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-derived. The porous structure and relatively small grain size of the host enclaves suggests that they originated from subvolcanic intrusions. Moreover, the preservation of zircon in hot, zircon undersaturated magmas requires brief residence times. Zircon megacrysts thus appear to have crystallized in highly differentiated magmas or nearly solidified intrusions from which crystals or rock aggregates were incorporated into more primitive magmas en route to surface. This implies that chemical signatures of apparently primitive magmas in basaltic volcanic fields can be modified by interaction with evolved melts that differentiated prior to eruption, mostly within an interval less than the ca. 10-25 ka uncertainty range of the radiometric ages.

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.

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.

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 of allanite standard reference materials. This method of correcting for matrix-dependent downhole fractionation evolution opens new possibilities in the field of LA-ICP-MS data acquisition, e.g. the use of a NIST standard glass to date all material types given a set of well constrained reference materials.

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.

Provenance of upper Triassic sandstone, southwest Iberia (Alentejo and Algarve basins): tracing variability in the sources

NASA Astrophysics Data System (ADS)

Pereira, M. F.; Ribeiro, C.; Gama, C.; Drost, K.; Chichorro, M.; Vilallonga, F.; Hofmann, M.; Linnemann, U.

2017-01-01

Laser ablation ICP-MS U-Pb analyses have been conducted on detrital zircon of Upper Triassic sandstone from the Alentejo and Algarve basins in southwest Iberia. The predominance of Neoproterozoic, Devonian, Paleoproterozoic and Carboniferous detrital zircon ages confirms previous studies that indicate the locus of the sediment source of the late Triassic Alentejo Basin in the pre-Mesozoic basement of the South Portuguese and Ossa-Morena zones. Suitable sources for the Upper Triassic Algarve sandstone are the Upper Devonian-Lower Carboniferous of the South Portuguese Zone (Phyllite-Quartzite and Tercenas formations) and the Meguma Terrane (present-day in Nova Scotia). Spatial variations of the sediment sources of both Upper Triassic basins suggest a more complex history of drainage than previously documented involving other source rocks located outside present-day Iberia. The two Triassic basins were isolated from each other with the detrital transport being controlled by two independent drainage systems. This study is important for the reconstruction of the late Triassic paleogeography in a place where, later, the opening of the Central Atlantic Ocean took place separating Europe from North America.

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 Huwan shear zone that bounds the Dabie terrane to the north. The central depocenter deposits reflect a later influx of bimodally distributed Precambrian zircon, signifying either a decrease in the influx of Paleozoic zircon grains due to stalled UHP exhumation and/or dilution of the same influx of Paleozoic zircons by spilling of Precambrian zircon from the northeastern depocenter into the central depocenter basin, perhaps due to infilling and bypass of sediment from the northern depocenter or due to initial collapse and constriction of the eastern Songpan-Ganzi complex basin. The southeastern depocenter of the eastern Songpan-Ganzi complex bears significant Paleozoic, Neoproterozoic, and Paleoproterozoic zircon populations derived from the South China block and Yidun arc complex, likely recording nascent uplift of the Longmenshan deformation belt due to impingement of the Yidun arc complex upon the western margin of the South China block. ?? 2010 Geological Society of America.

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 resolution. To avoid the different levels of analytical precision of the compiled TIMS, LA-ICP-MS, SHRIMP, and SIMS data, detrital zircon ages are plotted as kernel density estimates. Spatial and temporal distribution of the kernel density estimates, as well as further statistical techniques (e.g. multidimensional scaling) are used to discriminate groups of similar age distributions. Preliminary results reveal four major sources for the pre-orogenic sedimentary units (i.e. Saharan Metacraton, West-African craton, Amazonas craton and Fennoscandian shield). The mixing of several source signals in Gondwana derived sediment spectra point to vast deltaic systems along the Gondwanan shelf area.

In situ U-Th-Pb ages of the Miaoya carbonatite complex in the South Qinling orogenic belt, central China

NASA Astrophysics Data System (ADS)

Ying, Yuancan; Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Yang, Yueheng

2017-10-01

The Miaoya carbonatite complex in the South Qinling orogenic belt hosts one of the largest rare earth element (REE)-Nb deposits in China that is composed of carbonatite and syenite. The emplacement age of the complex and the geochronological relationship between the carbonatite and syenite have long been debated. In this study, in situ U-Th-Pb ages have been obtained for the constituent minerals zircon, monazite and columbite from carbonatite and syenite of the Miaoya complex, together with their chemical and isotopic compositions. In situ trace element compositions for zircon from carbonatite and syenite are highly variable. The zircon displays slightly heavy REE (HREE)-enriched chondrite-normalized patterns with no Eu anomaly and various light REE (LREE) contents. In situ Th-Pb dating for zircon from the Miaoya complex by laser ablation ICP-MS yields ages of 442.6 ± 4.0 Ma (n = 53) for syenite and 426.5 ± 8.0 Ma (n = 23) for carbonatite. Monazite from carbonatite and syenite shows similar chondrite-normalized REE patterns and yields a consistent Th-Pb age of 240 Ma. Based on petrographic and chemical composition, columbite from the carbonatite can be identified into two groups. The columbite dispersed within carbonatite is characterized by slightly LREE-enriched chondrite-normalized REE patterns, whereas columbite associated with apatite is characterized by LREE-depleted trends. Columbite has been further determined to have a weighted mean 206Pb/238U age of 232.8 ± 4.5 Ma (n = 9) using LA-ICP-MS. Detailed geochronological and chemical investigations suggest that there were two major episodes of magmatic/metasomatic activities in the formational history of the Miaoya carbonatite complex. The early alkaline magmatism emplaced in the Silurian was related to the opening of the Mianlue Ocean, whereas the late metasomatism or hydrothermal overprint occurred during the Triassic South Qinling orogeny. The latter serves as the major ore formation period for both REE (e.g., monazite) and Nb (e.g., columbite).

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 Angola. In addition to these geological findings, the first applications of QEMSCAN+LA-ICP-MS highlight some key advantages of the new workflow over traditional provenance analysis: (a) the new method not only increases sample throughput but also improves data quality by reducing significant biases associated with mineral separation and grain selection; (b) the three case studies highlight the importance of zircon 'fertility' for interpreting detrital zircon U-Pb datasets, and the ability of QEMSCAN to quantify this crucial parameter semi-automatically; (c) QEMSCAN+LA-ICP-MS provides an opportunity to add textural information to detrital geochronology and, for example, quantify possible grain-size dependence of U-Pb age distributions. But besides these advantages, the three case studies also reveal a number of limitations: (a) mineral identification by QEMSCAN is not as reliable as commonly achieved by human observers; (b) heavy mineral compositions obtained by QEMSCAN cannot easily be compared with conventional point counting data; and (c) apparent grain sizes can be greatly affected by polishing artefacts. In conclusion, QEMSCAN+LA-ICP-MS is a transformational new technique for provenance analysis but should be used with caution, in combination with conventional petrographic and heavy mineral techniques.

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 forearc units of the Transverse Ranges. Based on zircon U-Pb ages, geologic and petrographic relations, the Pescadero felsite and a capping, sheared metaconglomerate underlie the Pigeon Point Formation. We infer that the magma formed by anatexis of Franciscan or Great Valley clastic sedimentary rocks originating from a parental Mesozoic Sierran-Mojave-Salinian calcalkaline arc. The felsite erupted during Late Cretaceous time, was metamorphosed to pumpellyite-prehnite grade within the subduction zone, and then was rapidly exhumed, weakly zeolitized, and exposed before Pigeon Point forearc deposition. Pescadero vol canism apparently reflects a previously unrecognized ca. 86-90 Ma felsic igneous event in the accretionary margin. ?? 2011 Geological Society of America.

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

Detrital studies of both sand and rock are relevant to many problems, ranging from the climate and tectonics feedback debate to the long-term record of orogenic evolution. When applying the conventional (U-Th)/He technique to such studies, two important issues arise. Often, only euhedral grains are permissible for analysis in order to make simple geometric corrections for α-recoil. In detrital samples, this is problematic because euhedral grains can be scarce due to mechanical abrasion during transport, and potentially introduce bias in favour of more proximally sourced grains. Second, inherent to detrital studies is the need to date many grains (>100) per sample to ensure a representative sampling of the sediment source region, thus making robust conventional detrital studies both expensive and time-consuming. UV laser microprobes can improve this by permitting careful targeting of the grain interior away from the α-ejection zone, rendering the α-recoil correction unnecessary, thus eliminating bias toward euhedral grains. In the Noble Gas, Geochemistry, and Geochronology Laboratory at ASU, apatite and zircon have been successfully dated using in situ methods. For this study, the conventional and in situ techniques are compared by dating zircons from a modern river sand that drains a small catchment in the Mesozoic-Cenozoic Ladakh Batholith in NW India. This sample has a simple provenance, which allows us to demonstrate the robustness of the in situ method. Moreover, different microbeam techniques will be explored to establish the most efficient approach to obtain accurate and precise U-Th concentrations using synrock, which is our powdered, homogenized, and reconstituted zircon-rock standard. Without this, such in situ U-Th data would be difficult to obtain. 117 zircons were dated using the conventional (U-Th)/He method, revealing dates ranging from 9.70±0.35 to 106.6±3.5 Ma (2σ) with the major mode at 26 Ma. For comparison, 44 grains were dated using the in 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.

Two Late Cretaceous A-type granites related to the Yingwuling W-Sn polymetallic mineralization in Guangdong province, South China: Implications for petrogenesis, geodynamic setting, and mineralization

NASA Astrophysics Data System (ADS)

Zheng, Wei; Mao, Jingwen; Zhao, Haijie; Zhao, Caisheng; Yu, Xiaofei

2017-03-01

Major and trace elements, whole rock Sr-Nd-Pb isotopes, LA-ICP-MS U-Pb zircon dating, zircon trace elements and Hf isotope data are reported for a suite of A-type granites from Yingwuling pluton in western Guangdong province, South China. Zircon U-Pb ages obtained by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) show that biotite granite and alkali feldspar granite were emplaced in 81.3 ± 0.6 Ma and 80.6 ± 0.5 Ma, respectively. Both of the two suites have the petrographic and geochemical characteristics of A-type granite. These granitic rocks are metaluminous to weakly peraluminous and have pronounced contents of total alkalis (Na2O + K2O = 7.80-8.84%), Fe2O3T/MgO and Ga/Al ratios. They exhibit low MgO, CaO and TiO2 contents, enrichment in some LILEs and HFSEs (except for Zr, Eu and Y), depletion in Ba, Sr, P and Ti. They show A2 subtype affinity and were probably formed a temperature of 800 °C. The Yingwuling biotite granite has relatively high (87Sr/86Sr)i ratios of 0.70655 to 0.70928, low εNd(t) values of - 5.8 to - 4.2 and zircon εHf(t) values (- 5.70-1.37). Whole-rock Nd isotopic and zircon Hf isotopic two-stages model ages mostly vary from 1057 to 1506 Ma. The alkali feldspar granite display bulk rock εNd(t) values and (87Sr/86Sr)i ratios in the range of - 6.6 to - 6.1 and 0.70640 to 0.71077, respectively, and zircon εHf(t) values from - 5.44 to 0.54, with Mesoproterozoic T2DM for both Nd and Hf isotopes. Geochemical and isotopic data indicate the Yingwuling A-type granitic magmas were drived from mantle-crust interaction. Zircon grains of Yingwuling granites have relatively low Eu/Eu* and Ce4 +/Ce3 + ratios, indicating low oxygen fugacity. The visible tetrad effect in the Yingwuling granites indicates that it experienced strong fractionation and is close relationship to the W-Sn mineralization. Our new data together with previous published data indicate that Late Mesozoic A-type granitiods or alkaline intrusive rocks in South China can be grouped into four pulses: 195-180 Ma, 180-149 Ma, 136-116 Ma and 110-79 Ma. After 135 Ma, with a change in the polarity of the subduction of paleo-Pacific plate, the crust and lithospheric mantle in eastern China became progressively thinned causing the upwelling of asthenosphere, which would have triggered crustal rocks to partially melt and generate Yingwuling A-type granitic magmas.

Right Ventricular Pacing for Assessment of Cavo-Tricuspid Isthmus Block.

PubMed

Venkataraman, Ganesh; Wish, Marc; Friehling, Ted; Strickberger, S Adam

2016-01-01

Background: Cavo-tricuspid isthmus (CTI) dependent atrial flutter is typically treated with cardiac ablation. Standard techniques to assess CTI block after ablation can be technically challenging. Right ventricular (RV) pacing may allow for another technique to assess CTI block after ablation. Objective: The purpose of this study was to evaluate RV pacing as a method to assess CTI block after ablation of CTI dependent atrial flutter, and define endpoints of ablation using this technique. Methods: 28 patients undergoing ablation of CTI dependent atrial flutter with intact ventriculoatrial (VA) conduction were prospectively enrolled in this study and underwent the RV pacing protocol, as well as standard coronary sinus (CS) pacing techniques to assess CTI block. Results: The mean trans-isthmus conduction interval during CS pacing (TICI CS ) at 600 and 400ms after CTI ablation was 168 +/- 9ms and 175 +/- 18ms, respectively. The mean trans-isthmus conduction interval during RV pacing (TICI RV ) at 600ms and 400ms after CTI ablation was 109 +/- 5ms and 111 +/- 5ms, respectively. A TICI RV >100ms was associated with a successful outcome after CTI ablation. Conclusions: RV pacing may add incremental value in the assessment of CTI block in patients undergoing ablation of CTI dependent atrial flutter.

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 a kimberlitic origin unfavorable with respect to the regional geological history. Rather, trace elemental analyses (U, Th and Eu) suggest an eclogitic source for these zircons. The age distribution of detrital zircons allows in general a better understanding of collisional events that formed the Meratus orogen and identifies various North Australian Orogens as potential Pre-Mesozoic sediment sources. Our data support a model whereby the majority of Kalimantan diamonds were emplaced within the North Australian Craton by volcanic processes. Partly re-deposited into paleo-collectors or residing in their primary host, these diamond-deposits spread passively throughout Southeast Asia by terrane migration during the Gondwana breakup. Terrane amalgamation events largely metamorphosed these diamond-bearing lithologies while destroying the indicative mineral content. Orogenic uplift finally liberated their diamond-content into new, autochthonous placer deposits.

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 rocks above.

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.

QEMSCAN+LAICPMS: a new tool for petrochronology and sedimentary provenance analysis

NASA Astrophysics Data System (ADS)

Vermeesch, Pieter; Rittner, Martin; Omma, Jenny

2017-04-01

Only a relatively small number of rock-forming minerals contain sufficiently high concentrations of naturally occurring radioactive parent isotopes and sufficiently low background concentrations of the corresponding daughter isotopes to be suitable for geochronology. The first step in most geochronological studies is to extract these datable minerals from the host rock using a combination of magnetic and density separation techniques, a process that is tedious and time consuming. We here present a new method to avoid mineral separation by coupling a QEMSCAN electron microscope to an LA-ICP-MS instrument. Given a polished hand specimen, a petrographic thin section, or a grain mount, the QEMSCAN+LAICPMS 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. QEMSCAN+LAICPMS can be applied to a wide range of problems in igneous, metamorphic and sedimentary geology, as is illustrated with three case studies. In the first case study, a 3 × 4 cm slab of polished granite from the L'Erée pluton in Guernsey is scanned for zircon. This yields 23 U-Pb ages resulting in a concordia age of 615 ± 2 Ma. The second case study re-investigates a paragneiss from an ultra-high pressure terrane in the Qaidam Basin (Qinghai, China) that was previously analysed by conventional petrography, electron microscopy and SIMS zircon U-Pb analysis. In this example, the QEMSCAN revealed 107 small (20 μm) metamorphic zircons that were analysed by LA-ICP-MS to constrain the 430 Ma age of peak metamorphism. The third and final case study investigates the mineralogy and geochronology of sedimentary rocks of the Ordovician Sarah Formation (Saudi Arabia). We analysed 44 outcrop samples and a further 35 subsurface samples, resulting in a dataset comprising 10,000 detrital zircon U-Pb ages and 79 heavy mineral compositions and petrographic analyses. Jointly considering this enormous dataset by 3-way multidimensional scaling paints a remarkably simple picture of sandstone compositions that are determined by a combination of provenance and diagenesis. In conclusion, the QEMSCAN+LAICPMS method represents an efficient and cost effective way to obtain chemical and isotopic compositions on the same sample, which improves both the quantity and quality of geological data.

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.

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.

Triassic arc-derived detritus in the Triassic Karakaya accretionary complex was not derived from either the S Eurasian margin (Istanbul terrane) or the N Gondwana margin (Taurides)

NASA Astrophysics Data System (ADS)

Ustaömer, Timur; Ayda Ustaömer, Petek; Robertson, Alastair H. F.; Gerdes, Axel; Zulauf, Gernold

2014-05-01

We present new U-Pb zircon source age data for Upper Triassic sandstones of the Istanbul Terrane (S Eurasian margin) and also for Triassic sandstones of the Taurides (N Gondwana margin). The main aim is to detect and quantify the contribution of Triassic magmatism as detritus to either of these crustal blocks. This follows the recent discovery of a Triassic magmatic arc source for the Triassic sandstones of the Palaeotethyan Karakaya subduction-accretion complex (Ustaömer et al. 2013; this meeting). Carboniferous (Variscan) zircon grains also form a significant detrital population, plus several more minor populations. Six sandstone samples were studied, two from the İstanbul Terrane (Bakırlıkıran Formation of the Kocaeli Triassic Basin) and four from the Tauride Autochthon (latest Triassic Üzümdere Formation and Mid-Triassic Kasımlar Formations; Beyşehir region). Detrital zircon grains were dated by the laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) U-Pb method at Goethe University, Frankfurt. Our results do not reveal Triassic detritus in the Üzümdere Formation. The U-Pb age of the analysed zircon grains ranges from 267 Ma to 3.2 Ga. A small fraction of Palaeozoic zircons are Permian (267 to 296 Ma), whereas the remainder are Early Palaeozoic. Ordovician grains (4%) form two age clusters, one at ca. 450 Ma and the other at ca. 474 Ma. Cambrian-aged grains dominate the zircon population, while the second largest population is Ediacaran (576 to 642 Ma). Smaller populations occur at 909-997 Ma, 827-839 Ma, 1.8-2.0 Ga and 2.4-2.6 Ga. The sandstones of the Kasımlar Formation have similar zircon age cluster to those of the somewhat younger Üzümdere Formation, ranging from 239 Ma to 2.9 Ga. A few grains gave Anisian ages. Cambrian zircon grains are less pronounced than in the Kasımlar Formation compared to the Üzümdere Formation. The detrital zircon record of Tauride sandstones, therefore, not indicates significant contribution of Triassic or Carboniferous (Variscan) arc sources, in marked contrast to those of the Triassic Karakaya subduction complex. In comparison, the ages of the analysed zircons in the Upper Triassic sandstones of the Istanbul Terrane range from 294 Ma to 3.1 Ga. Triassic zircons are again absent, while Variscan-aged zircons (294 to 339 Ma) dominate the zircon population. Additional zircon populations are dated at 554 to 655 Ma, 0.9 to 1.2 Ga, 1.5 Ga, 1.65 Ga, 2.0 to 2.15 and 2.5 to 2.8 Ga. The Precambrian zircon age spectra are compatible with derivation from an Avalonian/Amazonian/Baltic crustal provenance. In summary, there is no evidence in either the Triassic sandstones of the İstanbul Terrane or of the Taurides of the Triassic magmatic arc source that dominates the Triassic Karakaya subduction-accretion complex. Where then was the source of the Karakaya arc detritus? A likely option is that the Karakaya subduction-accretion complex is an exotic terrane that was detached from a source magmatic arc and displaced to its present location, probably prior the initial deposition of the Early Jurassic cover sediments. This study was supported by TUBITAK, Project No: 111R015

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.

From opening to subduction of an oceanic domain constrained by LA-ICP-MS U-Pb zircon dating (Variscan belt, Southern Armorican Massif, France)

NASA Astrophysics Data System (ADS)

Paquette, J.-L.; Ballèvre, M.; Peucat, J.-J.; Cornen, G.

2017-12-01

In the Variscan belt of Western Europe, the lifetime and evolution of the oceanic domain is poorly constrained by sparse, outdated and unreliable multigrain ID-TIMS U-Pb zircon dating. In this article, we present a complete in situ LA-ICP-MS dataset of about 300 U-Pb zircon analyses obtained on most of the ophiolitic and eclogitic outcrops of Southern Brittany, comprising new dating of previously published zircon populations and newly discovered rock samples. In situ dating and cathodo-luminescence imaging of each zircon grain yields new absolute time-constraints on the evolution of the Galicia-Moldanubian Ocean. The new results confirm that the opening of this oceanic domain is well defined at about 490 Ma. In contrast, the generally-quoted 400-410 Ma-age for the high-pressure event related to the subduction of the oceanic crust is definitely not recorded in the zircons of the eclogites. In light of these new data, we propose that the obduction of oceanic rocks occurred at about 370-380 Ma while the high-pressure event is recorded at 355 Ma in only a few zircon grains of some eclogite samples. Additionally, this large scale dating project demonstrates that the zircons from eclogites do not systematically recrystallise during the high pressure event and consequently their U-Pb systems do not record that metamorphism systematically. These zircons rather preserve the isotopic memory of the magmatic crystallization of their igneous protolith. Another example of an eclogite sample from the French Massif Central illustrates the frequent mistake in the interpretation of the ages of the early hydrothermal alteration of zircons in the oceanic crust versus partial or complete recrystallization during eclogite facies metamorphism.

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.

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 rocks (45% < SiO 2  < 73%). However, we thought that the NH 4 HF 2 digestion method can be used as a new alternative in LA-ICP-MS for a wider range of geological samples, and will significantly accelerate the application of LA-ICP-MS for the whole-rock analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Laser ablation ICP-MS analysis on nano-powder pellets and applications to granite bulk rock analysis

NASA Astrophysics Data System (ADS)

Wu, Shitou; Karius, Volker; Wörner, Gerhard

2017-04-01

Granites are a ubiquitous component of the continental crust and knowing their precise trace element signatures is essential in understanding the origins and evolution of the continental crust. ICP-MS bulk analysis of granite is generally conducted on solution after acid-digestion. However this technique has several deficiencies related to the difficulty of completely dissolving accessary minerals such as zircon and the instability/adsorption of high valence trace elements (Nb, Ta et al.) in acid solutions. The development of a nano-powder pellet technique by using wet milling procedure, and its combination with laser ablation ICP-MS has been proposed to overcome these problems. In this study, we produced nano-powders from a series of granite rock standards by wet milling in agate using a high power planetary ball mill instrument. The procedure was tested and optimized by modifying parameters (ball to powder ratio, water to powder ratio, milling power etc.). Characterization of nano-powders was conducted by various techniques including electron microprobe (EMP), secondary electron imaging, polarizing microscope, and laser particle size analyzer (LPSA) and laser scanning confocal microscope (LSCM). Particle sizes range from a few nm to 5 μm with a small secondary mode at around 10 to 20 μm that probably represent particle aggregates rather than remaining crystal grains after milling. Pellets of 5 mm in diameter were pressed into molds of cellulose at 1.75 *103 N/cm2. Surface roughness of the pellets was measured by LSCM and gave a Ra of 0.494 μm, which is an order higher than the surface of polished ATGH-G reference glass surface (Ra: 0.048 μm), but sufficient for laser ablation. Sources of contamination either from abrading agate balls or from ultrapure water were evaluated and quantified. The homogeneity of powder pellets down to less than 5 μm size was documented based on EMPA element mapping and statistical analyses of LA-ICP-MS in discrete spot and line scanning analytical mode. We report data from major to trace element (to < 0.1 ppm) of currently available international granite reference materials (JG-2, JG-3, GWB07103, GEB07111, GSP-2 and G-3) to evaluate analytical precision and accuracy of LA-ICP-MS measurements. Our results illustrate the potential of this method for high precision analysis of trace elements and e.g. Zr/Hf and Nb/Ta ratios in granites.

Late Jurassic rhyolites from the Wuchagou region in the central Great Xing'an Range, NE China: Petrogenesis and tectonic implications

NASA Astrophysics Data System (ADS)

Ji, Zheng; Ge, Wen-Chun; Yang, Hao; Wang, Qing-hai; Zhang, Yan-long; Wang, Zhi-hui; Bi, Jun-Hui

2018-06-01

We report geochronological, whole-rock geochemical, and zircon Hf isotopic data for Late Jurassic rhyolites in the central Great Xing'an Range of northeastern China, to determine their petrogenesis, source, and tectonic setting. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U-Pb ages indicate that the rhyolites previously mapped as the lower Permian Dashizhai Formation in the Wuchagou region formed during the Late Jurassic (162-154 Ma). Geochemically, these rhyolites belong to the mid- to high-K calc-alkaline series and show peraluminous characteristics and consistent correlations between major elements and SiO2. They are characterized by enrichments in large ion lithophile elements (LILEs; e.g., Rb and K) and light rare earth elements (LREEs), and depletions in high field strength elements (HFSEs; e.g., Nb, Ta, and Ti) and heavy rare earth elements (HREEs). In situ Hf isotopic analyses of zircons from the rhyolites reveal relatively homogeneous Hf isotopic compositions, with εHf(t) values of +4.84 to +9.44, and two-stage model ages of 606-895 Ma. Based on their eruption ages, geochemical characteristics, and Hf isotopic compositions, we conclude that the magmas that formed the Late Jurassic rhyolites were produced during partial melting of a Neoproterozoic quartz-bearing amphibolite-facies mafic crust. These magmas subsequently underwent extensive fractional crystallization of plagioclase, hornblende, Ti-bearing phases, monazite, and apatite. Combined with previous data, our results demonstrate that the Late Jurassic volcanic rocks in the Great Xing'an Range were formed in a post-collisional extensional setting. The gravitational collapse of the orogenically thickened crust was caused by break-off of the subducted oceanic slab and upwelling of asthenosphere after closure of the Mongol-Okhotsk Ocean.

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 additional detritus derived from early to middle Neoproterozoic metamorphic rocks. The relic zircon core ages in the HC are comparable with those of the Trivandrum Block and Nagercoil Block of southern India. In contrast, those ages in the WC match the Achankovil Shear Zone and Southern Madurai Block of southern India. These comparisons are also supported by Th/U ratios of detrital zircon cores from paragneisses (Th/U ratios of >0.10 for the former and not only >0.10 but also ≤0.10 for the latter). Comparisons with the Lützow-Holm Complex of East Antarctica indicate that the geochronological characteristics of the HC and WC broadly match those of the Skallen Group, and the Ongul and Okuiwa Groups, respectively.

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 reveals remarkable fluctuations in Hf isotopic ratios recorded within and between melt-precipitated zircons of granitic and enclave samples. This can only be reconciled by open-system behaviour, though contrasting patterns of Hf isotope variation within zoned zircons demonstrate that this differed significantly between the two suites. The Cobargo Suite was generated by mixing between two contrasting magmas, followed by crustal assimilation. Zircons from the Why Worry Suite have more evolved Hf isotope ratios, consistent with recycling of older crust during granitic generation, though increase in eHf towards zircon rims manifests interaction with primitive magmas. Globules of these are represented by mafic enclaves, the mantle heritage of which is preserved by high eHf values of zircon cores, even though whole-rock isotope contrasts with the host have been erased by equilibration. Analysis of inherited zircons contained by the Why Worry Suite establishes that the 450-600 Ma age population have evolved eHf values, and thus meta-igneous rocks of this age are appropriate protoliths for these granites. The primitive eHf values of the Cobargo Suite preclude derivation from similar sources, instead suggesting formation from mantle-derived materials. Incorporating the existing geochemical and isotope datasets, the Hf-in-zircon data will be coupled with recent thermal simulations to erect a general model for granite formation and the evolution of the continental crust during Lachlan orogenesis.

Geological, geochronological, geochemical, and Sr-Nd-O-Hf isotopic constraints on origins of intrusions associated with the Baishan porphyry Mo deposit in eastern Tianshan, NW China

NASA Astrophysics Data System (ADS)

Wang, Yinhong; Xue, Chunji; Liu, Jiajun; Zhang, Fangfang

2016-10-01

The Baishan porphyry Mo deposit (0.72 Mt; 0.06 % Mo) is located in the interior of the eastern Tianshan orogenic belt in Xinjiang, NW China. The deposit comprises 15 orebodies that are associated with monzogranite and granite porphyry stocks and are structurally controlled by roughly EW-trending faults. Secondary ion mass spectrometry (SIMS) zircon U-Pb dating of the monzogranite and granite porphyry yielded the Middle Triassic age (228 ± 2 to 227 ± 2 Ma), which coincide with the molybdenite Re-Os model ages ranging from 226 ± 3 to 228 ± 3 Ma. The Triassic monzogranite and granite porphyry belong to high-K calc-alkaline series and are characterized by high SiO2 and Al2O3 and low MgO, TiO2, and P2O5 concentrations, with negative Eu anomalies (δEu = 0.55-0.91). The least-altered monzogranite and granite porphyry yield uniform ɛ Nd( t) values from +1.6 to +3.6, and wide (87Sr/86Sr) i ratios ranging between 0.7035 and 0.7071, indicating that they were derived from the lower crust. In situ O-Hf isotopic analyses on zircon using SIMS and laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) indicate that the δ18O and ɛ Hf( t) values of zircon from a monzogranite sample vary from 6.1 to 7.3 ‰ and +8.0 to +11.7, respectively, whereas zircon from a granite porphyry sample vary from 6.2 to 6.9 ‰ and +7.3 to +11.2, respectively. The geochemical and isotopic data imply that the primary magmas of the Baishan granite were likely derived from partial melts from the lower crust involving some mantle components. The Baishan Mo deposit and granitic emplacement were proposed to be most likely related to post-orogenic lithospheric extension and magmatic underplating. An extensional event coupled with the rising of hot mantle-derived melts triggered partial melting of the lower crust, as well as provided metals (Mo).

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

Coupling of Uranium and Thorium Series Isotope Systematics for Age Determination of Late Pleistocene Zircons using LA-ICP-MS

NASA Astrophysics Data System (ADS)

Sakata, S.; Hirakawa, S.; Iwano, H.; Danhara, T.; Hirata, T.

2014-12-01

Zircon U-Th-Pb dating method is one of the most important tools for estimating the duration of magmatism by means of coupling of uranium, actinium and thorium decay series. Using U-Pb dating method, its reliability is principally guaranteed by the concordance between 238U-206Pb and 235U-207Pb ages. In case of dating Quaternary zircons, however, the initial disequilibrium effect on 230Th and 231Pa should be considered. On the other hands, 232Th-208Pb dating method can be a simple but powerful approach for investigating the age of crystallization because of negligible influence from initial disequilibrium effect. We have developed a new correction model for accurate U-Pb dating of the young zircon samples by taking into consideration of initial disequilibrium and a U-Pb vs Th-Pb concordia diagram for reliable age calibration was successfully established. Hence, the U-Th-Pb dating method can be applied to various zircons ranging from Hadean (4,600 Ma) to Quaternary (~50 ka) ages, and this suggests that further detailed information concerning the thermal history of the geological sequences can be made by the coupling of U-Th-Pb, fission track and Ar-Ar ages. In this presentation, we will show an example of U-Th-Pb dating for zircon samples from Sambe Volcano (3 to 100 ka), southwest Japan and the present dating technique using LA-ICP-MS.

Age and Origin of Eclogite Xenoliths from Navajo Diatremes on the Colorado Plateau

NASA Astrophysics Data System (ADS)

Schulze, D. J.; Malik, L.; Davis, D. W.; Helmstaedt, H. H.

2017-12-01

Six eclogite xenoliths from the Moses Rock and Mule Ear diatremes of the Navajo Volcanic Field on the Colorado Plateau were studied to determine their age(s) and shed light on their origin. Laser ablation inductively-coupled plasma mass spectrometry was used to date zircons in situ by the U-Pb method. In all samples, most of the zircons have low Th/U ratios (<0.1) characteristic of metamorphic zircon and plot on or very near concordia with ages between 27 and 40 Ma, with a few outliers as old as 80 Ma. Some grains with higher Th/U, typically characteristic of magmatic zircon, yield older ages, as old as 1717 ± 25 Ma. In two samples, five zircon yielded data that fall on a discordia between 40 ± 20 and 1717 ± 25 Ma. This suggests that simple derivation from metamorphosed Mesozoic oceanic crust of the shallowly subducted Farallon Plate is not a viable hypothesis for the origin of these eclogites. Instead, the Proterozoic component may indicate that the Farallon Plate also transported material scraped from the overlying Proterozoic mantle during late Mesozoic to Cenozoic subduction. The relationship between the causes of zircon growth in Cenozoic time and the growth of monazite at 28-30 Ma in eclogites of the same suite is unclear, but both may be related to fluxing by water derived from dehydration of serpentinites of the Farallon Plate.

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.

Profiling of patterned metal layers by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

NASA Astrophysics Data System (ADS)

Bi, Melody; Ruiz, Antonio M.; Gornushkin, Igor; Smith, Ben W.; Winefordner, James D.

2000-02-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for profiling patterned thin metal layers on a polymer/silicon substrate. The parameters of the laser and ICP-MS operating conditions have been studied and optimized for this purpose. A new laser ablation chamber was designed and built to achieve the best spatial resolution. The results of the profiling by LA-ICP-MS were compared to those obtained from a laser ablation optical emission spectrometry (LA-OES) instrument, which measured the emission of the plasma at the sample surface, and thus, eliminated the time delay caused by the sample transport into the ICP-MS system. Emission spectra gave better spatial resolution than mass spectra. However, LA-ICP-MS provided much better sensitivity and was able to profile thin metal layers (on the order of a few nanometers) on the silicon surface. A lateral spatial resolution of 45 μm was achieved.

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.

Cover sequences at the northern margin of the Antongil Craton, NE Madagascar

USGS Publications Warehouse

Bauer, W.; Walsh, G.J.; De Waele, B.; Thomas, Ronald J.; Horstwood, M.S.A.; Bracciali, L.; Schofield, D.I.; Wollenberg, U.; Lidke, D.J.; Rasaona, I.T.; Rabarimanana, M.H.

2011-01-01

The island of Madagascar is a collage of Precambrian, generally high-grade metamorphic basement domains, that are locally overlain by unmetamorphosed sedimentary rocks and poorly understood low-grade metasediments. In the Antalaha area of NE Madagascar, two distinct cover sequences rest on high-grade metamorphic and igneous basement rocks of the Archaean Antongil craton and the Neoproterozoic Bemarivo belt. The older of these two cover sequences, the Andrarona Group, consists of low-grade metasedimentary rocks. The younger sequence, the newly defined Ampohafana Formation, consists of unmetamorphosed sedimentary rocks. The Andrarona Group rests on Neoarchaean granites and monzogranites of the Antongil craton and consists of a basal metagreywacke, thick quartzites and an upper sequence of sericite-chlorite meta-mudstones, meta-sandstones and a volcaniclastic meta-sandstone. The depositional age of the volcaniclastic meta-sandstone is constrained in age by U–Pb laser-ablation ICP-MS analyses of euhedral zircons to 1875 ± 8 Ma (2σ). Detrital zircons of Archaean and Palaeoproterozoic age represent an input from the Antongil craton and a newly defined Palaeoproterozoic igneous unit, the Masindray tonalite, which underlies the Andrarona Group, and yielded a U–Pb zircon age of 2355 ± 11 Ma (2σ), thus constraining the maximum age of deposition of the basal part of the Andrarona Group. The Andrarona Group shows a low-grade metamorphic overprint in the area near Antalaha; illite crystallinity values scatter around 0.17°Δ2Θ CuKα, which is within the epizone. The Ampohafana Formation consists of undeformed, polymict conglomerate, cross-bedded sandstone, and red mudstone. An illite crystallinity value of >0.25°Δ2Θ CuKα obtained from the rocks is typical of the diagenetic zone. Occurrences of rhyodacite pebbles in the Ampohafana Formation and the intrusion of a basaltic dyke suggest a deposition in a WSW-ENE-trending graben system during the opening of the Indian Ocean in the Upper Cretaceous, that was characterized by extensive rhyolitic to basaltic magmatism along Madagascar's eastern coast.

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.

Petrochronology in constraining early Archean Earth processes and environments: Barberton greenstone belt, South Africa

NASA Astrophysics Data System (ADS)

Grosch, Eugene

2017-04-01

Analytical and petrological software developments over the past decade have seen rapid innovation in high-spatial resolution petrological techniques, for example, laser-ablation ICP-MS, secondary ion microprobe (SIMS, nano-SIMS), thermodynamic modelling and electron microprobe microscale mapping techniques (e.g. XMapTools). This presentation will focus on the application of petrochronology to ca. 3.55 to 3.33 billion-year-old metavolcanic and sedimentary rocks of the Onverwacht Group, shedding light on the earliest geologic evolution of the Paleoarchean Barberton greenstone belt (BGB) of South Africa. The field, scientific drilling and petrological research conducted over the past 8 years, aims to illustrate how: (a) LA-ICP-MS and SIMS U-Pb detrital zircon geochronology has helped identify the earliest tectono-sedimentary basin and sediment sources in the BGB, as well as reconstructing geodynamic processes as early as ca. 3.432 billion-years ago; (b) in-situ SIMS multiple sulphur isotope analysis of sulphides across various early Archean rock units help to reconstruct atmospheric, surface and subsurface environments on early Archean Earth and (c) the earliest candidate textural traces for subsurface microbial life can be investigated by in-situ LA-ICP-MS U-Pb dating of titanite, micro-XANES Fe-speciation analysis and metamorphic microscale mapping. Collectively, petrochronology combined with high-resolution field mapping studies, is a powerful multi-disciplinary approach towards deciphering petrogenetic and geodynamic processes preserved in the Paleoarchean Barberton greenstone belt of South Africa, with implications for early Archean Earth evolution.

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 only a few detrital grains match gneiss zircons in age, morphology, and U concentration. The sources were probably distal, or perhaps destroyed or removed from the region during Neoarchean tectonism. In contrast, Mount Narryer zircons are similar to gneiss zircons, suggesting they were derived from the gneisses, which may include a minor, currently undiscovered 4200-4100 Ma granitic component. Such diversity in age and nature of Hadean detrital zircons is compelling evidence that Earth's crust was heterogeneous by 4200 Ma.

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.

The Permian-Triassic granitoids in Bayan Obo, North China Craton: A geochemical and geochronological study

NASA Astrophysics Data System (ADS)

Ling, Ming-Xing; Zhang, Hong; Li, He; Liu, Yu-Long; Liu, Jian; Li, Lin-Qing; Li, Cong-Ying; Yang, Xiao-Yong; Sun, Weidong

2014-03-01

Granitoids near the Bayan Obo giant rare earth element (REE) deposit at the north margin of the North China Craton (NCC), the world's largest light REE (LREE) deposit, have been taken by some authors as the key factors that controlled the mineralization. In contrast, others proposed that the REE deposit has been partially destructed by these granitoids. Here we report systematic studies on geochronology and geochemical characteristics of granitoids of different distances from the orebodies, to investigate the genesis and their relationship to the giant Bayan Obo deposit. Granitoids studied here, including granites and quartz monzonites, are peraluminous with A/CNK = 0.99-1.11, LREE enriched and heavy REE (HREE) depleted, with variable REE concentrations (total REE = 54-330 ppm) and large negative Eu anomaly (δEu = 0.19-0.70). The REE patterns are distinct from those of ore-bearing dolomites. Some samples have slightly higher LREE concentrations, which may have been contaminated by the orebodies during intrusion. Trace elements of the granitoids are characterized by positive Pb anomaly, strong negative Ti anomaly and Nb, Ta and Sr anomalies. The granites exhibit negative Ba anomaly. The granitoids plot within the post-collision granite field in the Pearce diagram, which is consistent with the tectonic regime. The quartz monzonites and one granite have A-type granite characteristics and belong to the A2 subgroup. Zircons in these granitoids have high Th/U values, which are typical for magmatic zircons. High precision U-Pb dating for these zircons by secondary ion mass spectrometry (SIMS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) yields Permian-Triassic 206Pb/238U ages ranging from 243.2 to 293.8 Ma. The formation of the granitoids is > 55 Ma later than the latest ore forming age. The zircons have low La concentrations (0.02-12 ppm), high (Sm/La)N (0.8-685) and Ce/Ce* (1.4-80). The Ti-in-zircon temperature of the granitoids ranges from 590 to 770 °C. All these evidences suggest that the granitoids have no contribution to the formation of the Bayan Obo deposit. Granitoids that are close to the orebodies had limited interaction with it and gained some LREE-enriched characteristics during magmatisms. Nevertheless, their effects to the orebodies are subtle. All the granitoids formed in a post-collisional tectonic regime at convergent margins, which is consistent with plate subduction during the closure of the Palaeo-Asian Ocean, which started in the Neoproterozoic and lasted until the Carboniferous/Permian.

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 TE/age trends. 3) Detrital zircons have long been used to investigate the location and geology of landforms in the past. By adding chemical information to the age data, a clearer history can be produced. Recent LASS data from Mesozoic sedimentary rocks indicate changes in chemistry of the Sierra Nevada-Peninsular Ranges batholith, as well and the exposure and erosion of distinct units (e.g., ophiolites) over discrete time periods. 4) Isotopic data retrieved in combination with age data across an orogeny or batholith can aid in the understanding of the areal and temporal evolution of both deformation and source rocks over time. This can be done with a number of petrochronometers: Hf in zircon, Nd in titanite and monazite, This study presents examples that show how significant advances can be made in understanding lithosphere evolution using this quick and efficient analytical technique.

Ca. 400 Ma Recrystallization of Norwegian Ultrahigh-pressure Eclogites: an ion Microprobe and Chemical Abrasion Study

NASA Astrophysics Data System (ADS)

Root, D. B.; Mattinson, J. M.; Hacker, B. R.; Wooden, J. L.

2002-12-01

Understanding the formation and exhumation of the ultrahigh-pressure (UHP) rocks of western Norway hinges on precise determination of the time of eclogite recrystallization. Our study consists of SHRIMP analysis, in conjunction with CL imagery, of zircon from four UHP and high-pressure (HP) eclogites; and detailed TIMS analysis of zircon from two samples subjected to combined thermal annealing and multi-step chemical abrasion (CA). SHRIMP analyses of the Otnheim and Langenes eclogites yield Caledonian spot ages of ca. 400 Ma from zircon rims. CL imagery and Th/U ratios from the Langenes eclogite indicate formation of rims by recrystallization of inherited zircon. SHRIMP analysis of the UHP Flatraket eclogite yielded a broad range of apparently concordant Caledonian ages. CA analyses of two fractions yielded moderate Pb loss from the first (lowest T) steps; possible minor Pb loss or minor growth at 400 Ma from the second steps; and a 407-404 Ma cluster of slightly discordant 206Pb/238U ages, most likely free from Pb loss, from the remaining steps. We interpret the latter to reflect recrystallization of inherited zircon, with possible new growth, at ca. 400-395 Ma. Alternatively, the high-temperature CA steps could represent growth at 407-404 Ma, with apparent discordance due to intermediate daughter product effects. HP/UHP zircon recrystallization in the Flatraket eclogite is inferred from three lines of evidence: i) zircon occurs as inclusions in garnet, omphacite, breunnerite, dolomite, and quartz, as well as in symplectites after phengite and omphacite; ii) association of zircon with rutile implies zircon formation during HP breakdown of Zr-ilmenite; and iii) chondrite-normalized ICP-MS analyses of the CA steps reveal small Eu anomalies and shallow HREE profiles, indicating zircon recrystallization in the presence of garnet. CA analysis of the Verpeneset eclogite yielded distinctly discordant step ages from two steps comprising <90% of the sample, with 206Pb/238U ages of 408 and 414 Ma. CL imagery indicates incomplete recrystallization of inherited igneous zircon, in keeping with steep HREE profiles determined from chondrite-normalized ICP-MS analyses. Our zircon age of ca. 400-395 Ma for the Flatraket eclogite is significantly younger than the 425 Ma age often cited for western Norway eclogite recrystallization, implying, in conjunction with 390-385 Ma 40Ar/39Ar white mica cooling ages, faster rates of exhumation (ca. 15 km/m.y.), and weakening the link between UHP metamorphism and ophiolite emplacement at 430-425 Ma.

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.

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.

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.

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.

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

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.

Geochemistry and geochronology of the Mesozoic Lanong ophiolitic mélange, northern Tibet: Implications for petrogenesis and tectonic evolution

NASA Astrophysics Data System (ADS)

Zhong, Yun; Liu, Wei-Liang; Xia, Bin; Liu, Jing-Nan; Guan, Yao; Yin, Zhen-Xing; Huang, Qiang-Tai

2017-11-01

The Lanong ophiolitic mélange is a typical ophiolitic mélange in the middle section of the Bangong-Nujiang suture zone in northern Tibet. It mainly consists of ultramafic and mafic rocks, and its tectonic setting and formation age remain poorly constrained. In this paper, new geochemical and LA-ICP-MS (laser ablation-inductively coupled plasma mass spectrometer) zircon U-Pb age data obtained from gabbro, gabbro-dolerite, dolerite and basalt of the Lanong ophiolitic mélange are provided. The pillow basalts exhibit N-MORB (normal mid-ocean ridge basalt)-like geochemical features with a zircon U-Pb age of 147.6 ± 2.3 Ma. They were generated by 20-30% partial melting of a depleted mantle source composed of spinel lherzolite. The gabbro, massive basalt and gabbro-dolerite samples are characterised by more depleted and "V"-shaped REE (rare earth element) patterns, and they exhibit variable degrees of boninite-like geochemical characteristics, with a zircon U-Pb age of 149.1 ± 1.2 Ma (gabbro-dolerite). They were derived from the remelting of a significantly refractory mantle source following one or more episodes of previous basaltic melt extraction. Geochemical data of these mafic rocks indicate that they were developed in a continental fore-arc setting, and magmas were derived from depleted mantle sources modified by subducted slab-derived fluids and melts with minor crustal contamination. On the other hand, the dolerites show distinct OIB (oceanic island basalt)-like geochemical features, with a zircon U-Pb age of 244.1 ± 3.0 Ma. They were formed in a rift setting on a continental shelf-slope and originated from a low degree of partial melting of a depleted asthenospheric magma source mixed with some ancient sub-continental lithospheric mantle materials. The signatures presented here, combined with the results of previous studies, suggest that the Lanong ophiolitic mélange probably developed in a convergent plate margin under the southward subduction of the Bangong-Nujiang Tethys Ocean beneath the Lhasa terrane during the Middle Triassic-Early Cretaceous. Namely, the OIB-like dolerites likely reflect an extensional rift setting featuring thin continental crust in the Middle Triassic, and the gabbros, gabbro-dolerites and basalts represent a later stage of a fore-arc basin during the Late Jurassic-Early Cretaceous.

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.

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.

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 juvenile magma sources, which are common in continental arc environments. Point counts of 32 sandstone thin sections were performed following the Gazzi-Dikinson method. 300-400 points were counted in each thin section. The sandstones are feldspathic litharenites and litharenites. Feldspar is dominantly plagioclase (> 90%) with minor amounts of K-feldspar. Most of the quartz grains (75%) are mono-crystalline but poly-crystalline ones (maximum 25%) also occur. Rock fragments are represented by sedimentary, volcanic and metamorphic grains. Volcanic rock-fragments mostly are andesites and volcanic chert. Sedimentary lithic grains comprise mostly sandstone, siltstone, limestone and dolomite. Metamorphic lithic grains generally are low-grade schists and phyllites. In various compositional ternary diagrams, the sources of the sandstones plot in the transitional to dissected arc and recycled orogenic fields. We selected 26 samples for heavy mineral study. 200-300 grain were identified and counted in each sample. Heavy mineral suites show a highly variable composition including (1) a group of ultra-stable minerals (zircon, monazite, tourmaline, rutile, brookite, anatase and sphene) derived from a granitic continental crust sources, (2) metastable minerals delivered from variable metamorphic-grade source rocks (epidote group, garnet, staurolite, chloritoid, kyanite, andalusite, glaucophane), (3) chromian spinel from ultrabasic rocks, (4) common hornblende either supplied from metamorphic or basic igneous series, and (5) a local pyroxene-rich source in the pyroclastic sandstone formation overlying pillow lavas. Glaucophane (5-20%) occurs in several samples, which indicates high-pressure/low-temperature metamorphic rocks in the detrital source areas for Eocene and Miocene sandstones. Earlier work in the Pakistani Makran suggested that pre-Miocene sediments were supplied from the Himalaya, whereas Miocene to Recent deposits were reworked older sediments of the accretionary wedge. Our data do not support this conclusion. Instead, we identified rifting-related detrital sources from Middle Jurassic to late Early Cretaceous (175 - 100 Ma) and the establishment of a continental volcanic arc from Late Cretaceous to Eocene (80 to 40 Ma). In addition, paleocurrent directions in Makran sandstone show general sediment transport from North to South; Cr-spinel as well as high-P/low-T heavy minerals most likely have been derived from the blueschist-bearing Makran ophiolitic and igneous belt to the North.

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.

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 Neoproterozoic. In addition, our data set shows that both passive margin clastic sequences had the same source area for all zircons older than Neoproterozoic. Therefore we infer that India and South China were close to each other and along the same passive margin during the breakup of Rodinia in the Late Neoproterozoic.

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 demonstrate that the occurrences of higher εHf (0), Grenvillian detrital zircons are decoupled from the sources of the bulk of the sedimentary detritus in which the zircons are entrained. The Cambrian Wood Canyon Formation and the underlying ;off craton; Neoproterozoic Johnnie Formation and Stirling Quartzite all contain higher εHf (0), Grenvillian detrital zircon, in some cases as the dominant detrital zircon population. However, only portions of the Wood Canyon Formation have whole rock Nd isotopic compositions consistent with a bulk sediment source in ∼1.1 Ga sources rocks. Whole rock Nd isotopic compositions of the remaining portions of this unit, and all of the Johnnie Formation and Stirling Quartzite, require bulk sediment sources principally in Paleoproterozoic continental crust. We consider the observed decoupling in the sources of Grenvillian detrital zircon and bulk sediment in the Wood Canyon Formation and underlying siliciclastic sediments as a demonstration that detrital zircon U-Pb and Hf isotopic data alone can provide an incomplete picture of the source of sediments that comprise a given siliciclastic stratigraphic unit.

Dating High Temperature Mineral Fabrics in Lower Crustal Granulite Facies Rocks

NASA Astrophysics Data System (ADS)

Stowell, H. H.; Schwartz, J. J.; Tulloch, A. J.; Klepeis, K. A.; Odom Parker, K.; Palin, M.; Ramezani, J.

2015-12-01

Granulite facies rocks may record strain that provides a record of compressional and/or extensional crustal events in hot orogenic cores and the roots of magmatic arcs. Although the precise timing of these events is important for constructing tectonic histories, it is often difficult to determine due to uncertain relationships between isotopic signatures, mineral growth, and textural features that record strain. In addition, there may be large uncertainties in isotope data due to intracrystalline diffusion and multiple crystallization events. L-S tectonites in lower crustal rocks from Fiordland, NZ record the early stages of extensional collapse of thickened magmatic arc crust. The precise age of these fabrics is important for constraining the timing of extension that led to opening of the Tasman Sea. High temperature granulite facies L-S fabrics in garnet reaction zones (GRZ) border syn- to post-deformational leucosomes. U-Pb zircon, Lu-Hf garnet, and Sm-Nd garnet ages, and trace elements in these phases indicate the complexity of assigning precise and useful ages. Zircon have soccer ball morphology with patchy and sector zoned CL. Zircon dates for igneous host and adjacent GRZ range over ca. 17 Ma. 236U-208Pb LA-ICP-MS are 108-125 Ma, N=124 (host & GRZ); however, chemical abrasion (CA) shifts GRZ dates ca. 2 Ma older. 236U-208Pb SHRIMP-RG dates cluster in 2 groups: 118.5±0.8 Ma, N=23 and 111.0±0.8 Ma, N=6. CA single crystal TIMS dates also fall into 2 groups: 117.6±0.1 Ma, N=4 and 116.6±0.2 Ma N=4. Garnet isochron ages determined from coarse garnet selvages adjacent to leucosomes range from 112.8±2.2 (147Sm-143Nd, 10 pts.) to 114.8±3.5 (177Lu-176Hf, 6 pts.) Ma. Zircon dates from all methods show ranges (>10 Ma) and 2 distinct populations. Host and GRZ zircon cannot be readily distinguished by age, lack younger rims, but have distinct Th/U trends and Eu/Eu* vs. Hf ratios. Difference in zircon trace element composition indicates either early leucosome emplacement or xenocrystic zircon in leucosomes. We conclude that the small number of oldest zircon grains are inherited, older zircon age populations (CA LA-ICP-MS, SHRIMP-RG and TIMS) are near identical ca. 118 Ma and date intrusion, and that the youngest zircon and indistinguishable garnet ages (113-116 Ma) date syn-deformational granulite facies metamorphism.

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.

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-to-the-north shearing, which post-dates the growth of blue amphiboles (crossite).

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.

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 constraints for detrital zircon provenance; 3) it may help explore the compositional evolution of magma differentiation.

Petrogenesis and tectonic implications of Early Cretaceous volcanic rocks from Lingshan Island in the Sulu Orogenic Belt

NASA Astrophysics Data System (ADS)

Meng, Yuanku; Santosh, M.; Li, Rihui; Xu, Yang; Hou, Fanghui

2018-07-01

The Dabie-Sulu orogenic belt in eastern China marks the boundary between the Yangtze Block and the North China Block. Here we investigate a suite of volcanic rocks from Lingshan Island in the Sulu belt comprising rhyolite, trachyte, trachyandesite and basaltic trachyandesite. We present petrological, geochemical and zircon Usbnd Pb ages and Hfsbnd O isotope data with a view to gain insights on the petrogenesis and tectonic implications. SHRIMP II analyses of zircon grains from the rhyolite yield 206Pb/238U age of 127.6 ± 1.3 Ma and LA-MC-ICP-MS dating show 126.3 ± 1.2 Ma and 127.3 ± 1.1 Ma, together constraining the eruption time as Early Cretaceous. LA-MC-ICP-MS analyses of zircon grains from the andesitic rocks yield 206Pb/238U ages of 129.0 ± 1.6 Ma, 129.8 ± 1.5 Ma and 130.9 ± 1.0 Ma. Geochemically, the rhyolite shows shoshonitic features with low MgO and Cr, but high Na2O + K2O. The zircon grains from these rocks yield negative εHf(t) values and low δ18O values, and these together with the presence of Neoproterozoic inherited zircons suggest that the magma source involved melting of the Yangtze crust. The andesitic rocks, including basaltic trachyandesite, trachyandesite and trachyte, show a wide range of SiO2, Mg# values, and Cr, enriched in LILE and LREE, depleted in HFSE (Nb, Ta and Ti), and have significantly negative zircon εHf(t) values, suggesting derivation from subcontinental lithosphere mantle that was metasomatized by felsic melts. Our results, integrated with those from previous studies suggest heterogeneous magma involving the mixing of mantle and crustal sources within an extensional setting in the Early Cretaceous.

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.

Histological examination of the oral mucosa after fractional diode laser irradiation with different power and pulse duration

NASA Astrophysics Data System (ADS)

Belikov, Andrey V.; Ermolaeva, Ludmila A.; Korzhevsky, Dmitriy E.; Sergeeva, Elena S.; Semyashkina, Yulia V.; Antropova, Maria M.; Fedotov, Denis Y.; Zaitseva, Maria A.; Kashina, Tatiana V.

2018-04-01

Optical and histological methods were used to examination of influence the power and pulse duration of 980-nm diode laser to the dimensions and morphology of tissue around fractional micro injuries created by the radiation of that laser in the oral mucosa of rats in vivo. The power of laser radiation (P) varied in the range of 1÷21 W, and its pulse duration (tp) - in the range 50÷500 ms. Histological examination showed that in the mucosa of the oral cavity after the laser fractional irradiation, there following effects are found: a tissue defect, a transudate in the lumen of ablative micro injury, stretching and compacting effect of the nuclei of the basal epithelium, the disappearance of granules of the keratohialin, destroying the structure of the connective tissue, erythrocyte stasis in the vessels, the disappearance of transverse striation in the muscle fibers in muscle layer. It has been found that ablative micro injury begins to form up at P = 5 W, tp = 100 ms and affects only the epithelial layer of the mucosa. At P = 7 W, tp = 120 ms, the ratio of width to depth of ablative micro injury is 1 : 1, and at P = 10 W, tp = 100 ms, an ablative micro column with ratio of 1 : 1.5 is formed in the epithelial and submucosal layers of the mucosa. The laser effect with P = 15 W, tp = 200 ms leads to lengthening of the ablation micro-column to 1 : 2, with the bottom of the ablative micro column reaching the muscular layer. With a further growth of laser power or pulse duration, the width of the micro injury increases, and the growth of the micro injury depth is slowed down so that the micro column buildup is ceased.

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

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.

Advances in Laser Microprobe (U-Th)/He Geochronology

NASA Astrophysics Data System (ADS)

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

2008-12-01

The development of the laser microprobe (U-Th)/He dating method has the potential to overcome many of the limitations that affect conventional (U-Th)/He geochronology. Conventional single- or multi-crystal (U- Th)/He geochronology requires the use of pristine, inclusion-free, euhedral crystals. Furthermore, the ages that are obtained require corrections for the effects of zoning and alpha ejection based on an ensemble of assumptions before interpretation of their geological relevance is possible. With the utilization of microbeam techniques many of the limitations of conventional (U-Th)/He geochronology can either be eliminated by careful spot selection or accounted for by detailed depth profiling analyses of He, U and Th on the same crystal. Combined He, Th, and U depth profiling on the same crystal potentially even offers the ability to extract thermal histories from the analyzed grains. Boyce et al. (2006) first demonstrated the laser microprobe (U-Th)/He dating technique by successfully dating monazite crystals using UV laser ablation to liberate He and determined U and Th concentrations using a Cameca SX-Ultrachron microprobe. At Arizona State University, further development of the microprobe (U-Th)/He dating technique continues using an ArF Excimer laser connected to a GVI Helix Split Flight Tube noble gas mass spectrometer for He analysis and SIMS techniques for U and Th. The Durango apatite age standard has been successfully dated at 30.7 +/- 1.7 Ma (2SD). Work on dating zircons by laser ablation is currently underway, with initial results from Sri Lanka zircon at 437 +/- 14 Ma (2SD) confirmed by conventional (U-Th)/He analysis and in agreement with the published (U-Th)/He age of 443 +/- 9 Ma (2SD) for zircons from this region in Sri Lanka (Nasdala et al., 2004). The results presented here demonstrate the laser microprobe (U-Th)/He method as a powerful tool that allows application of (U- Th)/He dating to areas of research such as detrital apatite and zircon dating, where conventional (U-Th)/He geochronology has limited applicability. Boyce et al. (2006) GCA 70 (3031-3039), Nasdala et al. (2004) Am. Min. 89 (219-231)

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 to be increased for an accurate content determination and complete release of analytes for geochronological studies. Larger test portion size reduces the heterogeneity issues in granites in particular [2]. No significant blanks issues were observed and interferences were controlled using QQQ MS mode of ICP-MS. References [1] Meisel, T., N. Schöner, et al. (2002). "Determination of Rare Earth Elements, Y, Th, Zr, Hf, Nb and Ta in Geological Reference Materials G-2, G-3, SCo-1 and WGB-1 by Sodium Peroxide Sintering and Inductively Coupled Plasma-Mass Spectrometry." Geostandards Newsletter 26(1): 53-61. [2] Bokhari SNH., Meisel T (2013) "The Determination of Homogeneity of Geological Reference Material" Mineralogical Magazine, 77(5): 731.

