ga. To establish the timing and intensity of the metamorphic and alteration events experienced by the zircon, we conducted 12 paleomagnetic field tests in combination with U-Pb geochronology on their host rocks (see Weiss et al. 2015, EPSL). Our data show that the Hadean zircon-bearing rocks and surrounding region have been pervasively remagnetized, with the final major overprinting likely from emplacement of the Warakurna large igneous province at 1.1 Ga (see Figure). Even if some Jack Hills zircons do record a pre-depositional magnetization, they still could have been remagnetized sometime during the 1.4 Gy between their crystallization and their deposition. First, the temperatures capable of remagnetizing magnetite inclusions are well below those that could reset a U-Pb date or result in significant discordance. Therefore, thermal events capable of completely remagnetizing Jack Hills zircons could be undetected by the techniques reported by Tarduno at al. (2015). Second, the zircons' magnetization might be dominated by secondary ferromagnetic inclusions or contamination. To address the latter possibility, we are conducting electron microscopy, x-ray tomography, and magnetic field mapping on the zircons. Our initial quantum diamond magnetometry high

Breaking through the uncertainty ceiling in LA-ICP-MS U-Pb geochronology

NASA Astrophysics Data System (ADS)

Horstwood, M.

2016-12-01

Sources of systematic uncertainty associated with session-to-session bias are the dominant contributor to the 2% (2s) uncertainty ceiling that currently limits the accuracy of LA-ICP-MS U-Pb geochronology. Sources include differential downhole fractionation (LIEF), `matrix effects' and ablation volume differences, which result in irreproducibility of the same reference material across sessions. Current mitigation methods include correcting for LIEF mathematically, using matrix-matched reference materials, annealing material to reduce or eliminate radiation damage effects and tuning for robust plasma conditions. Reducing the depth and volume of ablation can also mitigate these problems and should contribute to the reduction of the uncertainty ceiling. Reducing analysed volume leads to increased detection efficiency, reduced matrix-effects, eliminates LIEF, obviates ablation rate differences and reduces the likelihood of intercepting complex growth zones with depth, thereby apparently improving material homogeneity. High detection efficiencies (% level) and low sampling volumes (20um box, 1-2um deep) can now be achieved using MC-ICP-MS such that low volume ablations should be considered part of the toolbox of methods targeted at improving the reproducibility of LA-ICP-MS U-Pb geochronology. In combination with other strategies these improvements should be feasible on any ICP platform. However, reducing the volume of analysis reduces detected counts and requires a change of analytical approach in order to mitigate this. Appropriate strategies may include the use of high efficiency cell and torch technologies and the optimisation of acquisition protocols and data handling techniques such as condensing signal peaks, using log ratios and total signal integration. The tools required to break the 2% (2s) uncertainty ceiling in LA-ICP-MS U-Pb geochronology are likely now known but require a coherent strategy and change of approach to combine their implementation and realise

LA-SF-ICP-MS zircon U-Pb geochronology of granitic rocks from the central Bundelkhand greenstone complex, Bundelkhand craton, India

NASA Astrophysics Data System (ADS)

Verma, Sanjeet K.; Verma, Surendra P.; Oliveira, Elson P.; Singh, Vinod K.; Moreno, Juan A.

2016-03-01

The central Bundelkhand greenstone complex in Bundelkhand craton, northern India is one of the well exposed Archaean supracrustal amphibolite, banded iron formation (BIF) and felsic volcanic rocks (FV) and associated with grey and pink porphyritic granite, tonalite-trondhjemite-granodiorite (TTG). Here we present high precision zircon U-Pb geochronological data for the pinkish porphyritic granites and TTG. The zircons from the grey-pinkish porphyritic granite show three different concordia ages of 2531 ± 21 Ma, 2516 ± 38 Ma, and 2514 ± 13 Ma, which are interpreted as the best estimate of the magmatic crystallization age for the studied granites. We also report the concordia age of 2669 ± 7.4 Ma for a trondhjemite gneiss sample, which is so far the youngest U-Pb geochronological data for a TTG rock suite in the Bundelkhand craton. This TTG formation at 2669 Ma is also more similar to Precambrian basement TTG gneisses of the Aravalli Craton of north western India and suggests that crust formation in the Bundelkhand Craton occurred in a similar time-frame to that recorded from the Aravalli craton of the North-western India.

Zircons as a Probe of Early Lunar Impact History

NASA Astrophysics Data System (ADS)

Crow, C. A.; McKeegan, K. D.; Gilmour, J. D.; Crowther, S. A.; Taylor, D. J.

2013-08-01

Zircons are ideal for investigating the early lunar bombardment because we can measure both U-Pb crystallization ages and fissiongenic Xe degassing ages for the same crystal. We report U-Pb, Pb-Pb and U-Xe ages for two lunar zircons.

Crystallization process of zircon and fergusonite during hydrothermal alteration in Nechalacho REE deposit, Thor Lake, Canada

NASA Astrophysics Data System (ADS)

Hoshino, M.; Watanabe, Y.; Murakami, H.; Kon, Y.; Tsunematsu, M.

2012-04-01

The core samples of two drill holes, which penetrate sub-horizontal mineralized horizons at Nechalacho REE deposit in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify magmatic and hydrothermal processes that enriched HFSE (e.g. Zr, Nb, Y and REE). Zircon is the most common REE minerals in Nechalacho REE deposit. The zircon is divided into five types as follows: Type-1 zircon occurs as single grain in phlogopite and the chondrite-normalized REE pattern is characterized by a steeply-rising slope from the LREE to the HREE with a positive Ce-anomaly and negative Eu-anomaly. This chemical characteristic is similar to that of igneous zircon. Type-2 zircon consists of HREE-rich magmatic porous core and LREE-Nb-F-rich hydrothermal rim. This type zircon is mostly included in phlogopite and fluorite, and occasionally in microcline. Type-3 zircon is characterized by euhedral to anhedral crystal, occurring in a complex intergrowth with REE fluorocarbonates. Type-3 zircons have high contents of REE, Nb and fluorine. Type-4 zircon consists of porous-core and -rim zones, but their chemical compositions are similar to each other. This type zircon is a subhedral crystal rimmed by fergusonite. Type-5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircons are filled by fergusonite. Type-4 and -5 zircons show low REE and Nb contents. Occurrences of these five types of zircon are different according to the depth and degree of the alteration by hydrothermal solutions rich in F- and CO3 of the two drill holes, which permit a model for evolution of the zircon crystallization in Nechalacho REE deposit as follows: (1) type-1 (single magmatic zircon) is formed in miaskitic syenite. (2) LREE-Nb-F-rich hydrothermal zircon formed around HREE-rich magmatic zircon (type-2 zircon); (3) type-3 zircon crystallized thorough F and CO3-rich hydrothermal alteration of type-2 zircon which formed the complex

Developing Zircon as a Probe of Planetary Impact History

NASA Astrophysics Data System (ADS)

Wielicki, Matthew

2014-12-01

The identification of Meteor Crater in Arizona as an extraterrestrial impact by Eugene Shoemaker provided the first evidence of this geologic phenomenon and opened the door to a new field of research that has eventually lead to the identification of over ~150 terrestrial impact structures. Subsequently impacts have been evoked in the formation of the moon, delivery of volatiles and bio-precursors to early Earth, creation of habitats for the earliest life and, in more recent times, major mass extinction events. However, understanding the impact flux to the Earth-Moon system has been complicated by the constant weathering and erosion at Earth's surface and the complex nature of impactite samples such that only a hand full of terrestrial craters have been accurately and precisely dated. Currently 40Ar/39Ar step-heating analysis of impactite samples is commonly used to infer impact ages but can be problematic due to the presence of relic clasts, incomplete 40Ar outgassing or excess 40Ar, and recoil and shock effects. The work presented here attempts to develop zircon geochronology to probe planetary impact histories as an alternative to current methods and provides another tool by which to constrain the bolide flux to the Earth-Moon system. Zircon has become the premier geo-chronometer in earth science and geochemical investigation of Hadean zircon from Western Australia has challenged the long-standing, popular conception that the near-surface Hadean Earth was an uninhabitable and hellish world; Zircons may preserve environmental information regarding their formation and thus provide a rare window into conditions on early Earth. Isotopic and petrologic analyses of these ancient grains have been interpreted to suggest that early Earth was more habitable than previously envisioned, with water oceans, continental crust, and possibly even plate tectonics. The Hadean is also suspected to be a time of major planetary bombardment however identifying impact signatures within

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

A New Multielement Method for LA-ICP-MS Data Acquisition from Glacier Ice Cores.

PubMed

Spaulding, Nicole E; Sneed, Sharon B; Handley, Michael J; Bohleber, Pascal; Kurbatov, Andrei V; Pearce, Nicholas J; Erhardt, Tobias; Mayewski, Paul A

2017-11-21

To answer pressing new research questions about the rate and timing of abrupt climate transitions, a robust system for ultrahigh-resolution sampling of glacier ice is needed. Here, we present a multielement method of LA-ICP-MS analysis wherein an array of chemical elements is simultaneously measured from the same ablation area. Although multielement techniques are commonplace for high-concentration materials, prior to the development of this method, all LA-ICP-MS analyses of glacier ice involved a single element per ablation pass or spot. This new method, developed using the LA-ICP-MS system at the W. M. Keck Laser Ice Facility at the University of Maine Climate Change Institute, has already been used to shed light on our flawed understanding of natural levels of Pb in Earth's atmosphere.

Experimental shock deformation in zircon: a transmission electron microscopic study

NASA Astrophysics Data System (ADS)

Leroux, H.; Reimold, W. U.; Koeberl, C.; Hornemann, U.; Doukhan, J.-C.

1999-06-01

In recent years, apparently shock-induced and, thus, impact-characteristic microdeformations, in the form of planar microdeformation features and so-called strawberry (granular) texture, have been observed in zircons in rocks from confirmed impact structures and from the K/ T boundary. The nature of the planar microdeformations in this mineral is, however, still unknown, and critical information is needed regarding the shock pressure range in which these deformation effects are produced. We experimentally shock deformed two series of thin zircon (ZrSiO 4) target plates, cut perpendicular to the c-axis, at shock pressures of 20, 40, and 60 GPa. The recovered samples were characterized by optical and scanning electron microscopy. In addition, one sample series was studied by transmission electron microscopy (TEM). Microdeformation effects observed at 20 GPa include pervasive micro-cleavage and dislocation patterns. Plastic deformation is indicated by a high density of straight dislocations in glide configuration. The dominant glide systems are <100>{010}. Micro-cleavages, induced by shear stresses during the compression stage, occur mostly in the {100} planes. The large density of dislocations at crack tips shows that plastic deformation was initiated by the micro-cracking processs. At 40 GPa, the sample was partly transformed from the zircon (z) to a scheelite (CaWO 4)-type (s) structure. Planar deformation features (PDFs) containing an amorphous phase of zircon composition are present in the not yet transformed zircon relics. The phase with scheelite structure, initiated in the {100} planes of zircon, consists of thin (0.1 to several μm) bands that crosscut the zircon matrix. The phase transformation is displacive (martensitic) and can be related by {100} z // {112} s and [001] z // <110> s. The scheelite structure phase is densely twinned, with twins in the (112) plane. The 60-GPa sample consists completely of the scheelite structure phase. Crosscutting and

The effect of ultrafast laser wavelength on ablation properties and implications on sample introduction in inductively coupled plasma mass spectrometry

PubMed Central

LaHaye, N. L.; Harilal, S. S.; Diwakar, P. K.; Hassanein, A.; Kulkarni, P.

2015-01-01

We investigated the role of femtosecond (fs) laser wavelength on laser ablation (LA) and its relation to laser generated aerosol counts and particle distribution, inductively coupled plasma-mass spectrometry (ICP-MS) signal intensity, detection limits, and elemental fractionation. Four different NIST standard reference materials (610, 613, 615, and 616) were ablated using 400 nm and 800 nm fs laser pulses to study the effect of wavelength on laser ablation rate, accuracy, precision, and fractionation. Our results show that the detection limits are lower for 400 nm laser excitation than 800 nm laser excitation at lower laser energies but approximately equal at higher energies. Ablation threshold was also found to be lower for 400 nm than 800 nm laser excitation. Particle size distributions are very similar for 400 nm and 800 nm wavelengths; however, they differ significantly in counts at similar laser fluence levels. This study concludes that 400 nm LA is more beneficial for sample introduction in ICP-MS, particularly when lower laser energies are to be used for ablation. PMID:26640294

Residence, resorption and recycling of zircons in Devils Kitchen rhyolite, Coso Volcanic Field, California

USGS Publications Warehouse

Miller, J.S.; Wooden, J.L.

2004-01-01

Zircons from the Devils Kitchen rhyolite in the Pleistocene Coso Volcanic field, California have been analyzed by in situ Pb/U ion microprobe (SHRIMP-RG) and by detailed cathodoluminescence imaging. The zircons yield common-Pb-corrected and disequilibrium-corrected 206Pb/238U ages that predate a previously reported K-Ar sanidine age by up to 200 kyr, and the range of ages exhibited by the zircons is also approximately 200 kyr. Cathodoluminescence imaging indicates that zircons formed in contrasting environments. Most zircons are euhedral, and a majority of the zircons are weakly zoned, but many also have anhedral, embayed cores, with euhedral overgrowths and multiple internal surfaces that are truncated by later crystal zones. Concentrations of U and Th vary by two orders of magnitude within the zircon population, and by 10-20 times between zones within some zircon crystals, indicating that zircons were transferred between contrasting chemical environments. A zircon saturation temperature of ???750??C overlaps within error a previously reported phenocryst equilibration temperature of 740 ?? 25??C. Textures in zircons indicative of repeated dissolution and subsequent regrowth are probably caused by punctuated heating by mafic magma input into rhyolite. The overall span of ages and large variation in U and Th concentrations, combined with calculated zircon saturation temperatures and resorption times, are most compatible with crystallization in magma bodies that were emplaced piecemeal in the crust at Coso over 200 kyr prior to eruption, and that were periodically rejuvenated or melted by subsequent basaltic injections. ?? Oxford University Press 2004; all rights reserved.

Annealing effects on cathodoluminescence of zircon

NASA Astrophysics Data System (ADS)

Tsuchiya, Y.; Nishido, H.; Noumi, Y.

2011-12-01

U-Pb zircon dating (e. g., SHRIMP) is an important tool to interpret a history of the minerals at a micrometer-scale, where cathodoluminescence (CL) imaging allows us to recognize internal zones and domains with different chemical compositions and structural disorder at high spatial resolution. The CL of zircon is attributed by various types of emission centers, which are extrinsic ones such as REE impurities and intrinsic ones such as structural defects. Metamictization resulted from radiation damage to the lattice by alpha particles from the decay of U and Th mostly causes an effect on the CL features of zircon as a defect center. However, slightly radiation-damaged zircon, which is almost nondetectable by XRD, has not been characterized using CL method. In this study, annealing effects on CL of zircon has been investigated to clarify a recovery process of the damaged lattice at low radiation dose. A single crystal of zircon from Malawi was selected for CL measurements. It contains HfO2: 2.30 w.t %, U: 241 ppm and Th: 177 ppm. Two plate samples perpendicular to c and a axes were prepared for annealing experiments during 12 hours from room temperature to 1400 degree C. Color CL images were captured using a cold-cathode microscope (Luminoscope: Nuclide ELM-3R). CL spectral measurements were conducted using an SEM (JEOL: JSM-5410) combined with a grating monochromator (Oxford: Mono CL2) to measure CL spectra ranging from 300 to 800 nm in 1 nm steps with a temperature controlled stage. The dispersed CL was collected by a photoncounting method using a photomultiplier tube (Hamamatsu: R2228) and converted to digital data. All CL spectra were corrected for the total instrumental response. Spectral analysis reveals an anisotropy of the CL emission bands related to intrinsic defect center in blue region, radiation-induced defect center from 500 to 700 nm, and trivalent Dy impurity center at 480 and 580 nm, but their relative intensities are almost constant. CL on the

Ablation of "Background Tachycardia" in Long Standing Atrial Fibrillation: Improving the Outcomes by Unmasking a Residual Atrial Fibrillation Perpetuator.

PubMed

Pachón-M, José Carlos; Pachón-M, Enrique I; Santillana P, Tomas G; Lobo, Tasso Julio; Pachón, Carlos Thiene C; Pachón-M, Juán Carlos; Albornoz V, Remy Nelson; Zerpa A, Juán Carlos; Ortencio, Felipe; Arruda, Mauricio

2017-01-01

Catheter ablation of long-standing persistent AF (LSAF) remains challenging. Since AF-Nest (AFN) description, we have observed that a stable, protected, fast source firing, namely "Background Tachycardia"(BT), could be hidden beneath the chaotic AF. Following pulmonary vein isolation (PVI)+AFN ablation one or more BT may arise or be induced in 30-40% of patients, which could be the culprit forAF maintenance and ablation recurrences. We studied 114 patients, from 322 sequential LSAF regular ablations, having spontaneous or induced residual BT after EGM-guided PVI+AFN ablation of LSAF; 55.6±11y/o, 97males (85.1%), EF=65.5±8%, LA=42.8±6.7mm. Macroreentrant tachycardias were excluded. Pre-ablationAF 12-leads ECG Digital processing(DP) and spectral analysis(SA) was performed searching for BT before AF ablation and its correlation with BT during ablation.After PVI, 38.1±9 AFN sites/patient and 135 sustained BTs (1-3, 1.2±0.5/patient) were ablated. BT cycle length(CL) was 246.3±37.3ms. In 79 patients presenting suitable DP for SA, the BT-CL was 241.6±34.3ms with intra procedure BT-CL correlation r=0.83/p<0.01. Following BT ablation, AF could not be induced. During FU of 13→60 months(22.8±12m), AF freedom for BT RF(+) vs. BT RF(-) groups were 77.9% vs. 56.4% (p=0.009), respectively. There was no significant complication. BT ablation following PVI and AFN ablation improved long-term outcomes ofLSAF ablation. BT is likely due to sustained microreentry, protected during AF by entry block. BT can be suspected by spectral analysis of the pre-ablation ECG and is likely one important AF perpetuator by causing electrical resonance of the AFN. This ablation strategy warrants randomized, multicenter investigation.

U-Pb detrital zircon geochronology from the basement of the Central Qilian Terrane: implications for tectonic evolution of northeastern Tibetan Plateau

NASA Astrophysics Data System (ADS)

Liu, Changfeng; Wu, Chen; Zhou, Zhiguang; Yan, Zhu; Jiang, Tian; Song, Zhijie; Liu, Wencan; Yang, Xin; Zhang, Hongyuan

2018-03-01

The Tuolai Group dominates the Central Qilian Terrane, and there are different opinions on the age and tectonic attribute of the Tuolai Group. Based on large-scale geologic mapping and zircon dating, the Tuolai Group is divided into four parts: metamorphic supracrustal rocks, Neoproterozoic acid intrusive rocks, early-middle Ordovician acid intrusive rocks and middle Ordovician basic intrusive rocks. The metamorphic supracrustal rocks are the redefined Tuolai complex-group and include gneiss and schist assemblage by faulting contact. Zircon U-Pb LA-MC-ICP-MS dating was conducted on these samples of gneiss and migmatite from the gneiss assemblage, quartzite, two-mica schist and slate from the schist assemblage. The five detrital samples possess similar age spectra; have detrital zircon U-Pb main peak ages of 1.7 Ga with youngest U-Pb ages of 1150 Ma. They are intruded by Neoproterozoic acid intrusive rocks. Therefore, the Tuolai Group belonging to late Mesoproterozoic and early Neoproterozoic. With this caveat in mind, we believe that U-Pb detrital zircon dating, together with the geologic constraints obtained from this study and early work in the neighboring regions. We suggest that the formation age of the entire crystalline basement rocks of metasedimentary sequence from the Central Qilian Terrane should be constrained between the Late Mesoproterozoic and the Late Neoproterozoic, but not the previous Paleoproterozoic. The basement of the Central Qilian Terrane contains the typical Grenville ages, which indicates the Centre Qilian Terrane have been experienced the Grenville orogeny event.

Electrical conductivity measurement of excised human metastatic liver tumours before and after thermal ablation.

PubMed

Haemmerich, Dieter; Schutt, David J; Wright, Andrew W; Webster, John G; Mahvi, David M

2009-05-01

We measured the ex vivo electrical conductivity of eight human metastatic liver tumours and six normal liver tissue samples from six patients using the four electrode method over the frequency range 10 Hz to 1 MHz. In addition, in a single patient we measured the electrical conductivity before and after the thermal ablation of normal and tumour tissue. The average conductivity of tumour tissue was significantly higher than normal tissue over the entire frequency range (from 4.11 versus 0.75 mS cm(-1) at 10 Hz, to 5.33 versus 2.88 mS cm(-1) at 1 MHz). We found no significant correlation between tumour size and measured electrical conductivity. While before ablation tumour tissue had considerably higher conductivity than normal tissue, the two had similar conductivity throughout the frequency range after ablation. Tumour tissue conductivity changed by +25% and -7% at 10 Hz and 1 MHz after ablation (0.23-0.29 at 10 Hz, and 0.43-0.40 at 1 MHz), while normal tissue conductivity increased by +270% and +10% at 10 Hz and 1 MHz (0.09-0.32 at 10 Hz and 0.37-0.41 at 1 MHz). These data can potentially be used to differentiate tumour from normal tissue diagnostically.

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.

Trace element determination of zircons from adakites and granitoids: implications for petrogenetic processes

NASA Astrophysics Data System (ADS)

Chen, T. W.; Chu, M. F.; Chung, S. L.; Iizuka, Y.

2017-12-01

Zircon has long been proposed as a time capsule of crustal formation. Concerning of its high capacity of lithophile elements, the dramatic change of crustal chemical composition in late Archean, i.e. from TTG suites to granitoids, may be recorded in zircon remnants. In this study, major- and trace element contents of zircons from adakites, a modern analogue of TTG suites, in southern Tibet were determined by EPMA and LA-ICPMS, respectively, and compared with those in Gangdese granitoids and Sumatra high/low ΣREE granitoids in order to examine the hypothesis. The REE patterns of zircons in this study show little inter-sample discrepancy though there is significant difference in whole-rock HREE contents between adakites and granitoids. Since none of geochemical feature, including REE contents, of zircons correlates with SiO2 content or ASI of corresponding host rocks, fractional crystallization shows insignificant impact on the compositional variation in zircons. In addition to the influence of lattice strain and charge balance requirements, zircons in these rock samples are proposed to crystallize from the magma mush, so they record the composition with least composition difference, not that of the bulk melt. More specifically, the pre-/co-existing mineral phases, e.g. apatite, play a critical role in preferentially taking the LREE and MREE from melt, and eliminating the HREE depletion in residual melt and thus zircons of Gangdese adakites. With the aim of objectively identifying geochemical discriminants of zircons from adakites and granitoids, statistical analysis was used and then 8 parameters were selected, i.e. Ti, V, Yb, Hf, Sc/Yb, U/Yb, Eu/Eu*, ΣHREE. Despite the zircon populations of adakites- and granitoids-origins overlapping in any bivariate plot, the linear combination of discriminants provides a potential way to distinguish zircons from these two groups.

Peculiar Feldspar And Quartz Inclusions Within Zircons From Anorthosites, North Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Eliwa, H. A.; Dawoud, M. I.; Khalaf, I. M.; Negendank, J. F.; Itaya, T.

2004-12-01

Zircons from three anorthosite outcrops along Wadi Dib area, north Eastern Desert of Egypt contain abundant and conspicuous inclusions of quartz, feldspar, amphibole and apatite. These anorthosites, as (50-100m thick) layers, represent the top of mafic-ultramafic intrusions exhibiting rhythmic layering visible by reputation of melanocratic and leucocratic layers. Field and microscopic studies exhibit that these anorthosites were affected by the action of residual magmatic solutions associated with the late stage crystallization of the younger granites, which modified their mineralogical composition. They are composed totally of plagioclase with subordinate amount of clinoenstatite, augite, amphibole, biotite, K-feldspar, and quartz. Accessories are magnetite, ilmenite, apatite and zircon. The abundance and the mode of occurrence of K-feldspar, quartz, and biotite with apatite and zircon among the megacrysts suggest their formation is ascribed to the interaction with the residual solutions. The microprobe data exhibit difference between feldspar and amphiboles contained herein zircons and those as anorthosite mineral constituents. The genetic relationship between zircons and their inclusions suggests later growth of zircons than inclusions and most probably at the final stage of rock modification. Zircons are magmatic and found in the interstitial feldspar and quartz among plagioclase megacrysts in aggregates or as individual grains. The microscopic and SEM images investigation exhibit that most zircons are subhedral to euhedral equant and prismatic crystals. Most zircons have same range of crystal morphologies and internal growth structures with predominance of prism /{100/} and pyramid /{101/} and occasionally prism /{110/} and pyramid /{111/}. No evidences for poly-faceted grains, inherited cores or later overgrowths were detected. CL images distinguished zircons with visible core-rim structures and others with regular and continuous growth zones contained herein

Extinct 244Pu in ancient zircons.

PubMed

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

2004-10-01

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

Raman study of radiation-damaged zircon under hydrostatic compression

NASA Astrophysics Data System (ADS)

Nasdala, Lutz; Miletich, Ronald; Ruschel, Katja; Váczi, Tamás

2008-12-01

Pressure-induced changes of Raman band parameters of four natural, gem-quality zircon samples with different degrees of self-irradiation damage, and synthetic ZrSiO4 without radiation damage, have been studied under hydrostatic compression in a diamond anvil cell up to ~10 GPa. Radiation-damaged zircon shows similar up-shifts of internal SiO4 stretching modes at elevated pressures as non-damaged ZrSiO4. Only minor changes of band-widths were observed in all cases. This makes it possible to estimate the degree of radiation damage from the width of the ν3(SiO4) band of zircon inclusions in situ, almost independent from potential “fossilized pressures” or compressive strain acting on the inclusions. An application is the non-destructive analysis of gemstones such as corundum or spinel: broadened Raman bands are a reliable indicator of self-irradiation damage in zircon inclusions, whose presence allows one to exclude artificial color enhancement by high-temperature treatment of the specimen.

Combining Laser Ablation/Liquid Phase Collection Surface Sampling and High-Performance Liquid Chromatography Electrospray Ionization Mass Spectrometry

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

Ovchinnikova, Olga S; Kertesz, Vilmos; Van Berkel, Gary J

This paper describes the coupling of ambient pressure transmission geometry laser ablation with a liquid phase sample collection method for surface sampling and ionization with subsequent mass spectral analysis. A commercially available autosampler was adapted to produce a liquid droplet at the end of the syringe injection needle while in close proximity to the surface to collect the sample plume produced by laser ablation. The sample collection was followed by either flow injection or a high performance liquid chromatography (HPLC) separation of the extracted components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the analytical utility of thismore » coupling, thin films of a commercial ink sample containing rhodamine 6G and of mixed isobaric rhodamine B and 6G dyes on glass microscope slides were analyzed. The flow injection and HPLC/ESI-MS analysis revealed successful laser ablation, capture and, with HPLC, the separation of the two compounds. The ablated circular area was about 70 m in diameter for these experiments. The spatial sampling resolution afforded by the laser ablation, as well as the ability to use sample processing methods like HPLC between the sample collection and ionization steps, makes this combined surface sampling/ionization technique a highly versatile analytical tool.« less

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

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

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

USGS Publications Warehouse

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

2009-01-01

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

[Premature outflow tract ventricular contraction combined with complete bundle branch block: the characteristic electrocardiographic and ablation target potential features].

PubMed

Di, C Y; Wan, Z; Li, K; Ding, Y S; Lin, W H

2017-12-01

Objective: To explore the characteristics of electrocardiogram(ECG) and target potential features of premature ventricular contraction (PVC) in patients with complete left/right bundle branch block (CL/RBBB) and compare with those without CL/RBBB. Methods: A retrospective analysis was done in 8 outflow tract PVC patients with CL/RBBB, who successfully underwent radiofrequency ablation from August 2009 to June 2017. According to the bundle branch block chamber, patients were divided into the complete right bundle branch block (CRBBB) group ( n= 4) and the complete left bundle branch block (CLBBB) group ( n= 4). The control group were those who successfully underwent ablation at the same position as the above two groups but without CL/RBBB. The characteristics of ECG and target potential features were compared among groups. Results: One case in the CRBBB group was successfully ablated in the great cardiac vein with precordial R/S>1 transition at V(1) and one case in the CLBBB group was successfully ablated in the right coronary cusp with precordial R/S>1 transition at V(2), while other 6 cases were all with precordial R/S>1 transition at lead V(4). Precordial R/S>1 transition was not later than sinus rhythm (SR) in the CLBBB group. No statistical difference was found in the QRS complex duration between SR and PVC in the CL/RBBB patients [(134.38±23.80)ms vs (156.75±25.93)ms, P> 0.05], while statistical difference was shown in the control group [(92.63±5.76)ms vs (140.25±15.97)ms, P< 0.05]. Conclusion: Bundle branch block can lead to misjudgment of PVC origin with CL/RBBB during sinus rhythm, thus the origin chamber of the PVC should be determined according to the mapping and ablation result.

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.

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.

Trace element analysis of synthetic mono- and poly-crystalline CaF 2 by ultraviolet laser ablation inductively coupled plasma mass spectrometry at 266 and 193 nm

NASA Astrophysics Data System (ADS)

Koch, J.; Feldmann, I.; Hattendorf, B.; Günther, D.; Engel, U.; Jakubowski, N.; Bolshov, M.; Niemax, K.; Hergenröder, R.

