Precise and accurate isotopic measurements using multiple-collector ICPMS     

F. Albarède  Philippe Telouk  Maud Boyet  Bruce Nelson 《Geochimica et cosmochimica acta》2004,68(12):2725-2744

New techniques of isotopic measurements by a new generation of mass spectrometers equipped with an inductively-coupled-plasma source, a magnetic mass filter, and multiple collection (MC-ICPMS) are quickly developing. These techniques are valuable because of (1) the ability of ICP sources to ionize virtually every element in the periodic table, and (2) the large sample throughout. However, because of the complex trajectories of multiple ion beams produced in the plasma source whether from the same or different elements, the acquisition of precise and accurate isotopic data with this type of instrument still requires a good understanding of instrumental fractionation processes, both mass-dependent and mass-independent. Although physical processes responsible for the instrumental mass bias are still to be understood more fully, we here present a theoretical framework that allows for most of the analytical limitations to high precision and accuracy to be overcome. After a presentation of unifying phenomenological theory for mass-dependent fractionation in mass spectrometers, we show how this theory accounts for the techniques of standard bracketing and of isotopic normalization by a ratio of either the same or a different element, such as the use of Tl to correct mass bias on Pb. Accuracy is discussed with reference to the concept of cup efficiencies. Although these can be simply calibrated by analyzing standards, we derive a straightforward, very general method to calculate accurate isotopic ratios from dynamic measurements. In this study, we successfully applied the dynamic method to Nd and Pb as examples. We confirm that the assumption of identical mass bias for neighboring elements (notably Pb and Tl, and Yb and Lu) is both unnecessary and incorrect. We further discuss the dangers of straightforward standard-sample bracketing when chemical purification of the element to be analyzed is imperfect. Pooling runs to improve precision is acceptable provided the pooled measurements are shown to be part of a single population. Second-order corrections seem to be able to improve the precision on ¹⁴³Nd/¹⁴⁴Nd measurements. Finally, after discussing a number of potential pitfalls, such as the consequence of peak shape, correlations introduced by counting statistics, and the effect of memory on double-spike methods, we describe an optimal strategy for high-precision and accurate measurements by MC-ICPMS, which involves the repetitive calibration of cup efficiencies and rigorous assessment of mass bias combined with standard-sample bracketing. We suggest that, when these simple guidelines are followed, MC-ICPMS is capable of producing isotopic data precise and accurate to better than 15 ppm.  相似文献   

Ionization constants of aqueous amino acids at temperatures up to 250°C using hydrothermal pH indicators and UV-visible spectroscopy: Glycine, α-alanine, and proline     

Rodney G.F. Clarke  Jenene C. Roberts  Richard J. Bartholomew  Peter R. Tremaine 《Geochimica et cosmochimica acta》2005,69(12):3029-3043

Ionization constants for several simple amino acids have been measured for the first time under hydrothermal conditions, using visible spectroscopy with a high-temperature, high-pressure flow cell and thermally stable colorimetric pH indicators. This method minimizes amino acid decomposition at high temperatures because the data can be collected rapidly with short equilibration times. The first ionization constant for proline and α-alanine, K_a,COOH, and the first and second ionization constants for glycine, K_a,COOH and K_a,NH4+, have been determined at temperatures as high as 250°C. Values for the standard partial molar heat capacity of ionization, Δ_rC_p^o,_COOH and Δ_rC_p^o,_NH4+, have been determined from the temperature dependence of ln (K_a,COOH) and ln (K_a,NH4+). The methodology has been validated by measuring the ionization constant of acetic acid up to 250°C, with results that agree with literature values obtained by potentiometric measurements to within the combined experimental uncertainty.We dedicate this paper to the memory of Dr. Donald Irish (1932-2002) of the University of Waterloo—friend and former supervisor of two of the authors (R.J.B. and P.R.T.).  相似文献   

Alpha-decay damage in minerals of the pyrochlore group     

Gregory R. Lumpkin  Rodney C. Ewing 《Physics and Chemistry of Minerals》1988,16(1):2-20