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 setting with heat flow from the underlying arc granitoids.

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.

Mid to late Devonian back-arc rift basins in the Brooks Range, AK, and across the Arctic: a possible paleogeographic piercing point for Arctic reconstructions

NASA Astrophysics Data System (ADS)

Hoiland, C. W.; Miller, E. L.; Hourigan, J. K.

2013-12-01

The westernmost Brooks Range, Alaska, is underlain by basement of probable Baltic or Timanian affinity (e.g. Miller et al., 2011; Amato et al., 2009), while the eastern Brooks Range is underlain by Laurentian affinity basement (e.g. Strauss et al., 2013). A post-Timanian and pre-Mississippian suture or contact is thus required based on continuity of late Devonian and younger strata across the Brooks Range (e.g. Dumoulin et al., 2002). This inferred juxtaposition has been proposed as the distal and diachronous (though possibly non-collisional) continuation of the Caledonian orogen (e.g. Moore et al., 2012) but the actual location and character of this suture within basement rocks of the Brooks Range remain speculative. New laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb single grain detrital zircon (DZ) geochronology of basement rocks from the Cosmos Hills, Slate Creek, and Wiseman regions suggest that metamorphic rocks in these regions are Devonian, not pre-Devonian. New SHRIMP-RG analyses of the Kogoluktuk orthogneiss (Cosmos) (zircon: 383 Ma × 5 Ma, 2-sigma errors, consistent with Dillon et al. 1980) revealed no inherited cores from which to infer basement affinity. DZ spectra from metasedimentary and metavolcanic wall rock contain youngest detrital zircon populations with ages (390 Ma) just barely older than the cross-cutting intrusive age, providing tight bracketing of depositional age. These zircon ages are noticeably younger than Caledonian magmatic ages (430-420 Ma) suggesting deposition in a volcanically and tectonically active setting (likely extensional) as originally suggested by Hitzman et al (1986). Zircon spectra (Cosmos) contain notable amounts of "Timanian" age zircons (c. 700-550 Ma), and a spread of zircons from 1-2 Ga (including 1.5-1.6 Ga ages of the Laurentian "magmatic gap', e.g. Grove et al. 2008) more typical of derivation from Baltic rather than Laurentian sources. East in the Wiseman and Slate Creek localities, the detrital signature becomes characteristically Laurentian, with a notable absence of Timanian and "magmatic gap" ages. A youngest age population of 390 Ma still provides a maximum depositional age, but minimum age is poorly constrained. The coarse and feldspathic nature of many of these intercalated volcanic and clastic sequences suggests a proximal provenance, thus serving as a proxy for local pre-Devonian basement ages and affinity. We might, therefore, infer a non-Laurentian basement for the AACM at least as far east as the Cosmos Hills but not further east than the Wiseman region. These Devonian-age volcanic/rift basins may be related to slab roll-back and induced backarc rifting that occurred obliquely across a 'Caledonian' suture, possibly in response to global plate re-organization. Rifting, accompanied by bimodal volcanism (the Ambler Sequence), may have aided the removal and translation of peri-Baltic terranes to a position outboard of the proto-Cordilleran margin ('Northwestern Passage' of Colpron & Nelson, 2009). Further correlations might be drawn with the Sakmarian-Magnitogorsk arcs of the pre-Uralian margin of Europe. These Devonian backarc rift sequences - more widespread than previously thought - may serve as critical additional tie-points for paleogeographic reconstructions of the Arctic.

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.

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.

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.

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.

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.

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.g., fluid in equilibrium with eclogite garnet is depleted in heavy REE relative to middle REE, and has low Th/U.

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.

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

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.

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 been rarely attained.

Initiation of the Bukadaban Feng Normal Fault and Implications for the Topographic Evolution of Northern Tibet

NASA Astrophysics Data System (ADS)

Niemi, N. A.; Chang, H.; Li, L.; Molnar, P. H.

2017-12-01

The Bukadaban Feng massif in northern Tibet forms the footwall of an east-west trending graben that is kinematically linked to the Kunlun fault. Extension across this graben accommodates left-lateral slip on the Kunlun fault, as evidenced by the 2001 Kunlun earthquake rupture. New geochronologic and thermochronologic data from Bukadaban Feng provide insight into the evolution of this normal fault system. The Bukadaban Feng massif is composed of two plutonic units, an eastern unit of dacitic composition and a western unit of rhyolitic composition. Sixty-five LA-ICP-MS zircon U-Pb age determinations on the rhyolitic unit reveal a range of ages from 873 - 6.3 Ma. CA-TIMS U-Pb zircon geochronology on the nine youngest of these zircons yields an emplacement age of 6.8 Ma. Twenty-seven LA-ICP-MS zircon U-Pb ages on the dacite range from 208 to 7.9 Ma. No coherent population of young zircons was observed, and CA-TIMS analysis was not performed. Zircon (U-Th)/He analysis on the dacite and rhyolite yield ages of 3.9 and 5.0 Ma, respectively, while apatite (U-Th-Sm)/He thermochronology on 5 samples collected from both units along the trace of the normal fault yield ages ranging from 1.4 - 2.6 Ma. The emplacement ages and compositions of plutonic rocks at Bukadaban Feng are consistent with the eruptive timing and geochemistry of silicic volcanic rocks in the graben (Zhang et al., 2012). Silicic magmatism is often associated with the onset of crustal extension, and the combination of plutonism and correlative silicic volcanism provides an indirect constraint on the initiation of this graben at 7 Ma. The distinct zircon (U-Pb) and (U-Th)/He ages indicates that the rocks presently exposed at Bukadaban Feng were emplaced at ambient temperatures in excess of 180°C. The zircon and apatite thermochronologic data require exhumation at rates of 1-2 mm/yr since the late Miocene. A 7 Ma initiation age for the Bukadaban Feng normal fault is consistent with both published estimates of total offset across the Kunlun fault ( 70 km; Kidd and Molnar, 1988) and recent fault slip rates ( 10 mm/yr; van der Woerd et al., 2002). To the extent that the onset of extension and strike-slip faulting can be related to the attainment of high topography, these new data imply that northernmost Tibet may have reached maximum elevations as recently as the late Miocene.

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, № 16-05-00305, 16-05-00367, 16-05-00427) and theme of state assignment № 0231-2015-0005. References: 1. Boynton W.V. Cosmochemistry of the rare earth elements: meteorite studies // Ed. Henderson P. Rare earth element geochemistry. Amsterdam: Elsevier. 1984. P. 63-114. 2. Watson E. B., Wark D.A., Thomas J.B. Crystallization thermometers for zircon and rutile // Contrib. Miner. Petrol. 2006. V. 151. P. 413-433. 3. Hoskin P.W.O. and Schaltegger U. The Composition of zirconand igneous and metamorphic petrogenesis // Reviews in mineralogy & geochemistry. 2003. V. 53. P. 27-62.

Timing of metamorphism and exhumation in the Nordøyane ultra-high-pressure domain, Western Gneiss Region, Norway: New constraints from complementary CA-ID-TIMS and LA-MC-ICP-MS geochronology

NASA Astrophysics Data System (ADS)

Butler, J. P.; Jamieson, R. A.; Dunning, G. R.; Pecha, M. E.; Robinson, P.; Steenkamp, H. M.

2018-06-01

We present the results of a combined CA-ID-TIMS and LA-MC-ICP-MS U-Pb geochronology study of zircon and associated rutile and titanite from the Nordøyane ultra-high-pressure (UHP) domain in the Western Gneiss Region (WGR) of Norway. The dated samples include 4 eclogite bodies, 2 host-rock migmatites, and 2 cross-cutting pegmatites and leucosomes, all from the island of Harøya. Zircon from a coesite eclogite yielded an age of ca. 413 Ma, interpreted as the time of UHP metamorphism in this sample. Zircon data from the other eclogite bodies yielded metamorphic ages of ca. 413 Ma, 407 Ma, and 406 Ma; zircon trace-element data associated with 413 Ma and 407 Ma ages are consistent with eclogite-facies crystallization. In all of the eclogites, U-Pb dates from zircon cores, interpreted as the times of protolith crystallization, range from ca. 1680-1586 Ma, consistent with Gothian ages from orthogneisses in Nordøyane and elsewhere in the WGR. A zircon core age of ca. 943 Ma from one sample agrees with Sveconorwegian ages of felsic gneisses and pegmatites in the western part of the area. Migmatites hosting the eclogite bodies yielded zircon core ages of ca. 1657-1591 Ma and rim ages of ca. 395-392 Ma, interpreted as the times of Gothian protolith formation and Scandian partial melt crystallization, respectively. Pegmatite in an eclogite boudin neck yielded a crystallization age of ca. 388 Ma, interpreted as the time of melt crystallization. Rutile and titanite from 3 samples (an eclogite and two migmatites) yielded concordant ID-TIMS ages of 378-376 Ma. The results are similar to existing U-Pb data from other Nordøyane eclogites (415-405 Ma). In combination with previous pressure-temperature data from the coesite eclogite, these ages indicate that peak metamorphic conditions of 3 GPa/760 °C were reached ca. 413 Ma, followed by decompression to 1 GPa/810 °C by ca. 397 Ma and cooling below ca. 600 °C by ca. 375 Ma. The results are compatible with protracted UHP metamorphism followed by relatively slow exhumation. The question of whether partial melting began at UHP conditions is not resolved by this study.

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 presence of volcanic quartz. The absence of an earlier volcanic contribution is surprising since subduction is widely considered to have been active from the Eocene.

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.

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 in chromitites come from? It has been recognized that this ophiolite was formed at 110-120 Ma based on radiolaria in cherts overlying the pillow lavas (ALLEGRE et al., 1984; ZIABREV et al., 2003). In this study, the minimum age of 107 Ma, which we obtained from zircon in chromitites, is consistent to the age of the ophiolite. But, all other ages of zircons are much older than that of ophiolite. Yang et al. (2001) also reported U-Pb zircon ages of 450-910 Ma and Re-Os iridosmine age of 400 Ma from chromitites in Luobusa ophiolite. Mineral inclusions within zircons are crustal materials, which means that these zircons were crystallized in the low pressure crustal condition. Thus these zircons within chromitites are interpreted as xenocrysts from old crustal materials. Recently, old-age zircons (330 to 1600 Ma) were also reported from the Mid Atlantic Ridge MORBs (PILOT et al., 1998). They suggest one possibility that these old-age zircons may have derived from old continental crustal material, which have assimilated with the MORB magma during ascent. Moreover, Archean zircons were reported from pyroxenite dikes in Jormua ophiolite (PETRI et al., 2003). YU et al. (2001) reported that zircons from chromitites in Luobusa ophiolite have shorter inter-atomic distances of Zr-O and Si-O bonds. As a result, they concluded that Tibetan-zircons were derived from the high-pressure mantle environment. Judging from the line of evidence mentioned above, it is highly possible that these zircons captured by chromitites were originated from recycled crustal materials, convecting through upper mantle.

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-inductively coupled plasma-mass spectrometer (LA-MC-ICP-MS) at Goethe University, Frankfurt. A total of 399 U-Pb spot analyses were carried out on zircons from the sandstones of the Orhanlar Unit. 84% of the data yielded Precambrian ages, which is in marked contrast with the typical arkosic sandstones of the Karakaya Complex in which Precambrian zircons form only 10% of the population. Three zircon grains of Ladinian age suggest a maximum depositional age for the Orhanlar Unit. The most prominent zircon population is of Ediacaran-Cryogenian age (31%). The second largest population is Tonian-Stenian (22%), the third largest Cryogenian-Tonian (9%) and the fourth Devonian-Carboniferous (7%). There are also minor zircon populations of Palaeoproterozoic and Neo-Archean ages. The Precambrian zircon populations in the Orhanlar Unit sandstones are identical to those in the schists of the Sakarya continental crust (P.A. Ustaömer et al. 2012; this study). Their Hf isotope compositions also overlap, suggesting that the Sakarya continental crust could be a source for the sandstones of the Orhanlar Unit. On the other hand, the Hf(t) values of most of the Devonian and Carboniferous detrital zircons differ from those of the Devonian and Carboniferous granites that intrude the Sakarya continental crust. The Karakaya Complex as a whole appears to have been derived from two different source terranes, of which the Orhanlar Unit sandstones represent a minor, but significant component. Possible explanations are that two different source terranes already existed in the same region but that these were not exposed to erosion at the same time or, if exposed simultaneously, experienced different depositional pathways (without mixing); alternatively, the Orhanar Unit represents part of a different tectono-stratigraphic terrane from the other Karakaya Complex units, with which it was tectonically amalgamated prior to Early Jurassic deposition of a common sedimentary cover. Ustaömer PA, Ustaömer T, Robertson AHF (2012), Turkish Journal of Earth Sciences, doi:10.3906/yer-1103-1 Ustaömer T, Ustaömer PA, Robertson AHF, Gerdes A (2015), International Journal of Earth Sciences, DOI 10.1007/s00531-015-1225-8. This work was supported by TUBITAK, Project no 111R015

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.

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

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.

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.

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.

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 demonstrates the importance of the careful examination of compositional, microtextural and geochronological data obtained using microanalytical techniques to reconstruct the complex thermal histories recorded by accessory minerals.

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.

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

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.

Dating faults by quantifying shear heating

NASA Astrophysics Data System (ADS)

Maino, Matteo; Casini, Leonardo; Langone, Antonio; Oggiano, Giacomo; Seno, Silvio; Stuart, Finlay

2017-04-01

Dating brittle and brittle-ductile faults is crucial for developing seismic models and for understanding the geological evolution of a region. Improvement the geochronological approaches for absolute fault dating and its accuracy is, therefore, a key objective for the geological community. Direct dating of ancient faults may be attained by exploiting the thermal effects associated with deformation. Heat generated during faulting - i.e. the shear heating - is perhaps the best signal that provides a link between time and activity of a fault. However, other mechanisms not instantaneously related to fault motion can generate heating (advection, upwelling of hot fluids), resulting in a difficulty to determine if the thermal signal corresponds to the timing of fault movement. Recognizing the contribution of shear heating is a fundamental pre-requisite for dating the fault motion through thermochronometric techniques; therefore, a comprehensive thermal characterization of the fault zone is needed. Several methods have been proposed to assess radiometric ages of faulting from either newly grown crystals on fault gouges or surfaces (e.g. Ar/Ar dating), or thermochronometric reset of existing minerals (e.g. zircon and apatite fission tracks). In this contribution we show two cases of brittle and brittle-ductile faulting, one shallow thrust from the SW Alps and one HT, pseudotachylite-bearing fault zone in Sardinia. We applied, in both examples, a multidisciplinary approach that integrates field and micro-structural observations, petrographical characterization, geochemical and mineralogical analyses, fluid inclusion microthermometry and numerical modeling with thermochronometric dating of the two fault zones. We used the zircon (U-Th)/He thermochronometry to estimate the temperatures experienced by the shallow Alpine thrust. The ZHe thermochronometer has a closure temperature (Tc) of 180°C. Consequently, it is ideally suited to dating large heat-producing faults that were active at shallow depths (<6-7 km) where wall-rock temperature does not exceed Tc. On the other hand, the retrogressed pseudotachylites from the Variscan basement of Sardina developed in deeper crustal levels and produced considerably higher temperatures (>800 °C). They have been dated using laser ablation ICP-MS on monazites and zircons. This large dataset provides the necessary constraints to explore the potential causes of heating, its timing and how it is eventually related to fault motion.

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.

Thorium partitioning in Greek industrial bauxite investigated by synchrotron radiation and laser-ablation techniques

NASA Astrophysics Data System (ADS)

Gamaletsos, P.; Godelitsas, A.; Mertzimekis, T. J.; Göttlicher, J.; Steininger, R.; Xanthos, S.; Berndt, J.; Klemme, S.; Kuzmin, A.; Bárdossy, G.

2011-12-01

Typical red-brown (Fe-rich) and high-quality white-grey (Fe-depleted) bauxite samples from active mines of the Parnassos-Ghiona area, central Greece, were investigated. According to XRF and ICP-MS analyses their actinide content, and particularly of Th, is relatively increased. Fe-depleted samples contain up to 62.75 ppm Th corresponding to 220 Bq/kg due to 228Ac ( 232Th-series), whereas Fe-rich samples are less Th-radioactive (up to 58.25 ppm Th, 180 Bq/kg due to 228Ac). Powder-XRD patterns showed that Th-enriched (Fe-depleted) bauxite consists mostly of diaspore (AlOOH polymorph), anatase and rutile (TiO 2 polymorphs). SEM-EDS indicated the presence of Ti-Fe-containing phases (e.g. ilmenite, FeTiO 3), chromite (Cr-spinel) and besides LREE-minerals (mostly bastnäsite/parisite-group) and zircon (ZrSiO 4) hosting a part of the bulk Th. The presence of Th in diaspore and in Ti-containing phases (not detected by SEM-EDS as in the case of REE-minerals and zircon) was investigated, into distinct pisoliths of Fe-depleted bauxite, using μ-XRF and μ-XAFS in the SUL-X beamline of the ANKA Synchrotron facility (KIT, Germany). XAFS spectra of Th salts and Th-containing reference materials were obtained as well. Accordingly it was revealed, for the first time in the literature, that Ti-phases, and particularly anatase, host significant amounts of Th. This novel conclusion was complementary supported by LA-ICP-MS analyses indicated an average of 73 ppm Th in anatase grains together with abundant Nb (3356 ppm), Ta (247 ppm) and U (33 ppm). The Th LIII-edge XAFS spectra as compared to reference materials, give also evidence that Th 4+ may not replace Ti 4+ in distorted [TiO 6] fundamental octahedral units of anatase and ilmenite lattice (CN = 6). The occupation of either extraframework sites of higher coordination (CN = 6.9 or even CN = 7.4), according to EXAFS signals evaluation, or of defected/vacant (**) sites is more probable. This is likely explained by the difficulty of Th 4+ to replace directly Ti 4+ in [6]-coordinated (octahedral) sites due to the large difference in the relevant ionic radii (0.940 and 0.605 Å respectively).

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.

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.

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 synthetic basalt glasses. Instrumental drift is monitored during each run using two fused standards analyzed multiple times as unknowns. We routinely achieve an external precision of <5% on multiple replicates of standards run as unknowns, which are also within <5% of certified values. Elements analyzed include most first row transition metals, large ion lithophile elements, high field strength elements, lanthanide and actinide rare earth elements.

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

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

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.

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.

[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.

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.

U-Pb age constraints for the La Tuna Granite and Montevideo Formation (Paleoproterozoic, Uruguay): Unravelling the structure of the Río de la Plata Craton

NASA Astrophysics Data System (ADS)

Pamoukaghlián, Karina; Gaucher, Claudio; Frei, Robert; Poiré, Daniel G.; Chemale, Farid; Frei, Dirk; Will, Thomas M.

2017-11-01

The Río de la Plata Craton is a continental block that crops out in Uruguay, eastern Argentina, southernmost Brazil and Paraguay. It comprises in Uruguay the Piedra Alta, Tandilia and Nico Pérez terranes, separated by the Colonia and the Sarandí del Yí megashears. The La Tuna Granite, which intrudes the Araminda metasandstones in the Tandilia Terrane, was considered Cambrian in age and the intruded sandstones were assigned to the Neoproterozoic Piedras de Afilar Formation. We show that the granite is Paleoproterozoic in age and that the host metasandstones do not belong to the Piedras de Afilar Formation, but to the Paleoproterozoic Montevideo Formation. U-Pb LA ICP-MS of zircon ages for the La Tuna Granite yielded a concordant crystallization age of 2156 ± 26 Ma. Furthermore a metamorphic event at 2010 ± 9 Ma is revealed by Pb stepwise leaching dating of monazites. U-Pb detrital zircon ages of the host Araminda metasandstone yield an upper intercept discordia age of 2152 ± 29 Ma, which marks the intrusion of the La Tuna pluton, and which is in accordance with the zircon U-Pb LA ICP MS constraints. A concordant U-Pb detrital zircon age of 2465 ± 40 Ma provides a maximum depositional age constraint for the metapsammites. Comparing quartz arenites of the Ediacaran Piedras de Afilar Formation with the Araminda metaquartzites, we conclude that they are very similar regarding petrology but they differ in age and metamorphic overprint. Detrital zircons in quartz arenites of the Piedras de Afilar Formation show youngest ages of 1.0 Ga. On the other hand, detrital zircons recovered from the Araminda metasandstones and the age of the intruding granite allow interpreting a depositional age between 2465 and 2150 Ma. Nd model ages show crustal residence times in average more than 200 myr older for the Tandilia Terrane both in Uruguay and Argentina, with a significant Neoarchean component, which is lacking in the Piedra Alta Terrane. Whereas the Piedra Alta Terrane was formed rapidly from a juvenile source, the Tandilia Terrane shows a more protracted history. Our data support the interpretation of the Tandilia Terrane as a separate tectonostratigraphic unit.

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS for isotope analysis of long-lived radionuclides

NASA Astrophysics Data System (ADS)

Becker, J. Sabine

2005-04-01

For a few years now inductively coupled plasma mass spectrometry has been increasingly used for precise and accurate determination of isotope ratios of long-lived radionuclides at the trace and ultratrace level due to its excellent sensitivity, good precision and accuracy. At present, ICP-MS and also laser ablation ICP-MS are applied as powerful analytical techniques in different fields such as the characterization of nuclear materials, recycled and by-products (e.g., spent nuclear fuel or depleted uranium ammunitions), radioactive waste control, in environmental monitoring and in bioassay measurements, in health control, in geochemistry and geochronology. Especially double-focusing sector field ICP mass spectrometers with single ion detector or with multiple ion collector device have been used for the precise determination of long-lived radionuclides isotope ratios at very low concentration levels. Progress has been achieved by the combination of ultrasensitive mass spectrometric techniques with effective separation and enrichment procedures in order to improve detection limits or by the introduction of the collision cell in ICP-MS for reducing disturbing interfering ions (e.g., of 129Xe+ for the determination of 129I). This review describes the state of the art and the progress of ICP-MS and laser ablation ICP-MS for isotope ratio measurements of long-lived radionuclides in different sample types, especially in the main application fields of characterization of nuclear and radioactive waste material, environmental research and health controls.

A rapid and reliable method for Pb isotopic analysis of peat and lichens by laser ablation-quadrupole-inductively coupled plasma-mass spectrometry for biomonitoring and sample screening.

PubMed

Kylander, M E; Weiss, D J; Jeffries, T E; Kober, B; Dolgopolova, A; Garcia-Sanchez, R; Coles, B J

2007-01-16

An analytical protocol for rapid and reliable laser ablation-quadrupole (LA-Q)- and multi-collector (MC-) inductively coupled plasma-mass spectrometry (ICP-MS) analysis of Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb) in peats and lichens is developed. This technique is applicable to source tracing atmospheric Pb deposition in biomonitoring studies and sample screening. Reference materials and environmental samples were dry ashed and pressed into pellets for introduction by laser ablation. No binder was used to reduce contamination. LA-MC-ICP-MS internal and external precisions were <1.1% and <0.3%, respectively, on both (207)Pb/(206)Pb and (208)Pb/(206)Pb ratios. LA-Q-ICP-MS internal precisions on (207)Pb/(206)Pb and (208)Pb/(206)Pb ratios were lower with values for the different sample sets <14.3% while external precisions were <2.9%. The level of external precision acquired in this study is high enough to distinguish between most modern Pb sources. LA-MC-ICP-MS measurements differed from thermal ionisation mass spectrometry (TIMS) values by 1% or less while the accuracy obtained using LA-Q-ICP-MS compared to solution MC-ICP-MS was 3.1% or better using a run bracketing (RB) mass bias correction method. Sample heterogeneity and detector switching when measuring (208)Pb by Q-ICP-MS are identified as sources of reduced analytical performance.

Analysis and comparison of glass fragments by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and ICP-MS.

PubMed

Trejos, Tatiana; Montero, Shirly; Almirall, José R

2003-08-01

The discrimination potential of Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is compared with previously reported solution ICP-MS methods using external calibration (EC) with internal standardization and a newly reported solution isotope dilution (ID) method for the analysis of two different glass populations. A total of 91 different glass samples were used for the comparison study; refractive index and elemental composition were measured by the techniques mentioned above. One set consisted of 45 headlamps taken from a variety of automobiles that represents a range of 20 years of manufacturing dates. A second set consisted of 46 automotive glasses (side windows, rear windows, and windshields) representing casework glass from different vehicle manufacturers over several years. The element menu for the LA-ICP-MS and EC-ICP-MS methods include Mg, Al, Ca, Mn, Ce, Ti, Zr, Sb, Ga, Ba, Rb, Sm, Sr, Hf, La, and Pb. The ID method was limited to the analysis of two isotopes each of Mg, Sr, Zr, Sb, Ba, Sm, Hf, and Pb. Laser ablation analyses were performed with a Q switched Nd:YAG, 266 nm, 6 mJ output energy laser. The laser was used in depth profile mode while sampling using a 50 microm spot size for 50 sec at 10 Hz (500 shots). The typical bias for the analysis of NIST 612 by LA-ICP-MS was less than 5% in all cases and typically better than 5% for most isotopes. The precision for the vast majority of the element menu was determined generally less than 10% for all the methods when NIST 612 was measured (40 microg x g(-1)). Method detection limits (MDL) for the EC and LA-ICP-MS methods were similar and generally reported as less than 1 microg x g(-1) for the analysis of NIST 612. While the solution sample introduction methods using EC and ID presented excellent sensitivity and precision, these methods have the disadvantages of destroying the sample, and also involve complex sample preparation. The laser ablation method was simpler, faster, and produced comparable discrimination to the EC-ICP-MS and ID-ICP-MS. LA-ICP-MS can offer an excellent alternative to solution analysis of glass in forensic casework samples.

RN12 and RN30 Epidote anlayses

DOE Data Explorer

Andrew Fowler

2015-01-01

Results for laser ablation measurement of reare earth elments and electron microprobe analysis of major elments in hydrothermal epidote. Laser ablation measurements were completed using an Agilent 7700 quadrupole ICP-MS coupled with 193nm Photon Instruments Excimer laser.

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 Graywacke implies that it lay to the south when it was deposited and offscraped. Thus, although source areas as far north as the St. Elias Mountains and south-central Alaska are possible, they were most likely in coastal and interior British Columbia.

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.

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

We have analysed Pb isotopes in natural rutile crystals by laser ablation MC-ICP-MS to assess the potential of rapid Pb-Pb dating of rutile with this method. The rutile samples are from granulite-facies Mg- and Al-rich rocks from the Reynolds Range, Northern Territory, Australia. This metamorphic terrane has a well-constrained high-T cooling history (ca. 3^oC/Myr) defined by previous U-Pb dating of monazite and zircon (peak metamorphism at 1584 Ma), which we have supplemented with additional Rb-Sr dates of phlogopite, biotite and muscovite. The dated rutiles vary in size from 3 to 0.05 mm, have Pb concentrations of ca. 20 ppm, and were analysed with a 266 nm laser coupled to an AXIOM MC-ICP-MS (spot size of 200-50 μm). Individual larger crystals (>= 200 μm) exhibit sufficient Pb isotopic heterogeneity (206Pb/204Pb = 10000-80000) to perform isochron calculations on several short analyses of a single grain (30-60 s). The largest rutiles yielded Pb-Pb isochron ages of 1540-1555 Ma with typical uncertainties of ± 1 to 10 Ma. 207Pb/206Pb ages are typically within 1% of the Pb-Pb isochron ages testifying to the radiogenic nature of Pb in the rutile. A mean age for all the analysed rutiles was 1548.4 ± 9.1 Ma (n = 33). Comparable 207Pb/206Pb ages were also obtained from individual smaller crystals (50 μm) where the 204Pb ion beam could not be measured precisely. The results demonstrate that even small rutile crystals are extremely resistant to isotopic resetting, and that this mineral is a high-T chronometer. Phlogopite and muscovite Rb-Sr ages are <1454 and 1400-1480 Ma, respectively, with some of the phlogopite and biotite micas having been partially reset by later thermal events younger than 400 Ma. All the mica ages are considerably younger (100-70 My) than the rutile ages, which approach U-Pb ages for monazite and zircon overgrowths, even though the mica closure temperatures (350-500^oC) are comparable or slightly higher than earlier geological estimates [1] of the rutile closure temperature. Thus, our results confirm a recent experimental study [2] that suggested the closure temperature for Pb diffusion in rutile (e.g. 100 μm) is much higher (200^oC) than previously thought [1]. [1] Mezger et al., 1989. High precision U-Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. EPSL 96, 106-118. [2] Cherniak, 2000. Pb diffusion in rutile. Contrib. Mineral. Petrol., 139, 198-207.

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.

Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry

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

Ebert, Christopher Hysjulien

This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows thatmore » MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.« less

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.

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

Ruthenium in komatiitic chromite

NASA Astrophysics Data System (ADS)

Locmelis, Marek; Pearson, Norman J.; Barnes, Stephen J.; Fiorentini, Marco L.

2011-07-01

The distinction between Ru in solid solution and Ru-bearing inclusions is essential for the predictive modeling of platinum-group element (PGE) geochemistry in applications such as the lithogeochemical exploration for magmatic sulfide deposits in komatiites. This study investigates the role of chromite in the fractionation of Ru in ultramafic melts by analyzing chromite grains from sulfide-undersaturated komatiites and a komatiitic basalt from the Yilgarn Craton in Western Australia. In situ analysis using laser ablation ICP-MS yields uniform Ru concentrations in chromites both within-grain and on a sample scale, with concentrations between 220 and 540 ppb. All other platinum-group elements are below the detection limit of the laser ablation ICP-MS analysis. Carius tube digestion isotope dilution ICP-MS analysis of chromite concentrates confirms the accuracy of the in-situ method. Time resolved laser ablation ICP-MS analyses have identified the presence of sub-micron Ir-bearing inclusions in some chromite grains from the komatiitic basalt. However, Ru-bearing inclusions have not been recognized in the analyzed chromites and this combined with the in situ data suggests that Ru exists in solid solution in the crystal lattice of chromite. These results show that chromite can control the fractionation and concentration of Ru in ultramafic systems.

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 ejected spherical particles. The expansion of the laser aerosol was also investigated using polished brass substrates in the expansion path-way for particle collection.

Mesoproterozoic evolution of the Río de la Plata Craton in Uruguay: at the heart of Rodinia?

NASA Astrophysics Data System (ADS)

Gaucher, Claudio; Frei, Robert; Chemale, Farid; Frei, Dirk; Bossi, Jorge; Martínez, Gabriela; Chiglino, Leticia; Cernuschi, Federico

2011-04-01

Mesoproterozoic volcanosedimentary units and tectonic events occurring in the Río de la Plata Craton (RPC) are reviewed. A belt consisting of volcanosedimentary successions exhibiting greenschist-facies metamorphism is exposed in the eastern RPC (Nico Pérez Terrane) in Uruguay. The Parque UTE Group consists of basic volcanics and gabbros at the base (1,492 ± 4 Ma, U-Pb on zircon), carbonates in its middle part and interbedded carbonates, shales and acid volcanics (1,429 ± 21 Ma, U-Pb on zircon) at the top. The Mina Verdún Group is made up of rhyolites and acid pyroclastics at its base and top, and Conophyton-bearing limestones and massive dolostones in the middle. A U-Pb LA-ICP MS zircon age of 1,433 ± 6 Ma is reported here for lapilli-tuffs at the base of the Mina Verdún Group (Cerro de las Víboras Formation). This age shows that the Mina Verdún Group immediately postdates the Parque UTE Group, a fact supported by carbon isotope chemostratigraphy. Both units were deformed and metamorphosed between 1.25 and 1.20 Ga, as shown by K-Ar and Ar-Ar ages. This tectonic event affected most of the RPC and led to the accretion of the Nico Pérez Terrane to the remainder of the RPC along the Sarandí del Yí megashear. We report a U-Pb LA-ICP MS zircon age (upper intercept) of 3,096 ± 45 Ma for metatonalites of the La China Complex (Nico Pérez Terrane), which yield a lower intercept age of 1,252 Ma. A proto-Andean, Mesoproterozoic belt is envisaged to account for abundant Mesoproterozoic detrital zircon ages occurring in Ediacaran sandstones of the RPC. If the RPC is fringed at both sides by Mesoproterozoic, Grenville-aged belts it is likely that it occupied a rather central position in Rodinia. A possible location between Laurentia and the Kalahari Craton, and to the south of Amazonia, is suggested.

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. Analyses of zircons from selected western Snake River Plain silicic volcanic units further demonstrate the capability of our approach. These units are targeted with the overarching goal of better understanding magmatism in the region and to identify geochemical fingerprints to better distinguish among and to correlate between units. Several rhyolites distributed along the northern margin of the plain have LA-ICPMS ages of ca. 11 Ma, within error of each other and their CA-TIMS ages, and reveal differences in temperatures of crystallization and trace element contents and ratios. Individual units have crystallization temperatures that span 100 degrees or more, and show correlations with whole-rock major and trace element contents and ratios. In many cases, zircon geochemical parameters such as REE and Y contents, and Nb/Ta and Th/U ratios allow units proximal to each other to be distinguished from one another while also providing fingerprints to correlate to distal units on the south side of the plain or elsewhere in the province.

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 sources. It is likely that erosion, transport and deposition took place between 2116 and 821 Ma. Geochemical data show that the REE, Y, Yb, Sr/Y of some samples are similar to the known Archean craton formations (depletion in REE, Y ≤ 10 ppm, Yb ≤ 1 ppm, Sr/Y ≥ 30). These characteristics are known as specific for the Archean TTG (Tonalite-Trondhjemite-Granodiorite). It means that: i) Archean TTG contribute significantly to the detritus of the sedimentary basin, ii) The depositional basin and the source rock were close and the detritus was immature. Our results show that the Pre-Panafrican history of central Cameroon includes Meso- to Neo-Archean crustal accretion and associated magmatism prior to the Paleoproterozoic event of the West Central African Belt. In respect to this new insight, any evolutionary reconstruction of the area should integrate the presence of Archean crust.

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.

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 low in MORB-like samples from the north of the basin but are enriched in evolved lavas from propagating ridge tips.

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.

[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).

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.

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

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

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 this goal. This study will highlight these changes and efforts towards reducing the uncertainty contribution for LA-ICP-MS U-Pb geochronology.

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.

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 also share the similar plutono-metamorphic history with the Khanom and the Hub-Kapong to Pran Buri areas. This suggests that these three areas belong to the Sibumasu block, and the Sibumasu block records similar plutono-metamorphic history from Northern to Peninsular Thailand. Relative abundance of oceanic components in the Khao Chao gneiss, their Late Triassic magmatic ages, and the Early Jurassic metamorphic ages prefer the interpretation that the Khao Chao gneiss belongs to the Sukhothai Arc.

Foundering Triggered by the Collision of India and Asia Captured in Xenoliths

NASA Astrophysics Data System (ADS)

Shaffer, Madeline; Hacker, Bradley R.; Ratschbacher, Lothar; Kylander-Clark, Andrew R. C.

2017-10-01

Xenoliths that erupted in the SE Pamir of Tajikistan from 1000 to 1050°C and 90 km depth illuminate what happens when crust founders into the mantle. 40Ar/39Ar dating of minerals from the xenoliths and volcanic host rocks of the shoshonitic Dunkeldik pipe and dike field indicates eruption at 11.2 ± 0.2 Ma. U-Pb and trace element laser-ablation split stream inductively coupled plasma mass spectrometry of zircon shows that the igneous and metasedimentary xenoliths were likely derived from the crustal section into which they were intruded: the Jurassic-Cretaceous Andean-style magmatic arc and its Proterozoic-Mesozoic host rocks along the southern margin of Asia. Recrystallization of these zircons was extensive, yielding a range of dates down to 11 Ma. The zircons show distinct changes in Eu anomaly, Lu/Gd ratio, and Ti concentrations compatible with garnet growth and minimal heating at 22-20 Ma and then 200-300°C of heating, 25 km of burial, and alkali-carbonate melt injection at 14-11 Ma. These changes are interpreted to coincide with (i) heat input due to Indian slab breakoff at 22-20 Ma and (ii) rapid thickening and foundering of the Pamir lithosphere at 14-11 Ma, prior to and synchronous with collision between deep Indian and Asian lithospheres beneath the Pamir.

High Throughput Petrochronology and Sedimentary Provenance Analysis by Automated Phase Mapping and LAICPMS

NASA Astrophysics Data System (ADS)

Vermeesch, Pieter; Rittner, Martin; Petrou, Ethan; Omma, Jenny; Mattinson, Chris; Garzanti, Eduardo

2017-11-01

The first step in most geochronological studies is to extract dateable minerals from the host rock, which is time consuming, removes textural context, and increases the chance for sample cross contamination. We here present a new method to rapidly perform in situ analyses by coupling a fast scanning electron microscope (SEM) with Energy Dispersive X-ray Spectrometer (EDS) to a Laser Ablation Inductively Coupled Plasma Mass Spectrometer (LAICPMS) instrument. Given a polished hand specimen, a petrographic thin section, or a grain mount, Automated Phase Mapping (APM) by SEM/EDS produces chemical and mineralogical maps from which the X-Y coordinates of the datable minerals are extracted. These coordinates are subsequently passed on to the laser ablation system for isotopic analysis. We apply the APM + LAICPMS method to three igneous, metamorphic, and sedimentary case studies. In the first case study, a polished slab of granite from Guernsey was scanned for zircon, producing a 609 ± 8 Ma weighted mean age. The second case study investigates a paragneiss from an ultra high pressure terrane in the north Qaidam terrane (Qinghai, China). One hundred seven small (25 µm) metamorphic zircons were analyzed by LAICPMS to confirm a 419 ± 4 Ma age of peak metamorphism. The third and final case study uses APM + LAICPMS to generate a large provenance data set and trace the provenance of 25 modern sediments from Angola, documenting longshore drift of Orange River sediments over a distance of 1,500 km. These examples demonstrate that APM + LAICPMS is an efficient and cost effective way to improve the quantity and quality of geochronological data.

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 trace element enrichment and depletion are similar to those of the measured partition coefficients, consistent with a major role for extensive fractional crystallization in the origin of the Be enriched magma.

Timing and duration of Variscan high-pressure metamorphism in the French Massif Central: A multimethod geochronological study from the Najac Massif

NASA Astrophysics Data System (ADS)

Lotout, Caroline; Pitra, Pavel; Poujol, Marc; Anczkiewicz, Robert; Van Den Driessche, Jean

2018-05-01

Accurate dating of eclogite-facies metamorphism is of paramount importance in order to understand the tectonic evolution of an orogen. An eclogite sample from the Najac Massif (French Massif Central, Variscan belt) displays a zircon-bearing garnet-omphacite-amphibole-rutile-quartz peak assemblage. Pseudosection modeling suggests peak pressure conditions of 15-20 kbar, 560-630 °C. Eclogite-facies garnet displays Lu-enriched cores and Sm-rich rims and yields a Lu-Hf age of 382.8 ± 1.0 Ma and a Sm-Nd age of 376.7 ± 3.3 Ma. The ages are interpreted as marking the beginning of the prograde garnet growth during the initial stages of the eclogite-facies metamorphism, and the high-pressure (and temperature) peak reached by the rock, respectively. Zircon grains display chondrite-normalized REE spectra with variably negative, positive or no Eu anomalies and are characterized by either enriched or flat HREE patterns. However, they yield a well constrained in situ LA-ICP-MS U-Pb age of 385.5 ± 2.3 Ma, despite this REE pattern variability. Zr zonation in garnet, Y content in zircon and the diversity of zircon HREE spectra may suggest that zircon crystallized prior to and during incipient garnet growth on the prograde P-T path, recording the initial stages of the eclogite-facies conditions. Consequently, the zircon age of 385.5 ± 2.3 Ma, comparable within error with the Lu-Hf age obtained on garnet, is interpreted as dating the beginning of the eclogite-facies metamorphism. Accordingly, the duration of the prograde part of the eclogite-facies event is estimated at 6.1 ± 4.3 Myr. Subsequent exhumation is constrained by an apatite U-Pb age at 369 ± 13 Ma.

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.

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.

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.

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.

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

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).

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.

The Age of the intra-Danubian Suture (Southern Carpathians, Romania)

NASA Astrophysics Data System (ADS)

Balica, C.; Hann, H. P.; Chen, F.; Balintoni, I. C.; Zaharia, L.

2007-12-01

The Southern Carpathians, as an Alpine chain are formed of two domains, namely the Getic Domain (GD) and the Danubian Domain (DD). The basement of DD is represented by two terranes, named Dragsan and Lainici- Paius sutured through Tisovita-Iuti ophiolitic complex. The two terranes were invaded by large granitic plutons, some of them being dated as Late Proterozoic by U/Pb method. Yet, along the inferred suture there are four granitic bodies whose ages have been only assumed by their geological relations. From North to South the four bodies sampled for LA-ICP-MS zircon U/Pb dating are: Muntele Mic, Sfardinu, Cherbelezu and Ogradena. The previously CL imaged zircon crystals were ablated at the China's University of Geosciences facilities in Wuhan. The zircons from all samples showed quite complex structures, with many inherited cores or affected by lead loss processes. In order to get a mean age for every pluton, we used the weighted average plots by projecting the 206Pb/238U apparent ages. The crystallization age of the Poiana Marului pluton is around 326.7±7 Ma (MSWD 1.6). A set of sixteen apparent ages ranging between 400 to 648 Ma together with other tree points indicating 897, 1353 and 1693 Ma, represent inheritances. There was no observable lead loss process in this data set. The Sfardinu granite crystallized at 310±7.9 Ma (MSWD 4.8). The inheritances found in this sample are at 427 and 723 Ma, but an important lead loss process occurred later, as indicated by ten apparent ages between 240-292 Ma. Cherbelezu granite gave a crystallization mean age of 326.9±4.9 Ma (MSWD 1.9). A single inherited core appears at 502 Ma, yet eight apparent ages ranging between 239-295 Ma signalize again an important lead loss process. Other two ages at 176 and 193 Ma confirm the presence of this process. The Ogradena pluton zircons display two possible crystallization ages for the outer zones of zircon grains, at 356.6±7.8 Ma (twelve apparent ages, MSWD 12) and 314.1±7.8 Ma (nine apparent ages, MSWD 13) respectively. It is difficult to explain this situation, and we suppose the second figure as the probable crystallization age. Inheritances are represented by a number of 37 206Pb/238U apparent ages scattered between 400 and 612 Ma, only one apparent age of 265 Ma possibly proving the presence of lead loss. The geochemical parameters ASI, Fe-number and MALI calculated from the major oxides analyses showed that all four plutons are metaluminous and magnezian. Both Cherbelezu and Ogradena have a calcalkaline character near to alkalicalcic while Muntele Mic and Sfardinu are alkalicalcic. Geochemically, all four plutons are closed to Cordilleran type, main portion or a little inboard of it. Out of these data several conclusions can be drawn. The age of the intra-Danubian suture is late Visean to Bashkirian or late Variscan. Muntele Mic and Ogradena granites exhibit abundant Cadomian inheritances, while Cherbelezu and Sfardinu plutons seem affected by lead loss processes due to an important thermotectonic event happened during 250 to 290 Ma interval. The emplacement of the four plutons probably reflects a subductional process. Finally, the inheritances suggest a Gondwanan source for the anatectic material.

The Apuseni Mountains, Romania, a Variscan Collage of Ordovician Gondwanan Terranes

NASA Astrophysics Data System (ADS)

Balintoni, I. C.; Balica, C.; Zaharia, L.; Chen, F.; Cliveti, M.; Hann, H. P.; Ghergari, L.

2007-12-01

The basement of the Apuseni Mountains, Romania, consists of three pre-Variscan terranes, sutured during an Early Variscan amalgamation around 351 Ma (Balintoni et al., this volume). The northern Someş Terrane (ST) is predominantly gneissic, while the southern Baia de Arieş Terrane (BAT) is dominated by the presence of large carbonate lenses, although metagranites and other types of orthogneisses can be found. These two terranes are sutured through the Biharia terrane, probably an accreted island arc. LA-ICP-MS datings on zircons extracted from orthogneisses and metagranites were performed in order to constrain the age of ST and BAT. A number of previously CL-imaged crystals were ablated at the China's University of Geosciences, Wuhan. From ST we dated an orthogneiss occurring in structurally lowermost position, a metatuff situated in the upper strongly retrogressed part and a twenty detrital crystal population sampled from a metasandstone. The 206Pb/238U apparent ages were projected using the weighted average plots.A magmatic crystallization age of 472.8±5.0 Ma (Upper Early Ordovician) resulted for one of the orthogneiss samples, besides several older ages at 505.7, 566.3 and 708.2 Ma corresponding to inherited cores. Another sample from the same rock appeared strongly affected by lead loss during a later thermotectonic event, most of the apparent ages grouping around 352±14 Ma. This age is similar with the age of the suture between ST and BT (Balintoni et al., this volume). The main zircon population of one metatuff sample furnished an averaged age of 423±7.2 Ma, also found in two additional samples, but their significance is obscure for the moment. Two primary magmatic ages arise at 464.2 and 473.8 Ma, an older value of 758.7 Ma corresponding to an inherited core. Detrital zircon ages range between 534.8 and 2596.8 Ma. The younger value represents an upper age constraint for the protolith age of ST-rocks. From BAT we dated the Lupşa metaporphyroid and the Mihoeşti (MiG) and Muncel (MuG) metagranites. The 466±11 Ma age value recorded in the metaporphyroid was inferred to represent the primary crystallization age. Many inherited cores yielded ages scattered between 523±32 Ma and 1914 Ma, while no ages younger then 466±11 Ma were recorded. The MiG crystallized at 469.2±7.5 Ma, inherited ages of 501±22, 554.9 and 685.6 Ma being also recorded. A 468.4±4.8 Ma primary magmatic age was found for the MuG, this sample also containing abundant inherited ages dispersed between 507.3±5.5 Ma and 1018.2 Ma. A group of ages at 429±13 Ma, corresponds to the dominant population in the ST metatuff. The results indicate that the main episode of crustal construction for the ST and BAT was the Ordovician; both terranes possess an abundant Cadomian inheritance. Pre-Cadomian inheritances are rare, except for the detrital zircons. Only the zircons from the ST appear strongly affected by lead loss processes, possibly related with the profuse Variscan magmatism affecting the upper plate. The history of the ST and BAT is compatible with a primitive North-Gondwanan origin.

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-Gondwanaland) fold belts. Detrital zircons in Cambrian sediments of the Ellsworth-Whitmore Mountains block and Cambrian metasediments of the Welch Mountains with comparable properties suggest that the central Antarctic provenance operated also in the ˜ 500 Ma Cambrian.

Newly Described Tephra Provide Middle Pleistocene Age Constraints to Stegodon Fossils in West (Indonesian) Timor

NASA Astrophysics Data System (ADS)

Jensen, B. J. L.; Dufrane, A.; Mark, D.; Zaim, Y.; Rizal, Y.; Aswan, A.; Hascaryo, A.; Ciochon, R.; Gunnell, G.; Larick, R.; Zonnveld, J. P.

2017-12-01

As the Asian proboscidian Stegodon dispersed across Island Southeast Asia during the Pleistocene, multiple forms developed. On Timor, a southerly island east of Wallace's Line, the Ainaro gravels have yielded a highly dwarfed S. timorensis and a larger S. `trigonocephalus.' During a half-century of exploration, the age of the fossil bearing gravels remains in question, with only one age determination of >130 ka derived from six 230Th- 238U dates on a tusk fragment found in the Raebia area (Louys et al. 2016). Here we present radiometric ages for two tephra deposits bracketing Ainaro gravels at Raebia, a S. timorensis fossil locality 8 km northeast of Atambua city. The Raebia ravine exposes 2-10 meters of coarse-grained gravels incised into silt and clay deposits, bracketed by two indurated and largely devitrified tephras. Some intact glass was present to geochemically characterize each unit, which are both high-silica rhyolites. Biotite and zircons for 40Ar/39Ar and laser ablation U-Pb dating were extracted from the upper unit (Raebia Tuff 1; RT1), and zircons from the lower unit (Raebia Tuff 2; RT2). RT1 had zircons with two distinct age populations, but the youngest yield a 230Th deficiency corrected 206Pb/238U age of 665 ± 19 ka, (2s, n = 23, MSWD = 0.81), consistent with the 40Ar/39Ar age 614.9 ± 16.4 ka (2s, full external precision). Preliminary zircon dates on RT2 are more problematic, providing a large range that suggests inheritance by xenoliths and/or locally-sourced detrital zircons. However, a single zircon yielded 230Th deficiency corrected 206Pb/238U age of 708 ± 66 ka (2s, n=17, MSWD = 0.41), which is stratigraphically consistent. These are the first reliable age constraints on a higher elevation Ainaro gravel terrace and fossils they contain. The only other direct ages on the gravels are 230Th- 238U dates on lower terraces interbedded with coral, ranging from 130 ka to Holocene in age (Roosmawati and Harris 2009). These two newly described and dated tephra are likely regionally distributed and may represent important stratigraphic horizons for this portion of Southern Wallacea. They also provide useful data for calculating uplift rates for the region from the middle Pleistocene.

Geochemical (LA-ICP-MS) investigations of baddeleyite from the Palaeoproterozoic mafic and Palaeozoic alkaline intrusions in the Arctic part of the Baltic shield

NASA Astrophysics Data System (ADS)

Drogobuzhskaya, Svetlana; Bayanova, Tamara; Novikov, Andrey

2017-04-01

Baddeleyite is a zirconium dioxide mineral, which is very important, but less common as zircon. While the zircon microelementary composition study is widely applicable, the baddeleyite geochemical features are poorly known. The first data on REE concentrations and distribution in baddeleyite were published in the past century. Baddeleyite is used as a geochronometer for dating mafic and alkaline rocks. It may be noted that the data on its geochemical composition are quite contradictory with a strongly varying Ce anomaly value and absent Eu anomaly in some samples. The new data on the elementary composition of baddeleyite (REE, Hf, U, Th, Y, and Ti) from the Monchegorsk pluton mafic rocks (2.5 Ga) and Kovdor and Vuoriyarvi deposits (380 Ma) was obtained. The sample morphology was studied using an electronic spectroscopy method (Hitachi S-430), and the position of local analysis on baddeleyite crystals was chosen based on analyzed optic images of minerals. The content of REE and other elements was measured using LA-ICP-MS technique on quadrupole mass-spectrometer ELAN 9000 DRC-e (Perkin Elmer) with laser evaporator UP-266 MACRO (New Wave Research) with a wave length of 266 nm for sampling. The laser ablation was made in argon atmosphere in a 35 and 70 μm diameter spot or when scanning to a line with a pulse repetition rate of 10 Hz and pulse energy of 14-15 J/cm2. The device was calibrated using the NIST SRM 612 standard with a REE, U, and Th concentration of about 40 ppm. The baddeleyite from reference rocks of mafic intrusions are characterized by medium concentrations of Hf (0.69-1.9 %), Th (7.6-21.1), REE (50.3-162), U (164-357), Y (5.0-149) ppm for the sample M-2 from Monchegorsk. Another rocks of alkaline intrusions are depleted in Th (0.25-5.9), REE (9.2-103), U (1.8-48.1), Y(2.9-65.9) ppm and Hf (0.20-1.9%) for the sample Bd-400 from Vuoriyarvi and Hf (0.18-1.3 %), Th (0.4-5.2), REE (2.1-17.7), U (4.2-32.6), Y(2.2-68.4) ppm for the samples Bd-300 and Bd-300 prism. from Kovdor. The titanium content in the samples widely varies being 10-37 ppm for sample Bd-300 and 28-72 ppm for Bd-300 prism., 47-150 ppm for sample Bd-400 and 0.31-0.79% for older baddeleyite M-2. The average baddeleyite crystallization and U-Pb system closure temperature calculated using a zircon-applied method is 804-888°C (Kovdor) and 984°C (Vuoriyarvi). The baddeleyite from the Monchegorsk pluton has shown high crystallization temperatures of about 1,000 degrees centigrade. The research is supported by RFBR Grant No. 16-05-00305 and dedicated to the blessed memory of mentors: academicians of the RAS V.T. Kalinnikov and F.P. Mitrofanov.

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 U-Th/He methods, whole grain degassing and dissolution, that produced an age of 32.73±0.47 Ma for chips of the same Durango crystal. Further dating of other well characterized apatite crystals will be used to test the robustness of the method.

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 have a late Neoproterozoic basement, whereas the East European Platform (EEP) has a Paleoproterozoic-Archean basement. The zircon and the paleocurrent data indicate that the eastern and central part of the Early Cretaceous turbidite basin was mainly fed by EEP, whereas local sources were dominant in the western part of the basin and especially fed from a crystalline basement of the Istanbul zone. This in turn indicates that the Black Sea did not form a major barrier between the Pontides and the EEP and was probably not open during the Early Cretaceous. Keywords: Central Pontides, Early Cretaceous, Paleocurrent, Provenance, U-Pb Detrital zircon.

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.

Comparative tissue distribution of metals in birds in Sweden using ICP-MS and laser ablation ICP-MS.

PubMed

Ek, Kristine H; Morrison, Gregory M; Lindberg, Peter; Rauch, Sébastien

2004-08-01

Cadmium, copper, lead, palladium, platinum, rhodium, and zinc profiles were investigated along feather shafts of raptor and other bird species by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The distribution of external versus internal metal contamination of feathers was investigated. The species examined were peregrine falcon (Falco peregrinus), sparrowhawk ( Accipiter nisus), willow grouse (Lagopus lagopus), and house sparrow (Passer domesticus) in Sweden. For habitat comparisons, total Cu, Pb, Zn, and Cd concentrations were analyzed by ICP-MS in feathers of the examined species as well as captive peregrine falcon. For investigation of metal distribution and correlation in different biological materials of raptors, total concentrations of Cu, Pb, Cd, and Zn were also investigated by ICP-MS in feathers, eggs, blood, feces, liver, and kidney of wild peregrine falcon from southwestern Sweden. Laser ablation of feathers revealed that Pb contamination is both external and internal, Zn contamination is internal, and Cd and Cu contamination is predominantly internal, with a few externally attached particles of high concentration. Pb, Cu, and Cd signal intensities were highest in urban habitats and contamination was mainly external in feathers. The background signal intensity of Zn was also higher in birds from urban habitats. The laser ablation profile of PGE (Pt, Pd, Rh) demonstrated that PGE contamination of feathers consists almost exclusively of externally attached PGE-containing particles, with little evidence of internally deposited PGE.Generally, total metal concentrations in feathers were highest in sparrowhawk and house sparrow due to their urban habitat. Total Cu, Zn, and Cd concentrations were highest in liver and kidney due to binding to metallothionein, while the total Pb concentration was highest in feces due to the high excretion rate of Pb. A decreasing temporal trend for Pb in feathers, showing that Pb levels in feathers have decreased since the introduction of nonleaded petrol, is also discussed.

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 correlation with U in Zrc2 is best explained by diffusion of Pb and other incompatible elements (Y, REEs) into 5-10 nm domains that were damaged by α-recoil and may have been metamict as the result of single U- or Th-decay chains. Diffusion distances of ~20 nm for these elements in crystalline zircon require temperatures above 700 C for ~10 myrs (Cherniak 2010). This is consistent with the known history of Zrc2, as a xenocrystic 2.4 Ga zircon in a 29 Ma granodiorite phase of a long-lived, extension-related plutonic suite that experienced high-grade regional metamorphism. In contrast, the absence of enriched domains in Zrc1 suggests that this zircon did not experience similar high-grade metamorphism before or after its deposition within the ~3 Ga Jack Hills metaconglomerate.

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 correlation between internal zircon structures, chemistry, U-Pb isotope ratios and mylonitic fabric. U-Pb data return highly discordant and variable ages: in particular, the 206Pb/238U ages range from Carboniferous to Triassic within the same zircon grain. The youngest 206Pb/238U data derive from narrow axial stripes oriented parallel or at low angle with respect to the foliation planes. These stripes are characterized by an overall HREE, Y, U and Th enrichment possibly reflecting deformation of the grain in presence of interstitial fluid phases, likely related to a concomitant magmatic activity. Deformation related structures (cracks and fractures) within zircon grains acted as fast-diffusion pathways allowing fluids to modify the geochemistry and isotopic systems of zircon. Our results suggest that fluid-assisted brittle-ductile deformation can severely modify the trace elements and isotopic composition of zircon with unexpected patterns constrained by stress regime. In similar cases, our observations suggest that, for a more appropriate interpretation of the petrologic evolution and age variability, a direct characterization of the internal structures of zircons still placed in their microtextural site is highly recommended.

The Tonalite-Trondhjemite-Granodiorite (TTG) to Calc-alkaline Granodiorite-Granite Transition: Evolution of the Archaean Basement of the Quadrilátero Ferrífero Province (Southeast Brazil)

NASA Astrophysics Data System (ADS)

Farina, F.; Albert, C.; Lana, C.; Stevens, G.