2002-06-01

The analytical figures of merit for ultraviolet laser ablation-inductively coupled plasma mass spectrometry (UV-LA-ICP-MS) at 266 nm with respect to the trace element analysis of high-purity, UV-transmitting alkaline earth halides are investigated and discussed. Ablation threshold energy density values and ablation rates for mono- and poly-crystalline CaF 2 samples were determined. Furthermore, Pb-, Rb-, Sr-, Ba- and Yb-specific analysis was performed. For these purposes, a pulsed Nd:YAG laser operated at the fourth harmonic of the fundamental wavelength (λ=266 nm) and a double-focusing sector field ICP-MS detector were employed. Depending on the background noise and isotope-specific sensitivity, the detection limits typically varied from 0.7 ng/g for Sr to 7 ng/g in the case of Pb. The concentrations were determined using a glass standard reference material (SRM NIST612). In order to demonstrate the sensitivity of the arrangement described, comparative measurements by means of a commercial ablation system consisting of an ArF excimer laser (λ=193 nm) and a quadrupole-type ICP-MS (ICP-QMS) instrument were carried out. The accuracy of both analyses was in good agreement, whereas ablation at 266 nm and detection using sector-field ICP-MS led to a sensitivity that was one order of magnitude above that obtained at 193 nm with ICP-QMS.

Determination of zircon/melt trace element partition coefficients from SIMS analysis of melt inclusions in zircon

NASA Astrophysics Data System (ADS)

Thomas, J. B.; Bodnar, R. J.; Shimizu, N.; Sinha, A. K.

2002-09-01

Partition coefficients ( zircon/meltD M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques. D REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce 4+ in the melt results in elevated D Ce compared to neighboring REE due to the similar valence and size of Ce 4+ and Zr 4+. Predicted zircon/meltD values for Ce 4+ and Ce 3+ indicate that the Ce 4+/Ce 3+ ratios of the melt ranged from about 10 -3 to 10 -2. Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D M < 1.0), and Ti, Y and Nb showing compatible behavior (D M > 1.0). The effect of partition coefficients on melt evolution during

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

Effect of α-damage on fission-track annealing in zircon

USGS Publications Warehouse

Kasuya, Masao; Naeser, Charles W.

1988-01-01

The thermal stability of confined fission-track lengths in four zircon samples having different spontaneous track densities (i.e., different amounts of ??-damage) has been studied by one-hour isochronal annealing experiments. The thermal stability of spontaneous track lengths is independent of initial spontaneous track density. The thermal stability of induced track lengths in pre-annealed zircon, however, is significantly higher than that of spontaneous track lengths. The results indicate that the presence of ??-damage lowers the thermal stability of fission-tracks in zircon.

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

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

The role of detrital zircons in Hadean crustal research

NASA Astrophysics Data System (ADS)

Nebel, Oliver; Rapp, Robert P.; Yaxley, Gregory M.

2014-03-01

Meso-Archean sedimentary sequences at Mt. Narryer and the Jack Hills of the Narryer Terrane in Western Australia's Yilgarn Craton contain detrital zircon grains with ages as old as 4.37 Ga, the oldest preserved terrestrial matter. These grains are rare remnants of Hadean (4.5-4.0 Ga) terrestrial crust and their survival stems from the crystallographic properties of zircon during crustal reworking: they are resistant to physical and chemical weathering. Zircons are further suitable for single grain, precise age determinations making them a unique archive of the crustal past. Only a small proportion of all detrital zircons from the Narryer Terrane show Hadean age spectra and younger overgrowth rims on all 'Hadean' grains indicate multiple recycling events. Numerous studies that applied a spectacular range of analytical tools and proxies have been undertaken to decipher the geochemical nature of these zircons' host rocks, in order to place constraints on Hadean geodynamics and the processes responsible for creating the earliest terrestrial crust. Their elemental and isotope budget and mineral inclusions have helped to develop an emerging picture of a water-rich, evolved Hadean crust. However, subsequent studies have challenged this view and it seems that each piece of new evidence indicative of an early, evolved continental crust has non-unique interpretations also permissive of mafic to ultra-mafic crust. In this review we examine these disparate interpretations and their possible implications and conclude that at least parts of the earliest terrestrial crust were hydrated. However, to date there is no conclusive evidence for preserved granitic, continental crust. The protoliths of the Hadean detrital zircons were likely acidic in nature, yet the composition of the greater terrane from which these melts were derived was probably mafic. It remains unclear if the zircons formed in a geodynamic environment that includes Hadean subduction. We suspect that the Hadean

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

A detailed structural, geochemical and geochronological survey was performed on zircon grains from a leucocratic dioritic dyke discordantly intruded within meta-diorites/gabbros forming the External Gabbro unit of the Finero Mafic Complex. This latter is nowadays exposed as part of a near complete crustal section spanning from mantle rocks to upper crustal metasediments (Val Cannobina, Ivrea-Verbano Zone, Italy). The leucocratic dyke consists mainly of plagioclase (An18-24Ab79-82Or0.3-0.7) with subordinate amounts of biotite, spinel, zircon and corundum. Both the leucocratic dyke and the surrounding meta-diorites show evidence of ductile deformation occurred under amphibolite-facies conditions. Zircon grains (up to 2 mm in length) occur mainly as euhedral grains surrounded by fine grained plagioclase-dominated matrix and pressure shadows, typically filled by oxides. Fractures and cracks within zircon are common and can be associated with grain displacement or they can be filled by secondary minerals (oxides and chlorite). Cathodoluminescence (CL) images show that zircon grains have internal features typical of magmatic growth, but with local disturbances. However EBSD maps on two selected zircon grains revealed a profuse mosaic texture resulting in an internal misorientation of ca. 10o. The majority of the domains of the mosaic texture are related to parting and fractures, but some domains show no clear relation with brittle features. Rotation angles related to the mosaic texture are not crystallographically controlled. In addition, one of the analysed zircons shows clear evidence of plastic deformation at one of its corners due to indentation. Plastic deformation results in gradual misorientations of up to 12o, which are crystallographically controlled. Trace elements and U-Pb analyses were carried out by LA-ICP-MS directly on petrographic thin sections and designed to cover the entire exposed surface of selected grains. Such investigations revealed a strong

U-Pb zircon geochronologycal investigation on the Morro dos Seis Lagos Carbonatite Complex and associated Nb deposit (Amazonas, Brazil)

NASA Astrophysics Data System (ADS)

Rossoni, Marco B.; Bastos Neto, Artur C.; Souza, Valmir S.; Marques, Juliana C.; Dantas, Elton; Botelho, Nilson F.; Giovannini, Arthur L.; Pereira, Vitor P.

2017-12-01

We present results of U-Pb dating (by MC-ICP-MS) of zircons from samples that cover all of the known lithotypes in the Seis Lagos Carbonatite Complex and associated lateritic mineralization (the Morro dos Seis Lagos Nb deposit). The host rock (gneiss) yielded an age of 1828 ± 09 Ma interpreted as the crystallization time of this unit. The altered feldspar vein in the same gneiss yielded an age of 1839 ± 29 Ma. Carbonatite samples provided 3 groups of ages. The first group comprises inherited zircons with ages compatible with the gneissic host rock: 1819 ± 10 Ma (superior intercept), 1826 ± 5 Ma (concordant age), and 1812 ± 27 Ma (superior intercept), all from the Orosirian. The second and the third group of ages are from the same carbonatite sample: the superior intercept age of 1525 ± 21 Ma (MSWD = 0.77) and the superior intercept age of 1328 ± 58 Ma (MSWD = 1.4). The mineralogical study indicates that the ∼1.3 Ga zircons have affinity with carbonatite. It is, however, a tendence rather than a well-defined result. The data allow state that the age of 1328 ± 58 Ma represents the maximum age of the carbonatite. Without the same certainty, we consider that the data suggest that this age may be the carbonatite age, whose emplacement would have been related to the evolution of the K'Mudku belt. The best age obtained in laterite samples (a superior intercept age of 1828 ± 12 Ma) is considered the age of the main source for the inherited zircons related to the gneissic host rock.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

New Evidence for opening of the Black Sea; U-Pb analysis of detrital zircons and paleocurrent measurements of the Early Cretaceous turbidites

NASA Astrophysics Data System (ADS)

Akdoğan, Remziye; Okay, Aral I.; Sunal, Gürsel; Tari, Gabor; Kylander-Clark, Andrew R. C.

2015-04-01

Shelf to submarine turbidite fan deposits of the Early Cretaceous crop out over a large area along the southern coast of the Black Sea. Early Cretaceous turbidites have a thickness of over 2000 meters in the Central Pontides. The shelf of this turbidite basin, represented by shallow marine clastics and carbonates, crops out along the Black Sea coast between Zonguldak and Amasra. Paleocurrent directions in the Lower Cretaceous turbidites were measured in 90 localities using mostly flute and groove casts and to a lesser extend cross-beds. At the eastern part of the basin, the paleocurrents were from north to south. It is scattered in the west of the basin, however, the main paleocurrent directions were from the north. Detrital zircons were analyzed using LA-ICP-MS in eleven samples from the turbiditic sandstones and two samples from the shelf sandstones. Four samples are from the western part (two samples from shelf sediments), four samples from the central part and five samples from the eastern part of the Lower Cretaceous basin. 1085 of 1348 zircon analyses are concordant with rates of 95-105% and the zircon ages range between 141 ± 4 Ma (Berriasian) and 3469 ± 8 Ma (Paleoarchean). 22% of the detrital zircon ages are Paleoproterozoic, 20% Archean, 16% Carboniferous, 13% Neoproterozoic, 8% Permian, 6% Triassic, 5% Mesoproterozoic and 11% other ages. In the western part of the basin the Carboniferous zircons constitute the main population with a less dominant peak at Ordovician, Cambrian and Late Neoproterozoic. The zircons from the center of the basin show scattered distribution with dominant populations in the Triassic, Permian, Carboniferous, Silurian, Paleoproterozoic, Early Neoproterozoic-Late Mesoproterozoic, and minor peak at Late Neoarchean. On the other hand, zircons from the eastern most part of the basin, show dominant peaks in the Paleoproterozoic, Mesoarchean and Permian with minor peaks in Triassic, Carboniferous and Silurian. Anatolia and the Balkans

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

NASA Astrophysics Data System (ADS)

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

2008-08-01

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

What can zircon ages from the Jack Hills detrital zircon suite really tell us about Hadean geodynamics?

NASA Astrophysics Data System (ADS)

Whitehouse, Martin; Nemchin, Alexander

2015-04-01

As the only direct sample of the Hadean Earth, detrital zircon grains from the Jack Hills, Western Australia, have been the subject of intense investigation over the almost three decades since their discovery. A wide variety of geochemical and isotopic analyses of these grains, as well as their mineral inclusions, have been used variously to support two fundamentally different models for Hadean geodynamics: (i) Some form of (not necessarily modern-style) plate recycling generating felsic (continental-type?) crust at the boundaries [1, 2], or conversely (ii) the persistence of a long-lived, stagnant basaltic lid within which magmatism occurred as a result of internal temperature perturbations and/or impacts [3, 4], a model also generally consistent with a wide range of observations from post-Hadean geochemical reservoirs. Despite the considerable time and resources expended, the majority of these studies uncritically accept the individual U-Pb zircon ages, even though their veracity is key to many of the interpretations [5, 6]. We report here the results of an in-depth evaluation of all published (and new) U-Pb ages from the Jack Hills zircon suite in order to define age populations that can be used with a high degree of confidence in geodynamic interpretations. A notable problem in the interpretation of U-Pb data from ancient zircon grains (including those as young as the Neoarchean) is that disturbance of the systematics even several 100 Ma after crystallization causes data to spread along the concordia curve without becoming discernably discordant within the relatively large error bounds associated with U/Pb ages from in situ dating methods (e.g. SIMS). While 207Pb/206Pb ages are typically more precise, individually they provide no means to detect Pb-loss-induced younging. However, if two or preferably more analyses have been made in the same zircon growth zone, a reasonable evaluation of the possibility of Pb-loss can be made. In the available Jack Hills zircon

Paleomagnetism of Hadean and Archean Detrital Zircons from the Jack Hills, Western Australia

NASA Astrophysics Data System (ADS)

Weiss, B. P.; Lima, E. A.; Alexander, E.; Bell, E. A.; Boehnke, P.; Wielicki, M. M.; Harrison, M.; Fu, R. R.; Kehayias, P.; Glenn, D. R.; Walsworth, R. L.; Araujo, J. F. D.; Einsle, J. F.; Harrison, R.; Trail, D.; Watson, E. B.

2016-12-01

Determining the history of Earth's dynamo prior to the oldest known well-preserved rock record is one of the ultimate challenges in the field of paleomagnetism. The dynamo's early history has major implications for the evolution of the core, the initiation of plate tectonics, the physics of magnetic field generation, and the habitability of the early Earth. The only known minerals that might retain paleomagnetic records from well before 3.5 billion years ago (Ga) are detrital zircon crystals found in sedimentary rocks in Western Australia. Ranging up to 4.38 Ga in age, they are the oldest known terrestrial minerals. Tarduno et al. (2015) argued that detrital zircons contain records of an active dynamo dating back to 4.2 Ga. However, it has not been demonstrated that the zircons have escaped remagnetization during the intervening time since their formation (Weiss et al. 2016). Therefore, the age of magnetization in the Jack Hills zircons and the existence of a dynamo prior to 3.5 Ga have yet to be established. To address this issue, we have been studying the magnetism and thermal and aqueous alteration histories of single Archean and Hadean Jack Hills zircon crystals. Peak unblocking temperatures combined with electron backscatter diffraction indicate that the zircons contain inclusions of magnetite and hematite. Electron microscopy, X-ray tomography, and quantum diamond magnetometry indicate that much of the iron oxides in the zircons are associated with cracks and are therefore likely secondary. However, our newly developed Li-in-zircon geospeedometry technique shows for the first time that a small fraction of Hadean zircons retain sharp gradients in Li concentration (see figure), indicating they likely have never heated above the magnetite Curie temperature since their formation at >4 Ga. We describe thermal demagnetization and Thellier-Thellier paleointensity studies of these zircons and implications for the existence of a Hadean dynamo.

Comparison of remote magnetic navigation ablation and manual ablation of idiopathic ventricular arrhythmia after failed manual ablation.

PubMed

Kawamura, Mitsuharu; Scheinman, Melvin M; Tseng, Zian H; Lee, Byron K; Marcus, Gregory M; Badhwar, Nitish

2017-01-01

Catheter ablation for idiopathic ventricular arrhythmia (VA) is effective and safe, but efficacy is frequently limited due to an epicardial origin and difficult anatomy. The remote magnetic navigation (RMN) catheter has a flexible catheter design allowing access to difficult anatomy. We describe the efficacy of the RMN for ablation of idiopathic VA after failed manual ablation. Among 235 patients with idiopathic VA referred for catheter ablation, we identified 51 patients who were referred for repeat ablation after a failed manual ablation. We analyzed the clinical characteristics, including the successful ablation site and findings at electrophysiology study, in repeat procedures conducted using RMN as compared with manual ablation. Among these patients, 22 (43 %) underwent repeat ablation with the RMN and 29 (57 %) underwent repeat ablation with a manual ablation. Overall, successful ablation rate was significantly higher using RMN as compared with manual ablation (91 vs. 69 %, P = 0.02). Fluoroscopy time in the RMN was 17 ± 12 min as compared with 43 ± 18 min in the manual ablation (P = 0.009). Successful ablation rate in the posterior right ventricular outflow tract (RVOT) plus posterior-tricuspid annulus was higher with RMN as compared with manual ablation (92 vs. 50 %, P = 0.03). Neither groups exhibited any major complications. The RMN is more effective in selected patients with recurrent idiopathic VA after failed manual ablation and is associated with less fluoroscopy time. The RMN catheters have a flexible design enabling them to access otherwise difficult anatomy including the posterior tricuspid annulus and posterior RVOT.

Mapping age and trace elements using laser ablation split-stream (LASS) ICPMS

NASA Astrophysics Data System (ADS)

Kylander-Clark, A. R.; Hacker, B. R.; Cottle, J. M.

2012-12-01

One of the biggest challenges in the determination of the timing and rates of metamorphic processes is tying the age of a particular mineral to the conditions (i.e., pressure, temperature, fluid composition) at which that phase grew. Conventional microbeam techniques increase our understanding of crustal evolution by enabling this linkage; e.g., x-ray maps of monazite allow us to pinpoint grain segments that grew under a different set of conditions, cathodoluminescence images of zircon reveal zoning patterns and hence targets for dating different metamorphic and/or igneous events, and rare-earth element (REE) transects across garnet reveal the budget of a variety of trace elements during a metamorphic episode, to name but a few. More recent advances in LA-ICPMS and SIMS have allowed the ability to produce age maps or trace element maps—thus further our understanding of crystallization processes—but not both. Here we employ laser ablation split-stream (LASS) to quantitatively image the age, and trace element signature of datable phases such as zircon, monazite, titanite, and rutile in metamorphic rocks on the micron scale. By mapping the age and TE signature of a metamorphic phase, we can better interpret the metamorphic stage at which all portions of that phase grew, and relate it to other phases/portions of phases within that rock, such as garnet. For example, zircons and monazites from from eclogites reveal complex zoning in REEs indicating growth prior to, during, and post eclogite-facies metamorphism; those zones correspond to distinct age domains. Metamorphosed titanite reveals differences in diffusivities of TEs in inherited portions of the grain; e.g., Pb-loss is more prominent than diffusion of REEs, which in turn diffuse faster than higher charged ions, such as Th.

The influence of ns- and fs-LA plume local conditions on the performance of a combined LIBS/LA-ICP-MS sensor

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

LaHaye, Nicole L.; Phillips, Mark C.; Duffin, Andrew M.

2016-01-01

Both laser-induced breakdown spectroscopy (LIBS) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are well-established analytical techniques with their own unique advantages and disadvantages. The combination of the two analytical methods is a very promising way to overcome the challenges faced by each method individually. We made a comprehensive comparison of local plasma conditions between nanosecond (ns) and femtosecond (fs) laser ablation (LA) sources in a combined LIBS and LA-ICP-MS system. The optical emission spectra and ICP-MS signal were recorded simultaneously for both ns- and fs-LA and figures of merit of the system were analyzed. Characterization of the plasma was conductedmore » by evaluating temperature and density of the plume under various irradiation conditions using optical emission spectroscopy, and correlations to ns- and fs-LIBS and LA-ICP-MS signal were made. The present study is very useful for providing conditions for a multimodal system as well as giving insight into how laser ablation plume parameters are related to LA-ICP-MS and LIBS results for both ns- and fs-LA.« less

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.

Dating high-grade metamorphism: constraints from zircon and garnet REE compositions

NASA Astrophysics Data System (ADS)

Whitehouse, M. J.; Platt, J. P.

2001-12-01

We present high spatial resolution ion microprobe REE analyses of zircon and garnet from pelitic granulite adjacent to the Ronda peridotite, Betic Cordillera, southern Spain. The zircons exhibit polyphase growth, with thick structureless (in cathodoluminescence) overgrowths over detrital cores. These overgrowths yield a U-Pb age of 21.3 +/- 0.3 Ma [1, unpublished data] which we intepret as dating an episode of zircon growth during the Alpine orogeny. REE analyses of the dated portions of these zircons reveal profound differences between cores and rims. Cores show patterns typical of magmatic zircon (steep upward slopes from La to Lu with marked positive Ce anomaly), while the overgrowths are characterised by flat or even negatively sloping HREE profiles (Gd - Lu). Garnet, which occupies ca. 30 % by volume of the rock, is the most likely phase to host the HREEs in the rock and has been the subject of further ion-microprobe REE, textural and trace element investigations. The garnets are themselves zoned, with dominant central regions that are relatively free of inclusions overgrown by inclusion-rich, more calcic rims. Inclusions of kyanite +rutile in the central regions and sillimanite +ilmenite in the rims suggests that the garnets grew during decompression, and the Ca-enrichment in the rims suggests that their growth coincided with the initiation of partial melting. The presence of rimmed zircons only in the garnet rims and the matrix further suggests that the zircons also grew during this late decompressional history. An REE traverse of the garnet from core to rim reveals marked HREE depletion in the rims relative to the cores which we suggest is consistent with the textural evidence and probably results from early garnet core growth strongly depleting the HREEs available to subsequent growth. This mechanism can also be invoked to explain depletion in the zircon rims and more closely ties their formation to this stage of garnet growth. We therefore interpret the

The oldest rock of Ivory Coast

NASA Astrophysics Data System (ADS)

Kouamelan, Alain Nicaise; Djro, Sagbrou Chérubin; Allialy, Marc Ephrem; Paquette, Jean-Louis; Peucat, Jean-Jacques

2015-03-01

The tonalitic gneiss of Balmer (TGB), in the SASCA area of south-western Ivory Coast, previously dated at 3141 ± 2 Ma using the single zircon evaporation method, is regarded as a relic of Archean rock within the Paleoproterozoic (Birimian) formation of the West African Craton (WAC). We present new geochronological data for the TGB using the laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method. We obtain a U-Pb age of 3207 ± 7 Ma for abundant zircons extracted from the tonalitic gneiss, and interpret this age as that of the magmatic protolith because of the igneous-type homogeneous zircon population. Certain magmatic zircon edges and some round zircons define an upper intercept age of 3155 ± 17 Ma which could represent overgrowths during gneissification. It appears that the TGB was not affected by the events posterior to its genesis, i.e. the Liberian (2.9-2.7 Ga) and Eburnean (2.4-2.0 Ga) events. Additionally, the TGB proves to be a juvenile Leonian rock, as indicated by the Nd model age of 3456 Ma, and could also constitute the protolith of the granulitic grey gneisses and charnockites of the Man area, which are 150-400 Ma younger.

Investigating the Early Carbon Cycle Using Carbonaceous Inclusions and Dissolved Carbon in Detrital Zircon

NASA Astrophysics Data System (ADS)

Bell, E. A.; Boehnke, P.; Harrison, M.; Mao, W. L.

2015-12-01

Because the terrestrial rock record extends only to ~4 Ga and older materials thus far identified are limited to detrital zircons, information about volatile abundances and cycles on early Earth is limited. Carbon, for instance, plays an important role not only in the modern biosphere but also in deep recycling of materials between the crust and mantle. We are investigating the record of carbon abundance and origin in Hadean zircons from Jack Hills (W. Australia) using two main approaches. First, carbon may partition into the zircon structure at trace levels during crystallization from a magma, and better understanding of this partitioning behavior will allow for zircon's use as a monitor of magmatic carbon contents. We have measured carbon abundances in zircon from a variety of igneous rocks (gabbro; I-, A-, and S-type granitoids) via SIMS and found that although abundances are typically low (average raw 12C/30Si ~ 1x10-6), S-type granite zircons can reach a factor of 1000 over this background. Around 10% of Hadean zircons investigated show similar enrichments, consistent with other evidence for the derivation of many Jack Hills zircons from S-type granitoids and with the establishment of modern-level carbon abundances in the crust by ca. 4.2 Ga. Diamond and graphite inclusions reported in the Jack Hills zircons by previous studies proved to be contamination by polishing debris, leaving the true abundance of these materials in the population uncertain. On a second front, we have identified and investigated primary carbonaceous inclusions in these zircons. From a population of over 10,000 Jack Hills zircons, we identified one concordant 4.10±0.01 Ga zircon that contains primary graphite inclusions (so interpreted due to their enclosure in a crack-free zircon host as shown by transmission X-ray microscopy and their crystal habit). Their δ13CPDB of -24±5‰ is consistent with a biogenic origin and, in the absence of a likely inorganic mechanism to produce such a

Imaging Metals in Brain Tissue by Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry (LA-ICP-MS)

PubMed Central

Hare, Dominic J.; Kysenius, Kai; Paul, Bence; Knauer, Beate; Hutchinson, Robert W.; O'Connor, Ciaran; Fryer, Fred; Hennessey, Tom P.; Bush, Ashley I.; Crouch, Peter J.; Doble, Philip A.

2017-01-01

Metals are found ubiquitously throughout an organism, with their biological role dictated by both their chemical reactivity and abundance within a specific anatomical region. Within the brain, metals have a highly compartmentalized distribution, depending on the primary function they play within the central nervous system. Imaging the spatial distribution of metals has provided unique insight into the biochemical architecture of the brain, allowing direct correlation between neuroanatomical regions and their known function with regard to metal-dependent processes. In addition, several age-related neurological disorders feature disrupted metal homeostasis, which is often confined to small regions of the brain that are otherwise difficult to analyze. Here, we describe a comprehensive method for quantitatively imaging metals in the mouse brain, using laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS) and specially designed image processing software. Focusing on iron, copper and zinc, which are three of the most abundant and disease-relevant metals within the brain, we describe the essential steps in sample preparation, analysis, quantitative measurements and image processing to produce maps of metal distribution within the low micrometer resolution range. This technique, applicable to any cut tissue section, is capable of demonstrating the highly variable distribution of metals within an organ or system, and can be used to identify changes in metal homeostasis and absolute levels within fine anatomical structures. PMID:28190025

Provenance studies by fission-track dating of zircon-etching and counting procedures

USGS Publications Warehouse

Naeser, N.D.; Zeitler, P.K.; Naeser, C.W.; Cerveny, P.F.

1987-01-01

In sedimentary rocks that have not been heated to high enough temperatures to anneal fission tracks in zircon (greater than ≈ 160°C), fission-track ages of individual detrital zircon grains provide valuable information about the source rocks eroded to form the sediments. The success of such studies depends, however, on the degree to which the ages determined from the detrital suite accurately portray the range of grain ages that are present in the suite. This in turn depends to a large extent on using counting and, in particular, etching procedures that permit proper sampling of grains with a wide range of age and uranium concentrations. Results are reported here of an experimental study of a ‘detrital’ zircon suite manufactured from several zircon populations of known age. This study suggests that multiple etches are required when a complete spectrum of ages in a zircon suite is desired.

Provenance studies by fission-track dating of zircon-etching and counting procedures

USGS Publications Warehouse

Naeser, Nancy D.; Zeitler, Peter K.; Naeser, Charles W.; Cerveny, Philip F.

1987-01-01

In sedimentary rocks that have not been heated to high enough temperatures to anneal fission tracks in zircon (greater than approximately equals 160 degree C), fission-track ages of individual detrital zircon grains provide valuable information about the source rocks eroded to form the sediments. The success of such studies depends, however, on the degree to which the ages determined from the detrital suite accurately portray the range of grain ages that are present in the suite. This in turn depends to a large extent on using counting and, in particular, etching procedures that permit proper sampling of grains with a wide range of age and uranium concentrations. Results are reported here of an experimental study of a 'detrital' zircon suite manufactured from several zircon populations of known age. This study suggests that multiple etches are required when a complete spectrum of ages in a zircon suite is desired.

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

NASA Astrophysics Data System (ADS)

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

2011-01-01

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

The role of trace element partitioning between garnet, zircon and orthopyroxene on the interpretation of zircon U-Pb ages: an example from high-grade basement in Calabria (Southern Italy)

NASA Astrophysics Data System (ADS)

Fornelli, A.; Langone, A.; Micheletti, F.; Pascazio, A.; Piccarreta, G.

2014-03-01

The recognition of the coeval growth of zircon, orthopyroxene and garnet domains formed during the same metamorphic cycle has been attempted with detailed microanalyses coupled with textural analyses. A coronitic garnet-bearing granulite from the lower crust of Calabria has been considered. U-Pb zircon data and zircon, garnet and orthopyroxene chemistries, at different textural sites, on a thin section of the considered granulite have been used to test possible equilibrium and better constrain the geological significance of the U-Pb ages related to zircon separates from other rocks of the same structural level. The garnet is very rich in REE and is characterised by a decrease in HREE from core to outer core and an increase in the margin. Zircons show core-overgrowth structures showing different chemistries, likely reflecting episodic metamorphic new growth. Zircon grains in matrix, corona around garnet and within the inner rim of garnet, are decidedly poorer in HREE up to Ho than garnet interior. Orthopyroxene in matrix and corona is homogeneously poor in REE. Thus, the outer core of garnet and the analysed zircon grains grew or equilibrated in a REE depleted system due to the former growth of garnet core. Zircon ages ranging from 357 to 333 Ma have been determined in the matrix, whereas ages 327-320 Ma and around 300 Ma have been determined, respectively, on cores and overgrowths of zircons from matrix, corona and inner rim of garnet. The calculated DREEzrn/grt and DREEopx/grt are largely different from the equilibrium values of literature due to strong depletion up to Ho in zircon and orthopyroxene with respect to garnet. On the other hand, the literature data show large variability. In the case study, (1) the D zrn/grt values define positive and linear trends from Gd to Lu as many examples from literature do and the values from Er to Lu approach the experimental results at about 900 °C in the combination zircon dated from 339 to 305 Ma with garnet outer core

Femtosecond laser ablation-based mass spectrometry. An ideal tool for stoichiometric analysis of thin films

DOE PAGES

LaHaye, Nicole L.; Kurian, Jose; Diwakar, Prasoon K.; ...

2015-08-19

An accurate and routinely available method for stoichiometric analysis of thin films is a desideratum of modern materials science where a material’s properties depend sensitively on elemental composition. We thoroughly investigated femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs-LA-ICP-MS) as an analytical technique for determination of the stoichiometry of thin films down to the nanometer scale. The use of femtosecond laser ablation allows for precise removal of material with high spatial and depth resolution that can be coupled to an ICP-MS to obtain elemental and isotopic information. We used molecular beam epitaxy-grown thin films of LaPd (x)Sb 2 and T´-La 2CuOmore » 4 to demonstrate the capacity of fs-LA-ICP-MS for stoichiometric analysis and the spatial and depth resolution of the technique. Here we demonstrate that the stoichiometric information of thin films with a thickness of ~10 nm or lower can be determined. Furthermore, our results indicate that fs-LA-ICP-MS provides precise information on the thin film-substrate interface and is able to detect the interdiffusion of cations.« less

Strontium isotope ratios (87Sr/86Sr) of tooth enamel: a comparison of solution and laser ablation multicollector inductively coupled plasma mass spectrometry methods.