X-ray diffraction analysis and transmission electron microscopy have been used to study the effects of alpha-decay damage in pyrochlore group minerals, characterized by the general formula A _1?m B ₂O₆(O,OH,F)_1?n ·pH₂O. As defined by the XRD intensity ratio I/I ₀ , both the saturation dose (for which I/I ₀ =0.1?0.0) and the dose which signifies the initial loss of crystallinity (for which I/I ₀ =1.0?0.8) increase as a function of geologic age. The increase is attributed to annealing of isolated alpha-recoil tracks back to the original crystalline structure. The tracks have calculated mean lives, τ_a, on the order of 10⁸ years. In contrast, minerals which remain crystalline (e.g., uraninite, UO₂) despite doses of up to 10¹⁸ alpha-events/mg have mean alpha-recoil track lives ≈10⁴ years (Eyal and Fleischer 1985). After correcting the calculated dose for annealing of alpha-recoil damage, I/I ₀ is observed to decrease exponentially to zero over the dose range 0.02–1.0 × 10¹⁶ alpha-events/mg. The relationship between I/I ₀ and “corrected” dose was used to calculate an average alpha-recoil track diameter of 4.6 nm, in which < 2600 atoms are displaced. XRD line broadening due to strain dominates the first half of the crystalline-to-metamict transition, reaching a maximum of 0.003, then decreasing to < 0.001. Line broadening due to decreasing crystallite size dominates the latter half of the transition. Estimated crystallite dimensions decrease from 450 nm to < 15 nm prior to reaching the fully metamict state. With increasing dose HRTEM images of microlites from the Harding pegmatite sequentially exhibit: 1) mottled diffraction contrast, 2) isolated 1–5 nm aperiodic areas, 3) coexisting aperiodic and crystalline areas, 4) relict “islands” of crystalline material in an aperiodic matrix, and 5) complete loss of lattice fringe periodicity. With no consideration given to alpha-recoil track fading, the transition covers a dose range of 0.04–1.7 × 10¹⁷ alpha-events/mg. Using a value of τ_a=10⁸ years, this dose range is corrected down to 0.02–1.2 × 10¹⁶ alpha-events/mg. The metamict state is characterized by a range of M-M and M-O distances which give rise to bands of diffuse scattering centered at 0.30 nm and 0.18 nm, respectively, in x-ray and electron diffraction patterns. Random image contrast shown by HRTEM is consistent with a random network type structure, an interpretation supported by EXAFS/XANES studies (Greegor et al. 1985a, b, 1987). The structure of metamict pyrochlore consists of an aperiodic framework of corner-sharing B-O polyhedra. Compared to the crystalline precursor, the metamict state displays a reduced M-O coordination number and mean bond length, increased distortion of the B-site, and a slight increase in the average M-M distance.  相似文献   

Numerical quantification of sources and phase partitioning of chemical species in cloud: application to wintertime anthropogenic air masses at the Puy de Dôme station     

Maud Leriche  R. Lyana Curier  Laurent Deguillaume  Dimitri Caro  Karine Sellegri  Nadine Chaumerliac 《Journal of Atmospheric Chemistry》2007,57(3):281-297

The Model of Multiphase Cloud Chemistry M2C2 has recently been extended to account for nucleation scavenging of aerosol particles in the cloud water chemical composition. This extended version has been applied to multiphase measurements available at the Puy de Dôme station for typical wintertime anthropogenic air masses. The simulated ion concentrations in cloud water are in reasonable agreement with the experimental data. The analysis of the sources of the chemical species in cloud water shows an important contribution from nucleation scavenging of particles which prevails for nitrate, sulphate and ammonium. Moreover, the simulation shows that iron, which comes only from the dissolution of aerosol particles in cloud water, has a significant contribution in the hydroxyl radical production. Finally, the simulated phase partitioning of chemical species in cloud are compared with measurements. Numerical results show an underestimation of interstitial particulate phase fraction with respect to the measurements, which could be due to an overestimation of activated mass by the model. However, the simulated number scavenging efficiency of particles agrees well with the measured value of 40% of total number of aerosol particles activated in cloud droplets. Concerning the origin of chemical species in cloud water, the model reproduces quite well the contribution of gas and aerosol scavenging estimated from measurements. In addition, the simulation provides the contribution of in-cloud chemical reactivity to cloud water concentrations.  相似文献   

Low-temperature anisotropic diffusion of helium in zircon: Implications for zircon (U-Th)/He thermochronometry     

Martin Reich  Rodney C. Ewing  Udo Becker 《Geochimica et cosmochimica acta》2007,71(12):3119-3130