2014-12-01

The Bação, Bonfim and Belo Horizonte domes are the largest domes in the Archaean Southern São Francisco craton (Quadrilátero Ferrífero, Brazil). These domes are mainly formed by fine-grained banded gneisses typically intruded by leucogranitic veins and by weakly foliated granites, cropping out as large batholiths and small scale-domains closely associated to the gneisses. Granites and gneisses have high silica content (70-76 wt%), K2O ranging from 2wt% to 6wt%, Sr from 600 to 40 ppm and La/Yb from 150 to 5. Based on their K2O/Na2O ratios, these rocks are subdivided in three groups: sodic (K2O/Na2O≤0.7), transitional (0.7

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.

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.

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.

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 zircons are Meso- to Paleoarchaean ones and provide evidence for the input of very old cratonic basement, most likely from cratonic inliers of the West African craton (Leonian, Liberian). Because of the potential input of detrital zircon from the Amazonian craton, which is reflected in the Mesoproterozoic and late Paleoproterozoic grains, we speculate that some of the Paleoproterozoic to Neoarchean (2.0 Ga to 2.6 Ga) zircons were also derived from Amazonia. Due to the total lack of 1.0-1.2 Ga old zircon, our data set excludes all crustal domains situated in the Arabian-Nubian shield and the East African belt, as well as the Sunsás belt of Amazonia ("Sunsás-Grenvillian") as potential sediment sources. Sedimentation in the Tassili Ouan Ahaggar basin started in uppermost Cambrian to Ordovician time due to the opening of the Rheic Ocean. This event led to subsidence related to the rift and drift of Avalonia and related terranes from the northwestern Gondwanan margin. The basal Early Tassili quartzite has detrital zircon populations that suggest a local provenance either from West African or from a related terrane in the Tuareg shield. A dramatic change occurs in the deltaic to shallow marine strata of the Lower Ordovician Ajjers Formation and in the overlying marine sandstones of the Middle Ordovician d'In Azaoua Formation. Our data for both formations indicate the Pan-African orogen, and very likely Cadomian terranes as the main source for the detritus. During this time, the region was affected by rift tectonics due to the opening of the Rheic Ocean and therefore amenable to erosion at rift shoulders and escarpments. Our data also indicate that glacial erosion in Upper Ordovician (Hirnantian) time must have affected larger areas of old cratonic surfaces as the populations of Paleoproterozoic to Archaean zircons are significantly higher than in other age clusters. Large parts of highly mature sands of the Cambro-Ordovician section in the Tassili Ouan Ahaggar basin were derived from a peneplain in the interior of Gondwana, that formed during Cambrian times. This peneplain was formed under warm-humid climate on a vegetation-free land surface and in an extreme corrosive environment that was influenced by high atmospheric pCO 2 caused by Pan-African and Avalonian-Cadomian volcanism, volcanic activity related to the opening of the Iapetus, and Late Cambrian-Early Ordovician rift volcanism as well.

New evidence for an old idea: Geochronological constraints for a paired metamorphic belt in the central European Variscides

NASA Astrophysics Data System (ADS)

Will, T. M.; Schmädicke, E.; Ling, X.-X.; Li, X.-H.; Li, Q.-L.

2018-03-01

New geochronological data reveal a prolonged tectonothermal evolution of the Variscan Odenwald-Spessart basement, being part of the Mid-German Crystalline Zone in central Europe. We report the results from (i) secondary ion mass spectrometry (SIMS) U-Pb dating of zircon, rutile and monazite, (ii) SIMS zircon oxygen isotope analyses, (iii) laser ablation-multicollector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS) zircon Lu-Hf isotope analyses and, (iv) LA-ICPMS zircon and rutile trace element data for a suite of metamorphic rocks (five amphibolite- and eclogite-facies mafic meta-igneous rocks and one granulite-facies paragneiss). The protoliths of the mafic rocks formed from juvenile as well as depleted mantle sources in distinct tectonic environments at different times. Magmatism took place at a divergent oceanic margin (possibly in a back-arc setting) at 460 Ma, in an intraoceanic basin at ca. 445 Ma and at a continental margin at 329 Ma. Regardless of lithology, zircon in eclogite, amphibolite and high-temperature paragneiss provide almost identical Carboniferous ages of 333.7 ± 4.1 Ma (eclogite), 329.1 ± 1.8 to 328.4 ± 8.9 Ma (amphibolite), and 334.0 ± 2.0 Ma (paragneiss), respectively. Rutile yielded ages of 328.6 ± 4.7 and 321.4 ± 7.0 Ma in eclogite and amphibolite, and monazite in high-temperature paragneiss grew at 330.1 ± 2.4 Ma (all ages are quoted at the 2σ level). The data constrain coeval high-pressure eclogite- and high-temperature granulite-facies metamorphism of the Odenwald-Spessart basement at ca. 330 Ma. Amphibolite-facies conditions were attained shortly afterwards. The lower plate eclogite formed in a fossil subduction zone and the upper plate high-temperature, low-pressure rocks are the remains of an eroded Carboniferous magmatic arc. The close proximity of tectonically juxtaposed units of such radically different metamorphic conditions and thermal gradients is characteristic for a paired metamorphic belt sensu Miyashiro (1961). Thus, the Odenwald-Spessart basement represents the first recognised paired metamorphic belt in the European Variscides.

Multiple age components in individual molybdenite grains

USGS Publications Warehouse

Aleinikoff, John N.; Creaser, Robert A.; Lowers, Heather; Magee, Charles W.; Grauch, Richard I.

2012-01-01

Re–Os geochronology of fractions composed of unsized, coarse, and fine molybdenite from a pod of unusual monazite–xenotime gneiss within a granulite facies paragneiss, Hudson Highlands, NY, yielded dates of 950.5 ± 2.5, 953.8 ± 2.6, and 941.2 ± 2.6 Ma, respectively. These dates are not recorded by co-existing zircon, monazite, or xenotime. SEM–BSE imagery of thin sections and separated grains reveals that most molybdenite grains are composed of core and rim plates that are approximately perpendicular. Rim material invaded cores, forming irregular contacts, probably reflecting dissolution/reprecipitation. EPMA and LA-ICP-MS analyses show that cores and rims have different trace element concentrations (for example, cores are relatively enriched in W). On the basis of inclusions of zircon with metamorphic overgrowths, we conclude that molybdenite cores and rims formed after high-grade regional metamorphism. The discovery of cores and rims in individual molybdenite grains is analogous to multi-component U-Pb geochronometers such as zircon, monazite, and titanite; thus, molybdenite should be carefully examined before dating to ensure that the requirement of age homogeneity is fulfilled.

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.

A new apatinib microcrystal formulation enhances the effect of radiofrequency ablation treatment on hepatocellular carcinoma.

PubMed

Xie, Hui; Tian, Shengtao; Yu, Haipeng; Yang, Xueling; Liu, Jia; Wang, Huaming; Feng, Fan; Guo, Zhi

2018-01-01

Radiofrequency ablation (RFA) is the foremost treatment option for advanced hepatocellular carcinoma (HCC), however, rapid and aggressive recurrence of HCC often occurs after RFA due to epithelial-mesenchymal transition process. Although combination of RFA with sorafenib, a molecular targeted agent, could attenuate the recurrence of HCC, application of this molecular targeted agent poses a heavy medical burden and oral administration of sorafenib also brings severe side effects. In this study, we prepared an apatinib microcrystal formulation (Apa-MS) that sustainably releases apatinib, a novel molecular targeted agent, for advanced HCC treatment. We injected apatinib solution or Apa-MS into subcutaneous HCC tumors. It was found that Apa-MS exhibited slow apatinib release in vivo and in turn inhibited the epithelial-mesenchymal transition of HCC cells for extended time. Moreover, in rodent HCC model, Apa-MS enhanced the antitumor effect of RFA treatment. Based on these results, we conclude that Apa-MS, a slow releasing system of apatinib, allows apatinib to remain effective in tumor tissues for a long time and could enhance the antitumor effect of RFA on HCC.

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.

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.

Solid Sampling with a Diode Laser for Portable Ambient Mass Spectrometry

PubMed Central

2017-01-01

A hand-held diode laser is implemented for solid sampling in portable ambient mass spectrometry (MS). Specifically, a pseudocontinuous wave battery-powered surgical laser diode is employed for portable laser diode thermal desorption (LDTD) at 940 nm and compared with nanosecond pulsed laser ablation at 2940 nm. Postionization is achieved in both cases using atmospheric pressure photoionization (APPI). The laser ablation atmospheric pressure photoionization (LAAPPI) and LDTD-APPI mass spectra of sage leaves (Salvia officinalis) using a field-deployable quadrupole ion trap MS display many similar ion peaks, as do the mass spectra of membrane grown biofilms of Pseudomonas aeruginosa. These results indicate that LDTD-APPI method should be useful for in-field sampling of plant and microbial communities, for example, by portable ambient MS. The feasibility of many portable MS applications is facilitated by the availability of relatively low cost, portable, battery-powered diode lasers. LDTD could also be coupled with plasma- or electrospray-based ionization for the analysis of a variety of solid samples. PMID:28632988

Solid Sampling with a Diode Laser for Portable Ambient Mass Spectrometry.

PubMed

Yung, Yeni P; Wickramasinghe, Raveendra; Vaikkinen, Anu; Kauppila, Tiina J; Veryovkin, Igor V; Hanley, Luke

2017-07-18

A hand-held diode laser is implemented for solid sampling in portable ambient mass spectrometry (MS). Specifically, a pseudocontinuous wave battery-powered surgical laser diode is employed for portable laser diode thermal desorption (LDTD) at 940 nm and compared with nanosecond pulsed laser ablation at 2940 nm. Postionization is achieved in both cases using atmospheric pressure photoionization (APPI). The laser ablation atmospheric pressure photoionization (LAAPPI) and LDTD-APPI mass spectra of sage leaves (Salvia officinalis) using a field-deployable quadrupole ion trap MS display many similar ion peaks, as do the mass spectra of membrane grown biofilms of Pseudomonas aeruginosa. These results indicate that LDTD-APPI method should be useful for in-field sampling of plant and microbial communities, for example, by portable ambient MS. The feasibility of many portable MS applications is facilitated by the availability of relatively low cost, portable, battery-powered diode lasers. LDTD could also be coupled with plasma- or electrospray-based ionization for the analysis of a variety of solid samples.

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.

Zircon and cassiterite U-Pb ages, petrogeochemistry and metallogenesis of Sn deposits in the Sibao area, northern Guangxi: constraints on the neoproterozoic granitic magmatism and related Sn mineralization in the western Jiangnan Orogen, South China

NASA Astrophysics Data System (ADS)

Chen, Lei; Wang, Zongqi; Yan, Zhen; Gong, Jianghua; Ma, Shouxian

2018-01-01

A number of Sn deposits associated with Neoproterozoic granites are located in the western Jiangnan Orogen of northern Guangxi. The distribution of Sn mineralization is controlled by faults occurring within and around the Neoproterozoic granites. The hydrothermal alteration and mineralization of these Sn deposits exhibit zoning from the granite to the wall rock. The laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb ages of the cassiterite and zircon from ore-bearing granite in the Menggongshan Sn deposit are 829 ± 19 Ma and 822 ± 4 Ma, respectively, indicating that the Sn mineralization and granites formed in the Neoproterozoic and can considered to be products of coeval magmatic and hydrothermal activities. The ore-bearing granite and Neoproterozoic granites in northern Guangxi are high-K, calc-alkaline, peraluminous, S-type granites that are depleted in Nb, Ti, Sr and Ba and highly enriched in Rb, U and Pb. All the granites show steep fractionated light rare earth element (LREE) and flat heavy rare earth element (HREE) patterns, with strongly negative Eu anomalies. The ɛHf(t) values of the ore-bearing granite vary from - 9.0 to - 1.7, with an average value of - 4.1. Additionally, the ore-bearing granite exhibits low oxygen fugacity values. The magmatic source experienced partial melting during their evolution, and the source was dominated by recycled heterogeneous continental crustal materials. Our evidence confirms that the Neoproterozoic granites in northern Guangxi formed in a collisional tectonic setting. The collision between the Cathaysia and Yangtze blocks or between the Sibao arc (Jiangnan arc) and the Yangtze Block caused asthenospheric upwelling, leading to partial melting and recycling of the crust, forming the peraluminous S-type granites in the Neoproterozoic. The Sn mineralization has a close genetic relationship with the Neoproterozoic granite. The highly differentiated, peraluminous, B-enriched, crustally derived Neoproterozoic granites provided the heat source and ore-forming material for the Sn mineralization. Furthermore, the low oxygen fugacity of these Neoproterozoic granites also favoured the Sn mineralization.

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.

Restoration of visual orienting into a cortically blind hemifield by reversible deactivation of posterior parietal cortex or the superior colliculus.

PubMed

Lomber, Stephen G; Payne, Bertram R; Hilgetag, Claus C; Rushmore, JarrettR

2002-02-01

A contralateral hemineglect of the visual field can be induced by unilateral cooling deactivation of posterior middle suprasylvian (pMS) sulcal cortex of the posterior parietal region, and this neglect can be reversed by additional cooling deactivation of pMS cortex in the opposite hemisphere. The purpose of the present study was to test whether an enduring hemianopia induced by removal of all contiguous visual cortical areas of one hemisphere could be reversed by local cooling of pMS cortex in the opposite hemisphere. Two cats sustained large unilateral ablations of the contiguous visual areas, and cooling loops were placed in the pMS sulcus, and in contact with adjacent area 7 or posterior ectosylvian (PE) cortex of the opposite hemisphere. In both instances cooling of pMS cortex, but neither area 7 nor PE, restored a virtually normal level of orienting performance to stimuli presented anywhere in the previously hemianopic field. The reversal was highly sensitive to the extent of cooling deactivation. In a third cat, cooling deactivation of the superficial layers of the contralateral superior colliculus also restored orienting performance to a cortical ablation-induced hemianopia. This reversal was graded from center-to-periphery in a temperature-dependent manner. Neither the cortical ablation nor any of the cooling deactivations had any impact on an auditory detection and orienting task. The deactivations were localized and confirmed by reduced uptake of radiolabeled 2-deoxyglucose to be limited to the immediate vicinity of each cooling loop. The results are discussed in terms of excitation and disinhibition of visual circuits.

New Robust Reference Materials for In Situ Single Grain Rutile U-Pb Geochronology and Method Refinements for Detrital Rutile Analysis by LA-MC-ICP-MS

NASA Astrophysics Data System (ADS)

Parrish, R. R.; Bracciali, L.; Condon, D. J.; Horstwood, M. S.; Najman, Y.

2012-12-01

While rutile (TiO2) occurs in the heavy mineral suite of detrital sediments and originates mainly in medium- to high-grade metamorphic and some igneous rocks, there are very few applications of U-Pb dating of rutile to provenance studies; this is due to an overreliance on zircon, low U content of rutile limiting measurement quality by in situ methods, a higher proportion of common Pb relative to zircon, and a lack of widely available good quality reference materials. We have addressed these issues and characterized two ~ 1.8 Ga rutile reference materials by SEM, trace elements, U-Pb ID-TIMS, and intra-grain and inter-grain U-Pb LA-MC-ICP-MS analysis using mixed faraday and multiple ion counting detectors with high sensitivity. We have assessed U-Pb discordance and in situ variations in relative common Pb and age and their bearing on the quality of the reference materials for in situ U-Pb dating. The rutiles (Sugluk-4 and PCA-S207) come from granulite facies belts of the Canadian Shield, namely the northern Cape Smith Belt of Quebec and the Snowbird Tectonic Zone (Sasatchewan). The ID-TIMS data are slightly discordant due to variable common Pb and limited Pb loss; the variation in 6 single grains of Sugluk-4, that we use as the primary reference material, is <1% in 206Pb/238U, and <2% for 207Pb/206Pb (95 % conf.); after common Pb correction these variations are <1%. The measured variations are smaller than in existing reference materials (i.e. R10) in current use. LA-ICP-MC-MS data (n ~ 500 for each) have a reproducibility of 206Pb/238U and 207Pb/206Pb of ~2-4% (at the 2S level), which is only modestly worse than long-term data for multiple zircon standards, this being due to the real variation in measured values arising from limited Pb loss, age variation, and common Pb variability [1]. We have applied our refined method to the provenance of rutile from drainages from British Columbia, Bhutan, and the Brahmaputra River of NE India (predominant rutile ages ~ 50, 15, and 2 Ma, respectively; Bracciali et al., this meeting). Our method successfully dates >75% of all rutile grains in a sediment; unsuccessful analyses are due to poor quality rutiles with massive common Pb and/or U contents < ~1ppm. While some analyses are therefore unusable, unlike zircon age zoning is rare to absent in rutile and there is little need to image grains to identify 'inheritance' to arrive at a correct interpretation of measured ages. Rutile has a ~ 500°C closure temperature and thus records mainly the time of cooling; it is therefore a sensitive recorder of metamorphic thermochronological information, and an excellent complement to detrital zircon analysis. There appears to be huge scope of in situ application of U-Pb dating to detrital rutile in provenance studies in the future. [1] Bracciali L., Parrish R.R., Condon D., Horstwood M.S.A., Najman,Y., Two new rutile reference materials for in situ U-Pb LA-MC-ICP-MS dating and applications to sedimentary provenance, submitted to Chem. Geol.

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

The ultramafic-mafic Noril'sk-1 intrusion in the northwestern part of the Siberian Craton (Russia) represents one of three known Noril'sk-type, ore-bearing intrusions, which host one of the world's major economic sulphide platinum-group-element (PGE)-Cu-Ni deposits. Zircon and baddeleyite dated previously both by SHRIMP (i.e. 248.0 ± 3.7 Ma, Campbell et al. 1992) and ID-TIMS (251.1 ± 3.6 Ma, Kamo et al. 1996) have been restricted to one lithology (e.g. leucogabbro) of the Noril'sk-1 intrusion. To better constrain the age of igneous event and sources involved in its generation our multi-technique study utilized ten rock samples characteristic of unmineralized and mineralized lithologies. The rocks investigated comprise (from top to bottom) gabbro-diorite (sample N1-1), leucogabbro (N1-3), olivine-free gabbro (N1-2 and N1-4), olivine-bearing gabbro (N1-5), olivine gabbro (N1-6), plagiowehrlite and plagiodunite (N1-7), taxitic-textured rocks comprising melanotroctolite, olivine gabbro with relics of ultramafic rocks (N1-8, N1-9) and contact fine-grained gabbro (N1-10). Sulphide PGE-Cu-Ni ores occur in ultramafic (N1-7) and taxitic-textured rocks (N1-8 and N1-9), which have thickness of about 17 m, whereas the low-sulphide horizon of about 1 m thick occurs in the upper part of intrusion (N1-3). In situ U-Pb analyses of zircon from these rocks, combined with detailed study of crystal morphology and internal structure, identify four zircon populations (Malitch et al. 2012). The U-Pb ages of baddeleyite and the defined zircon populations cover a significant time span, from Late Paleozoic to Early Mesozoic (e.g., 290 ± 2.8; 261.3 ± 1.6; 245.7 ± 1.1; 236.5 ± 1.8 and 226.7 ± 0.9 Ma). The established distribution of U-Pb ages implies that crystallization of baddeleyite and zircon corresponds to several stages of protracted evolution of ultramafic-mafic magmas at deep-seated staging chambers and/or probably characterizes interaction of distinct magmas during formation 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 subcontinental lithospheric source probably at least Neoproterozoic in age. We propose that the SCLM component is especially prominent in the mineralized portions of the intrusion. This is consistent with the suggestion of Zhang et al (2008) that ancient cratonic lithospheric mantle may have contributed significantly to the PGE and Ni budget of the "fertile" Siberian Large Igneous Province. Small population of zircons from the gabbro-diorite show the least 'radiogenic' Hf-isotope values, indicating the input of a distinctly older lithospheric, possibly crustal, component, being consistent with a hybrid nature of this lithology. Our approach for deciphering the origin of zircon and baddeleyite from mafic and ultramafic rocks provides a unique set of U-Pb and Hf-isotope constraints on temporal evolution and petrologic history of the Noril'sk-1 intrusion. The study was supported by Uralian Branch of Russian Academy of Sciences (12-U-5-1038). Refereneces: Campbell I.H., Czamanske G.K., Fedorenko V.A., Hill R.I., Stepanov V. (1992) Synchronism of the Siberian traps and the Permian-Triassic boundary. Science 255, 1760-1763. Griffin W.L., Wang X., Jackson S.E., Pearson N.J., O'Reilly S.Y., Xu X., Zhou X. (2002) Zircon chemistry and magma genesis, SE China: in-situ analysis of Hf isotopes, Pingtan and Tonglu igneous complexes. Lithos 61, 237-269. Kamo S.L., Czamanske G.K., Krogh T.E. (1996) A minimum U-Pb age for Siberian flood-basalt volcanism. Geochim. Cosmochim. Acta 60, 3505-3511. Malitch K.N., Badanina I.Yu., Belousova E.A., Tuganova E.V. (2012) Results of U-Pb dating of zircon and baddeleyite from the Noril'sk-1 ultramafic-mafic intrusion (Russia). Russian Geology and Geophysics 53(2), 123-130. Zhang M., O'Reilly S.Y., Wang K-L., Hronsky J., Griffin W.L. (2008) Flood basalts and metallogeny: The lithospheric connection. Earth-Science Reviews 86, 145-174.

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 rifting. Western Sulawesi is composed of several blocks separated from Inner Banda block with different histories, which is supported by the varieties of zircon population distribution in the basement rocks in the Western Sulawesi and also difference of general orientations of structural features between the Bantimala and Barru Complexes.

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

Separation of the Guajira-Bonaire pair in the southern margin of the Caribbean: 65-50 Ma exhumation followed by 300 km right-lateral transtensional deformation

NASA Astrophysics Data System (ADS)

Zapata Henao, S.; Cardona, A.; Montes, C.; Valencia, V.; Vervoort, J. D.; Reiners, P. W.

2012-12-01

Middle to upper Eocene fluvial strata in the island of Bonaire contains detrital components that were tracked to the basement massifs of the Guajira Peninsula in northern Colombia. These detrital components confirm previous hypothesis that the Guajira-Bonaire pair constitute a tectonic piercing point along the southern Caribbean plate margin that was right-laterally displaced approximately 300 km after middle Eocene times. Other possible sources, the nearby Curacao and the far away Santa Marta massif, did not pass statistical similarity and overlap tests. U-Pb LA-ICP-MS from the metamorphic boulders of the Soebi Blanco Formation in Bonaire yield Grenvillian ages (1084 Ma, 1130 Ma and 1184 Ma), while the detrital zircons recovered from the sandy matrix of the conglomerates contains populations with peaks of 1000 Ma - 1200 Ma, 750 Ma - 950 Ma, and 200 Ma - 300 Ma. Overlap and Similarity tests run between these populations and published data from Guajira yield values of 0.750 and 0.680, which are significantly higher than the same comparison against the Santa Marta Massif (0.637 and 0.522), and the Curacao island (0.629 and 0.467). Thermochronological results from the metamorphic clasts yield Paleocene-middle Eocene ages (65 - 50 Ma) that confirm not only a regional-scale cooling event in this time period, but also help constrain the maximum depositional age (50 Ma) of the poorly dated Soebi Blanco Formation. Figure 6. U-Pb results from analyzed samples and other Caribbean provinces. (A), Detrital zircons from Soebi Blanco conglomerate matrix; (B), Zircon ages from metamorphic clasts (C), detrital zircons from late Cretaceous Etpana Formation in Guajira Peninsula (Weber et al., 2010); (D), detrital zircons from late Cretaceous Santa Marta San Lorenzo schists (Cardona et al., 2010a); (E), detrital zircons from late Cretaceous Knip Group (Wrigth and Wyld, 2010); (F), overlap and similarity values.

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.

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 Cretaceous forearc units of the Transverse Ranges. Based on zircon U-Pb ages, geologic and petrographic relations, the Pescadero felsite and a capping, sheared metaconglomerate underlie the Pigeon Point Formation. We infer that the magma formed by anatexis of Franciscan or Great Valley clastic sedimentary rocks originating from a parental Mesozoic Sierran-Mojave-Salinian calc-alkaline arc. The felsite erupted during Late Cretaceous time, was metamorphosed to pumpellyite-prehnite grade within the subduction zone, and then was rapidly exhumed, weakly zeolitized, and exposed before Pigeon Point forearc deposition. Pescadero volcanism apparently reflects a previously unrecognized ca. 86–90 Ma felsic igneous event in the accretionary margin.

ARO - Terrestrial Research Program, Methodologies and Protocols for Characterization of Geomaterials

DTIC Science & Technology

2015-05-14

of ice involves melting, digestion, and analysis using inductively coupled plasma – mass spectrometry (ICPMS). ICP-MS analysis established elemental...4] have distinct chemical compositions. Knowledge of the chemical composition of the mineral assemblage present in a rock is critical to...activation analysis (INAA), to inductively-coupled plasma analysis and mass spectrometry (ICP & ICP-MS), mass spectrometry (MS), and laser-ablation

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

Laser Induced Breakdown Spectroscopy (LIBS)

DTIC Science & Technology

2010-03-31

mass spectrometry and laser induced breakdown spectroscopy, Spe T Trejos, A Flores and JR. Almirall, Micro-spectrochemical analysis of document paper...and gel inks by laser ablation inductively coupled plasma mass spectrometry and laser induced breakdown spectroscopy, Spectrochimica Acta Part B...abstracts): 1. *Schenk, E.R. “Elemental analysis of unprocessed cotton by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser

Timing of tectonic evolution of the East Kunlun Orogen, Northern Tibet Plateau

NASA Astrophysics Data System (ADS)

Dong, Yunpeng

2017-04-01

The East Kunlun Orogen, located at the northern Tibet Plateau, represents the western segment of the Central China Orogenic Belt which was formed by amalgamation of the North China blocks and South China blocks. It is a key to understanding the formation of Eastern Asian continent as well as the evolution of the Pangea supercontinent. Based on detailed geological mapping, geochemical and geochronological investigations, the orogen is divided into three main tectonic belts, from north to south, including the Northern Qimantagh, Central Kunlun and Southern Kunlun Belts by the Qimantagh suture, Central Kunlun suture and South Kunlun fault. The Qimantagh suture is marked by the Early Paleozoic ophiolites outcropped in the Yangziquan, Wutumeiren, and Tatuo areas, which consist mainly of peridotites, gabbros, diabases and basalts. Besides, the ophiolite in the Wutumeiren is characterized by occurring anorthosite while the ophiolite in the Tatuo occurring chert. The basalts and diabases from both Yaziquan and Tatuo areas display depletion of Nb, Ta, P and Ti, and enrichment of LILE, suggesting a subduction related tectonic setting. LA-ICP-MS zircon U-Pb age of 421 Ma for the diabase represents the formation age of the Yaziquan ophiolite, while the U-Pb ages of 490 Ma and 505 Ma for gabbro and anorthosite, respectively, constrain the formation age of the Tatuo ophiolite. The basaltic rocks in the Wutumeiren area display flat distribution of HFSEs (such as Nb, Ta, K, La, Ce, Pr, Nd, Zr, Sm, Eu, Ti, Dy, Y, Yb and Lu) and slightly enrichment in LREEs, while the peridotites showing depletion in MREEs. The LA-ICP-MS zircon U-Pb age of 431 Ma for the gabbro represents the formation age of the Wutumeiren ophiolite. Together with regional geology, we suggest herewith a back-arc basin tectonic setting during ca. 505-421 Ma at least for the Qimantagh suture. The Central Kunlun suture is represented by the ophiolite in the Wutuo area, which is characterized by depletion of Nb, Ta, P and Ti, and enrichment of LILEs, LREEs, K, Pb, Sr and Nd, accounting for a subduction relation setting. The gabbro yields a LA-ICP-MS zircon U-Pb age of 243 Ma, representing the formation age of the ophiolite. Taking into account of evidence from the Early Paleozoic ophiolites in the Buqinshan ( Bian Qiantao et al., 2001, 2007; Li Zuochen et al., 2013; Li Ruibao et al., 2014; Liu Zhanqing et al., 2011) and the Derni areas (Chen Liang et al., 2001, 2003), the Central Kunlun ocean might be existed from Early Paleozoic to Middle Triassic time. The Northern Qimantagh tectonic belt, to the north of the Qimantagh suture, exposes a large volume of Early Paleozoic granitic plutons and volcanic rocks. Geochemistry of the granites suggests an arc setting. LA-ICP-MS zircon U-Pb ages ranging from ca. 440 to 402 Ma constrain the time of the subduction and arc setting. The Central Kunlun tectonic belt is characterized by occurring of Paleo-Proterozoic basement which was intruded by large amounts of Triassic granitoids. The basement represented by the Jinshuikou Group including gneisses, amphibolites and marbles, yields a protolith formation age of 2.2 Ga which was overprinted by Neoproterozoic tectono-thermal event. The plutonic intrusions display LA-ICP-MS zircon ages mainly of 260-200 Ma with minor ages of 470-400 Ma, revealing a long-lived subduction from Early Paleozoic to Late Triassic. Taken into together all above evidence, trench-arc-back arc basin tectonics were suggested here accounting for the tectonic evolution of the East Kunlun Orogeny during Early Paleozoic to Triassic time.

Duration of convergence at the Pacific-Gondwana plate margin: insights from accessory phase petrochronology of the Alpine Schist, New Zealand

NASA Astrophysics Data System (ADS)

Briggs, S. I.; Cottle, J. M.; Smit, M. A.; Arnush, N. F.

2016-12-01

The timing, duration and along-strike synchroneity of metamorphism and anataxis in the Alpine Schist of New Zealand is a matter of considerable debate. Our preliminary data indicate that metamorphism resulting in garnet growth occurred from 97 - 75 Ma, and anatectic melting occurred from 80 - 51 Ma. These events are contemporaneous with rifting of Zealandia from East Gondwana, and Tasman Sea spreading from 83 - 52 Ma. An important implication of these results is that Late Cretaceous convergence along the Zealandia segment of the Pacific-Gondwana plate margin may have persisted much later than previously thought, and that convergence and extension occurred coevally in adjacent areas. This poses the question: for how long did convergence continue along the Pacific-Gondwana plate margin during East Gondwana breakup? To fully decipher the multiple stages of the complex metamorphic history recorded in the Alpine Schist, we combine Lu-Hf garnet geochronology with U-Th/Pb and REE analyses of zircon and monazite. We use the newly developed `single-shot laser ablation split stream' (SS-LASS) analysis method to obtain depth profiles through 5-10 µm metamorphic zircon overgrowths at 100 nm depth resolution to constrain both the timing and petrological context of discrete metamorphic zircon (re-)crystallization events recorded in the Alpine Schist. We also employ high spatial resolution LASS analysis to target rare 5 - 20 µm monazite in thin section to augment garnet and zircon data. Our multi-accessory phase petrochronology approach is capable of resolving discrete short-duration thermal events, strengthening the geological interpretation of `mean' Lu-Hf garnet ages and discerning between an episodic versus a prolonged history of metamorphism. In addition, comparison with geochronology from anatectic pegmatites clarifies the temporal relationship between metamorphism and melting in the Alpine Schist, while providing direct constraints on the timing and duration of convergence along the Zealandia segment of the Pacific-Gondwana margin.

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.

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.

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.

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-six automotive glasses (side windows and windshields) representing casework glass from different vehicle manufacturers over several years was also characterized by RI and elemental composition analysis. The solution sample introduction techniques (external calibration and isotope dilution) provide for excellent sensitivity and precision but have the disadvantages of destroying the sample and also involve complex sample preparation. The laser ablation method was simpler, faster and produced comparable discrimination to the EC-ICP-MS and ID-ICP-MS. LA-ICP-MS can provide for an excellent alternative to solution analysis of glass in forensic casework samples. Paints and coatings are frequently encountered as trace evidence samples submitted to forensic science laboratories. A LA-ICP-MS method has been developed to complement the commonly used techniques in forensic laboratories in order to better characterize these samples for forensic purposes. Time-resolved plots of each sample can be compared to associate samples to each other or to discriminate between samples. Additionally, the concentration of lead and the ratios of other elements have been determined in various automotive paints by the reported method. A sample set of eighteen (18) survey automotive paint samples have been analyzed with the developed method in order to determine the utility of LA-ICP-MS and to compare the method to the more commonly used scanning electron microscopy (SEM) method for elemental characterization of paint layers in forensic casework.

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 University of Brasilia. In this way the source areas of these terranes can be compared. The sampled formations are: in Eastern Sardinia, the Cuccuru 'e Flores Conglomerate (CFC); in the Eastern Corsica, the Solaro Flysch (SF); in the Southern Calabria (Aspromonte sub-region), the Stilo Capo d'Orlando Fm. (SCOF) and in the Northern Calabria (Sila subregion), the Paludi Fm. (PF). The data about Northern CPA (NCPA) and SCB show similar zircons population inputs suggesting an analogous source areas. Zircons from the Southern CPA (SCPA) show different input spectra. In SCPA lack at all the Grenvillian ages (0.9-1.8 Ga) and an important crustal signature. These data suggest a different position during the tectonic evolution of the Gondwana margin of SCPA respect of NCPA and SCB. Following these data is it possible to infer the SCPA a North Africa derivation, well fitting with the Gondwanan European Variscan terranes, characterized by the lacking of mesoproterozoic age (KOBER et alii, 2004).

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 the arc.

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 methods and then reanalyzed using our new Laser ablation approach. The laser ablation results are consistent with those obtained using conventional methods, confirming that apatite laser ablation U-Th-Sm/He thermochronology is a viable alternative for collecting large low temperature thermochronology data sets from detrital samples.

On the elemental analysis of different cigarette brands using laser induced breakdown spectroscopy and laser-ablation time of flight mass spectrometry

NASA Astrophysics Data System (ADS)

Ahmed, Nasar; Umar, Zeshan A.; Ahmed, Rizwan; Aslam Baig, M.

2017-10-01

We present qualitative and quantitative analysis of the trace elements present in different brands of tobacco available in Pakistan using laser induced breakdown spectroscopy (LIBS) and Laser ablation Time of Flight Mass Spectrometer (LA-TOFMS). The compositional analysis using the calibration free LIBS technique is based on the observed emission spectra of the laser produced plasma plume whereas the elemental composition analysis using LA-TOFMS is based on the mass spectra of the ions produced by laser ablation. The optical emission spectra of these samples contain spectral lines of calcium, magnesium, sodium, potassium, silicon, strontium, barium, lithium and aluminum with varying intensities. The corresponding mass spectra of the elements were detected in LA-TOF-MS with their composition concentration. The analysis of different brands of cigarettes demonstrates that LIBS coupled with a LA-TOF-MS is a powerful technique for the elemental analysis of the trace elements in any solid sample.

Validation of the determination of the B isotopic composition in Roman glasses with laser ablation multi-collector inductively coupled plasma-mass spectrometry

NASA Astrophysics Data System (ADS)

Devulder, Veerle; Gerdes, Axel; Vanhaecke, Frank; Degryse, Patrick

2015-03-01

The applicability of laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) for the determination of the B isotopic composition in Roman glasses was investigated. The δ11B values thus obtained provide information on the natron flux used during the glass-making process. The glass samples used for this purpose were previously characterized using pneumatic nebulization (PN) MC-ICP-MS. Unfortunately, this method is time-consuming and labor-intensive and consumes some 100 mg of sample, which is a rather high amount for ancient materials. Therefore, the use of the less invasive and faster LA-MC-ICP-MS approach was explored. In this work, the results for 29 Roman glasses and 4 home-made glasses obtained using both techniques were compared to assess the suitability of LA-MC-ICP-MS in this context. The results are in excellent agreement within experimental uncertainty. No difference in overall mass discrimination was observed between the Roman glasses, NIST SRM 610 reference glass and B6 obsidian. The expanded uncertainty of the LA-MC-ICP-MS approach was estimated to be < 2‰, which is similar to that obtained upon sample digestion and PN-MC-ICP-MS measurement.

In vitro assessment of induced phrenic nerve cryothermal injury.

PubMed

Goff, Ryan P; Bersie, Stephanie M; Iaizzo, Paul A

2014-10-01

Phrenic nerve injury, both left and right, is considered a significant complication of cryoballoon ablation for treatment of drug-refractory atrial fibrillation, and functional recovery of the phrenic nerve can take anywhere from hours to months. The purpose of this study was to focus on short periods of cooling to determine the minimal amount of cooling that may terminate nerve function related to cryo ablation. Left and/or right phrenic nerves were dissected from the pericardium and connective tissue of swine (n = 35 preparations). Nerves were placed in a recording chamber modified with a thermocouple array. This apparatus was placed in a digital water bath to maintain an internal chamber temperature of 37°C. Nerves were stimulated proximally with a 1-V, 0.1-ms square wave. Bipolar compound action potentials were recorded proximal and distal to the site of ablation both before and after ablation, then analyzed to determine changes in latency, amplitude, and duration. Temperatures were recorded at a rate of 5 Hz, and maximum cooling rates were calculated. Phrenic nerves were found to elicit compound action potentials upon stimulation for periods up to 4 hours minimum. Average conduction velocity was 56.7 ± 14.7 m/s preablation and 49.8 ± 16.6 m/s postablation (P = .17). Cooling to mild subzero temperatures ceased production of action potentials for >1 hour. Taking into account the data presented here, previous publications, and a conservative stance, during cryotherapy applications, cooling of the nerve to below 4°C should be avoided whenever possible. Copyright © 2014 Heart Rhythm Society. Published by Elsevier Inc. All rights reserved.

High spatial resolution analysis of ferromanganese concretions by LA-ICP-MS†

PubMed Central

Axelsson, Mikael D; Rodushkin, Ilia; Baxter, Douglas C; Ingri, Johan; Öhlander, Björn

2002-01-01

A procedure was developed for the determination of element distributions in cross-sections of ferromanganese concretions using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The effects of carrier flow rates, rf forward power, ablation energy, ablation spot size, repetition rate and number of shots per point on analyte intensity were studied. It is shown that different carrier gas flow rates are required in order to obtain maximum sensitivities for different groups of elements, thus complicating the optimisation of ICP parameters. On the contrary, LA parameters have very similar effects on almost all elements studied, thus providing a common optimum parameter set for the entire mass range. However, for selected LA parameters, the use of compromise conditions was necessary in order to compensate for relatively slow data acquisition by ICP-MS and maintain high spatial resolution without sacrificing the multielemental capabilities of the technique. Possible variations in ablation efficiency were corrected for mathematically using the sum of Fe and Mn intensities. Quantification by external calibration against matrix-matched standards was successfully used for more than 50 elements. These standards, in the form of pressed pellets (no binder), were prepared in-house using ferromanganese concentrates from a deep-sea nodule reference material as well as from shallow-marine concretions varying in size and having different proportions of three major phases: aluminosilicates, Fe- and Mn-oxyhydroxides. Element concentrations in each standard were determined by means of conventional solution nebulisation ICP-MS following acid digestion. Examples of selected inter-element correlations in distribution patterns along the cross-section of a concretion are given.

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.

Printing metal-spiked inks for LA-ICP-MS bioimaging internal standardization: comparison of the different nephrotoxic behavior of cisplatin, carboplatin, and oxaliplatin.

PubMed

Moraleja, Irene; Esteban-Fernández, Diego; Lázaro, Alberto; Humanes, Blanca; Neumann, Boris; Tejedor, Alberto; Luz Mena, M; Jakubowski, Norbert; Gómez-Gómez, M Milagros

2016-03-01

The study of the distribution of the cytostatic drugs cisplatin, carboplatin, and oxaliplatin along the kidney may help to understand their different nephrotoxic behavior. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) allows the acquisition of trace element images in biological tissues. However, results obtained are affected by several variations concerning the sample matrix and instrumental drifts. In this work, an internal standardization method based on printing an Ir-spiked ink onto the surface of the sample has been developed to evaluate the different distributions and accumulation levels of the aforementioned drugs along the kidney of a rat model. A conventional ink-jet printer was used to print fresh sagittal kidney tissue slices of 4 μm. A reproducible and homogenous deposition of the ink along the tissue was observed. The ink was partially absorbed on top of the tissue. Thus, this approach provides a pseudo-internal standardization, due to the fact that the ablation sample and internal standard take place subsequently and not simultaneously. A satisfactory normalization of LA-ICP-MS bioimages and therefore a reliable comparison of the kidney treated with different Pt-based drugs were achieved even for tissues analyzed on different days. Due to the complete ablation of the sample, the transport of the ablated internal standard and tissue to the inductively coupled plasma-mass spectrometry (ICP-MS) is practically taking place at the same time. Pt accumulation in the kidney was observed in accordance to the dosages administered for each drug. Although the accumulation rate of cisplatin and oxaliplatin is high in both cases, their Pt distributions differ. The strong nephrotoxicity observed for cisplatin and the absence of such side effect in the case of oxaliplatin could explain these distribution differences. The homogeneous distribution of oxaliplatin in the cortical and medullar areas could be related with its higher affinity for cellular transporters such as MATE2-k.

Self-aliquoting micro-grooves in combination with laser ablation-ICP-mass spectrometry for the analysis of challenging liquids: quantification of lead in whole blood.

PubMed

Nischkauer, Winfried; Vanhaecke, Frank; Limbeck, Andreas

2016-08-01

We present a technique for the fast screening of the lead concentration in whole blood samples using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The whole blood sample is deposited on a polymeric surface and wiped across a set of micro-grooves previously engraved into the surface. The engraving of the micro-grooves was accomplished with the same laser system used for LA-ICP-MS analysis. In each groove, a part of the liquid blood is trapped, and thus, the sample is divided into sub-aliquots. These aliquots dry quasi instantly and are then investigated by means of LA-ICP-MS. For quantification, external calibration against aqueous standard solutions was relied on, with iron as an internal standard to account for varying volumes of the sample aliquots. The (208)Pb/(57)Fe nuclide ratio used for quantification was obtained via a data treatment protocol so far only used in the context of isotope ratio determination involving transient signals. The method presented here was shown to provide reliable results for Recipe ClinChek® Whole Blood Control levels I-III (nos. 8840-8842), with a repeatability of typically 3 % relative standard deviation (n = 6, for Pb at 442 μg L(-1)). Spiked and non-spiked real whole blood was analysed as well, and the results were compared with those obtained via dilution and sectorfield ICP-MS. A good agreement between both methods was observed. The detection limit (3 s) for lead in whole blood was established to be 10 μg L(-1) for the laser ablation method presented here. Graphical Abstract Micro-grooves are filled with whole blood, dried, and analyzed by laser ablation ICP-mass spectrometry. Notice that the laser moves in perpendicular direction with regard to the micro-grooves.

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.

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.

Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

PubMed

Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

2016-09-28

Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous stable isotope measurement and chemical composition analysis LASS-ICP-MS in combination with MC-ICP-MS is the method of choice. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

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. Thus, early exhumation from a mantle depth of 120-100 km to about 60 km occurred at an average rate of 0.3 cm/y, while subsequent exhumation to a middle crustal level took place at approximately 0.54 cm/y. These exhumation rates are considerably slower than those obtained for UHP rocks in the Dora Maira and Kokchetav massifs (2-3 cm/y). Based on similar P-T estimates and trace element and Hf isotope compositions, Sulu amphibolites can be identified as retrograde UHP eclogites. The εHf(800) of +8 implies a significant input from the depleted mantle to the Sulu-Dabie terrane during the middle Neoproterozoic. Overgrown rims are characterized by a distinct trace element composition with low Lu/Hf and Th/U and significantly higher 176Hf/177Hf ratios than inherited cores, consistent with formation during/after garnet (re-)crystallization and fractionation of the Lu-Hf system during UHP metamorphism. The combined dataset suggests homogenization of the 176Hf/177Hf ratio within the metamorphic mineral assemblage and during protolith formation. Observed variations are explained by mixing of material from both domains during laser ablation, e.g., due to partial recrystallization of inherited cores.

Crustal evolution at mantle depths constrained from Pamir xenoliths

NASA Astrophysics Data System (ADS)

Kooijman, E.; Hacker, B. R.; Smit, M. A.; Kylander-Clark, A. R.; Ratschbacher, L.

2012-12-01

Lower crustal xenoliths erupted in the Pamir at ~11 Ma provide an exclusive opportunity to study the evolution of crust at mantle depths during a continent-continent collision. To investigate, and constrain the timing of, the petrologic processes that occurred during burial to the peak conditions (2.5-2.8 GPa, 1000-1100 °C; [1]), we performed chemical- and isotope analyses of accessory minerals in 10 xenoliths, ranging from eclogites to grt-ky-qtz granulites. In situ laser ablation split-stream ICPMS yielded 1) U-Pb ages, Ti concentrations and REE in zircon, 2) U/Th-Pb ages and REE in monazite, and 3) U-Pb ages and trace elements in rutile. In addition, garnet, and biotite and K-feldspar were dated using Lu-Hf and 40Ar/39Ar geochronology, respectively. Zircon and monazite U-(Th-)Pb ages are 101.9±1.8, 53.7±1.0, 39.1±0.8, 21.7±0.4, 18.2±0.5, 16.9±0.8, 15.1±0.3 (2σ) and 12.5-11.1 Ma; most samples showed several or all of these populations. The 53.7 Ma and older ages are xenocrystic or detrital. For younger ages, zircon and monazite in individual samples recorded different ages-although zircon in one rock and monazite in another can be the same age. The 39.1 Ma zircon and monazite mostly occur as inclusions in minerals of the garnet-bearing assemblage that represents the early, low-P stages of burial. Garnet Lu-Hf ages of 37.8±0.3 Ma support garnet growth at this time. Spinifex-like textures containing 21.7-11.1 Ma zircon and monazite record short-lived partial melting events during burial. Aligned kyanite near these patches indicates associated deformation. Zircons yielding ≤12.5 Ma exhibit increased Eu/Eu* and markedly decreased HREE concentrations, interpreted to record feldspar breakdown and omphacite growth during increasing pressure. Rutile U-Pb cooling ages are 10.8±0.3 Ma in all samples. This agrees with the weighted mean 40Ar/39Ar age of eight biotite, K-feldspar and whole rock separates of 11.00+0.16/-0.09 Ma. Rutile in eclogites provides Zr/Hf and Nb/Ta trends that indicate clinopyroxene fractionation. This is consistent with the occurrence of rutile in omphacite-rich parts of the rocks and supports their HP petrogenesis. In the felsic granulites rutile is associated with the amphibolite-facies garnet-bearing assemblage and its Nb/Ta and Zr/Hf primarily reflect fractionation by rutile. Zirconium-in-rutile temperatures are 800-835 °C for the felsic granulites and 860-895 °C for the eclogites. Titanium-in-zircon temperatures increase from ~735 °C (0.7-1.0 GPa) at 39.1 Ma to ~900 °C (>2.5 GPa) at 11.5 Ma; a further, abrupt increase toward 1000 °C at 11.1 Ma marks melting at the onset of eruption. The analytical uncertainty on the Miocene ages is small compared to the 28-Myr burial record, enabling precise dating of individual reaction and deformation events. These events are at least an order of magnitude shorter than the duration of burial, and evidently occurred in pulses recorded by the (re)crystallization of zircon or monazite. Reference: [1] Hacker et al. (2005) J Petrol 46 (8): 1661-1687.

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.

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

NASA Astrophysics Data System (ADS)

Chen, W.

2016-12-01

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

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 melting of a felsic older crust, neither evolved North American Proterozoic basement nor Jurassic metasedimentary rocks of the Guerrero terrane. Instead, the magma was primarily derived from partial melting of mantle related sources, possibly in the subcontinental mantle wedge above the Farallon plate. Our younger U-Pb zircon-apatite ages are well correlated with the late-stage cogenetic porphyry Cu-Au mineralization at 57 to 59 Ma. If the origin of ore mineralization is related to the magma sources of host batholiths, then a minimal input from crustal melt is suggested in the genesis of Cu-Au porphyry system.

Interaction of graphite and ablative materials with CO2-laser, carbon-arc, and xenon-arc radiation. M.S. Thesis - George Washington Univ., Washington, D. C.

NASA Technical Reports Server (NTRS)

Brewer, W. D.

1975-01-01

The behavior of graphite and several charring ablators in a variety of high radiative heat flux environments was studied in various radiative environments produced by a CO2 laser and a carbon arc facility. Graphite was also tested in xenon arc radiation. Tests were conducted in air nitrogen, helium, and a mixture of CO2 and nitrogen, simulating the Venus atmosphere. The experimental results are compared with theoretical results obtained with a one dimensional charring ablator analysis and a two dimensional subliming ablator analysis. Photomicroscopy showed no significant differences in appearance or microstructure of the charring ablators or graphite after testing in the three different facilities, indicating that the materials respond fundamentally the same to the radiation of different frequencies. The performance of phenolic nylon and graphite was satisfactorily predicted with existing analyses and published material property data.

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.

New Zircon U-Pb Age Constrain of the Origin of Devil's River Uplift (SW Texas) and Insights into the Late Proterozoic and Paleozoic Evolution of the Southern Margin of Laurentia

NASA Astrophysics Data System (ADS)

Rodriguez, E.; Dickerson, P. W.; Stockli, D. F.

2017-12-01

The Devils River Uplift (DRU) in SW Texas records the evolution of the southern Laurentian margin from Grenvillian orogenesis and assembly of Rodinia, to its fragmentation by rifting, and to the amalgamation of Pangaea. It was cored by a well (Shell No. 1 Stewart), penetrating Precambrian gneisses and Cambrian metasediments and sandstones. New zircon LA-ICP-MS data from a total of 10 samples elucidate the crystallization and depositional ages, as well as the detrital provenance, of Precambrian and Cambrian rocks from the DRU. Zircons from five Precambrian crystalline basement samples (6000-9693') yield uniform U-Pb crystallization ages of 1230 Ma that are similar to ages for young gneisses of the Valley Spring Domain (Llano uplift) in central Texas, where they mark the cessation of arc magmatism within the Grenville orogenic belt. The 1230 Ma igneous basement is overlain by L.-M. Cambrian metasedimentary rocks ( 4000-6000') with maximum depositional ages of 533-545 Ma. Detrital zircons from Cambrian strata are dominated by a 1070-1080 Ma population, likely derived from basement units exposed in Texas (Llano uplift, Franklin Mts.), with minor contributions from local 1230 Ma Precambrian basement and the 1380-1500 Ma Granite Rhyolite Province. The L.-M. Cambrian interval is dominated (>80%) by Neoproterozoic detrital magmatic zircons with two major distinct age clusters at 570-700 Ma and 780-820 Ma, supporting a two-stage Rodinia rift model and providing strong evidence for major Cryogenian-Eocambrian intraplate magmatism along the southern margin of Rodinia. Moreover, detrital zircon signatures for L.-M. and U. Cambrian strata strongly correlate with those from the Cuyania terrane of W. Argentina - notably the W. Sierras Pampeanas (Sa. Pie de Palo, Sa. de Maz): 1230 Ma from metasandstones (PdP); 1081-1038 Ma from metasiliciclastics (PdP, SdM); Cryogenian-Eocambrian [774 & 570 Ma] plutons (SdM, PdP). In summary, these new zircon U-Pb data from DRU in SW Texas show that it is part of the Grenville orogenic belt, characterized by 1230 Ma magmatism, and that it experienced Cryogenian-Eocambrian intraplate magmatism as well. Significant correlations between DRU and the Cuyania terrane imply that both participated in Rodinia rifting and creation of the southern Laurentian margin.

Ages of the Xinghuadukou Group in the Erguna Block, NE China

NASA Astrophysics Data System (ADS)

Liu, X.; Hou, W.

2016-12-01

The Xinghuadukou group is outcropped in the Erguna block (EB) of NE China, which is an important component of the eastern segment of the Central Asian Orogenic Belt (CAOB). This group was previously classified as Paleoproterozoic in age. However, recent studies reported Paleozoic ages from the meta-volcanic rocks, Paleoproterozoic to Neoarchean detrital zircon ages from the meta-sedimentary rocks and Neoproterozoic ages from the granitoids. The tectonic affinity of the EB is still debated. In order to clarify the aforementioned issues, 19 samples were collected from the Xinghuadukou group from the Mohe region in NE China. All samples underwent gneiss facies metamorphism, including two-mica granitic gneiss and quartz biotite gneiss. Based on the protolith discrimination diagram of Si—(al+fm)-(c+alk) system, 7 samples originated from sedimentary rocks and the other 12 of igneous origin. The orthogneiss samples were plotted as diorite, granodiorite and granite respectively in TAS, showing felsic character (SiO2 57% - 74%). One orthogneiss and one paragneiss samples were chosen to conduct the LA-ICP-MS U-Pb zircon age analysis. Apart from one zircon with the age of 742 Ma shows evident metamorphic rim, all zircons from the orthogneiss show euhedral to subhedral prismatic shape and typical concentric or oscillatory structure indicating the igneous origin. The concordant age of 2478±26 Ma was generated, indicating the existence of the near Archean basement of the EB. The detrital zircons from the paragneiss produced age populations cluster at 0.6, 0.8, 1.9, 2.6 and 2.7 Ga, lacking of the Grenville event age. The youngest zircon age is 395 Ma, taken as the maximum depositional age of the sedimentary protolith. According to the new data obtained, it is suggested that the Xinghuadukou group comprises the early Paleoproterozoic granite-gneiss, which proves the granitic basement of the Erguna block. The sedimentary rocks formed overlying the basement during the early Paleozoic and underwent metamorphism afterward. Compared with the detrital zircon ages profile of S. Siberia, NCC, Tarim, Mongolia and NE Gondwana, the EB is suggested most likely affiliated with NE Gondwana. Therefore, this study prefers a tectonic scenario that the EB drifted from the NE Gondwana and joined the CAOB tectonic domain during the Paleozoic.

Interesting Inclusions From Podiform Chromitites in Luobusa Ophiolite, Tibet

NASA Astrophysics Data System (ADS)

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

2003-12-01

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). These minerals were found from heavy mineral separation of chromitites. These minerals include (1) native elements, (2) alloys, (3) carbide (SiC, CrC), (4) platinium group elements (PGE) and arsenides, (5) silicates (Ol, Opx, Cpx, Amp, Srp, Chl, Uv, Prp, Alm, Wo, Zrn, Ap, Bt, Spn, Rt, Pl, Kfs, Phl, Sil, Qz and octahedral serpentine (possible pseduomorph after ringwoodite?), (5) oxide (corundum and chromite), (6) carbonates. 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, octahedral serpentine was discovered both on a thin section and from the heavy mineral separation. These octahedral inclusions exist within chromites, forming a line. These minerals are approximately 5-15μ m in diameter and have well octahedral morphology. EPMA, laser raman spectrometer and transmission electron microscopy (TEM) were used to determine the structure and chemical composition of this crystal. For the present, there are several interpretations of this octahedral silicate. One possibility is that if the octahedral structuer is euhedral so this octahedral serpentine may be pseudomorph after ringwoodite because of its chemical composition and octahedral crystal shape. Another is that ocahedral minerals are melt inclusions. Linear occurrence of octahedral minerals is similar to that of fuluid inclusions. If the octahedral structuer is negative crystal shape reflecting octahedral crystal of cromian spinel, then octahedral inclusions may be melt inclusions judging from linear occurrence. At the same time, zircons were obtained from the mineral separation from chromitites. U-Pb dating of these zircons by LA-ICP-MS yielded two different ages. One group has relatively younger age 107-534 Ma, which nearly plots on a concordia line. Another group has older age 1460-1822 Ma, which plots off the concordia line. Cathode luminescence images of these zircons indicate that some zircons have clear oscillatory zoning whereas other zircons show apparent homogeneous overgrowth. But any correlation between CL image and the U-Pb age was not identified in particular. Luobusa ophiolite has been recognized as fragment of Tethys oceanic crust formed in Cretaceous at 100-120 Ma (Allegre et al. 1984). The minimum age 107 Ma corresponds to the age of the formation of Luobusa ophiolite and all other age of zircons in chromitites is much older than that of ophiolite. In addition, the inclusions in the zircons were analyzed by EPMA and laser raman spectrometer. Several zircons contain some inclusions, which are quartz, feldsper, mica, apatite, titanite and others. These inclusions are the minerals composed of crustal material, which means that these zircons were crystalized in the low pressuer crustal condition. On the other hand, Yu et al. (2001) reported that zircons from chromitites in Luobusa ophiolite have shorter inter-atomic distances for Zr-O and Si-O bonds. They concluded that Tibetan-zircons were derived from the high-pressure mantle environment. Judging from the line of evidence mentioned avobe, it is highly possible that these zircons captured by chromitites were originated from recycled crustal materials convecting through upper mantle.

Aerosol detection efficiency in inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Hubbard, Joshua A.; Zigmond, Joseph A.

2016-05-01

An electrostatic size classification technique was used to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Size-segregated particles were counted with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized by the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10- 5 to 10- 11. Free molecular heat and mass transfer theory was applied, but evaporative phenomena were not sufficient to explain the dependence of aerosol detection on particle diameter. Additional work is needed to correlate experimental data with theory for metal-oxides where thermodynamic property data are sparse relative to pure elements. Lastly, when matrix effects and the diffusion of ions inside the plasma were considered, mass loading was concluded to have had an effect on the dependence of detection efficiency on particle diameter.

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 after a period of extensional post-collisional intraplate evolution, strong compressive forces affected the area.

Paleoproterozoic Keulik-Kenirim Ore-Bearing Gabbro-Peridotite Complex, Kola Region: A New Occurrence of Ferropicritic Magmatism

NASA Astrophysics Data System (ADS)

Smolkin, V. F.; Lokhov, K. I.; Skublov, S. G.; Sergeeva, L. Yu.; Lokhov, D. K.; Sergeev, S. A.

2018-03-01

Comprehensive research of ore-bearing differentiated intrusions of the Keulik-Kenirim structural unit, which represents a fragment of the Paleoproterozoic Pechenga-Varzuga Belt, has been carried out for the first time. The intrusions are subvolcanic by type and lenticular in shape, nearly conformable and steeply dipping. They are made up of peridotite, olivine and plagioclase pyroxenites, and gabbro metamorphosed under amphibolite facies conditions along with host basic volcanics. All intrusive rocks are enriched in TiO2 and FeO. Sulfide Cu-Ni mineralization is represented by disseminated, pocket, and stringer-disseminated types, which are clustered in the peridotitic zone as hanging units and bottom lodes. The Ni content in disseminated ore is estimated at 0.45-0.55 wt % and 1.15-3.32 wt % in ore pockets; the Cu grades are 0.17-0.20 and 0.46-5.65 wt %, respectively. To determine the age of intrusions and metamorphism of intrusive and volcanic rocks, various isotopic systems have been used: Sm-Nd (TIMS) in rock and U-Pb (SIMS SHRIMP) and Lu-Hf (LA-ICP-MS) in zircon. Conclusions on the origin of zircons are based on concentrations of trace elements including REE therein and Hf-Nd correlation in zircons and rocks. The U-Pb system of zircons reflects episodes of igneous rock formation (1982 ± 12 Ma) and their postmagmatic transformation (1938 ± 20 Ma). The last disturbance of the U-Pb isotopic system occurred 700 and 425 Ma. Xenogenic zircons dated from 3.17 to 2.65 Ga have been revealed in the studied samples. These zircons were captured by magma from the Archean basement during its ascent. The intrusions were emplaced synchronously with economic ore formation in the Pechenga ore field (1985 ± 10 Ma). The peak metamorphism of intrusive rocks under amphibolite facies conditions is recorded at 40 Ma later. The differentiated intrusions of the Keulik-Kenirim structural unit are close in their internal structure, mineralogy, and geochemistry, as well as in age and features of related Cu-Ni mineralization to ore-bearing intrusions of the Pechenga ore field, which are derivatives of ferropicritic (ferriferous) magmatism.