PubMed

Copeland, Sandi R; Sponheimer, Matt; le Roux, Petrus J; Grimes, Vaughan; Lee-Thorp, Julia A; de Ruiter, Darryl J; Richards, Michael P

2008-10-01

Strontium isotope ratios (87Sr/86Sr) in tooth enamel provide a means to investigate migration and landscape use in humans and other animals. Established methods for measuring (87)Sr/(86)Sr in teeth use bulk sampling (5-20 mg) and labor-intensive elemental purification procedures before analysis by either thermal ionization mass spectrometry (TIMS) or multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Another method for measuring 87Sr/86Sr is laser ablation MC-ICP-MS, but concerns have been expressed about its accuracy for measuring tooth enamel. In this study we test the precision and accuracy of the technique by analyzing 30 modern rodent teeth from the Sterkfontein Valley, South Africa by laser ablation MC-ICP-MS and solution MC-ICP-MS. The results show a mean difference in 87Sr/86Sr measured by laser ablation and by solution of 0.0003 +/- 0.0002. This degree of precision is well within the margin necessary for investigating the potential geographic origins of humans or animals in many areas of the world. Because laser ablation is faster, less expensive, and less destructive than bulk sampling solution methods, it opens the possibility for conducting 87Sr/86Sr analyses of intra-tooth samples and small and/or rare specimens such as micromammal and fossil teeth.

Multivariate classification of edible salts: Simultaneous Laser-Induced Breakdown Spectroscopy and Laser-Ablation Inductively Coupled Plasma Mass Spectrometry Analysis

NASA Astrophysics Data System (ADS)

Lee, Yonghoon; Nam, Sang-Ho; Ham, Kyung-Sik; Gonzalez, Jhanis; Oropeza, Dayana; Quarles, Derrick; Yoo, Jonghyun; Russo, Richard E.

2016-04-01

Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), both based on laser ablation sampling, can be employed simultaneously to obtain different chemical fingerprints from a sample. We demonstrated that this analysis approach can provide complementary information for improved classification of edible salts. LIBS could detect several of the minor metallic elements along with Na and Cl, while LA-ICP-MS spectra were used to measure non-metallic and trace heavy metal elements. Principal component analysis using LIBS and LA-ICP-MS spectra showed that their major spectral variations classified the sample salts in different ways. Three classification models were developed by using partial least squares-discriminant analysis based on the LIBS, LA-ICP-MS, and their fused data. From the cross-validation performances and confusion matrices of these models, the minor metallic elements (Mg, Ca, and K) detected by LIBS and the non-metallic (I) and trace heavy metal (Ba, W, and Pb) elements detected by LA-ICP-MS provided complementary chemical information to distinguish particular salt samples.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

This study documents the strain accommodation mechanisms in zircon under amphibolite-facies metamorphic conditions in simple shear. Microstructural data from undeformed, fractured and crystal-plastically deformed zircon crystals are described in the context of the host shear zone, and evaluated in the light of zircon elastic anisotropy. Our work challenges the existing model of zircon evolution and shows previously undescribed rheological characteristics for this important accessory mineral. Crystal-plastically deformed zircon grains have axis oriented parallel to the foliation plane, with the majority of deformed grains having axis parallel to the lineation. Zircon accommodates strain by a network of stepped low-angle boundaries, formed by switching between tilt dislocations with the slip systems <100>{010} and < 1 bar 10>{110} and rotation axis [001], twist dislocations with the rotation axis [001], and tilt dislocations with the slip system <100>{001} and rotation axis [010]. The slip system < 1 bar 10>{110} is newly described for zircon. Most misorientation axes in plastically-deformed zircon grains are parallel to the XY plane of the sample and have [001] crystallographic direction. Such behaviour of strained zircon lattice is caused by elastic anisotropy that has a direct geometric control on the rheology, deformation mechanisms and dominant slip systems in zircon. Young's modulus and P wave velocity have highest values parallel to zircon [001] axis, indicating that zircon is elastically strong along this direction. Poisson ratio and Shear modulus demonstrate that zircon is also most resistant to shearing along [001]. Thus, [001] axis is the most common rotation axis in zircon. The described zircon behaviour is important to take into account during structural and geochronological investigations of (poly)metamorphic terrains. Geometry of dislocations in zircon may help reconstructing the geometry of the host shear zone(s), large-scale stresses in the

Possibilities of LA-ICP-MS technique for the spatial elemental analysis of the recent fish scales: Line scan vs. depth profiling

NASA Astrophysics Data System (ADS)

Holá, Markéta; Kalvoda, Jiří; Nováková, Hana; Škoda, Radek; Kanický, Viktor

2011-01-01

LA-ICP-MS and solution based ICP-MS in combination with electron microprobe are presented as a method for the determination of the elemental spatial distribution in fish scales which represent an example of a heterogeneous layered bone structure. Two different LA-ICP-MS techniques were tested on recent common carp ( Cyprinus carpio) scales: A line scan through the whole fish scale perpendicular to the growth rings. The ablation crater of 55 μm width and 50 μm depth allowed analysis of the elemental distribution in the external layer. Suitable ablation conditions providing a deeper ablation crater gave average values from the external HAP layer and the collagen basal plate. Depth profiling using spot analysis was tested in fish scales for the first time. Spot analysis allows information to be obtained about the depth profile of the elements at the selected position on the sample. The combination of all mentioned laser ablation techniques provides complete information about the elemental distribution in the fish scale samples. The results were compared with the solution based ICP-MS and EMP analyses. The fact that the results of depth profiling are in a good agreement both with EMP and PIXE results and, with the assumed ways of incorporation of the studied elements in the HAP structure, suggests a very good potential for this method.

Mass Spectrometric Imaging Using Laser Ablation and Solvent Capture by Aspiration (LASCA)

NASA Astrophysics Data System (ADS)

Brauer, Jonathan I.; Beech, Iwona B.; Sunner, Jan

2015-09-01

A novel interface for ambient, laser ablation-based mass spectrometric imaging (MSI) referred to as laser ablation and solvent capture by aspiration (LASCA) is presented and its performance demonstrated using selected, unaltered biological materials. LASCA employs a pulsed 2.94 μm laser beam for specimen ablation. Ablated materials in the laser plumes are collected on a hanging solvent droplet with electric field-enhanced trapping, followed by aspiration of droplets and remaining plume material in the form of a coarse aerosol into a collection capillary. The gas and liquid phases are subsequently separated in a 10 μL-volume separatory funnel, and the solution is analyzed with electrospray ionization in a high mass resolution Q-ToF mass spectrometer. The LASCA system separates the sampling and ionization steps in MSI and combines high efficiencies of laser plume sampling and of electrospray ionization (ESI) with high mass resolution MS. Up to 2000 different compounds are detected from a single ablation spot (pixel). Using the LASCA platform, rapid (6 s per pixel), high sensitivity, high mass-resolution ambient imaging of "as-received" biological material is achieved routinely and reproducibly.

The effect of α-damage on fission-track annealing in zircon

USGS Publications Warehouse

Kasuya, M.; Naeser, C.W.

1988-01-01

The thermal stability of confined fission-track lengths in four zircon samples having different spontaneous track densities (i.e. different amounts of ??-damage) has been studied by one hour isochronal annealing experiments. The thermal stability of spontaneous track lengths is independent of initial spontaneous track density. The thermal stability of induced track lengths in pre-annealed zircon, however, is significantly higher than that of spontaneous track lengths. The results indicate that the presence of ??-damage lowers the thermal stability of fission-tracks in zircon. ?? 1988.

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

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Constraints on the timing of multiple thermal events and re-equilibration recorded by high-U zircon and xenotime: Case study of pegmatite from Piława Górna (Góry Sowie Block, SW Poland)

NASA Astrophysics Data System (ADS)

Budzyń, Bartosz; Sláma, Jiří; Kozub-Budzyń, Gabriela A.; Konečný, Patrik; Holický, Ivan; Rzepa, Grzegorz; Jastrzębski, Mirosław

2018-06-01

The application of zircon and xenotime geochronometers requires knowledge of their potential and limitations related to possible disturbance of the age record. The alteration of the intergrown zircon and xenotime in pegmatite from the Góry Sowie Block (SW Poland) was studied using the electron microprobe analysis, X-ray WDS compositional mapping, micro-Raman analysis, and LA-ICP-MS U-Pb dating of zircon and xenotime, as well as the U-Th-total Pb dating of uraninite. These microanalytical techniques were applied to understand the formation mechanisms of the secondary textures related to post-magmatic processes in the zircon and xenotime intergrowth, and to constrain their timing. Textural and compositional features combined with U-Pb data indicate that the pegmatite-related crystallization of the zircon and xenotime intergrowth occurred ca. 2.09 Ga (2086 ± 35 Ma for zircon and 2093 ± 52 Ma for xenotime), followed by the re-equilibration of zircon and xenotime ca. 370 Ma (373 ± 18 Ma and 368 ± 6 Ma, respectively) during the formation of the younger pegmatite. The zircon and xenotime were most likely derived from Precambrian basement rocks and emplaced in the pegmatite as a restite. The zircon preserved textures related to diffusion-reaction processes that affected its high-U core (up to ca. 9.6 wt% UO2), which underwent further metamictization and amorphization due to self-radiation damage. The zircon rim and xenotime were affected by coupled dissolution-reprecipitation processes that resulted in patchy zoning, age disturbance and sponge-like textures. Xenotime was also partially replaced by fluorapatite or hingganite-(Y) and Y-enriched allanite-(Ce). The termination of the low-temperature alteration was constrained by the U-Th-total Pb age of the uraninite inclusions that crystallized in zircon at 281 ± 2 Ma, which is consistent with the age of 278 ± 15 Ma obtained from the youngest cluster of U-Pb ages in the re-equilibrated high-U zircon domains. This study

Zircon U-Pb Age Distributions in Cogenetic Crystal-Rich Dacitic and Crystal-Poor Rhyolitic Members of Zoned Ignimbrites in the Southern Rocky Mountains by Chemical Abrasion Inductively-Coupled-Plasma Mass Spectrometry (CA-LA-ICP-MS).

NASA Astrophysics Data System (ADS)

Sliwinski, J.; Zimmerer, M. J.; Guillong, M.; Bachmann, O.; Lipman, P. W.

2015-12-01

The San Juan locus of the Southern Rocky Mountain Volcanic Field (SRMVF) in SW Colorado represents an erosional remnant of a mid-Tertiary (~37-23 Ma) ignimbrite flare up that produced some of the most voluminous ignimbrites on Earth. A key feature of many SRMVF ignimbrites is compositional zonation, with many volcanic units comprising both dacitic and rhyolitic horizons. Geochemical, field and petrographic evidence suggests that dacites and rhyolites are cogenetic. Here, we report U-Pb zircon ages by chemical abrasion inductively-coupled-plasma mass spectrometry (CA-LA-ICPMS) for rhyolitic and dacitic components in four units: the Bonanza, Rat Creek, Carpenter Ridge and Nelson Mountain Tuffs. All units show zircon age spectra that are either within analytical uncertainty of Ar/Ar ages or are appreciably older, indicating prolonged magma residence times (~500 ka) prior to eruption. Anomalously young Pb-loss zones in zircon have been largely removed by chemical abrasion. Older, inherited zircons and zircon cores (60-2000 Ma) are rare in all samples, suggesting limited assimilation of upper crustal Precambrian country rock or complete resorption during recharge events and magma chamber growth.

Opening the closed box: lattice diffusion in zircon?

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Alps to Apennines zircon roller coaster along the Adria microplate margin.

PubMed

Jacobs, J; Paoli, G; Rocchi, S; Ksienzyk, A K; Sirevaag, H; Elburg, M A

2018-02-09

We have traced the particle path of high-pressure metasedimentary rocks on Elba Island, Northern Apennines, with the help of a U-Pb-Hf detrital zircon study. One quarter of the analysed zircons are surprisingly young, 41-30 Ma, with a main age peak at ca. 32 Ma, indicating an unexpected early Oligocene maximum deposition age. These Oligocene ages with negative εHf indicate a volcanic source region in the central-southern Alps. Though young by geological means, these zircons record an extraordinary geodynamic history. They originated in a volcanic arc, during the convergence/collision of the the Adria microplate with Europe from ca. 65 to 30 Ma. Thereafter, the Oligocene zircons travelled ca. 400 km southward along the Adria margin and the accretionary prism to present-day Tuscany, where they were subducted to depths of at least 40 km. Shortly thereafter, they were brought to the surface again in the wake of hinge roll back of the Apennine subduction zone and the resulting rapid extensional exhumation. Such a zircon roller coaster requires a microplate that has back-to-back subduction zones with opposing polarities on two sides.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Chemical-abrasion SIMS dating of zircon from the Eocene Caetano caldera, Nevada

NASA Astrophysics Data System (ADS)

Colgan, J.; Watts, K. E.; John, D. A.; Henry, C. D.; Coble, M. A.; Vazquez, J. A.

2012-12-01

The Eocene Caetano caldera in northern Nevada formed during eruption of ~1100 km3 of crystal-rich rhyolite. Miocene extension cut the caldera into a set of fault blocks that expose minor pre-caldera volcanic rocks, two units of intracaldera Caetano Tuff up to 4 km thick, ash-flow tuff feeder dikes and ring-fracture intrusions, caldera collapse breccias, and post-collapse resurgent intrusions. Single-crystal 40Ar/39Ar sanidine dates on all parts of the caldera system overlap, yielding a 34.01 ± 0.05 Ma (n=17, Fish Canyon sanidine = 28.201 Ma) age for the eruption. 40Ar/39Ar dating also documents several preceding episodes of magmatism: 35.69 ± 0.06 Ma (sanidine, n =13) rhyolite dikes in the nearby Cortez gold district, 35.21 ± 0.18 Ma (plagioclase, n=1) andesite lava underlying Caetano Tuff, and a 38.90 ± 0.11 Ma (biotite, n=1), dacite dike in the northeastern caldera wall. Extensive U-Pb SHRIMP dating of zircon from both the Cortez dikes and all phases of the Caetano system suggests continuous magmatism from 40-34 Ma. However, all samples contain at least some—sometimes many—zircons with U-Pb ages younger than the 34.0 Ma argon age. To determine if anomalously young zircon ages are due to Pb-loss, we analyzed representative samples of the upper Caetano Tuff and the Redrock Canyon resurgent pluton with and without chemical abrasion to mitigate Pb-loss. Bulk zircon separates were annealed at 850°C for 48 hours, then chemically abraded with 10:1 HF/HNO3 vapor in a Parr bomb at 225°C for 8 hours, based on protocols outlined by Mattinson (2005). Both treated and untreated zircons from the same sample were mounted in epoxy and polished to their midsections, then imaged on the SEM using BSE and CL. The SHRIMP-RG at Stanford University was used to determine U-Pb ages and trace element concentrations in single spots for ~25 to 30 individual zircons per sample, using a round-robin procedure and two zircon age standards (R33 and 080) to monitor external precision

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

Refractory Materials of Zirconate. Part 2: Synthesis and some properties of strontium, zirconate, calcium zirconate and barium zirconate

NASA Technical Reports Server (NTRS)

Okubo, Tsutomo; Yonemochi, Osamu; Nakamura, Kazuo; Maeda, Minoru

1988-01-01

Chemical compounds SrZrO3, CaZrO3, and BaZrO3 were synthesized by solid reaction and arc fusion, and their properties examined. Results were as follows: (1) in the synthesis of CaZrO3 by solid reaction, ZrO2 solid solution with cubic form was produced, which then changed into CaZrO3; (2) the BaZrO3 was a cubic form and did not show any transformation, while SrZrO3 and CaZrO3 with an orthorhombic form transformed to a cubic form at high temperature; and (3) the solubility of BaZrO3 in acid and its vaporization rate at a high temperature were greater than those of zirconates.

Ablation article and method

NASA Technical Reports Server (NTRS)

Erickson, W. D.; Sullivan, E. M. (Inventor)

1973-01-01

An ablation article, such as a conical heat shield, having an ablating surface is provided with at least one discrete area of at least one seed material, such as aluminum. When subjected to ablation conditions, the seed material is ablated. Radiation emanating from the ablated seed material is detected to analyze ablation effects without disturbing the ablation surface. By providing different seed materials having different radiation characteristics, the ablating effects on various areas of the ablating surface can be analyzed under any prevailing ablation conditions. The ablating article can be provided with means for detecting the radiation characteristics of the ablated seed material to provide a self-contained analysis unit.

U-Pb zircon and CHIME monazite dating of granitoids and high-grade metamorphic rocks from the Eastern and Peninsular Thailand - A new report of Early Paleozoic granite

NASA Astrophysics Data System (ADS)

Kawakami, T.; Nakano, N.; Higashino, F.; Hokada, T.; Osanai, Y.; Yuhara, M.; Charusiri, P.; Kamikubo, H.; Yonemura, K.; Hirata, T.

2014-07-01

In order to understand the age and tectonic framework of Eastern to Peninsular Thailand from the viewpoint of basement (metamorphic and plutonic) geology, the LA-ICP-MS U-Pb zircon dating and the chemical Th-U-total Pb isochron method (CHIME) monazite dating were performed in the Khao Chao, Hub-Kapong to Pran Buri, and Khanom areas in Eastern to Peninsular Thailand. The LA-ICP-MS U-Pb zircon dating of the garnet-hornblende gneiss from the Khao Chao area gave 229 ± 3 Ma representing the crystallization age of the gabbro, and that of the garnet-biotite gneisses gave 193 ± 4 Ma representing the timing of an upper amphibolite facies metamorphism. The CHIME monazite dating of pelitic gneiss from the Khao Chao gneiss gave scattered result of 68 ± 22 Ma, due to low PbO content and rejuvenation of older monazite grains during another metamorphism in the Late Cretaceous to Tertiary time. The U-Pb ages of zircon from the Hua Hin gneissic granite in the Hub-Kapong to Pran Buri area scatter from 250 Ma to 170 Ma on the concordia. Granite crystallization was at 219 ± 2 Ma, followed by the sillimanite-grade regional metamorphism at 185 ± 2 Ma. Monazite in the pelitic gneiss from this area also preserves Early to Middle Jurassic metamorphism and rejuvenation by later contact metamorphism by non-foliated granite or by another fluid infiltration event in the Late Cretaceous to Tertiary time. The Khao Dat Fa granite from the Khanom area of Peninsular Thailand gave a U-Pb zircon age of 477 ± 7 Ma. This is the second oldest granite pluton ever reported from Thailand, and is a clear evidence for the Sibumasu block having a crystalline basement that was formed during the Pan-African Orogeny. The Khao Pret granite gives U-Pb zircon concordia age of 67.5 ± 1.3 Ma, which represents the timing of zircon crystallization from the granitic melt and accompanied sillimanite-grade contact metamorphism against surrounding metapelites and gneisses. Metamorphic rocks in the Doi Inthanon area

New Insights on the Recrystallization and New Growth of Extensively Radiation-damaged Zircon

NASA Astrophysics Data System (ADS)

Hanchar, J. M.; Schmitz, M. D.; Wirth, R.

2012-12-01

Approximately 10 grams of cm-sized nearly metamict zircon crystals from the Saranac Prospect in the Bancroft District of Ontario were combined by breaking into small pieces and then ground under ethanol to a fine powder with an agate mortar and pestle in order to make enough homogeneously mixed material for multiple powder X-Ray and diffraction scans, high-resolution transmission electron microscopy (HR-TEM) measurements, and chemical abrasion isotope dilution thermal ionization mass spectrometry (CA-TIMS). While these large zircon crystals ground to a powder have a larger surface area and not in the same physical state (i.e., brown and metamict) as what is typically analyzed in single zircon CA-ID-TIMS U-Pb analysis (clear euhedral grains), the physical and chemical changes that occur during the heat treatment used in CA-TIMS are thought to be similar processes. Aliquots of the ground zircon powder were annealed in situ using a Pt furnace in a powder diffractometer during which time simultaneous powder diffraction patterns were acquired starting at 25°C, at elevated temperature (from 500°C to 1400°C) at selected time intervals, and then again at 25°C. The powder X-ray diffraction results indicate that below ~900°C the recrystallization of the zircon powder commences but is incomplete, even after 36 hours, with diffuse low intensity diffraction peaks. At 1150°C the zircon powder shows significant recrystallization. At 1150°C, the recrystallization is essentially complete in less than one hour. Before heating the zircon powder samples consisted of clear, transparent to brown, translucent, complexly zoned fragments. After heating at 900°C the zircon powder retained a smaller percentage of clear or brown complexly zoned fragments, while the majority of material had transformed to oscillatory or irregularly zoned, dominantly white opaque microcrystalline fragments. The clear fragments were hypothesized to be preexisting original crystalline zircon, the brown

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Lithium granule ablation and penetration during ELM pacing experiments at DIII-D

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

Lunsford, R.; Bortolon, A.; Roquemore, A. L.

At DIII-D, lithium granules were radially injected into the plasma at the outer midplane to trigger and pace edge localized modes (ELMs). Granules ranging in size from 300 to 1000 microns were horizontally launched into H-mode discharges with velocities near 100 m/s, and granule to granule injection frequencies less than 500 Hz. While the smaller granules were only successful in triggering ELMs approximately 20% of the time, the larger granules regularly demonstrated ELM triggering efficiencies of greater than 80%. A fast visible camera looking along the axis of injection observed the ablation of the lithium granules. We used the durationmore » of ablation as a benchmark for a neutral gas shielding calculation, and approximated the ablation rate and mass deposition location for the various size granules, using measured edge plasma profiles as inputs. In conclusion, this calculation suggests that the low triggering efficiency of the smaller granules is due to the inability of these granules to traverse the steep edge pressure gradient region and reach the top of the pedestal prior to full ablation.« less

Lithium granule ablation and penetration during ELM pacing experiments at DIII-D

DOE PAGES

Lunsford, R.; Bortolon, A.; Roquemore, A. L.; ...

2016-05-25

At DIII-D, lithium granules were radially injected into the plasma at the outer midplane to trigger and pace edge localized modes (ELMs). Granules ranging in size from 300 to 1000 microns were horizontally launched into H-mode discharges with velocities near 100 m/s, and granule to granule injection frequencies less than 500 Hz. While the smaller granules were only successful in triggering ELMs approximately 20% of the time, the larger granules regularly demonstrated ELM triggering efficiencies of greater than 80%. A fast visible camera looking along the axis of injection observed the ablation of the lithium granules. We used the durationmore » of ablation as a benchmark for a neutral gas shielding calculation, and approximated the ablation rate and mass deposition location for the various size granules, using measured edge plasma profiles as inputs. In conclusion, this calculation suggests that the low triggering efficiency of the smaller granules is due to the inability of these granules to traverse the steep edge pressure gradient region and reach the top of the pedestal prior to full ablation.« less

Value of local electrogram characteristics predicting successful catheter ablation of left-versus right-sided accessory atrioventricular pathways by radiofrequency current.

PubMed

Lin, J L; Schie, J T; Tseng, C D; Chen, W J; Cheng, T F; Tsou, S S; Chen, J J; Tseng, Y Z; Lien, W P

1995-01-01

Despite similar guidance by local electrogram criteria, catheter ablation of right-sided accessory atrioventricular (AV) pathways by radiofrequency current has been less effective than that of left-sided ones. In order to elucidate the possible diversities in local electrosignal criteria, we systematically analyzed the morphological and timing characteristics of 215 bipolar local electrograms from catheter ablation sites of 65 left-sided accessory AV pathways and of 356 from those of 37 right-sided ones in 92 consecutive patients with Wolff-Parkinson-White syndrome or AV reentrant tachycardia incorporating concealed accessory AV pathways. After stepwise multivariate analysis, we selected the presence of a possible accessory pathway potential, local ventricular activation preceding QRS complex for 20 ms or more during ventricular insertion mapping, and the local retrograde ventriculoatrial (VA) continuity, local retrograde VA interval < or = 50 ms, electrogram stability (left-sided targets only), retrograde accessory pathway potential (right-sided targets only) during atrial insertion mapping, as independent local electrogram predictors for successful ablation of left- and right-sided accessory AV pathways. Combination of all local electrogram predictors could have moderate chance of success (80 and 51%) for the ventricular and atrial insertion ablation of left-sided accessory AV pathways, but only low probability of success (40% in ventricular insertion ablation) or very low sensitivity (12.5% in atrial insertion ablation) for right-sided ones. In conclusion, with the present approach, successful catheter ablation of right-sided accessory AV pathways, compared to left-sided ones, still necessitate a breakthrough in the precision mapping and the efficiency of energy delivery.

Trace-element record in zircons during exhumation from UHP conditions, North-East Greenland Caledonides

USGS Publications Warehouse

McClelland, W.C.; Gilotti, J.A.; Mazdab, F.K.; Wooden, J.L.

2009-01-01

Coesite-bearing zircon formed at ultrahigh-pressure (UHP) conditions share general characteristics of eclogite-facies zircon with trace-element signatures characterized by depleted heavy rare earth elements (HREE), lack of an Eu anomaly, and low Th/ U ratios. Trace-element signatures of zircons from the Caledonian UHP terrane in North-East Greenland were used to examine the possible changes in signature with age during exhumation. Collection and interpretation of age and trace-element analyses of zircon from three samples of quartzofeldspathic gneiss and two leucocratic intrusions were guided by core vs. rim zoning patterns as imaged by cathodoluminesence. Change from igneous to eclogite-facies metamorphic trace-element signature in protolith zircon is characterized by gradual depletion of HREE, whereas newly formed metamorphic rims have flat HREE patterns and REE concentrations that are distinct from the recrystallized inherited cores. The signature associated with eclogite-facies metamorphic zircon is observed in coesite-bearing zircon formed at 358 ?? 4 Ma, metamorphic rims formed at 348 ?? 5 Ma during the initial stages of exhumation, and metamorphic rims formed at 337 ?? 5 Ma. Zircons from a garnet-bearing granite emplaced in the neck of an eclogite boudin and a leucocratic dike that cross-cuts amphibolite-facies structural fabrics have steeply sloping HREE patterns, variably developed negative Eu anomalies, and low Th/U ratios. The granite records initial decompression melting and exhumation at 347 ?? 2 Ma and later zircon rim growth at 329 ?? 5. The leucocratic dike was likely emplaced at amphibolite-facies conditions at 330 ?? 2 Ma, but records additional growth of compositionally similar zircon at 321 ??2 Ma. The difference between the trace-element signature of metamorphic zircon in the gneisses and in part coeval leucocratic intrusions indicates that the zircon signature varies as a function of lithology and context, thus enhancing its ability to aid in

In situ sulfur isotopes (δ(34)S and δ(33)S) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS.

PubMed

Fu, Jiali; Hu, Zhaochu; Zhang, Wen; Yang, Lu; Liu, Yongsheng; Li, Ming; Zong, Keqing; Gao, Shan; Hu, Shenghong

2016-03-10

The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis

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

NASA Astrophysics Data System (ADS)

Schaltegger, U.; Wotzlaw, J. F.

2014-12-01

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

Effects of linear ablation at the isthmus between the tricuspid annulus and inferior vena cava for atrial flutter on autonomic nervous activity: analysis of heart rate variability.

PubMed

Li, Aiyan; Kuga, Keisuke; Suzuki, Akihiro; Endo, Masae; Niho, Bumpei; Enomoto, Mami; Kanemoto, Miyako; Yamaguchi, Iwao

2002-01-01

Heart rate is largely affected by the autonomic nervous system. However, little is known about the anatomic pathway of autonomic nerve fibers innervating the sinus node. The present study: (1) evaluates the effects of cavotricuspid isthmus ablation for common atrial flutter (AFL) on autonomic nervous function by using heart rate variability analysis, and (2) investigates the distribution of autonomic nerve pathways innervating the sinus node. Twelve patients with paroxysmal common atrial flutter who maintained sinus rhythm both before and after radiofrequency ablation were selected for the study. Holter ambulatory recordings were performed before and after (2.3 +/- 1.0 days) radiofrequency ablation of cavotricuspid isthmus. Heart rate and time domain (SDANN, rMSSD, pNN50) and frequency domain (low frequency (LF), high frequency (HF), LF/HF) analysis of heart rate variability were compared before and after ablation. Mean heart rate did not change significantly after ablation (59 +/- 6 vs 61 +/- 9 beats/min); parasympathetic indices of heart rate variability (SDANN, rMSSD, pNN50, HF) did not change significantly (110 +/- 37 vs 117 +/- 20 ms; 32 +/- 21 vs 28 +/- 9 ms; 4.8 +/- 0.9 vs 4.7 +/- 0.71n(ms2)); and sympathetic indices of heart rate variability (LF/HF) did not change significantly (1.1 +/- 0.2 vs 1.2 +/- 0.1). Cavotricuspid isthmus ablation for atrial flutter did not significantly change heart rate and heart rate variability because parasympathetic and sympathetic fibers innervating the sinus node are scarce in this region.

Characterization Of Nuclear Materials Using Time-Of-Flight ICP-MS

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

Buerger, Stefan; Riciputi, Lee R; Bostick, Debra A

2006-01-01

The investigation of illicit trafficking of nuclear materials, nuclear safeguards analysis, and non-proliferation control requires sensitive and isotope-selective detection methods to gain crucial nuclear forensic information like isotope 'fingerprints' and multi-element signatures. The advantage of time-of-flight (TOF) mass spectrometry - quasi-simultaneous multi-mass analysis - combined with an inductively coupled plasma (ICP) ion source provides an analytical instrument with multi-element and multi-isotope capability and good detection limits. A TOF-ICP-MS system thus appears to be an advantageous choice for the investigation and characterization of nuclear materials. We present here results using a GBC OptiMass 8000 time-of-flight ICP-MS for the isotope screening ofmore » solid samples by laser ablation and the multi-element determination of impurities in uranium ore concentrates using matrix matched standards. A laser ablation system (New Wave Research, UP 213) coupled to the TOF-ICP-MS instrument has been used to optimize the system for analysis of non-radioactive metal samples of natural isotopic composition for a variety of elements including Cu, Sr, Zr, Mo, Cd, In, Ba, Ta, W, Re, Pt, and Pb in pure metals, alloys, and glasses to explore precision, accuracy, and detection limits. Similar methods were then applied to measure uranium. When the laser system is optimized, no mass bias correction is required. Precision and accuracy for the determination of the isotopic composition is typically 1 - 3% for elemental concentrations of as little as 50 ppm in the matrix, with no requirement for sample preparation. The laser ablation precision and accuracy are within ~10x of the instrumental limits for liquid analysis (0.1%). We have investigated the capabilities of the TOF-ICP-MS for the analysis of impurities in uranium matrices. Matrix matching has been used to develop calibration curves for a range of impurities (alkaline, earth-alkaline, transition metals, and

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Paleozoic and Paleoproterozoic Zircon in Igneous Xenoliths Assimilated at Redoubt Volcano, Alaska

NASA Astrophysics Data System (ADS)

Bacon, C. R.; Vazquez, J. A.; Wooden, J. L.