In the last decade the zircon (U-Th)/He (ZHe) thermochronometer has been applied to a variety of geologic problems. Although bulk diffusion coefficients for He in zircon are available from laboratory step-heating experiments, little is known about the diffusion mechanism(s) and their dependence on the crystallographic structure of zircon. Here, we investigate the diffusion of He in perfectly crystalline zircon using atomistic simulation methods that provide insights into the structural pathways of He migration in zircon. Empirical force fields and quantum-mechanical calculations reveal that the energy barriers for He diffusion are strongly dependent on structure. The most favorable pathway for He diffusion is the [0 0 1] direction through the open channels parallel to the c-axis (, activation energy for tracer diffusion of a He atom along [0 0 1]). In contrast, energy barriers are higher in other directions where narrower channels for He diffusion are identified, such as [1 0 0], [1 0 1], and [1 1 0] (ΔE^∗ of 44.8, 101.7, and 421.3 kJ mol⁻¹, respectively). Molecular dynamics simulations are in agreement with these results and provide additional insight in the diffusion mechanisms along different crystallographic directions, as well as the temperature dependence. Below the closure temperature of He in zircon [T_c ∼ 180 °C, Reiners P. W., Spell T. L., Nicolescu S., and Zanetti K. A. (2004) Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar-40/Ar-39 dating. Geochim. Cosmochim. Acta68, 1857-1887], diffusion is anisotropic as He moves preferentially along the [0 0 1] direction, and calculated tracer diffusivities along the two most favorable directions differ by approximately five orders of magnitude (D_[001]/D_[100] ∼ 10⁵, at T = 25 °C). Above this temperature, He atoms start to hop between adjacent [0 0 1] channels, along [1 0 0] and [0 1 0] directions (perpendicular to the c-axis). The diffusion along [1 0 0] and [0 1 0] is thermally activated, such that at higher temperatures, He diffusion in zircon becomes nearly isotropic (D_[001]/D_[100] ∼ 10, at T = 580 °C). These results suggest that the anisotropic nature of He diffusion at temperatures near the closure temperature should be considered in future diffusivity experiments. Furthermore, care should be taken when making geologic interpretations (e.g., exhumation rates, timing of cooling, etc.) from this thermochronometer until the effects of anisotropic diffusion on bulk ages and closure temperature estimates are better quantified.  相似文献   

Irradiation-induced stabilization of zircon (ZrSiO₄) at high pressure     

Maik Lang  Fuxiang Zhang  Jie Lian  Christina Trautmann  Reinhard Neumann  Rodney C. Ewing   《Earth and Planetary Science Letters》2008,269(1-2):291-295

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Landslides associated with the colluvial soils overlying the Natal Group in the greater Durban region of Natal, South Africa   总被引：3，自引：1，他引：2  

F. G. Bell  R. R. Maud 《Environmental Geology》2000,39(9):1029-1038

In the last 25 years, many of the landslides that have occurred in the greater Durban region have been associated with the colluvial soils overlying the Natal Group, most of which occurred during the very heavy rains of September 1987. Subsequently, a very heavy rainfall event in February 1999 also gave rise to landslides. In fact, prior to 1987 these colluvial soils were considered relatively stable. A critical precipitation coefficient has been developed which included the cumulative precipitation up to a landslide event. In addition, an attempt has been made to establish a threshold value for triggering of landslides for the colluvial soils from a study of pluviometric data. The results indicate that when a rainfall event exceeds 12% of the mean annual rainfall, small-scale landslides are likely to occur. When a rainfall event is greater than 16% of the mean annual rainfall, a moderate number of landslides take place. Major landslides are associated with rainfall events with intensities in excess of 20% of the mean annual precipitation. An example of a landslide which occurred on the Natal Group due to construction operations is provided, as well as an account of those which took place during September 1987. In the latter case, most of the slides took the form of mudflows and were responsible for some of the worst damage which has occurred in the Durban region. The colluvial soils involved were relatively thin and therefore became quickly saturated by the heavy rainfall. In some places the situation was further aggravated by liquefaction of the soils. Received: 15 June 1999 · Accepted: 30 August 1999  相似文献   

A shallow subsurface controlled release facility in Bozeman, Montana, USA, for testing near surface CO2 detection techniques and transport models   总被引：1，自引：0，他引：1  

Lee H. Spangler  Laura M. Dobeck  Kevin S. Repasky  Amin R. Nehrir  Seth D. Humphries  Jamie L. Barr  Charlie J. Keith  Joseph A. Shaw  Joshua H. Rouse  Alfred B. Cunningham  Sally M. Benson  Curtis M. Oldenburg  Jennifer L. Lewicki  Arthur W. Wells  J. Rodney Diehl  Brian R. Strazisar  Julianna E. Fessenden  Thom A. Rahn  James E. Amonette  Jon L. Barr  William L. Pickles  James D. Jacobson  Eli A. Silver  Erin J. Male  Henry W. Rauch  Kadie S. Gullickson  Robert Trautz  Yousif Kharaka  Jens Birkholzer  Lucien Wielopolski 《Environmental Earth Sciences》2010,60(2):227-239