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.

In Situ Determination of Trace Elements in Fish Otoliths by Laser Ablation Double Focusing Sector Field Inductively Coupled Plasma Mass Spectrometry Using a Solution Standard Addition Calibration Method

NASA Astrophysics Data System (ADS)

Chen, Z.; Jones, C. M.

2002-05-01

Microchemistry of fish otoliths (fish ear bones) is a very useful tool for monitoring aquatic environments and fish migration. However, determination of the elemental composition in fish otolith by ICP-MS has been limited to either analysis of dissolved sample solution or measurement of limited number of trace elements by laser ablation (LA)- ICP-MS due to low sensitivity, lack of available calibration standards, and complexity of polyatomic molecular interference. In this study, a method was developed for in situ determination of trace elements in fish otoliths by laser ablation double focusing sector field ultra high sensitivity Finnigan Element 2 ICP-MS using a solution standard addition calibration method. Due to the lack of matrix-match solid calibration standards, sixteen trace elements (Na, Mg, P, Cr, Mn, Fe, Ni, Cu, Rb, Sr, Y, Cd, La, Ba, Pb and U) were determined using a solution standard calibration with Ca as an internal standard. Flexibility, easy preparation and stable signals are the advantages of using solution calibration standards. In order to resolve polyatomic molecular interferences, medium resolution (M/delta M > 4000) was used for some elements (Na, Mg, P, Cr, Mn, Fe, Ni, and Cu). Both external calibration and standard addition quantification strategies are compared and discussed. Precision, accuracy, and limits of detection are presented.

Early cretaceous lower crustal reworking in NE China: insights from geochronology and geochemistry of felsic igneous rocks from the Great Xing'an range

NASA Astrophysics Data System (ADS)

Li, Yinglei; Liu, Huichuan; Huangfu, Pengpeng; He, Hongyun; Liu, Yongzheng

2018-01-01

This paper presents new zircon LA-ICP-MS U-Pb ages and whole-rock geochemical data for two granitic plutons and rhyolites of the Baiyingaolao Formation in the western Xing'an range (NE China). The two syenogranite granitic plutons yield identical zircon U-Pb age of 142 ± 1 Ma, and the Baiyingaolao rhyolites yield zircon U-Pb age of 138 ± 2 Ma. The granites contain some hornblendes, and show low Zr and Zr + Nb + Ce + Y contents, and low A/CNK (0.98-1.11), Mg# (6-55), and FeOT/MgO values. Rhyolite samples show similar geochemical characteristics with A/CNK of 0.99-1.10 and Mg# of 14-21. In combination with the high K2O contents (4.43-5.61 wt%) and negative correlations between P2O5 and SiO2, both the granites and rhyolites were classified as high-K calc-alkaline I-type granitoids. All samples give high zirconium saturation temperature of 794-964 °C with few initially inherited zircons, and belong to high-temperature I-type granitoids. They were generated by dehydration melting of biotite/muscovite from sub-alkaline meta-basalts in lower crust depth, leaving garnet, amphibole, and plagioclase as the major residual minerals. The syenogranites and rhyolites are likely formed in Mongol-Okhotsk oceanic subduction setting. Incorporating other lower crust-originated felsic rocks in Erguna and Xing'an massifs and Songliao basin, it is argued that lower crustal reworking is pronounced in NE China during Early Cretaceous.

An autochthonous Avalonian basement source for the latest Ordovician Brenton Pluton in the Meguma terrane of Nova Scotia: U-Pb-Hf isotopic constraints and paleogeographic implications

NASA Astrophysics Data System (ADS)

Duncan Keppie, J.; Gregory Shellnutt, J.; Dostal, Jaroslav; Fraser Keppie, D.

2018-04-01

The Ediacaran-Ordovician Meguma Supergroup was thrust over Avalonia basement prior to the intrusion of post-Acadian, ca. 370 Ma, S-type granitic batholiths. This has led to two main hypotheses regarding the original location of the Meguma terrane, a continental rise prism bordering either NW Africa or Avalonia. On the other hand, the pre-Acadian, ca. 440 Ma Brenton pluton has yielded the following U/Pb LA-ICP-MS zircon data: (1) 448 ± 3 Ma population peak inferred to be the intrusive age and (2) ca. 550 and 700 Ma inherited ages common to both Avalonia and NW Africa. In contrast, Hf isotopic analyses of zircon yielded model ages ranging from 814 to 1127 Ma with most between 940 and 1040 Ma: such ages are typical of Avalonia and not NW Africa. The ages of the inherited zircons found within the Brenton pluton suggest that it was probably derived by partial melting of sub-Meguma, mid-crustal Avalonian rocks, upon which the Meguma Supergroup was deposited. Although Avalonia is commonly included in the peri-Gondwanan terranes off NW Africa or Amazonia, paleomagnetic data, faunal provinciality, and Hf data suggest that, during the Ediacaran-Early Cambrian, it was an island chain lying near the tropics (ca. 20-30 °S) and was possibly a continuation of the Bolshezemel volcanic arc accreted to northern Baltica during the Ediacaran Timanide orogenesis. This is consistent with the similar derital zircon population in the Ediacaran-Cambrian Meguma Supergroup and the Dividal Group in northeastern Baltica.

Investigation of heavy-metal accumulation in selected plant samples using laser induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Galiová, M.; Kaiser, J.; Novotný, K.; Novotný, J.; Vaculovič, T.; Liška, M.; Malina, R.; Stejskal, K.; Adam, V.; Kizek, R.

2008-12-01

Single-pulse Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass-Spectrometry (LA-ICP-MS) were applied for mapping the silver and copper distribution in Helianthus Annuus L. samples treated with contaminant in controlled conditions. For Ag and Cu detection the 328.07 nm Ag(I) and 324.75 nm Cu(I) lines were used, respectively. The LIBS experimental conditions (mainly the laser energy and the observation window) were optimized in order to avoid self-absorption effect in the measured spectra. In the LA-ICP-MS analysis the Ag 107 and Cu 63 isotopes were detected. The capability of these two analytical techniques for high-resolution mapping of selected trace chemical elements was demonstrated.

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 altered country rock can be a tracer of fluid alternation events. The split-stream U-Pb ages agrees with new high precision ID-TIMS U-Pb ages from the same monazite grains. These results demonstrate how monazite age and Sm-Nd isotopic data, coupled with delta 18O, can identify hydrothermal monazite and constrain the timing and potential sources of fluid events. [1] Ayers et al., Geology 34 (2006) 653-656.

Visualizing fossilization using laser ablation-inductively coupled plasma-mass spectrometry maps of trace elements in Late Cretaceous bones

USGS Publications Warehouse

Koenig, A.E.; Rogers, R.R.; Trueman, C.N.

2009-01-01

Elemental maps generated by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) provide a previously unavailable high-resolution visualization of the complex physicochemical conditions operating within individual bones during the early stages of diagenesis and fossilization. A selection of LA-ICP-MS maps of bones collected from the Late Cretaceous of Montana (United States) and Madagascar graphically illustrate diverse paths to recrystallization, and reveal unique insights into geochemical aspects of taphonomic history. Some bones show distinct gradients in concentrations of rare earth elements and uranium, with highest concentrations at external bone margins. Others exhibit more intricate patterns of trace element uptake related to bone histology and its control on the flow paths of pore waters. Patterns of element uptake as revealed by LA-ICP-MS maps can be used to guide sampling strategies, and call into question previous studies that hinge upon localized bulk samples of fossilized bone tissue. LA-ICP-MS maps also allow for comparison of recrystallization rates among fossil bones, and afford a novel approach to identifying bones or regions of bones potentially suitable for extracting intact biogeochemical signals. ?? 2009 Geological Society of America.

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.

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.

Liquid chromatography coupled with inductively coupled plasma mass spectrometry in the pharmaceutical industry: selected examples.

PubMed

Marshall, Peter S; Leavens, Bill; Heudi, Olivier; Ramirez-Molina, Cesar

2004-11-12

Both LC and capillary LC (CapLC) have been successfully interfaced with inductively coupled plasma mass spectrometry (ICP-MS). Gradients of acetonitrile and aqueous based solvents have been employed to separate several compounds of pharmaceutical interest. This paper will describe four application areas in the pharmaceutical industry, and examples will be shown where CapLC, LC and gel electrophoresis via laser ablation have been coupled with ICP-MS. The four areas highlighted in this paper are: (1) the use of derivatisation reactions to "make the invisible visible". Methods involving derivatisations with copper and iron will be described that can be used for the analysis of amines and carboxylic acids by ICP-MS. (2) The profiling of metal ion content (in particular bromine) in biological samples such as human plasma, this study will focus on the metabolism of bromine-labelled peptides (e.g. substance P). (3) The analysis of materials derived from single, solid-phase beads used in combinatorial chemistry, and (4) also discussed will be our findings from investigations into the use of laser ablation ICP-MS on the determination of protein phosphorylation on electrophoresis gel blots.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

The Narryer Gneiss Terrane of the Yilgarn Craton, Western Australia, is an important area for studies of early crustal evolution because of the preservation of (1) detrital zircons of Hadean to Archean age in the Jack Hills and Mt. Narryer metasedimentary belts, and (2) several widespread units of granitic gneisses emplaced between ca. 3.7 and 2.6 Ga. We have analyzed the U-Pb geochronology and Hf-isotope geochemistry of magmatic zircons from 38 samples of the granitic gneisses using laser ablation - (multicollector) - ICPMS. The sample suite is dominated by the Meeberrie gneiss, a banded quartz-microcline-oligoclase-biotite gneiss of monzogranite to granodiorite composition, and the Dugel gneiss, a leucocratic, pegmatite-layered syenogranite gneiss, but gneisses of dioritic to tonalitic composition, as well as less deformed granite sheets, are also represented. Magmatic zircons were identified on the basis of the preservation of oscillatory zoning in BSE and CL images, igneous Th/U ratios (>0.2), and concordant U-Pb isotopic systematics with low common Pb contents. The results indicate many of the gneisses are composed of the products of multiple magmatic events, as has been reported previously for samples of the Meeberrie gneiss (Kinny & Nutman, 1996, Precambrian Res. 78, 165-178). Major ages of magmatism preserved in the gneisses occurred at ca. 3685-3665 Ma, 3620-3565 Ma, 3495-3440 Ma, 3375-3330 Ma, and 3300-3260 Ma. The late granite sheets crystallized at 2710-2645 Ma. Hf-isotope compositions of the zircons trend to less radiogenic values with decreasing age, with ɛHf values of ca. 0 to -5 for 3.7-3.4 Ga gneisses, ca. -1 to -9 for 3.4-3.2 Ga gneisses and ca. -5 to -20 for the late granite sheets. The array of the Hf isotopic compositions with time for the entire sample set are fit well by a regression indicating a source reservoir with a 176Lu/177Hf of 0.022 extracted from the depleted mantle at 3.9 Ga. This suggests that the Narryer gneisses and late granite sheets were derived by repeated partial melting of an Eoarchean mafic to intermediate crustal source that persisted throughout the Archean. The ɛHf evolution trend for the Narryer gneisses plots distinctly above the ɛHf trend of the Hadean mafic crustal reservoir inferred for the source of the Hadean detrital zircons from the Jack Hills. The implication is that the inferred Hadean crustal reservoir was not an important source of the Narryer gneisses, either because it was largely isolated from zones of melting in the crust of the Narryer Gneiss Terrane during the Archean, or because it was simply of limited volume.

A 565 Ma old glaciation in the Ediacaran of peri-Gondwanan West Africa

NASA Astrophysics Data System (ADS)

Linnemann, Ulf; Pidal, Agustín Pieren; Hofmann, Mandy; Drost, Kerstin; Quesada, Cecilio; Gerdes, Axel; Marko, Linda; Gärtner, Andreas; Zieger, Johannes; Ulrich, Jens; Krause, Rita; Vickers-Rich, Patricia; Horak, Jana

2018-04-01

In the Cadomian orogen of the NE Bohemian Massif and of SW Iberia, a post-Gaskiers glacial event dated at c. 565 Ma has been detected. Such Ediacaran-aged glaciomarine deposits occur in the Weesenstein and Clanzschwitz groups of the Saxo-Thuringian zone (Bohemia) and in the Lower Alcudian group of the southern Central Iberian zone (Iberia). Both areas are parts of Cadomia situated in the Western and Central European Variscides. Glaciomarine sedimentary rocks are characterized by such features as dropstones, flat iron-shaped pebbles (" Bügeleisen- Geschiebe"), facetted pebbles, dreikanters, and zircon grains affected by ice abrasion. For age and provenance determination, LA-ICP-MS U-Pb ages ( n = 1124) and Hf isotope ( n = 446) analyses were performed. The maximum age of the glaciomarine deposits within a Cadomian back-arc basin based on U-Pb analytics resulted in the youngest detrital zircon populations showing ages of 562-565 Ma and of c. 566-576 Ma old zircon derived from granitoid pebbles within the diamictites. The youngest age recorded was 538-540 Ma based on zircon from the plutons which had intruded the previously deformed Ediacaran metasedimentary rocks. Previously described glaciomarine diamictites of Cadomia (Weesenstein, Clanzschwitz, and Orellana diamictites) are most definitely younger than the c. 579-581 Ma Gaskiers glaciation in Newfoundland (Gaskiers) and in SE New England (Squantum). We propose the term Weesenstein- Orellana glaciation for this new Ediacaran glacial event, named after the most relevant regions of exposure. Palaeogeographically, these glaciomarine diamictites and related sedimentary deposits lie on the periphery of the West African Craton (western peri-Gondwana), and evidence has been provided by detrital zircon U-Pb ages and their Hf isotope composition. Correlation with similar glaciomarine deposits in the Anti-Atlas (Bou Azzer) and Saudi Arabia suggests a continued distribution of post-Gaskiers glacial deposits along the Gondwana margin of Northern Africa. The Weesenstein- Orellana glaciation correlates in part with the Shuram-Wonoka δ13C anomaly.

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] Dilles (1987) Econ Geol 82:1750-1789.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

The Age of the Moon

NASA Astrophysics Data System (ADS)

Barboni, M.; Boehnke, P.; Keller, C. B.; Kohl, I. E.; McKeegan, K. D.; Schoene, B.; Young, E. D.

2016-12-01

Knowledge of the age of the Moon is important for understanding the early evolution of the solar system, including the timing of the hypothesized Giant Impact (GI). There have been many attempts to determine the Moon's age, but significant disagreement remains with some authors favoring an early formation and others arguing for a relatively young Moon formed at 4.4 Ga. Attempts to date the GI indirectly through its effects on the asteroid belt are problematic as there is no way to uniquely ascertain the cause of the observed disturbances (e.g., GI or meteorite parent body breakup). Determining the timing of the Lunar Magma Ocean (LMO) crystallization provides a more direct constraint on the age of the Moon, but interpreting the chronologic significance of LMO products is complicated by the fact that the only rock samples available are breccias. A better approach is to construct a model age for the fractional crystallization of the LMO since this should provide a global signature. Zircons from the Apollo samples are ancient, robust against later disturbances, and amenable to precise U-Pb geochronology and Hf isotope analyses that can be used to construct Lu-Hf model ages for the silicate differentiation of the Moon. Previous isotopic studies of Apollo zircons yielded artificially young Hf model ages because of the (then unknown) effect of neutron capture on Hf isotopic ratios generated by long exposure to cosmic radiation, and were unable to determine whether or not the U-Pb dates were concordant due to insufficient precision of in situ dating techniques. We have addressed these issues by carrying out CA-ID-TIMS U-Pb geochronology on Apollo 14 zircon fragments, followed by Hf isotope determination by solution MC-ICP-MS on the same volume of zircon. By constructing Hf model ages from zircons that are concordant to the sub-permil level, we show that the minimum age for the end of differentiation of the LMO, and by extension, the formation of the Moon, is 4.52 ± 0.01 Ga.

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 oxygen-hafnium isotope paradox in the early post Columbia River Basalt silicic volcanism: Evidence for complex batch assembly of upper crustal, lower crustal and low-δ18O silicic magmas

NASA Astrophysics Data System (ADS)

Colon, D.; Bindeman, I. N.; Ellis, B. S.; Schmitt, A. K.; Fisher, C. M.; Vervoort, J. D.

2013-12-01

Eruptions of the Columbia River flood basalts were immediately followed by large eruptions of silicic magmas; some may have been coeval, others genetically-linked to the CRB. Among the most voluminous of these eruptions was the Jarbidge Rhyolite, which comprises ~500 km3 of lava erupted from 16.1-15.0 Ma in northern Nevada. Activity at Jarbidge was followed at 15.0 Ma by a series of rhyolitic ignimbrites and lavas in the J-P Desert of Idaho ~50 km NW of the Jarbidge Rhyolite center. To constrain magmatic origins and upper crustal magma storage conditions of these two silicic magmatic systems, we conducted bulk and high spatial resolution analysis of whole rocks and minerals (quartz, feldspar, and zircon). Bulk quartz and plagioclase δ18O values of the J-P Desert units are only moderately lower than mantle values, with δ18O-quartz of 5.0-5.5‰ and plagioclase δ18O of ~3.9-5.8‰, along with slightly unradiogenic Nd and Hf whole rock values (average ɛHf and ɛNd of -13.1 and -10.0, respectively), while quartz from the Jarbidge Rhyolite has normal δ18O (+8.4‰), but very unradiogenic ɛHf-ɛNd (ɛHf = -34.7, ɛNd = -24.0), fingerprinting Archean upper crust. SIMS analysis of J-P Desert zircons reveals considerably diverse δ18O values, ranging from -0.6‰ to +6.5‰ in a single unit. The same zircon spots yielded U-Pb SIMS ages which generally agree with the 40Ar/39Ar eruption ages, with no evidence of inheritance of pre-Miocene zircons. Combined with LA-MC-ICP-MS analysis of Hf isotopes overlapping the earlier SIMS spots, these zircons show a clear near-linear correlation between ɛHf and δ18O values observed in individual zircons. This relationship suggests variable mixing of two distinct silicic magmas prior to eruption of the J-P Desert rhyolites. One of these, characterized by extremely low ɛHf values and normal δ18O values, is likely a mantle magma strongly contaminated with shallow Archean crust, represented by the Jarbidge Rhyolite. The other is characterized by primitive mantle-like ɛHf values and very low δ18O values, between 0‰ and -1‰. We conclude that the J-P Desert magmas were assembled from multiple batches of magmas in the shallow crust that had melted and mixed with varying degrees of ancient continental crust of normal δ18O composition and another crustal component that was younger, had undergone considerable hydrothermal alteration, and had ɛNd and ɛHf near 0. The lack of pre-Miocene ages in all analyzed zircons implies thermal resorption of ancient zircons above the zircon saturation temperature, assuming the local crust contained zircon. The source of this hydrothermally altered component is likely related to the hotspot, because low-δ18O magmas occur throughout the hotspot track, despite differences in the local geology. After these diverse magma batches had cooled and formed new zircons, they extensively mixed, forming final giant magma chambers which subsequently erupted. We suggest that this shallow batch-assembly and crustal assimilation is a common feature of large silicic magma systems, made easily resolvable here due to the eruptions' location along the boundary between two extremely distinct types of shallow continental crust.

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 rare earth elements). These calibration curves have been used to measure impurities in a number of uranium samples. The results from the TOF-ICP-MS will be compared with other mass spectrometric methods.« less

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.

Depth profiling and imaging capabilities of an ultrashort pulse laser ablation time of flight mass spectrometer

PubMed Central

Cui, Yang; Moore, Jerry F.; Milasinovic, Slobodan; Liu, Yaoming; Gordon, Robert J.; Hanley, Luke

2012-01-01

An ultrafast laser ablation time-of-flight mass spectrometer (AToF-MS) and associated data acquisition software that permits imaging at micron-scale resolution and sub-micron-scale depth profiling are described. The ion funnel-based source of this instrument can be operated at pressures ranging from 10−8 to ∼0.3 mbar. Mass spectra may be collected and stored at a rate of 1 kHz by the data acquisition system, allowing the instrument to be coupled with standard commercial Ti:sapphire lasers. The capabilities of the AToF-MS instrument are demonstrated on metal foils and semiconductor wafers using a Ti:sapphire laser emitting 800 nm, ∼75 fs pulses at 1 kHz. Results show that elemental quantification and depth profiling are feasible with this instrument. PMID:23020378

CO2-laser ablation of Bi-Sr-Ca-Cu oxide by millisecond pulse lengths

NASA Astrophysics Data System (ADS)

Meskoob, M.; Honda, T.; Safari, A.; Wachtman, J. B.; Danforth, S.; Wilkens, B. J.

1990-03-01

We have achieved ablation of Bi-Sr-Ca-Cu oxide from single targets of superconducting pellets by CO2-laser pulses of l ms length to grow superconducting thin films. Upon annealing, the 6000-Å thin films have a Tc (onset) of 90 K and zero resistance at 78 K. X-ray diffraction patterns indicate the growth of single-phase thin films. This technique allows growth of uniform single-phase superconducting thin films of lateral area greater than 1 cm2.

The Chahnaly low sulfidation epithermal gold deposit, western Makran volcanic arc, southeastern Iran

USGS Publications Warehouse

Sholeh, Ali; Rastad, Ebrahim; Huston, David L.; Gemmell, J. Bruce; Taylor, Ryan D.

2016-01-01

The Chahnaly Au deposit formed during the early stages of magmatism. LA-ICP-MS zircon U-Pb geochronology of host andesite and 40Ar/39Ar dating of two samples of gold-associated adularia show that the ore-stage adularia (19.83 ± 0.10 and 19.2 ± 0.5 Ma) is younger, by as much as 1.5 million years, than the volcanic host rock (20.32 ± 0.4 Ma). Therefore, either hydrothermal activity continued well after volcanism or a second magmatic event rejuvenated hydrothermal activity. This second magmatic event may be related to eruption of porphyritic andesite at ~20.32 ± 0.40 Ma, which is within error of ~19.83 ± 0.10 Ma adularia. The new LA-ICP-MS zircon U-Pb host rock and vein adularia 40Ar/39Ar ages suggest that early Miocene magmatism and mineralization in the Bazman area is of a similar age to that of the Saindak porphyry and Tanjeel porphyry center of the giant Reko Diq deposit. This confirms the existence of early Miocene arc magmatism and mineralization along the Iranian part of the Makran volcanic arc. Ore, alteration mineralogy, and alteration patterns indicate that the Chahnaly deposit is a typical low-sulfidation epithermal Au deposit, located in a poorly explored part of the Makran volcanic arc in Iran.                   

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 may also be suspect. The Dob's Linn site is therefore unsuitable for calibrating the biostratigraphic horizons. Work in progress will provide more U-Pb dating of bentonites from around the Ordovician-Silurian boundary in Canada, United States, Britain and Scandinavia with the aim of calibrating the local series and stages in order to help in International correlations.

Zinc isotope ratio imaging of rat brain thin sections from stable isotope tracer studies by LA-MC-ICP-MS.

PubMed

Urgast, Dagmar S; Hill, Sarah; Kwun, In-Sook; Beattie, John H; Goenaga-Infante, Heidi; Feldmann, Jörg

2012-10-01

Zinc stable isotope tracers (⁶⁷Zn and ⁷⁰Zn) were injected into rats at two different time points to investigate the feasibility of using tracers to study zinc kinetics at the microscale within distinct tissue features. Laser ablation coupled to multi-collector ICP-MS was used to analyse average isotope ratios in liver thin sections and to generate bio-images showing zinc isotope ratio distribution in brain thin sections. Average isotope ratios of all samples from treated animals were found to be statistically different (P < 0.05) from samples from untreated control animals. Furthermore, differing isotope ratios in physiological features of the brain, namely hippocampus, amygdala, cortex and hypothalamus, were identified. This indicates that these regions differ in their zinc metabolism kinetics. While cortex and hypothalamus contain more tracer two days after injection than 14 days after injection, the opposite is true for hippocampus and amygdala. This study showed that stable isotope tracer experiments can be combined with laser ablation MC-ICP-MS to measure trace element kinetics in tissues at a microscale level.

Ore genesis and geodynamic setting of the Lianhuashan porphyry tungsten deposit, eastern Guangdong Province, SE China: constraints from muscovite 40Ar-39Ar and zircon U-Pb dating and Hf isotopes

NASA Astrophysics Data System (ADS)

Liu, Peng; Mao, Jingwen; Pirajno, Franco; Jia, Lihui; Zhang, Feng; Li, Yang

2017-12-01

The Lianhuashan deposit has long been regarded as a typical tungsten porphyry deposit, located in the eastern Guangdong Province, in the Southeastern Coastal Metallogenic Belt (SCMB). LA-MC-ICP-MS zircon U-Pb dating of the quartz porphyry yielded a weighted mean 206Pb/238U age of 137.3 ± 2.0 Ma, which is interpreted as the emplacement age of the quartz porphyry. Hydrothermal muscovite yielded a plateau 40Ar/39Ar age of 133.2 ± 0.9 Ma, which is consistent with the zircon U-Pb age, suggesting that the tungsten mineralization is genetically related to the quartz porphyry. Combined with previous studies, we suggest that there is a 145-135 Ma episode linking the granitic magmas with W-Sn ore systems in the SCMB. Zircon ɛHf (t) values of the quartz porphyry are in range of - 3.8 to 0.9, and the two-stage Hf model ages (TDM2) are 1.1-1.4 Ga, which is younger than the basement rocks in the Cathaysia Block (1.8-2.2 Ga), signifying that the quartz porphyry was predominantly derived from melting of Mesoproterozoic crust containing variable amounts of mantle components. In combination with the newly recognized coeval alkaline/bimodal magmatism and A-type granites in eastern Guangdong, we suggest that the 145-135 Ma W-Sn metallogenic event of the SCMB is related to a geodynamic setting of large-scale lithospheric extension and thinning, which can be ascribed to melting of the crust caused by mantle upwelling, triggered by the oblique subduction of the Izanagi plate.

Aerosol detection efficiency in inductively coupled plasma mass spectrometry

DOE PAGES

Hubbard, Joshua A.; Zigmond, Joseph A.

2016-03-02

We used an electrostatic size classification technique to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Moreover, we counted size-segregated particles with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized bymore » the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10 -5 to 10 -11. Free molecular heat and mass transfer theory was applied, but evaporative phenomena were not sufficient to explain the dependence of aerosol detection on particle diameter. Additional work is needed to correlate experimental data with theory for metal-oxides where thermodynamic property data are sparse relative to pure elements. Finally, when matrix effects and the diffusion of ions inside the plasma were considered, mass loading was concluded to have had an effect on the dependence of detection efficiency on particle diameter.« less

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

Witte, Travis

This dissertation provides a general introduction to Inductively coupled plasma-mass spectrometry (ICP-MS) and laser ablation (LA) sampling, with an examination of analytical challenges in the employment of this technique. It discusses the origin of metal oxide ions (MO+) in LA-ICP-MS, as well as the effect of introducing helium and nitrogen to the aerosol gas flow on the formation of these polyatomic interferences. It extends the study of polyatomic ions in LA-ICP-MS to metal argide (MAr+) species, an additional source of possible significant interferences in the spectrum. It describes the application of fs-LA-ICP-MS to the determination of uranium isotope ratios inmore » particulate samples.« less

Late Early-Cretaceous quartz diorite-granodiorite-monzogranite association from the Gaoligong belt, southeastern Tibet Plateau: Chemical variations and geodynamic implications

NASA Astrophysics Data System (ADS)

Zhu, Ren-Zhi; Lai, Shao-Cong; Qin, Jiang-Feng; Zhao, Shao-Wei; Wang, Jiang-Bo

2017-09-01

Geochemical variations in granitic rocks may be controlled by their source rocks, melting reactions and subsequent magmatic processes, which resulted from various geodynamic processes related to subduction, collision, or slab break-off. Here we report new LA-ICP-MS zircon U-Pb ages and Hf isotopes, whole-rock chemistry and Sr-Nd isotopes for the late Early Cretaceous quartz diorite, granodiorite and monzogranite in the Gaoligong belt, southeastern Tibet Plateau. The zircon U-Pb dating yield ages of 113.9 ± 1.6, 111.7 ± 0.8, and 112.8 ± 1.7 Ma for the quartz diorite, granodiorite, and monzogranite, respectively, which are coeval with bimodal magmatism in the central and northern Lhasa sub-terrane. There are the distinct sources regions for the quartz diorite and granodiorite-monzogranite association. The quartz diorites are sodic, calc-alkaline and have high Mg# (52-54) values. They also have elevated initial 87Sr/86Sr (0.707019 to 0.709176) and low εNd(t) (- 5.16 to - 7.63), with variable zircon εHf(t) values (+ 5.65 to - 9.02). Zircon chemical data indicate a typical crustal-derived character with high Th (142-1260 ppm) and U (106-1082 ppm) and moderate U/Yb ratios (0.30 to 2.32) and Y content (705-1888 ppm). Those data suggest that the quartz diorites were derived from partial melting of ancient basaltic lower crust by a mantle-derived magma in source region. The granodiorite-monzogranite association has high-K calc-alkaline, weakly peraluminous characters. They show lower Nb/Ta (5.57 to 13.8), CaO/Na2O (0.62 to 1.21), higher Al2O3/TiO2 (24.4 to 44.4) ratios, more evolved whole-rock Sr-Nd and zircon Hf isotopic signatures, all of which suggest derivation from mixed basaltic and metasedimentary source rocks in a deep crustal zone. We propose that the granitic magmatisms at ca. 113-110 Ma in the Gaologong belt was triggered by the slab break-off of Bangong-Nujiang Tethyan oceanic lithosphere. Supplementary Dataset Table 2. Single-grain zircon Hf isotopic data for granitic rocks in the Gaoligong belt, SW China.

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 overlap with the Grenville, Taconic and Acadian orogenies of eastern North America. This study demonstrates that dating of detrital zircon is a powerful tool for determining the provenance of soil and limestone.

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 geochronological and isotope geochemical structure of either the basement and/or distant sources having supplied material to the basement rocks. If unrecognized, sediment formed from such granitoid sources may erroneously be used to infer the exposure of, and direct detrital contributions from, a variety of older source rocks in fact not directly involved in the studied source-sink system.

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.

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.

Dynamic behavior of photoablation products of corneal tissue in the mid-IR: a study with FELIX

NASA Astrophysics Data System (ADS)

Auerhammer, J. M.; Walker, R.; van der Meer, A. F. G.; Jean, B.

The properties of pulsed IR-laser ablation of biological soft tissue (porcine cornea) were studied in vitro systematically and quantitatively with a free-electron laser in the wavelength range 6<=λ<=20 μm at fluences ranging from 3.1 to 9.4 J/cm2. Dynamic parameters such as the extension of the ablation cloud, the initial velocity and momentum of the ablated particles as well as the ablation threshold, the ablated mass, and the particle size were investigated. The ablation plume was made visible with a stroboscopic technique. For a fluence of 3.1 J/cm2 the average initial velocity of the ejected particles was deduced from the extension of the plume to range from 120-400 m/s. Measurements of the recoil momentum using a sensitive pendulum led to values between 0.5 and 2.0 mmg/s. All measured properties were related to the spectroscopically determined absorption coefficient of cornea αcornea. Where absorption due to proteins is high (at λ=6.2 and 6.5 μm), ablated mass, velocity and recoil momentum behave according to αcornea. For the first time, variations of the ablation plume from pulse to pulse were observed. Those, as well as the particle size, not only depend on the absorption coefficient, but also on the predominant absorber.

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.

Linear ablation of right atrial free wall flutter: demonstration of bidirectional conduction block as an endpoint associated with long-term success.

PubMed

Snowdon, Richard L; Balasubramaniam, Richard; Teh, Andrew W; Haqqani, Haris M; Medi, Caroline; Rosso, Raphael; Vohra, Jitendra K; Kistler, Peter M; Morton, Joseph B; Sparks, Paul B; Kalman, Jonathan M

2010-05-01

Ablation for atypical atrial flutter (AFL) is often performed during tachycardia, with termination or noninducibility of AFL as the endpoint. Termination alone is, however, an inadequate endpoint for typical AFL ablation, where incomplete isthmus block leads to high recurrence rates. We assessed conduction block across a low lateral right atrial (RA) ablation line (LRA) from free wall scar to the inferior vena cava (IVC) or tricuspid annulus in 11 consecutive patients with atypical RA free wall flutter. LRA block was assessed following termination of AFL, by pacing from the ablation catheter in the low lateral RA posterior to the ablation line and recording the sequence and timing of activation anterior to the line with a duodecapole catheter, and vice versa for bidirectional block. LRA block resulted in a high to low activation pattern on the halo and a mean conduction time of 201 +/- 48 ms to distal halo. LRA conduction block was present in only 2 out of 6 patients after termination of AFL by ablation. Ablation was performed during sinus rhythm (SR) in 9 patients to achieve LRA conduction block. No recurrence of AFL was observed at long-term follow-up (22 +/- 12 months); 3 patients developed AF. Termination of right free wall flutter is often associated with persistent LRA conduction and additional radiofrequency ablation (RFA) in SR is usually required. Low RA pacing may be used to assess LRA conduction block and offers a robust endpoint for atypical RA free wall flutter ablation, which results in a high long-term cure rate.

Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Lazarov, Marina; Horn, Ingo

2015-09-01

Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ65Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as (32S33S)+ and (32S-16O17O)+ do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn-H or doubly-charged Sn2 + that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ65Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm2 for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm2 which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible to measure Cu isotopic ratios in native copper and Cu-bearing sulfides, carbonates and oxides in situ with a precision of better than 0.1‰ (2SD) without using a matrix-matched standard during laser ablation analyses. Thus, this is a suitable tool to resolve Cu isotopic zoning larger than 0.1‰ in Cu-sulfides, carbonates and oxides.

Conformable amplified lead zirconate titanate sensors with enhanced piezoelectric response for cutaneous pressure monitoring.

PubMed

Dagdeviren, Canan; Su, Yewang; Joe, Pauline; Yona, Raissa; Liu, Yuhao; Kim, Yun-Soung; Huang, YongAn; Damadoran, Anoop R; Xia, Jing; Martin, Lane W; Huang, Yonggang; Rogers, John A

2014-08-05

The ability to measure subtle changes in arterial pressure using devices mounted on the skin can be valuable for monitoring vital signs in emergency care, detecting the early onset of cardiovascular disease and continuously assessing health status. Conventional technologies are well suited for use in traditional clinical settings, but cannot be easily adapted for sustained use during daily activities. Here we introduce a conformal device that avoids these limitations. Ultrathin inorganic piezoelectric and semiconductor materials on elastomer substrates enable amplified, low hysteresis measurements of pressure on the skin, with high levels of sensitivity (~0.005 Pa) and fast response times (~0.1 ms). Experimental and theoretical studies reveal enhanced piezoelectric responses in lead zirconate titanate that follow from integration on soft supports as well as engineering behaviours of the associated devices. Calibrated measurements of pressure variations of blood flow in near-surface arteries demonstrate capabilities for measuring radial artery augmentation index and pulse pressure velocity.

Forensic analysis of printing inks using tandem Laser Induced Breakdown Spectroscopy and Laser Ablation Inductively Coupled Plasma Mass Spectrometry

NASA Astrophysics Data System (ADS)

Subedi, Kiran; Trejos, Tatiana; Almirall, José

2015-01-01

Elemental analysis, using either LA-ICP-MS or LIBS, can be used for the chemical characterization of materials of forensic interest to discriminate between source materials originating from different sources and also for the association of materials known to originate from the same source. In this study, a tandem LIBS/LA-ICP-MS system that combines the benefits of both LIBS and LA-ICP-MS was evaluated for the characterization of samples of printing inks (toners, inkjets, intaglio and offset.). The performance of both laser sampling methods is presented. A subset of 9 black laser toners, 10 colored (CMYK) inkjet samples, 12 colored (CMYK) offset samples and 12 intaglio inks originating from different manufacturing sources were analyzed to evaluate the discrimination capability of the tandem method. These samples were selected because they presented a very similar elemental profile by LA-ICP-MS. Although typical discrimination between different ink sources is found to be > 99% for a variety of inks when only LA-ICP-MS was used for the analysis, additional discrimination was achieved by combining the elemental results from the LIBS analysis to the LA-ICP-MS analysis in the tandem technique, enhancing the overall discrimination capability of the individual laser ablation methods. The LIBS measurements of the Ca, Fe, K and Si signals, in particular, improved the discrimination for this specific set of different ink samples previously shown to exhibit very similar LA-ICP-MS elemental profiles. The combination of these two techniques in a single setup resulted in better discrimination of the printing inks with two distinct fingerprint spectra, providing information from atomic/ionic emissions and isotopic composition (m/z) for each ink sample.

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.

Use of laser ablation-inductively coupled plasma-time of flight-mass spectrometry to identify the elemental composition of vanilla and determine the geographic origin by discriminant function analysis.

PubMed

Hondrogiannis, Ellen M; Ehrlinger, Erin; Poplaski, Alyssa; Lisle, Meredith

2013-11-27

A total of 11 elements found in 25 vanilla samples from Uganda, Madagascar, Indonesia, and Papua New Guinea were measured by laser ablation-inductively coupled plasma-time-of-flight-mass spectrometry (LA-ICP-TOF-MS) for the purpose of collecting data that could be used to discriminate among the origins. Pellets were prepared of the samples, and elemental concentrations were obtained on the basis of external calibration curves created using five National Institute of Standards and Technology (NIST) standards and one Chinese standard with (13)C internal standardization. These curves were validated using NIST 1573a (tomato leaves) as a check standard. Discriminant analysis was used to successfully classify the vanilla samples by their origin. Our method illustrates the feasibility of using LA-ICP-TOF-MS with an external calibration curve for high-throughput screening of spice screening analysis.

Geochronological, geochemical, and Sr-Nd-Hf isotopic characteristics of Cretaceous monzonitic plutons in western Zhejiang Province, Southeast China: New insights into the petrogenesis of intermediate rocks

NASA Astrophysics Data System (ADS)

Liu, Liang; Qiu, Jian-Sheng; Zhao, Jiao-Long; Yang, Ze-Li

2014-05-01

We present comprehensive petrological, geochemical, and Sr-Nd-Hf isotopic data for the Matou and Dalai plutons in western Zhejiang Province, Southeast China, with the aim of constraining the petrogenesis of monzonites and to offer new insights into the deep processes of interaction between crustal- and mantle-derived magmas beneath SE China. The Matou pluton comprises quartz monzonite, whereas the Dalai pluton consists of quartz monzodiorite. Zircon U-Pb ages obtained by laser ablation-inductively coupled plasma-mass spectrometry show that both plutons were emplaced at 99-101 Ma. Rocks of both plutons are intermediate to silicic, metaluminous to weakly peraluminous, subalkaline, and K-rich in composition. Samples of the plutons are enriched in large ion lithophile (e.g., Rb, K, and Pb) and light rare earth elements, depleted in high-field strength elements (e.g., Nb, Ta, and Ti), and have small negative or no Eu anomalies. In addition, the rocks have high Mg# values (up to 53.9), high zircon ɛHf(t) values (up to - 1.4), and low Nb/U and Ta/U ratios. Geochemical evidence suggests that both depleted asthenospheric and metasomatically enriched mantle components were involved in the formation of these monzonitic rocks. The presence of inherited zircons with Palaeoproterozoic ages and zircons with unusually low ɛHf(t) values (- 12.9) in the Matou quartz monzonites indicates that ancient crustal materials were also involved in their petrogenesis. In combination with the presence of abundant mafic microgranular enclaves (MMEs) with spheroidal to ellipsoidal-ovoidal shapes and xenocrysts within the more diffused enclaves, and the results of trace element modelling, we suggest that the Matou quartz monzonites were generated by mixing between mantle-derived mafic magmas and crustally derived silicic magmas. The Dalai pluton is relatively homogeneous and contains fewer MMEs than the Matou pluton. Zircons from the Dalai pluton show no inherited components, indicating that crustal materials have played a limited role in the petrogenesis of the quartz monzodiorites. The Dalai quartz monzodiorites have lower SiO2 contents, higher Mg# values, and considerably higher and variable Cr, Co, and Ni concentrations than the Matou quartz monzonites. Zircon Hf isotopic compositions of the Dalai pluton are relatively homogeneous (ɛHf(t) = - 5.2 to - 3.2). The combined petrological, geochemical, and isotopic features indicate that the Dalai monzodiorites were generated by olivine- and pyroxene-dominated fractional crystallisation from basaltic magmas, which were in turn produced by mixing between melts from depleted asthenosphere and subduction-enriched mantle. Our interpretation implies that Late Mesozoic monzonitic rocks in Southeast China require a significant input of mantle melts, and some may have been generated solely by fractionation of basaltic magmas. This petrogenetic model may be applicable to other monzonitic rocks in Southeast China, and to similar tectonic settings and sites of monzonitic magma generation worldwide.

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

High-speed photography of plasma during excimer laser-tissue interaction.

PubMed

Murray, Andrea K; Dickinson, Mark R

2004-08-07

During high fluence laser-tissue interaction, ablation of tissue occurs, debris is removed from the ablation site and is then ejected at high velocity. This debris may be observed as a combination of luminous plasma and non-luminous plume, both of which have the potential to shield the ablation site. This study examined the role of ablation debris in shielding the tissue and determined its effects on the ablation rate over a range of laser pulse energies, pulse repetition rates and pulse numbers for dentine; the velocity differences between hard and soft tissues were also examined. High-speed photography was carried out at up to 1 x 10(8) frames per second. A maximum velocity of 2.58 +/- 0.52 x 10(4) m s(-1) was recorded for dentine debris within the first 10 ns following ejection. The maximum duration of tissue shielding due to a single pulse, determined by attenuation of a probe beam, was found to be approximately 7 ms, approximately 80 micros of which was due to luminous plasma and the remainder due to the non-luminous plume.

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

A comparison of laser ablation-inductively coupled plasma-mass spectrometry and high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers

NASA Astrophysics Data System (ADS)

de Gois, Jefferson S.; Van Malderen, Stijn J. M.; Cadorim, Heloisa R.; Welz, Bernhard; Vanhaecke, Frank

2017-06-01

This work describes the development and comparison of two methods for the direct determination of Br in polymer samples via solid sampling, one using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and the other using high-resolution continuum source graphite furnace molecular absorption spectrometry with direct solid sample analysis (HR-CS SS-GF MAS). The methods were optimized and their accuracy was evaluated by comparing the results obtained for 6 polymeric certified reference materials (CRMs) with the corresponding certified values. For Br determination with LA-ICP-MS, the 79Br+ signal could be monitored interference-free. For Br determination via HR-CS SS-GF MAS, the CaBr molecule was monitored at 625.315 nm with integration of the central pixel ± 1. Bromine quantification by LA-ICP-MS was performed via external calibration against a single CRM while using the 12C+ signal as an internal standard. With HR-CS SS-GF MAS, Br quantification could be accomplished using external calibration against aqueous standard solutions. Except for one LA-ICP-MS result, the concentrations obtained with both techniques were in agreement with the certified values within the experimental uncertainty as evidenced using a t-test (95% confidence level). The limit of quantification was determined to be 100 μg g- 1 Br for LA-ICP-MS and 10 μg g- 1 Br for HR-CS SS-GF MAS.

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

NASA Astrophysics Data System (ADS)

Becker, Johanna Sabine

2002-12-01

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.

Elemental analysis of glass by laser ablation inductively coupled plasma optical emission spectrometry (LA-ICP-OES).

PubMed

Schenk, Emily R; Almirall, José R

2012-04-10

The elemental analysis of glass evidence has been established as a powerful discrimination tool for forensic analysts. Laser ablation inductively coupled plasma optical emission spectrometry (LA-ICP-OES) has been compared to laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and energy dispersive micro X-ray fluorescence spectroscopy (μXRF/EDS) as competing instrumentation for the elemental analysis of glass. The development of a method for the forensic analysis of glass coupling laser ablation to ICP-OES is presented for the first time. LA-ICP-OES has demonstrated comparable analytical performance to LA-ICP-MS based on the use of the element menu, Al (Al I 396.15 nm), Ba (Ba II 455.40 nm), Ca (Ca II 315.88 nm), Fe (Fe II 238.20 nm), Li (Li I 670.78 nm), Mg (Mg I 285.21 nm), Sr (Sr II 407.77 nm), Ti (Ti II 368.51 nm), and Zr (Zr II 343.82 nm). The relevant figures of merit, such as precision, accuracy and sensitivity, are presented and compared to LA-ICP-MS. A set of 41 glass samples was used to assess the discrimination power of the LA-ICP-OES method in comparison to other elemental analysis techniques. This sample set consisted of several vehicle glass samples that originated from the same source (inside and outside windshield panes) and several glass samples that originated from different vehicles. Different match criteria were used and compared to determine the potential for Type I and Type II errors. It was determined that broader match criteria is more applicable to the forensic comparison of glass analysis because it can reduce the affect that micro-heterogeneity inherent in the glass fragments and a less than ideal sampling strategy can have on the interpretation of the results. Based on the test set reported here, a plus or minus four standard deviation (± 4s) match criterion yielded the lowest possibility of Type I and Type II errors. The developed LA-ICP-OES method has been shown to perform similarly to LA-ICP-MS in the discrimination among different sources of glass while offering the advantages of a lower cost of acquisition and operation of analytical instrumentation making ICP-OES a possible alternative elemental analysis method for the forensic laboratory. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Zircon Zoning, Trace Elements and U-Pb Dates Reveal Crustal Foundering Beneath the Pamir

NASA Astrophysics Data System (ADS)

Hacker, B. R.; Shaffer, M. E. F.; Ratschbacher, L.; Kylander-Clark, A. R.

2017-12-01

Xenoliths that erupted in the SE Pamir of Tajikistan at 11.2 Ma from 1000-1050°C and 90 km depth illuminate what happens when crust founders into the mantle. The xenoliths are a broad range of crustal rock types and contain abundant xenoliths whose U-Pb isotopic ratios and trace-element contents were examined by laser-ablation split stream inductively coupled plasma mass spectrometry. Cathodoluminescence imaging of the grains shows igneous cores with oscillatory zoning overprinted by substantial recrystallization. The bulk of the U-Pb dates are concordant and range from 160 Ma to 11 Ma. The range of dates suggest that the xenoliths were likely derived from the Jurassic-Cretaceous Andean-style magmatic arc and its Proterozoic-Mesozoic host rocks along the southern margin of Asia. The zircons show distinct changes in Eu anomaly, Lu/Gd ratio, and Ti concentrations that are interpreted to indicate garnet growth and minimal heating at 22-20 Ma, and then 200-300°C of heating, 25 km of burial, and alkali-carbonate melt injection at 14-11 Ma. These changes are interpreted to coincide with: i) heat input due to Indian slab breakoff at 22‒20 Ma; ii) rapid thickening and foundering of the Pamir lithosphere at 14‒11 Ma, prior to and synchronous with collision between deep Indian and Asian lithospheres beneath the Pamir.

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 intergrowth with REE fluorocarbonates; (4) the CO3-rich hydrothermal fluid corroded type-3, forming Nb-REE-poor zircons (type-3). Niobium and REE was no longer stable in the zircon structure and crystallized as fergusonite around the REE-Nb-leached zircon (type-4); (5) type-5 zircons are formed from more CO3-rich hydrothermal alteration of type-3 zircon. Therefore, type-4 and -5 zircons are often included in ankerite. Type 3-5 zircons at Nechalacho REE deposit were formed by leaching and/or dissolution of type-2 zircon in the presence of F- and/or CO3-rich hydrothermal fluid. The above mineral association indicates that three hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (1) F-rich hydrothermal stage caused the crystallization of REE-Nb-rich zircon (type-2 rim and type-3), with abundant formation of phlogophite and fluorite, (2) F-CO3-rich hydrothermal stage led to the replacement of a part of REE-Nb-F-rich zircon by REE fluorocarbonate and (3) hydrothermal stage rich in CO3 resulted in crystallization of REE-Nb-F-poor zircon and fergusonite, with ankerite. Increases of HFSE contents, REE-Nb-F-poor zircon (type-4 and -5) and fergusonite contents during progress of hydrothermal alteration show that REE and Nb in hydrothermal fluid in the Nechalacho REE deposit were finally concentrated into fergusonite by way of zircon.

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.

LA-ICP-MS depth profile analysis of apatite: Protocol and implications for (U-Th)/He thermochronometry

NASA Astrophysics Data System (ADS)

Johnstone, Samuel; Hourigan, Jeremy; Gallagher, Christopher

2013-05-01

Heterogeneous concentrations of α-producing nuclides in apatite have been recognized through a variety of methods. The presence of zonation in apatite complicates both traditional α-ejection corrections and diffusive models, both of which operate under the assumption of homogeneous concentrations. In this work we develop a method for measuring radial concentration profiles of 238U and 232Th in apatite by laser ablation ICP-MS depth profiling. We then focus on one application of this method, removing bias introduced by applying inappropriate α-ejection corrections. Formal treatment of laser ablation ICP-MS depth profile calibration for apatite includes construction and calibration of matrix-matched standards and quantification of rates of elemental fractionation. From this we conclude that matrix-matched standards provide more robust monitors of fractionation rate and concentrations than doped silicate glass standards. We apply laser ablation ICP-MS depth profiling to apatites from three unknown populations and small, intact crystals of Durango fluorapatite. Accurate and reproducible Durango apatite dates suggest that prolonged exposure to laser drilling does not impact cooling ages. Intracrystalline concentrations vary by at least a factor of 2 in the majority of the samples analyzed, but concentration variation only exceeds 5x in 5 grains and 10x in 1 out of the 63 grains analyzed. Modeling of synthetic concentration profiles suggests that for concentration variations of 2x and 10x individual homogeneous versus zonation dependent α-ejection corrections could lead to age bias of >5% and >20%, respectively. However, models based on measured concentration profiles only generated biases exceeding 5% in 13 of the 63 cases modeled. Application of zonation dependent α-ejection corrections did not significantly reduce the age dispersion present in any of the populations studied. This suggests that factors beyond homogeneous α-ejection corrections are the dominant source of overdispersion in apatite (U-Th)/He cooling ages.

Inductively coupled plasma mass spectrometry with a twin quadrupole instrument using laser ablation sample introduction and monodisperse dried microparticulate injection

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

Allen, Lloyd A.

1996-10-17

The focus of this dissertation is the use of a twin quadrupole inductively coupled plasma mass spectrometer (ICP-MS) for the simultaneous detection of two m/z values. The twin quadrupole ICP-MS is used with laser ablation sample introduction in both the steady state (10 Hz) and single pulse modes. Steady state signals are highly correlated and the majority of flicker noise cancels when the ratio is calculated. Using a copper sample, the isotope ratio 63Cu +/ 65Cu + is measured with a relative standard deviation (RSD) of 0.26%. Transient signals for single laser pulses are also obtained. Copper isotope ratio measurementsmore » for several laser pulses are measured with an RSD of 0.85%. Laser ablation (LA) is used with steel samples to assess the ability of the twin quadrupole ICP-MS to eliminate flicker noise of minor components of steel samples. Isotopic and internal standard ratios are measured in the first part of this work. The isotope ratio 52Cr +/ 53Cr + (Cr present at 1.31 %) can be measured with an RSD of 0.06 % to 0.1 %. For internal standard elements, RSDs improve from 1.9 % in the Cr + signal to 0.12% for the ratio of 51V + to 52Cr +. In the second part of this work, one mass spectrometer is scanned while the second channel measures an individual m/z value. When the ratio of these two signals is calculated, the peak shapes in the mass spectrum are improved significantly. Pulses of analyte and matrix ions from individual drops are measured simultaneously using the twin quadrupole ICP-MS with monodisperse dried microparticulate injection (MDMI). At modest Pb concentrations (500 ppm), a shoulder on the leading edge of the Li + signal becomes apparent. Space charge effects are consistent with the disturbances seen.« less

In situ x-ray surface diffraction chamber for pulsed laser ablation film growth studies

NASA Astrophysics Data System (ADS)

Tischler, J. Z.; Eres, G.; Lowndes, D. H.; Larson, B. C.; Yoon, M.; Chiang, T.-C.; Zschack, Paul

2000-06-01

Pulsed laser deposition is highly successful for growing complex films such as oxides for substrate buffer layers and HiTc oxide superconductors. A surface diffraction chamber has been constructed to study fundamental aspects of non-equilibrium film growth using pulsed laser deposition. Due to the pulsed nature of the ablating laser, the deposited atoms arrive on the substrate in short sub-millisecond pulses. Thus monitoring the surface x-ray diffraction following individual laser pulses (with resolution down to ˜1 ms) provides direct information on surface kinetics and the aggregation process during film growth. The chamber design, based upon a 2+2 surface diffraction geometry with the modifications necessary for laser ablation, is discussed, and initial measurements on homo-epitaxial growth of SrTiO3 are presented.

Updates of the KArLE Experiment: New Libs Calibration Under High Vacuum for the Quantification of Potassium in Basalt for In Situ Geochronology

NASA Technical Reports Server (NTRS)

Devismes, D.; Cohen, B. A.; Li, Z.-H.; Miller, J. S.

2014-01-01

In planetary exploration, in situ absolute geochronology is one of the main important measurements that needs to be accomplished. Until now, on Mars, the age of the surface is only determined by crater density counting, which gives relative ages. These ages can have a lot of uncertainty as they depend on many parameters. More than that, the curves must be ties to absolute ages. Thus far, only the lost lander Beagle 2 was designed to conduct absolute geochronology measurements, though some recent attempts using MSL Curiosity show that this investigation is feasible and should be strongly encouraged for future flight. Experimental: The Potassium (K)-Argon Laser Experiment (KArLE) is being developed at MSFC through the NASA Planetary Instrument Definition and Development Program (PIDDP). The goal of this experiment is to provide in situ geochronology based on the K-Ar method. A laser ablates a rock under high vacuum, creating a plasma which is sensed by an optical spectrometer to do Laser Induced Breakdown Spectroscopy (LIBS). The ablated material frees gases, including radiogenic 40Ar,which is measured by a mass spectrometer (MS). As the potassium is a content and the 40Ar is a quantity, the ablated mass needed in order to relate them. The mass is given by the product of the ablated volume by the density of this material. So we determine the mineralogy of the ablated material with the LIBS spectra and images and calculate its density. The volume of the pit is measured by using microscopy. LIBS measurement of K under high vacuum: Three independant projects [1, 2, 3] including KArLE, are developing geochronological instruments based on this LA-LIBS-MS method. Despite several differences in their setup, all of them have validated the methods with analyses and ages. However, they all described difficulties with the LIBS measurements of K [3,4]. At ambient pressure, the quantification of K by LIBS on geological materials can be accurate [5]. However the protocol of the LA-LIBS-MS experiment required hundreds of shots under high vacuum in order to free enough 40Ar* to be measured by the QMS. This long duration of ablation may induces significant changes in the LIBS spectra. The pressure may increases by orders of magnitudewithin the chamber and the laser pit geometry can change the effectiveness of ablation and intensity of plasma light received. These effects introduce variation between the first and last spectra and so the quantification of K is more complex. The ablation of one crater can give, depending on the protocol of acquisition, from tens to hundreds of spectra. Protocol and results: We are in the process of further characterizing the variation introduced into LIBS spectra by the use of hundreds of laser shots, and definining a protocol that can be used to ensure accuracy and reporoducibility in the results.We are using natural rock powder standards fused in a furnace, as well as mars analog samples with known K content. We will show the result of the calibration and some new statistical approaches in order to apprehend the effects of the long time ablation on rocks under high vacuum.

Age and source of terrigenous rocks of the turan group of the bureya terrane of the eastern part of the central Asian foldbelt: Results of geochemical (Sm-Nd) and geochronological (U-Pb LA-ICP-MS) studies

NASA Astrophysics Data System (ADS)

Sorokin, A. A.; Smirnov, Yu. V.; Kotov, A. B.; Kovach, V. P.

2014-06-01

According to Sm-Nd isotopic-geochemical studies, the t Nd(DM) of the terrigenous rocks of the Turan Group of the Bureya terrane is 1.4-1.5 Ga and their sources are Precambrian rocks and (or) younger effusive rocks, the formation of which is related to the reworking of the Late Precambrian continental crust. The U-Pb LA-ICP-MS geochronological studies indicate dominant Vendian-Cambrian (588-483 Ma) and Late Riphean (865-737 Ma) detrital zircons. Our data point to their accumulation at the beginning of the Paleozoic rather than in the Precambrian as is accepted in modern stratigraphic schemes.