2010-12-01

Historically active Redoubt Volcano is a basalt-to-dacite cone constructed upon the Jurassic-early Tertiary Alaska-Aleutian Range batholith. New SHRIMP-RG U-Pb age and trace-element concentration results for zircons from gabbroic xenoliths and crystal-rich andesitic mush from a late Pleistocene pyroclastic deposit indicate that ~310 Ma and ~1865 Ma igneous rocks underlie Redoubt at depth. Two gabbros have sharply terminated prismatic zircons that yield ages of ~310 Ma. Zircons from a crystal mush sample are overwhelmingly ~1865 Ma and appear rounded due to incomplete dissolution. Binary plots of element concentrations or ratios show clustering of data for ~310-Ma grains and markedly coherent trends for ~1865-Ma grains; e.g., ~310-Ma grains have higher Eu/Eu* than most of the ~1865-Ma grains, the majority of which form a narrow band of decreasing Eu/Eu* with increasing Hf content which suggests that ~1865-Ma zircons come from igneous source rocks. It is very unlikely that detrital zircons from a metasedimentary rock would have this level of homogeneity in age and composition. One gabbro contains abundant ~1865 Ma igneous zircons, ~300-310 Ma fluid-precipitated zircons characterized by very low U and Th concentrations and Th/U ratios, and uncommon ~100 Ma zircons. We propose that (1) ~310 Ma gabbro xenoliths from Redoubt Volcano belong to the same family of plutons dated by Aleinikoff et al. (USGS Circular 1016, 1988) and Gardner et al. (Geology, 1988) located ≥500 km to the northeast in basement rocks of the Wrangellia and Alexander terranes and (2) ~1865 Ma zircons are inherited from igneous rock, potentially from a continental fragment that possibly correlates with the Fort Simpson terrane or Great Bear magmatic zone of the Wopmay Orogen of northwestern Laurentia. Possibly, elements of these Paleoproterozoic terranes intersected the Paleozoic North American continental margin where they may have formed a component of the basement to the Wrangellia

Detrital Zircon Geochronology of Cretaceous and Paleogene Strata Across the South-Central Alaskan Convergent Margin

USGS Publications Warehouse

Bradley, Dwight; Haeussler, Peter J.; O'Sullivan, Paul; Friedman, Rich; Till, Alison; Bradley, Dan; Trop, Jeff

2009-01-01

Ages of detrital zircons are reported from ten samples of Lower Cretaceous to Paleogene metasandstones and sandstones from the Chugach Mountains, Talkeetna Mountains, and western Alaska Range of south-central Alaska. Zircon ages are also reported from three igneous clasts from two conglomerates. The results bear on the regional geology, stratigraphy, tectonics, and mineral resource potential of the southern Alaska convergent margin. Chugach Mountains - The first detrital zircon data are reported here from the two main components of the Chugach accretionary complex - the inboard McHugh Complex and the outboard Valdez Group. Detrital zircons from sandstone and two conglomerate clasts of diorite were dated from the McHugh Complex near Anchorage. This now stands as the youngest known part of the McHugh Complex, with an inferred Turonian (Late Cretaceous) depositional age no older than 91-93 Ma. The zircon population has probability density peaks at 93 and 104 Ma and a smattering of Early Cretaceous and Jurassic grains, with nothing older than 191 Ma. The two diorite clasts yielded Jurassic U-Pb zircon ages of 179 and 181 Ma. Together, these findings suggest a Mesozoic arc as primary zircon source, the closest and most likely candidate being the Wrangellia composite terrane. The detrital zircon sample from the Valdez Group contains zircons as young as 69 and 77 Ma, consistent with the previously assigned Maastrichtian to Campanian (Late Cretaceous) depositional age. The zircon population has peaks at 78, 91, 148, and 163 Ma, minor peaks at 129, 177, 330, and 352 Ma, and no concordant zircons older than Devonian. A granite clast from a Valdez Group conglomerate yielded a Triassic U-Pb zircon age of 221 Ma. Like the McHugh Complex, the Valdez Group appears to have been derived almost entirely from Mesozoic arc sources, but a few Precambrian zircons are also present. Talkeetna Mountains - Detrital zircons ages were obtained from southernmost metasedimentary rocks of the

Zircon Messengers Reveal the Age and History of Great Basin Crust, Kern Mountains, Nevada

NASA Astrophysics Data System (ADS)

Gottlieb, E. S.; Miller, E. L.; Wooden, J. L.

2011-12-01

Results of SHRIMP-RG analyses of complexly zoned zircons from muscovite-bearing granitic rocks exposed in the Kerns Mountains of East-Central Nevada constrain the timing, duration, and loci of zircon growth within the interior of the U.S. Cordillera during Late Cretaceous through Eocene time. The Kern Mountains are an exhumed block of greenschist to amphibolite facies metamorphosed miogeoclinal rocks that were pervasively intruded by the Late Cretaceous Tungstonia granite pluton and the Eocene Skinner Canyon and Uvada plutons (Best et al., 1974). Euhedral zircons separated from a coarse-grained (2-3 cm) muscovite-bearing phase of the Tungstonia pluton exhibit complex cathodeluminescence (CL) zonation. Sub-angular to sub-rounded cores with highly variable CL are overgrown by oscillatory-zoned zircon which in turn is rimmed by dark CL zircon (U>5000 ppm). A weighted mean Pb/U age of 70.2±0.9 Ma (n=20, MSWD=2.5) obtained from the oscillatory-zoned zircon coincides with the end of Cretaceous peak metamorphism at shallow crustal levels. Pb/U ages from core zones (n=18) predominantly are 0.9-1.4 Ga (n=11; 7 of which <15% discordant) or 2.4-2.7 Ga (n=5; 1 of which <15% discordant), consistent with ages of detrital zircons within the Late Proterozoic McCoy Creek Group exposed in adjacent ranges. A previously undated muscovite-bearing dike in Skinner Canyon yielded a texturally complex population of subhedral zircon grains. CL imaging of these grains reveals fragmental, ghost-like cores surrounded by irregularly shaped overgrowth zones with diffuse boundaries which are rimmed by oscillatory-zoned zircon. Both oscillatory zoned and gradational rim areas (n=32) yielded Late Cretaceous to Eocene ages. Twelve spots define the age of intrusion at 41.7±0.3 Ma (MSWD=1.8), consistent with the local onset of Eocene magmatism. An older period of zircon growth from ~75-45 Ma, coincident with the proposed duration of the Laramide shallow slab, is defined by zircon with flat to

Alpha-Recoil Damage Annealing Effecfs on Zircon Crystallinity and He Diffusivity: Improving Damage-Diffusivity Models

NASA Astrophysics Data System (ADS)

Thurston, O. G.; Guenthner, W.; Garver, J. I.

2017-12-01

The effects of radiation damage on He diffusion in zircon has been a major research focus in thermochronology over the past decade. In the zircon-He system, alpha-recoil damage effects He diffusivity in two ways: a decrease in He diffusivity at low radiation damage levels, and an increase in He diffusivity at high radiation damage levels. The radiation damage accumulation process within zircon is well understood; however, the kinetics of annealing of alpha-recoil damage at geologic timescales as they pertain to damage-diffusivity models, and for metamict zircon (i.e. transition from crystalline to amorphous glass via damage accumulation), has not been well constrained. This study aims to develop a more complete model that describes the annealing kinetics for zircon grains with a broad range of pre-annealing, alpha-induced radiation damage. A suite of zircon grains from the Lucerne pluton, ME were chosen for this study due to their simple thermal history (monotonic cooling), notable range of effective uranium (eU, eU = [U] +0.235*[Th]) (15 - 34,239 ppm eU), and large range of radiation damage as measured by Raman shift from crystalline (>1005 cm-1) to metamict (<1000 cm-1). The zircon grains selected represent the full range of eU and radiation damage present in the pluton. The zircon grains were first mapped for overall crystallinity using Raman spectroscopy, then annealed at different time-temperature (t-T) schedules from 1 hr to 24 hrs at temperatures ranging from 700-1100 °C, followed by remapping with Raman spectroscopy to track the total Raman shift for each t-T step. The temperature window selected is at the "roll-over" point established in prior studies (Zhang et al., 2000), at which most laboratory annealing occurs. Our data show that high radiation damage zircon grains show larger Raman shifts than low radiation damage zircon grains when exposed to the same t-T step. The high damage zircon grains typically show a Raman shift of 4 cm-1 toward crystalline

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Point defects in crystalline zircon (zirconium silicate), ZrSiO4: electron paramagnetic resonance studies

NASA Astrophysics Data System (ADS)

Tennant, W. C.; Claridge, R. F. C.; Walsby, C. J.; Lees, N. S.

This article outlines the present state of knowledge of paramagnetic defects in crystalline zircon as obtained mainly, but not exclusively, from electron paramagnetic resonance (EPR) studies in crystalline zircon (zirconium silicate, ZrSiO4). The emphasis is on single-crystal studies where, in principle, unambiguous analysis is possible. Firstly, the crystallography of zircon is presented. Secondly, the relationships between available crystal-site symmetries and the symmetries of observed paramagnetic species in zircon, and how these observations lead to unambiguous assignments of point-group symmetries for particular paramagnetic species are detailed. Next, spin-Hamiltonian (SH) analysis is discussed with emphasis on the symmetry relationships that necessarily exist amongst the Laue classes of the crystal sites in zircon, the paramagnetic species occupying those sites and the SH itself. The final sections of the article then survey the results of EPR studies on zircon over the period 1960-2002.

First U-Pb geochronology on detrital zircons from Early-Middle Cambrian strata of the Torgau-Doberlug Syncline (eastern Germany) and palaeogeographic implications

NASA Astrophysics Data System (ADS)

Abubaker, Atnisha; Hofmann, Mandy; Gärtner, Andreas; Linnemann, Ulf; Elicki, Olaf

2017-10-01

LA-ICP-MS U-Pb data from detrital zircons of the Ediacaran to Cambrian siliciclastic sequence of the Torgau-Doberlug Syncline (TDS, Saxo-Thuringia, Germany) are reported for the first time. The majority of 203 analysed zircon grains is Proterozoic with minor amount of Archean and Palaeozoic grains. The U-Pb ages fall into three groups: 2.8-2.4 Ga (3%), Neoarchean to earliest Palaeoproterozoic; 2.3-1.6 Ga (46%), early to late Palaeoproterozoic; 1.0-0.5 Ga (47%), Neoproterozoic to Cambrian. This age distribution is typical for the West African Craton as the source area and for Cadomian orogenic events in northwestern Gondwana. The samples show an age gap between 1.6 and 1.0 Ga, which is characteristic for West African provenance and diagnostic in distinguishing this unit from East Avalonia and Baltica. The dataset shows clusters of Palaeoproterozoic ages at 2.2-1.7 Ga, that is typical for western Gondwana, which was affected by abundant magmatic intrusions (ca. 2.2-1.8 Ga) during the Eburnean orogeny (West African craton). Neoarchean zircon ages (3%) point to recycling of magmatic rocks formed during the Liberian and Leonian orogenies. Ediacaran to earliest Cambrian rocks of the TDS originated in an active margin regime of the Gondwanan shelf. The following early Palaeozoic overstep sequence was deposited within rift settings that reflects instability of the West-Gondwanan shelf and the separation of terranes from Ordovician onward. The results of this study demonstrate distinct northwestern African provenance of the Cambrian siliciclastics of the TDS. Due to Th-U ratios from concordant zircon analysis, igneous origin from felsic melts is concluded as the source of these grains.

Geochronological study of zircons from continental crust rocks in the Frido Unit (southern Apennines)

NASA Astrophysics Data System (ADS)

Laurita, Salvatore; Prosser, Giacomo; Rizzo, Giovanna; Langone, Antonio; Tiepolo, Massimo; Laurita, Alessandro

2015-01-01

Zircon crystals have been separated from gneisses and metagranitoids of the Pollino area (southern Apennines) in order to unravel the origin of these crustal slices within the ophiolite-bearing Frido Unit. The morphology of the zircon has been investigated by SEM, and the internal structure was revealed by cathodoluminescence. Data obtained by U/Pb dating have been used to deduce the age and significance of the different crystallization stages of zircon, connected to the evolutionary stages of the continental crust (Late Paleozoic-Early Mesozoic). Zircons in gneisses are characterized by inherited cores of magmatic origin, bordered by metamorphic rims. Inherited zircons generally show Paleoproterozoic to Ordovician ages, indicating the provenance of the sedimentary protolith from different sources. The exclusive presence of Late Neoproterozoic zircon cores in leucocratic gneisses may suggest a different magmatic source possibly connected to Pan-African events. Late Carboniferous-Early Permian ages are found mainly in zircon rims of metamorphic origin. These are similar to the emplacement ages of protolith of the metagranites in the middle crust portion. Late Carboniferous-Early Permian metamorphism and magmatism testify the extensional collapse of the Hercynian belt, recorded in European, particularly, in the Corsica-Sardinia block and in Calabria. Late Permian-Triassic ages have been detected in zircon rims from gneisses and metagranitoids. These younger ages appear related to deformation and emplacement of albite-quartz veins in both lithologies, and are related to an extensional episode predating the Middle Triassic to Middle Jurassic rifting in the Tethyan domain, followed by Middle to Late Jurassic spreading.

Origin of northern Gondwana Cambrian sandstone revealed by detrital zircon SHRIMP dating

USGS Publications Warehouse

Avigad, D.; Kolodner, K.; McWilliams, M.; Persing, H.; Weissbrod, T.

2003-01-01

Voluminous Paleozoic sandstone sequences were deposited in northern Africa and Arabia following an extended Neoproterozoic orogenic cycle that culminated in the assembly of Gondwana. We measured sensitive high-resolution ion microprobe (SHRIMP) U-Pb ages of detrital zircons separated from several Cambrian units in the Elat area of southern Israel in order to unravel their provenance. This sandstone forms the base of the widespread siliciclastic section now exposed on the periphery of the Arabian-Nubian shield in northeastern Africa and Arabia. Most of the detrital zircons we analyzed yielded Neoproterozoic concordant ages with a marked concentration at 0.55–0.65 Ga. The most likely provenance of the Neoproterozoic detritus is the Arabian-Nubian shield; 0.55–0.65 Ga was a time of posttectonic igneous activity, rift-related volcanism, and strike-slip faulting there. Of the zircons, 30% yielded pre-Neoproterozoic ages grouped at 0.9–1.1 Ga (Kibaran), 1.65–1.85 Ga, and 2.45–2.7 Ga. The majority of the pre-Neoproterozoic zircons underwent Pb loss, possibly as a consequence of the Pan-African orogeny resetting their provenance. Rocks of the Saharan metacraton and the southern Afif terrane in Saudi Arabia (∼1000 km south of Elat) are plausible sources of these zircons. Kibaran basement rocks are currently exposed more than 3000 km south of Elat (flanking the Mozambique belt), but the shape of the detrital zircons of that age and the presence of feldspar in the host sandstone are not fully consistent with such a long-distance transport. Reworking of Neoproteorozoic glacial detritus may explain the presence of Kibaran detrital zircons in the Cambrian of Elat, but the possibility that the Arabian-Nubian shield contains Kibaran rocks (hitherto not recognized) should also be explored.

The age of unusual xenogenic zircons from Yakutian kimberlites

NASA Astrophysics Data System (ADS)

Vladykin, N. V.; Lepekhina, E. A.

2009-12-01

Several spindle-shaped grains of zircon, which have a small size (<0.25 mm) and a distinct purplish pink coloration were found in the crushed samples of kimberlites from the Aykhal, Komsomolskaya-Magnitnaya, Botuobinskaya (Siberian platform), and Nyurbinskaya (Yakutia) pipes and olivine lamproites of the Khani massif (West Aldan). U-Pb SHRIMP II zircon dating performed at the VSEGEI Center for Isotopic Research yielded the ages of 1870-1890 Ma for the pipes of the Western province (Aykhal and Komsomolskaya) and 2200-2750 Ma for the pipes of the eastern province (Nyurbinskaya and Botuobinskaya), which allowed us to consider these zircons to be xenogenic to kimberlites. Although these zircons resemble in their age and color those from the granulite xenoliths in the Udachnaya pipe [2], no other granulite minerals are found there. Thus, major geological events in the mantle and lower crust, which led to the formation of zircon-bearing rocks, happened at 1800-1900 Ma in the northern part of the kimberlite province, whereas in the Eastern part of the province (Nakyn field) these events were much older (2220-2700 Ma). It is known that the period of 1800-1900 Ma in the Earth’s history was accompanied by intense tectonic movements and widespread alkaline-carbonatite magmatism. This magmatism was related to plume activity responsible for overheating the large portions of the mantle to the temperatures at which some diamonds in mantle rocks would burn (northern part of the kimberlite province). In the Nakyn area, the mantle underwent few or no geological processes at that time, and perhaps for this reason this area hosts more diamondiferous kimberlites. The age of olivine lamproites from the Khani massif is 2672-2732 Ma. Thus, these are some of the world’s oldest known K-alkaline rocks.

A study of processing parameters in thermal-sprayed alumina and zircon mixtures

NASA Astrophysics Data System (ADS)

Li, Y.; Khor, K. A.

2002-06-01

A method of plasma spraying of alumina and zircon mixtures to form ZrO2-mullite composites has been proposed and developed. The feedstock is prepared by a combination of mechanical alloying, which allows formation of fine-grained, homogeneous solid-solution mixtures, followed by plasma spheroidization that yields rapid solidified microstructures and enhanced compositional homogeneity. The effects of ball-milling duration and milling media were studied. It was found that zirconia is a more efficient milling media and that increasing milling duration enhanced the dissociation of zircon. Flame spray and plasma spray processes were used to spheroidize the spray-dried powders. The temperature of the flame spray was found to be insufficient to melt the powders completely. The processing parameters of the plasma spray played an important role in zircon decomposition and mullite formation. Increasing the arc current or reducing secondary gas pressure caused more zircon to decompose and more mullite to form after heat treatment at 1200 °C for 3 h. Dissociation of zircon and the amount of mullite for med can be enhanced significantly when using the more efficient, computerized plasma-spraying system and increasing the ball-milling duration from 4 to 8 h.

A Further Investigation of the Exceptional Zircon Aggregate in Lunar Thin Section 73235,82

NASA Technical Reports Server (NTRS)

Pidgeon, R. T.; Nemchin, a. A.; Meyer, C.

2005-01-01

Introduction: Smith et al. described an exceptional zircon assemblage in thin section 82 from lunar breccia 73235 which, in transmitted light, resembles a cluster of pomegranate seeds, situated in a clast dominated by bytownite (Fig.1). They reported that high-contrast back-scattered electron (BSE) images of the zircon assemblage clearly show an overgrowth around most of the crystals. Most significantly these authors reported that the age of the rims of ca 4.18Ga is 120 million years younger than age of the interiors, dated at ca 4.31Ga. Smith et al. concluded that ca 4.31 billion years ago a relatively large (500+micron) zircon crystallized within a clast of Ca rich plagioclase. The zircon was fractured into numerous smaller crystals and was subsequently overgrown by a second generation of zircon at approximately 4.18Ga.

Nonequilibrium Ablation of Phenolic Impregnated Carbon Ablator

NASA Technical Reports Server (NTRS)

Milos, Frank S.; Chen, Yih K.; Gokcen, Tahir

2012-01-01

In previous work, an equilibrium ablation and thermal response model for Phenolic Impregnated Carbon Ablator was developed. In general, over a wide range of test conditions, model predictions compared well with arcjet data for surface recession, surface temperature, in-depth temperature at multiple thermocouples, and char depth. In this work, additional arcjet tests were conducted at stagnation conditions down to 40 W/sq cm and 1.6 kPa. The new data suggest that nonequilibrium effects become important for ablation predictions at heat flux or pressure below about 80 W/sq cm or 10 kPa, respectively. Modifications to the ablation model to account for nonequilibrium effects are investigated. Predictions of the equilibrium and nonequilibrium models are compared with the arcjet data.

Evaluation of thermometric monitoring for intradiscal laser ablation in an open 1.0 T MR scanner.

PubMed

Wonneberger, Uta; Schnackenburg, Bernhard; Wlodarczyk, Waldemar; Rump, Jens; Walter, Thula; Streitparth, Florian; Teichgräber, Ulf Karl Mart

2010-01-01

The purpose of this study was to evaluate different methods of magnetic resonance thermometry (MRTh) for the monitoring of intradiscal laser ablation therapy in an open 1.0 Tesla magnetic resonance (MR) scanner. MRTh methods based on the two endogenous MR temperature indicators of spin-lattice relaxation time T1 and water proton resonance frequency (PRF) shift were optimised and compared in vitro. For the latter, we measured the effective spin-spin relaxation times T2* in intervertebral discs of volunteers. Then we compared four gradient echo-based imaging techniques to monitor laser ablations in human disc specimens. Criteria of assessment were outline of anatomic detail, immunity against needle artefacts, signal-to-noise ratio (SNR) and accuracy of the calculated temperature. T2* decreased in an inverse and almost linear manner with the patients' age (r = 0.9) from 70 to 30 ms (mean of 49 ms). The optimum image quality (anatomic details, needle artefacts, SNR) and temperature accuracy (+/-1.09 degrees C for T1-based and +/-1.11 degrees C for PRF-based MRTh) was achieved with a non-spoiled gradient-echo sequence with an echo time of TE = 10 ms. Combination of anatomic and thermometric non-invasive monitoring of laser ablations in the lumbar spine is feasible. The temperature accuracy of the investigated T1- and PRF-based MRTh methods in vitro is high enough and promises to be reliable in vivo as well.

Theoretical modeling of zircon's crystal morphology according to data of atomistic calculations

NASA Astrophysics Data System (ADS)

Gromalova, Natalia; Nikishaeva, Nadezhda; Eremin, Nikolay

2017-04-01

Zircon is an essential mineral that is used in the U-Pb dating. Moreover, zircon is highly resistant to radioactive exposure. It is of great interest in solving both fundamental and applied problems associated with the isolation of high-level radioactive waste. There is significant progress in forecasting of the most energetically favorable crystal structures at the present time. Unfortunately, the theoretical forecast of crystal morphology at high technological level is under-explored nowadays, though the estimation of crystal equilibrium habit is extremely important in studying the physical and chemical properties of new materials. For the first time, the thesis about relation of the equilibrium shape of a crystal with its crystal structure was put forward in the works by O.Brave. According to it, the idealized habit is determined in the simplest case by a correspondence with the reticular densities Rhkl of individual faces. This approach, along with all subsequent corrections, does not take into account the nature of atoms and the specific features of the chemical bond in crystals. The atomistic calculations of crystal surfaces are commonly performed using the energetic characteristics of faces, namely, the surface energy (Esurf), which is a measure of the thermodynamic stability of the crystal face. The stable crystal faces are characterized by small positive values of Esurf. As we know from our previous research (Gromalova et al.,2015) one of the constitutive factors affecting the value of the surface energy in calculations is a choice of potentials model. In this regard, we studied several sets of parameters of atomistic interatomic potentials optimized previously. As the first test model («Zircon 1») were used sets of interatomic potentials of interaction Zr-O, Si-O and O-O in the form of Buckingham potentials. To improve playback properties of zircon additionally used Morse potential for a couple of Zr-Si, as well as the three-particle angular harmonic

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Detrital zircon geochronology of quartzose metasedimentary rocks from parautochthonous North America, east-central Alaska

USGS Publications Warehouse

Dusel-Bacon, Cynthia; Holm-Denoma, Christopher S.; Jones, James V.; Aleinikoff, John N.; Mortensen, James K.

2017-01-01

We report eight new U-Pb detrital zircon ages for quartzose metasedimentary rocks from four lithotectonic units of parautochthonous North America in east-central Alaska: the Healy schist, Keevy Peak Formation, and Sheep Creek Member of the Totatlanika Schist in the northern Alaska Range, and the Butte assemblage in the northwestern Yukon-Tanana Upland. Excepting 1 of 3 samples from the Healy schist, all have dominant detrital zircon populations of 1.9–1.8 Ga and a subordinate population of 2.7–2.6 Ga. Three zircons from Totatlanika Schist yield the youngest age of ca. 780 Ma. The anomalous Healy schist sample has abundant 1.6–0.9 Ga detrital zircon, as well as populations at 2.0–1.8 Ga and 2.7–2.5 Ga that overlap the ages from the rest of our samples; it has a minimum age population of ca. 1007 Ma.Detrital zircon age populations from all but the anomalous sample are statistically similar to those from (1) other peri-Laurentian units in east-central Alaska; (2) the Snowcap assemblage in Yukon, basement of the allochthonous Yukon-Tanana terrane; (3) Neoproterozoic to Ordovician Laurentian passive margin strata in southern British Columbia, Canada; and (4) Proterozoic Laurentian Sequence C strata of northwestern Canada. Recycling of zircon from the Paleoproterozoic Great Bear magmatic zone in the Wopmay orogen and its Archean precursors could explain both the Precambrian zircon populations and arc trace element signatures of our samples. Zircon from the anomalous Healy schist sample resembles that in Nation River Formation and Adams Argillite in eastern Alaska, suggesting recycling of detritus in those units.

Record of Hybridization Preserved in Zircon, Aztec Wash Pluton, NV

NASA Astrophysics Data System (ADS)

Bromley, S. A.; Miller, C. F.; Claiborne, L. L.; Wooden, J. L.; Mazdab, F. K.

2007-12-01

The mid-Miocene Aztec Wash pluton comprises a smaller granite zone and a larger, highly heterogeneous zone in which evidence for interaction between basaltic and granitic magmas is ubiquitous. Granitic rocks in both zones show textural and compositional evidence for crystal accumulation and melt fractionation. In the heterogeneous zone, basalts have chilled, crenulate margins against granitic rocks, and there is widespread evidence for mechanical contamination of each lithology (coarse resorbed alkali feldspar in fine-grained mafic rock; mafic enclaves in granite). "Grey rocks" of intermediate composition are exposed on dm to 100's of m-scale as enclaves, pods, and initially subhorizontal sheets. They are variable texturally, but most are dominantly fine- grained and equigranular. Textures of grey rocks are consistent with rapid solidification from melt-rich magma, and, in combination with isotopic compositions intermediate between felsic and mafic rocks of the pluton, suggest an origin by near-complete homogenization of a hybrid melt (Bleick et al. 2005; Ericksen 2005). The elemental chemistry of zircon preserves information about the evolving magmatic environment in which it was hosted (Claiborne et al., 2006). Owing to its slow dissolution rate, it has the potential to survive periods of undersaturation with only partial resorption. Thus, it may record drastic shifts in T and melt chemistry that would accompany mafic-felsic hybridization. We are investigating zircon zoning patterns by cathodoluminescence (CL) and elemental compositions by SHRIMP-RG to evaluate the record of processes that they preserve. Temperatures of zircon growth are estimated using Ti-in-zircon thermometry (Watson et al. 2006), assuming a(TiO2) of ca. 0.7 (sphene +/-ilmenite are ubiquitous). Zircons from the granite zone yield estimated T's of 700-860 C, whereas those from grey rocks range from 710- 910 C. While both granite and grey zircon populations show dramatic T variations among and

Effect of pressure on Zircon's (ZrSiO4) Raman active modes: a first-principles study

NASA Astrophysics Data System (ADS)

Sheremetyeva, Natalya; Cherniak, Daniele; Watson, Bruce; Meunier, Vincent

Zircon is a mineral commonly found in the Earth crust. Its remarkable properties have given rise to considerable attention. This includes possible inclusion of radioactive elements in natural samples, which allows for geochronological investigations. Subsequently, Zircon was proposed as possible host material for radioactive waste management. Internal radiation damage in zircon leads to the destruction of its crystal structure (an effect known as metamictization) which is subject to ongoing research. Recently, the effect of pressure and temperature on synthetic zircon has been analyzed experimentally using Raman spectroscopy which led to the calibration of zircon as a pressure sensor in diamond-anvil cell experiments. While there have been a number of theoretical studies, the effect of pressure on the Raman active modes of zircon has not been investigated theoretically. Here we present a first-principles pressure calibration of the Raman active modes in Zircon employing density-functional theory (DFT). We find excellent quantitative agreement of the slopes ∂ω / ∂P with the experimental ones and are able to rationalize the ω vs. P behavior based on the details of the vibrational modes.

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

B cell depletion therapy ameliorates autoimmune disease through ablation of IL-6–producing B cells

PubMed Central

Shen, Ping; Brown, Sheila; Lampropoulou, Vicky; Roch, Toralf; Lawrie, Sarah; Fan, Boli; O’Connor, Richard A.; Anderton, Stephen M.; Bar-Or, Amit; Fillatreau, Simon; Gray, David

2012-01-01

B cells have paradoxical roles in autoimmunity, exerting both pathogenic and protective effects. Pathogenesis may be antibody independent, as B cell depletion therapy (BCDT) leads to amelioration of disease irrespective of autoantibody ablation. However, the mechanisms of pathogenesis are poorly understood. We demonstrate that BCDT alleviates central nervous system autoimmunity through ablation of IL-6–secreting pathogenic B cells. B cells from mice with experimental autoimmune encephalomyelitis (EAE) secreted elevated levels of IL-6 compared with B cells from naive controls, and mice with a B cell–specific IL-6 deficiency showed less severe disease than mice with wild-type B cells. Moreover, BCDT ameliorated EAE only in mice with IL-6–sufficient B cells. This mechanism of pathogenesis may also operate in multiple sclerosis (MS) because B cells from MS patients produced more IL-6 than B cells from healthy controls, and this abnormality was normalized with B cell reconstitution after Rituximab treatment. This suggests that BCDT improved disease progression, at least partly, by eliminating IL-6–producing B cells in MS patients. Taking these data together, we conclude that IL-6 secretion is a major mechanism of B cell–driven pathogenesis in T cell–mediated autoimmune disease such as EAE and MS. PMID:22547654

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

Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

2017-04-01

In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

Ancient xenocrystic zircon in young volcanic rocks of the southern Lesser Antilles island arc

NASA Astrophysics Data System (ADS)

Rojas-Agramonte, Yamirka; Williams, Ian S.; Arculus, Richard; Kröner, Alfred; García-Casco, Antonio; Lázaro, Concepción; Buhre, Stephan; Wong, Jean; Geng, Helen; Echeverría, Carlos Morales; Jeffries, Teresa; Xie, Hangqian; Mertz-Kraus, Regina

2017-10-01

The Lesser Antilles arc is one of the best global examples in which to examine the effects of the involvement of subducted sediment and crustal assimilation in the generation of arc crust. Most of the zircon recovered in our study of igneous and volcaniclastic rocks from Grenada and Carriacou (part of the Grenadines chain) is younger than 2 Ma. Within some late Paleogene to Neogene ( 34-0.2 Ma) lavas and volcaniclastic sediments however, there are Paleozoic to Paleoarchean ( 250-3469 Ma) xenocrysts, and Late Jurassic to Precambrian zircon ( 158-2667 Ma) are found in beach and river sands. The trace element characteristics of zircon clearly differentiate between different types of magmas generated in the southern Lesser Antilles through time. The zircon population from the younger arc (Miocene, 22-19 Ma, to Present) has minor negative Eu anomalies, well-defined positive Ce anomalies, and a marked enrichment in heavy rare earth elements (HREE), consistent with crystallization from very oxidized magmas in which Eu2 + was in low abundance. In contrast, zircon from the older arc (Eocene to mid-Oligocene, 30-28 Ma) has two different REE patterns: 1) slight enrichment in the light (L)REE, small to absent Ce anomalies, and negative Eu anomalies and 2) enriched High (H)REE, positive Ce anomalies and negative Eu anomalies (a similar pattern is observed in the xenocrystic zircon population). The combination of positive Ce and negative Eu anomalies in the zircon population of the older arc indicates crystallization from magmas that were variably, but considerably less oxidized than those of the younger arc. All the igneous zircon has positive εHf(t), reflecting derivation from a predominantly juvenile mantle source. However, the εHf(t) values vary significantly within samples, reflecting considerable Hf isotopic heterogeneity in the source. The presence of xenocrystic zircon in the southern Lesser Antilles is evidence for the assimilation of intra-arc crustal sediments and

The plutonic-volcanic connection in porphyry copper deposits: Evidence from zircon geochemistry and high-precision CA-ID-TIMS geochronology

NASA Astrophysics Data System (ADS)

Buret, Y.; Von Quadt, A.; Wotzlaw, J. F.; Heinrich, C. A.

2016-12-01

Porphyry Cu deposits represent the interface between plutonic and volcanic domains of upper crustal magmatic systems. These deposits are typically composed of multiple porphyritic intrusions which constrain the duration of ore formation to a maximum of several 104 years [1] and are commonly intruded into the base of volcanoes. The relationship between volcanic activity and porphyry stocks is often difficult to establish, as they are rarely exposed together unless later faulting and/or tilting occurred [2]. In order to investigate the relationships between extrusive magmatism and porphyry Cu formation we compare zircon petrochronology from late stage volcanic units with the nearby world class Bajo de la Alumbrera porphyry Cu deposit, from the Late Miocene Farallón Negro Volcanic Complex (FNVC) in Northwest Argentina. In this study we texturally characterise zircon crystals by CL-imaging prior to obtaining in-situ geochemical and geochronological information by LA-ICP-MS. Analysed zircon grains were then extracted and analysed by high precision CA-ID-TIMS. This approach has the two-fold benefit of screening for inherited cores, and obtaining texturally defined geochemical information, prior to dissolution of the zircon crystal for CA-ID-TIMS analysis. We use this information to establish temporal and geochemical links between studied volcanic and porphyry units in the FNVC. The results of this study suggest a close temporal and genetic link between the Bajo de la Alumbrera porphyry Cu deposit and the late stage volcanism at the FNVC. Voluminous explosive volcanism immediately following porphyry formation has important implications for the thermal and rheological state of the magma that is parental to the porphyries and fed the eruption. Further work investigating the geochemistry of other accessory and major minerals could shed further light on the evolution of the magmatic body prior to eruption/ emplacement. References: [1] Buret et al. (2016) EPSL 450:120-131; [2

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

PubMed

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

2015-11-24

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

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

PubMed Central

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

2015-01-01

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

Central Antarctic provenance of Permian sandstones in Dronning Maud Land and the Karoo Basin: Integration of U Pb and TDM ages and host-rock affinity from detrital zircons

NASA Astrophysics Data System (ADS)

Veevers, J. J.; Saeed, A.

2007-12-01

In conjugate SE Africa and Antarctica, Early Permian sandstones of the Swartrant Formation of the Ellisras Basin, Vryheid Formation of the Karoo Basin, and Amelang Plateau Formation of Dronning Maud Land (DML) were deposited after Gondwanan glaciation on a westward paleoslope. We analysed detrital zircons for U-Pb ages by a laser ablation microprobe-inductively coupled plasma mass spectrometer (LAM-ICPMS) and attached age significance only to clusters of three or more overlapping analyses. We analysed Hf-isotope compositions by a multi-collector spectrometer (LAM-MC-ICPMS) and trace elements by electron microprobe (EMP) and ICPMS. These analyses indicate the rock type and source (whether crustal or juvenile mantle) of the host magma, and a "crustal" model age ( TDMC). The integrated analysis gives a more distinctive, and more easily interpreted, picture of crustal evolution in the provenance area than age data alone. Zircons from the Ellisras Basin are aged 2700-2540 Ma with minor populations about 2815 Ma and 2040 Ma, which correspond with the ages of the upslope parts of the proximal Kaapvaal Craton and Limpopo Belt. Mafic rock is the dominant host rock, and it reflects the Archean granite-greenstone terrane of the Kaapvaal Craton. The three Karoo Basin samples and the two DML samples have zircons with these common properties: (1) 1160-880 Ma, host magma mafic granitoid (< 65% SiO 2) derived from juvenile depleted mantle sources ( ɛHf positive) at 1.65 Ga and 1.35 Ga, with TDMC of 2.0-0.9 Ga; (2) 760 to 480 Ma, host magma granitoid and low-heavy rare earth element rock (?alkaline rock-carbonatite), derived from mixed crustal and juvenile depleted mantle sources ( ɛHf positive and negative) at 1.50 Ga and 1.35 Ga, with TDMC of 2.0-0.9 Ga. Together with similar detrital zircons in Triassic sandstone of SE Australia, these properties reflect those in upslope central Antarctica, indicating a provenance of ˜ 1000 Ma (Grenville) cratons embedded in 700-500 Ma (Pan

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

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

Zircon geochronology is a critical tool for establishing geologic ages and time scales of processes in the Earth's crust. However, for zircons compromised by open system behavior, achieving robust dates can be difficult. Chemical abrasion (CA) is a routine step prior to thermal ionization mass spectrometry (TIMS) dating of zircon to remove radiation-damaged parts of grains that may have experienced open system behavior and loss of radiogenic Pb. While this technique has been shown to improve the accuracy and precision of TIMS dating, its application to high-spatial resolution dating methods, such as secondary ion mass spectrometry (SIMS), is relatively uncommon. In our efforts to U-Pb date zircons from the late Eocene Caetano caldera by SIMS (SHRIMP-RG: sensitive high resolution ion microprobe, reverse geometry), some grains yielded anomalously young U-Pb ages that implicated Pb-loss and motivated us to investigate with a comparative CA and non-CA dating study. We present CA and non-CA 206Pb/238U ages and trace elements determined by SHRIMP-RG for zircons from three Caetano samples (Caetano Tuff, Redrock Canyon porphyry, and a silicic ring-fracture intrusion) and for R33 and TEMORA-2 reference zircons. We find that non-CA Caetano zircons have weighted mean or bimodal U-Pb ages that are 2–4% younger than CA zircons for the same samples. CA Caetano zircons have mean U-Pb ages that are 0.4–0.6 Myr older than the 40Ar/39Ar sanidine eruption age (34.00 ± 0.03 Ma; error-weighted mean, 2σ), whereas non-CA zircons have ages that are 0.7–1.3 Myr younger. U-Pb ages do not correlate with U (~ 100–800 ppm), Th (~ 50–300 ppm) or any other measured zircon trace elements (Y, Hf, REE), and CA and non-CA Caetano zircons define identical trace element ranges. No statistically significant difference in U-Pb age is observed for CA versus non-CA R33 or TEMORA-2 zircons. Optical profiler measurements of ion microprobe pits demonstrate consistent depths of ~ 1.6�

Studies of LA-ICP-MS on quartz glasses at different wavelengths of a Nd:YAG laser.

PubMed

Becker, J S; Tenzler, D

2001-07-01

The capability of LA-ICP-MS for determination of trace impurities in transparent quartz glasses was investigated. Due to low or completely lacking absorption of laser radiation, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) proves difficult on transparent solids, and in particular the quantification of measurement results is problematic in these circumstances. Quartz glass reference materials of various compositions were studied by using a Nd:YAG laser system with focused laser radiation of wavelengths of 1064 nm, 532 nm and 266 nm, and an ICP-QMS (Elan 6000, Perkin Elmer). The influence of ICP and laser ablation conditions in the analysis of quartz glasses of different compositions was investigated, with the laser power density in the region of interaction between laser radiation and solid surface determining the ablation process. The trace element concentration was determined via calibration curves recorded with the aid of quartz glass reference materials. Under optimized measuring conditions the correlation coefficients of the calibration curves are in the range of 0.9-1. The relative sensitivity factors of the trace elements determined in the quartz glass matrix are 0.1-10 for most of the trace elements studied by LA-ICP-MS. The detection limits of the trace elements in quartz glass are in the low ng/g to pg/g range.

Zircon evidence for incorporation of terrigenous sediments into the magma source of continental basalts.

PubMed

Xu, Zheng; Zheng, Yong-Fei; Zhao, Zi-Fu

2018-01-09

Crustal components may be incorporated into continental basalts by either shallow contamination or deep mixing. While the former proceeds at crustal depths with common preservation of refractory minerals, the latter occurs at mantle depths with rare survival of relict minerals. Discrimination between the two mechanisms has great bearing to subcontinental mantle geochemistry. Here we report the occurrence of relict zircons in Cenozoic continental basalts from eastern China. A combined study of zircon U-Pb ages and geochemistry indicates that detrital zircons were carried by terrigenous sediments into a subcontinental subduction zone, where the zircon were transferred by fluids into the magma sources of continental basalts. The basalts were sampled from three petrotectonic units with distinct differences in their magmatic and metamorphic ages, making the crustal contamination discernible. The terrigenous sediments were carried by the subducting oceanic crust into the asthenospheric mantle, producing both soluble and insoluble materials at the slab-mantle interface. These materials were served as metasomatic agents to react with the overlying mantle wedge peridotite, generating a kind of ultramafic metasomatites that contain the relict zircons. Therefore, the occurrence of relict zircons in continental basalts indicates that this refractory mineral can survive extreme temperature-pressure conditions in the asthenospheric mantle.

Quantitative bioimaging of trace elements in the human lens by LA-ICP-MS.

PubMed

Konz, Ioana; Fernández, Beatriz; Fernández, M Luisa; Pereiro, Rosario; González-Iglesias, Héctor; Coca-Prados, Miguel; Sanz-Medel, Alfredo

2014-04-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of Fe, Cu and Zn in cryostat sections of human eye lenses and for depth profiling analysis in bovine lenses. To ensure a tight temperature control throughout the experiments, a new Peltier-cooled laser ablation cell was employed. For quantification purposes, matrix-matched laboratory standards were prepared from a pool of human lenses from eye donors and spiked with standard solutions containing different concentrations of natural abundance Fe, Cu and Zn. A normalisation strategy was also carried out to correct matrix effects, lack of tissue homogeneity and/or instrumental drifts using a thin gold film deposited on the sample surface. Quantitative images of cryo-sections of human eye lenses analysed by LA-ICP-MS revealed a homogeneous distribution of Fe, Cu and Zn in the nuclear region and a slight increase in Fe concentration in the outer cell layer (i.e. lens epithelium) at the anterior pole. These results were assessed also by isotope dilution mass spectrometry, and Fe, Cu and Zn concentrations determined by ID-ICP-MS in digested samples of lenses and lens capsules.

Zircon and monazite response to prograde metamorphism in the Reynolds Range, central Australia

NASA Astrophysics Data System (ADS)

Rubatto, Daniela; Williams, Ian S.; Buick, Ian S.

2001-01-01

We report an extensive field-based study of zircon and monazite in the metamorphic sequence of the Reynolds Range (central Australia), where greenschist- to granulite-facies metamorphism is recorded over a continuous crustal section. Detailed cathodoluminescence and back-scattered electron imaging, supported by SHRIMP U-Pb dating, has revealed the different behaviours of zircon and monazite during metamorphism. Monazite first recorded regional metamorphic ages (1576 ± 5 Ma), at amphibolite-facies grade, at ˜600 °C. Abundant monazite yielding similar ages (1557 ± 2 to 1585 ± 3 Ma) is found at granulite-facies conditions in both partial melt segregations and restites. New zircon growth occurred between 1562 ± 4 and 1587 ± 4 Ma, but, in contrast to monazite, is only recorded in granulite-facies rocks where melt was present (≥700 °C). New zircon appears to form at the expense of pre-existing detrital and inherited cores, which are partly resorbed. The amount of metamorphic growth in both accessory minerals increases with temperature and metamorphic grade. However, new zircon growth is influenced by rock composition and driven by partial melting, factors that appear to have little effect on the formation of metamorphic monazite. The growth of these accessory phases in response to metamorphism extends over the 30 Ma period of melt crystallisation (1557-1587 Ma) in a stable high geothermal regime. Rare earth element patterns of zircon overgrowths in leucosome and restite indicate that, during the protracted metamorphism, melt-restite equilibrium was reached. Even in the extreme conditions of long-lasting high temperature (750-800 °C) metamorphism, Pb inheritance is widely preserved in the detrital zircon cores. A trace of inheritance is found in monazite, indicating that the closure temperature of the U-Pb system in relatively large monazite crystals can exceed 750-800 °C.

Precise U/Pb zircons dates of bentonites in Upper Ordovician and Lower Silurian reference sections in North America and Britain.

NASA Astrophysics Data System (ADS)

Suarez, S. E.; Brookfield, M. E.; Catlos, E. J.; Stockli, D. F.; Batchelor, R. A.

2016-12-01

The end of the Ordovician marks one of the greatest of the Earth's mass extinctions. One hypothesis explains this mass extinction as the result of a short-lived, major glaciation preceded by episodes of increased volcanism brought on by the Taconic orogeny. K-bentonites, weathered volcanic ash, provide evidence for increased volcanism. However, there is a lack of modern precise U-Pb dating of these ashes and some confusion in the biostratigraphy. The aim of this study is to obtain more precise U-Pb zircon ages from biostratigraphically constrained bentonites which will lead to better correlation of the Upper Ordovician and Lower Silurian relative time scales, as well as time the pulses of eruption. Zircon grains were extracted from the samples by heavy mineral separation and U-Pb dated using the Laser Ablation-Inductively Coupled Plasma-Mass Spectrometer at the University of Texas-Austin. We report here 3 precise U-Pb zircon ages from the Trenton Group, Ontario, Canada, and Dob's Linn, Scotland. The youngest age from the top of the Kirkfield Formation in Ontario is 448.0 +/- 18 Ma, which fits with existing late Ordovician stratigraphic ages. At Dob's Linn, Scotland, the site of the Ordovician/Silurian Global Boundary Stratigraphic Section and Point (GSSP), the youngest age for DL7, a bentonite 5 meters below the GSSP is 402.0 +/- 12.0 Ma, and for DL24L, a bentonite 8 meters above the GSSP is 358.2 +/- 7.9 Ma. These are Devonian ages in current timescales - the current age for the GSSP is 443.8 +/- 1.8 Ma, based on an U/Pb dates from a bentonite 1.6 meters above the GSSP at Dob's Linn. We are confident that our techniques rule out contamination and the most likely explanation is that the small zircons we analyzed either suffered Pb loss, or grew overgrowths during low grade hydrothermal metamorphism of the sediments during the intrusion of the Southern Upland Devonian granites during the Caledonian orogeny. These Devonian ages suggest that the 443.8 +/- 1.8 Ma age

Mapping of lead, magnesium and copper accumulation in plant tissues by laser-induced breakdown spectroscopy and laser-ablation inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Kaiser, J.; Galiová, M.; Novotný, K.; Červenka, R.; Reale, L.; Novotný, J.; Liška, M.; Samek, O.; Kanický, V.; Hrdlička, A.; Stejskal, K.; Adam, V.; Kizek, R.

2009-01-01

Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) were utilized for mapping the accumulation of Pb, Mg and Cu with a resolution up to 200 μm in a up to cm × cm area of sunflower ( Helianthus annuus L.) leaves. The results obtained by LIBS and LA-ICP-MS are compared with the outcomes from Atomic Absorption Spectrometry (AAS) and Thin-Layer Chromatography (TLC). It is shown that laser-ablation based analytical methods can substitute or supplement these techniques mainly in the cases when a fast multi-elemental mapping of a large sample area is needed.

2D elemental mapping of sections of human kidney stones using laser ablation inductively-coupled plasma-mass spectrometry: Possibilities and limitations

NASA Astrophysics Data System (ADS)

Vašinová Galiová, Michaela; Čopjaková, Renata; Škoda, Radek; Štěpánková, Kateřina; Vaňková, Michaela; Kuta, Jan; Prokeš, Lubomír; Kynický, Jindřich; Kanický, Viktor

2014-10-01

A 213 nm Nd:YAG-based laser ablation (LA) system coupled to quadrupole-based inductively coupled plasma-mass spectrometer and an ArF* excimer-based LA-system coupled to a double-focusing sector field inductively coupled plasma-mass spectrometer were employed to study the spatial distribution of various elements in kidney stones (uroliths). Sections of the surfaces of uroliths were ablated according to line patterns to investigate the elemental profiles for the different urolith growth zones. This exploratory study was mainly focused on the distinguishing of the main constituents of urinary calculus fragments by means of LA-ICP-mass spectrometry. Changes in the ablation rate for oxalate and phosphate phases related to matrix density and hardness are discussed. Elemental association was investigated on the basis of 2D mapping. The possibility of using NIST SRM 1486 Bone Meal as an external standard for calibration was tested. It is shown that LA-ICP-MS is helpful for determination of the mineralogical composition and size of all phases within the analyzed surface area, for tracing down elemental associations and for documenting the elemental content of urinary stones. LA-ICP-MS results (elemental contents and maps) are compared to those obtained with electron microprobe analysis and solution analysis ICP-MS.

Detrital zircon provenance of Mesoproterozoic to Cambrian arenites in the Western United States and Northwestern Mexico

USGS Publications Warehouse

Stewart, John H.; Gehrels, G.E.; Barth, A.P.; Link, P.K.; Christie-Blick, N.; Wrucke, C.T.

2001-01-01

U-Pb isotopic dating of detrital zircon from supracrustal Proterozoic and Cambrian arenites from the western United States and northern Mexico reveal three main age groups, 1.90 to 1.62 Ga, 1.45 to 1.40 Ga, and 1.2 to 1.0 Ga. Small amounts of zircons with ages of 3.1 to 2.5 Ga, 1.57 Ga, 1.32 Ga, 1.26 Ga, 0.7 Ga, and 0.5 Ga are also present. Detrital zircons ranging in age from 1.90 to 1.62 Ga and from 1.45 to 1.40 Ga are considered to have been derived from Proterozoic crystalline basement rocks of these known ages, and probably in part from reworked Proterozoic supracrustal sedimentary rocks, of the western United States. The 1.2 to 1.0 Ga detrital zircon ages from California, Arizona, and Sonora are characterized by distinct spikes (1.11 Ga, in particular) in the age-probability plots. These spikes are interpreted to indicate the influx of zircon from major silicic volcanic fields. Igneous rocks such as the Pikes Peak Granite (1.093 Ga) of Colorado, and the Aibo Granite (1.110 Ga) of Sonora, Mexico, may represent the deeply eroded roots of such volcanic fields. Samples from farther north along the Cordilleran margin that contain abundant 1.2-1.0 Ga detrital zircons do not show spikes in the age distribution, but rather ages spread out across the entire 1.2-1.0 Ga range. These age spectra resemble those for detrital zircons from the Grenville province, which is considered their source. Less common detrital zircons had a variety of sources. Zircons ranging in age from 3.36 to 2.31 Ga were apparently derived from inland parts of the North American continent from Wyoming to Canada. Zircons of about 1.577 Ga are highly unusual and may have had an exotic source; they may have come from Australia and been deposited in North America when Australia and North America were juxtaposed as part of the hypothetical Rodinian supercontinent. Detrital zircon of ??1.320 Ga apparently had the same source as that for tuff (1.320 Ga) in the Pioneer Shale of the Apache Group in Arizona

Microwave ablation versus radiofrequency ablation in the kidney: high-power triaxial antennas create larger ablation zones than similarly sized internally cooled electrodes.

PubMed

Laeseke, Paul F; Lee, Fred T; Sampson, Lisa A; van der Weide, Daniel W; Brace, Christopher L

2009-09-01

To determine whether microwave ablation with high-power triaxial antennas creates significantly larger ablation zones than radiofrequency (RF) ablation with similarly sized internally cooled electrodes. Twenty-eight 12-minute ablations were performed in an in vivo porcine kidney model. RF ablations were performed with a 200-W pulsed generator and either a single 17-gauge cooled electrode (n = 9) or three switched electrodes spaced 1.5 cm apart (n = 7). Microwave ablations were performed with one (n = 7), two (n = 3), or three (n = 2) 17-gauge triaxial antennas to deliver 90 W continuous power per antenna. Multiple antennas were powered simultaneously. Temperatures 1 cm from the applicator were measured during two RF and microwave ablations each. Animals were euthanized after ablation and ablation zone diameter, cross-sectional area, and circularity were measured. Comparisons between groups were performed with use of a mixed-effects model with P values less than .05 indicating statistical significance. No adverse events occurred during the procedures. Three-electrode RF (mean area, 14.7 cm(2)) and single-antenna microwave (mean area, 10.9 cm(2)) ablation zones were significantly larger than single-electrode RF zones (mean area, 5.6 cm(2); P = .001 and P = .0355, respectively). No significant differences were detected between single-antenna microwave and multiple-electrode RF. Ablation zone circularity was similar across groups (P > .05). Tissue temperatures were higher during microwave ablation (maximum temperature of 123 degrees C vs 100 degrees C for RF). Microwave ablation with high-power triaxial antennas created larger ablation zones in normal porcine kidneys than RF ablation with similarly sized applicators.

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

Ablation mass features in multi-pulses femtosecond laser ablate molybdenum target

NASA Astrophysics Data System (ADS)

Zhao, Dongye; Gierse, Niels; Wegner, Julian; Pretzler, Georg; Oelmann, Jannis; Brezinsek, Sebastijan; Liang, Yunfeng; Neubauer, Olaf; Rasinski, Marcin; Linsmeier, Christian; Ding, Hongbin

2018-03-01

In this study, the ablation mass features related to reflectivity of bulk Molybdenum (Mo) were investigated by a Ti: Sa 6 fs laser pulse at central wavelength 790 nm. The ablated mass removal was determined using Confocal Microscopy (CM) technique. The surface reflectivity was calibrated and measured by a Lambda 950 spectrophotometer as well as a CCD camera during laser ablation. The ablation mass loss per pulse increase with the increasing of laser shots, meanwhile the surface reflectivity decrease. The multi-pulses (100 shots) ablation threshold of Mo was determined to be 0.15 J/cm2. The incubation coefficient was estimated as 0.835. The reflectivity change of the Mo target surface following multi-pulses laser ablation were studied as a function of laser ablation shots at various laser fluences from 1.07 J/cm2 to 36.23 J/cm2. The results of measured reflectivity indicate that surface reflectivity of Mo target has a significant decline in the first 3-laser pulses at the various fluences. These results are important for developing a quantitative analysis model for laser induced ablation and laser induced breakdown spectroscopy for the first wall diagnosis of EAST tokamak.

Tungsten carbide precursors as an example for influence of a binder on the particle formation in the nanosecond laser ablation of powdered materials.

PubMed

Holá, Markéta; Mikuska, Pavel; Hanzlíková, Renáta; Kaiser, Jozef; Kanický, Viktor

2010-03-15

A study of LA-ICP-MS analysis of pressed powdered tungsten carbide precursors was performed to show the advantages and problems of nanosecond laser ablation of matrix-unified samples. Five samples with different compositions were pressed into pellets both with silver powder as a binder serving to keep the matrix unified, and without any binder. The laser ablation was performed by nanosecond Nd:YAG laser working at 213 nm. The particle formation during ablation of both sets of pellets was studied using an optical aerosol spectrometer allowing the measurement of particle concentration in two size ranges (10-250 nm and 0.25-17 microm) and particle size distribution in the range of 0.25-17 microm. Additionally, the structure of the laser-generated particles was studied after their collection on a filter using a scanning electron microscope (SEM) and the particle chemical composition was determined by an energy dispersive X-ray spectroscope (EDS). The matrix effect was proved to be reduced using the same silver powdered binder for pellet preparation in the case of the laser ablation of powdered materials. The LA-ICP-MS signal dependence on the element content present in the material showed an improved correlation for Co, Ti, Ta and Nb of the matrix-unified samples compared to the non-matrix-unified pellets. In the case of W, the ICP-MS signal of matrix-unified pellets was influenced by the changes in the particle formation. Copyright (c) 2009 Elsevier B.V. All rights reserved.

Dating kimberlite emplacement with zircon and perovskite (U-Th)/He geochronology

NASA Astrophysics Data System (ADS)

Stanley, Jessica; Flowers, Rebecca

2017-04-01

Kimberlites provide rich information about the composition and evolution of cratonic lithosphere. They can entrain xenoliths and xenocrysts from the entire lithospheric column as they transit rapidly to the surface, providing information on the state of the deep lithosphere as well as any sedimentary units covering the craton at the time of eruption. Accurate geochronology of these eruptions is key for interpreting this information and discerning spatiotemporal trends in lithospheric evolution, but kimberlites can sometimes be difficult to date with available methods. Here we explore whether (U-Th)/He dating of zircon and perovskite can serve as reliable techniques for determining kimberlite emplacement ages by dating a suite of sixteen southern African kimberlites by zircon and/or perovskite (U-Th)/He (ZHe, PHe). Most samples with abundant zircon yielded ZHe dates reproducible to ≤15% dispersion that are in good agreement with published eruption ages, though there were several samples that were more scattered. Since the majority of dated zircon were xenocrystic, zircon with reproducible dates were fully reset during eruption or resided at temperatures above the ZHe closure temperature ( 180 °C) prior to entrainment in the kimberlite magma. We attribute scattered ZHe dates to shallowly sourced zircon that underwent incomplete damage annealing and/or partial He loss during the eruptive process. All seven kimberlites dated with PHe yielded dates reproducible to ≤15% dispersion and reasonable results. As perovskite has not previously been used as a (U-Th)/He chronometer, we conducted two preliminary perovskite 4He diffusion experiments to obtain initial estimates of its temperature sensitivity. These experiments suggest a PHe closure temperature of >300 °C. Perovskite in kimberlites is unlikely to be xenocrystic and its relatively high temperature sensitivity suggests that PHe dates will typically record emplacement rather than post-emplacement processes. ZHe

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

Zircon from historic eruptions in Iceland: reconstructing storage and evolution of silicic magmas

NASA Astrophysics Data System (ADS)

Carley, Tamara L.; Miller, Calvin F.; Wooden, Joseph L.; Bindeman, Ilya N.; Barth, Andrew P.

2011-10-01

Zoning patterns, U-Th disequilibria ages, and elemental compositions of zircon from eruptions of Askja (1875 AD), Hekla (1158 AD), Öræfajökull (1362 AD) and Torfajökull (1477 AD, 871 AD, 3100 BP, 7500 BP) provide insights into the complex, extended, histories of silicic magmatic systems in Iceland. Zircon compositions, which are correlated with proximity to the main axial rift, are distinct from those of mid-ocean ridge environments and fall at the low-Hf edge of the range of continental zircon. Morphology, zoning patterns, compositions, and U-Th ages all indicate growth and storage in subvolcanic silicic mushes or recently solidified rock at temperatures above the solidus but lower than that of the erupting magma. The eruptive products were likely ascending magmas that entrained a zircon "cargo" that formed thousands to tens of thousands of years prior to the eruptions.

Global ablation techniques.

PubMed

Woods, Sarah; Taylor, Betsy

2013-12-01

Global endometrial ablation techniques are a relatively new surgical technology for the treatment of heavy menstrual bleeding that can now be used even in an outpatient clinic setting. A comparison of global ablation versus earlier ablation technologies notes no significant differences in success rates and some improvement in patient satisfaction. The advantages of the newer global endometrial ablation systems include less operative time, improved recovery time, and decreased anesthetic risk. Ablation procedures performed in an outpatient surgical or clinic setting provide advantages both of potential cost savings for patients and the health care system and improved patient convenience. Copyright © 2013. Published by Elsevier Inc.

Association of glass fragments by their trace elemental content using ICP-MS and LA-ICP-MS in the analysis scheme

NASA Astrophysics Data System (ADS)

Almirall, Jose R.; Montero, Shirly; Furton, Kenneth G.