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 the Proterozoic age peaks are consistent with a Dalradian source. Although the age spectra for each formation are broadly similar, the proportions of age populations differ and age peaks present in the Anstruther Formation are absent in other formations. For instance, the Anstruther Formation has a significantly larger proportion of Archaean-aged zircons compared to the Pittenweem Formation, and contains a 1.3 Ga peak which is absent in the other formations. This suggests that source areas evolved throughout the deposition of the Strathclyde Group. The dominance of Mesoproterozoic and Palaeoproterozoic ages relative to Palaeozoic ages contrasts to similar ages units in the Pennine Basin and offshore North Sea, where the latter dominate the age spectra (Hallsworth et al., 2000; Morton et al., 2001). This may reflect the proximity of the Dalradian terrane and organisation of river systems draining into the Fife section of the Midland Valley during the Dinantian. References: Browne, M.A. et al. (1997). A lithostratigraphical framework for the Carboniferous rocks of the Midland Valley of Scotland. BGS Technical Report WA/96/29 Owens, B. et al. (2005). Reappraisal of the Mississippian palynostratigraphy of the East Fife coast, Scotland, United Kingdom. Palynology, 29, 23-47 Hallsworth et al (2000). Carboniferous sand provenance in the Pennine Basin. Sedimentary Geology, 137, 137-145 Morton et al (2001). Zircon age and heavy mineral constraints on provenance of North Sea Carboniferous sandstones. Marine and petroleum geology, 18, 319-337

Timing of crust formation and recycling in accretionary orogens: Insights learned from the western margin of South America

NASA Astrophysics Data System (ADS)

Bahlburg, Heinrich; Vervoort, Jeffrey D.; Du Frane, S. Andrew; Bock, Barbara; Augustsson, Carita; Reimann, Cornelia

2009-12-01

Accretionary orogens are considered major sites of formation of juvenile continental crust. In the central and southern Andes this is contradicted by two observations: siliciclastic fills of Paleozoic basins in the central Andean segment of the accretionary Terra Australis Orogen consist almost exclusively of shales and mature sandstones; and magmatic rocks connected to the Famatinian (Ordovician) and Late Paleozoic magmatic arcs are predominantly felsic and characterized by significant crustal contamination and strongly unradiogenic Nd isotope compositions. Evidence of juvenile crustal additions is scarce. We present laser ablation (LA)-ICPMS U-Pb ages and LA-MC-ICPMS Hf isotope data of detrital zircons from seven Devonian to Permian turbidite sandstones incorporated into a Late Paleozoic accretionary wedge at the western margin of Gondwana in northern Chile. The combination with Nd whole-rock isotope data permits us to trace the evolution of the South American continental crust through several Proterozoic and Paleozoic orogenic cycles. The analyzed detrital zircon spectra reflect all Proterozoic orogenic cycles representing the step-wise evolution of the accretionary SW Amazonia Orogenic System between 2.0 and 0.9 Ga, followed by the Terra Australis Orogen between 0.9 and 0.25 Ga. The zircon populations are characterized by two prominent maxima reflecting input from Sunsas (Grenville) age magmatic rocks (1.2-0.9 Ga) and from the Ordovician to Silurian Famatinian magmatic arc (0.52-0.42 Ga). Grains of Devonian age are scarce or absent from the analyzed zircon populations. The Hf isotopic compositions of selected dated zircons at the time of their crystallization ( ɛHf ( T) ; T = 3.3-0.25 Ga) vary between - 18 and + 11. All sandstones have a significant juvenile component; between 20 and 50% of the zircons from each sedimentary rock have positive ɛHf ( T) and can be considered juvenile. The majority of the juvenile grains have Hf-depleted mantle model ages (Hf TDM) between 1.55 and 0.8 Ga, the time of the Rondonia-San Ignacio and Sunsas orogenic events on the Amazonia craton. The corresponding whole-rock ɛNd ( T) values fot these same rocks are between - 8 and - 3 indicating a mixture of older evolved and juvenile sources. Nd-depleted mantle model ages (Nd TDM*) are between 1.5 and 1.2 Ga and coincide broadly with the zircon Hf model ages. Our data indicate that the Paleo- and Mesoproterozoic SW Amazonia Orogenic System, and the subsequent Neoproterozoic and Paleozoic Terra Australis Orogen in the region of the central and southern Andes, developed following two markedly different patterns of accretionary orogenic crustal evolution. The SW Amazonia Orogenic System developed by southwestward growth over approximately 1.1 Ga through a combination of accretion of juvenile material and crustal recycling typical of the extensional or retreating mode of accretionary orogens. In contrast, the central Andean segment of the Terra Australis Orogen evolved from 0.9 to 0.25 Ga in the compressional or advancing mode in a relatively fixed position without the accretion of oceanic crustal units or large scale input of juvenile material to the orogenic crust. Here, recycling mainly of Mesoproterozoic continental crust has been the dominant process of crustal evolution.

An Impaired View of Earth's Early History

NASA Astrophysics Data System (ADS)

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

2014-12-01

The Hf and Nd isotope records of Earth's early history are sparse, difficult to interpret, and controversial, much like the few remnants of crust older than 4 Ga. New analytical techniques have been brought to bear on this problem but despite this recent work­-or, perhaps, because of it-the record is no clearer than it was 15 years ago. Several studies, based on highly variable calculated initial isotopic compositions, have argued for highly heterogeneous crust and mantle reservoirs in the early Earth1,2 and an ultra-depleted Eoarchean mantle3. These data come mostly from two sources: Hf-Nd isotope analyses of ultramafic rocks and Hf isotope analyses of zircons by solution or laser ablation. An important question for understanding the chemical evolution of the early Earth is: Do these data offer a unique window into the early Earth or are they artefacts not representative of crust/mantle evolution, giving an impaired view of the Earth's early history? In complex samples, measured isotopic compositions can result from open-system behavior in easily altered ultramafic compositions, in multicomponent, polymetamorphic gneisses, or in zircons with multiple generations of growth. Perhaps most importantly, accurate age assignment is often lacking, compromised, or impossible in these rocks, making calculation of initial epsilon Hf and Nd values ambiguous at best. In order to gain insight into crust mantle evolution in the early Earth we need, above all, a robust and unambiguous isotopic record to work with. This can be achieved by integrating zircon U-Pb and Hf and whole-rock Hf and Nd isotope compositions in relatively undisturbed igneous rocks with well-constrained ages. When this approach is used apparent isotopic heterogeneity decreases and a simpler model for crust-mantle evolution in the early Earth emerges. Careful screening of geological relationships, petrology, and geochemistry of samples from the early Earth should be done before interpreting isotopic data. Indiscriminate inclusion of isotope data from disturbed and multicomponent rocks and zircons will do more to obscure our understanding of the Hf-Nd isotope evolution of the Earth than to clarify it. [1] Harrison et al. 2005, Science 310, 1947-1950. [2] Blichert-Toft and Albarède, 2008, EPSL 265, 686-702. [3] Hoffmann et al., 2010, GCA, 74, 7236-7260.

Role of laser ablation-inductively coupled plasma-mass spectrometry in cultural heritage research: a review.

PubMed

Giussani, Barbara; Monticelli, Damiano; Rampazzi, Laura

2009-03-02

Cultural heritage represents a bridge between the contemporary society and the past populations, and a strong collaboration between archaeologists, art historians and analysts may lead to the decryption of the information hidden in an ancient object. Quantitative elemental compositional data play a key role in solving questions concerning dating, provenance, technology, use and the relationship of ancient cultures with the environment. Nevertheless, the scientific investigation of an artifact should be carried out complying with some important constraints: above all the analyses should be as little destructive as possible and performed directly on the object to preserve its integrity. Laser ablation sampling coupled to inductively coupled plasma-mass spectrometry (LA-ICP-MS) fulfils these requirements exhibiting comparably strong analytical performance in trace element determination. This review intends to show through the applications found in the literature how valuable is the contribution of LA-ICP-MS in the investigation of ancient materials such as obsidian, glass, pottery, human remains, written heritage, metal objects and miscellaneous stone materials. The main issues related to cultural heritage investigation are introduced, followed by a brief description of the features of this technique. An overview of the exploitation of LA-ICP-MS is then presented. Finally, advantages and drawbacks of this technique are critically discussed: the fit for purpose and prospects of the use of LA-ICP-MS are presented.

Cluster formation in laser-induced ablation and evaporation of solids observed by laser ionization time-of-flight mass spectrometry and scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Tench, R. J.; Balooch, M.; Bernardez, L.; Allen, Mike J.; Siekhaus, W. J.; Olander, D. R.; Wang, W.

1990-04-01

Laser ionization time-of-flight mass analysis (LIMA) used pulses (5ns) of a frequency-quadrupled Nd-YAG laser (266 nm) focused onto spots of 4 to 100 microns diameter to ablate material, and a reflectron time of flight tube to mass-analyze the plume. The observed mass spectra for Si, Pt, SiC, and UO 2 varied in the distribution of ablation products among atoms, molecules and clusters, depending on laser power density and target material. Cleaved surfaces of highly oriented pyrolytic graphite (HOPG) positioned at room temperature either 10 cm away from materials ablated at 10(exp -5) Torr by 1 to 3 excimer laser (308 nm) pulses of 20 ns duration or 1 m away from materials vaporized at 10(exp -8) Torr by 10 Nd-Glass laser pulses of 1 ms duration were analyzed by Scanning Tunneling Microscopy (STM) in air with angstrom resolution. Clusters up to 30 A in diameter were observed.

The pre-Atlantic Hf isotope evolution of the east Laurentian continental margin: Insights from zircon in basement rocks and glacial tillites from northern New Jersey and southeastern New York

NASA Astrophysics Data System (ADS)

Zirakparvar, N. Alex; Setera, Jacob; Mathez, Edmond; Vantongeren, Jill; Fossum, Ryanna

2017-02-01

This paper presents laser ablation U-Pb age and Hf isotope data for zircons from basement rocks and glacial deposits in northern New Jersey and southeastern New York. The purpose is to understand the eastern Laurentian continental margin's Hf isotope record in relation to its geologic evolution prior to the opening of the Atlantic Ocean. The basement samples encompass a Meso- to Neoproterozoic continental margin arc, an anatectic magmatic suite, as well as a Late Ordovician alkaline igneous suite emplaced during post-orogenic melting of the lithospheric mantle. Additional samples were collected from terminal moraines of two Quaternary continental ice sheets. Across the entire dataset, zircons with ages corresponding to the timing of continental margin arc magmatism ( 1.4 Ga to 1.2 Ga) have positive εHf(initial) values that define the more radiogenic end of a crustal evolution array. This array progresses towards more unradiogenic εHf(initial) values along a series of low 176Lu/177Hf (0.022 to 0.005) trajectories during subsequent anatectic magmatism ( 1.2 Ga to 1.0 Ga) and later metamorphic and metasomatic re-working ( 1.0 Ga to 0.8 Ga) of the continental margin arc crust. In contrast, nearly chondritic εHf(initial) values from the Late Ordovician alkaline magmas indicate that the Laurentian margin was underlain by a re-fertilized mantle source. Such a source may have developed by subduction enrichment of the mantle wedge beneath the continental margin during the Mesoproterozoic. Additionally, preliminary data from a metasedimentary unit of unknown provenance hints at the possibility that some of the sediments occupying this portion of the Laurentian margin prior to the Ordovician were sourced from crust older than 1.9 Ga.

Paleoproterozoic multistage metamorphic events in Jining metapelitic rocks from the Khondalite Belt in the North China Craton: Evidence from petrology, phase equilibria modelling and U-Pb geochronology

NASA Astrophysics Data System (ADS)

Cai, Jia; Liu, Fulai; Liu, Pinghua

2017-05-01

Metapelitic rocks of the Jining Complex (sillimanite-cordierite-garnet (Sil-Crd-Grt) gneisses, sillimanite-garnet (Sil-Grt) gneisses and quartzofeldspathic rocks) are exposed in the eastern segment of the Khondalite Belt (KB) in the North China Craton (NCC). The Sil-Crd-Grt gneisses have preserved polyphase mineral assemblages and microstructural evidence of anatexis, resulting from biotite dehydration melting. Petrological observations revealed that the Sil-Crd-Grt gneisses contain three metamorphic assemblages: a peak assemblage of garnet porphyroblast and matrix biotite + sillimanite + K-feldspar + plagioclase + quartz + ilmenite + magnetite, a post-peak near-isothermal decompressional assemblage of garnet + cordierite + biotite + sillimanite + K-feldspar + plagioclase + quartz + ilmenite + magnetite, and a decompressional cooling assemblage of garnet + biotite + cordierite + K-feldspar + plagioclase + quartz + ilmenite + magnetite. A clockwise P-T path was defined involving the inferred peak stage followed by post-peak near-isothermal decompression and decompressional cooling stages, with P-T conditions of 790-825 °C and 9-10 kbar, 810-890 °C and 6.0-6.5 kbar, and 780-810 °C and 4.0-5.5 kbar, respectively. Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) U-Pb analyses of the Sil-Crd-Grt gneisses and Sil-Grt gneisses for the detrital and metamorphic zircons yielded a protolith age of ∼2.0 Ga and the late Paleoproterozoic metamorphic age of 1895-1885 Ma. The results reveal that the metapelitic rocks of the Jining Complex underwent continent-continent subduction or collision in the peak metamorphic stage, followed by a post-collisional exhumation event in the post-peak decompressional stage, and a subsequent decompressional cooling stage between the Yinshan and Ordos blocks to form the Paleoproterozoic KB.

The Middlesex Fells Volcanic Complex: A Revised Tectonic Model based on Geochronology, Geochemistry, and Field Data

NASA Astrophysics Data System (ADS)

Hampton, R.

2017-12-01

The Boston Bay area is composed of several terranes originating on the paleocontinent of Avalonia, an arc terrane that accreted onto the continent of Laurentia during the Devonian. Included in these terranes is the Middlesex Fells Volcanic Complex, a bimodal complex composed of both intrusive and extrusive igneous rocks. Initial studies suggested that this volcanic complex formed during a rift event as the Avalonian continent separated from its parent continent 700-900 Ma. New geochemical and geochronological data and field relationships observed in this study establishes a new tectonic model. U-Pb laser ablation zircon data on four samples from different units within the complex reveal that the complex erupted 600 Ma. ICP-MS geochemical analysis of the metabasalt member of the complex yield a trace element signature enriched in Rb, Pb, and Sr and depleted in Th, indicating a subduction component to the melt and interpreted as an eruption into a back-arc basin. The felsic units similarly have an arc related signature when plotted on trace element spider diagrams and tectonic discrimination diagrams. Combined with the field relationships, including an erosional unconformity, stratigraphic and intrusional relationships and large faults from episodic extension events, this data suggests that the Middlesex Fells Volcanic Complex was erupted as part of the arc-sequence of Avalonia and as part of the formation of a back-arc basin well after Avalonia separated from its parent continent. This model presents a significantly younger eruption scenario for the Middlesex Fells Volcanics than previously hypothesized and may be used to study and compare to other volcanics from Avalon terranes in localities such as Newfoundland and the greater Boston area.

Lutetian arc-type magmatism along the southern Eurasian margin: New U-Pb LA-ICPMS and whole-rock geochemical data from Marmara Island, NW Turkey

NASA Astrophysics Data System (ADS)

Ustaömer, P. Ayda; Ustaömer, Timur; Collins, Alan S.; Reischpeitsch, Jörg

2009-07-01

The rocks of Turkey, Greece and Syria preserve evidence for the destruction of Tethys, the construction of much of the continental crust of the region and the formation of the Tauride orogenic belt. These events occurred between the Late Cretaceous and Miocene, but the detailed evolution of the southern Eurasian margin during this period of progressive continental accretion is largely unknown. Marmara Island is a basement high lying at a key location in the Cenozoic Turkish tectonic collage, with a Palaeogene suture zone to the south and a deep Eocene sedimentary basin to the north. North-dipping metamorphic thrust sheets make up the island and are interlayered with a major metagranitoid intrusion. We have dated the intrusion by Laser Ablation ICP-MS analysis of U and Pb isotopes on zircon separates to 47.6 ± 2 Ma. We also performed major- and trace-elemental geochemical analysis of 16 samples of the intrusion that revealed that the intrusion is a calc-alkaline, metaluminous granitoid, marked by Nb depletion relative to LREE and LIL-element enrichment when compared to ocean ridge granite (ORG). We interpret the metagranitoid sill as a member of a mid-Eocene magmatic arc, forming a 30 km wide and more than 200 km long arcuate belt in NW Turkey that post-dates suturing along the İzmir-Ankara-Erzincan Suture zone. The arc magmatism was emplaced at the early stages of mountain building, related to collision of Eurasia with the Menderes-Taurus Platform in early Eocene times. Orogenesis and magmatism loaded the crust to the north creating coeval upward-deepening marine basins partially filled by volcanoclastic sediments.

Progress integrating ID-TIMS U-Pb geochronology with accessory mineral geochemistry: towards better accuracy and higher precision time

NASA Astrophysics Data System (ADS)

Schoene, B.; Samperton, K. M.; Crowley, J. L.; Cottle, J. M.

2012-12-01

It is increasingly common that hand samples of plutonic and volcanic rocks contain zircon with dates that span between zero and >100 ka. This recognition comes from the increased application of U-series geochronology on young volcanic rocks and the increased precision to better than 0.1% on single zircons by the U-Pb ID-TIMS method. It has thus become more difficult to interpret such complicated datasets in terms of ashbed eruption or magma emplacement, which are critical constraints for geochronologic applications ranging from biotic evolution and the stratigraphic record to magmatic and metamorphic processes in orogenic belts. It is important, therefore, to develop methods that aid in interpreting which minerals, if any, date the targeted process. One promising tactic is to better integrate accessory mineral geochemistry with high-precision ID-TIMS U-Pb geochronology. These dual constraints can 1) identify cogenetic populations of minerals, and 2) record magmatic or metamorphic fluid evolution through time. Goal (1) has been widely sought with in situ geochronology and geochemical analysis but is limited by low-precision dates. Recent work has attempted to bridge this gap by retrieving the typically discarded elution from ion exchange chemistry that precedes ID-TIMS U-Pb geochronology and analyzing it by ICP-MS (U-Pb TIMS-TEA). The result integrates geochemistry and high-precision geochronology from the exact same volume of material. The limitation of this method is the relatively coarse spatial resolution compared to in situ techniques, and thus averages potentially complicated trace element profiles through single minerals or mineral fragments. In continued work, we test the effect of this on zircon by beginning with CL imaging to reveal internal zonation and growth histories. This is followed by in situ LA-ICPMS trace element transects of imaged grains to reveal internal geochemical zonation. The same grains are then removed from grain-mount, fragmented, and analyzed by U-Pb TIMS-TEA. In situ trace element transects are used to model predicted TIMS-TEA trace element concentrations to test whether complicated trace element profiles undermine U-Pb TIMS-TEA data. We find good agreement between predicted and measured TIMS-TEA data, and can argue that the measured ID-TIMS U-Pb date corresponds to the time at which the geochemical signature measured by TIMS-TEA was acquired. Thus, in a hypothetical magma that is differentiating through AFC processes on timescales resolvable by geochronology, U-Pb TIMS-TEA should usually be a robust indicator of magma evolution through time. We present data from two ca. 40-30 Ma alpine intrusions from northern Italy: the southern Adamello batholith and the Bergell intrusion. The relatively young age of these intrusions permits uncertainties on individual zircon or zircon fragments as good as 10 ka, while zircon populations from individual hand samples often record zircon growth of >200 ka. Using the methodologies described above, we explore whether these zircons record in situ magmatic differentiation or introduction of antecrystic zircon to magma batches, and integrate these data to gain a better understanding of magma storage, differentiation and emplacement as a function of pressure, temperature, and time. These methods are a promising step towards interpreting complicated geochronologic data in ashbed samples as well through a better understanding of magmatic processes that precede eruption.

High-Precision Measurement of Eu/Eu* in Geological Glasses via LA-ICP-MS Analysis

NASA Technical Reports Server (NTRS)

Tang, Ming; McDonough, William F.; Arevalo, Ricardo, Jr.

2014-01-01

Elemental fractionation during laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis has been historically documented between refractory and volatile elements. In this work, however, we observed fractionation between light rare earth elements (LREEs) and heavy rare earth elements (HREEs) when using ablation strategies involving large spot sizes (greater than 100 millimeters) and line scanning mode. In addition: (1) ion yields decrease when using spot sizes above 100 millimeters; (2) (Eu/Eu*)(sub raw) (i.e. Europium anomaly) positively correlates with carrier gas (He) flow rate, which provides control over the particle size distribution of the aerosol reaching the ICP; (3) (Eu/Eu*)(sub raw) shows a positive correlation with spot size, and (4) the changes in REE signal intensity, induced by the He flow rate change, roughly correlate with REE condensation temperatures. The REE fractionation is likely driven by the slight but significant difference in their condensation temperatures. Large particles may not be completely dissociated in the ICP and result in preferential evaporation of the less refractory LREEs and thus non-stoichiometric particle-ion conversion. This mechanism may also be responsible for Sm-Eu-Gd fractionation as Eu is less refractory than Sm and Gd. The extent of fractionation depends upon the particle size distribution of the aerosol, which in turn is influenced by the laser parameters and matrix. Ablation pits and lines defined by low aspect ratios produce a higher proportion of large particles than high aspect ratio ablation, as confirmed by measurements of particle size distribution in the laser induced aerosol. Therefore, low aspect ratio ablation introduces particles that cannot be decomposed and/or atomized by the ICP and thus results in exacerbated elemental fractionation. Accurate quantification of REE concentrations and Eu/Eu* requires reduction of large particle production during laser ablation. For the reference materials analyzed in this work, the 100 millimeters spot measurements of Eu/Eu* agreed with GeoRem preferred values within 3 percent. Our long-term analyses of Eu/Eu* in MPI-DING glass KL-2G and USGS glass BIR-1G were reproducible at 3 percent (2 RSD).

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.

Detrital and volcanic zircon U-Pb ages from southern Mendoza (Argentina): An insight on the source regions in the northern part of the Neuquén Basin

NASA Astrophysics Data System (ADS)

Naipauer, Maximiliano; Tapia, Felipe; Mescua, José; Farías, Marcelo; Pimentel, Marcio M.; Ramos, Victor A.

2015-12-01

The infill of the Neuquén Basin recorded the Meso-Cenozoic geological and tectonic evolution of the southern Central Andes being an excellent site to investigate how the pattern of detrital zircon ages varies trough time. In this work we analyze the U-Pb (LA-MC-ICP-MS) zircon ages from sedimentary and volcanic rocks related to synrift and retroarc stages of the northern part of the Neuquén Basin. These data define the crystallization age of the synrift volcanism at 223 ± 2 Ma (Cerro Negro Andesite) and the maximum depositional age of the original synrift sediments at ca. 204 Ma (El Freno Formation). Two different pulses of rifting could be recognized according to the absolute ages, the oldest developed during the Norian and the younger during the Rhaetian-Sinemurian. The source regions of the El Freno Formation show that the Choiyoi magmatic province was the main source rock of sediment supply. An important amount of detrital zircons with Triassic ages was identified and interpreted as a source area related to the synrift magmatism. The maximum depositional age calculated for the Tordillo Formation in the Atuel-La Valenciana depocenter is at ca. 149 Ma; as well as in other places of the Neuquén Basin, the U-Pb ages calculated in the Late Jurassic Tordillo Formation do not agree with the absolute age of the Kimmeridgian-Tithonian boundary (ca. 152 Ma). The main source region of sediment in the Tordillo Formation was the Andean magmatic arc. Basement regions were also present with age peaks at the Carboniferous, Neoproterozoic, and Mesoproterozoic; these regions were probably located to the east in the San Rafael Block. The pattern of zircon ages summarized for the Late Jurassic Tordillo and Lagunillas formations were interpreted as a record of the magmatic activity during the Triassic and Jurassic in the southern Central Andes. A waning of the magmatism is inferred to have happened during the Triassic. The evident lack of ages observed around ca. 200 Ma suggests cessation of the synrift magmatism. The later increase in magmatic activity during the Early Jurassic is attributed to the onset of Andean subduction, with maximum peaks at ca. 191 and 179 Ma. The trough at ca. 165 Ma and the later increase in the Late Jurassic could be explained by changes in the relative convergence rate in the Andean subduction regime, or by the shift to a more mafic composition of the magmatism with minor zircon fertility.

U-Pb ages of detrital zircon from Cenozoic sediments in the southwestern Tarim Basin, NW China: Implications for Eocene-Pliocene source-to-sink relations and new insights into Cretaceous-Paleogene magmatic sources

NASA Astrophysics Data System (ADS)

Yang, Wei; Fu, Ling; Wu, Chaodong; Song, Yan; Jiang, Zhenxue; Luo, Qun; Zhang, Ziya; Zhang, Chen; Zhu, Bei

2018-05-01

A detailed investigation of potential provenance is still lacking in the southwestern Tarim Basin, which restricts our complete understanding of Cenozoic source-to-sink relations between the basin interior and the Pamir salient - western Kunlun Mountain Range. Debate also exists concerning the potential sources of the Paleogene and Cretaceous igneous detritus present in the Cenozoic sedimentary sequences. Here, we present U-Pb (LA-ICP-MS) ages of detrital zircons from the continuous Eocene-Pliocene sediment series in the well-exposed Aertashi section to investigate changes in sediment provenance through time. The U-Pb detrital zircon ages range widely from 45 to 3204 Ma and can be divided into seven main groups: 45-65 Ma (sub-peak at 49 Ma), 67-103 Ma (sub-peak at 95 Ma), 196-251 Ma (sub-peak at 208 Ma), 252-416 Ma (sub-peak at 296 Ma), 417-540 Ma (sub-peak at 446 Ma), 550-1429 Ma (sub-peaks at 614 Ma, 828 Ma and 942 Ma) and 1345-3204 Ma (sub-peaks at 1773 Ma and 2480 Ma). These zircons were mainly derived from the western Kunlun Mountain Range and northern Pamir salient to the west and south. The evolution of the provenance and source-to-sink relationship patterns in the southwestern Tarim Basin can be divided into three stages: (1) The Middle Eocene to Lower Oligocene sediments display a wide variety of detrital zircon ages, suggesting that the source area was extensive. (2) A major change in provenance occurred during the Late Oligocene to Early Miocene and was characterized by an abrupt increase in the proportion of Triassic and Lower Paleozoic igneous components, implying a significant adjustment in topography induced by the initial uplift and exhumation of the western Kunlun Mountain Range and northern Pamir salient. (3) In the Late Miocene, the source-to-sink system transformed again, and contributions of Triassic to Lower Paleozoic material weakened substantially due to the sufficient indentation of the Pamir salient. Our integrated analyses of zircon geochronology indicate that the main source terranes of the Paleogene and Cretaceous igneous detritus are the central and southern Pamir salient, respectively, which are speculated to have been continuously connected to the study area during Eocene-Pliocene times, although such detritus is scarce in certain formations and has not yet been detected.

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 intermediate to acidic metagranitoids with I-type affinity. The detrital zircon age spectra suggest a Neoproterozoic ancestry of the Glaneck Metamorphic Suite, which was located west of the Arabian Nubian Shield, probably next to the Trans-Saharan Belt. The early Paleozoic evolution of the recent Seckau Complex shows similarities to basement units of the Southalpine Unit, parts of the Austroalpine Unit and the Tatric and Veporic units of the Central Western Carpathians.

Direct determination of platinum group elements and their distributions in geological and environmental samples at the ng g(-1) level using LA-ICP-IDMS.

PubMed

Boulyga, Sergei F; Heumann, Klaus G

2005-10-01

Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) was applied to the direct and simultaneous determination of the platinum group elements (PGEs) Pt, Pd, Ru, and Ir in geological and environmental samples. A special laser ablation system with high ablation rates was used, along with sector field ICP-MS. Special attention was paid to deriving the distributions of PGEs in the pulverized samples. IDMS could not be applied to the (mono-isotopic) Rh, but the similar ablation behavior of Ru and Rh allowed Rh to be simultaneously determined via relative sensitivity coefficients. The laser ablation process produces hardly any oxide ions (which usually cause interference in PGE analysis with liquid sample injection), so the ICP-MS can be run in its low mass resolution but high-sensitivity mode. The detection limits obtained for the geological samples were 0.16 ng g(-1), 0.14 ng g(-1), 0.08 ng g(-1), 0.01 ng g(-1) and 0.06 ng g(-1) for Ru, Rh, Pd, Ir and Pt, respectively. LA-ICP-IDMS was applied to different geological reference materials (TDB-1, WGB-1, UMT-1, WMG-1, SARM-7) and the road dust reference material BCR-723, which are only certified for some of the PGEs. Comparisons with certified values as well as with indicative values from the literature demonstrated the validity of the LA-ICP-IDMS method. The PGE concentrations in subsamples of the road dust reference material correspond to a normal distribution, whereas the distributions in the geological reference materials TDB-1, WGB-1, UMT-1, WMG-1, and SARM-7 are more complex. For example, in the case of Ru, a logarithmic normal distribution best fits the analyzed concentrations in TDB-1 subsamples, whereas a pronounced nugget effect was found for Pt in most geological samples.

Petrography and zircon U-Pb isotopic study of the Bayanwulashan Complex: Constrains on the Paleoproterozoic evolution of the Alxa Block, westernmost North China Craton

NASA Astrophysics Data System (ADS)

Wu, Sujuan; Hu, Jianmin; Ren, Minghua; Gong, Wangbin; Liu, Yang; Yan, Jiyuan

2014-11-01

The Bayanwulashan Metamorphic Complex (BMC) exposes along the eastern margin of the Alxa Block, the westernmost part of the North China Craton (NCC). BMC is principally composed of metamorphic rocks with amphibole plagiogneiss, biotite plagioclase gneiss and granitic gneiss. Our research has been focused on the petrography and zircon U-Pb geochronology of the BMC to better understand the evolution of the Alxa Block and its relationship with the NCC. Evidences from field geology, petrography, and mineral chemistry indicate that two distinct metamorphic assemblages, the amphibolite and greenschist facies, had overprinted the preexisting granitic gneiss and suggest that the BMC experienced retrograde metamorphic episodes. The LA-ICP-MS zircon U-Pb ages reveal that the primary magmatic activities of BMC were at ca. 2.30-2.24 Ga and the two metamorphic events were at ca. 1.95-1.91 Ga and ca. 1.88-1.85 Ga respectively. These ages indicate that BMC initially intruded during Paleoproterozoic, not as previously suggested at Archean period. The Early Paleoproterozoic metamorphic records and the magmatic thermochronological data in BMC exhibit different evolution paths between the Alxa Block and the NCC. The Alxa Block was most likely an independent Early Paleoproterozoic terrain. Following different amalgamation processes, The Alxa Block combined with Western Block at ca. 1.95 Ga and then united with NCC at ca. 1.85 Ga.

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.

Laboratory technology and cosmochemistry

PubMed Central

Zinner, Ernst K.; Moynier, Frederic; Stroud, Rhonda M.

2011-01-01

Recent developments in analytical instrumentation have led to revolutionary discoveries in cosmochemistry. Instrumental advances have been made along two lines: (i) increase in spatial resolution and sensitivity of detection, allowing for the study of increasingly smaller samples, and (ii) increase in the precision of isotopic analysis that allows more precise dating, the study of isotopic heterogeneity in the Solar System, and other studies. A variety of instrumental techniques are discussed, and important examples of discoveries are listed. Instrumental techniques and instruments include the ion microprobe, laser ablation gas MS, Auger EM, resonance ionization MS, accelerator MS, transmission EM, focused ion-beam microscopy, atom probe tomography, X-ray absorption near-edge structure/electron loss near-edge spectroscopy, Raman microprobe, NMR spectroscopy, and inductively coupled plasma MS. PMID:21498689

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 should be less than 10 μm. Under the selected optimized analytical conditions, excellent agreements between the determined values and the reference values were achieved for the IAEA-S series standard reference materials and a set of six well-characterized, isotopic homogeneous sulfide standards (PPP-1, MoS2, MASS-1, P-GBW07267, P-GBW07268, P-GBW07270), validating the capability of the developed method for providing high-quality in situ S isotope data in sulfides and elemental sulfur. Copyright © 2016. Published by Elsevier B.V.

High temperature ultrasonic transducers for the generation of guided waves for non-destructive evaluation of pipes

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

Sinding, K.; Searfass, C.; Malarich, N.

2014-02-18

Applications for non-destructive evaluation and structural health monitoring of steam generators require ultrasonic transducers capable of withstanding the high temperatures of the pipes and heat exchangers. These applications require a strong coupling of the transducer to the heat exchanger’s complex geometry at the elevated temperatures. Our objective is to use spray-on piezo-electrics for depositing comb transducers onto the curved surfaces. This paper shows results for composite transducers such as lead zirconate titanate/ bismuth titanate and bismuth titanate/ lithium niobate. The comb transducers were prepared by precision laser ablation. The feasibility of producing second harmonic waves in rods with these spay-onmore » comb transducers was demonstrated and paves the way toward measuring material degradation early-on before crack initiation occurs.« less

Impact of stepwise ablation on the biatrial substrate in patients with persistent atrial fibrillation and heart failure.

PubMed

Jones, David G; Haldar, Shouvik K; Jarman, Julian W E; Johar, Sofian; Hussain, Wajid; Markides, Vias; Wong, Tom

2013-08-01

Ablation of persistent atrial fibrillation can be challenging, often involving not only pulmonary vein isolation (PVI) but also additional linear lesions and ablation of complex fractionated electrograms (CFE). We examined the impact of stepwise ablation on a human model of advanced atrial substrate of persistent atrial fibrillation in heart failure. In 30 patients with persistent atrial fibrillation and left ventricular ejection fraction ≤35%, high-density CFE maps were recorded biatrially at baseline, in the left atrium (LA) after PVI and linear lesions (roof and mitral isthmus), and biatrially after LA CFE ablation. Surface area of CFE (mean cycle length ≤120 ms) remote to PVI and linear lesions, defined as CFE area, was reduced after PVI (18.3±12.03 to 10.2±7.1 cm(2); P<0.001) and again after linear lesions (7.7±6.5 cm(2); P=0.006). Complete mitral isthmus block predicted greater CFE reduction (P=0.02). Right atrial CFE area was reduced by LA ablation, from 25.9±14.1 to 12.9±11.8 cm(2) (P<0.001). Estimated 1-year arrhythmia-free survival was 72% after a single procedure. Incomplete linear lesion block was an independent predictor of arrhythmia recurrence (hazard ratio, 4.69; 95% confidence interval, 1.05-21.06; P=0.04). Remote LA CFE area was progressively reduced following PVI and linear lesions, and LA ablation reduced right atrial CFE area. Reduction of CFE area at sites remote from ablation would suggest either regression of the advanced atrial substrate or that these CFE were functional phenomena. Nevertheless, in an advanced atrial fibrillation substrate, linear lesions after PVI diminished the target area for CFE ablation, and complete lesions resulted in a favorable clinical outcome.

Coated conductors

DOEpatents

Arendt, Paul N.; Foltyn, Stephen R.; Stan, Liliana; Usov, Igor O.; Wang, Haiyan

2010-06-15

Articles are provided including a base substrate having a layer of an IBAD oriented material thereon, and, a layer of barium-containing material selected from the group consisting of barium zirconate, barium hafnate, barium titanate, barium strontium titanate, barium dysprosium zirconate, barium neodymium zirconate and barium samarium zirconate, or a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates upon the layer of an IBAD oriented material. Such articles can further include thin films of high temperature superconductive oxides such as YBCO upon the layer of barium-containing material selected from the group consisting of barium zirconate, barium hafnate, barium titanate, barium strontium titanate, barium dysprosium zirconate, barium neodymium zirconate and barium samarium zirconate, or a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates.

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.

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 principal multi-component analysis.

Elemental bioimaging by means of LA-ICP-OES: investigation of the calcium, sodium and potassium distribution in tobacco plant stems and leaf petioles.

PubMed

Thyssen, G M; Holtkamp, M; Kaulfürst-Soboll, H; Wehe, C A; Sperling, M; von Schaewen, A; Karst, U

2017-06-21

Laser ablation-inductively coupled plasma-optical emission spectroscopy (LA-ICP-OES) is presented as a valuable tool for elemental bioimaging of alkali and earth alkali elements in plants. Whereas LA-ICP-OES is commonly used for micro analysis of solid samples, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) has advanced to the gold standard for bioimaging. However, especially for easily excitable and ubiquitous elements such as alkali and earth alkali elements, LA-ICP-OES holds some advantages regarding simultaneous detection, costs, contamination, and user-friendliness. This is demonstrated by determining the calcium, sodium and potassium distribution in tobacco plant stem and leaf petiole tissues. A quantification of the calcium contents in a concentration range up to 1000 μg g -1 using matrix-matched standards is presented as well. The method is directly compared to a LA-ICP-MS approach by analyzing parallel slices of the same samples.

Volume Measurements of Laser-generated Pits for In Situ Geochronology using KArLE (Potassium-Argon Laser Experiment)

NASA Technical Reports Server (NTRS)

French, R. A.; Cohen, B. A.; Miller, J. S.

2014-01-01

The Potassium-Argon Laser Experiment( KArLE), is composed of two main instruments: a spectrometer as part of the Laser-Induced Breakdown Spectroscopy (LIBS) method and a Mass Spectrometer (MS). The LIBS laser ablates a sample and creates a plasma cloud, generating a pit in the sample. The LIBS plasma is measured for K abundance in weight percent and the released gas is measured using the MS, which calculates Ar abundance in mols. To relate the K and Ar measurements, total mass of the ablated sample is needed but can be difficult to directly measure. Instead, density and volume are used to calculate mass, where density is calculated based on the elemental composition of the rock (from the emission spectrum) and volume is determined by pit morphology. This study aims to reduce the uncertainty for KArLE by analyzing pit volume relationships in several analog materials and comparing methods of pit volume measurements and their associated uncertainties.

Multielemental analysis of prehistoric animal teeth by laser-induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry

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

Galiova, Michaela; Kaiser, Jozef; Fortes, Francisco J.

2010-05-01

Laser-induced breakdown spectroscopy (LIBS) and laser ablation (LA) inductively coupled plasma (ICP) mass spectrometry (MS) were utilized for microspatial analyses of a prehistoric bear (Ursus arctos) tooth dentine. The distribution of selected trace elements (Sr, Ba, Fe) was measured on a 26 mmx15 mm large and 3 mm thick transverse cross section of a canine tooth. The Na and Mg content together with the distribution of matrix elements (Ca, P) was also monitored within this area. The depth of the LIBS craters was measured with an optical profilometer. As shown, both LIBS and LA-ICP-MS can be successfully used for themore » fast, spatially resolved analysis of prehistoric teeth samples. In addition to microchemical analysis, the sample hardness was calculated using LIBS plasma ionic-to-atomic line intensity ratios of Mg (or Ca). To validate the sample hardness calculations, the hardness was also measured with a Vickers microhardness tester.« less

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 content from core to rim, or correlation with zoning, age, U content, Th/U ratio, or concordance in U-Pb age. Thus, it is likely that other variables, in addition to temperature and a_{TiO2}, are important in controlling the Ti content of zircon. The Ti contents of igneous zircons from different rock types worldwide overlap significantly. However, on a more restricted regional scale, apparent Ti-in-zircon temperatures correlate with whole-rock SiO2 and HfO2 for plutonic rocks of the Sierra Nevada batholith, averaging 750°C at 50 wt.% SiO2 and 600°C at 75 wt.%. Among felsic plutons in the Sierra, peraluminous granites average 610 ± 88°C, while metaluminous rocks average 694 ± 94°C. Detrital zircons from the Jack Hills, Western Australia with ages from 4.4 to 4.0 Ga have apparent temperatures of 717 ± 108°C, which are intermediate between values for felsic rocks and those for mafic rocks. Although some mafic zircons have higher Ti content, values for Early Archean detrital zircons from a proposed granitic provenance are similar to zircons from many mafic rocks, including anorthosites from the Adirondack Mts (709 ± 76°C). Furthermore, the Jack Hills zircon apparent Ti-temperatures are significantly higher than measured values for peraluminous granites (610 ± 88°C). Thus the Ti concentration in detrital zircons and apparent Ti-in-zircon temperatures are not sufficient to independently identify parent melt composition.

Geochonology and Tectonic Significance of post-collisional porphyry in Qulong area, southeast segment of the Gangdese belt, Tibet, China

NASA Astrophysics Data System (ADS)

Liu, D.; Zeren, Z.; Du, C.; Feng, L.; Nima, C.; Zhang, L.

2012-12-01

With the collision of Indian plate and Eura-Asian plate, there developed complicated tectono-magmanism during Meso-Cenozoic in Gangdese belt, Xizang Tibet. Therefore, it resulted that plentiful tectonism and post-collision high-K calc-alkaline magmatism related to mineralization distrubted from east to west in the belt. And this is quite significant for us to do some rearch on large-scale metallogenetics, uplifting epoch and EW-striking extension during the post-collision in Xizang-Qinghai Plateau. Zircon samples from Cangrila Granodiorite-porphyry in Qulong area, Southeast of Gangdese porphyry copper belt, Xiangbeishan diorite-porphyrite and from Jiama Granite-porphyry give LA-ICPMS U-Pb ages of 16.3Ma, 14. 4Ma, and 15.4Ma, respectively, and all these ages represent the porphyries' forming ages. From barren Xiangbeishan diorite-porphyrite through intermediately mineralized Jiama Granite-porphyry to stongly mineralized Cangrila Granodiorite-porphyry, the LA-ICPMS U-Pb ages of zircon become younger and younger. According to the regional data and geochemical characteristics, these porphyries were mainly derived directly from the thickened mafic lower-crust formed in south Tibet during collision and epeirogeny. During post-collisional extension stage, for inter-earth thermal flowing, SN-striking normal faulting systems across the Tibetan orogen caused rapid rising and localization of porphyry magmas and adequately separating of massive ore-bearing fluids from the magmatic hydrothermal systems. All these data indicate that Gandese belt has experienced from post-collisional extrusion changed into intra-plate extension since Miocene. During Miocene, Gangdese belt undergone violent intraplate extension, post-collisional porphyry intrusion and paroxysmal massive mineralization of porphyry-type, and all these was controlled by deep dynamics. Key Words: Qulong area; Gangdese tectonic belt; Tibet;Zircon La-ICP-MS U-Pb dating; intra-plate extension; Image Information For CL images of zircon grains from porphyries

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Timing of anatexis and melt crystallization in the Socorro-Guaxupé Nappe, SE Brazil: Insights from trace element composition of zircon, monazite and garnet coupled to Usbnd Pb geochronology

NASA Astrophysics Data System (ADS)

Rocha, B. C.; Moraes, R.; Möller, A.; Cioffi, C. R.; Jercinovic, M. J.

2017-04-01

The timing of partial melting and melt crystallization in granulite facies rocks of the Socorro-Guaxupé Nappe (SGN), Brazil is constrained using a combination of imaging techniques, LA-ICP-MS and EPMA dating, trace element geochemistry and thermobarometry. (Orthopyroxene)-garnet-bearing migmatite that records extensive biotite dehydration melting shows evidence for a clockwise P-T-t path. UHT peak conditions were attained at 1030 ± 110 °C, 11.7 ± 1.4 kbar, with post-peak cooling to 865 ± 38 °C, 8.9 ± 0.8 kbar. Cryogenian igneous inheritance of ca. 720-640 Ma is identified in oscillatory zoned zircon cores (n = 167) with steep HREE patterns. Resorbed, Y-rich monazite cores preserve a prograde growth stage at 631 ± 4 Ma prior to the partial melting event, providing an upper age limit for the granulite facies metamorphism in the SGN. REE-rich, Th-depleted monazite related to apatite records the initial stages of decompression at 628 ± 4 Ma. Multiple monazite growth episodes record melt crystallization events at 624 ± 3 Ma, 612 ± 5 Ma and 608 ± 6 Ma. Stubby, equant "soccer ball" zircon provide evidence for melt crystallization at 613 ± 2 Ma and 607 ± 4 Ma. The excess scatter in zircon and monazite age populations between 629 ± 4 and 601 ± 3 Ma is interpreted as discontinuous and episodic growth within this age range, characterizing a prolonged metamorphic event in the SGN lasting ca. 30 m.y. The development of Y + HREE-rich monazite rims at ca. 600 Ma documents retrograde garnet breakdown, extensive biotite growth and the final stages of melt crystallization. Th-rich, Y + HREE-poor monazite rims at ca. 590 Ma record monazite recrystallization.

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

Magma hybridization in the Western Tatra Mts. granitoid intrusion (S-Poland, Western Carpathians).

PubMed

Burda, Jolanta; Gawęda, Aleksandra; Klötzli, Urs

In the Variscan Western Tatra granites hybridization phenomena such as mixing and mingling can be observed at the contact of mafic precursors of dioritic composition and more felsic granitic host rocks. The textural evidence of hybridization include: plagioclase-K-feldspar-sphene ocelli, hornblende- and biotite-rimmed quartz ocelli, plagioclase with Ca-rich spike zonation, inversely zoned K-feldspar crystals, mafic clots, poikilitic plagioclase and quartz crystals, mixed apatite morphologies, zoned K-feldspar phenocrysts. The apparent pressure range of the magma hybridization event was calculated at 6.1 kbar to 4.6 kbar, while the temperature, calculated by independent methods, is in the range of 810°C-770°C. U-Pb age data of the hybrid rocks were obtained by in-situ LA-MC-ICP-MS analysis of zircon. The oscillatory zoned zircon crystals yield a concordia age of 368 ± 8 Ma (MSWD = 1.1), interpreted as the age of magma hybridization and timing of formation of the magmatic precursors. It is the oldest Variscan magmatic event in that part of the Tatra Mountains.

Zircon U-Pb and molybdenite Re-Os geochronology and geological significance of the Baoshan porphyry Cu polymetallic deposit in Jiangxi province

NASA Astrophysics Data System (ADS)

Jia, Liqiong; Wang, Liang

2017-10-01

Baoshan porphyry Cu polymetallic deposit belongs to Jiujiang-Ruichang Cu-Au ore field, which is a component part of the Middle-Lower Yangtze River Cu-Au metallogenic belt. The U-Pb LA-MC-TCP MS dating of the zircons from Baoshan granodiorite porphyry yields an age of 147.81±0.48Ma (MSWD=1.07). Six molybdenite samples separated from Baoshan deposit are used for Re-Os dating and obtained the weighted average age of 147.42±0.84Ma and an isochron age of 147.7±1.2Ma. These ages suggest that the mineralization in the Baoshan deposit is genetically associated to the granodiorite porphyry, and the process of rock-and ore-forming is continuous. These data indicate that ages of intrusion and ore-body from Baoshan deposit are almost identical to other typical magmatic intrusion and deposits in Jiujiang-Ruichang metallogenic district. Tt is inferred that the Baoshan deposit was formed in the transition from EW-striking Tndosinian tectonic domain to NE-striking Paleo-Pacific tectonic domain.

The 190Pt-186Os Decay System Applied to Dating Platinum-Group Element Mineralization in Layered Intrusions, Ophiolites and Detrital Deposits

NASA Astrophysics Data System (ADS)

Coggon, J. A.; Nowell, G.; Pearson, G.; Oberthür, T.; Lorand, J.; Melcher, F.; Parman, S. W.

2010-12-01

Discrete platinum-group minerals (PGM) occur as accessory phases in mafic-ultamafic intrusions and ophiolitic chromitites, as well as numerous detrital deposits globally. The 190Pt-186Os decay system, measured by laser ablation MC-ICPMS (LA-MC-ICPMS) provides a useful geochronometric tool for direct dating of PGM. Here we present two examples that verify the accuracy of the technique in geologically well constrained situations and demonstrate the potential for using the 190Pt-186Os PGM method to accurately date layered mafic intrusions, ophiolitic chromitites and detrital PGM deposits. Fifty PGM grains from three different horizons within the Bushveld complex yield a Pt-Os isochron age of 2012 ± 47 Ma (2σ, MSWD = 1.19, 186Os/188Osi = 0.119818 ± 0.000006). This is consistent with the published U-Pb zircon age of 2054 Ma (Scoates and Friedman, 2008). The younger PGM isochron age is not likely to be a function of difference in blocking temperatures in the different systems. Pt-Os model ages are possible in high pt grains because initial 186Os/188Os can be well constrained. Using this approach we obtained Pt-Os model ages of 2113 ± 106 Ma and 2042 ± 102 Ma for a Bushveld Pt-Fe alloy and sperrylite respectively. Detrital PGM derived from the Meratus ophiolite, southeast Borneo yield a 190Pt-186Os isochron age of 202.5 Ma ± 8.3 Ma (2σ, n = 260, MSWD = 0.90, 186Os/188Osi = 0.119830 ± 0.000003), consistent with radiometric and biostratigraphic age constraints (Wakita et al., 1998). We interpret this as the age of formation of the PGM grains in during chromitite genesis in the lower oceanic lithosphere. Our combined data demonstrate the utility of the LA-MC-ICPMS method as a tool for accurate Pt-Os dating of detrital PGM as well as their igneous parent bodies. We can constrain Pt/Os fractionation at the ablation site as being < 2.5%, while within-grain heterogeneity is ultimately one of the strongest controls on isochron and single-grain ages given the partial sampling represented by laser ablation. Scoates, J.S. and Friedman, R.M. 2008. Precise age of the platiniferous Merensky reef, Bushveld Complex, South Africa, by the U-Pb zircon chemical abrasion ID-TIMS technique; Economic Geology 103, p. 465-471. Wakita, K., Miyazaki, K., Zulkarnain, I., Sopaheluwakan, J. and Sanyoto, P. 1998. Tectonic implications of new age data for the Meratus complex of south Kalimantan, Indonesia; Island Arc 7, p. 202-222.

Selective ablation of rabbit atherosclerotic plaque with less thermal effect by the control of pulse structure of a quantum cascade laser in the 5.7 μm wavelength range

NASA Astrophysics Data System (ADS)

Hashimura, Keisuke; Ishii, Katsunori; Awazu, Kunio

2016-03-01

Cholesteryl esters are main components of atherosclerotic plaques and have an absorption peak at the wavelength of 5.75 μm originated from C=O stretching vibration mode of ester bond. Our group achieved the selective ablation of atherosclerotic lesions using a quantum cascade laser (QCL) in the 5.7 μm wavelength range. QCLs are relatively new types of semiconductor lasers that can emit mid-infrared range. They are sufficiently compact and considered to be useful for clinical application. However, large thermal effects were observed because the QCL worked as quasicontinuous wave (CW) lasers due to its short pulse interval. Then we tried macro pulse irradiation (irradiation of pulses at intervals) of the QCL and achieved effective ablation with less-thermal effects than conventional quasi-CW irradiation. However, lesion selectivity might be changed by changing pulse structure. Therefore, in this study, irradiation effects of the macro pulse irradiation to rabbit atherosclerotic plaque and normal vessel were compared. The macro pulse width and the macro pulse interval were set to 0.5 and 12 ms, respectively, because the thermal relaxation time of rabbit normal and atherosclerotic aortas in the oscillation wavelength of the QCL was 0.5-12 ms. As a result, cutting difference was achieved between rabbit atherosclerotic and normal aortas by the macro pulse irradiation. Therefore, macro pulse irradiation of a QCL in the 5.7 μm wavelength range is effective for reducing thermal effects and selective ablation of the atherosclerotic plaque. QCLs have the potential of realizing less-invasive laser angioplasty.

Development of dried serum spot sampling techniques for the assessment of trace elements in serum samples by LA-ICP-MS.

PubMed

Chantada-Vázquez, María Pilar; Moreda-Piñeiro, Jorge; Cantarero-Roldán, Alicia; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

2018-08-15

A novel approach for serum analysis by dried matrix spot (DMS) technique is proposed. The methodology consists of sampling filter paper discs (2.7 mm in diameter) containing the large amount of serum retained after a single spotting. Several oxidizers (sodium chlorate, sodium azide, acetic acid, formic acid, 1-butyl-3-methylimidazoliumm chloride/bromide) were tested (oxidizers premixed with the sample before spotting, and papers previously soaked in concentrated additive/oxidizer solutions). Direct multi-element determination (Al, Be, Ca, Cu, Fe, K, Li, Mg, Mn, Mo, Na, P, Rb, Se, V, and Zn) in dried serum spots at very low levels was therefore assessed by laser ablation (LA) coupled with inductively coupled plasma - mass spectrometry (ICP-MS). Laser ablation was performed using a focused Nd: YAG laser beam in lineal scan mode (wavelength 213 nm, laser fluency 2.2 J cm -2 , repetition rate 20 Hz, laser spot diameter 90 µm, depth 0 µm, scanning speed 12 µm s -1 ). Matrix-matched calibration mode and 13 C as internal standard (for signal intensities normalization) was used throughout the work. Limits of quantification were found to be from 21 µg L -1 to 221 mg L -1 . Repeatability (seven ablations of the same dried serum spot) and reproducibility (two ablations of seven dried serum spot from the same material) offered RSDs below 12% for all analytes, which seems satisfactory for clinical purposes. The method was validated by analyzing several certified reference materials (Seronorm™ level I and II trace elements in serum), and it was applied to several DMS from serum samples from healthy adults. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrophysiologic profile and results of invasive risk stratification in asymptomatic children and adolescents with the Wolff-Parkinson-White electrocardiographic pattern.

PubMed

Kubuš, Peter; Vít, Pavel; Gebauer, Roman A; Materna, Ondřej; Janoušek, Jan

2014-04-01

Data on the results and clinical effect of an invasive risk stratification strategy in asymptomatic young patients with the Wolff-Parkinson-White electrocardiographic pattern are scarce. Eighty-five consecutive patients aged<18 years with a Wolff-Parkinson-White pattern and persistent preexcitation at maximum exercise undergoing invasive risk stratification were retrospectively studied. Adverse accessory pathway (AP) properties were defined according to currently consented criteria as any of the following: shortest preexcited RR interval during atrial fibrillation/rapid atrial pacing≤250 ms (or antegrade effective refractory period≤250 ms if shortest preexcited RR interval was not available) or inducible atrioventricular re-entrant tachycardia. Age at evaluation was median 14.9 years. Eighty-two patients had a structurally normal heart and 3 had hypertrophic cardiomyopathy. A single manifest AP was present in 80, 1 manifest and 1 concealed AP in 4, and 2 manifest APs in 1 patient. Adverse AP properties were present in 32 of 85 patients (37.6%) at baseline and in additional 16 of 44 (36.4%) after isoproterenol. Ablation was performed in 41 of these 48 patients. Ablation was deferred in the remaining 7 for pathway proximity to the atrioventricular node. In addition, 18 of the low-risk patients were ablated based on patient/parental decision. Adverse AP properties at baseline were exhibited by 37.6% of the evaluated patients with an asymptomatic Wolff-Parkinson-White preexcitation persisting at peak exercise. Isoproterenol challenge yielded additional 36.4% of those tested at higher risk. Ablation was performed in a total of 69.4% of patients subjected to invasive risk stratification.

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 U-Pb ages, Hf isotope data, and tectonic implications of Early-Middle Triassic granitoids in the Ailaoshan high-grade metamorphic belt of Southeast Tibet

NASA Astrophysics Data System (ADS)

Wu, Wenbin; Liu, Junlai; Chen, Xiaoyu; Zhang, Lisheng

2017-04-01

The Ailaoshan tectonic belt, where the effects of the Paleo-Tethyan ocean evolution and Indian-Eurasian plate collision are superimposed, is one of the most significant geological discontinuities in western Yunnan province of southeast Tibet. An Ailaoshan micro-block within the belt is bounded by the Ailaoshan suture zone to the west and the Red River Fault to the east, and consists of low- and high-grade metamorphic belts. Late Permian-Middle Triassic granitoids that are widely distributed to the west of the Ailaoshan suture zone and within the Ailaoshan micro-block may yield significant information on the Tethyan tectonic evolution of the Ailaoshan tectonic belt. This study reports new LA-ICP-MS zircon U-Pb geochronology and Hf isotope data of four granitoids from the Ailaoshan high-grade metamorphic belt. Zircon grains from the Yinjie granitoid do not have inherited cores and yield a weighted mean U-Pb age of 247.1 ± 2.0 Ma. The zircon ɛ Hf( t) values range from 7.8 to 12.1, and Hf model ages from 775 to 546 Ma, indicating that the granitoid was derived from juvenile crust. The rims of zircons from the Majie and Yuanjiang granitoids yield weighted mean U-Pb ages of 239.5 ± 1.8 and 237.9 ± 2.6 Ma, respectively, whereas the cores yield ages of 1608-352 Ma. The ɛ Hf( t) values of zircon rims range from -20.4 to -5.3, yielding Hf model ages from 2557 to 1606 Ma and suggesting that the source magma of the Majie and Yuanjiang granitoids was derived from ancient crust. An additional granitoid located near the Majie Village yields a zircon U-Pb age of 241.2 ± 1.0 Ma. Based on our geochronological and geochemical data, combined with geological observations, we propose that the Ailaoshan micro-block was derived from the western margin of the Yangtze block, and is comparable to the Zhongzan and Nam Co micro-blocks. The presence of late Permian mafic rocks with rift-related geochemical characteristics within the Ailaoshan micro-block, together with granitoids derived from partial melting of ancient/juvenile crust, indicates the presence of an Ailaoshan rift. This possible rift may correspond to the Ganzi-Litang Ocean to the northwest and the Jinping-Song Da rift to the southeast. It is suggested that westward subduction of the Jinshajiang-Ailaoshan-Song Ma oceanic lithosphere triggered the separation of the Zhongzan, Ailaoshan, and Nam Co micro-blocks from the western passive continental margin of the Yangtze block through the opening of the Ganzi-Litang-Ailaoshan-Jinping-Song Da ocean/rift. This ocean/rift may represent a subsidiary branch of the Paleo-Tethyan Ocean along the western margin of the Yangtze block.

Unraveling the Switch from Subduction to Exhumation within a Collisional Orogen: Split-stream U-Pb and Trace-element Results from the Western Gneiss Region, Norway (Invited)

NASA Astrophysics Data System (ADS)

Gordon, S. M.; Whitney, D. L.; Teyssier, C. P.; Fossen, H.; Desormeau, J. W.; Jessen, B.

2013-12-01

During continental collision, crustal material may be subducted to great depths and subsequently exhumed. Ultrahigh-pressure (UHP) terranes preserve a record of the subduction of crustal material during suturing of colliding continents and the exhumation of this material during extension and, in some cases, collapse of the orogen. The UHP rocks of the Western Gneiss Region (WGR), Norway, resulted from the collision of Baltica with Laurentia during the final stages of the Caledonian orogeny. The WGR represents one of the two largest UHP terranes on Earth and consists of a UHP eclogite-bearing domain south of the Møre-Trøndelag strike-slip fault and a HP mafic granulite-bearing domain north of the fault. At least some of the HP granulite is overprinted eclogite. To evaluate the metamorphic and structural relationship of mafic rocks and associated migmatite in both regions, we obtained LA-ICP-MS U-Pb dates and trace-element analyses for zircon from a variety of textural types of leucosome associated with mafic layers and lenses. Five leucosomes within highly deformed migmatite in the HP granulite complex on the Roan Peninsula reveal U-Pb lower-intercept ages from ca. 405 to 409 Ma and upper-intercept Proterozoic dates. These zircons have distinct trace-elements patterns: all of the zircons that yield Proterozoic dates have overall much higher REE concentrations, a more significant negative Eu anomaly (-0.3 to -0.7) and steeper HREE patterns (Lu/Dy = 5-12). In comparison, the Caledonian zircons reveal flatter Eu anomalies (-0.3 to 0.2) and less steep HREE patterns (Lu/Dy = 2-7), although the individual patterns do not seem to correlate with age. The Caledonian zircon patterns suggest crystallization at high-pressures and are distinct from the inherited Proterozoic grains. Similar results were obtained from zircon rims extracted from layer-parallel to crosscutting leucosomes from the UHP domain. Trace elements in zircon in these samples record the transition from high-pressure (garnet-present, plagioclase-absent) crystallization to lower-pressure (plagioclase-present) crystallization with garnet-present × plagioclase-absent REE patterns. Moreover, dates from the layer-parallel leucosomes are as old as 410-406 Ma. The new U-Pb dates suggest a similar melt crystallization history that was coeval with previously determined ages of (U)HP metamorphism of WGR eclogite. The More-Trondelag fault acted as a transform fault and accommodated coeval extension that exhumed both the (U)HP and granulite domains. Results are consistent with the presence of partially molten crust in a large part of the WGR at HP or UHP conditions during the latest stages of the Caledonian orogeny. The decreased viscosity and increased buoyancy and strain weakening induced by partial melting may have triggered or at least contributed to the switch from subduction to exhumation in the WGR, marking the end of collisional orogeny.