2002-08-01

The importance of glass as evidence of association between a crime event and a suspect has been recognized for some time. Glass is a fragile material that is often found at the scenes of crimes such as burglaries, hit-and-run accidents and violent crime offenses. The physical and chemical properties of glass can be used to differentiate between possible sources and as evidence of association between two fragments of glass thought to originate from the same source. Refractive index (RI) comparisons have been used for this purpose but due to the improved control over glass manufacturing processes, RI values often cannot differentiate glasses, even if the glass originates from different sources. Elemental analysis methods such as NAA, XRF, ICP-AES, and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) have also been used for the comparison of trace elemental compositions and these techniques have been shown to provide an improvement in the discrimination of glass fragments over RI comparisons alone. The multi-element capability and the sensitivity of ICP-MS combined with the simplified sample introduction of laser ablation prior to ion detection provides for an excellent and relatively non-destructive technique for elemental analysis of glass fragments. The methodology for solution analysis (digestion procedure) and solid sample analysis (laser ablation) of glass is reported and the analytical results are compared. An isotope dilution method is also reported as a high precision technique for elemental analysis of glass fragments. The optimum sampling parameters for laser ablation, for semi-quantitative analysis and element ratio comparisons are also presented. Finally, the results of a case involving the breaking of 15 vehicle windows in an airport parking lot and the association of a suspect to the breakings by the glass fragments found on his person are also presented.

When the CA-TIMS therapy fails: the over-enthusiastic, the mixed-up, and the stubborn zircon

NASA Astrophysics Data System (ADS)

Corfu, F.

2009-12-01

Mattinson’s CA-TIMS technique has proven to be highly successful in efficiently removing disturbed domains of zircon, thus enabling the determination of precise and accurate ages in a variety of geological situations. The method generally produces equal or better results than mechanical abrasion. There are, however, cases where CA-TIMS fails to achieve perfect concordance, and occasionally actually increases the degree of discordance. Such a behaviour (the over-reaction) is observed for example in U-rich (>1000 ppm) but texturally homogeneous zircon, a type quite common in highly differentiated portions of mafic intrusions, in granitic pegmatites, and in some metamorphic rocks. Because of their internal uniformity, such zircons do not exhibit large contrasts in crystallinity and solubility and after the baking stage of the CA-TIMS procedure they will either totally dissolve in the first HF attack, or produce discordant results. By contrast, mechanical abrasion of this type of zircon can isolate alteration-free zircon domains that yield concordant and reproducible data. This is due to the homogeneity of the crystals, the lack of zoning limiting contrasts in the degrees of metamictization and brittleness and preventing fracturing. The absence of fractures helps to confine alteration of zircon to the marginal domains, and these can be removed very efficiently by mechanical abrasion. This behaviour is exemplified by zircon populations from 252.0 Ma and 182.5 Ma mafic sills in Siberia and the Karoo basin. Another class of zircons that in general does not, or only partially comply with CA-TIMS includes populations from metamorphic and poly-orogenic rocks, typical of many Proterozoic orogens. The metamorphic reprocessing of zircon into low-U domains can freeze-in old Pb-loss patterns that cannot be undone by any technique. New metamorphic zircon growth can also create mixtures of different aged domains that cannot be resolved by CA-TIMS. In favourable circumstances

Simulation of eye-tracker latency, spot size, and ablation pulse depth on the correction of higher order wavefront aberrations with scanning spot laser systems.

PubMed

Bueeler, Michael; Mrochen, Michael

2005-01-01

The aim of this theoretical work was to investigate the robustness of scanning spot laser treatments with different laser spot diameters and peak ablation depths in case of incomplete compensation of eye movements due to eye-tracker latency. Scanning spot corrections of 3rd to 5th Zernike order wavefront errors were numerically simulated. Measured eye-movement data were used to calculate the positioning error of each laser shot assuming eye-tracker latencies of 0, 5, 30, and 100 ms, and for the case of no eye tracking. The single spot ablation depth ranged from 0.25 to 1.0 microm and the spot diameter from 250 to 1000 microm. The quality of the ablation was rated by the postoperative surface variance and the Strehl intensity ratio, which was calculated after a low-pass filter was applied to simulate epithelial surface smoothing. Treatments performed with nearly ideal eye tracking (latency approximately 0) provide the best results with a small laser spot (0.25 mm) and a small ablation depth (250 microm). However, combinations of a large spot diameter (1000 microm) and a small ablation depth per pulse (0.25 microm) yield the better results for latencies above a certain threshold to be determined specifically. Treatments performed with tracker latencies in the order of 100 ms yield similar results as treatments done completely without eye-movement compensation. CONCWSIONS: Reduction of spot diameter was shown to make the correction more susceptible to eye movement induced error. A smaller spot size is only beneficial when eye movement is neutralized with a tracking system with a latency <5 ms.

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

DOE PAGES

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

2015-10-19

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

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

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

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

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

Triassic deposits of the Chukotka Arctic continental margin (sedimentary implications and detrital zircon data)

NASA Astrophysics Data System (ADS)

Tuchkova, Marianna; Sokolov, Sergey; Verzhbitsky, Vladimir

2013-04-01

Triassic clastic deposits of Chukotka are represented by rhythmic intercalation of sandstones, siltstones and mudstones. During the Triassic, sedimentation was represented by continental slope progradation. Detrital zircons from Triassic sedimentary rocks were collected for constrain its paleogeographic links to source terranes. Zircons populations from three Chukotka's samples are very similar, and youngest zircon ages show peaks at 236-255 Ma (Miller et al., 2006). Lower Triassic sandstones from the Chaun subterrane do not contain the young population 235-265 Ma that is characteristic of the Upper Triassic rocks from the Anyui subterrane and Wrangel Island. The young zircon population is missing also from the coeval Sadlerochit Group (Alaska) and Blind Fiord Formation of the Sverdrup basin (Miller et al., 2006; Omma et al., 2011). Our data of Triassic sandstones of Wrangel island demonstrate detrital zircons ages dominated by Middle Triassic (227-245 Ma), Carboniferous (309-332 Ma) and Paleoproterozoic (1808-2500 Ma) ages. The new data on Chukotka show that populations of detrital zircons from Chukotka, the Sverdrup basin, and Alaska, the Sadlerochit Mountains included, demonstrate greater similarity than it was previously thought. Consequently, it may be assumed that they originate from a single source situated in the north. The data on zircon age of gabbro-dolerite magmatism in eastern Chukotka (252 Ma. Ledneva et al., 2011) and K-Ar ages obtained for sills and small intrusive bodies (Geodynamics…, 2006) in Lower Triassic deposits allow the local provenance. The presence of products of synchronous magmatism and shallow-water facies in the Lower Triassic sequences confirm this assumption. At the same time, coeval zircons appear only in the Upper Triassic strata. It is conceivable that the young zircon population originates from intrusive, not volcanic rocks, which were subjected to erosion only in the Late Triassic. In our opinion, the assumption of the local

Speed of sound estimation for thermal monitoring using an active ultrasound element during liver ablation therapy (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kim, Younsu; Audigier, Chloé; Dillow, Austin; Cheng, Alexis; Boctor, Emad M.

2017-03-01

Thermal monitoring for ablation therapy has high demands for preserving healthy tissues while removing malignant ones completely. Various methods have been investigated. However, exposure to radiation, cost-effectiveness, and inconvenience hinder the use of X-ray or MRI methods. Due to the non-invasiveness and real-time capabilities of ultrasound, it is widely used in intraoperative procedures. Ultrasound thermal monitoring methods have been developed for affordable monitoring in real-time. We propose a new method for thermal monitoring using an ultrasound element. By inserting a Lead-zirconate-titanate (PZT) element to generate the ultrasound signal in the liver tissues, the single travel time of flight is recorded from the PZT element to the ultrasound transducer. We detect the speed of sound change caused by the increase in temperature during ablation therapy. We performed an ex vivo experiment with liver tissues to verify the feasibility of our speed of sound estimation technique. The time of flight information is used in an optimization method to recover the speed of sound maps during the ablation, which are then converted into temperature maps. The result shows that the trend of temperature changes matches with the temperature measured at a single point. The estimation error can be decreased by using a proper curve linking the speed of sound to the temperature. The average error over time was less than 3 degrees Celsius for a bovine liver. The speed of sound estimation using a single PZT element can be used for thermal monitoring.

Evidence of extinct 244Pu in ancient terrestrial zircons

NASA Astrophysics Data System (ADS)

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

2003-04-01

The Pu/U ratio of the early Earth is an important parameter in models of mantle evolution based on noble gas isotopes. Current estimates assume the Earth accreted with a chondritic Pu/U and are based on analyses of the chondrite St Severin and the achondrite Angra dos Reis. These estimates are poorly constrained, ranging from 0.004 to 0.008. On account of its short, 82 Ma, half-life, 244Pu was essentially extinct 3,900 Ma ago, and consequently there exists no reliable measurement of Pu/U for the Earth. The discovery of zircons dating from the period when 244Pu was "live" offers the first opportunity to measure the former terrestrial abundance of 244Pu directly. Xenon isotopes are produced by spontaneous fission and, in principle, are readily distinguishable from those produced by 238U-fission (e.g. 131Xe/136Xe = 0.24 and 0.08 respectively). However the expected levels of fission xenon in individual zircons, weighing 1 - 2 μg and containing 100 - 200 ppm U, are below, or at best comparable to, the Xe blank levels (˜10-15 ccSTP) typical of conventional noble gas mass spectrometers. In order to analyse these minute amounts of xenon we have made use of a uniquely sensitive instrument, developed in Manchester, based on the principle of laser resonance ionisation. RELAX (Refrigerator Enhanced Laser Analyser for Xenon) is capable of analysing samples of only a few thousand atoms, some two orders of magnitude smaller than conventional mass spectrometers. We have carried out preliminary analyses of 4 individual 4,150 Ma zircons and one 3,600 Ma zircon from Jack Hills, Western Australia, and obtained five clear fission spectra. All but one were essentially free from significant atmospheric blank (the average 130Xe blank was 3× 10-18 ccSTP, i.e. 80 atoms). The spectra of the older zircons clearly demonstrated the presence of varying amounts of 244Pu fission xenon. The highest 131Xe/136Xe, 0.136 ± 0.003, corresponds to an initial Pu/U ratio of 0.0057. The lower ratios

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

NASA Astrophysics Data System (ADS)

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

2006-04-01

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

Detrital zircon age patterns and provenance of the metamorphic complexes of southern Chile

NASA Astrophysics Data System (ADS)

Hervé, F.; Fanning, C. M.; Pankhurst, R. J.

2003-05-01

Zircon SHRIMP U-Pb age patterns are reported for 13 metasedimentary rocks from the low grade metamorphic complexes of the Patagonian Andes. Combined with four recently published patterns, these provide the first detailed survey of the provenance of these complexes. The youngest dated zircons, corresponding to maximum sedimentation ages, are Devonian-Late Triassic in the eastern Andes metamorphic complex, Carboniferous in the main range metamorphic complex, Permian in the Duque de York complex, and Late Triassic in the Chonos metamorphic complex. In the last two cases, these ages are in agreement with their respective fossil ages. Older components in the eastern Andes metamorphic complex include a large proportion of Proterozoic (predominantly 1000-1200 Ma) zircons, which may indicate distribution, probably by rivers, of detrital material from regions currently in northern South America, Africa, or east Antarctica. The abundance of Proterozoic zircons is very much less in the Duque de York complex, possibly because of the rise of an inferred Permian magmatic arc related to the Gondwanan orogeny and consequent westward migration of the watershed. A Late Triassic magmatic episode is registered in the Chonos metamorphic complex, where reappearance of significant Proterozoic zircons indicates exhumation of the cratonic areas or of recycled sedimentary material.

Zircon Age Distributions Provide Magma Fluxes in the Earth's Crust

NASA Astrophysics Data System (ADS)

Caricchi, L.; Simpson, G.; Schaltegger, U.

2014-12-01

Magma fluxes control the growth of continents, the frequency and magnitude of volcanic eruptions and are important for the genesis of magmatic ore deposits. A significant part of the magma produced in the Earth's mantle solidifies at depth and this limits our capability of determining magma fluxes, which, in turn, compromises our ability to establish a link between global heat transfer and large-scale geological processes. Using thermal modelling in combination with high precision zircon dating we show that populations of zircon ages provide an accurate mean to retrieve magma fluxes. The characteristics of zircon age populations vary significantly and systematically as function of the flux and total volume of magma accumulated at depth. This new approach provides results that are identical to independent determinations of magma fluxes and volumes of magmatic systems. The analysis of existing age population datasets by our method highlights that porphyry-type deposits, plutons and large eruptions each require magma input over different timescales at characteristic average fluxes.

Geochemistry, zircon U-Pb dating and Hf isotopies composition of Paleozoic granitoids in Jinchuan, NW China: Constraints on their petrogenesis, source characteristics and tectonic implication

NASA Astrophysics Data System (ADS)

Zeng, Renyu; Lai, Jianqing; Mao, Xiancheng; Li, Bin; Ju, Peijiao; Tao, Shilong

2016-05-01

Granitoids are widely distributed in Jinchuan at the southwestern margin of the North China plate, which is also an important area of mineral deposits. The research subject of this article are two Paleozoic granitoids, a cataclastic syenogranite and a granodiorite porphyry. This study presents whole rock geochemistry and zircon U-Pb-Hf isotope data for the two granitoids to determine their petrogenesis, source characteristics and tectonic significance. The cataclastic syenogranite is characterized by metaluminous composition with high potassium, and LaN/YbN from 39 to 48. The composition with strong negative Eu anomalies and Zircon saturation temperatures (TZr) from 947 to 1072 °C classify this intrusion as an A-type granite. The granodiorite porphyry is metaluminous with high sodium, sub-alkaline, LaN/YbN ratios from 27 to 32. These I-type intrusions have no Eu anomalies and TZr ranges from 818 to 845 °C. Both the cataclastic syenogranite and granodiorite porphyry show enrichment of LREE and LILE and depletion of HREE and HFSE, except Hf and Zr. Using single zircon LA-ICP-MS U-Pb dating, the emplacement age of the cataclastic syenogranite and granodiorite porphyry are determined at 433.4 ± 3.7 Ma and 361.7 ± 4.6 Ma, respectively. Zircons from the cataclastic syenogranits have uniform negative εHf(t) values (-11 ± 0.5 to -9 ± 0.5), implying the involvement of an old Palaeoproterozoic crustal source in magma genesis. The zircons from the granodiorite porphyry have εHf(t) values that range from -8 ± 1.0 to +10 ± 0.6, suggesting heterogeneous source materials involving both juvenile and ancient crust reworked crustal components. Based on the geological significance of granites at the southwestern margin of the North China plate, the closure of the North Qilian Ocean occurred at ∼444 Ma. Geochemical features suggest that the cataclastic syenogranite and granodiorite porphyry formed in an intraplate extensional and compressional setting, respectively. Hence

Robotically assisted ablation produces more rapid and greater signal attenuation than manual ablation.

PubMed

Koa-Wing, Michael; Kojodjojo, Pipin; Malcolme-Lawes, Louisa C; Salukhe, Tushar V; Linton, Nick W F; Grogan, Aaron P; Bergman, Dale; Lim, Phang Boon; Whinnett, Zachary I; McCarthy, Karen; Ho, Siew Yen; O'Neill, Mark D; Peters, Nicholas S; Davies, D Wyn; Kanagaratnam, Prapa

2009-12-01

Robotic remote catheter ablation potentially provides improved catheter-tip stability, which should improve the efficiency of radiofrequency energy delivery. Percentage reduction in electrogram peak-to-peak voltage has been used as a measure of effectiveness of ablation. We tested the hypothesis that improved catheter-tip stability of robotic ablation can diminish signals to a greater degree than manual ablation. In vivo NavX maps of 7 pig atria were constructed. Separate lines of ablation were performed robotically and manually, recording pre- and postablation peak-to-peak voltages at 10, 20, 30, and 60 seconds and calculating signal amplitude reduction. Catheter ablation settings were constant (25W, 50 degrees , 17 mL/min, 20-30 g catheter tip pressure). The pigs were sacrificed and ablation lesions correlated with NavX maps. Robotic ablation reduced signal amplitude to a greater degree than manual ablation (49 +/- 2.6% vs 29 +/- 4.5% signal reduction after 1 minute [P = 0.0002]). The mean energy delivered (223 +/- 184 J vs 231 +/- 190 J, P = 0.42), power (19 +/- 3.5 W vs 19 +/- 4 W, P = 0.84), and duration of ablation (15 +/- 9 seconds vs 15 +/- 9 seconds, P = 0.89) was the same for manual and robotic. The mean peak catheter-tip temperature was higher for robotic (45 +/- 5 degrees C vs 42 +/- 3 degrees C [P < 0.0001]). The incidence of >50% signal reduction was greater for robotic (37%) than manual (21%) ablation (P = 0.0001). Robotically assisted ablation appears to be more effective than manual ablation at signal amplitude reduction, therefore may be expected to produce improved clinical outcomes.

Analysis of iodinated contrast delivered during thermal ablation: is material trapped in the ablation zone?

PubMed

Wu, Po-Hung; Brace, Chris L

2016-08-21

Intra-procedural contrast-enhanced CT (CECT) has been proposed to evaluate treatment efficacy of thermal ablation. We hypothesized that contrast material delivered concurrently with thermal ablation may become trapped in the ablation zone, and set out to determine whether such an effect would impact ablation visualization. CECT images were acquired during microwave ablation in normal porcine liver with: (A) normal blood perfusion and no iodinated contrast, (B) normal perfusion and iodinated contrast infusion or (C) no blood perfusion and residual iodinated contrast. Changes in CT attenuation were analyzed from before, during and after ablation to evaluate whether contrast was trapped inside of the ablation zone. Visualization was compared between groups using post-ablation contrast-to-noise ratio (CNR). Attenuation gradients were calculated at the ablation boundary and background to quantitate ablation conspicuity. In Group A, attenuation decreased during ablation due to thermal expansion of tissue water and water vaporization. The ablation zone was difficult to visualize (CNR  =  1.57  ±  0.73, boundary gradient  =  0.7  ±  0.4 HU mm(-1)), leading to ablation diameter underestimation compared to gross pathology. Group B ablations saw attenuation increase, suggesting that iodine was trapped inside the ablation zone. However, because the normally perfused liver increased even more, Group B ablations were more visible than Group A (CNR  =  2.04  ±  0.84, boundary gradient  =  6.3  ±  1.1 HU mm(-1)) and allowed accurate estimation of the ablation zone dimensions compared to gross pathology. Substantial water vaporization led to substantial attenuation changes in Group C, though the ablation zone boundary was not highly visible (boundary gradient  =  3.9  ±  1.1 HU mm(-1)). Our results demonstrate that despite iodinated contrast being trapped in the ablation zone, ablation visibility

Late accretion to the Moon recorded in zircon (U-Th)/He thermochronometry

NASA Astrophysics Data System (ADS)

Kelly, Nigel M.; Flowers, Rebecca M.; Metcalf, James R.; Mojzsis, Stephen J.

2018-01-01

We conducted zircon (U-Th)/He (ZHe) analysis of lunar impact-melt breccia 14311 with the aim of leveraging radiation damage accumulated in zircon over extended intervals to detect low-temperature or short-lived impact events that have previously eluded traditional isotopic dating techniques. Our ZHe data record a coherent date vs. effective Uranium concentration (eU) trend characterized by >3500 Ma dates from low (≤75 ppm) eU zircon grains, and ca. 110 Ma dates for high (≥100 ppm) eU grains. A progression between these date populations is apparent for intermediate (75-100 ppm) eU grains. Thermal history modeling constrains permissible temperatures and cooling rates during and following impacts. Modeling shows that the data are most simply explained by impact events at ca. 3950 Ma and ca. 110 Ma, and limits allowable temperatures of heating events between 3950-110 Ma. Modeling of solar cycling thermal effects at the lunar surface precludes this as the explanation for the ca. 110 Ma ZHe dates. We propose a sample history characterized by zircon resetting during the ca. 3950 Ma Imbrium impact event, with subsequent heating during an impact at ca. 110 Ma that ejected the sample to the vicinity of its collection site. Our data show that zircon has the potential to retain 4He over immense timescales (≥3950 Myrs), thus providing a valuable new thermochronometer for probing the impact histories of lunar samples, and martian or asteroidal meteorites.

Archaean zircons in Miocene oceanic hotspot rocks establish ancient continental crust beneath Mauritius

PubMed Central

Ashwal, Lewis D.; Wiedenbeck, Michael; Torsvik, Trond H.

2017-01-01

A fragment of continental crust has been postulated to underlie the young plume-related lavas of the Indian Ocean island of Mauritius based on the recovery of Proterozoic zircons from basaltic beach sands. Here we document the first U–Pb zircon ages recovered directly from 5.7 Ma Mauritian trachytic rocks. We identified concordant Archaean xenocrystic zircons ranging in age between 2.5 and 3.0 Ga within a trachyte plug that crosscuts Older Series plume-related basalts of Mauritius. Our results demonstrate the existence of ancient continental crust beneath Mauritius; based on the entire spectrum of U–Pb ages for old Mauritian zircons, we demonstrate that this ancient crust is of central-east Madagascar affinity, which is presently located ∼700 km west of Mauritius. This makes possible a detailed reconstruction of Mauritius and other Mauritian continental fragments, which once formed part of the ancient nucleus of Madagascar and southern India. PMID:28140395

Detrital zircon geochronology of pre- and syncollisional strata, Acadian orogen, Maine Appalachians

USGS Publications Warehouse

Bradley, Dwight C.; O'Sullivan, Paul B.

2017-01-01

The Central Maine Basin is the largest expanse of deep-marine, Upper Ordovician to Devonian metasedimentary rocks in the New England Appalachians, and is a key to the tectonics of the Acadian Orogeny. Detrital zircon ages are reported from two groups of strata: (1) the Quimby, Rangeley, Perry Mountain and Smalls Falls Formations, which were derived from inboard, northwesterly sources and are supposedly older; and (2) the Madrid, Carrabassett and Littleton Formations, which were derived from outboard, easterly sources and are supposedly younger. Deep-water deposition prevailed throughout, with the provenance shift inferred to mark the onset of foredeep deposition and orogeny. The detrital zircon age distribution of a composite of the inboard-derived units shows maxima at 988 and 429 Ma; a composite from the outboard-derived units shows maxima at 1324, 1141, 957, 628, and 437 Ma. The inboard-derived units have a greater proportion of zircons between 450 and 400 Ma. Three samples from the inboard-derived group have youngest age maxima that are significantly younger than the nominal depositional ages. The outboard-derived group does not share this problem. These results are consistent with the hypothesised provenance shift, but they signal potential problems with the established stratigraphy, structure, and (or) regional mapping. Shallow-marine deposits of the Silurian to Devonian Ripogenus Formation, from northwest of the Central Maine Basin, yielded detrital zircons featuring a single age maximum at 441 Ma. These zircons were likely derived from a nearby magmatic arc now concealed by younger strata. Detrital zircons from the Tarratine Formation, part of the Acadian foreland-basin succession in this strike belt, shows age maxima at 1615, 980 and 429 Ma. These results are consistent with three episodes of zircon recycling beginning with the deposition of inboard-derived strata of the Central Maine Basin, which were shed from post-Taconic highlands located to the

Zircon reveals protracted magma storage and recycling beneath Mount St. Helens

USGS Publications Warehouse

Claiborne, L.L.; Miller, C.F.; Flanagan, D.M.; Clynne, M.A.; Wooden, J.L.

2010-01-01

Current data and models for Mount St. Helens volcano (Washington, United States) suggest relatively rapid transport from magma genesis to eruption, with no evidence for protracted storage or recycling of magmas. However, we show here that complex zircon age populations extending back hundreds of thousands of years from eruption age indicate that magmas regularly stall in the crust, cool and crystallize beneath the volcano, and are then rejuvenated and incorporated by hotter, young magmas on their way to the surface. Estimated dissolution times suggest that entrained zircon generally resided in rejuvenating magmas for no more than about a century. Zircon elemental compositions reflect the increasing influence of mafic input into the system through time, recording growth from hotter, less evolved magmas tens of thousands of years prior to the appearance of mafic magmas at the surface, or changes in whole-rock geochemistry and petrology, and providing a new, time-correlated record of this evolution independent of the eruption history. Zircon data thus reveal the history of the hidden, long-lived intrusive portion of the Mount St. Helens system, where melt and crystals are stored for as long as hundreds of thousands of years and interact with fresh influxes of magmas that traverse the intrusive reservoir before erupting. ?? 2010 Geological Society of America.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Microstructure and Properties of Zircon-Added Carbon Refractories for Blast Furnace

NASA Astrophysics Data System (ADS)

Zhu, Tianbin; Li, Yawei; Sang, Shaobai; Chen, Xilai; Zhao, Lei; Li, Yuanbing; Li, Shujing

2012-11-01

Microstructure and properties of zircon-added carbon refractory specimens for blast furnace (BF) were investigated with the aid of X-ray diffraction (XRD), a scanning electron microscope (SEM), energy-dispersive X-ray, mercury porosimetry, and a laser thermal conductivity (TC) meter. Additives could influence the matrix structures and improve the properties of specimens. With the increase of zircon powder content, the amount of SiC whiskers formed increased and their aspect ratio became larger, and the SiC whiskers tended to be distributed homogeneously. Zircon powder additions decreased the mean pore diameter and increased <1- μm pore volume by filling in pores via SiC, improved the TC and the cold crushing strength (CCS) due to the in-situ formation of the more well-developed SiC whiskers with high TC, and significantly reduced the molten iron attack to carbon specimens.

Ablation enhancement of silicon by ultrashort double-pulse laser ablation

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

Zhao, Xin; Shin, Yung C.

In this study, the ultrashort double-pulse ablation of silicon is investigated. An atomistic simulation model is developed to analyze the underlying physics. It is revealed that the double-pulse ablation could significantly increase the ablation rate of silicon, compared with the single pulse ablation with the same total pulse energy, which is totally different from the case of metals. In the long pulse delay range (over 1 ps), the enhancement is caused by the metallic transition of melted silicon with the corresponding absorption efficiency. At ultrashort pulse delay (below 1 ps), the enhancement is due to the electron excitation by the first pulse.more » The enhancement only occurs at low and moderate laser fluence. The ablation is suppressed at high fluence due to the strong plasma shielding effect.« less

Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

PubMed

d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

2013-12-17

The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP.

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

Endometrial Ablation

MedlinePlus

... or lighter levels. If ablation does not control heavy bleeding, further treatment or surgery may be needed. ... ablation is used to treat many causes of heavy bleeding. In most cases, women with heavy bleeding ...

Rock-magnetic properties of single zircon crystals sampled from the Tanzawa tonalitic pluton, central Japan

NASA Astrophysics Data System (ADS)

Sato, Masahiko; Yamamoto, Shinji; Yamamoto, Yuhji; Okada, Yoshihiro; Ohno, Masao; Tsunakawa, Hideo; Maruyama, Shigenori

2015-09-01

This paper reports on the rock-magnetic properties of single zircon crystals, which are essential for future work establishing the reliable paleointensity method using single zircon crystals. Zircon crystals used in this study were sampled from the Nakagawa River, which crosses the Tanzawa tonalitic pluton in central Japan. Rock-magnetic measurements were conducted on 1037 grains of zircons, but many of these measurements are below the limits of the sensitivity of the magnetometers employed. Isothermal remanent magnetizations (IRMs) of 876 zircon crystal are below the practical resolution of this study; we infer that these crystals contain no or only minute quantities of ferromagnetic minerals. The other zircon crystals contain enough magnetic minerals to be measured in the DC SQUID magnetometer. For 81 zircon crystals, IRM intensities ( M IRM) are larger than 4 × 10-12 Am2, while natural remanent magnetization (NRM) intensities ( M NRM) are below 4 × 10-12 Am2, indicating that these crystals are inappropriate for the paleomagnetic study. For the samples that had values of M NRM ≥ 4 × 10-12 Am2 and M IRM ≥ 4 × 10-12 Am2 (80 zircons), combining the rock-magnetic parameter, we proposed the sample-selection criteria for future study of paleointensity experiments using single zircon crystals. In the case that the samples had high coercivity ( B c) values (>10 mT) or high M NRM/ M IRM values (>~0.1), main remanence carriers are probably pyrrhotite and these samples are inappropriate for the paleointensity study. In the case that the samples had low B c values (<10 mT) and low M NRM/ M IRM values (<~0.1), main remanence carriers seem to be nearly pure magnetite with pseudo-single-domain grain sizes, and these samples are expected to appropriate for the paleointensity study. Total thermoremanent magnetization (TRM) acquisition experiments were also carried out for 12 samples satisfying the above criteria. The TRM intensity was comparable with that of NRM, and a

Micro-scale novel stable isotope fractionation during weathering disclosed by femtosecond laser ablation

NASA Astrophysics Data System (ADS)

Schuessler, J. A.; von Blanckenburg, F.

2012-12-01

The stable isotope fractionation of metals and metalloids during chemical weathering and alteration of rocks at low temperature is a topic receiving increasing scientific attention. For these systems, weathering of primary minerals leads to selective partitioning of isotopes between the secondary minerals formed from them, and the dissolved phase of soil or river water. While the isotopic signatures of these processes have been mapped-out at the catchment or the soil scale, the actual isotopic fractionation is occurring at the mineral scale. To identify the processes underlying such micro-scale fractionation, the development of micro-analytical tools allows to investigate mechanisms of isotope fractionation in-situ, in combination with textural information of weathering reactions. We have developed a second-generation UV femtosecond (fs) laser system at GFZ Potsdam. The advantage of UV-fs laser ablation is the reduction of laser-induced isotopic and elemental fractionation by avoiding 'thermal effects' during ablation, such that accurate isotope ratios can be measured by standard-sample-standard bracketing using laser ablation multicollector ICP-MS; where the matrix of the bracketing standard does not need to match that of the sample [1]. Our system consists of the latest generation femtosecond solid-state laser (Newport Spectra Physics Solstice), producing an ultra short pulse width of about 100 femtoseconds at a wavelength of 196 nm. The system is combined with a custom-build computer-controlled sample stage and allows fully automated isotope analyses through synchronised operation of the laser with the Neptune MC-ICP-MS. To assess precision and accuracy of our laser ablation method, we analysed various geological reference materials. We obtained δ30Si values of -0.31 ± 0.23 (2SD, n = 13) for basalt glass BHVO-2G, and -1.25 ± 0.21 (2SD, n = 27) for pure Si IRMM17 when bracketed against NBS-28 quartz. δ56Fe and δ26Mg values obtained from non-matrix matched

Extinct Plutonium Geochemistry of Ancient Hadean Zircons

NASA Astrophysics Data System (ADS)

Turner, G.; Gilmour, J.; Crowther, S.; Busfield, A.; Mojzsis, S.; Harrison, M.

2005-12-01

The abundance of 244Pu in the early solar system has important implications for r-process nucleosynthesis and models of noble gas transport within the Earth's mantle. Our recent discovery(1) of xenon isotopes from the in-situ decay of 244Pu in ancient Jack Hills zircons promises to provide a new time-sensitive window on the first 500 Ma of Earth history. We have extended this initial work by the use of resonance ioniisation mass spectrometry to analyse xenon released by stepped heating from 17 individual zircons with Pb-Pb ages in the range 3.95 to 4.18 Ga. Our immediate objectives are to determine the causes of variations in the inferred Pu/U ratios and in the longer term to determine the initial Pu/U ratio of the Earth. The Pu/U ratios calculated for individual zircons may be expected to vary as a result of igneous fractionation and also from differential loss of Pu and U fission xenon in the last 4 Ga. We have studied the effects of xenon loss by irradiating the zircons with thermal neutrons to generate xenon from 235U neutron fission in order to determine U/Xe ratios and apparent ages. 131Xe/134Xe and 132Xe/134Xe ratios can be used to calculate the relative contributions from 244Pu and 238U spontaneous fission and 235U neutron fission. The measured Pu/U ratios (back calculated to 4.56 Ga on the basis of the individual Pb-Pb ages) range from zero to 0.012. The highest ratio in our initial study was 0.008 (note that the published ratio has been revised upwards on the basis of improved decay parameters for 238U spontaneous fission). Comparison of Pb-Pb and U-Xe ages indicate varying amounts of xenon loss, over 50% in some cases. While this accounts for some of the variability in the inferred Pu/U, igneous fractionation may also play a part, and we are currently attempting to investigate this by a comparison with REE abundances. Reference: (1) Turner et al. (2004) Science, 306, 89-91.

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.

Momentum and velocity of the ablated material in laser machining of carbon fiber preforms

NASA Astrophysics Data System (ADS)

Mucha, P.; Speker, N.; Weber, R.; Graf, T.

2013-11-01

The automation in fabrication of CFRP (carbon-fiber-reinforced plastics) parts demands efficient and low-cost machining technologies. In conventional cutting technologies, tool-wear and low process speeds are some of the reasons for high costs. Thus, the use of lasers is an attractive option for cutting CF-preforms. A typical effect degrading the quality in laser cutting CF-preform is a bulged cutting edge. This effect is assumed to be caused by interaction of the fibers with the ablated material, which leaves the kerf at high velocity. Hence, a method for measuring the momentum and the velocity of the vapor is presented in this article. To measure the momentum of the ablated material, the CF-preform is mounted on a precision scale while cutting it with a laser. The direction of the momentum was determined by measuring the momentum parallel and orthogonal to the CF-preform surface. A change of the direction of the momentum with different cutting-speeds is assessed at constant laser-power. Averaged velocities of the ablation products of up to 300 m/s were determined by measuring the ablated mass and the momentum.

Interpretation of zircon coronae textures from metapelitic granulites of the Ivrea-Verbano Zone, northern Italy: two-stage decomposition of Fe-Ti oxides

NASA Astrophysics Data System (ADS)

Kovaleva, Elizaveta; Austrheim, Håkon O.; Klötzli, Urs S.

2017-07-01

In this study, we report the occurrence of zircon coronae textures in metapelitic granulites of the Ivrea-Verbano Zone. Unusual zircon textures are spatially associated with Fe-Ti oxides and occur as (1) vermicular-shaped aggregates 50-200 µm long and 5-20 µm thick and as (2) zircon coronae and fine-grained chains, hundreds of micrometers long and ≤ 1 µm thick, spatially associated with the larger zircon grains. Formation of such textures is a result of zircon precipitation during cooling after peak metamorphic conditions, which involved: (1) decomposition of Zr-rich ilmenite to Zr-bearing rutile, and formation of the vermicular-shaped zircon during retrograde metamorphism and hydration; and (2) recrystallization of Zr-bearing rutile to Zr-depleted rutile intergrown with quartz, and precipitation of the submicron-thick zircon coronae during further exhumation and cooling. We also observed hat-shaped grains that are composed of preexisting zircon overgrown by zircon coronae during stage (2). Formation of vermicular zircon (1) preceded ductile and brittle deformation of the host rock, as vermicular zircon is found both plastically and cataclastically deformed. Formation of thin zircon coronae (2) was coeval with, or immediately after, brittle deformation as coronae are found to fill fractures in the host rock. The latter is evidence of local, fluid-aided mobility of Zr. This study demonstrates that metamorphic zircon can nucleate and grow as a result of hydration reactions and mineral breakdown during cooling after granulite-facies metamorphism. Zircon coronae textures indicate metamorphic reactions in the host rock and establish the direction of the reaction front.

Complex Histories of Two Lunar Zircons as Evidenced by their Internal Structures and U-Pb Ages

NASA Technical Reports Server (NTRS)

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

2006-01-01

The U-Pb dating of lunar zircon by ion-microprobe provides a robust technique for investigating the timing of lunar events [1,2]. However, we have now identified two cases where the U-Pb systems in a single zircon show more than one age. These complex zircons provide new opportunities for extending our knowledge on the timing of events in the early history of the Moon.

A detrital zircon provenance study of the Lower Carboniferous sequences in the East Fife section of the Midland Valley of Scotland

NASA Astrophysics Data System (ADS)

Murchie, Sean; Robinson, Ruth, ,, Dr; Lancaster, Penelope, ,, Dr

2014-05-01

Detrital zircons from the Lower Carboniferous clastic rocks of the Midland Valley of Scotland have been dated using U-Pb laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) to determine which source areas contributed sediment to the basin during its development, and to investigate whether provenance changed during deposition of these units. Specific provenance detection using U/Pb dating of zircons has never been attempted in these rocks, and there are uncertainties remaining about the regional paleogeographic setting for the Midland Valley. Four samples from the Dinantian Strathclyde Group have been analysed, and the units are locally known as the Fife Ness, Anstruther, Pittenweem, Sandy Craig, and Pathhead formations. The formations are composed of shallow marine, deltaic, fluvial and floodplain deposits and these predominantly siliciclastic sedimentary rocks are interbedded with thin fossiliferous carbonate bands. The samples are quartz arenitic, sub-arkosic and lithic arkosic medium-grained sandstones, predominantly from a fluvial origin. The British Geological Survey developed a lithostratigraphy which is the most used framework for the Strathclyde Group (Browne et al., 1997), but a different biostratigraphical framework based on palynology has been proposed by Owens et al. (2005). In addition to identifying provenance, the zircon age populations for each formation are compared to test which stratigraphic framework is correct. More broadly, the provenance data provides a way to improve the regional palaeogeographic setting for the Midland Valley. Zircon ages in the Strathclyde Group are dominated by Late Mesoproterozoic to Late Palaeoproterozoic (0.9 - 2.0 Ga) and Early Palaeozoic (350 - 450 Ma) ages which reflect Caledonide (Laurentian-Baltica margin including Scotland, Scandinavia, Greenland, Newfoundland), Grampian and internal Midland Valley source areas. Notable peaks occur at 400 Ma, 1.0 --1.1 Ga, 1.3 Ga, 1.6 - 1.7 Ga, and 2.7 Ga, and

Low heat flow inferred from >4 Gyr zircons suggests Hadean plate boundary interactions.

PubMed

Hopkins, Michelle; Harrison, T Mark; Manning, Craig E

2008-11-27

The first approximately 600 million years of Earth history (the 'Hadean' eon) remain poorly understood, largely because there is no rock record dating from that era. Detrital Hadean igneous zircons from the Jack Hills, Western Australia, however, can potentially provide insights into the conditions extant on our planet at that time. Results of geochemical investigations using these ancient grains have been interpreted to suggest the presence of a hydrosphere and continental crust before 4 Gyr. An underexploited characteristic of the >4 Gyr zircons is their diverse assemblage of mineral inclusions. Here we present an examination of over 400 Hadean zircons from Jack Hills, which shows that some inclusion assemblages are conducive to thermobarometry. Our thermobarometric analyses of 4.02-4.19-Gyr-old inclusion-bearing zircons constrain their magmatic formation conditions to about 700 degrees C and 7 kbar. This result implies a near-surface heat flow of approximately 75 mW m(-2), about three to five times lower than estimates of Hadean global heat flow. As the only site of magmatism on modern Earth that is characterized by heat flow of about one-quarter of the global average is above subduction zones, we suggest that the magmas from which the Jack Hills Hadean zircons crystallized were formed largely in an underthrust environment, perhaps similar to modern convergent margins.

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.;

[Successful transcatheter ablation of fascicular potential in pediatric patients with left posterior fascicular tachycardia].

PubMed

Zeng, Shao-ying; Shi, Ji-jun; Li, Hong; Zhang, Zhi-wei; Li, Yu-fen

2010-08-01

To simplify the methods of transcatheter mapping and ablation in the pediatric patients with left posterior fascicular tachycardia. While in sinus rhythm, the fascicular potential can be mapped at the posterior septal region (1 - 2 cm below inferior margin of orifice of coronary sinus vein), which display a biphasic wave before ventricular wave, and exist equipotential lines between them. When the fascicular potential occurs 20 ms later than the bundle of His' potential, radiofrequency was applied. Before applying radiofrequency, catheter position must be observed using double angle viewing (LAO 45°RAO 30°), and it should be made sure that the catheter is not at His' bundle. If the electrocardiogram displays left posterior fascicular block, the correct region is identified and ablation can continue for 60 s. Electrocardiogram monitoring should continue for 24 - 48 hours after operation, and notice abnormal repolarization after termination of ventricular tachycardia. Aspirin [2 - 3 mg/(kg·d)] was used for 3 months, and antiarrhythmic drug was discontinued. Surface electrocardiogram, chest X-ray and ultrasound cardiography were rechecked 1 d after operation. Follow-up was made at 1 month and 3 months post-discharge. Recheck was made half-yearly or follow-up was done by phone from then on. Fifteen pediatric patients were ablated successfully, and their electrocardiograms all displayed left posterior fascicular block after ablation. None of the patients had recurrences during the 3 to 12 months follow-up period. In one case, the electrocardiogram did not change after applying radiofrequency ablation and the ventricular tachycardia remained; however, on second attempt after remapping, the electrocardiogram did change. The radiofrequency lasted for 90 seconds and ablation was successful. This case had no recurrences at 6 months follow-up. Transcatheter ablation of the fascicular potential in pediatric patients with left posterior fascicular tachycardia can simplify

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.

The first discovery of Hadean zircon in garnet granulites from the Sutam River (Aldan Shield)

NASA Astrophysics Data System (ADS)

Glukhovskii, M. Z.; Kuz'min, M. I.; Bayanova, T. B.; Lyalina, L. M.; Makrygina, V. A.; Shcherbakova, T. F.

2017-09-01

For the first time in Russia, a Hadean zircon grain with an age of 3.94 Ga (ID-TIMS) has been discovered in high-aluminous garnet granulites of the Aldan Shield among the U-Pb zircons with an age from 1.92 Ga. In this connection, the problems of its parental source, the petrogenesis of granulites that captured this zircon, and the mechanism of occurrence of these deep rocks in the upper horizons of the crust have been solved. The comparison of the geochemistry of garnet granulites and the middle crust has shown that the granulites are enriched in the entire range of rare-earth elements (except for the Eu minimum), as well as in Al2O3, U, and Th and are depleted in the most mobile elements (Na, Ca, Sr). In the upper part of the allitic weathering zone of the middle crust, which formed under conditions of arid climate, this zircon grain was originated from the weathered granites from the middle crust. In the latter case, they were empleced discretely in the upper granite-gneiss crust under high pressure conditions (the rutile age is 1.83-1.82 Ga). The zircon with an age of 3.94 Ga is comparable to the Hadean zircons from orthogneisses of the Acasta region (Canadian Shield, 4.03-3.94 Ga).

Milling assisted synthesis of calcium zirconate СаZrО3

NASA Astrophysics Data System (ADS)

Kalinkin, A. M.; Nevedomskii, V. N.; Kalinkina, E. V.; Balyakin, K. V.

2014-08-01

Monophase calcium zirconate (CaZrO3) has been prepared from the equimolar ZrO2 + CaCO3 mixture by two-step synthesis process. In the first step, mechanical treatment of the mixture is performed in an AGO-2 planetary ball mill. In the second step, the milled mixture is annealed to form calcium zirconate. High-energy ball milling of the (ZrO2+CaCO3) mixture results in decrease in the temperature of CaZrO3 formation during annealing at 950 °C. The enhancement of CaZrO3 synthesis is due to accumulation of excess energy by the reagents, decreasing the particle size and notable increase in the interphase area because of “smearing” of CaCO3 on ZrO2 particles during milling. Nanocrystalline calcium zirconate has been produced by controlling the annealing temperature and time.

Zircon-pyrochlore ores of Proterozoic Gremyakha-Vyrmes polyphase massif, Kola Peninsula: source and evolution

NASA Astrophysics Data System (ADS)

Sorokhtina, Natalia; Belyatsky, Boris; Antonov, Anton; Kononkova, Natalia; Lepekhina, Elena; Kogarko, Lia

2017-04-01

The alkaline-ultrabasic Gremyakha-Vyrmes massif occurs within the Central Kola terrane in the northern part of the Fennoscandian Shield and consists of diverse rock complexes: basic-ultrabasic rocks, foidolites, alkaline metasomatic rocks and carbonatites, alkaline granites and granosyenites. Nb-Zr ore deposit is confined to alkaline metasomatic rocks developed over foidolites. The metasomatites are represented by albitites and aegirinites occur as submeridionally orientated zones extending up to 6-8 km and several hundred meters thickness. They are mainly composed of albite and aegirine, but amphibole, annite, microcline, fluorapatite, titanite, ilmenite, pyrochlore group minerals, zircon are present [Sorokhtina et al., 2016]. Carbonatites are developed sporadically and accessory zircon but not the pyrochlore is observed only in contact zones with albitites and aegerinites. In metasomatites, zircon and pyrochlore are main rare metal minerals, which are formed at the latest stages of crystallization. Ca-dominant fluorcalcio- and hydroxycalciopyrochlores are the most abundant, whereas U-dominant pyrochlore, oxyuranobetafite, zero-valent-dominant (Ba, Sr-dominant) pyrochlore, hydro- or kenopyrochlore are rare. The pyrochlore-group minerals form heterogeneous metacrystals containing inclusions of host rock minerals, calcite, ilmenite, zircon, sulfides, and graphite. While pyrochlore is replaced by Si-rich "pyrochlore" (SiO2 is up to 18 wt.%.), cation-deficient hydrated pyrochlore, Fe-Si-Nb, U-Si-Nb, and Al-Si-Nb phases along fracture zones and margins. The early generation zircon is represented by large heterogeneous metacrystals filled with inclusions of various host rock minerals, calcite, ilmenite, thorite, thorianite and sulfides, while the late zircons are empty of inclusions. Zircons are nearly stoichiometric in composition; but intermediate zones are enriched in Pb, Y and Th, and overgrowths are enriched Hf only. According to CL and ion-microprobe analysis

Zircon ion microprobe dating of high-grade rocks in Sri Lanka

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

Kroener, A.; Williams, I.S.; Compston, W.

1987-11-01

The high-grade gneisses of Sri Lanka display spectacular in-situ granulitization phenomena similar to those observed in southern India and of current interest for evolutionary models of the lower continental crust. The absolute ages of these rocks are poorly constrained and so, using the SHRIMP ion microprobe, the authors have analyzed small spots on zircons from upper amphibolite to granulite grade quartzitic and pelitic metasediments. Detrital grains from a metaquartzite of the Highland Group preserve premetamorphic U-Pb ages of between 3.17 and 2.4 Ga and indicate derivation of the sediment from an unidentified Archean source terrain. The Pb-loss patterns of thesemore » zircons and the other samples suggest severe disturbance at ca 1100 Ma ago, which the authors attribute to high-grade regional metamorphism. Two pelitic gneisses contain detrital zircons with ages up to 2.04 Ga and also record an approx. = 1100 Ma event that is also apparent from metamorphic rims around old cores and new zircon growth. A granite intrusive into the Highland Group granulites records an emplacement age of 1000-1100 Ma as well as metamorphic disturbance some 550 Ma ago but also contains older, crustally derived xenocrysts. Zircons from a metaquartzite xenolith within the granitoid Vijayan Complex are not older than approx. 1100 Ma; therefore the Vijayan is neither Archean in age nor acted as basement to the Highland Group, as previously proposed. The authors suggest that the Vijayan Complex formed significantly later than the Highland Group and that the two units were brought into contact through post-1.1 Ga thrusting. Although the granulitization phenomena in India and Sri Lanka are similar, the granulite event in Sri Lanka is not Archean in age but took place in the late Proterozoic.« less

Lithofacies control in detrital zircon provenance studies: Insights from the Cretaceous Methow basin, southern Canadian Cordillera

USGS Publications Warehouse

DeGraaff-Surpless, K.; Mahoney, J.B.; Wooden, J.L.; McWilliams, M.O.

2003-01-01

High-frequency sampling for detrital zircon analysis can provide a detailed record of fine-scale basin evolution by revealing the temporal and spatial variability of detrital zircon ages within clastic sedimentary successions. This investigation employed detailed sampling of two sedimentary successions in the Methow/Methow-Tyaughton basin of the southern Canadian Cordillera to characterize the heterogeneity of detrital zircon signatures within single lithofacies and assess the applicability of detrital zircon analysis in distinguishing fine-scale provenance changes not apparent in lithologic analysis of the strata. The Methow/Methow-Tyaughton basin contains two distinct stratigraphic sequences of middle Albian to Santonian clastic sedimentary rocks: submarine-fan deposits of the Harts Pass Formation/Jackass Mountain Group and fluvial deposits of the Winthrop Formation. Although both stratigraphic sequences displayed consistent ranges in detrital zircon ages on a broad scale, detailed sampling within each succession revealed heterogeneity in the detrital zircon age distributions that was systematic and predictable in the turbidite succession but unpredictable in the fluvial succession. These results suggest that a high-density sampling approach permits interpretation of finescale changes within a lithologically uniform turbiditic sedimentary succession, but heterogeneity within fluvial systems may be too large and unpredictable to permit accurate fine-scale characterization of the evolution of source regions. The robust composite detrital zircon age signature developed for these two successions permits comparison of the Methow/Methow-Tyaughton basin age signature with known plutonic source-rock ages from major plutonic belts throughout the Cretaceous North American margin. The Methow/Methow-Tyaughton basin detrital zircon age signature matches best with source regions in the southern Canadian Cordillera, requiring that the basin developed in close proximity to the

Investigating sources of ignimbrites in the Altiplano-Puna Volcanic Complex using U-Pb dating of zircons

NASA Astrophysics Data System (ADS)

Kern, J. M.; de Silva, S. L.; Schmitt, A. K.

2011-12-01

Large silicic volcanic fields (LSVFs) are thought to represent the surface expression of upper crustal batholith emplacement, with the spatiotemporal distribution of the vents and eruptions representing the development of the system. The Altiplano-Puna Volcanic Complex (APVC) in the Central Andes is a LSVF active from 11-1 Ma that erupted over 13,000 km3 of magma from large, multicyclic caldera centers and smaller ignimbrite shields during 3 distinct pulses of volcanism at 8.4, 5.5, and 4.0 Ma. Links to the magmatic system beneath are being pursued through U-Pb zircon dating of APVC ignimbrites. Initial results comprise 61 238U/206Pb zircon ages of mostly marginal crystal domains from five APVC ignimbrites-the 0.98 ± 0.03 Ma Purico, 3.96 ± 0.08 Ma Atana, 4.0 ± 0.9 Ma Toconao, 4.09 ± 0.02 Ma Puripicar, and 8.33 ± 0.06 Ma Sifon ignimbrites-dated by high-resolution secondary ionization mass spectrometry (SIMS). Each zircon analyzed was less than 350 μm in length and cathodoluminescence images reveal zonations within individual zircons, though significant core-rim age differences are rare. The ~1 Ma Purico ignimbrite displays multiple zircon age populations significantly predating the 40Ar/39Ar eruption age, but younger than ages from the nearby large-volume Atana ignimbrite erupted from La Pacana caldera. Some peaks do, however, coincide with later resurgent activity within La Pacana as expressed by the 2.7 Ma Cerro Bola dome. Zircon ages in the Atana ignimbrite are indistinguishable from its eruption, while those from the 4.0 Ma Toconao ignimbrite-the volatile-rich cap of the Atana magma chamber-contains three populations of xenocrystic zircons from the Proterozoic-Ordivician, ~13 Ma, and ~9 Ma. The ~9 Ma zircons correlate with K-Ar ages from an underlying ignimbrite, whereas the 13 Ma xenocrysts likely have a plutonic source. The Purico ignimbrite thus provides direct evidence of zircon inheritance from previous eruption cycles, while the Toconao records a

Quasi ?non-destructive? laser ablation-inductively coupled plasma-mass spectrometry fingerprinting of sapphires

NASA Astrophysics Data System (ADS)

Guillong, M.; Günther, D.

2001-07-01

A homogenized 193 nm excimer laser with a flat-top beam profile was used to study the capabilities of LA-ICP-MS for 'quasi' non-destructive fingerprinting and sourcing of sapphires from different locations. Sapphires contain 97-99% of Al 2O 3 (corundum), with the remainder composed of several trace elements, which can be used to distinguish the origin of these gemstones. The ablation behavior of sapphires, as well as the minimum quantity of sample removal that is required to determine these trace elements, was investigated. The optimum ablation conditions were a fluency of 6 J cm -2, a crater diameter of 120 μm, and a laser repetition rate of 10 Hz. The optimum time for the ablation was determined to be 2 s, equivalent to 20 laser pulses. The mean sample removal was 60 nm per pulse (approx. 3 ng per pulse). This allowed satisfactory trace element determination, and was found to cause the minimum amount of damage, while allowing for the fingerprinting of sapphires. More than 40 isotopes were measured using different spatial resolutions (20-120 μm) and eight elements were reproducibly detected in 25 sapphire samples from five different locations. The reproducibility of the trace element distribution is limited by the heterogeneity of the sample. The mean of five or more replicate analyses per sample was used. Calibration was carried out using NIST 612 glass reference material as external standard. The linear dynamic range of the ICP-MS (nine orders of magnitude) allowed the use of Al, the major element in sapphire, as an internal standard. The limits of detection for most of the light elements were in the μg g -1 range and were better for heavier elements (mass >85), being in the 0.1 μg g -1 range. The accuracy of the determinations was demonstrated by comparison with XRF analyses of the same set of samples. Using the quantitative analyses obtained using LA-ICP-MS, natural sapphires from five different origins were statistically classified using ternary plots and

Microwave Ablation Compared with Radiofrequency Ablation for Breast Tissue in an Ex Vivo Bovine Udder Model

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

Tanaka, Toshihiro, E-mail: toshihir@bf6.so-net.ne.jp; Westphal, Saskia, E-mail: swestphal@ukaachen.de; Isfort, Peter, E-mail: isfort@hia.rwth-aachen.de

2012-08-15

Purpose: To compare the effectiveness of microwave (MW) ablation with radiofrequency (RF) ablation for treating breast tissue in a nonperfused ex vivo model of healthy bovine udder tissue. Materials and Methods: MW ablations were performed at power outputs of 25W, 35W, and 45W using a 915-MHz frequency generator and a 2-cm active tip antenna. RF ablations were performed with a bipolar RF system with 2- and 3-cm active tip electrodes. Tissue temperatures were continuously monitored during ablation. Results: The mean short-axis diameters of the coagulation zones were 1.34 {+-} 0.14, 1.45 {+-} 0.13, and 1.74 {+-} 0.11 cm for MWmore » ablation at outputs of 25W, 35W, and 45W. For RF ablation, the corresponding values were 1.16 {+-} 0.09 and 1.26 {+-} 0.14 cm with electrodes having 2- and 3-cm active tips, respectively. The mean coagulation volumes were 2.27 {+-} 0.65, 2.85 {+-} 0.72, and 4.45 {+-} 0.47 cm{sup 3} for MW ablation at outputs of 25W, 35W, and 45W and 1.18 {+-} 0.30 and 2.29 {+-} 0.55 cm{sup 3} got RF ablation with 2- and 3-cm electrodes, respectively. MW ablations at 35W and 45W achieved significantly longer short-axis diameters than RF ablations (P < 0.05). The highest tissue temperature was achieved with MW ablation at 45W (P < 0.05). On histological examination, the extent of the ablation zone in MW ablations was less affected by tissue heterogeneity than that in RF ablations. Conclusion: MW ablation appears to be advantageous with respect to the volume of ablation and the shape of the margin of necrosis compared with RF ablation in an ex vivo bovine udder.« less

Benign thyroid nodule unresponsive to radiofrequency ablation treated with laser ablation: a case report.

PubMed

Oddo, Silvia; Balestra, Margherita; Vera, Lara; Giusti, Massimo

2018-05-11

Radiofrequency ablation and laser ablation are safe and effective techniques for reducing thyroid nodule volume, neck symptoms, and cosmetic complaints. Therapeutic success is defined as a nodule reduction > 50% between 6 and 12 months after the procedure, but a percentage of nodules inexplicably do not respond to thermal ablation. We describe the case of a young Caucasian woman with a solid benign thyroid nodule who refused surgery and who had undergone radiofrequency ablation in 2013. The nodule did not respond in terms of either volume reduction or improvement in neck symptoms. After 2 years, given the patient's continued refusal of thyroidectomy, we proposed laser ablation. The nodule displayed a significant volume reduction (- 50% from radiofrequency ablation baseline volume, - 57% from laser ablation baseline), and the patient reported a significant improvement in neck symptoms (from 6/10 to 1/10 on a visual analogue scale). We conjecture that some benign thyroid nodules may be intrinsically resistant to necrosis when one specific ablation technique is used, but may respond to another technique. To the best of our knowledge, this is the first description of the effect of performing a different percutaneous ablation technique in a nodule that does not respond to radiofrequency ablation.

Multi-mode Li diffusion in natural zircons: Evidence for diffusion in the presence of step-function concentration boundaries

NASA Astrophysics Data System (ADS)

Tang, Ming; Rudnick, Roberta L.; McDonough, William F.; Bose, Maitrayee; Goreva, Yulia

2017-09-01

Micron- to submicron-scale observations of Li distribution and Li isotope composition profiles can be used to infer the mechanisms of Li diffusion in natural zircon. Extreme fractionation (20-30‰) within each single crystal studied here confirms that Li diffusion commonly occurs in zircon. Sharp Li concentration gradients frequently seen in zircons suggest that the effective diffusivity of Li is significantly slower than experimentally determined (Cherniak and Watson, 2010; Trail et al., 2016), otherwise the crystallization/metamorphic heating of these zircons would have to be unrealistically fast (years to tens of years). Charge coupling with REE and Y has been suggested as a mechanism that may considerably reduce Li diffusivity in zircon (Ushikubo et al., 2008; Bouvier et al., 2012). We show that Li diffused in the direction of decreasing Li/Y ratio and increasing Li concentration (uphill diffusion) in one of the zircons, demonstrating charge coupling with REE and Y. Quantitative modeling reveals that Li may diffuse in at least two modes in natural zircons: one being slow and possibly coupled with REE+Y, and the other one being fast and not coupled with REE+Y. The partitioning of Li between these two modes during its diffusion may depend on the pre-diffusion substitution mechanism of REE and Y in the zircon lattice. Based on our results, sharp Li concentration gradients are not indicative of limited diffusion, and can be preserved at temperatures >700 °C on geologic timescales. Finally, large δ7 Li variations observed in the Hadean Jack Hills zircons may record kinetic fractionation, rather than a record of ancient intense weathering in the granite source materials.

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

Effects of material composition on the ablation performance of low density elastomeric ablators

NASA Technical Reports Server (NTRS)

Tompkins, S. S.; Kabana, W. P.

1973-01-01

The ablation performance of materials composed of various concentrations of nylon, hollow silica spheres, hollow phenolic spheres, and four elastomeric resins was determined. Both blunt-body and flat-panel specimens were used, the cold-wall heating-rate ranges being 0.11 to 0.8 MW/sq m, respectively. The corresponding surface pressure ranges for these tests were 0.017 to 0.037 atmosphere and 0.004 to 0.005 atmosphere. Some of the results show that (1) the addition of nylon significantly improved the ablation performance, but the nylon was not compatible with one resin system; (2) panel and blunt-body specimen data do not show the same effect of phenolic sphere content on ablation effectiveness; and (3) there appears to be an optimum concentration of hollow silica spheres for good ablation performance. The composition of an efficient, nonproprietary ablator for lifting body application is identified and the ablation performance of this ablator is compared with the performance of three commercially available materials.

LA-ICP-MS of magnetite: Methods and reference materials

USGS Publications Warehouse

Nadoll, P.; Koenig, A.E.