Spatial resolution of pace mapping of idiopathic ventricular tachycardia/ectopy originating in the right ventricular outflow tract.

PubMed

Bogun, Frank; Taj, Majid; Ting, Michael; Kim, Hyungjin Myra; Reich, Stephen; Good, Eric; Jongnarangsin, Krit; Chugh, Aman; Pelosi, Frank; Oral, Hakan; Morady, Fred

2008-03-01

Pace mapping has been used to identify the site of origin of focal ventricular arrhythmias. The spatial resolution of pace mapping has not been adequately quantified using currently available three-dimensional mapping systems. The purpose of this study was to determine the spatial resolution of pace mapping in patients with idiopathic ventricular tachycardia or premature ventricular contractions originating in the right ventricular outflow tract. In 16 patients with idiopathic ventricular tachycardia/ectopy from the right ventricular outflow tract, comparisons and classifications of pace maps were performed by two observers (good pace map: match >10/12 leads; inadequate pace map: match < or =10/12 leads) and a customized MATLAB 6.0 program (assessing correlation coefficient and normalized root mean square of the difference (nRMSd) between test and template signals). With an electroanatomic mapping system, the correlation coefficient of each pace map was correlated with the distance between the pacing site and the effective ablation site. The endocardial area within the 10-ms activation isochrone was measured. The ablation procedure was effective in all patients. Sites with good pace maps had a higher correlation coefficient and lower nRMSd than sites with inadequate pace maps (correlation coefficient: 0.96 +/- 0.03 vs 0.76 +/- 0.18, P <.0001; nRMSd: 0.41 +/- 0.16 vs 0.89 +/- 0.39, P <.0001). Using receiver operating characteristic curves, appropriate cutoff values were >0.94 for correlation coefficient (sensitivity 81%, specificity 89%) and < or =0.54 for nRMSd (sensitivity 76%, specificity 80%). Good pace maps were located a mean of 7.3 +/- 5.0 mm from the effective ablation site and had a mean activation time of -24 +/- 7 ms. However, in 3 (18%) of 16 patients, the best pace map was inadequate at the effective ablation site, with an endocardial activation time at these sites of -25 +/- 12 ms. Pace maps with correlation coefficient > or =0.94 were confined to an area of 1.8 +/- 0.6 cm2. The 10-ms isochrone measured 1.2 +/- 0.7 cm2. The spatial resolution of a good pace map for targeting ventricular tachycardia/ectopy is 1.8 cm2 in the right ventricular outflow tract and therefore is inferior to the spatial resolution of activation mapping as assessed by isochronal activation. In approximately 20% of patients, pace mapping is unreliable in identifying the site of origin, possibly due a deeper site of origin and preferential conduction via fibers connecting the focus to the endocardial surface.

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 recrystallized inherited zircons.

Rare earth elements profile in a cultivated and non-cultivated soil determined by laser ablation-inductively coupled plasma mass spectrometry.

PubMed

Neves, Vinicius M; Heidrich, Graciela M; Hanzel, Flavia B; Muller, Edson I; Dressler, Valderi L

2018-05-01

Rare earth elements (REEs) have several applications but the effects on environment are not well known. Therefore, the aim of this work is to establish a method for direct solid sample analysis by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) to evaluate the concentration and distribution of REEs in cultivated and non-cultivated soil. Samples were collected in two areas to 40 cm of depth. The LA-ICP-MS method is easy to be implemented and the sample treatment is very fast comprising only its drying, grounding and pressing as a pellet. The accuracy of the method was evaluated by using a certified reference material (BCR 667 - Estuarine Sediment, Institute for Reference Materials and Measurements (IRMM)) where good agreement with the certified values was obtained. Analyte recovery at two levels of concentration (2.5 and 15.0 μg g -1 ) was also performed and recoveries in the range of 85%-120% were achieved, values that are acceptable for LA-ICP-MS analysis. In general, the concentration of the REEs is higher in the cultivated soil and increased from the surface to deeper layers, which can be a consequence of fertilizer application. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

From Compression to Extension: Cretaceous A-type Granite as Indicator of Geodynamic Changes in the Adria Part of the European Neotethys Suture Zone

NASA Astrophysics Data System (ADS)

Balen, D.; Schneider, P.; Massonne, H. J.; Opitz, J.; Petrinec, Z.

2017-12-01

The Cretaceous suture zone between the colliding plates of European and Adria (Gondwana) marks the closure of the W Neotethys branch. This zone, partly located in the northern Croatia, comprises reddish alkali granite which is mainly composed of alkali feldspar and quartz, with small amounts of albite, white mica and hematite with ilmenite exsolutions. Accessory minerals include zircon, apatite and Fe-(Ti)-oxides. This granite shows a geochemical signature typical for A2-type granite characterized by a highly siliceous composition and an enrichment in alkalies (high-K calc-alkaline series) and Al (strongly peraluminous, ASI>1.1). The rock belongs to the group of oxidized and ferroan granites with low CaO, MgO, MnO and FeO* contents. Characteristic trace element ratios, primitive mantle and OIB normalized spider-diagrams show significant positive anomalies of Rb, Th, U, K, Zr and Pb accompanied with clear negative anomalies of Ba, Nb, Sr, P, Eu and Ti. The negative anomalies suggest fractionation of plagioclase, apatite and Fe-Ti oxide. Based on the geochemical characteristics the magma originated mainly from melting of lower continental crust (granulite facies metasediments) although a mantle contribution cannot be excluded. The melting process could have been triggered by a heat from the upwelling upper mantle as inferred from zircon typology (D and J5 types prevail), as well from the zircon and whole-rock chemistry accompanied with high zircon saturation temperatures (T=860-950°C). Subsequent ascent of granitic magma was localized along the Europe-Adria suture i.e. the Sava Zone segment of the Late Cretaceous collisional zone where granite was emplaced at ca. 20 km depth. The emplacement followed a long period of Mesozoic orogenic compressional activity. Typical for A-type granites, although in our case related to the subduction of the Adria plate underneath the European plate, is their formation in an extensional tectonic regime. Thus, the studied A-type granite indicates the onset of transition from compression to extension at the European margin. This event occurred in the interval between 87.7-85.8 Ma as shown by 207Pb/235U, 206Pb/238U and 208Pb/232Th ratios measured with LA-ICP-MS on zircon. Support by the Croatian Science Foundation (IP-2014-09-9541) is acknowledged.

Growth of a Large Composite Magma System: the EJB Pluton, Eastern California.

NASA Astrophysics Data System (ADS)

Matty, D. J.; Vervoort, J.; Dufrane, A.; Hart, G.; Student, J.; Morgan, S.

2008-12-01

The composite EJB pluton crops out in the White-Inyo Mountains of eastern California, and comprises the Eureka Valley monzonite (EVM), the Joshua Flat quartz monzonite (JFQM), the Beer Creek granite (BCG), and an unnamed diorite. While sometimes equivocal, field relationships suggest that the EVM was emplaced first, followed by the JFQM, and finally the BCG; the diorite predates the BCG. Sylvester and others (GSAB, 1978) reported zircon U-Pb ages of 179±2 Ma for the EVM and 174±5 Ma for the JFQM. Coleman and others (GSAB, 2003) determined a U-Pb age of 179±3 Ma (via Pb-loss trajectory) for the BCG. Because of the uncertainty in the ages and ambiguous field relations, the sequence and duration of EJB magmatism remain unclear. To understand more fully the timing of EJB magmatism, we separated zircons from 12 samples collected from each of the main EJB units. These samples were characterized using light microscopy, SEM and CL techniques. U-Pb ages were determined from individual zircons by LA-ICP-MS following the method of Chang and others (G3, 2006). For the ages reported below, the reported uncertainties are based on factors within the analysis, but do not include external factors such as sample/standard bias or other matrix effects. Overall uncertainty in LA-ICPMS U-Pb geochronology is hard to assess, but we estimate that all ages reported below are subject to a minimum 2% uncertainty. We determined a concordant U-Pb age of 180±2 Ma for the EVM, which agrees with the results of Sylvester and others (1978). The unnamed diorite produced a concordant U-Pb age of 177±3 Ma. Concordant U-Pb ages of 172±2, 172±3, 173±2, 174±2, and 175±2 Ma were determined for individual samples of the JFQM and agree with the age reported by Sylvester and others (1978) of 174±5 Ma. Concordant U-Pb ages of 168±4, 168±3, 169±1, 172±2, and 172±2 Ma were determined for individual BCG samples. Within the reported error, there is no difference in age between individual samples of the BCG, but taken as absolute, the ages tantalizingly decrease from NW to SE within the exposed area of the BCG. No such pattern is suggested within the JFQM. Collectively, these new LA-ICP-MS zircon age data support the observed field relationships and suggest that the EJB magma system was periodically active for as long as 10-12 million years. This time scale agrees well with current models of incremental growth of plutons and has important implications for strain accumulation in mid-crustal arc environments.

Elemental and Isotopic Analysis of Uranium Oxide an NIST Glass Standards by FEMTOSECOND-LA-ICP-MIC-MS

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

Ebert, Chris; Zamzow, Daniel S.; McBay, Eddie H.

2009-06-01

The objective of this work was to test and demonstrate the analytical figures of merit of a femtosecond-laser ablation (fs-LA) system coupled with an inductively coupled plasma-multi-ion collector-mass spectrometer (ICP-MIC-MS). The mobile fs-LA sampling system was designed and assembled at Ames Laboratory and shipped to Oak Ridge National Laboratory (ORNL), where it was integrated with an ICP-MIC-MS. The test period of the integrated systems was February 2-6, 2009. Spatially-resolved analysis of particulate samples is accomplished by 100-shot laser ablation using a fs-pulsewidth laser and monitoring selected isotopes in the resulting ICP-MS transient signal. The capability of performing high sensitivity, spatiallymore » resolved, isotopic analyses with high accuracy and precision and with virtually no sample preparation makes fs-LA-ICP-MIC-MS valuable for the measurement of actinide isotopes at low concentrations in very small samples for nonproliferation purposes. Femtosecond-LA has been shown to generate particles from the sample that are more representative of the bulk composition, thereby minimizing weaknesses encountered in previous work using nanosecond-LA (ns-LA). The improvement of fs- over ns-LA sampling arises from the different mechanisms for transfer of energy into the sample in these two laser pulse-length regimes. The shorter duration fs-LA pulses induce less heating and cause less damage to the sample than the longer ns pulses. This results in better stoichiometric sampling (i.e., a closer correlation between the composition of the ablated particles and that of the original solid sample), which improves accuracy for both intra- and inter-elemental analysis. The primary samples analyzed in this work are (a) solid uranium oxide powdered samples having different {sup 235}U to {sup 238}U concentration ratios, and (b) glass reference materials (NIST 610, 612, 614, and 616). Solid uranium oxide samples containing {sup 235}U in depleted, natural, and enriched abundances were analyzed as particle aggregates immobilized in a collodion substrate. The uranium oxide samples were nuclear reference materials (CRMs U0002, U005-A, 129-A, U015, U030-A, and U050) obtained from New Brunswick Laboratory-USDOE.« less

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and its Application in Life Sciences

NASA Astrophysics Data System (ADS)

Xu, Gu-feng; Wang, Hong-mei

2001-08-01

Inductively-coupled plasma mass spectrometry (ICP-MS) has made much progress since its birth in the late 1990s. This paper will give a rather systematic overview on the use of this technique in new devices and technologies related to plasma source, sample-introducing device and detecting spectrometer etc. In this overview, an emphasis will be put on the evaluation of the ICP-MS technique in combination with a series of physical, chemical and biological techniques, such as laser ablation (LA), capillary electrophoresis (CE) and high performance liquid chromatograph (HPLC), along with their representative high accuracy and high sensitivity. Finally, comprehensive and fruitful applications of the ICP-MS and its combinative techniques in the detection of trace metallic elements and isotopes in complex biological and environmental samples will be revealed.

Flowing atmospheric pressure afterglow combined with laser ablation for direct analysis of compounds separated by thin-layer chromatography.

PubMed

Cegłowski, Michał; Smoluch, Marek; Reszke, Edward; Silberring, Jerzy; Schroeder, Grzegorz

2016-01-01

A thin-layer chromatography-mass spectrometry (TLC-MS) setup for characterization of low molecular weight compounds separated on standard TLC plates has been constructed. This new approach successfully combines TLC separation, laser ablation, and ionization using flowing atmospheric pressure afterglow (FAPA) source. For the laser ablation, a low-priced 445-nm continuous-wave diode laser pointer, with a power of 1 W, was used. The combination of the simple, low-budget laser pointer and the FAPA ion source has made this experimental arrangement broadly available, also for small laboratories. The approach was successfully applied for the characterization of low molecular weight compounds separated on TLC plates, such as a mixture of pyrazole derivatives, alkaloids (nicotine and sparteine), and an extract from a drug tablet consisting of paracetamol, propyphenazone, and caffeine. The laser pointer used was capable of ablating organic compounds without the need of application of any additional substances (matrices, staining, etc.) on the TLC spots. The detection limit of the proposed method was estimated to be 35 ng/cm(2) of a pyrazole derivative.

Key stages of material expansion in dielectrics upon femtosecond laser ablation revealed by double-color illumination time-resolved microscopy

NASA Astrophysics Data System (ADS)

Garcia-Lechuga, Mario; Solis, Javier; Siegel, Jan

2018-03-01

The physical origin of material removal in dielectrics upon femtosecond laser pulse irradiation (800 nm, 120 fs pulse duration) has been investigated at fluences slightly above ablation threshold. Making use of a versatile pump-probe microscopy setup, the dynamics and different key stages of the ablation process in lithium niobate have been monitored. The use of two different illumination wavelengths, 400 and 800 nm, and a rigorous image analysis combined with theoretical modelling, enables drawing a clear picture of the material excitation and expansion stages. Immediately after excitation, a dense electron plasma is generated. Few picoseconds later, direct evidence of a rarefaction wave propagating into the bulk is obtained, with an estimated speed of 3650 m/s. This process marks the onset of material expansion, which is confirmed by the appearance of transient Newton rings, which dynamically change during the expansion up to approximately 1 ns. Exploring delays up to 15 ns, a second dynamic Newton ring pattern is observed, consistent with the formation of a second ablation front propagating five times slower than the first one.

Retro Rocket Motor Self-Penetrating Scheme for Heat Shield Exhaust Ports

NASA Technical Reports Server (NTRS)

Marrese-Reading, Colleen; St.Vaughn, Josh; Zell, Peter; Hamm, Ken; Corliss, Jim; Gayle, Steve; Pain, Rob; Rooney, Dan; Ramos, Amadi; Lewis, Doug;

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.

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.

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 standard-sample-bracketing laser ablation analyses on sulfides, oxides and silicates agree within 0.15 permil to measurements done by solution MC-ICP-MS after chromatographic matrix separation. With our laser ablation method all compartments of the weathering zone can be analysed with minimal sample preparation [2]. In a first application, we investigate Si isotope fractionation during deep (10 m) core stone weathering, where crystalline rock is altered, producing secondary clay minerals along 20 micrometer wide (biogenic?) alteration textures. While unweathered centers of plagioclase grains show a homogenous Si isotope composition of δ30Si = -0.20 ± 0.17 permil (2SD, n=12), the secondary weathering products found in fissures within and between plagioclase grains consistently show negative δ30Si values - as low as -1.13 permil. Comparison with isotope studies at the soil and catchment scale suggests that the isotopic weathering signatures found in dissolved and particulate Si in rivers can be traced to processes operating at the micro scale. [1] Horn & von Blanckenburg, Spectrochimica Acta B. 62, 2007 [2] Steinhoefel et al., Chem. Geol. 286, 2011

Self-limiting and complete oxidation of silicon nanostructures produced by laser ablation in water

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

Vaccaro, L.; Messina, F.; Camarda, P.

2016-07-14

Oxidized Silicon nanomaterials produced by 1064 nm pulsed laser ablation in deionized water are investigated. High-resolution transmission electron microscopy coupled with energy dispersive X-ray spectroscopy allows to characterize the structural and chemical properties at a sub-nanometric scale. This analysis clarifies that laser ablation induces both self-limiting and complete oxidation processes which produce polycrystalline Si surrounded by a layer of SiO{sub 2} and amorphous fully oxidized SiO{sub 2}, respectively. These nanostructures exhibit a composite luminescence spectrum which is investigated by time-resolved spectroscopy with a tunable laser excitation. The origin of the observed luminescence bands agrees with the two structural typologies: Si nanocrystalsmore » emit a μs-decaying red band; defects of SiO{sub 2} give rise to a ns-decaying UV band and two overlapping blue bands with lifetime in the ns and ms timescale.« less

Laser ablation inductively coupled plasma mass spectrometry measurement of isotope ratios in depleted uranium contaminated soils.

PubMed

Seltzer, Michael D

2003-09-01

Laser ablation of pressed soil pellets was examined as a means of direct sample introduction to enable inductively coupled plasma mass spectrometry (ICP-MS) screening of soils for residual depleted uranium (DU) contamination. Differentiation between depleted uranium, an anthropogenic contaminant, and naturally occurring uranium was accomplished on the basis of measured 235U/238U isotope ratios. The amount of sample preparation required for laser ablation is considerably less than that typically required for aqueous sample introduction. The amount of hazardous laboratory waste generated is diminished accordingly. During the present investigation, 235U/238U isotope ratios measured for field samples were in good agreement with those derived from gamma spectrometry measurements. However, substantial compensation was required to mitigate the effects of impaired pulse counting attributed to sample inhomogeneity and sporadic introduction of uranium analyte into the plasma.

A Henry's Law Test for Experimental Partitioning Studies of Iron Meteorites

NASA Technical Reports Server (NTRS)

Chabot, N. L.; Campbell, A. J.; Humayun, M.; Agee, C. B.

2001-01-01

Low-level doped solid metal/liquid metal experiments analyzed by laser ablation ICP-MS allow Henry's Law to be tested. The results indicate Henry's Law is obeyed and the experimental partition coefficients can be applied to iron meteorites. Additional information is contained in the original extended abstract.

Application of LA-MC-ICP-MS for analysis of Sr isotope ratios in speleothems

NASA Astrophysics Data System (ADS)

Weber, Michael; Scholz, Denis; Wassenburg, Jasper A.; Jochum, Klaus Peter; Breitenbach, Sebastian

2017-04-01

Speleothems are well established climate archives. In order to reconstruct past climate variability, several geochemical proxies, such as δ13C and δ18O as well as trace elements are available. Since several factors influence each individual proxy, robust interpretation is often hampered. This calls for multi-proxy approaches involving additional isotope systems that can help to delineate the role of different sources of water within the epikarst and changes in soil composition. Sr isotope ratios (87Sr/86Sr) have been shown to provide useful information about water residence time and water mixing in the host rock. Furthermore, Sr isotopes are not fractionated during calcite precipitation, implying that the 87Sr/86Sr ratio of the speleothem provides a direct record of the drip water. While most speleothem studies applying Sr isotopes used the TIMS methodology, LA-MC-ICP-MS has been utilized for several other archives, such as otoliths and teeth. This method provides the advantage of faster data acquisition, higher spatial resolution, larger sample throughput and the absence of chemical treatment prior to analysis. Here we present the first LA-MC-ICP-MS Sr isotope data for speleothems. The analytical uncertainty of our LA-MC-ICP-MS Sr data is in a similar range as for other carbonate materials. The results of different ablation techniques (i.e. line scan and spots) are reproducible within error, implying that the application of this technique on speleothems is possible. In addition, several comparative measurements of different carbonate reference materials (i.e. MACS-3, JCt-1, JCp-1), such as tests with standard bracketing and comparison of the 87Sr/86Sr ratios with nanosecond laser ablation system and a state-of-the-art femtosecond laser ablation system, show the robustness of the method. We applied the method to samples from Morocco (Grotte de Piste) and India (Mawmluh Cave). Our results show only very small changes in the 87Sr/86Sr ratios of both speleothems. However, one speleothem from Mawmluh Cave shows a slight increase of 87Sr/86Sr within the error, which is reproducible with line scans and spots.

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 preparation creates additional problems (e.g. NiS fire assay beads). I will give examples of applications for this technique in the study of ore minerals, meteorites and precipitates from hydrothermal vents.

Strontium isotope measurement of basaltic glasses by laser ablation multiple collector inductively coupled plasma mass spectrometry based on a linear relationship between analytical bias and Rb/Sr ratios.

PubMed

Zhang, Le; Ren, Zhong-Yuan; Wu, Ya-Dong; Li, Nan

2018-01-30

In situ strontium (Sr) isotope analysis of geological samples by laser ablation multiple collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) provides useful information about magma mixing, crustal contamination and crystal residence time. Without chemical separation, during Sr isotope analysis with laser ablation, many kinds of interference ions (such as Rb + and Kr + ) are on the Sr isotope spectrum. Most previous in situ Sr isotope studies only focused on Sr-enriched minerals (e.g. plagioclase, calcite). Here we established a simple method for in situ Sr isotope analysis of basaltic glass with Rb/Sr ratio less than 0.14 by LA-MC-ICP-MS. Seven Faraday cups, on a Neptune Plus MC-ICP-MS instrument, were used to receive the signals on m/z 82, 83, 84, 85, 86, 87 and 88 simultaneously for the Sr isotope analysis of basaltic glass. The isobaric interference of 87 Rb was corrected by the peak stripping method. The instrumental mass fractionation of 87 Sr/ 86 Sr was corrected to 86 Sr/ 88 Sr = 0.1194 with an exponential law. Finally, the residual analytical biases of 87 Sr/ 86 Sr were corrected with a relationship between the deviation of 87 Sr/ 86 Sr from the reference values and the measured 87 Rb/ 86 Sr. The validity of the protocol present here was demonstrated by measuring the Sr isotopes of four basaltic glasses, a plagioclase crystal and a piece of modern coral. The measured 87 Sr/ 86 Sr ratios of all these samples agree within 100 ppm with the reference values. In addition, the Sr isotopes of olivine-hosted melt inclusions from the Emeishan large igneous province (LIP) were measured to show the application of our method to real geological samples. A simple but accurate approach for in situ Sr isotope measurement by LA-MC-ICP-MS has been established, which should greatly facilitate the wider application of in situ Sr isotope geochemistry, especially to volcanic rock studies. Copyright © 2017 John Wiley & Sons, Ltd.

Low-threshold ablation of enamel and dentin using Nd:YAG laser assisted with chromophore with different pulse shapes

NASA Astrophysics Data System (ADS)

Bonora, Stefano; Benazzato, Paolo; Stefani, Alessandro; Villoresi, Paolo

2004-05-01

Neodimium laser treatment has several drawbacks when used in the hard tissue cutting, because of the low absorption of the dental tissues at its wavelength. This investigation proved that the Nd:YAG radiation is a powerful ablation tool if it is used with the dye assisted method. Several in vitro tests on enamel and dentin were accomplished changing some laser parameters to have different pulse shapes and durations from 125μs up to 1.4ms. The importance of short time high power peaks, typical of crystal lasers, in the ablation process was investigated. The pulse shapes were analyzed by their intensity in space and time profiles. A first set of results found the optimum dye concentration be used in all the following tests. Furthermore the ablation threshold for this technique was found for each different pulse shapes and durations. A low energy ablation method was found to avoid temperature increase and surface cracks formation. In vitro temperature analysis was reported comparing the differences between no dye application laser treatment and with a dye spray applied. A strong reduction of the temperature increase was found in the dye assisted method. A discussion on the general findings and their possible clinical applications is presented.

Petrogenesis and tectonic implications of the Yadong leucogranites, southern Himalaya

NASA Astrophysics Data System (ADS)

Gou, Zhengbin; Zhang, Zeming; Dong, Xin; Xiang, Hua; Ding, Huixia; Tian, Zuolin; Lei, Hengcong

2016-07-01

The leucogranites in the Higher Himalayan Sequence (HHS) provide a probe to elucidate the crustal melting of continental collisional orogen. An integrated geochemical and geochronological study of the Yadong leucogranites, southern Himalaya, shows that these rocks have relatively high SiO2 contents of 69.77 to 75.32 wt.% and alumina saturation index (A/CNK) of 1.09-1.40, typical of peraluminous granites. They show moderately fractionated REE patterns with negative Eu anomalies, and are characterized by enriched LILE (Rb and Cs) and depleted HFSE (Zr, Hf, Nb and Ta). LA-ICP-MS U-Pb zircon dating of ten samples yields crystallization ages ranging from 21.0 to 11.7 Ma. The zircons have variable εHf(t) values of - 26.3 to - 3.5 and corresponding Hf two-stage model ages of 2.77-1.33 Ga. The present study reveals that the muscovite-biotite leucogranites (2ML) have higher TiO2, MgO, CaO, Sr, Ba and Zr contents, lower Rb/Sr ratios than the tourmaline-muscovite leucogranites (TML). Zircon and monazite saturation thermometry results show that the melt temperatures (681-784 °C) of the 2ML are 20-80 °C higher than those (663-705 °C) of the TML. Combining with previous results, we propose that the TML were derived from the muscovite-dehydration melting, whereas the 2ML dominantly resulted from the biotite-dehydration melting during the prograde metamorphism of the pelitic and felsic granulites of the HHS. Therefore, the Himalayan leucogranites were probably formed during the subduction of the Indian crust following the India and Asia collision.

Pulmonary vein activity does not predict the outcome of catheter ablation for persistent atrial fibrillation: A long-term multicenter prospective study.

PubMed

Prabhu, Sandeep; Kalla, Manish; Peck, Kah Y; Voskoboinik, Aleksandr; McLellan, Alex J A; Pathik, Bupesh; Nalliah, Chrishan J; Wong, Geoff R; Sugumar, Hariharan; Azzopardi, Sonia M; Lee, Geoffrey; Ling, Liang-Han; Kalman, Jonathan M; Kistler, Peter M

2018-03-02

Pulmonary vein (PV) isolation (PVI) remains the cornerstone of catheter ablation (CA) in persistent atrial fibrillation (AF) (PeAF), although less successful than for paroxysmal AF. Whether rapid or fibrillatory (PV AF) PV firing may identify patients with PeAF more likely to benefit from a PV-based ablation approach is unclear. The purpose of this study was to determine the relationship between the PV cycle length (PVCL) and the PV AF outcome after CA. Before ablation, the multipolar catheter was placed in each PV and the left atrial appendage (LAA) for 100 consecutive cycles. The presence of PV AF, the average PVCL of all 4 veins (PV 4VAverage ), the fastest vein average (PV FVAverage ), the fastest cycle length (PV Fast ) both individually and relative to the average LAA cycle length were calculated. The ablation strategy included PVI and posterior wall isolation with a minimum of 12 months follow-up. A total of 123 patients underwent CA (age 62 ± 9.1 years; CHA 2 DS 2 -VASC score 1.6 ± 1.1; left ventricular ejection fraction 48% ± 13%; left atrial area 31 ± 8.7 cm 2 ; AF duration 16 ± 17 months). PVI was achieved in 100% of patients. Multiprocedure success (MPS; freedom from AF/atrial tachycardia episodes lasting >30 seconds) was achieved in 76% of patients at 24 ± 8.1 months of follow-up after 1.2 ± 0.4 procedures. PV activity was not associated with MPS either absolutely (PV 4VAverage [MPS no vs yes: 178 ± 27 ms vs 177 ± 24 ms; P = .92], PV FVAverage [P = .69], or PV Fast [P = .82]) or as a ratio relative to the LAA cycle length (PV 4VAverage /LAA 1.05 ± 0.11 vs 1.06 ± 0.21; P = .87). The presence of PV AF (31% vs 47%; P = .13) did not predict MPS. The rapidity of PV firing or presence of fibrillation within the PV was not predictive of outcome of CA for PeAF. PV activity does not identify patients most likely to benefit from a PV-based ablation strategy. Copyright © 2018 Heart Rhythm Society. Published by Elsevier Inc. All rights reserved.

Trace Element Study of MORB Glasses from 14¡ã-16¡ãN along Mid-Atlantic Ridge by LA-ICP- MS

NASA Astrophysics Data System (ADS)

Barzoi, C. A.; Casey, J. F.; Gao, Y.; Lapen, T.

2007-12-01

A comparison of 20 MORB glasses from 14°-16° N along the Mid-Atlantic Ridge using both solution-based and in situ laser ablation-based ICP-MS trace element analyses on the same samples was conducted. Li, Be, Sc, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Gd, Dy, Ho, Er, Tm, Yb,Lu, Hf, Ta, Pb, Th, and U were analyzed using the Varian 810 quadrupole ICP-MS. The instrument features a 90 degree ion mirror and low noise double-off-axis quadrupole that allows high sensitivity and low backgrounds. Precision in term of relative standard deviation (RSD) of the measurements for both methods based on repeated analyses of USGS BIR-1G and BHVO-2G glass standards and Max Planck KL-2G glass standard is within 5 % for all trace elements with the exception of Pb, which averaged 12 %. Measured trace element abundances are within 2% of recommended standard values using both solution and laser ablation methods. Comparison between the analyte concentrations obtained by solution-based ICP-MS and in situ microanalysis by laser ablation reveals little systematic differences in abundances(<5% for all elements). The two-method correlation and strong repeatability of the results indicate that rapid in situ trace element analysis by laser ablation ICP-MS is likely to become a preferred method of trace element analysis for MORB glasses. Our geochemical results and previous studies of MORB glasses in the region of the MAR between 14°-16°N show that basalts are characterized isotopic and incompatible element enrichment.The nature of the enrichment has been the topic of significant discussion and speculation because a specific mantle plume is not well defined in the region. Likewise the magma supply is probably small in the region as the magmatic crust is interpreted to be very thin in most of the area studied. Integrated studies of major element, trace element, and isotopic variations among basalts, gabbroic rocks and igneous and residual ultramafic rocks in the region indicate that 1) the enriched basalts have positive Ta-Nb anomalies, enriched relative to U, Th, and La 2) basalts have relatively high SiO2 abundances compared to the global average, 3) basalts show a HIMU isotopic signature, and 4) bulk major element abundances and mineral chemistry in mantle rocks indicate that they are among the most depleted,although variably refertilized, residual mantle assemblages sampled to date along MORs.We suggest that much of the regional variation in major and trace element data, as well as isotopic data and the unusual regional geology (multiple core complexes) can be explained by melting of a sub-axial mantle that contains two end members, one highly depleted and the other enriched. These components appear to involve ancient recycled ocean crust and lithospheric mantle.

Igneous Complexes of the Orochenka Caldera of the East Sikhote-Alin Belt: U-Pb (SHRIMP) Age, Trace and Rare Earth Element Composition, and Au-Ag Mineralization

NASA Astrophysics Data System (ADS)

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

2018-04-01

New data are presented on the geology and composition of volcanic and intrusive rocks of the Orochenka caldera, which is located in the western part of the East Sikhote Alin volcanic belt. The SHRIMP and ICP MS age of zircons of volcanic and intrusive rocks, respectively, and the composition of the volcanic rocks allow comparison of these complexes with volcanic rocks of the eastern part of the volcanic structure. New data indicate the period of transition between subduction to transform regimes.

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 crystallization and our data suggests that zircons do in fact reflect changes in isotopic and in trace element signatures on 100 ka timescales. Although we observe changes in our trace elements, the TIMS-TEA method provides an average of trace element concentrations from a zircon volume, dominated by more marginal growth zones. Therefore we will compare our data with in situ methods to determine how our trace element data compares with trace elements across zircon profiles. We acknowledge funding of FNS in the frame of ProDoc Adamello 4-D. Michel et al., 2008, Geol. 36 : 459-462 ; Schaltegger et al., 2009, Earth Planet. Sci.Lett. 286: 208-218; Schoene et al., 2010, Geochim. Cosmochim. Acta 74, 7144-7159.

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.

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.

(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 yield uniform 25 Ma zircon He dates over 1800 ppm eU. We apply simple thermal history models that account for the coevolution of zircon radiation damage and He-diffusivity to demonstrate that visible zircon metamictization and He diffusivity can be either coupled or decoupled depending on a sample's thermal history.

[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 mapping, reduce operative difficulty and produce a distinct endpoint for ablation.

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

Comparison of femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements

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

Havrilla, George Joseph; McIntosh, Kathryn Gallagher; Judge, Elizabeth

2016-10-20

Feasibility tests were conducted using femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for rapid uranium isotopic measurements. The samples used in this study consisted of a range of pg quantities of known 235/238 U solutions as dried spot residues of 300 pL drops on silicon substrates. The samples spanned the following enrichments of 235U: 0.5, 1.5, 2, 3, and 15.1%. In this direct comparison using these particular samples both pulse durations demonstrated near equivalent data can be produced on either system with respect to accuracy and precision. There is no question that either LA-ICP-MS method offers themore » potential for rapid, accurate and precise isotopic measurements of U10Mo materials whether DU, LEU or HEU. The LA-ICP-MS equipment used for this work is commercially available. The program is in the process of validating this work for large samples using center samples strips from Y-12 MP-1 LEU-Mo Casting #1.« less

Fourier Transform Infrared (FT-IR) and Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) Imaging of Cerebral Ischemia: Combined Analysis of Rat Brain Thin Cuts Toward Improved Tissue Classification.

PubMed

Balbekova, Anna; Lohninger, Hans; van Tilborg, Geralda A F; Dijkhuizen, Rick M; Bonta, Maximilian; Limbeck, Andreas; Lendl, Bernhard; Al-Saad, Khalid A; Ali, Mohamed; Celikic, Minja; Ofner, Johannes

2018-02-01

Microspectroscopic techniques are widely used to complement histological studies. Due to recent developments in the field of chemical imaging, combined chemical analysis has become attractive. This technique facilitates a deepened analysis compared to single techniques or side-by-side analysis. In this study, rat brains harvested one week after induction of photothrombotic stroke were investigated. Adjacent thin cuts from rats' brains were imaged using Fourier transform infrared (FT-IR) microspectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The LA-ICP-MS data were normalized using an internal standard (a thin gold layer). The acquired hyperspectral data cubes were fused and subjected to multivariate analysis. Brain regions affected by stroke as well as unaffected gray and white matter were identified and classified using a model based on either partial least squares discriminant analysis (PLS-DA) or random decision forest (RDF) algorithms. The RDF algorithm demonstrated the best results for classification. Improved classification was observed in the case of fused data in comparison to individual data sets (either FT-IR or LA-ICP-MS). Variable importance analysis demonstrated that both molecular and elemental content contribute to the improved RDF classification. Univariate spectral analysis identified biochemical properties of the assigned tissue types. Classification of multisensor hyperspectral data sets using an RDF algorithm allows access to a novel and in-depth understanding of biochemical processes and solid chemical allocation of different brain regions.

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.

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.

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.

Foraminiferal Stable Isotope Geochemistry At The Micrometer Scale: Is It A Dream Or Reality?

NASA Astrophysics Data System (ADS)

Misra, S.; Shuttleworth, S.; Lloyd, N. S.; Sadekov, A.; Elderfield, H.

2012-12-01

Over last few decades trace metals and stable isotope compositions of foraminiferal shells became one of the major tools to study past oceans and associated climate change. Empirical calibrations of δ11B, δ18O, Mg/Ca, Cd/Ca, Ba/Ca shells compositions have linked them to various environmental parameters such as seawater pH, temperature, salinity and productivity. Despite their common use as proxies, little is known about mechanisms of trace metals incorporation into foraminiferal calcite. Trace metals partition coefficients for foraminiferal calcite is significantly different from inorganic calcite precipitates underlining strong biological control on metal transport to the calcification sites and their incorporation into the calcite. Microscale distribution of light elements isotopes (e.g. Li, B, Mg) could potentially provide unique inside into these biomineralization processes improving our understanding of foraminiferal geochemistry. In this work we explore potentials of using recent advances in analytical geochemistry by employing laser ablation and multi-collector ICP-MS to study microscale distribution of Mg isotopes across individual foraminiferal shells and δ11B, and δ7Li analyses of individual shell chambers. The analytical setup includes an Analyte.G2 193nm excimer laser ablation system with two volume ablation cell connected to a Thermo Scientific NEPTUNE Plus MC-ICP-MS with Jet Interface option. We will discuss method limitations and advantages for foraminiferal geochemistry as well as our data on Mg isotopes distribution within shells of planktonic foraminifera.

Isotope and chemical age of the Greater Caucasus basement metamorphic rocks

NASA Astrophysics Data System (ADS)

Konilov, A. N.; Somin, M. L.; Mukhanova, A. A.

2009-04-01

It is widely accepted that metamorphic basement of the Greater Caucasus is essentially Proterozoic [i.e. Gamkrelidze & Shengelia, 2005 ]. New results of geochronological study, mainly on magmatic zircon, contradict this opinion [Somin, 2007; Somin et al., 2007a, b, c and references therein]. To precise age of metamorphism we tried to apply CHIME method on monazite [Suzuki, Adachi, 1991]. The facility consists of Tescan SEM VEGA II xmu equipped with EDS Energy 400 and WDS Wave 500 from Oxford Instruments. This system and analytical protocol for monazite analysis are close to described by Slagstad [2006]. Samples of three metamorphic units were used with purpose to investigate their PT conditions and chemical composition of accessory monazite, xenotime and zircon. In the Blyb Complex Ky-bearing St-Grt-Bt schist was studied. Temperature calculated using Grt-St and Grt-Bt thermometers are 550-600 oC at 10 kb. Because xenotime absence and very low Y2O3 content in monazite, temperature determination on Mnz thermometer was impossible. Isochron chemical age of monazite is 288±24 Ma. In the Gondary Complex the Sil-bearing Grt-Bt gneiss was studied. Temperature calculated using Grt-Bt thermometer and Grt-Pl-Sil-Qtz geobarometer correspond to 610 oC at 4 kb. Monazite thermometer [Pyle et al., 2001] indicates temperature range 533-640 oC for three samples. Monazite chemical age is 303±31 Ma, zircon of leucosome yields SHRIMP age 321-288 Ma. In the Makera Complex the And-Bt-Ms and Grt-Bt-Ms metapelites were examinated. Temperature calculated using Grt-Bt thermometer and Grt-Pl-And-Qtz geobarometer correspond to 500 oC at 2,5 kb. Monazite thermometer indicates average temperatures 293-433-447 oC. Two isochrones correspond to 239±28 Ma and 282±19 Ma. Our results of monazite dating are close to the U-Pb zircon data although not similar being some younger. Therefore conclusion on Precambrian metamorphic events in the studied complexes of the Greater Caucasus is erroneous. These complexes independently of baric type seem to be formed roughly synchronously during Variscan epoch. References: Gamkrelidze I.P., Shengelia D.M. ( 2005).The Precambrian-Paleozoic Regional Metamorphism, Granitoid Magmatism, and Geodynamics of the Caucasus. M: Nauchnyi Mir [in Russian]. Pyle J.M., Frank S. Spear F.S. et al. (2001). Monazite-Xenotime-Garnet Equilibrium in Metapelites and a New Monazite-Garnet Thermometer. Journal of Petrology, , 42, 2083-2107. Slagstad T. (2006).Chemical (U-Th-Pb) dating of monazite: Analytical protocol for a LEO 1450VP scanning electron microscope and examples from Rogaland and Finnmark, Norway. Norges geologiske undersøkelse Bulletin, 446, 11-18. Somin M.L. (2007a). Pre-Alpine basement of the Greater Caucasus: main features. In: Alpine history of the Greater Caucasus (Yu.G. Leonovб Ed.). GEOS. Moscow. P.15-38. Somin M.L., Lepekhina E.N., Konilov A.N. ( 2007b). Age of the High-Temperature Gneiss Core of the Central Caucasus. Doklady Earth Sciences, 415, 690-694. Somin M.L., Levchenkov O.A., Kotov A.B. et al. (2007c). The Paleozoic Age of High-Pressure Metamorphic Rocks in the Dakhov Salient, North-Western Caucasus: Results of U-Pb Geochronological Investigations. Doklady Earth Sciences, 416, 1018-1021. Suzuki K., Adachi M. (1991). Precambrian provenance and Silurian metamorphism of the Tsunosava paragneiss in South Kitakami terrane, northeast Japan, revealed by the chemical Th-U-total Pb isochron ages of monazite, zircon and xenotime. Journal of Geochemistry, 25, 357-376.

Timing of Late Cretaceous Gulf Coast volcanism and chronostratigraphic constraints on deposition of the Ripley Formation from a newly recognized bentonite bed, Pontotoc County, Mississippi

NASA Astrophysics Data System (ADS)

Vitale, E. J.; Gifford, J.; Platt, B. F.

2017-12-01

The Upper Cretaceous Ripley Formation is present throughout the Mississippi (MS) Embayment and contains local bentonite lenses related to regional volcanism. The Pontotoc bentonite is such a lens located near the town of Pontotoc, MS, that was strip-mined and has not been accessible since reclamation of the land. Recent investigations in Pontotoc County south of the Pontotoc bentonite site resulted in the discovery of a previously unknown bentonite bed. Litho- and biostratigraphy indicate that the bentonite is younger than known volcanism from MS. The purposes of the present investigation are 1) to test whether the new bentonite bed is correlative to the Pontotoc bentonite & 2) to recover volcanogenic zircons for U-Pb dating to better constrain timing of volcanism and chronostratigraphy of the Ripley Fm. Outcrops in an active sand pit in the field area expose 2.5 m of fine sand, and an upper gradational contact with an overlying 2.5 m of sandy clay, containing the bentonite bed. Two trenches were excavated through the outcrop, and in each trench a stratigraphic section was measured and bulk samples collected for zircons. Sampling began in the lower bounding sand and continued upsection in 1 m intervals, corresponding to the gradational contact with the bentonite, and 2 locations within the bentonite. The Ripley Fm. consists of 73 m of fossiliferous clay, sand, and calcareous sand beds. Recent stratigraphic revisions of the lateral facies in MS recognize a lower transitional clay facies, a limestone, marl, and calcareous sand facies, a sandy upper Ripley facies, and the formally named Chiwapa Sandstone Member. Ammonite biostratigraphy places the contact between the Chiwapa and the overlying Owl Creek/Prairie Bluff at 68.5 Ma. Unlike the mined area north of Pontotoc where the bentonite is within the Chiwapa, the bed here is directly above the Chiwapa section and its upper contact represents the Ripley Fm. / Owl Creek Fm. contact. Where the bentonite is present, it forms a synchronous surface in this part of the Cretaceous section. This is significant due to it being a potential previously unknown bout of volcanism, which, if the source can be found, implies a new region that may have experienced thermal maturation of hydrocarbon source rocks at a shallower depth than would have been expected under the normal geothermal gradient.

[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.

87Sr/86Sr isotope ratio analysis by laser ablation MC-ICP-MS in scales, spines, and fin rays as a nonlethal alternative to otoliths for reconstructing fish life history

USGS Publications Warehouse

Willmes, Malte; Glessner, Justin J. G.; Carleton, Scott A.; Gerrity, Paul C.; Hobbs, James A.

2016-01-01

Strontium isotope ratios (87Sr/86Sr) in otoliths are a well-established tool to determine origins and movement patterns of fish. However, otolith extraction requires sacrificing fish, and when working with protected or endangered species, the use of nonlethal samples such as scales, spines, and fin rays is preferred. Unlike otoliths that are predominantly aragonite, these tissues are composed of biological apatite. Laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) analysis of biological apatite can induce significant interference on mass 87, causing inaccurate 87Sr/86Sr measurements. To quantify this interference, we applied LA-MC-ICP-MS to three marine samples (white seabass (Atractoscion nobilis) otolith; green sturgeon (Acipenser medirostris) pectoral fin ray; salmon shark (Lamna ditropis) tooth), and freshwater walleye (Sander vitreus) otoliths, scales, and spines). Instrument conditions that maximize signal intensity resulted in elevated 87Sr/86Sr isotope ratios in the bioapatite samples, related to a polyatomic interference (40Ca31P16O, 40Ar31P16O). Retuning instrument conditions to reduce oxide levels removed this interference, resulting in accurate 87Sr/86Sr ratios across all tissue samples. This method provides a novel, nonlethal alternative to otolith analysis to reconstruct fish life histories.

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 impact ages within our sample population, and suggest at least one large impact is contemporaneous with the most common time of magmatic zircon formation on the Moon's crust visited by the Apollo missions.

Effects of 532 nm pulsed-KTP laser parameters on vessel ablation in the avian chorioallantoic membrane: implications for vocal fold mucosa.

PubMed

Broadhurst, Matthew S; Akst, Lee M; Burns, James A; Kobler, James B; Heaton, James T; Anderson, R Rox; Zeitels, Steven M

2007-02-01

Selective vascular ablation (photoangiolysis) using pulsed lasers that target hemoglobin is an effective treatment strategy for many vocal fold lesions. However, vessel rupture with extravasation of blood reduces selectivity for vessels, which is frequently observed with the 0.45-ms, 585-nm pulsed dye laser. Previous studies have shown that vessel rupture is the result of vaporization of blood, an event that varies with laser pulse width and pulse fluence (energy per unit area). Clinical observations using a 532-nm wavelength pulsed potassium-titanyl-phosphate (KTP) laser revealed less laser-induced hemorrhage than the pulsed dye laser. This study investigated settings for the pulsed KTP laser to achieve selective vessel destruction without rupture using the avian chorioallantoic membrane under conditions similar to flexible laryngoscopic delivery of the laser in clinical practice. The chick chorioallantoic membrane offers convenient access to many small blood vessels similar in size to those targeted in human vocal fold. Using a 532-nm pulsed KTP laser, pulse width, pulse energy, and working distance from the optical delivery fiber were varied to assess influence on the ability to achieve vessel coagulation without vessel wall rupture. Third-order vessels (n = 135) were irradiated: Energy (471-550 mJ), pulse width (10, 15, 30 ms), and fiber-to-tissue distance (1 mm, 3 mm) were varied systematically. Selective vessel destruction without vessel wall rupture was more often achieved by increasing pulse width, increasing the fiber-to-tissue distance, and decreasing energy. Vessel destruction without rupture was consistently achieved using 15- or 30-ms pulses with a fiber-to-tissue distance of 3 mm (pulse fluence of 13-16 J/cm). This study substantiates our clinical observation that a 532-nm pulsed KTP laser was effective for ablating microcirculation while minimizing vessel wall rupture and hemorrhage.

A novel predictive pharmacokinetic/pharmacodynamic model of repolarization prolongation derived from the effects of terfenadine, cisapride and E-4031 in the conscious chronic av node--ablated, His bundle-paced dog.

PubMed

Nolan, Emily R; Feng, Meihua Rose; Koup, Jeffrey R; Liu, Jing; Turluck, Daniel; Zhang, Yiqun; Paulissen, Jerome B; Olivier, N Bari; Miller, Teresa; Bailie, Marc B

2006-01-01

Terfenadine, cisapride, and E-4031, three drugs that prolong ventricular repolarization, were selected to evaluate the sensitivity of the conscious chronic atrioventricular node--ablated, His bundle-paced Dog for defining drug induced cardiac repolarization prolongation. A novel predictive pharmacokinetic/pharmacodynamic model of repolarization prolongation was generated from these data. Three male beagle dogs underwent radiofrequency AV nodal ablation, and placement of a His bundle-pacing lead and programmable pacemaker under anesthesia. Each dog was restrained in a sling for a series of increasing dose infusions of each drug while maintained at a constant heart rate of 80 beats/min. RT interval, a surrogate for QT interval in His bundle-paced dogs, was recorded throughout the experiment. E-4031 induced a statistically significant RT prolongation at the highest three doses. Cisapride resulted in a dose-dependent increase in RT interval, which was statistically significant at the two highest doses. Terfenadine induced a dose-dependent RT interval prolongation with a statistically significant change occurring only at the highest dose. The relationship between drug concentration and RT interval change was described by a sigmoid E(max) model with an effect site. Maximum RT change (E(max)), free drug concentration at half of the maximum effect (EC(50)), and free drug concentration associated with a 10 ms RT prolongation (EC(10 ms)) were estimated. A linear correlation between EC(10 ms) and HERG IC(50) values was identified. The conscious dog with His bundle-pacing detects delayed cardiac repolarization related to I(Kr) inhibition, and detects repolarization change induced by drugs with activity at multiple ion channels. A clinically relevant sensitivity and a linear correlation with in vitro HERG data make the conscious His bundle-paced dog a valuable tool for detecting repolarization effect of new chemical entities.

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 eruption by tens of ka, domains that could be difficult to detect by single crystal analyses. SIMS analyses can selectively sample more interior portions of grains whereas whole grain TIMS analyses will be volumetrically biased towards the outermost ~20% of the BT zircons. Spots centered on BT zircon cores sample a domain representing only a few volume percent of the crystal; if mantled completely by eruption-aged growth, single crystal zircon ages are predicted to be <5 ka older than eruption, extrapolating from the SIMS dates. When, compared to grain interiors, the greater average near-rim U concentrations are factored into this mass balance, the influence of these older domains is further diminished. A scenario that can at least partially reconcile the disparate zircon dates in the context of evolution of the BT and the dynamics of zircon crystallization is as follows: (1) zircon nucleation and relatively rapid growth an average of ~100 ka before eruption; (2) significant decay in zircon growth rates as temperatures and Zr melt gradients relax; and, finally, (3) mantling of earlier zircon cores by rejuvenation and renewed BT zircon growth during the lead-up to eruption. Comparisons between spot and single grain dating show that most zircon growth likely occurred close to eruption. [1] Crowley et al., 2007.Geology 35, 1123. [2] Rivera et al., 2011. Earth Planet. Sci. Lett. 311, 420. [3] Simon and Reid, 2005. Earth Planet. Sci. Lett. 235, 123.

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.

New zircon U-Pb LA-ICP-MS ages and Hf isotope data from the Central Pontides (Turkey): Geological and geodynamic constraints

NASA Astrophysics Data System (ADS)

Çimen, Okay; Göncüoğlu, M. Cemal; Simonetti, Antonio; Sayit, Kaan

2018-05-01

The Central Pontides in northern Anatolia is located on the accretionary complex formed by the closure of Neotethyan Intra-Pontide Ocean between the southern Eurasian margin (Istanbul-Zonguldak Terrane) and the Cimmerian Sakarya Composite Terrane. Among other components of the oceanic lithosphere, it comprises not yet well-dated felsic igneous rocks formed in arc-basin as well as continent margin settings. In-situ U-Pb age results for zircons from the arc-basin system (öangaldağ Metamorphic Complex) and the continental arc (Devrekani Metadiorite and Granitoid) yield ages of 176 ± 6 Ma, 163 ± 9 Ma and 165 ± 3 Ma, respectively. Corresponding in-situ average (initial) 176Hf/177Hf initial ratios are 0.28261 ± 0.00003, 0.28267 ± 0.00002 and 0.28290 ± 0.00004 for these units and indicative of a subduction-modified mantle source. The new U-Pb ages and Hf isotope data from these oceanic and continental arc units together with regional geological constraints support the presence of a multiple subduction system within the Intra-Pontide Ocean during the Middle Jurassic.

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 source. Close age and geochemical affinity of U1438 detrital zircons to igneous zircons in Eocene leucotonalite from the partially exhumed intrusive suite at Komahashi-Daini Seamount in the northernmost KPR suggests that these zircons also can yield insight into the link between silicic volcanism and evolving tonalitic intrusions in the Paleogene IB arc.

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 stages of initial crystallisation. These results provide the first evidence of crystal plastic dislocation creep in zircon associated with magmatic crystallisation and indicate that the development of crystal-plastic microstructures in zircon is not restricted to high-strain rocks. Such microstructures have previously been shown to enhance bulk diffusion of trace elements (U, Th and REE) in zircon. The development of deformation microstructures, and therefore multiple diffusion pathways in zircon in the magmatic environment, has significant implications for the interpretation of geochemical data from igneous zircon and the trace element budgets of melts due to the potential enhancement of bulk diffusion and dissolution rates.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Where is the exact origin of narrow premature ventricular contractions manifesting qR in inferior wall leads?

PubMed

Zheng, Cheng; Li, Jin; Lin, Jia-Xuan; Wang, Lu-Ping; Lin, Jia-Feng

2016-04-04

In recent years, radiofrequency catheter ablation(RFCA) has been established as an effective therapy for idiopathic premature ventricular contractions (PVCs), however, its effect on the narrow PVCs (QRS duration < 130 msec) with qR pattern in inferior leads, may not been fully concluded. Characteristics of 12-lead electrocardiogram (ECG) and electrophysiologic recordings were analyzed in 40 patients with symptomatic PVCs manifesting narrow QRS complex with qR pattern in inferior leads. The procedure of RFCA was performed based on pace mapping and activation mapping. Among the 40 patients with narrow PVCs, complete elimination of PVCs was achieved by RFCA in 35 patients during a median follow-up period of 23 months. Successful ablation was achieved on 19 patients at the sites where earliest Purkinje potentials were recorded in left ventricular anterosuperior septum, thus PVCs arising from left anterior fascicle (LAF) were confirmed, for these PVCs, the QRS morphology were right bundle branch and left posterior fascicle block (RBBB + LPFB) with rightward axis, the average QRS duration 116.07 ± 7.96 ms, R or rsR'in lead V1,with transition zone ahead of lead V1 in precordial leads. Another 16 successful RFCA were achieved by energy delivery at interleaflet triangle(ILT) between right coronary cusp(RCC) and left coronary cusp(LCC) where no Purkinje potentials were recorded, for narrow PVCs arising from the L-RCC ILT, the QRS morphology were similar to the PVCs arising from LAF but much narrower in QRS duration (100.44 ± 3.49 vs. 116.07 ± 7.96 ms, p < 0.05), they were also R or Rs in lead V1 with the transition zone ahead of lead V1. For 5 symptomatic narrow PVCs failed to the procedure of RFCA, their electrocardiographic characteristics showed that the narrowest QRS duration (91.80 ± 6.94 vs. 100.44 ± 3.49, 116.07 ± 7.96 ms, p < 0.05), rs or rS (r/s or r/S≦1) morphology in lead V1 with the precordial transition zone behind lead V3. Most of idiopathic PVCs of narrow QRS duration (<130 msec) with qR pattern in inferior leads can be cured by the procedure of RFCA. On the basis of our study, we proposed that for narrow PVCs presenting qR pattern in inferior leads, when the ablation procedure failed at proximity of LAF within left anterosuperior septum, mapping and ablation in L-RCC ILT can be tried. The present findings can be helpful for planning catheter ablation for narrow PVCs manifesting qR in inferior leads.

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 partial Hf isotope homogenization in the melt, and melt infiltration from an external source. New zircon was most likely formed by a peritectic reaction with melt above the wet solidus (peritectic zircon). Conversely, the amphibolite-facies host gneisses lack indications of significant melt production. Pre-metamorphic zircons experienced mainly solid-state recrystallization and variable Pb loss with only minor new zircon formation. However, subtle changes in cathodoluminescence pattern, in the Hf and O isotopes, and in the Lu/Hf, Yb/Hf ratios of zircons suggest that small volumes of melt were locally present. In difference to granulites, melt was internally produced. The detection of low degree melts (inferred from zircon geochemistry) is extremely important for the rheology because these amphibolite-facies rocks could act as large scale ductile shear zones. The new zircon data support a different P-T path for closely spaced amphibolite- and granulite-facies rocks.

Origin and geodynamic significance of the early Mesozoic Weiya LP and HT granulites from the Chinese Eastern Tianshan

NASA Astrophysics Data System (ADS)

Mao, Ling-Juan; He, Zhen-Yu; Zhang, Ze-Ming; Klemd, Reiner; Xiang, Hua; Tian, Zuo-Lin; Zong, Ke-Qing

2015-12-01

The Chinese Tianshan in the southwestern part of the Central Asian Orogenic Belt (CAOB) is characterized by a variety of high-grade metamorphic rocks, which provide critical constraints for understanding the geodynamic evolution of the CAOB. In this paper, we present detailed petrological and zircon U-Pb geochronological studies of the Weiya low-pressure and high-temperature (LP-HT) granulites of the Chinese Eastern Tianshan. These granulites were previously considered to be a product of a regional metamorphic orogenic event. Due to different bulk-rock chemistries the Weiya granulites, which occur as lenses within the contact metamorphic aureole of the Weiya granitic ring complex, have a variety of felsic-pelitic and mafic granulites with different textural equilibrium mineral assemblages including garnet-cordierite-sillimanite-bearing granulites, cordierite-sillimanite-bearing granulites, cordierite-orthopyroxene-bearing granulites, and orthopyroxene-clinopyroxene-bearing granulites. Average P-T thermobarometric calculations and conventional geothermobarometry indicates that the Weiya granulites underwent early prograde metamorphism under conditions of 600-650 °C at 3.2-4.2 kbar and peak metamorphism of 750-840 °C at 2.9-6.3 kbar, indicating a rather high geothermal gradient of ca. 60 °C/km. Zircon U-Pb LA-ICP-MS dating revealed metamorphic ages between 244 ± 1 to 237 ± 3 Ma, which are in accordance with the crystallization age of the Weiya granitic ring complex. We suggest that the formation of the Weiya granulites was related to contemporaneous granitic magmatism instead of a regional metamorphic orogenic event. In addition, a Late Devonian metamorphic age of ca. 380 Ma was recorded in zircon mantle domains from two pelitic samples which is consistent with the metamorphic age of the Xingxingxia metamorphic complex in the Chinese Eastern Tianshan. This suggests that the mantle domains of the zircon grains of the Weiya granulites probably formed during the Late Devonian regional metamorphism and were overprinted by the Early Triassic contact metamorphism. Therefore, Early Triassic geodynamic models for the southwestern part of the CAOB, which are based on a previously suggested regional metamorphic orogenic event of the Weiya granulites, need to be viewed with caution.

Petrology and zircon U-Pb geochronology of metagabbros from a mafic-ultramafic suite at Aniyapuram: Neoarchean to Early Paleoproterozoic convergent margin magmatism and Middle Neoproterozoic high-grade metamorphism in southern India

NASA Astrophysics Data System (ADS)

Koizumi, Tatsuya; Tsunogae, Toshiaki; Santosh, M.; Tsutsumi, Yukiyasu; Chetty, T. R. K.; Saitoh, Yohsuke

2014-12-01

Several mafic-ultramafic complexes occur within the Palghat-Cauvery Suture Zone (PCSZ) in southern India. The PCSZ is regarded in recent models as the zone along which crustal blocks were amalgamated during the Late Neoproterozoic-Cambrian (550-530 Ma) Gondwana assembly. Here we report petrologic and zircon U-Pb geochronologic data from gabbros associated with the Aniyapuram mafic-ultramafic suite in the central domain of the PCSZ. Geothermobarometry and pseudosection approach in the system NCFMASHTO for the metagabbro (Grt + Cpx + Opx + Hbl + Pl + Qtz + Ilm + Rt) yield peak P-T condition of 9.8-10.6 kbar and 730-790 °C, which was followed by decompression to 6.5-8.0 kbar and ca. 750 °C as inferred from the formation of Opx + Pl symplectite around garnet, probably along a clockwise P-T path. Zircon U-Pb data analyzed by LA-ICP-MS plot along a well-defined discordia with upper and lower intercepts in the concordia at 2436 ± 22 Ma and 731 ± 11 Ma respectively, suggesting Neoarchean-Early Paleoproterozoic magmatic emplacement of the protolith and progressive Pb loss related to the Middle Neoproterozoic (Cryogenian) thermal event (or high-grade metamorphism). These results closely compare with the available Neoarchean magmatic ages of mafic-ultramafic complexes (e.g., Sittampundi, Devanur, Agali Hills, and Kanja Malai) and Middle Neoproterozoic magmatic event (e.g., Manamedu and Kadavur) in the PCSZ and adjacent granulite blocks. The 650 Ma concordia ages obtained from unzoned zircons might indicate the timing of high-grade metamorphism or post-peak hydration event. The P-T conditions obtained from Aniyapuram are significantly lower than the high-pressure and ultrahigh-temperature conditions of the 550-530 Ma final collisional event (P > 14 kbar and T > 950 °C). The Middle Neoproterozoic (ca. 730 Ma or 650 Ma) high-grade metamorphism in Aniyapuram reported for the first time from the PCSZ is possibly associated with magmatism in arc tectonic setting.

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.

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 age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (˜1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the 207Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.

Trace element analysis of rough diamond by LA-ICP-MS: a case of source discrimination?

PubMed

Dalpé, Claude; Hudon, Pierre; Ballantyne, David J; Williams, Darrell; Marcotte, Denis

2010-11-01

Current profiling of rough diamond source is performed using different physical and/or morphological techniques that require strong knowledge and experience in the field. More recently, chemical impurities have been used to discriminate diamond source and with the advance of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) empirical profiling of rough diamonds is possible to some extent. In this study, we present a LA-ICP-MS methodology that we developed for analyzing ultra-trace element impurities in rough diamond for origin determination ("profiling"). Diamonds from two sources were analyzed by LA-ICP-MS and were statistically classified by accepted methods. For the two diamond populations analyzed in this study, binomial logistic regression produced a better overall correct classification than linear discriminant analysis. The results suggest that an anticipated matrix match reference material would improve the robustness of our methodology for forensic applications. © 2010 American Academy of Forensic Sciences.

S-type granite generation and emplacement during a regional switch from extensional to contractional deformation (Central Iberian Zone, Iberian autochthonous domain, Variscan Orogeny)

NASA Astrophysics Data System (ADS)

Pereira, M. F.; Díez Fernández, R.; Gama, C.; Hofmann, M.; Gärtner, A.; Linnemann, U.

2018-01-01

Zircon grains extracted from S-type granites of the Mêda-Escalhão-Penedono Massif (Central Iberian Zone, Variscan Orogen) constrain the timing of emplacement and provide information about potential magma sources. Simple and composite zircon grains from three samples of S-type granite were analyzed by LA-ICP-MS. New U-Pb data indicate that granites crystallized in the Bashkirian (318.7 ± 4.8 Ma) overlapping the proposed age range of ca. 321-317 Ma of the nearby S-type granitic rocks of the Carrazeda de Anciães, Lamego and Ucanha-Vilar massifs. The timing of emplacement of such S-type granites seems to coincide with the waning stages of activity of a D2 extensional shear zone (i.e. Pinhel shear zone) developed in metamorphic conditions that reached partial melting and anatexis (ca. 321-317 Ma). Dykes of two-mica granites (resembling diatexite migmatite) are concordant and discordant to the compositional layering and S2 (main) foliation of the high-grade metamorphic rocks of the Pinhel shear zone. Much of the planar fabric in these dykes was formed during magmatic crystallization and subsequent solid-state deformation. Field relationships suggest contemporaneity between the ca. 319-317 Ma old magmatism of the study area and the switch from late D2 extensional deformation to early D3 contractional deformation. Inherited zircon cores are well preserved in these late D2-early D3 S-type granite plutons. U-Pb ages of inherited zircon cores range from ca. 2576 to ca. 421 Ma. The spectra of inherited cores overlap closely the range of detrital and magmatic zircon grains displayed by the Ediacaran to Silurian metasedimentary and metaigneous rocks of the Iberian autochthonous and parautochthonous domains. This is evidence of a genetic relationship between S-type granites and the host metamorphic rocks. There is no substantial evidence for the addition of mantle-derived material in the genesis of these late D2-early D3 S-type granitic rocks. The ɛNd arrays of heterogeneous crustal anatectic melts may be just inherited from the source, probably reflecting mixing of a range of crustal materials with different ages and primary isotopic signatures. The generation of the Bashkirian S-type granites has been dominated by continental crust recycling, rather than the addition of new material from mantle sources.

Zircon U-Pb ages, geochemistry, and Nd-Hf isotopes of the TTG gneisses from the Jiaobei terrane: Implications for Neoarchean crustal evolution in the North China Craton

NASA Astrophysics Data System (ADS)

Shan, Houxiang; Zhai, Mingguo; Wang, Fang; Zhou, Yanyan; Santosh, M.; Zhu, Xiyan; Zhang, Huafeng; Wang, Wei

2015-02-01

The Precambrian basement in the Jiaobei terrane is largely composed of Tonalite-Trondhjemite-Granodiorite (TTG) suite of rocks and offers important insights into the crustal evolution history of the North China Craton (NCC). The LA-ICP-MS zircon U-Pb age data presented in this study show that the magmatic protoliths of the TTG gneisses formed during 2508-2547 Ma and recorded the Paleoproterozoic metamorphism (∼1905 Ma). The rocks are enriched in LILE (Rb, Ba and Sr) and depleted in HFSE (Nb, Ta, Zr and Hf). They are characterized by high Sr contents (406-2906 ppm), Sr/Y ratios (31.3-355) and subchondritic Nb/Ta ratios (18.5-68.9). The TTGs show relatively high ΣREE contents (72.0-266 ppm) with strongly enriched LREE ((La/Yb)N = 11.5-121) and positive or negligible negative Eu anomalies (Eu/Eu∗ = 0.84-1.89). These geochemical features suggest that the magma source might have been rutile-bearing amphibole eclogite. Their high Mg# numbers (42-56) and high Cr (153-285 ppm) and Ni contents (22.2-74.5 ppm) indicate interaction with the mantle wedge during magma ascent. The whole rock εNd (t) values (+2.6 to +3.8) and most of the magmatic zircon εHf (t) values (+1.3 to +7.6) suggest juvenile to evolved isotopic signatures. All these lines of evidence suggest that the TTG rocks in this study formed through partial melting of subducted oceanic slab in a continental arc environment. The drill holes in the Jiaobei terrane are dominated by ∼2.5 Ga TTG gneisses, suggesting that the TTG magma at ∼2.5 Ga is more widely distributed deep underground than that of ∼2.7-2.9 Ga, at least within the approachable depth range of our research. Some zircon grains from Jiaobei TTGs give high εHf (t) values plotting above the curve of 0.75 ∗ εHf of DM, and their TCDM ages are very close to the time of the zircon crystallization. However, the majority of the εHf (t) values fall below the curve of 0.75 ∗ εHf of DM and their TCDM ages are concentrated between ∼2.7-2.9 Ga. Therefore, combining with other related studies, we propose that the ∼2.5-2.6 Ga magmatism in the NCC probably represents a coherent event of crustal growth and major reworking (remelting).

A Silurian-early Devonian slab window in the southern Central Asian Orogenic Belt: Evidence from high-Mg diorites, adakites and granitoids in the western Central Beishan region, NW China

NASA Astrophysics Data System (ADS)

Zheng, Rongguo; Xiao, Wenjiao; Li, Jinyi; Wu, Tairan; Zhang, Wen

2018-03-01

The Beishan orogenic belt is a key region for deciphering the accretionary processes of the southern Central Asian Orogenic Belt. Here in this paper we present new zircon U-Pb ages, bulk-rock major and trace element, and zircon Hf isotopic data for the Baitoushan, and Bagelengtai plutons in the western Central Beishan region to address the accretionary processes. The Baitoushan pluton consists of quartz diorites, monzonites and K-feldspar granites, with zircon LA-ICP-MS U-Pb ages of 435 Ma, 421 Ma and 401 Ma, respectively. The Baitoushan quartz diorites and quartz monzonites exhibit relatively high MgO contents and Mg# values (63-72), display enrichments in LILEs and LREEs, and exhibit high Ba (585-1415 ppm), Sr (416-570 ppm) and compatible element (such as Cr and Ni) abundances, which make them akin to typical high-Mg andesites. The Baitoushan quartz diorites and quartz monzonites were probably generated by the interaction of subducted oceanic sediment-derived melts and mantle peridotites. The Baitoushan K-feldspar granites are ascribed to fractionated I-type granites with peraluminous and high-K calc-alkaline characteristics. They exhibit positive εHf(t) values (2.43-7.63) and Mesoproterozoic-Neoproterozoic zircon Hf model ages (0.92-1.60 Ga). Those early Devonian granites, including Baitoushan K-feldspar granite and Gongpoquan leucogranites (402 Ma), are derived from melting of the mafic lower crust and/or sediments by upwelling of hot asthenospheric mantle. The Bagelengtai granodiorites exhibit similar geochemical signatures with that of typical adakites, with a zircon SHRIMP U-Pb age of 435 Ma. They exhibit relatively high Sr (502-628 ppm) and Al2O3 (16.40-17.40 wt.%) contents, and low MgO (1.02-1.29 wt.%), Y (3.37-6.94 ppm) and HREEs contents, with relatively high Sr/Y and (La/Yb)N ratios. The Bagelengtai granodiorites were derived from partial melting of subducted young oceanic crust, with significant contributions of subducted sediments, subsequently hybridized by the mantle peridotite. On the basis of our data and combined with previous data, we conclude that a Silurian-early Devonian slab window model accounts for all geological records in the western segment of the Central Beishan. We further propose that magmatic events associated with a slab window played an important role in crustal growth of the Central Asian Orogenic Belt.

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 intervals of relatively temperate conditions from 4.4 to 4.0 Ga that were conducive to oceans and possibly life.

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 signal in a felsic igneous setting, may be evidence that a terrestrial biosphere had emerged by 4.1 Ga, or ~300 Ma earlier than has been previously proposed.

Difference Between Dormant Conduction Sites Revealed by Adenosine Triphosphate Provocation and Unipolar Pace-Capture Sites Along the Ablation Line After Pulmonary Vein Isolation.

PubMed

Kogawa, Rikitake; Okumura, Yasuo; Watanabe, Ichiro; Sonoda, Kazumasa; Sasaki, Naoko; Takahashi, Keiko; Iso, Kazuki; Nagashima, Koichi; Ohkubo, Kimie; Nakai, Toshiko; Kunimoto, Satoshi; Hirayama, Atsushi

2016-01-01

Dormant pulmonary vein (PV) conduction revealed by adenosine/adenosine triphosphate (ATP) provocation test and exit block to the left atrium by pacing from the PV side of the ablation line ("pace and ablate" method) are used to ensure durable pulmonary vein isolation (PVI). However, the mechanistic relation between ATP-provoked PV reconnection and the unexcitable gap along the ablation line is unclear.Forty-five patients with atrial fibrillation (AF) (paroxysmal: 31 patients, persistent: 14 patients; age: 61.1 ± 9.7 years) underwent extensive encircling PVI (EEPVI, 179 PVs). After completion of EEPVI, an ATP provocation test (30 mg, bolus injection) and unipolar pacing (output, 10 mA; pulse width, 2 ms) were performed along the previous EEPVI ablation line to identify excitable gaps. Dormant conduction was revealed in 29 (34 sites) of 179 PVs (16.2%) after EEP-VI (22/45 patients). Pace capture was revealed in 59 (89 sites) of 179 PVs (33.0%) after EEPVI (39/45 patients), and overlapping sites, ie, sites showing both dormant conduction and pace capture, were observed in 22 of 179 (12.3%) PVs (17/45 patients).Some of the ATP-provoked dormant PV reconnection sites were identical to the sites with excitable gaps revealed by pace capture, but most of the PV sites were differently distributed, suggesting that the main underling mechanism differs between these two forms of reconnection. These findings also suggest that performance of the ATP provocation test followed by the "pace and ablate" method can reduce the occurrence of chronic PV reconnections.

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

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 constraints on impact ages within our sample population, and suggest at least one large impact is contemporaneous with the most common time of magmatic zircon formation on the Moon’s crust visited by the Apollo missions.« less

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 constraints on impact ages within our sample population, and suggest at least one large impact is contemporaneous with the most common time of magmatic zircon formation on the Moon’s crust visited by the Apollo missions.« less

5-Year Outcome of Pulmonary Vein Isolation by Loss of Pace Capture on the Ablation Line Versus Electrical Circumferential Pulmonary Vein Isolation.

PubMed

Moser, Julia; Sultan, Arian; Lüker, Jakob; Servatius, Helge; Salzbrunn, Tim; Altenburg, Manuel; Schäffer, Benjamin; Schreiber, Doreen; Akbulak, Ruken Ö; Vogler, Julia; Hoffmann, Boris A; Willems, Stephan; Steven, Daniel

2017-11-01

This study sought to compare long-term arrhythmia-free survival between electrical circumferential pulmonary vein isolation (PVI) and PVI with the endpoint of unexcitability along the ablation line. PVI is the standard ablation strategy of paroxysmal atrial fibrillation, although arrhythmia recurrence in long-term follow-up (FU) is high. The endpoint of unexcitability along the ablation line results in decreased arrhythmia recurrence compared to electrical PVI in 1-year FU. Seventy-four consecutive patients (age 62.5 ± 10.6 years; 70.3% male) with de novo paroxysmal atrial fibrillation who were initially included in our randomized trial and underwent catheter ablation at our institution were analyzed. Patients who were randomized to either a conventional group (PVI, guided by circumferential catheter signals) or a pace-guided group (PG, anatomical ablation line encircling, ablation until loss of pace capture at 10 V, 2-ms pulse width on the ablation line) underwent long-term FU. The primary endpoint was recurrence of any atrial fibrillation or atrial tachycardia after a blanking period of 3 months. Sixty-nine patients completed a mean FU period of 5.14 ± 0.98 years. Arrhythmia-free survival without antiarrhythmic drug therapy was significantly higher in the PG group (71.05% vs. 25.81%, p = 0.002). Furthermore, multiple procedure success (1.29 ± 0.61 procedures in PG vs. 1.97 ± 1.06 procedures in conventional group, p < 0.001) was higher in the PG group compared to the conventional group (89.47% vs. 58.06%, p = 0.005). The endpoint of unexcitability along the PVI line improves success rates, resulting in a significant reduction of exposure to invasive procedures in 5-year FU. Copyright © 2017 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.

Preliminary characterisation of new glass reference materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by laser ablation-inductively coupled plasma-mass spectrometry using 193 nm, 213 nm and 266 nm wavelengths

USGS Publications Warehouse

Guillong, M.; Hametner, K.; Reusser, E.; Wilson, S.A.; Gunther, D.

2005-01-01

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.

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 with Nd crustal residence ages from the possible sources in Australia, Antarctica and Laurentia reveals the possible sources of the zircons. Based on the paleogeographic setting in Cambrian time the Grenville-age zircons were most likely derived from Drauning Maud Land (Antarctica), thus confirming earlier models by [1] and [3]. The Archean zircons were most likely derived from W-Australia (Yilgarn or Pilbara Kraton) or E-Antarctica (Miller Range). [1] Wombacher and Münker 2000: J. Geol. 108, [2] Ireland et al. 1998: Geology 26, [3] Flöttmann et al. 1998: J. Geol. Soc. 155.

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.

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.

Loss of pace capture on the ablation line: a new marker for complete radiofrequency lesions to achieve pulmonary vein isolation.

PubMed

Steven, Daniel; Reddy, Vivek Y; Inada, Keiichi; Roberts-Thomson, Kurt C; Seiler, Jens; Stevenson, William G; Michaud, Gregory F

2010-03-01

Catheter ablation procedures for atrial fibrillation (AF) often involve circumferential antral isolation of pulmonary veins (PV). Inability to reliably identify conduction gaps on the ablation line necessitates placing additional lesions within the intended lesion set. This pilot study investigated the relationship between loss of pace capture directly along the ablation line and electrogram criteria for PV isolation (PVI). Using a 3-dimensional anatomic mapping system and irrigated-tip radiofrequency (RF) ablation catheter, lesions were placed in the PV antra to encircle ipsilateral vein pairs until pace capture at 10 mA/2 ms no longer occurred along the line. During ablation, a circular mapping catheter was placed in an ipsilateral PV, but the electrograms were not revealed until loss-of-pace capture. The procedural end point was PVI (entrance and exit block). Thirty patients (57 +/- 12 years; 15 male [50%]) undergoing PVI in 2 centers (3 primary operators) were included (left atrial diameter 40 +/- 4 mm, left ventricular ejection fraction 60 +/- 7%). All patients reached the end points of complete PVI and loss of pace capture. When PV electrograms were revealed after loss of pace capture along the line, PVI was present in 57 of 60 (95%) vein pairs. In the remaining 3 of 60 (5%) PV pairs, further RF applications achieved PVI. The procedure duration was 237 +/- 46 minutes, with a fluoroscopy time of 23 +/- 9 minutes. Analysis of the blinded PV electrograms revealed that even after PVI was achieved, additional sites of pace capture were present on the ablation line in 30 of 60 (50%) of the PV pairs; 10 +/- 4 additional RF lesions were necessary to fully achieve loss of pace capture. After ablation, the electrogram amplitude was lower at unexcitable sites (0.25 +/- 0.15 mV vs. 0.42 +/- 0.32 mV, P < .001), but there was substantial overlap with pace capture sites, suggesting that electrogram amplitude lacks specificity for identifying pace capture sites. Complete loss of pace capture directly along the circumferential ablation line correlates with entrance block in 95% of vein pairs and can be achieved without circular mapping catheter guidance. Thus, pace capture along the ablation line can be used to identify conduction gaps. Interestingly, more RF ablation energy was required to achieve loss of pace capture along the ablation line than for entrance block into PVs. Further study is warranted to determine whether this method results in more durable ablation lesions that reduce recurrence of AF. Copyright 2010 Heart Rhythm Society. Published by Elsevier Inc. All rights reserved.

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 Cenozoic. All these populations are complex and suggest multiple episodes of magmatism for each. Permian-Triassic detrital zircons were derived from two distinct source areas, the SE Asian tin belt and eastern Indonesia (Banggai-Sula and West Papua). It is notable that in both these areas zircon ages show a gap in magmatism around 260-250 Ma. In West Papua, North Banda and Sulawesi, detrital Triassic zircons are present in many metamorphic rocks, suggesting Triassic or post-Triassic metamorphism in these areas, in rocks previously thought to be Paleozoic or older metamorphic basement. Cretaceous zircons are common in Sumatra, Borneo, Vietnam, Malaysia, Thailand, on the Sunda shelf, and in Sulawesi. They were produced during multiple magmatic events that are unlikely to have a common cause. Cretaceous zircons have also been found in all metamorphic rocks from SW Borneo previously suggested to be Palaeozoic or older. Cenozoic zircons were largely derived from subduction volcanism and are widely distributed, but are a relatively small proportion of the total data set, reflecting a combination of natural, sampling and analytical reasons. Zircon age data suggest that SE Asia records crustal growth mainly by re-assembly of continental fragments rather than by creation of significant new crust.

Laser-ablation electrospray ionization mass spectrometry with ion mobility separation reveals metabolites in the symbiotic interactions of soybean roots and rhizobia.

PubMed

Stopka, Sylwia A; Agtuca, Beverly J; Koppenaal, David W; Paša-Tolić, Ljiljana; Stacey, Gary; Vertes, Akos; Anderton, Christopher R

2017-07-01

Technologies enabling in situ metabolic profiling of living plant systems are invaluable for understanding physiological processes and could be used for rapid phenotypic screening (e.g., to produce plants with superior biological nitrogen-fixing ability). The symbiotic interaction between legumes and nitrogen-fixing soil bacteria results in a specialized plant organ (i.e., root nodule) where the exchange of nutrients between host and endosymbiont occurs. Laser-ablation electrospray ionization mass spectrometry (LAESI-MS) is a method that can be performed under ambient conditions requiring minimal sample preparation. Here, we employed LAESI-MS to explore the well characterized symbiosis between soybean (Glycine max L. Merr.) and its compatible symbiont, Bradyrhizobium japonicum. The utilization of ion mobility separation (IMS) improved the molecular coverage, selectivity, and identification of the detected biomolecules. Specifically, incorporation of IMS resulted in an increase of 153 differentially abundant spectral features in the nodule samples. The data presented demonstrate the advantages of using LAESI-IMS-MS for the rapid analysis of intact root nodules, uninfected root segments, and free-living rhizobia. Untargeted pathway analysis revealed several metabolic processes within the nodule (e.g., zeatin, riboflavin, and purine synthesis). Compounds specific to the uninfected root and bacteria were also detected. Lastly, we performed depth profiling of intact nodules to reveal the location of metabolites to the cortex and inside the infected region, and lateral profiling of sectioned nodules confirmed these molecular distributions. Our results established the feasibility of LAESI-IMS-MS for the analysis and spatial mapping of plant tissues, with its specific demonstration to improve our understanding of the soybean-rhizobial symbiosis. © 2017 The Authors The Plant Journal © 2017 John Wiley & Sons Ltd.

Laser ablation-inductively coupled plasma mass spectrometry: an emerging technology for detecting rare cells in tissue sections.

PubMed

Managh, Amy J; Hutchinson, Robert W; Riquelme, Paloma; Broichhausen, Christiane; Wege, Anja K; Ritter, Uwe; Ahrens, Norbert; Koehl, Gudrun E; Walter, Lisa; Florian, Christian; Schlitt, Hans J; Reid, Helen J; Geissler, Edward K; Sharp, Barry L; Hutchinson, James A

2014-09-01

Administering immunoregulatory cells to patients as medicinal agents is a potentially revolutionary approach to the treatment of immunologically mediated diseases. Presently, there are no satisfactory, clinically applicable methods of tracking human cells in patients with adequate spatial resolution and target cell specificity over a sufficient period of time. Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) represents a potential solution to the problem of detecting very rare cells in tissues. In this article, this exquisitely sensitive technique is applied to the tracking of gold-labeled human regulatory macrophages (Mregs) in immunodeficient mice. Optimal conditions for labeling Mregs with 50-nm gold particles were investigated by exposing Mregs in culture to variable concentrations of label: Mregs incubated with 3.5 × 10(9) particles/ml for 1 h incorporated an average of 3.39 × 10(8) Au atoms/cell without loss of cell viability. Analysis of single, gold-labeled Mregs by LA-ICP-MS registered an average of 1.9 × 10(5) counts/cell. Under these conditions, 100% labeling efficiency was achieved, and label was retained by Mregs for ≥36 h. Gold-labeled Mregs adhered to glass surfaces; after 24 h of culture, it was possible to colabel these cells with human-specific (154)Sm-tagged anti-HLA-DR or (174)Yb-tagged anti-CD45 mAbs. Following injection into immunodeficient mice, signals from gold-labeled human Mregs could be detected in mouse lung, liver, and spleen for at least 7 d by solution-based inductively coupled plasma mass spectrometry and LA-ICP-MS. These promising results indicate that LA-ICP-MS tissue imaging has great potential as an analytical technique in immunology. Copyright © 2014 by The American Association of Immunologists, Inc.

Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

PubMed

Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

2010-07-30

The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. Copyright 2010 John Wiley & Sons, Ltd.

Laser-ablation electrospray ionization mass spectrometry with ion mobility separation reveals metabolites in the symbiotic interactions of soybean roots and rhizobia

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

Stopka, Sylwia A.; Agtuca, Beverly J.; Koppenaal, David W.

Technologies enabling in situ metabolic profiling of living plant systems are invaluable for understanding physiological processes and could be used for rapid phenotypic screening (e.g., to produce plants with superior biological nitrogen fixing ability). The symbiotic interaction between legumes and nitrogen-fixing soil bacteria results in a specialized plant organ (i.e., root nodule), where the exchange of nutrients between host and endosymbiont occurs. Laser ablation electrospray ionization mass spectrometry (LAESI-MS) is a method that can be performed under ambient conditions requiring minimal sample preparation. Here, we employed LAESI-MS to explore the well-characterized symbiosis between soybean (Glycine max L. Merr.) and itsmore » compatible symbiont, Bradyrhizobium japonicum. The utilization of ion mobility separation (IMS) improved the molecular coverage, selectivity, and identification of the detected biomolecules. Specifically, incorporation of IMS resulted in an increase of 153 detected metabolites in the nodule samples. The data presented demonstrates the advantages of using LAESI-IMS-MS for the rapid analysis of intact root nodules, uninfected root segments, and free-living rhizobia. Untargeted pathway analysis revealed several metabolic processes within the nodule (e.g., zeatin, riboflavin, and purine synthesis). Compounds specific to the uninfected root and bacteria were also detected. Lastly, we performed depth-profiling of intact nodules to reveal the location of metabolites to the cortex and inside the infected region, and lateral profiling of sectioned nodules confirmed these molecular distributions. Our results established the feasibility of LAESI-IMS-MS for the analysis and spatial mapping of plant tissues, with its specific demonstration to improve our understanding of the soybean-rhizobial symbiosis.« less

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 (±0.07)- 0.046 (±0.003)× SSTl These calibrations agree with literature within experimental errors, except for Mg which displays a 35% greater temperature dependence than reported previously. None of the elements in the coral appear to be sensitive to decreases in salinity associated with heavy rainfall in the summer of 1991/1992.

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.

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

Flying Drosophila stabilize their vision-based velocity controller by sensing wind with their antennae

PubMed Central

Fuller, Sawyer Buckminster; Straw, Andrew D.; Peek, Martin Y.; Murray, Richard M.; Dickinson, Michael H.

2014-01-01

Flies and other insects use vision to regulate their groundspeed in flight, enabling them to fly in varying wind conditions. Compared with mechanosensory modalities, however, vision requires a long processing delay (~100 ms) that might introduce instability if operated at high gain. Flies also sense air motion with their antennae, but how this is used in flight control is unknown. We manipulated the antennal function of fruit flies by ablating their aristae, forcing them to rely on vision alone to regulate groundspeed. Arista-ablated flies in flight exhibited significantly greater groundspeed variability than intact flies. We then subjected them to a series of controlled impulsive wind gusts delivered by an air piston and experimentally manipulated antennae and visual feedback. The results show that an antenna-mediated response alters wing motion to cause flies to accelerate in the same direction as the gust. This response opposes flying into a headwind, but flies regularly fly upwind. To resolve this discrepancy, we obtained a dynamic model of the fly’s velocity regulator by fitting parameters of candidate models to our experimental data. The model suggests that the groundspeed variability of arista-ablated flies is the result of unstable feedback oscillations caused by the delay and high gain of visual feedback. The antenna response drives active damping with a shorter delay (~20 ms) to stabilize this regulator, in exchange for increasing the effect of rapid wind disturbances. This provides insight into flies’ multimodal sensory feedback architecture and constitutes a previously unknown role for the antennae. PMID:24639532

Comparison of KTP, Thulium, and CO2 laser in stapedotomy using specialized visualization techniques: thermal effects.

PubMed

Kamalski, Digna M A; Verdaasdonk, Rudolf M; de Boorder, Tjeerd; Vincent, Robert; Trabelzini, Franco; Grolman, Wilko

2014-06-01

High-speed thermal imaging enables visualization of heating of the vestibule during laser-assisted stapedotomy, comparing KTP, CO2, and Thulium laser light. Perforation of the stapes footplate with laser bears the risk of heating of the inner ear fluids. The amount of heating depends on absorption of the laser light and subsequent tissue ablation. The ablation of the footplate is driven by strong water absorption for the CO2 and Thulium laser. For the KTP laser wavelength, ablation is driven by carbonization of the footplate and it might penetrate deep into the inner ear without absorption in water. The thermal effects were visualized in an inner ear model, using two new techniques: (1) high-speed Schlieren imaging shows relative dynamic changes of temperatures up to 2 ms resolution in the perilymph. (2) Thermo imaging provides absolute temperature measurements around the footplate up to 40 ms resolution. The high-speed Schlieren imaging showed minimal heating using the KTP laser. Both CO2 and Thulium laser showed heating below the footplate. Thulium laser wavelength generated heating up to 0.6 mm depth. This was confirmed with thermal imaging, showing a rise of temperature of 4.7 (±3.5) °C for KTP and 9.4 (±6.9) for Thulium in the area of 2 mm below the footplate. For stapedotomy, the Thulium and CO2 laser show more extended thermal effects compared to KTP. High-speed Schlieren imaging and thermal imaging are complimentary techniques to study lasers thermal effects in tissue.

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.

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.

Application of 1013 ohm Faraday cup current amplifiers for boron isotopic analyses by solution mode and laser ablation multicollector inductively coupled plasma mass spectrometry.

PubMed

Lloyd, Nicholas S; Sadekov, Aleksey Yu; Misra, Sambuddha

2018-01-15

Boron isotope ratios (δ 11 B values) are used as a proxy for seawater paleo-pH, amongst several other applications. The analytical precision can be limited by the detection of low intensity ion beams from limited sample amounts. High-gain amplifiers offer improvements in signal/noise ratio and can be used to increase measurement precision and reduce sample amounts. 10 13 ohm amplifier technology has previously been applied to several radiogenic systems, but has thus far not been applied to non-traditional stable isotopes. Here we apply 10 13 ohm amplifier technology for the measurement of boron isotope ratios using solution mode MC-ICP-MS and laser ablation mode (LA-)MC-ICP-MS techniques. Precision is shown for reference materials as well as for low-volume foraminifera samples. The baseline uncertainty for a 0.1 pA 10 B + ion beam is reduced to <0.1 ‰ for a typical measurement period. The external precision is better than 0.2 ‰ (2SD) for δ 11 B measurements for solution samples containing as little as 0.8 ng total boron. For in situ microanalyses with LA-MC-ICP-MS, the external precision of 11 B/ 10 B from an in-house calcite standard was 1 ‰ (2SD) for individual spot analyses, and 0.3 ‰ for the mean of ≥10 replicate spot analyses. 10 13 ohm amplifier technology is demonstrated to offer advantages for the determination of δ 11 B values by both MC-ICP-MS and LA-MC-ICP-MS for small samples of biogenic carbonates, such as foraminifera shells. 10 13 ohm amplifier technology will also be of benefit to other non-traditional stable isotope measurements. Copyright © 2017 John Wiley & Sons, Ltd.

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 to correlate trace element variations with changes in environmental variables. Such studies are proving informative in climate change and habitat management. Again, such variations have been quantified with the availability of appropriate organic, carbonate and phosphate calibration standards.

Permian single crystal U-Pb zircon age of the Rožňava Formation volcanites (Southern Gemeric Unit, Western Carpathians, Slovakia)

NASA Astrophysics Data System (ADS)

Vozárová, Anna; Šmelko, Miloš; Paderin, Ilya

2009-12-01

Zircon populations from the Rožňava Formation volcanic rock complex have been analysed. Euhedral zircons from the 1st volcanogenic horizon with fine oscillatory growth zoning, typical of magmatic origin, gave the average concordia age of 273.3 ± 2.8 Ma, with Th/U ratios in the range of 0.44-0.73. The Permian ages ranging from 266 to 284 Ma were identified in the wider, zoned or unzoned, central zircon parts, as well as in their fine-zoned oscillatory rims. The average concordia age of 275.3 ± 2.9 was obtained from the euhedral zircon population of the 2nd volcanogenic horizon of the Rožňava Formation. The analyses were performed on zoned magmatic zircons in the age interval from 267 to 287 Ma, with Th/U ratios in the range of 0.39-0.75. In the later zircon population two inherited zircon grains were dated giving the age of 842 ± 12 Ma (Neoproterozoic) and 456 ± 7 Ma (Late Ordovician). The magmatic zircon ages document the Kungurian age of Permian volcanic activity and contemporaneous establishment of the south-Gemeric basin. The time span of volcanic activity corresponds to the collapse of the Western Carpathian Variscan foreland which expanded southward.

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.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

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 various inclusions. The dark CL cores in the core-rim structured zircons are higher in U, Y and sometimes Hf relative to the CL bright rims. Microprobe data and x-ray chemical mapping of various zoned zircons suggest that U and Y with sometimes Hf have a negative correlation to the CL brightness, while Th doesn't exhibit any significant correlation.

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 important implications for the studies of detrital populations, suggesting that even zircon from a supposedly single population can form a complex age distribution pattern. Notably, the age groups are also very similar to those identified at this time interval in the zircon population from Jack Hills in Western Australia. Interestingly 18O in zircon from the Greenland tonalite sample is very consistent at the mantle value and independent of the behavior of the U-Pb system, suggesting general stability of even metamict zircon as related to the O isotope exchange. At least it indicates that if this exchange takes place as it appears to be the case for the Hadean zircon, factors other than just the radiation damage have to play a role in the zircon modification.

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 μm for CA and non-CA Caetano, R33 and TEMORA-2 zircons, and do not indicate variations in secondary ion sputtering rates due to chemical or structural changes from the CA treatment. Our new data underscore the potential for cryptic Pb-loss to go unrecognized in other geologically young magmatic centers that do not have zircons with high U, statistically discordant isotope ratios, high common Pb, or metamict textures.

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.

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 in the zircon record are often given as prima facie evidence of crustal reworking and recycling during Earth's early history, and underpin models for large volumes of ancient continental crust. For many of these old zircons it may have nothing to do with crustal reworking, but simply reflect unrecognized ancient Pb loss. A more robust picture of the isotopic evolution of the Earth can be gained from an integrated approach of Hf and Nd isotopes in well age-constrained magmatic samples: careful U-Pb zircon geochronology to determine the crystallization age of the rock; Hf isotopic composition of the zircons; and Hf and Nd isotopic measurements of the whole-rocks. We demonstrate this with respect to evolution of the depleted mantle, and discuss the implications for the timing of crust formation. An important part of this approach is the realization that not all rock samples (or zircons!) yield useful, unambiguous results. Inclusion of all Hf isotope data from large zircon databases, unscrutinized for quality and lacking in context, will do more to obscure our understanding of the isotopic evolution of the Earth than to clarify it.

Timing of the Cenozoic basins of Southern Mexico and its relationship with the Pacific truncation process: Subduction erosion or detachment of the Chortís block

NASA Astrophysics Data System (ADS)

Silva-Romo, Gilberto; Mendoza-Rosales, Claudia Cristina; Campos-Madrigal, Emiliano; Hernández-Marmolejo, Yoalli Bianii; de la Rosa-Mora, Orestes Antonio; de la Torre-González, Alam Israel; Bonifacio-Serralde, Carlos; López-García, Nallely; Nápoles-Valenzuela, Juan Ivan

2018-04-01

In the central sector of the Sierra Madre del Sur in Southern Mexico, between approximately 36 and 16 Ma ago and in the west to east direction, a diachronic process of the formation of ∼north-south trending fault-bounded basins occurred. No tectono-sedimentary event in the period between 25 and 20 Ma is recognized in the study region. A period during which subduction erosion truncated the continental crust of southern Mexico has been proposed. The chronology, geometry and style of the formation of the Eocene Miocene fault-bounded basins are more congruent with crustal truncation by the detachment of the Chortís block, thus bringing into question the crustal truncation hypothesis of the Southern Mexico margin. Between Taxco and Tehuacán, using seven new Laser Ablation- Inductively-coupled plasma mass spectrometry (LA-ICP-MS) U-Pb ages in magmatic zircons, we refine the stratigraphy of the Tepenene, Tehuitzingo, Atzumba and Tepelmeme basins. The analyzed basins present similar tectono-sedimentary evolutions as follows: Stage 1, depocenter formation and filling by clastic rocks accumulated as alluvial fans and Stage 2, lacustrine sedimentation characterized by calcareous and/or evaporite beds. Based on our results, we propose the following hypothesis: in Southern Mexico, during Eocene-Miocene times, the diachronic formation of fault-bounded basins with general north-south trend occurred within the framework of the convergence between the plates of North and South America, and once the Chortís block had slipped towards the east, the basins formed in the cortical crust were recently left behind. On the other hand, the beginning of the basins' formation process related to left strike slip faults during Eocene-Oligocene times can be associated with the thermomechanical maturation cortical process that caused the brittle/ductile transition level in the continental crust to shallow.

Timing of multiple hydrothermal events in the iron oxide-copper-gold deposits of the Southern Copper Belt, Carajás Province, Brazil

NASA Astrophysics Data System (ADS)

Moreto, Carolina P. N.; Monteiro, Lena V. S.; Xavier, Roberto P.; Creaser, Robert A.; DuFrane, S. Andrew; Melo, Gustavo H. C.; Delinardo da Silva, Marco A.; Tassinari, Colombo C. G.; Sato, Kei

2015-06-01

The Southern Copper Belt, Carajás Province, Brazil, hosts several iron oxide-copper-gold (IOCG) deposits, including Sossego, Cristalino, Alvo 118, Bacuri, Bacaba, Castanha, and Visconde. Mapping and U-Pb sensitive high-resolution ion microprobe (SHRIMP) IIe zircon geochronology allowed the characterization of the host rocks, situated within regional WNW-ESE shear zones. They encompass Mesoarchean (3.08-2.85 Ga) TTG orthogneiss, granites, and remains of greenstone belts, Neoarchean (ca. 2.74 Ga) granite, shallow-emplaced porphyries, and granophyric granite coeval with gabbro, and Paleoproterozoic (1.88 Ga) porphyry dykes. Extensive hydrothermal zones include albite-scapolite, biotite-scapolite-tourmaline-magnetite alteration, and proximal potassium feldspar, chlorite-epidote and chalcopyrite formation. U-Pb laser ablation multicollector inductively coupled mass spectrometry (LA-MC-ICP-MS) analysis of ore-related monazite and Re-Os NTIMS analysis of molybdenite suggest multiple Neoarchean (2.76 and 2.72-2.68 Ga) and Paleoproterozoic (2.06 Ga) hydrothermal events at the Bacaba and Bacuri deposits. These results, combined with available geochronological data from the literature, indicate recurrence of hydrothermal systems in the Southern Copper Belt, including 1.90-1.88-Ga ore formation in the Sossego-Curral ore bodies and the Alvo 118 deposit. Although early hydrothermal evolution at 2.76 Ga points to fluid migration coeval with the Carajás Basin formation, the main episode of IOCG genesis (2.72-2.68 Ga) is related to basin inversion coupled with Neoarchean (ca. 2.7 Ga) felsic magmatism. The data suggest that the IOCG deposits in the Southern Copper Belt and those in the Northern Copper Belt (2.57-Ga Salobo and Igarapé Bahia-Alemão deposits) do not share a common metallogenic evolution. Therefore, the association of all IOCG deposits of the Carajás Province with a single extensive hydrothermal system is precluded.

Genetic relationship of high-Mg dioritic pluton to iron mineralization: A case study from the Jinling skarn-type iron deposit in the North China Craton

NASA Astrophysics Data System (ADS)

Jin, Ziliang; Zhang, Zhaochong; Hou, Tong; Santosh, M.; Han, Liu

2015-12-01

The Jinling complex is spatially and temporally associated with the Jinling skarn-type iron deposit. The complex is composed of biotite diorite, hornblende diorite, monzonite and quartz diorite. U-Pb dating of zircons from the biotite diorite and monzonite using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) yields ages of 126 ± 1.9 Ma and 128 ± 1.4 Ma, respectively. The unaltered rocks in the complex are characterized by variable contents of SiO2 (54.6-65.3 wt.%), MgO (2.7-9.2 wt.%), total FeO (3.5-8.8 wt.%), Na2O + K2O (5.2-8.9 wt.%), high Mg# values (73-88), Cr (103-452 ppm) and Ni (49-212 ppm) contents. The altered monzonite has lower MgO (2.1-3.7 wt.%), total FeO (1.2-2.6 wt.%) and higher Na2O + K2O (8.5-9.9 wt.%) contents. The initial (87Sr/86Sr)t ranges from 0.70450 to 0.70555 and εNd(t) shows a range of -3.0 to -8.0. The geochemical characteristics suggest that the primary magma witnessed the interaction between the partial melts of relatively oxidized delaminated ancient crust and mantle peridotite. Fractional crystallization and crustal contamination during the magmatic ascent and emplacement are also indicated. The Jinling skarn-type Fe deposit is of hydrothermal origin and the Fe enrichment can be ascribed to multiple factors. The delaminated ancient crustal source contributed to the high oxygen fugacity of the primary magma. Two-stage Fe-enrichment process involving fractional crystallization of the primary magma giving rise to high Cl and Fe contents in the magmatic hydrothermal fluid and later Fe-leaching process, accounts for the high-grade ore bodies.

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 Talkeetna Mountains (schist of Hatcher Pass) and, immediately to the south, the northernmost sedimentary sequence of the Matanuska forearc basin (Arkose Ridge Formation). Detrital zircons from the Paleogene Arkose Ridge Formation are as young as 61 and 70 Ma; the population is dominated by a single Late Cretaceous peak at 76 Ma; the oldest zircon is 181 Ma. Sedimentological evidence clearly shows that the conglomeratic Arkose Ridge Formation was derived from the Talkeetna Mountains; our detrital zircon data support this inference. Zircons dated at ca. 90 Ma in the Arkose Ridge sample suggest that buried or unmapped plutons of this age may exist in the Talkeetnas. This is a particularly interesting age as it corresponds to the age of the supergiant Pebble gold-molybdenum-copper porphyry prospect near Iliamna and suggests a new area of prospectivity for Pebble-type deposits. The schist of Hatcher Pass, which was previously assigned a Jurassic depositional age, yielded surprisingly young Late Cretaceous detrital zircons, the youngest at 75 Ma. The probability density curve has four Cretaceous peaks from 76 to 102 Ma, a pair of Late Jurassic peaks at 155 and 166 Ma, three Early Jurassic to Late Triassic peaks at 186, 197, and 213 Ma, minor Carboniferous peaks at 303 and 346 Ma, and a minor Paleoproterozoic peak at 1828 Ma. The schist of Hatcher Pass was largely derived from Mesozoic arc sources, most likely the Wrangellia composite terrane, with some contribution from one or more older, inboard sources, probably including the Yukon-Tanana terrane. We postulate that the schist of Hatcher Pass represents metamorphosed rocks of the Valdez Group that were subducted and then exhumed along the Chugach terrane's 'backstop' during Paleogene transtension. Western Alaska Range - Six detrital zircon samples were collected from a little studied belt of turbidites in Tyonek quadrangle on strike with the Kahiltna assemblage of the central Alaska Range. Many of the sandstones ar

Determination of Os by isotope dilution-inductively coupled plasma-mass spectrometry with the combination of laser ablation to introduce chemically separated geological samples

NASA Astrophysics Data System (ADS)

Sun, Yali; Ren, Minghao; Xia, Xiaoping; Li, Congying; Sun, Weidong

2015-11-01

A method was developed for the determination of trace Os in geological samples by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) with the combination of chemical separation and preconcentration. Samples are digested using aqua regia in Carius tubes, and the Os analyte is converted into volatile OsO4, which is distilled and absorbed with HBr. The HBr solution is concentrated for further Os purification using the microdistillation technique. The purified Os is dissolved in 10 μl of 0.02% sucrose-0.005% H3PO4 solution and then evaporated on pieces of perfluoroalkoxy (PFA) film, resulting in the formation of a tiny object (< 3 × 104 μm2 superficial area). Using LA-ICP-MS measurements, the object can give Os signals at least 100 times higher than those provided by routine solution-ICP-MS while successfully avoiding the memory effect. The procedural blank and detection limit in the developed technique are 3.0 pg and 1.8 pg for Os, respectively when 1 g of samples is taken. Reference materials (RM) are analyzed, and their Os concentrations obtained by isotope dilution are comparable to reference or literature values. Based on the individual RM results, the precision is estimated within the range of 0.6 to 9.4% relative standard deviation (RSD), revealing that this method is applicable to the determination of trace Os in geological samples.

Whale baleen trace element signatures: a predictor of environmental life history?

NASA Astrophysics Data System (ADS)

Wilcox Freeburg, E.; Brault, S.; Mayo, C.; Oktay, S.; Hannigan, R.

2009-12-01

The analysis of trace element composition of biogenic structures (e.g., otoliths, feathers) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) provides unique insights into the environmental life history of individuals. We studied the trace element chemistry of right whale baleens in an attempt to reconstruct migration patterns. Though much is known about the feeding and breeding habitats of these whales, little is known about the location in which they spend most of their adult years. Baleens, made of keratin, grow continuously and are metabolically inactive. Previous work showed that the stable isotope chemistry along the length of a baleen records changes in diet, such as weaning. Baleen chemistry should, therefore, also record the environmental life history of the individual. Trace metal chemistry along a single baleen plate from a right whale were analyzed by LA-ICP-MS. Semi-quantitative elemental signatures were obtained using NIST 612 (glass standard) and MACS-3 (calcium carbonate standard). These concentrations were then compared for accuracy to acid digested baleen laterally adjacent to the laser ablation site via aqueous ICP-MS. Elemental chemistry was compared to known feeding/breeding locations of the individual (water chemistry). Using these comparisons as well as principal components analysis, life history of the individual was reconstructed. Development of an in-house keratin standard is in progress and is expected to strengthen the confidence in results. Future work is expected to bring a more complete knowledge of right whale wintering habits.

Real-time circumferential mapping catheter tracking for motion compensation in atrial fibrillation ablation procedures

NASA Astrophysics Data System (ADS)

Brost, Alexander; Bourier, Felix; Wimmer, Andreas; Koch, Martin; Kiraly, Atilla; Liao, Rui; Kurzidim, Klaus; Hornegger, Joachim; Strobel, Norbert

2012-02-01

Atrial fibrillation (AFib) has been identified as a major cause of stroke. Radiofrequency catheter ablation has become an increasingly important treatment option, especially when drug therapy fails. Navigation under X-ray can be enhanced by using augmented fluoroscopy. It renders overlay images from pre-operative 3-D data sets which are then fused with X-ray images to provide more details about the underlying soft-tissue anatomy. Unfortunately, these fluoroscopic overlay images are compromised by respiratory and cardiac motion. Various methods to deal with motion have been proposed. To meet clinical demands, they have to be fast. Methods providing a processing frame rate of 3 frames-per-second (fps) are considered suitable for interventional electrophysiology catheter procedures if an acquisition frame rate of 2 fps is used. Unfortunately, when working at a processing rate of 3 fps, the delay until the actual motion compensated image can be displayed is about 300 ms. More recent algorithms can achieve frame rates of up to 20 fps, which reduces the lag to 50 ms. By using a novel approach involving a 3-D catheter model, catheter segmentation and a distance transform, we can speed up motion compensation to 25 fps which results in a display delay of only 40 ms on a standard workstation for medical applications. Our method uses a constrained 2-D/3-D registration to perform catheter tracking, and it obtained a 2-D tracking error of 0.61 mm.

Characterization of an electrothermal plasma source for fusion transient simulations

NASA Astrophysics Data System (ADS)

Gebhart, T. E.; Baylor, L. R.; Rapp, J.; Winfrey, A. L.

2018-01-01

The realization of fusion energy requires materials that can withstand high heat and particle fluxes at the plasma material interface. In this work, an electrothermal (ET) plasma source has been designed as a transient heat flux source for a linear plasma material interaction device. An ET plasma source operates in the ablative arc regime driven by a DC capacitive discharge. The current channel width is defined by the 4 mm bore of a boron nitride liner. At large plasma currents, the arc impacts the liner wall, leading to high particle and heat fluxes to the liner material, which subsequently ablates and ionizes. This results in a high density plasma with a large unidirectional bulk flow out of the source exit. The pulse length for the ET source has been optimized using a pulse forming network to have durations of 1 and 2 ms. The peak currents and maximum source energies seen in this system are 1.9 kA and 1.2 kJ for the 2 ms pulse and 3.2 kA and 2.1 kJ for the 1 ms pulse, respectively. This work is a proof of the principal project to show that an ET source produces electron densities and heat fluxes comparable to those anticipated in transient events in large future magnetic confinement fusion devices. Heat flux, plasma temperature, and plasma density were determined for each shot using infrared imaging and optical spectroscopy techniques. This paper will discuss the assumptions, methods, and results of the experiments.

Quantitative analysis of a brass alloy using CF-LIBS and a laser ablation time-of-flight mass spectrometer

NASA Astrophysics Data System (ADS)

Ahmed, Nasar; Abdullah, M.; Ahmed, Rizwan; Piracha, N. K.; Aslam Baig, M.

2018-01-01

We present a quantitative analysis of a brass alloy using laser induced breakdown spectroscopy, energy dispersive x-ray spectroscopy (EDX) and laser ablation time-of-flight mass spectrometry (LA-TOF-MS). The emission lines of copper (Cu I) and zinc (Zn I), and the constituent elements of the brass alloy were used to calculate the plasma parameters. The plasma temperature was calculated from the Boltzmann plot as (10 000  ±  1000) K and the electron number density was determined as (2.0  ±  0.5)  ×  1017 cm-3 from the Stark-broadened Cu I line as well as using the Saha-Boltzmann equation. The elemental composition was deduced using these techniques: the Boltzmann plot method (70% Cu and 30% Zn), internal reference self-absorption correction (63.36% Cu and 36.64% Zn), EDX (61.75% Cu and 38.25% Zn), and LA-TOF (62% Cu and 38% Zn), whereas, the certified composition is (62% Cu and 38% Zn). It was observed that the internal reference self-absorption correction method yields analytical results comparable to that of EDX and LA-TOF-MS.

New application of the long-pulsed Nd-YAG laser as an ablative resurfacing tool for skin rejuvenation: a 7-year study.

PubMed

Alshami, Mohammad Ali

2013-09-01

Carbon dioxide (CO2 ) and erbium-yttrium aluminum garnet (Er-YAG) lasers are the gold standards in ablative skin resurfacing. Neodymium-doped yttrium aluminum garnet (Nd-YAG) laser is considered a nonablative skin resurfacing laser whose usage is limited due to its high cost. To assess the efficacy and safety of Nd-YAG as an ablative resurfacing laser and to compare the results with those previously published for CO2 and Erbium-YAG lasers. A total of 296 patients (251 female and 45 male) with Fitzpatrick skin types III-IV and dermatological conditions amenable to ablative skin resurfacing participated in this study. Nd-YAG laser parameters assessed were wavelength (1064 nm), pulse duration (5 ms), fluence (10 J/cm(2) ), and spot size (8-10 mm). Efficacy of Nd-YAG laser was assessed by comparing pre- and posttreatment photographs. An improvement of 30-80% was observed in treated patients. The degree of improvement correlated positively with the number of laser sessions. The most common side effect was hyperpigmentation. Other side effects were less common and mild in intensity compared with published results for gold standard ablative lasers. Not only was the Nd-YAG laser found to be as effective as Er-YAG and CO2 lasers, but treated patients also had shorter recovery and treatment times, and at lower cost. © 2013 Wiley Periodicals, Inc.

Elemental analysis of soils using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS) with multivariate discrimination: tape mounting as an alternative to pellets for small forensic transfer specimens.

PubMed

Jantzi, Sarah C; Almirall, José R

2014-01-01

Elemental analysis of soil is a useful application of both laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS) in geological, agricultural, environmental, archeological, planetary, and forensic sciences. In forensic science, the question to be answered is often whether soil specimens found on objects (e.g., shoes, tires, or tools) originated from the crime scene or other location of interest. Elemental analysis of the soil from the object and the locations of interest results in a characteristic elemental profile of each specimen, consisting of the amount of each element present. Because multiple elements are measured, multivariate statistics can be used to compare the elemental profiles in order to determine whether the specimen from the object is similar to one of the locations of interest. Previous work involved milling and pressing 0.5 g of soil into pellets before analysis using LA-ICP-MS and LIBS. However, forensic examiners prefer techniques that require smaller samples, are less time consuming, and are less destructive, allowing for future analysis by other techniques. An alternative sample introduction method was developed to meet these needs while still providing quantitative results suitable for multivariate comparisons. The tape-mounting method involved deposition of a thin layer of soil onto double-sided adhesive tape. A comparison of tape-mounting and pellet method performance is reported for both LA-ICP-MS and LIBS. Calibration standards and reference materials, prepared using the tape method, were analyzed by LA-ICP-MS and LIBS. As with the pellet method, linear calibration curves were achieved with the tape method, as well as good precision and low bias. Soil specimens from Miami-Dade County were prepared by both the pellet and tape methods and analyzed by LA-ICP-MS and LIBS. Principal components analysis and linear discriminant analysis were applied to the multivariate data. Results from both the tape method and the pellet method were nearly identical, with clear groupings and correct classification rates of >94%.

Morphology and structure of TixOy nanoparticles generated by femtosecond laser ablation in water

NASA Astrophysics Data System (ADS)

Donėlienė, Jolanta; Rudzikas, Matas; Rades, Steffi; Dörfel, Ilona; Peplinski, Burkhard; Sahre, Mario; Pellegrino, Francesco; Maurino, Valter; Ulbikas, Juras; Galdikas, Algirdas; Hodoroaba, Vasile-Dan

2018-04-01

In this work femto-second pulsed laser ablation in liquid (PLAL) procedure for the generation of titanium oxide nanoparticles (NP) is reported with the purpose of understanding morphology and structure of the newly generated NPs. Ablation duration was varied for optimization of NP generation processes between 10 and 90 min. Surface morphology of NPs as well as their size and shape (distribution) were analysed by various complementary electron microscopy techniques, i.e. SEM, TSEM and TEM. The crystalline structure of titanium oxide particles was investigated by XRD (two instruments operated in different geometries) and HR-TEM. Concentration of generated titanium oxide NPs in liquid was analysed by ICP-MS. A mix of crystalline (mainly anatase), partly crystalline and amorphous spherical titanium oxide NPs can be reported having a mean size between 10 and 20 nm, which is rather independent of the laser ablation (LA) duration. A second component consisting of irregularly shaped, but crystalline titanium oxide nanostructures is co-generated in the LA water, with more pronounced occurrence at longer LA times. The provenance of this component is assigned to those spherical particles generated in suspension and passing through the converging laser beam, being hence subject to secondary irradiation effects, e. g. fragmentation.

Multi-elemental bio-imaging of rat tissue from a study investigating the bioavailability of bismuth from shotgun pellets.

PubMed

Urgast, Dagmar S; Ellingsen, Dag G; Berlinger, Balázs; Eilertsen, Einar; Friisk, Grete; Skaug, Vidar; Thomassen, Yngvar; Beattie, John H; Kwun, In-Sook; Feldmann, Jörg

2012-07-01

In recent years, bismuth has been promoted as a "green element" and is used as a substitute for the toxic lead in ammunition and other applications. However, the bioavailability and toxicity of bismuth is still not very well described. Following a hunting accident with bismuth-containing shots, a bioavailability study of bismuth from metal pellets inoculated into rat limb muscles was carried out. Bismuth could be found in urine and blood of the animals. Bio-imaging using laser ablation ICP-MS of thin sections of the tissue around the metal implant was carried out to find out more about the distribution of the metal diffusing into the tissue. Two laser ablation systems with different ablation cell designs were compared regarding their analytical performance. Low concentrations of bismuth showing a non-symmetrical pattern were detected in the tissue surrounding the metal implant. This was partly an artefact from cutting the thin sections but also bio-mobilisation of the metals of the implant could be seen. An accumulation of zinc around the implant was interpreted as a marker of inflammation. Challenges regarding sample preparation for laser ablation and bio-imaging of samples of diverse composition became apparent during the analysis.

Noninvasive evaluation of reverse atrial remodeling after catheter ablation of atrial fibrillation by P wave dispersion.

PubMed

Fujimoto, Yuhi; Yodogawa, Kenji; Takahashi, Kenta; Tsuboi, Ippei; Hayashi, Hiroshi; Uetake, Shunsuke; Iwasaki, Yu-Ki; Hayashi, Meiso; Miyauchi, Yasushi; Shimizu, Wataru

2017-11-01

Atrial fibrillation (AF) itself creates structural and electrophysiological changes such as atrial enlargement, shortening of refractory period and decrease in conduction velocity, called "atrial remodeling", promoting its persistence. Although the remodeling process is considered to be reversible, it has not been elucidated in detail. The aim of this study was to assess the feasibility of P wave dispersion in the assessment of reverse atrial remodeling following catheter ablation of AF. Consecutive 126 patients (88 males, age 63.0 ± 10.4 years) who underwent catheter ablation for paroxysmal AF were investigated. P wave dispersion was calculated from the 12 lead ECG before, 1 day, 1 month, 3 months and 6 months after the procedure. Left atrial diameter (LAD), left atrial volume index (LAVI), left ventricular ejection fraction (LVEF), transmitral flow velocity waveform (E/A), and tissue Doppler (E/e') on echocardiography, plasma B-type natriuretic peptide (BNP) concentrations, serum creatinine, and estimated glomerular filtration rate (eGFR) were also measured. Of all patients, 103 subjects remained free of AF for 1 year follow-up. In these patients, P wave dispersion was not changed 1 day and 1 month after the procedure. However, it was significantly decreased at 3 and 6 months (50.1 ± 14.8 to 45.4 ± 14.4 ms, p < 0.05, 45.2 ± 9.9 ms, p < 0.05, respectively). Plasma BNP concentrations, LAD and LAVI were decreased (81.1 ± 103.8 to 44.8 ± 38.3 pg/mL, p < 0.05, 38.2 ± 5.7 to 35.9 ± 5.6 mm, p < 0.05, 33.3 ± 14.2 to 29.3 ± 12.3 mL/m 2 , p < 0.05) at 6 months after the procedure. There were no significant changes in LVEF, E/A, E/e', serum creatinine, and eGFR during the follow up period. P wave dispersion was decreased at 3 and 6 months after catheter ablation in patients without recurrence of AF. P wave dispersion is useful for assessment of reverse remodeling after catheter ablation of AF.