2011-01-01

Magnetite (Fe3O4) is a common accessory mineral in many geologic settings. Its variable geochemistry makes it a powerful petrogenetic indicator. Electron microprobe (EMPA) analyses are commonly used to examine major and minor element contents in magnetite. Laser ablation ICP-MS (LA-ICP-MS) is applicable to trace element analyses of magnetite but has not been widely employed to examine compositional variations. We tested the applicability of the NIST SRM 610, the USGS GSE-1G, and the NIST SRM 2782 reference materials (RMs) as external standards and developed a reliable method for LA-ICP-MS analysis of magnetite. LA-ICP-MS analyses were carried out on well characterized magnetite samples with a 193 nm, Excimer, ArF LA system. Although matrix-matched RMs are sometimes important for calibration and normalization of LA-ICP-MS data, we demonstrate that glass RMs can produce accurate results for LA-ICP-MS analyses of magnetite. Cross-comparison between the NIST SRM 610 and USGS GSE-1G indicates good agreement for magnetite minor and trace element data calibrated with either of these RMs. Many elements show a sufficiently good match between the LA-ICP-MS and the EMPA data; for example, Ti and V show a close to linear relationship with correlation coefficients, R2 of 0.79 and 0.85 respectively. ?? 2011 The Royal Society of Chemistry.

Thermal events documented in Hadean zircons by ion microprobe depth profiles

NASA Astrophysics Data System (ADS)

Trail, Dustin; Mojzsis, Stephen J.; Harrison, T. Mark

2007-08-01

We report the first U-Th-Pb ion microprobe depth profiles of four Hadean zircons from the Jack Hills and Mount Narryer supracrustal belts of the Narryer Gneiss Complex (NGC), Western Australia. This ultra-high spatial resolution technique probes the age and origin of sub-micron features in individual crystals that can record episodes of zircon growth. Near-surface grain dates of 2700 Ma or older are coincident with post-depositional growth/modification. Some ages may coincide with documented pre-deposition metamorphic events for the NGC and igneous emplacement at ca. 3700 Ma. Separate events that do not correlate in time with known geologic episodes prior to the preserved rock record are also present on pre-4000 Ma zircons. We find evidence for a ˜3.9 Ga event, which is coterminous within age uncertainty with one or several large basin-forming impacts (e.g. Nectaris) on the Moon attributed to the late heavy bombardment of the inner solar system.

Zircon: Free Energy of Formation by Aqueous Solubility Measurements at High T and P

NASA Astrophysics Data System (ADS)

Newton, R. C.; Manning, C. E.; Hanchar, J. M.

2002-12-01

We measured the silica solubility at 800 °C, 12 kbar, of small (~0.5 mg) limpid euhedral zircon crystals grown by a flux-melt method (Hanchar et al., Am. Min., 86, 667, 2001). Incongruent solution occurs according to ZrSiO4 = ZrO2 + SiO2,aq. Zircon lost ~0.1 mg after exposure of 1-2 mg of zircon to ~32 mg H2O in welded Pt envelopes for 90-120 hr in piston-cylinder apparatus using NaCl-graphite furnaces. The average solubility was 0.0645+/-0.007 molal (m), or a mole fraction (XS) of 0.00116. Reversibility was established by rerunning the baddeleyite-coated zircons with a fluid initially slightly SiO2-oversaturated, as determined by the forward experiments, resulting in weight gains of the composite crystals. Similar runs on sintered ZrO2 compacts yielded spontaneous surface nucleation and growth of zircons up to 1 mm. Concentrations were corrected for a small, measured solubility of ZrO2 (0.001 m). Nonideality of aqueous silica was calculated assuming that SiO2,aq consists of a mixture of monomers and dimers (Zotov and Keppler (Chem. Geol., 184, 71, 2002; Newton and Manning, GCA, in press). Our zircon solubility and that of quartz at the same conditions (XS=0.02634, Manning, GCA, 58, 4831, 1994) give activity coefficients at the two concentrations of 0.730 and 0.255, respectively. The activity coefficients and concentrations yield the free energy of formation of zircon from the oxides at 800 °C, 12 kbar of -18.46+/-0.96 kJ/mol, which translates to -11.91+/-0.96 kJ/mol at 800 °C, 1 bar. Our value is compatible with previous estimates based on experiment (Schuiling et al., Am. Min., 61, 166, 1976) and high-T oxide-melt calorimetry (Ellison and Navrotsky, J. Am. Ceram. Soc., 75, 1430, 1992), but is four times more precise than these estimates.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Femtosecond laser ablation of dentin and enamel: relationship between laser fluence and ablation efficiency.

PubMed

Chen, Hu; Liu, Jing; Li, Hong; Ge, Wenqi; Sun, Yuchun; Wang, Yong; Lü, Peijun

2015-02-01

The objective was to study the relationship between laser fluence and ablation efficiency of a femtosecond laser with a Gaussian-shaped pulse used to ablate dentin and enamel for prosthodontic tooth preparation. A diode-pumped thin-disk femtosecond laser with wavelength of 1025 nm and pulse width of 400 fs was used for the ablation of dentin and enamel. The laser spot was guided in a line on the dentin and enamel surfaces to form a groove-shaped ablation zone under a series of laser pulse energies. The width and volume of the ablated line were measured under a three-dimensional confocal microscope to calculate the ablation efficiency. Ablation efficiency for dentin reached a maximum value of 0.020 mm3∕J when the laser fluence was set at 6.51 J∕cm2. For enamel, the maximum ablation efficiency was 0.009 mm3∕J at a fluence of 7.59 J∕cm2.Ablation efficiency of the femtosecond laser on dentin and enamel is closely related to the laser fluence and may reach a maximum when the laser fluence is set to an appropriate value. © 2015 Society of Photo-Optical Instrumentation Engineers (SPIE)

Rapid cooling rates at an active mid-ocean ridge from zircon thermochronology

USGS Publications Warehouse

Schmitt, Axel K.; Perfit, Michael R.; Rubin, Kenneth H.; Stockli, Daniel F.; Smith, Matthew C.; Cotsonika, Laurie A.; Zellmer, Georg F.; Ridley, W. Ian

2011-01-01

Oceanic spreading ridges are Earth's most productive crust generating environment, but mechanisms and rates of crustal accretion and heat loss are debated. Existing observations on cooling rates are ambiguous regarding the prevalence of conductive vs. convective cooling of lower oceanic crust. Here, we report the discovery and dating of zircon in mid-ocean ridge dacite lavas that constrain magmatic differentiation and cooling rates at an active spreading center. Dacitic lavas erupted on the southern Cleft segment of the Juan de Fuca ridge, an intermediate-rate spreading center, near the intersection with the Blanco transform fault. Their U–Th zircon crystallization ages (29.3-4.6+4.8 ka; 1δ standard error s.e.) overlap with the (U–Th)/He zircon eruption age (32.7 ± 1.6 ka) within uncertainty. Based on similar 238U-230Th disequilibria between southern Cleft dacite glass separates and young mid-ocean ridge basalt (MORB) erupted nearby, differentiation must have occurred rapidly, within ~ 10–20 ka at most. Ti-in-zircon thermometry indicates crystallization at 850–900 °C and pressures > 70–150 MPa are calculated from H2O solubility models. These time-temperature constraints translate into a magma cooling rate of ~ 2 × 10-2 °C/a. This rate is at least one order-of-magnitude faster than those calculated for zircon-bearing plutonic rocks from slow spreading ridges. Such short intervals for differentiation and cooling can only be resolved through uranium-series (238U–230Th) decay in young lavas, and are best explained by dissipating heat convectively at high crustal permeability.

Detrital zircon ages from southern Norway - implications for the Proterozoic evolution of the southwestern Baltic Shield

NASA Astrophysics Data System (ADS)

Knudsen, T.-L.; Andersen, T.; Whitehouse, M. J.; Vestin, J.

An ion-microprobe (SIMS) U-Pb zircon dating study on four samples of Precambrian metasediments from the high-grade Bamble Sector, southern Norway, gives the first information on the timing of discrete crust-forming events in the SW part of the Baltic Shield. Recent Nd and Pb studies have indicated that the sources of the clastic metasediments in this area have crustal histories extending back to 1.7 to 2.1Ga, although there is no record of rocks older than 1.6Ga in southern Norway. The analysed metasediments are from a sequence of intercalated, centimetre to 10-metre wide units of quartzites, semi-metapelites, metapelites and mafic granulites. The zircons can be grouped in two morphological populations: (1) long prismatic; (2) rounded, often flattened. The BSE images reveal that both populations consist of oscillatory zoned, rounded and corroded cores (detrital grains of magmatic origin), surrounded by homogeneous rims (metamorphic overgrowths). The detrital zircons have 207Pb/206Pb ages between 1367 and 1939Ma, with frequency maxima in the range 1.85 to 1.70Ga and 1.60 to 1.50Ga. There is no correlation between crystal habit and age of the zircon. One resorbed, inner zircon core in a detrital grain is strongly discordant and gives a composite inner core-magmatic outer core 207Pb/206Pb age of 2383 Ma. Two discrete, unzoned zircons have 207Pb/206Pb ages of 1122 and 1133Ma, representing zircon growth during the Sveconorwegian high-grade metamorphism. Also the μm wide overgrowths, embayments in the detrital cores and apparent ``inner cores'' which represent secondary metamorphic zircon growth in deep embayments in detrital grains, are of Sveconorwegian age. The composite-detrital-metamorphic zircon analyses give generally discordant 206Pb/238U versus 207Pb/235U ratios and maximum 207Pb/206Pb ages of 1438Ma. These data demonstrate the existence of a protocrust of 1.7 to 2.0Ga in the southwestern part of the Baltic Shield, implying a break in the overall westward

U-Pb SHRIMP geochronology and trace-element geochemistry of coesite-bearing zircons, North-East Greenland Caledonides

USGS Publications Warehouse

McClelland, W.C.; Power, S.E.; Gilotti, J.A.; Mazdab, F.K.; Wopenka, B.

2006-01-01

Obtaining reliable estimates for the timing of eclogite-facies metamorphism is critical to establishing models for the formation and exhumation of high-pressure and ultrahigh-pressure (UHP) metamorphic terranes in collisional orogens. The presence of pressure-dependent phases, such as coesite, included in metamorphic zircon is generally regarded as evidence that zircon growth occurred at UHP conditions and, ifdated, should provide the necessary timing information. We report U-Pb sensitive high-resolution ion microprobe (SHRIMP) ages and trace-element SHRIMP data from coesite-bearing zircon suites formed during UHP metamorphism in the North- East Greenland Caledonides. Kyanite eclogite and quartzofeldspathic host gneiss samples from an island in J??kelbugt (78??00'N, 18??04'W) contained subspherical zircons with well-defined domains in cathodoluminescence (CL) images. The presence of coesite is confirmed by Raman spectroscopy in six zircons from four samples. Additional components of the eclogite-facies inclusion suite include kyanite, omphacite, garnet, and rutile. The trace-element signatures in core domains reflect modification of igneous protolith zircon. Rim signatures show flat heavy rare earth element (HREE) patterns that are characteristic of eclogite-facies zircon. The kyanite eclogites generally lack a Eu anomaly, whereas a negative Eu anomaly persists in all domains of the host gneiss. The 207Pb- corrected 206Pb/238U ages range from 330 to 390 Ma for the host gneiss and 330-370 Ma for the kyanite eclogite. Weighted mean 206Pb/238U ages for coesite-bearing domains vary from 364 ?? 8 Ma for the host gneiss to 350 ?? 4 Ma for kyanite eclogite. The combined U-Pb and REE data interpreted in conjunction with observed CL domains and inclusion suites suggest that (1) Caledonian metamorphic zircon formed by both new zircon growth and recrystallization, (2) UHP metamorphism occurred near the end of the Caledonian collision, and (3) the 30-50m.y. span of ages

Localization of gaps during redo ablations of paroxysmal atrial fibrillation: Preferential patterns depending on the choice of cryoballoon ablation or radiofrequency ablation for the initial procedure.

PubMed

Galand, Vincent; Pavin, Dominique; Behar, Nathalie; Auffret, Vincent; Fénéon, Damien; Behaghel, Albin; Daubert, Jean-Claude; Mabo, Philippe; Martins, Raphaël P

2016-11-01

Pulmonary vein (PV) isolation, using cryoballoon or radiofrequency ablation, is the cornerstone therapy for symptomatic paroxysmal atrial fibrillation (AF) refractory to antiarrhythmic drugs. One-third of the patients have recurrences, mainly due to PV reconnections. To describe the different locations of reconnection sites in patients who had previously undergone radiofrequency or cryoballoon ablation, and to compare the characteristics of the redo procedures in both instances. Demographic data and characteristics of the initial ablation (cryoballoon or radiofrequency) were collected. Number and localization of reconduction gaps, and redo characteristics were reviewed. Seventy-four patients scheduled for a redo ablation of paroxysmal AF were included; 38 had been treated by radiofrequency ablation and 36 by cryoballoon ablation during the first procedure. For the initial ablation, procedural and fluoroscopy times were significantly shorter for cryoballoon ablation (147.8±52.6min vs. 226.6±64.3min [P<0.001] and 37.0±17.7min vs. 50.8±22.7min [P=0.005], respectively). Overall, an identical number of gaps was found during redo procedures of cryoballoon and radiofrequency ablations. However, a significantly higher number of gaps were located in the right superior PV for patients first ablated with radiofrequency (0.9±1.0 vs. 0.5±0.9; P=0.009). Gap localization displayed different patterns. Although not significant, redo procedures of cryoballoon ablation were slightly shorter and needed shorter durations of radiofrequency to achieve PV isolation. During redo procedures, gap localization pattern is different for patients first ablated with cryoballoon or radiofrequency ablation, and right superior PV reconnections occur more frequently after radiofrequency ablation. Redo ablation of a previous cryoballoon ablation appears to be easier. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

New Ca-Tims and La-Icp Analyses of GJ-1, Plesovice, and FC1 Reference Materials

NASA Astrophysics Data System (ADS)

Feldman, J. D.; Möller, A.; Walker, J. D.

2014-12-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U-Pb zircon geochronology relies on external reference standards to monitor and correct for different mass fractionation effects and instrument drift. Common zircon reference materials used within the community, including the KU Isotope Geochemistry Laboratory, are GJ-1 (207Pb/206Pb age: 608.53 +/- 0.37Ma; Jackson et al., 2004), Plesovice (337.13 +/- 0.37 Ma; Slama et al., 2008), and FC-1 (1099.0 +/-0.6 Ma; Paces and Miller, 1993). The age distribution of zircon reference material varies slightly from sample fraction to sample fraction, and the published results for GJ-1 are slightly discordant. As a result, using the published data for the distributed standard splits can lead to small systematic variations when comparing datasets from different labs, and more high precision data are needed to evaluate potential inhomogeneity of sample splits used in different laboratories. Here we characterize these reference materials with cathodoluminescence, LA-ICP-MS traverses across grains, and high precision CA-TIMS to better constrain the ages and assess zoning of these standards, and present the data for comparison with other laboratories. Reducing systematic error by dating our own reference material lends confidence to our analyses and allows for inter-laboratory age reproducibility of unknowns. Additionally, the reduction in propagated uncertainties (especially in GJ-1, for which both the red and yellow variety will be analyzed) will be used to improve long-term reproducibility, comparisons between samples of similar age, detrital populations and composite pluton zircons. Jackson, S.E., et al., 2004, Chemical Geology, v. 211, p. 47-69. Paces, J.B. & Miller, J.D., 1993, Journal of Geophysical Research, v. 80, p. 13997-14013. Slama, J., et al., 2008, Chemical Geology, v. 249. p. 1-35.

Micron-Scale Correlations Among Ti, P, Ce, and Y in Hadean Jack Hills Zircons

NASA Astrophysics Data System (ADS)

Hofmann, A. E.; Cavosie, A. J.; Valley, J. W.; Eiler, J. M.

2007-12-01

Detrital zircons and the inclusions found therein are our only mineralogical constraints on geologic events that occurred on the Hadean Earth. These zircons are commonly small (ca. <100 μm in the longest dimension) and preserve micron to sub-micron chemical zonations indicative of a dynamic petrological history. Trace elements within zircon are of particular interest because concentrations and ratios of these elements can provide information regarding chemical and physical conditions during zircon growth. In this study, we analyzed Hadean-age detrital zircons from Archean metasediment in the Jack Hills (Australia) using the Caltech Microanalysis Center Cameca NanoSIMS 50L. Trace elements analyzed included Ti, P, Ce, and Y. Ti- thermometry [1,2,3] can potentially constrain growth and/or re-equilibration temperatures of zircons; P, Ce, and Y are known to enter the zircon lattice by the coupled xenotime-type substitution mechanism: (Y, REE)3+ + P5+ = Zr4+ + Si4+ [5]. The 89Y/28Si ratio was observed to correlate with, and was used as a proxy for, cathodoluminescence (CL) banding. Growth features manifested in CL (e.g., sector, oscillatory zoning) were observed in all zircons analyzed. CL zones vary from <1 μm to several microns in width; therefore, the NanoSIMS---with a beam diameter resolved to ca. 250 nm on the sample surface when operating with an O- primary beam---is uniquely suited for this scale of analysis. Regions displaying CL banding were imaged as 20 x 20 μm areas. All elements were normalized to 28Si; 49Ti/28Si ratios were converted to [Ti] via calibration based on analyses of synthetic, high-Ti zircons (provided by B. Watson) that were independently analyzed on Caltech's JEOL JXA-8200 electron microprobe. We observe three types of relationships between trace element distribution and CL banding in the zircons imaged: 1) strong positive correlations between CL banding, P, Ce, and Ti; 2) subtle positive correlations between CL banding, P, Ce, and Ti; 3) no

High resolution mass spectrometric brain proteomics by MALDI-FTICR-MS combined with determination of P, S, Cu, Zn and Fe by LA-ICP-MS

NASA Astrophysics Data System (ADS)

Becker, J. Susanne; Zoriy, Miroslav; Przybylski, Michael; Becker, J. Sabine

2007-03-01

The combination of atomic and molecular mass spectrometric methods was applied for characterization and identification of several human proteins from Alzheimer's diseased brain. A brain protein mixture was separated by two-dimensional (2D) gel electrophoresis and the protein spots were fast screened by microlocal analysis using LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry) in respect to phosphorus, sulfur, copper, zinc and iron content. Five selected protein spots in 2D gel containing these elements were investigated after tryptic digestion by matrix assisted laser desorption ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS). Than element concentrations (P, Cu, Zn and Fe) were determined in three identified human brain proteins by LA-ICP-MS in the 2D gel. Results of structure analysis of human brain proteins by MALDI-FTICR-MS were combined with those of the direct determination of phosphorus, copper, zinc and iron concentrations in protein spots with LA-ICP-MS. From the results of atomic and molecular mass spectrometric techniques the human brain proteins were characterized in respect to their structure, sequence, phosphorylation state and metal content as well.

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

USGS Publications Warehouse

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

1993-01-01

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

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

Petrology of Zircon-Bearing Diogenite Northwest Africa 10666

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Detrital zircon geochronology of some neoproterozoic to triassic rocks in interior alaska

USGS Publications Warehouse

Bradley, D.C.; McClelland, W.C.; Wooden, J.L.; Till, A.B.; Roeske, S.M.; Miller, M.L.; Karl, Susan M.; Abbott, J.G.

2007-01-01

We report 777 U-Pb SHRIMP detrital zircon ages from thirteen sandstones and metasandstones in interior Alaska. About sixty grains per sample were analyzed; typically, half to three-fourths of these were concordant within ?? 10%. Farewell terrane. Two quartzites were collected from Ruby quadrangle and a third from Taylor Mountains quadrangle. All three are interpreted to represent a low stratigraphic level in the Nixon Fork platform succession; the samples from Ruby quadrangle are probably late Neoproterozoic, and the sample from Taylor Mountains quadrangle is probably Cambrian in age. The youngest detrital zircon in any of the three is 851 Ma. The two Ruby quadrangle samples area almost identical: one has a major age cluster at 1980-2087 and minor age clusters at 944-974 and 1366-1383 Ma; the other has a major age cluster at 1993-2095 Ma and minor age clusters at 912-946 and 1366-1395 Ma. The Taylor Mountains sample shows one dominant peak at 1914-2057 Ma. Notably absent are zircons in the range 1800-1900 Ma, which are typical of North American sources. The detrital zircon populations are consistent with paleontological evidence for a peri- Siberian position of the Farewell terrane during the early Paleozoic. Mystic subterrane of the Farewell terrane. Three graywackes from flysch of the Mystic subterrane, Talkeetna quadrangle, were sampled with the expectation that all three were Pennsylvanian. Asample from Pingston Creek is Triassic (as revealed by an interbedded ash dated at ca. 223 Ma) and is dominated by age clusters of 341-359 and 1804-1866 Ma, both consistent with a sediment source in the Yukon-Tanana terrane. Minor age clusters at 848-869 and 1992-2018 Ma could have been sourced in the older part of the Farewell terrane. Still other minor age clusters at 432-461, 620-657, 1509-1536, and 1627-1653 Ma are not readily linked to sources that are now nearby. Asample from Surprise Glacier is mid-Mississippian or younger. Adominant age cluster at 1855-1883 and a

Intra- and inter-tooth variation in strontium isotope ratios from prehistoric seals by laser ablation (LA)-MC-ICP-MS.

PubMed

Glykou, A; Eriksson, G; Storå, J; Schmitt, M; Kooijman, E; Lidén, K

2018-05-04

Strontium isotope ratios ( 87 Sr/ 86 Sr) in modern-day marine environments are considered to be homogeneous (~0.7092). However, in the Baltic Sea, the Sr ratios are controlled by mixing seawater and continental drainage from major rivers discharging into the Baltic. This pilot study explores if variations in Sr can be detected in marine mammals from archaeological sites in the Baltic Sea. 87 Sr/ 86 Sr ratios were measured in tooth enamel from three seal species by laser ablation (LA)-MC-ICP-MS. The method enables micro-sampling of solid materials. This is the first time that the method has been applied to marine samples from archaeological collections. The analyses showed inter-tooth 87 Sr/ 86 Sr variation suggesting that different ratios can be detected in different regions of the Baltic Sea. Furthermore, the intra-tooth variation suggests possible different geographic origin or seasonal movement of seals within different regions in the Baltic Sea through their life time. The method was successfully applied to archaeological marine samples showing that: (1) the 87 Sr/ 86 Sr ivalue n marine environments is not uniform, (2) 87 Sr/ 86 Sr differences might reflect differences in ecology and life history of different seal species, and (3) archaeological mobility studies based on 87 Sr/ 86 Sr ratio in humans should therefore be evaluated together with diet reconstruction. This article is protected by copyright. All rights reserved.

Voltage and pace-capture mapping of linear ablation lesions overestimates chronic ablation gap size.

PubMed

O'Neill, Louisa; Harrison, James; Chubb, Henry; Whitaker, John; Mukherjee, Rahul K; Bloch, Lars Ølgaard; Andersen, Niels Peter; Dam, Høgni; Jensen, Henrik K; Niederer, Steven; Wright, Matthew; O'Neill, Mark; Williams, Steven E

2018-04-26

Conducting gaps in lesion sets are a major reason for failure of ablation procedures. Voltage mapping and pace-capture have been proposed for intra-procedural identification of gaps. We aimed to compare gap size measured acutely and chronically post-ablation to macroscopic gap size in a porcine model. Intercaval linear ablation was performed in eight Göttingen minipigs with a deliberate gap of ∼5 mm left in the ablation line. Gap size was measured by interpolating ablation contact force values between ablation tags and thresholding at a low force cut-off of 5 g. Bipolar voltage mapping and pace-capture mapping along the length of the line were performed immediately, and at 2 months, post-ablation. Animals were euthanized and gap sizes were measured macroscopically. Voltage thresholds to define scar were determined by receiver operating characteristic analysis as <0.56 mV (acutely) and <0.62 mV (chronically). Taking the macroscopic gap size as gold standard, error in gap measurements were determined for voltage, pace-capture, and ablation contact force maps. All modalities overestimated chronic gap size, by 1.4 ± 2.0 mm (ablation contact force map), 5.1 ± 3.4 mm (pace-capture), and 9.5 ± 3.8 mm (voltage mapping). Error on ablation contact force map gap measurements were significantly less than for voltage mapping (P = 0.003, Tukey's multiple comparisons test). Chronically, voltage mapping and pace-capture mapping overestimated macroscopic gap size by 11.9 ± 3.7 and 9.8 ± 3.5 mm, respectively. Bipolar voltage and pace-capture mapping overestimate the size of chronic gap formation in linear ablation lesions. The most accurate estimation of chronic gap size was achieved by analysis of catheter-myocardium contact force during ablation.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

On the tectonic evolution of the Tyrrhenian basin: new data from detrital zircons sampled in the Sardinia-Corsica Block and in the Calabria-Peloritain Arc

NASA Astrophysics Data System (ADS)

Pavanetto, Pamela; Funedda, Antonio; Matteini, Massimo; Loi, Alfredo

2013-04-01

Geodynamic models and palinspastic reconstructions of pery-Thyrrenian terranes in the Western Mediterranean area are still extremely complex and speculative (Stampfly & Borel 2002, Trombetta et al., 2004; Alvarez & Shimabukuro, 2009; Carminati et al., 2012).A contribute can be done by considering the relationships between Sardinia-Corsica Block (SCB) and Calabria-Peloritain Arc (CPA). They shared a similar Variscan evolution and were the western part of the Briançonnais plate until the opening of the Algero-Provençal Basin during Burdigalian and then were separated in Late Tertiary during the spreading of South-Tyrrhenian Basin. During this period the CPA moved southeastward, with respect to the SCB, driven by a progressive roll-back of the subducted slab. However, is still ambiguous if the CPA was a single terrane during the Middle and Late Tertiary (Amodio Morelli et alii, 1976) or formed by the amalgamation of two or more continental "terranes" that collided during the Tertiary (Bonardi et al., 1980; Scandone, 1982; Alvarez & Shimabukuro, 2009). The data about the paleo-tectonic linkages, the terranes derivations, and the tectonic setting of the SCB and CPA as peri-Tyrrhenian blocks during Tertiary are still poor. Some evidence of their early evolution could be found in coeval Tertiary deposits cropping out both in the SCB and CPA. These deposits represent the early stage of the estensional event developed in the Tyrrhenian region during late Oligocene-Lower Miocene in a broader regional context dominated by the opening of Atlantic Ocean and the resulting convergence of Europe and Apulia microplate (Oggiano et al., 2009). To improve the knowledge on this topic, combined U-Pb and Lu-Hf analyses on zircons from Tertiary detrital sediments from Sardinia, Corsica, and both North and South Calabria have been performed using a Thermo-Fisher Neptune MC-ICP-MS coupled with a Nd:YAG UP213 New Wave laser ablation system, at the Laboratory of Geochronology of the

Ablation for Atrial Fibrillation

PubMed Central

2006-01-01

Executive Summary Objective To review the effectiveness, safety, and costing of ablation methods to manage atrial fibrillation (AF). The ablation methods reviewed were catheter ablation and surgical ablation. Clinical Need Atrial fibrillation is characterized by an irregular, usually rapid, heart rate that limits the ability of the atria to pump blood effectively to the ventricles. Atrial fibrillation can be a primary diagnosis or it may be associated with other diseases, such as high blood pressure, abnormal heart muscle function, chronic lung diseases, and coronary heart disease. The most common symptom of AF is palpitations. Symptoms caused by decreased blood flow include dizziness, fatigue, and shortness of breath. Some patients with AF do not experience any symptoms. According to United States data, the incidence of AF increases with age, with a prevalence of 1 per 200 people aged between 50 and 60 years, and 1 per 10 people aged over 80 years. In 2004, the Institute for Clinical Evaluative Sciences (ICES) estimated that the rate of hospitalization for AF in Canada was 582.7 per 100,000 population. They also reported that of the patients discharged alive, 2.7% were readmitted within 1 year for stroke. One United States prevalence study of AF indicated that the overall prevalence of AF was 0.95%. When the results of this study were extrapolated to the population of Ontario, the prevalence of AF in Ontario is 98,758 for residents aged over 20 years. Currently, the first-line therapy for AF is medical therapy with antiarrhythmic drugs (AADs). There are several AADs available, because there is no one AAD that is effective for all patients. The AADs have critical adverse effects that can aggravate existing arrhythmias. The drug selection process frequently involves trial and error until the patient’s symptoms subside. The Technology Ablation has been frequently described as a “cure” for AF, compared with drug therapy, which controls AF but does not cure it

Late Pleistocene granodiorite source for recycled zircon and phenocrysts in rhyodacite lava at Crater Lake, Oregon

USGS Publications Warehouse

Bacon, C.R.; Lowenstern, J. B.

2005-01-01

Rhyodacite tephra and three lavas erupted ???27 ka, interpreted to be early leaks from the climactic magma chamber of Mount Mazama, contain ubiquitous resorbed crystals (antecrysts) that were recycled from young granodiorite and related plutonic rocks of the same magmatic system. The shallow composite pluton is represented by blocks ejected in the 7.7-ka climactic eruption that formed Crater Lake caldera. Plagioclase crystals in both rhyodacite and granodiorites commonly have cores with crystallographically oriented Fe-oxide needles exsolved at subsolidus conditions. At least 80% of plagioclase crystals in the rhyodacite are antecrysts derived from plutonic rocks. Other crystals in the rhyodacite, notably zircon, also were recycled. SIMS 238U- 230Th dating indicates that zircons in 4 granodiorite blocks crystallized at various times between ???20 ka and ???300 ka with concentrations of analyses near 50-70, ???110, and ???200 ka that correspond to periods of dacitic volcanism dated by K- Ar. U-Th ages of zircon from a rhyodacite sample yield similar results. No analyzed zircons from the granodiorite or rhyodacite are pre-Quaternary. Zircon minimum ages in blocks from different locations around the caldera reflect ages of nearby volcanic vents and may map the distribution of intrusions within a composite pluton. Survival of zircon in zircon-undersaturated hydrous magma and of Fe-oxide needles in plagioclase suggests that little time elapsed from entrainment of antecrysts to the ???27-ka eruption of the rhyodacite. The ???27-ka rhyodacite is an example of young silicic magma that preserved unstable antecrysts from a known source early during growth of a large high-level magma chamber. In contrast, the voluminous 7.7-ka climactic rhyodacite pumice is virtually lacking in zircon, indicating dissolution of any granodioritic debris in the intervening period. Mineralogical evidence of assimilation may be destroyed in hot, vigorously growing silicic magma bodies such as

Observations and controls on the occurrence of inherited zircon in Concord-type granitoids, New Hampshire