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.

Left septal atrial tachycardia after open-heart surgery: relevance to surgical approach, anatomical and electrophysiological characteristics associated with catheter ablation, and procedural outcomes.

PubMed

Adachi, Toru; Yoshida, Kentaro; Takeyasu, Noriyuki; Masuda, Keita; Sekiguchi, Yukio; Sato, Akira; Tada, Hiroshi; Nogami, Akihiko; Aonuma, Kazutaka

2015-02-01

Septal atrial tachycardia (AT) can occur in patients without structural heart disease and in patients with previous catheter ablation of atrial fibrillation. We aimed to assess septal AT that occurs after open-heart surgery. This study comprised 20 consecutive patients undergoing catheter ablation of macroreentrant AT after open-heart surgery. Relevance to surgical approach, mechanisms, anatomic and electrophysiological characteristics, and outcomes were assessed. Septal AT was identified in 7 patients who had all undergone mitral valve surgery. All septal ATs were localized in the left atrial septum, whereas 10 of 13 nonseptal ATs originated from the right atrium. Patients with left septal AT had a thicker fossa ovalis (median, 4.0; 25th-75th percentile, 3.6-4.2 versus 2.3; 1.6-2.6 mm; P=0.006) and broader area of low voltage (<0.3 mV) in the septum than patients with nonseptal AT (82; 76-89 versus 31; 28%-36%; P=0.02). Repeated gradual prolongations of the tachycardia cycle length without change of the septal circuit were observed in all patients with septal AT (70; 63-100 versus 15; 10-40 ms; P=0.0008). Although ablation terminated all ATs, recurrence of targeted ATs was more frequent in patients with left septal AT during 30-month follow-up (71 versus 0%; P=0.001). Left septal AT after open-heart surgery was characterized by a thicker septum, more scar burden in the septum, and repeated prolongations of the tachycardia cycle length during ablation. Such an arrhythmogenic substrate may interfere with transmural lesion formation by ablation and may account for higher likelihood of recurrence of left septal AT. © 2014 American Heart Association, Inc.

Early repolarization in Wolff-Parkinson-White syndrome: prevalence and clinical significance.

PubMed

Mizumaki, Koichi; Nishida, Kunihiro; Iwamoto, Jotaro; Nakatani, Yosuke; Yamaguchi, Yoshiaki; Sakamoto, Tamotsu; Tsuneda, Takayuki; Inoue, Hiroshi; Sakabe, Masao; Fujiki, Akira

2011-08-01

Idiopathic ventricular fibrillation (IVF) with early repolarization (ER) has recently been reported; however, ER is a common finding in healthy subjects and is also found sporadically in patients with Wolff-Parkinson-White (WPW) syndrome. The present study was designed to evaluate the prevalence and clinical significance of ER in patients with WPW syndrome. One hundred and eleven patients with WPW syndrome were studied retrospectively. Early repolarization was defined as QRS slurring or notching with J-point elevation ≥ 1 mm. The prevalence of ER was determined before and after successful catheter ablation. Before ablation, ER was found in 35 of 75 patients with a left free wall, 6 of 23 with a right free wall, and 7 of 13 with a septal accessory pathway (48 of 111, 43% as a whole). Early repolarization was always observed in leads with positive deflection of the initial part of the delta wave. After successful ablation of accessory pathways, ER was preserved in 28 (25%), disappeared in 20 (18%), and newly developed in 8 (7%) patients. In the remaining 55 (50%) patients, ER was not observed either before or after ablation. In patients with persistent ER, the amplitude and width of ER were significantly decreased 3-7 days after the ablation (1.7 ± 0.7 vs. 1.4 ± 0.6 mm, P < 0.005 and 42 ± 11 vs. 34 ± 9 ms, P < 0.001, respectively). In patients with WPW syndrome, ER could be partly related to early depolarization through the accessory pathway. However, persistent ER and new ER appearing after the ablation were frequently found. Therefore, in these patients, mechanisms other than early depolarization may be involved in the genesis of ER.

Phase analysis of ZrO2-SiO2 systems synthesized through Ball milling mechanical activations

NASA Astrophysics Data System (ADS)

Nurlaila, Rizka; Musyarofah, Muwwaqor, Nibras Fuadi; Triwikantoro, Kuswoyo, Anton; Pratapa, Suminar

2017-01-01

Zircon powders have been produced from raw materials of amorphous zirconia and amorphous silica powders obtained from natural zircon sand of Kalimantan Tengah, Indonesia. Synthesis process was started with the extraction of zircon powder to produce sodium silicate solution and pure zircon powder. The amorphous zirconia and silica powders were prepared by alkali fusion and co-precipitation techniques. The powders were mixed using a planetary ball mill, followed by a calcination of various holding time of 3, 10, and 15 h. Phase characterization was done using X-Ray Diffraction (XRD) technique and analysis of the diffraction data was carried out using Rietica and MAUD software. The identified phases after the calcination were zircon, tetragonal zirconia, and cristobalite. The highest zircon content was obtained in the sample calcinated for15 hours - reaching 99.66 %wt. Crystallite size analysis revealed that the samples calcinated for 3, 10, and 15 h exhibited zircon crystal size of 176 (1) nm, 191 (1) nm and 233 (1) nm respectively.

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

Zircon U-Th and U-Pb Ages From Quaternary Silicic Volcanic and Plutonic Rocks, and Their Bearing on Granitoid Batholiths

NASA Astrophysics Data System (ADS)

Bacon, C. R.

2007-12-01

In the ten years since publication of M. Reid et al.'s seminal paper on zircon ages from rhyolites (EPSL 150:2-39, 1997) >20 papers have appeared on SIMS 238U-230Th and 238U-206Pb geochronology of zircon from silicic volcanic rocks, plutonic xenoliths, and young intrusions. In some cases, as well as for U-Pb studies of Tertiary granitoids, plutonic samples are interpreted in the context of related volcanism. These geochronologic data have advanced conceptual models of silicic magma genesis and pluton construction. Of fundamental importance are discoveries that zircons in volcanic rocks typically pre-date eruption by 10's to 100's of kyr and that multiple zircon populations are common; these crystals are "antecrysts" recycled from intrusive rocks or crystal mush of the system that vented. Resolving such age differences is possible with U-Th at <300 ka but is challenging with U-Pb, where SIMS precision limits resolution of differences on the order of 100 kyr for Pleistocene-Miocene zircons. Cathodoluminescence (CL) imaging of polished crystals guides beam placement but leads to sampling bias that favors high-U regions. Thus, although model-age histograms and relative probability plots identify zircon age populations, they are unlikely to accurately define relative abundances of age groups. Microbeam analysis collects data for the entire volume sampled but only SIMS depth-profiling into crystal faces can spatially resolve fine zones. ID-TIMS analysis of CL-imaged zircon fragments can improve U-Pb precision. SIMS complements geochronology with trace element fingerprints of zircon growth environments and enables Ti-in-zircon thermometry. Literature examples illustrate recent findings: (1) rhyodacite lava at Crater Lake contains zircons derived from late Pleistocene granodiorite represented by blocks ejected in the caldera-forming eruption; (2) zircons in Mount St. Helens dacites grew at sub-eruption temperatures and pre-date eruptions by up to 250 kyr; (3) Miocene plutons near Mount Rainier and the Colorado River were emplaced and crystallized in pulses over ~2-3-Myr periods, some with coeval volcanics; and (4) Cretaceous batholiths in the Sierra Nevada and North Cascades preserve evidence of assembly over as much as 10 Myr; individual samples contain zircons that crystallized during intervals of >1 Myr. Zircon ages and wide-ranging trace element concentrations suggest crystallization mainly in differentiated melt pockets in high-crystallinity magmas that may repeatedly freeze and thaw. Some high-Th/U, incompatible-element rich, spongy textured zircons grew very late, in the presence of oxidizing fluid. Not all zircons survive recycling into undersaturated magmas, in which zircon will dissolve given enough time, depending on temperature and dissolved volatiles. Recent zircon geochronologic results for volcanic and plutonic rocks lend credence to the "mush model" of rhyolite genesis and batholith consolidation. Crystal-poor rhyolites and leucogranites are melts segregated by compaction or gas-driven filter pressing from granitoid crystal mush emplaced incrementally in the middle to upper crust and powered by basaltic magma repeatedly injected into the lower reaches of the mush column. Balance between heat loss and basaltic influx determines whether the mush freezes or partially thaws at any given time, blurs internal contacts in resulting plutons, and can produce large volumes of crystal-rich ignimbrite or rapid separation and eruption of crystal-poor rhyolite. Lifetimes of the largest volcano-plutonic systems, such as the Altiplano-Puna or Southern Rocky Mountains volcanic fields, are comparable to the ~10 Myr of the Tuolumne Intrusive Suite.

Trace element geochemistry of zircons from mineralizing and non-mineralizing igneous rocks related to gold ores at Yanacocha, Peru

NASA Astrophysics Data System (ADS)

Koleszar, A. M.; Dilles, J. H.; Kent, A. J.; Wooden, J. L.

2012-12-01

Zircons record important details about the evolution of magmatic systems, are relatively insensitive to alteration, and have been used to investigate the geochemistry, temperature, and oxidation state of volcanic and plutonic system. We examine zircons that span 6-7 m.y. of calc-alkaline volcanic activity in the Yanacocha district of northern Peru, where dacitic intrusions are associated with high-sulfidation gold deposits. The 14.5-8.4 Ma Yanacocha Volcanics include cogenetic lavas and pyroclastic rocks and are underlain by the andesites and dacites of the Calipuy Group, the oldest Cenozoic rocks in the region. We present data for magmatic zircons from the Cerro Fraile dacitic pyroclastics (15.5-15.1 Ma) of the Calipuy Group, and multiple eruptive units within the younger Yanacocha Volcanics: the Atazaico Andesite (14.5-13.3 Ma), the Quilish Dacite (~14-12 Ma), the Azufre Andesite (12.1-11.6 Ma), the San Jose Ignimbrite (11.5-11.2 Ma), and the Coriwachay Dacite (11.1-8.4 Ma). Epithermal high sulfidation (alunite-bearing) gold deposits are associated with the dacite intrusions of the Coriwachay and Quilish Dacites. Zircons from the non-mineralizing rocks typically have lower Hf concentrations and record Ti-in-zircon temperatures that are ~100°C hotter than zircons from the mineralizing intrusions. Temperatures recorded by zircons from the mineralizing intrusions are remarkably similar to those of the underlying Cerro Fraile dacite pyroclastics, but the zircons discussed here generally record SHRIMP-RG 206Pb/238U ages within error of previously published Ar-Ar eruption ages (eliminating antecrystic or xenocrystic origins). These observations suggest that zircons in the mineralizing intrusions form after greater extents of crystallization (and thus record elevated Hf concentrations and lower temperatures) than do zircons in the non-mineralized deposits. Unlike zircons from mineralized units associated with the porphyry Cu(Mo) deposits in Yerington, Nevada, which generally have Eu/Eu* ratios approaching 1 (i.e., Eu-anomalies that decrease in magnitude) with increasing Hf (and thus increasing crystallization), zircons associated with mineralized deposits in the Coriwachay and Quilish intrusions at Yanacocha typically have Eu-anomalies that are highly variable but do not vary systematically during magma evolution. These Eu/Eu* versus Hf trends are inconsistent with observations from the porphyry Cu-Mo(Au) deposit at El Salvador, Chile, where zircons from all porphyry intrusions have Eu-anomalies that become systematically more negative during magma evolution but with highest Eu/Eu* occurring in mineralized intrusions. We explore a variety of scenarios to explain the Eu/Eu* systematics of zircons from Yanacocha, including changes to the magmatic oxidation state as a consequence of anhydrite breakdown and progressive degassing.

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. Detrital zircons of about 1.26 Ga in the Apache Group and Troy Quartzite appear to be related to local, approximately coeval volcanic fields. Zircons of about 0.7 Ga may have had a source in igneous rocks related to rifting of the Proterozoic supercontinent of Rodinia, and 0.5 Ga zircons a source in relatively small areas of granitic rocks of this known, or inferred, age in Oklahoma, Texas, New Mexico, and Colorado.

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, while low radiation damage grains show a shift of 2 cm-1. These shifts suggest that the annealing process occurs at a faster rate in high damage zircon grains, and slower rates in more crystalline grains. That is, the initial level of radiation damage prior to annealing must be considered in damage-diffusivity models that contain thermal histories from zircon-He dates.

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] and [Th] (2σ = 37% and 33% for 238U/30Si and 232Th/30Si, respectively, n = 8) has yet to be achieved. Modeling shows that homogenization of [U] and [Th] within these pellets requires preparation of powders with <2 micron sized particles, which has yet to be achieved in sample preparation. Thus, the zircon synrock pellet remains a viable potential [U], [Th] standard, although the preparation of a sufficiently fine grained, homogeneous pellet is a work in progress.

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 environments. Many of the >3.9 Ga zircons have mildly elevated δ18O (6.0-7.5‰), but such values have not been identified in any zircons from the large sample suite examined here. The difference in δ18O, in combination with newly acquired lithium concentrations and published trace element data, clearly shows that the >3.9 Ga detrital zircons did not originate by processes analogous to those in modern mid-ocean ridge settings.

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-hydrothermal deposit, and empirical observations suggest that this threshold may be marked by zircon Eu/Eu* values of ca. < 0.08. The isotope and trace element signatures of both magmatic and detrital zircons can be developed into a useful exploration tool.

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 the interpretation of U-Pb data and track the exhumation history of UHP terranes. The differences may reflect variation in elemental availability through breakdown reactions in quartzofeldpathic gneiss vs. availability during melt production and/or crystallization. UHP rocks in North-East Greenland began exhumation by 347 ?? 2 Ma, were still at HP eclogite-facies conditions at 337 ?? 5 Ma and were at amphibolite-facies conditions by 330 ?? 2 Ma. ?? 2009 E. Schweizerbart'sche Verlagsbuchhandlung.

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

NASA Astrophysics Data System (ADS)

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

2005-07-01

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

Complicated secondary textures in zircon record evolution of the host granitic rocks: Studies from Western Tauern Window and Ötztal-Stubai Crystalline Complex (Eastern Alps, Western Austria)

NASA Astrophysics Data System (ADS)

Kovaleva, Elizaveta; Harlov, Daniel; Klötzli, Urs

2017-07-01

Samples of metamorphosed and deformed granitic rocks were collected from two Alpine complexes with well-constrained metamorphic history: Western Tauern Window and Ötztal-Stubai Crystalline Complex. Zircon grains from these samples were investigated in situ by a combination of scanning electron microscope techniques, cathodoluminescence (CL) imaging and Raman spectroscopy. The aims were: to describe and interpret complicated secondary textures and microstructures in zircon; based on cross-cutting relationships between secondary microstructures, reconstruct the sequence of processes, affecting zircon crystals; link the evolution of zircon with the history of the host rocks. The results indicate that zircon in the sampled granitic rocks forms growth twins and multi-grain aggregates, which are unusual for this mineral. Moreover, various secondary textures have been found in the sampled zircon, often cross-cutting each other in a single crystal. These include: distorted oscillatory CL zoning with inner zones forming inward-penetrating, CL-bright embayments, which are the evidence of dry recrystallization via annealing/lattice recovery; CL mosaicism with no preservation of growth zoning, but abundant nano- and micro-scale pores and mineral inclusions, which are the evidence of recrystallization by coupled dissolution-reprecipitation and/or leaching; embayed zircon boundaries filled with apatite, monazite, epidote and mylonitic matrix, indicating mineral-fluid reactions resulting in zircon dissolution and fragmentation; overgrowth CL-dark rims, which contain nano-pores and point to transport and precipitation of dissolved zircon matter. We conclude that zircon in our meta-granites is sensitive to metamorphism/deformation events, and was reactive with metamorphic fluids. Additionally, we have found evidence of crystal-plastic deformation in the form of low angle boundaries and bent grain tips, which is a result of shearing and ductile deformation of the host rock. We suggest that the observed complicated secondary textures in zircon can be linked to the evolutionary stages of the host rocks such as magmatic crystallization, prograde metamorphism, peak of amphibolite-facies metamorphism, post-peak cooling and exhumation, formation of ductile shear zones and final cooling to 250 °C.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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-resolution (<20 um) imaging has found that the magnetization of many zircons resides in grain exteriors, suggesting a dominantly secondary origin. We conclude that there is currently no robust evidence for pre-depositional (>3.0 Ga) magnetization in the Jack Hills detrital zircons. We are continuing to search for such magnetic records.

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.

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.

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 Russian Foundation of Basic Research (project: 13-05-00035.) and the DES-6 program.

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.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Facilitating the Hyphenation of CIEF and MALDI-MS for Two-Dimensional Separation of Proteins

PubMed Central

Cheng, Chang; Lu, Joann J.; Wang, Xiayan; Roberts, Jonathan; Liu, Shaorong

2011-01-01

Both CIEF and MALDI-MS are frequently used in protein analysis, but hyphenation of the two is not investigated proportionally. One of the major reasons is that the additives (such as carrier ampholytes and detergent) in CIEF severely suppress the MALDI-MS signal, which hampers the hyphenation of the two. In this paper, we develop a simple means to alleviate the above signal-suppressing effect. We first deposit 1 µL of water onto a MALDI-MS target, deliver a fraction of CIEF-separated protein (~0.1 µL) to the water droplet, evaporate the solvent, add 0.5 µL of MALDI matrix to the sample spot, dry the matrix, and move the target plate to a MALDI-TOF-MS for mass spectrum measurement. We optimize the droplet volume and the laser-ablation region. Under the optimized conditions, we improve the signal to noise ratio by 2–10 fold. We also apply this method for two-dimensional separations of standard proteins and Apolipoprotein A-I, a membrane protein expressed in E. Coli cells. PMID:20603827

The formation of the Late Cretaceous Xishan Sn-W deposit, South China: Geochronological and geochemical perspectives

NASA Astrophysics Data System (ADS)

Zhang, Lipeng; Zhang, Rongqing; Hu, Yongbin; Liang, Jinlong; Ouyang, Zhixia; He, Junjie; Chen, Yuxiao; Guo, Jia; Sun, Weidong

2017-10-01

The Xishan Sn-W deposit is spatially related to K-feldspar granites in the Yangchun basin, western Guangdong Province, South China. LA-ICP-MS zircon U-Pb dating for the Xishan pluton defines an emplacement age of 79 Ma (78.1 ± 0.9 Ma; 79.0 ± 1.2 Ma; 79.3 ± 0.8 Ma), consistent with the mineralization age of the Xishan Sn-W deposit constrained by molybdenite Re-Os isochron age (79.4 ± 4.5 Ma) and LA-ICP-MS cassiterite U-Pb ages (78.1 ± 0.9 Ma and 79.0 ± 1.2 Ma) for the cassiterite-quartz vein. These indicate a close genetic relationship between the granite and Sn-W mineralization. The Xishan K-feldspar granites have geochemical characteristics of A-type granites, e.g., high total alkali (Na2O + K2O = 7.88-10.07 wt.%), high Ga/Al ratios (10000*Ga/Al > 2.6) and high Zr + Nb + Ce + Y concentrations (> 350 ppm). They are further classified as A2-type granites. The whole-rock isotopic compositions of K-feldspar granites (initial 87Sr/86Sr = 0.705256-0.706181; εNd(t) = - 5.4 to - 4.8) and zircon εHf(t) values (- 7.8 to 2.0) suggest a mixed magma source. The low zircon Ce4 +/Ce3 + ratios (12-88) of K-feldspar granites suggest low oxygen fugacities, which is key for enrichment of tin in primary magmas. The K-feldspar granites have experienced strong differentiation as indicated by their high Rb/Sr and K/Rb ratios, and low Nb/Ta and Zr/Hf ratios, which play an important role in ore-forming element transportation and concentration. A-type granite characteristics of the Xishan pluton show that it formed in an extensional environment. The high F and low Cl characteristics of the K-feldspar granite are most probably attributed to slab rollback. In the Late Cretaceous, the Xishan Sn-W deposit was located near the interaction of the circum-Pacific and the Tethys tectonic realms. Late Cretaceous Sn-W deposits, including the Xishan deposit, form an EW-trending belt from Guangdong to Yunnan Province in South China. This belt is in accordance with the direction of the Neo-Tethys slab rollback in the Late Cretaceous. In addition, the NS-trending extension has been recognized in the Late Cretaceous in South China. We propose that the Xishan Sn-W deposit should be attributed to the Neo-Tethys slab rollback in the Late Cretaceous.

Baddeleyite in PGE paleoproterozoic layered intrusions on Fennoscandian Shield (Arctic region): significance for timing, duration and continental reconstraction

NASA Astrophysics Data System (ADS)

Bayanova, Tamara; Korchagin, Aleksey; Chachshin, Viktor; Nerovich, Ludmila; Drogobuzhskaya, Svetlana

2017-04-01

Baddeleyite was firstly found and U-Pb dating in PGE layered intrusions of the Fennoscandian Shield in the rock-forming orthopyroxene (Lukkulaisvaara intrusion in Karelia region) and in magmatic zircon from gabbronorite Mt. Generalskaya (Kola region). Real crystals of baddeleyite were separated and U-Pb measured from Fedorovo-Pansky complex in gabbronorites lower part of the Pt-Pd reef intrusion (as first phase 2.50 Ga) and in upper part of Pt-Pd reef in anorthosites (second phase -2.45 Ga) and reflect time interval about 50 Ma of magmatic complex activity. In basite dykes from Cr-Ti-V Imandra lopolith baddeleyite were dating by U-Pb with 2.40 Ga. Therefore total duration time of Kola LIP and magmatic origin of the multimetal deposits are estimated as 100 Ma [1]. New additional isotope Nd-Sr-He data for the WR of the layered PGE intrusions in the Kola-Karelia-Finland big belt more than 500 km reflect EM-1 mantle reservoir. New REE (ELAN- 9000) distributions in the WR and dykes complexes of the Fedorovo-Pansky and Monshegorck Cu-Ni and PGE ore deposits gave OIB, N-MORB and E-MORB primary plume mantle source due to Re-Os data [2]. LA-ICP-MS data of REE investigations in baddeleyite crystals from Monchegorsk ore region yielded 1000 C forming of the grains and high U-Pb closure temperatures compared with zircon. Baddeleyite also primary magmatic minerals in the layered PGE intrusions and dykes complexes from Fennoscandian Shield and U-Pb precise data using artificial 205 Pb spike of the crystals together with time data for different continents gave new important information concerning break up and super continental reconstruction of geological history in paleoproterozoic time [3]. Acknowledgements: Many thanks to G.Wasserburg for 205 Pb artificial spike, J. Ludden, F. Corfu, V. Todt and U. Poller for assistance in the establishing of the U-Pb for single zircon and baddeleyite. All studies are supported by RFBR 16-05-00305. All investigations are devoted to memory of academician RAS F.P. Mitrofanov due to whom baddeleyite was found, separation and studied by U-Pb (ID-TIMS and LA-ICP-MS) methods. References: [1] Bayanova et al. (2014), INTECH, 143-193; [2] Yang Sheng-Hong et. al. (2016), Mineralium Deposita 51, 1055-1073; [3] Ernst R. Large igneous provinces. (2016), London, 500

Tracking magmatic processes through Zr/Hf ratios in rocks and Hf and Ti zoning in zircons: An example from the Spirit Mountain batholith, Nevada

USGS Publications Warehouse

Lowery, Claiborne L.E.; Miller, C.F.; Walker, B.A.; Wooden, J.L.; Mazdab, F.K.; Bea, F.

2006-01-01

Zirconium and Hf are nearly identical geochemically, and therefore most of the crust maintains near-chondritic Zr/Hf ratios of ???35-40. By contrast, many high-silica rhyolites and granites have anomalously low Zr/Hf (15-30). As zircon is the primary reservoir for both Zr and Hf and preferentially incorporates Zr, crystallization of zircon controls Zr/ Hf, imprinting low Zr/Hf on coexisting melt. Thus, low Zr/Hf is a unique fingerprint of effective magmatic fractionation in the crust. Age and compositional zonation in zircons themselves provide a record of the thermal and compositional histories of magmatic systems. High Hf (low Zr/ Hf) in zircon zones demonstrates growth from fractionated melt, and Ti provides an estimate of temperature of crystallization (TTiZ) (Watson and Harrison, 2005). Whole-rock Zr/Hf and zircon zonation in the Spirit Mountain batholith, Nevada, document repeated fractionation and thermal fluctuations. Ratios of Zr/Hf are ???30-40 for cumulates and 18-30 for high-SiO2 granites. In zircons, Hf (and U) are inversely correlated with Ti, and concentrations indicate large fluctuations in melt composition and TTiZ (>100??C) for individual zircons. Such variations are consistent with field relations and ion-probe zircon geochronology that indicate a >1 million year history of repeated replenishment, fractionation, and extraction of melt from crystal mush to form the low Zr/Hf high-SiO2 zone. ?? 2006 The Mineralogical Society.

Generation of Silicic Melts in the Early Izu-Bonin Arc Recorded by Detrital Zircons in Proximal Arc Volcaniclastic Rocks From the Philippine Sea

NASA Astrophysics Data System (ADS)

Barth, A. P.; Tani, K.; Meffre, S.; Wooden, J. L.; Coble, M. A.; Arculus, R. J.; Ishizuka, O.; Shukle, J. T.

2017-10-01

A 1.2 km thick Paleogene volcaniclastic section at International Ocean Discovery Program Site 351-U1438 preserves the deep-marine, proximal record of Izu-Bonin oceanic arc initiation, and volcano evolution along the Kyushu-Palau Ridge (KPR). Pb/U ages and trace element compositions of zircons recovered from volcaniclastic sandstones preserve a remarkable temporal record of juvenile island arc evolution. Pb/U ages ranging from 43 to 27 Ma are compatible with provenance in one or more active arc edifices of the northern KPR. The abundances of selected trace elements with high concentrations provide insight into the genesis of U1438 detrital zircon host melts, and represent useful indicators of both short and long-term variations in melt compositions in arc settings. The Site U1438 zircons span the compositional range between zircons from mid-ocean ridge gabbros and zircons from relatively enriched continental arcs, as predicted for melts in a primitive oceanic arc setting derived from a highly depleted mantle source. Melt zircon saturation temperatures and Ti-in-zircon thermometry suggest a provenance in relatively cool and silicic melts that evolved toward more Th and U-rich compositions with time. Th, U, and light rare earth element enrichments beginning about 35 Ma are consistent with detrital zircons recording development of regional arc asymmetry and selective trace element-enriched rear arc silicic melts as the juvenile Izu-Bonin arc evolved.

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.

Mapping trace element distribution in fossil teeth and bone with LA-ICP-MS

NASA Astrophysics Data System (ADS)

Hinz, E. A.; Kohn, M. J.

2009-12-01

Trace element profiles were measured in fossil bones and teeth from the late Pleistocene (c. 25 ka) Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Laser-ablation ICP-MS can collect element counts along predefined tracks on a sample’s surface using a constant ablation speed allowing for rapid spatial sampling of element distribution. Key elements analyzed included common divalent cations (e.g. Sr, Zn, Ba), a suite of REE (La, Ce, Nd, Sm, Eu, Yb), and U, in addition to Ca for composition normalization and standardization. In teeth, characteristic diffusion penetration distances for all trace elements are at least a factor of 4 greater in traverses parallel to the dentine-enamel interface (parallel to the growth axis of the tooth) than perpendicular to the interface. Multiple parallel traverses in sections parallel and perpendicular to the tooth growth axis were transformed into trace element maps, and illustrate greater uptake of all trace elements along the central axis of dentine compared to areas closer to enamel, or within the enamel itself. Traverses in bone extending from the external surface, through the thickness of cortical bone and several mm into trabecular bone show major differences in trace element uptake compared to teeth: U and Sr are homogeneous, whereas all REE show a kinked profile with high concentrations on outer surfaces that decrease by several orders of magnitude within a few mm inward. The Eu anomaly increases uniformly from the outer edge of bone inward, whereas the Ce anomaly decreases slightly. These observations point to major structural anisotropies in trace element transport and uptake during fossilization, yet transport and uptake of U and REE are not resolvably different. In contrast, transport and uptake of U in bone must proceed orders of magnitude faster than REE as U is homogeneous whereas REE exhibit strong gradients. The kinked REE profiles in bone unequivocally indicate differential transport rates, consistent with a double-medium diffusion model in which microdomains with slow diffusivities are bounded by fast-diffusing pathways.

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.

High Resolution Laser Mass Spectrometry Bioimaging

PubMed Central

Murray, Kermit K.; Seneviratne, Chinthaka A.; Ghorai, Suman

2016-01-01

MSI (MSI) was introduced more than five decades ago with secondary ion mass spectrometry (SIMS) and a decade later with laser desorption/ionization (LDI) mass spectrometry (MS). Large biomolecule imaging by matrix-assisted laser desorption/ionization (MALDI) was developed in the 1990s and ambient laser MS a decade ago. Although SIMS has been capable of imaging with a moderate mass range at sub-micrometer lateral resolution from its inception, laser MS requires additional effort to achieve a lateral resolution of 10 μm or below which is required to image at the size scale of single mammalian cells. This review covers untargeted large biomolecule MSI using lasers for desorption/ionization or laser desorption and post-ionization. These methods include laser microprobe (LDI) MSI, MALDI MSI, laser ambient and atmospheric pressure MSI, and near-field laser ablation MS. Novel approaches to improving lateral resolution are discussed, including oversampling, beam shaping, transmission geometry, reflective and through-hole objectives, microscope mode, and near-field optics. PMID:26972785

High resolution laser mass spectrometry bioimaging.

PubMed

Murray, Kermit K; Seneviratne, Chinthaka A; Ghorai, Suman

2016-07-15

Mass spectrometry imaging (MSI) was introduced more than five decades ago with secondary ion mass spectrometry (SIMS) and a decade later with laser desorption/ionization (LDI) mass spectrometry (MS). Large biomolecule imaging by matrix-assisted laser desorption/ionization (MALDI) was developed in the 1990s and ambient laser MS a decade ago. Although SIMS has been capable of imaging with a moderate mass range at sub-micrometer lateral resolution from its inception, laser MS requires additional effort to achieve a lateral resolution of 10μm or below which is required to image at the size scale of single mammalian cells. This review covers untargeted large biomolecule MSI using lasers for desorption/ionization or laser desorption and post-ionization. These methods include laser microprobe (LDI) MSI, MALDI MSI, laser ambient and atmospheric pressure MSI, and near-field laser ablation MS. Novel approaches to improving lateral resolution are discussed, including oversampling, beam shaping, transmission geometry, reflective and through-hole objectives, microscope mode, and near-field optics. Copyright © 2016 Elsevier Inc. All rights reserved.

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 fractionation rather than magmatic oxidation conditions. Zircons typically have positive Ce anomalies that rise as T falls and Hf increases. This reflects either fractionation of minerals that incorporate Ce+3 but little Ce+4, or oxidation. U and Th concentrations are typically highest in low-T zones but often show very irregular patterns with T and Hf. Molar ratios of total 3+ ions over P are mostly 1-5, suggesting charge compensation other than the xenotime substitution (Mazdab and Wooden 2006). Random analyses of zircons for T and composition are of limited use given wide variation within single zircons. Process interpretations should be based on trends observed in multiple zircons from individual samples, as many samples have characteristics distinct from general trends. Hydrothermal zircon (Hoskin 2005) is not unusual as a rim zone and may reflect a fine intergrowth of other minerals (apatite, titanite, oxides) or unusual late stage growth conditions. Ti temperatures from these zones are often unreliable, and all analyses for Ti and trace elements should include screens (i.e. F, Al, Ca, Fe) for Ti-bearing minerals and other accessories. While trace element concentrations of zircons may not be diagnostic of rock types in general, careful analyses as described above provide invaluable information about magmatic and metamorphic processes.

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.

Effective LA-ICP-MS dating of common-Pb bearing accessory minerals with new data reduction schemes in Iolite

NASA Astrophysics Data System (ADS)

Kamber, Balz S.; Chew, David M.; Petrus, Joseph A.

2014-05-01

Compared to non-destructive geochemical analyses, LA-ICP-MS consumes ca. 0.1 μm of material per ablation pulse. It is therefore to be expected that the combined analyses of ca. 200 pulses will encounter geochemical and isotopic complexities in all but the most perfect minerals. Experienced LA-ICP-MS analysts spot down-hole complexities and choose signal integration areas accordingly. In U-Pb geochronology, the task of signal integration choice is complex as the analyst wants to avoid areas of common Pb and Pb-loss and separate true (concordant) age complexity. Petrus and Kamber (2012) developed VizualAge as a tool for reducing and visualising, in real time, U-Pb geochronology data obtained by LA-ICP-MS as an add-on for the freely available U-Pb geochronology data reduction scheme of Paton et al. (2010) in Iolite. The most important feature of VizualAge is its ability to display a live concordia diagram, allowing users to inspect the data of a signal on a concordia diagram as the integration area it is being adjusted, thus providing immediate visual feedback regarding discordance, uncertainty, and common lead for different regions of the signal. It can also be used to construct histograms and probability distributions, standard and Tera-Wasserburg style concordia diagrams, as well as 3D U-Th-Pb and total U-Pb concordia diagrams. More recently, Chew et al. (2014) presented a new data reduction scheme (VizualAge_UcomPbine) with much improved common Pb correction functionality. Common Pb is a problem for many U-bearing accessory minerals and an under-appreciated difficulty is the potential presence of (possibly unevenly distributed) common Pb in calibration standards, introducing systematic inaccuracy into entire datasets. One key feature of the new method is that it can correct for variable amounts of common Pb in any U-Pb accessory mineral standard as long as the standard is concordant in the U/Pb (and Th/Pb) systems after common Pb correction. Common Pb correction can be undertaken using either the 204Pb, 207Pb or 208Pb(no Th) methods. After common Pb correction to the user-selected age standard integrations, the scheme fits session-wide model U-Pb fractionation curves to the time-resolved U-Pb standard data. This down hole fractionation model is next applied to the unknowns and sample-standard bracketing (using a user specified interpolation method) is used to calculate final isotopic ratios and ages. 204Pb- and 208Pb(no Th)-corrected concordia diagrams and 204Pb-, 207Pb- and 208Pb(no Th)-corrected age channels can be calculated for user-specified initial Pb ratio(s). All other conventional common Pb correction methods (e.g. intercept or isochron methods on co-genetic analyses) can be performed offline. Apatite, titanite, rutile and very young zircon data will be presented, obtained using a Thermo Scientific iCAP-Qc (Q-ICP-MS) coupled to a Photon Machines Analyte Excite 193 nm ArF Excimer laser with a novel signal smoothing device Chew, D.M., Petrus, J.A., and Kamber, B.S. (2014); Chemical Geology, 363, 185-199. Paton C., Woodhead J.D., Hellstrom J.C., Hergt J.M., Greig A. and Maas R. (2010); Geochemistry Geophysics Geosystems, 11, 1-36. Petrus, J.A. and Kamber, B.S. (2012): Geostandards and Geoanalytical Research, 36, 247-270.

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.

Gamma-rays attenuation of zircons from Cambodia and South Africa at different energies: A new technique for identifying the origin of gemstone

NASA Astrophysics Data System (ADS)

Limkitjaroenporn, P.; Kaewkhao, J.

2014-10-01

In this work, the gamma-rays interaction properties of zircons from Cambodia and South Africa have been studied. The densities of Cambodian and South African's zircons are 4.6716±0.0040 g/cm3 and 4.5505±0.0018 g/cm3, respectively. The mass attenuation coefficient and the effective atomic number of gemstones were measured with the gamma-ray in energies range 223-662 keV using the Compton scattering technique. The mass attenuation coefficients of both zircons decreased with the increasing of gamma-rays energies. The different mass attenuation coefficients between the two zircons observed at gamma-ray energies below 400 keV are attributed to the differences in the photoelectric interaction. The effective atomic number of zircons was decreased with the increasing of gamma-ray energies and showed totally different values between the Cambodia and South Africa sources. The origins of the two zircons could be successfully identified by the method based on gamma-rays interaction with matter with advantage of being a non-destructive testing.

Mass spectrometry imaging under ambient conditions.

PubMed

Wu, Chunping; Dill, Allison L; Eberlin, Livia S; Cooks, R Graham; Ifa, Demian R

2013-01-01

Mass spectrometry imaging (MSI) has emerged as an important tool in the last decade and it is beginning to show potential to provide new information in many fields owing to its unique ability to acquire molecularly specific images and to provide multiplexed information, without the need for labeling or staining. In MSI, the chemical identity of molecules present on a surface is investigated as a function of spatial distribution. In addition to now standard methods involving MSI in vacuum, recently developed ambient ionization techniques allow MSI to be performed under atmospheric pressure on untreated samples outside the mass spectrometer. Here we review recent developments and applications of MSI emphasizing the ambient ionization techniques of desorption electrospray ionization (DESI), laser ablation electrospray ionization (LAESI), probe electrospray ionization (PESI), desorption atmospheric pressure photoionization (DAPPI), femtosecond laser desorption ionization (fs-LDI), laser electrospray mass spectrometry (LEMS), infrared laser ablation metastable-induced chemical ionization (IR-LAMICI), liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS), nanospray desorption electrospray ionization (nano-DESI), and plasma sources such as the low temperature plasma (LTP) probe and laser ablation coupled to flowing atmospheric-pressure afterglow (LA-FAPA). Included are discussions of some of the features of ambient MSI for example the ability to implement chemical reactions with the goal of providing high abundance ions characteristic of specific compounds of interest and the use of tandem mass spectrometry to either map the distribution of targeted molecules with high specificity or to provide additional MS information on the structural identification of compounds. We also describe the role of bioinformatics in acquiring and interpreting the chemical and spatial information obtained through MSI, especially in biological applications for tissue diagnostic purposes. Finally, we discuss the challenges in ambient MSI and include perspectives on the future of the field. Copyright © 2012 Wiley Periodicals, Inc.

Mass Spectrometry Imaging under Ambient Conditions

PubMed Central

Wu, Chunping; Dill, Allison L.; Eberlin, Livia S.; Cooks, R. Graham; Ifa, Demian R.

2012-01-01

Mass spectrometry imaging (MSI) has emerged as an important tool in the last decade and it is beginning to show potential to provide new information in many fields owing to its unique ability to acquire molecularly specific images and to provide multiplexed information, without the need for labeling or staining. In MSI, the chemical identity of molecules present on a surface is investigated as a function of spatial distribution. In addition to now standard methods involving MSI in vacuum, recently developed ambient ionization techniques allow MSI to be performed under atmospheric pressure on untreated samples outside the mass spectrometer. Here we review recent developments and applications of MSI emphasizing the ambient ionization techniques of desorption electrospray ionization (DESI), laser ablation electrospray ionization (LAESI), probe electrospray ionization (PESI), desorption atmospheric pressure photoionization (DAPPI), femtosecond laser desorption ionization (fs-LDI), laser electrospray mass spectrometry (LEMS), infrared laser ablation metastable-induced chemical ionization (IR-LAMICI), liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS), nanospray desorption electrospray ionization (nano-DESI), and plasma sources such as the low temperature plasma (LTP) probe and laser ablation coupled to flowing atmospheric-pressure afterglow (LA-FAPA). Included are discussions of some of the features of ambient MSI including the ability to implement chemical reactions with the goal of providing high abundance ions characteristic of specific compounds of interest and the use of tandem mass spectrometry to either map the distribution of targeted molecules with high specificity or to provide additional MS information in the structural identification of compounds. We also describe the role of bioinformatics in acquiring and interpreting the chemical and spatial information obtained through MSI, especially in biological applications for tissue diagnostic purposes. Finally, we discuss the challenges in ambient MSI and include perspectives on the future of the field. PMID:22996621

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

Located in the east section of the Central Asian orogen in northeastern China, the Xilamulun district comprises several newly discovered molybdenum deposits, primarily of porphyry type and Mesozoic ages. This district is divided by the Xilamulun fault into the southern and the northern parts. In this paper, we present new zircon U-Pb dating, trace elements and Hf isotope, and/or whole rock Sr-Nd-Pb isotopic results for the host granitoids from three Mo deposits (Yangchang, Haisugou and Shabutai) in northern Xilamulun. Our aim is to constrain the age and petrogenesis of these intrusions and their implications for Mo mineralization. Zircon U-Pb LA-ICP-MS dating shows that the monzogranites from the Shabutai and Yangchang deposits formed at 138.4 ± 1.5 and 137.4 ± 2.1 Ma, respectively, which is identical to the molybdenite Re-Os ages and coeval well with the other Mo deposits in this region, thereby indicating an Early Cretaceous magmatism and Mo mineralization event. Zircon Ce/Nd ratios from the mineralized intrusions are significantly higher than the barren granites, implying that the mineralization-related magmas are characterized by higher oxygen fugacity. These mineralized intrusions share similar zircon in-situ Hf and whole rock Sr-Nd isotopic compositions, with slightly negative to positive εHf(t) ranging from - 0.8 to + 10.0, restricted εNd(t) values from - 3.7 to + 1.6 but a little variable (87Sr/86Sr)i ratios between 0.7021 and 0.7074, indicative of formation from primary magmas generated from a dominantly juvenile lower crust source derived from depleted mantle, despite diverse consequent processes (e.g., magma mixing, fractional crystallization and crustal contamination) during their evolution. The Pb isotopes (whole rock) also show a narrow range of initial compositions, with (206Pb/204Pb)i = 18.03-18.88, (207Pb/204Pb)i = 15.48-15.58 and (208Pb/204Pb)i = 37.72-38.28, in agreement with Sr-Nd-Hf isotopes reflecting the dominance of a mantle component. An integration of geochronological and isotopic data points to three stages of Mo mineralization events (i.e., Triassic, Late Jurassic, and Early Cretaceous) associated with magmas generated from three different source regions in the Xilamulun district, NE China. The variation in the origin of the magmas from which the porphyry Mo systems were generated suggests that the formation of Mo deposit lies not in the composition of magma sources. Other factors, including high magma oxygen fugacity, may have taken a fundamental role in Mo enrichment and subsequent mineralization.

Advances and limitations on interpreting the erosional record from isotopic analysis of single detrital mineral grains

NASA Astrophysics Data System (ADS)

Parrish, Randall

2010-05-01

The analysis of provenance of clastic sediments is useful for reconstructing the characteristics and rates of exhumation of source areas, and sometimes placing minimum age constraints on depositional age. Due largely to increased availability and ease of access to LA-ICP-MS instrumentation, the analysis of provenance using single detrital accessory minerals has grown very rapidly over recent years. With this however is a culture of casual users who may not fully appreciate subtleties of measurement and isotope interpretation. The isotopic provenance literature is dominated by zircon-centric studies that use U-Pb dating and Hf isotope measurements of single zircons, but unfortunately an increasing number of these studies appear to lack sufficient understanding of U-Pb and Hf systematics; misleading interpretations are increasingly common. The inherent information contained in detrital accessory minerals is potentially immense, scientifically, but comprehensive interpretations attempting to reconstruct the geological make-up and evolution of sources require dating of multiple types of accessory minerals (i.e. zircon, titanite, monazite, garnet inclusions, micas, allanite, rutile, apatite) by various methods (U-Pb, fission track, Ar-Ar…) at times accompanied by isotope geochemical data (Lu-Hf, Sm-Nd, Rb-Sr) of phases where Sr, Hf, or REE comprise a major element (≥0.5%). Many approaches have been demonstrated but the mix of methodologies needs to be tailored to the problem, in view of the variable effort and expense needed to acquire good datasets. To date there are few comprehensive multi-mineral, multi-isotope system applications, and too many studies that follow a prescriptive cookbook that lacks innovation and fails to address a problem. The field needs to focus effort on the approaches that can solve a problem well rather than doing either just the easy methods or too many methods only moderately well. Zircon studies require strategies that reduce or eliminate discordance, collect sufficient data on each grain to make a robust age interpretation, improve accuracy of data by more attention to standards and uncertainties, can analyze thin overgrowths that reveal the magmatic or metamorphic age, and minimize sample consumption, not an easy task for the vast majority of laboratories doing provenance applications. Detrital monazite, monazite-in garnet, titanite and rutile can reveal much of the higher temperature metamorphic time-temperature path, and coupled U-Pb and fission track studies of single zircon and apatite grains can be useful for determining lower temperature exhumation rates. Isotope geochemistry (Hf-Nd-Sr-O) is more time consuming but can be pivotal to distinguish subtle differences in sources and to test specific hypotheses. Examples of improved methods and applications will be presented to illustrate the presentation.

Zirconium and hafnium in the southeastern Atlantic States

USGS Publications Warehouse

Mertie, J.B.

1958-01-01

The principal source of zirconium and hafnium is zircon, though a minor source is baddeleyite, mined only in Brazil. Zircon is an accessory mineral in igneous, metamorphic, and sedimentary rocks, but rarely occurs in hardrock in minable quantities. The principal sources of zircon are therefore alluvial deposits, which are mined in many countries of five continents. The principal commercial deposits in the United States are in Florida, though others exist elsewhere in the southeastern Coastal Plain. The evidence indicates that conditions for the accumulation of workable deposits of heavy minerals were more favorable during the interglacial stages of the Pleistocene epoch than during Recent time. Therefore detrital ores of large volume and high tenor are more likely to be found in the terrace deposits than along the present beaches. Other concentrations of heavy minerals, however, are possible at favored sites close to the Fall Line where the Tuscaloosa formation rests upon the crystalline rocks of the Piedmont province. A score of heavy and semiheavy minerals occur in the detrital deposits of Florida, but the principal salable minerals are ilmenite, leucoxene, rutile, and zircon, though monazite and staurolite are saved at some mining plants. Commercial deposits of heavy minerals are generally required to have a tenor of 4 percent, though ores with a lower tenor can be mined at a profit if the content of monazite is notably high. The percentages of zircon in the concentrates ranges from 10 to 16 percent, and in eastern Florida from 13 to 15 percent. Thus the tenor in zircon of the ore-bearing sands ranges from 0.4 to 0.6 percent. The content of hafnium in zircon is immaterial for many uses, but for some purposes very high or very low tenors in hafnium are required. Alluvial zircon cannot be separated into such varieties, which, if needed, must be obtained from sources in bedrock. It thus becomes necessary to determine the Hf : Zr ratios in zircon from many kinds of bedrock.Granitic rocks are the principal sources of zircon, though not the best sources of zircon with a high tenor in hafnium. A general study by the Geological Survey of the granitic rocks of the Southeastern Atlantic States has been in progress for 10 years, and hundreds of samples of granitic accessory minerals have been acquired. Thirty samples of zircon from these collections were selected for spectrographic and X-ray determinations of their tenors in hafnium. Nine other samples of alluvial zircon were included, of which three are from Florida and six from foreign countries. No domestic zircon was discovered with very high or very low tenors in hafnium.The volume of zircon in the southeastern Coastal Plain is enormous, but most of it is not recoverable. The minable reserves of heavy minerals, however, are very large, and from these it is estimated conservatively that 10 million short tons of zircon can be obtained. The corresponding amounts of zirconium and hafnium, using the mean Hf:Zr ratio of the deposits in Florida, are 4,868,000 and 112,000 tons, respectively. These reserves could be delivered, if needed, at the rate of 100,000 tons a year.

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, however, CA-TIMS could provide elegant ways to isolate the metamorphic components. A third category includes zircon populations that fail to achieve consistent ages, or concordant plateaus in multi-step partial dissolutions, even though they may have all the attributes of ideal CA-TIMS objects. The category is exemplified by a 62 Ma magmatic suite with a simple geological history and good quality zircon populations. The zircons have moderate U contents, regular growth zoning and few visible imperfections, yet the data reveal very extensive Pb loss requiring the almost total dissolution of the zircon before reaching the concordant residues. Baking of some of these zircon populations turns the colourless crystals brick-red (but still transparent), the red colour persisting long into the partial dissolution procedure. These features suggest that Pb loss may be related to a submicroscopic network of impurities and primary defects in the crystal structures which form pathways for the diffusion of Pb. Subsequent annealing appears to make the discordant domains impervious to partial dissolution. In conclusion, it is evident that CA-TIMS is a very helpful new technique for U-Pb geochronology, but some limitations must be considered that require case-by-case judgment and good Krogh-type abraders in reserve.

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 rheological lockup by the crystals. Last crystallizing zircons in the interstitial melt may therefore postdate emplacement of the magma. The range of 206Pb/238U ages may yield a time frame for the cooling of a given magma batch, which could be added to quantitative thermal models of magma emplacement and cooling. Hf isotopes and trace elements of the dated zircon are used to trace the nature of the dated grains [4], specifically for identification of crystals that form earlier at lower crustal levels (antecrysts). Autocrystic zircons typically show, e.g., distinctly different (higher or lower) Th/U ratios. Cautiously interpreted high-precision U-Pb data of chemically abraded zircons may resolve the evolution of a magmatic system from its roots to final emplacement or eruption, trace fractional crystallization of zircon and other accessory and major phases in a magma batch, and add quantitative temporal constraints to thermal models. The proposed interpretation scheme thus adds significant information compared to conventional statistics. [1] Mattinson J., 2005, Chem. Geol. 200, 47-66; ; [2] Slama et al., 2008, Chem. Geol. 249, 1-35; [3] Miller et al., 2007, J. Volc. Geotherm. Res. 167, 282-299; [4] Schoene et al., 2010, Geochim. Cosmochim. Acta 74, 7144-7159

Geochemistry and Temperatures Recorded by Zircon During the Final Stages of the Youngest Toba Tuff Magma Chamber, Sumatra, Indonesia

NASA Astrophysics Data System (ADS)

Gaither, T.; Reid, M. R.; Vazquez, J. A.

2009-12-01

The ~74 ka eruption of the Youngest Toba Tuff (YTT) in Sumatra, Indonesia, was one of the largest single volcanic eruptions in geologic history, on par with other voluminous silicic eruptions such as the Huckleberry Ridge Tuff of Yellowstone and the Bishop Tuff of Long Valley, California. We are exploring how zircon and other accessory mineral phases record compositional and thermal changes that occurred in the YTT magma, and the important clues these crystal scale records hold for magma chamber dynamics and processes that lead up to supervolcano eruptions. In this study, we report trace element (REE, U, Th, Ti, and Hf) characteristics, Ti-in-zircon crystallization temperatures, and apparent REE partition coefficients obtained for YTT zircon rims. Twenty-nine zircons from pumices with a compositional range of 70-76 wt% SiO2 were analyzed on the UCLA Cameca ims 1270 ion microprobe. The grains were mounted so that only the outermost ~1.5 microns of the crystals were analyzed. Median Zr/Hf ratios of 34 to 38 characterize zircons from the pumices; the high silica rhyolite grains have lower Zr/Hf. Chondrite-normalized REE patterns are strongly LREE-depleted. Positive Ce anomalies are large (Ce/Ce* ranges up to 88) and Eu/Eu* varies by a factor of four (0.05 to 0.21). Eu/Eu*, Nd/Yb, and Th/U decrease with decreasing Zr/Hf, showing that the variation in zircon rim compositions may be related by co-precipitation of feldspar and allanite along with zircon. Titanium contents also decrease with decreasing Zr/Hf, suggesting that the chemical differences could be related to temperature changes. REE partition coefficients calculated from zircon rim compositions and pumice glass compositions give a good fit to a lattice strain model. They are also quite similar to the partition coefficients of Sano et al. (2002) which have been shown to be successful at reproducing melt compositions in other settings. Temperatures of crystallization calculated using the Ti-in-zircon geothermometer (Watson et al., 1996), assuming a melt aTiO2 of 0.5, yield very low median values (even without a possible pressure correction of -40 to -80°C), ranging from 640-667°C. Virtually all of the zircon rims record temperatures lower than eruption temperatures of 700-780°C estimated for the YTT by Chesner (1998) using FeTi oxide equilibria. It is possible that the low zircon temperatures reflect uncertainties in the Ti-in-zircon geothermometer but they are nonetheless permissive of re-entrainment of zircon from a near-solidus mush close to the time of eruption. The analytically significant chemical variations within the individual zircon populations, especially those of Zr/Hf, Eu/Eu*, and Nd/Yb, suggest that crystals from distinct compositional domains were brought together during a final merging/coalescence of magma that catalyzed the eruption.

Provenance of sediments from Sumatra, Indonesia

NASA Astrophysics Data System (ADS)

Liebermann, Christof; Hall, Robert; Gough, Amy

2017-04-01

The island of Sumatra is situated at the south-western margin of the Indonesian archipelago. Sumatra is affected by active continental margin volcanism along the Sunda Trench, west of Sumatra as a result of active northeast subduction of the Indian plate under the Eurasian plate. Exposures of the Palaeozoic meta-sedimentary basement are mainly limited in extent to the northeast-southwest trending Barisan Mountain chain. The younger Cenozoic rocks are widespread across Sumatra, but can be grouped into structurally subdivided 'fore-arc', 'intramontane', and 'back-arc' basins. However, the formation of the basins pre-dates the current magmatic arc, thus a classical arc-related generation model can not be applied. The Cenozoic formations are well studied due to hydrocarbon enrichment, but little is known about their provenance history. A comprehensive sedimentary provenance study of the Cenozoic formations can aid in the wider understanding of Sumatran petroleum plays, can contribute to palaeographic reconstruction of western SE Asia, and might help to simplify the overall stratigraphy of Sumatra. This work represents a multi-proxy provenance study of sedimentary rocks from the main Cenozoic basins of Sumatra, alongside sediment from present-day river systems. The project refines the provenance in two ways: first, by studying the heavy mineral assemblages of the targeted formations, and secondly, by U-Pb detrital zircon dating using LA-ICP-MS to identify the age-range of the potential sediment sources. Preliminary U-Pb zircon age-data of >1500 concordant grains (10% discordant cut-off), heavy mineral compositions, and thin section analysis from two fieldwork seasons indicate a mixed provenance model, with a proximal igneous source, and mature basement rocks. An increase of the proximal signature in Lower-Miocene strata indicated by the occurrence of unstable heavy mineral phases such as apatite, and clinopyroxene suggests a major change of the source at the Oligocene-Miocene boundary. This can be interpreted as a pulse in the uplift of the Barisan Mountains. The presence of volcanic quartz in thin section supports this hypothesis. On the contrary, older sedimentary strata are characterised by ultra-stable heavy minerals such as zircon, tourmaline, and rutile; the presence of garnet in both pre-, and post-uplift affected strata indicates a contribution from metamorphic basement rocks, either from the local Sumatran basement or the Malay-Peninsula. Detrital zircon ages as old as Archean are present in all sedimentary formations; a prominent Triassic age group can be correlated with the Main Range Province granitoids reported from the Malay-Peninsula. It is noteworthy that zircon age spectra from Sumatra lack some diagnostic age groups commonly found in central- and western SE Asia, such as Cretaceous ages, correlated with igneous rock in the Schwaner Mountains, SW Borneo. The analysis of modern river sands suggests that the current sedimentary fluvial systems are mainly sourced from the recent Barisan-related volcanic arc. Zircon age patterns of the modern river sands resemble the populations found in the sedimentary strata, whereas, the heavy mineral composition is highly diluted by the recent igneous sources.

New Constraints for Tectono-Thermal Alpine Evolution of the Pyrenees: Combining Zircon Fission-Track and (U-Th)/He Analyses with Raman Spectrometry and In-Situ K-Ar Geochronology

NASA Astrophysics Data System (ADS)

Waldner, M.; Bellahsen, N.; Mouthereau, F.; Pik, R.; Bernet, M.; Scaillet, S.; Rosenberg, C.

2017-12-01

The pyrenean range was formed by the convergence of European and Iberian plates following the inversion of the Mesozoic rifting in the north of Pyrenees. In the Axial Zone, the collision caused an antiformal nappe-stacking of tectonic units. Recent studies pointed out the importance of pre-collision structural and thermal inheritance that may play a major role for orogeny such as: 1) Paleozoic Variscan inheritance; 2) Mesozoic rift-related high geothermal gradients, which are maintained during the onset of convergence in the North Pyrenean Zone. From a mineralogical point of view, pre-collision feldspars have been destabilized and influenced the development of alpine phyllonite in brittle-ductile conditions which suggests a weak crustal behavior during the formation of the orogenic wedge. Our aim is to get a better understanding of alpine deformation and exhumation by coupling different thermochronological, geochronological and thermometric methods. We document the thermal evolution of each tectonic unit by using low-temperature thermochronometers (Zircon Fission Tracks, U-Th/He on zircons including laser ablation profiles). Our data on vertical profiles combined to existing dataset on apatite allows to model alpine exhumation across the Axial zone. Structural observations through alpine thrusts coupled to geochronology (in situ K/Ar on phengites), Raman and chlorite-phengite thermo(baro)metry provide new key data to unravel the alpine evolution of the Pyrenees. According to preliminary ZFT results on granite massifs in the central part of Pyrenean Axial zone (near ECORS profile), exhumation ages potentially indicates a migration of exhumation towards the south. Exhumation ages of the northern massifs seems to have preserved the North Pyrenean Cretaceous rift evolution. Further south, the onset of exhumation is as old as Paleocene, which precedes the Eocene ages of the literature. The low burial estimated in the northern massifs may indicate a high thermal gradient. This dataset coupled to the above-cited other methods provide the most exhaustive and detailed image of the thermo-structural evolution of the Axial Zone that enables us to discuss the crustal rheology during collision. This study is part of the Orogen project, a partnership between academy and industry (Total, BRGM, CNRS)

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.

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.