A controlled field pilot has been developed in Bozeman, Montana, USA, to study near surface CO₂ transport and detection technologies. A slotted horizontal well divided into six zones was installed in the shallow subsurface. The scale and CO₂ release rates were chosen to be relevant to developing monitoring strategies for geological carbon storage. The field site was characterized before injection, and CO₂ transport and concentrations in saturated soil and the vadose zone were modeled. Controlled releases of CO₂ from the horizontal well were performed in the summers of 2007 and 2008, and collaborators from six national labs, three universities, and the U.S. Geological Survey investigated movement of CO₂ through the soil, water, plants, and air with a wide range of near surface detection techniques. An overview of these results will be presented.  相似文献   

Origin of LateTriassic high-Mg adakitic granitoid rocks from the Dongjiangkou area,Qinling orogen,central China: Implications for subduction of continental crust     

Jiang-Feng Qin  Shao-Cong Lai  Rodney Grapes  Chun-rong Diwu  Yin-Juan Ju  Yong-Fei Li 《Lithos》2010,120(3-4):347-367

The origin of high-Mg adakitic granitoids in collisional orogens can provide important information about the nature of the lower crust and upper mantle during the orogenic process. Late-Triassic high-Mg adakitic granite and its mafic enclaves from the Dongjiangkou area, the Qinling orogenic belt, central China, were derived by partial melting of subducted continental crust and underwent interaction with the overlying mantle wedge peridotite. Adakitic affinity of the different facies of the Dongjiangkou granite body are: high Sr, Ba, high La/Yb and Sr/Y, low Y,Yb, Yb/Lu and Dy/Yb, and no significant Eu anomalies, suggesting amphibole + garnet and plagioclase-free restite in their source region. Evolved Sr-Nd-Pb isotopic compositions [(⁸⁷Sr/⁸⁶Sr)_i = 0.7050 to 0.7055,ε_Nd(t) = –6.6 to –3.3; (²⁰⁶Pb/²⁰⁴Pb)_i = 17.599 to 17.799, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.507 to 15.526, (²⁰⁸Pb/²⁰⁴Pb)_i = 37.775 to 37.795] and high K₂O, Rb, together with a large variation in zircon Hf isotopic composition (ε_Hf(t) = ?9.8 to + 5.0), suggest that the granite was derived from reworking of the ancient lower continental crust. CaO, P₂O₅, K₂O/Na₂O, Cr, Ni, Nb/Ta, Rb/Sr and Y increase, and SiO₂, Sr/Y and Eu/Eu* decrease with increasing MgO, consistent with interaction of primitive adakitic melt and overlying mantle peridotite. Zircons separated from the host granites have U-Pb concordia ages of 214 ± 2 Ma to 222 ± 2 Ma, compatible with exhumation ages of Triassic UHP metamorphic rocks in the Dabie orogenic belt. Mafic microgranular enclaves and mafic dykes associated with the granite have identical zircon U-Pb ages of 220 Ma, and are characterized by lower SiO₂, high TiO₂, Mg# and similar evolved Sr-Nd-Pb isotopic composition. Zircons from mafic microgranular enclaves (MMEs) and mafic dykes also show a large variation in Hf isotopic composition with ε_Hf(t) between ?11.3 and + 11.3. It is inferred that they were formed by partial melting of enriched mantle lithosphere and contaminated by the host adakitic granite magma.In combination with the regional geology, high-Mg# adakitic granitoid rocks in the Dongjiangkou area are considered to have resulted from interaction between subducted Yangtze continental crust and the overlying mantle wedge. Triassic continental collision caused detachment of the Yangtze continental lithosphere subducted beneath the North China Craton, at ca. 220 Ma causing asthenosphere upwelling and exhumation of the continental crust. Triassic clockwise rotation of the Yangtze Craton caused extension in the Dabie area which led to rapid exhumation of the subducted continental lithosphere, while compression in the Qinling area and high-P partial melting (amphibole ± garnet stability field) of the subducted continental crust produced adakitic granitic magma that reacted with peridotite to form Mg-rich hybrid magma.  相似文献   

Origin of the structure of the Kuiper belt during a dynamical instability in the orbits of Uranus and Neptune     

Harold F. Levison  Alessandro Morbidelli  Rodney Gomes 《Icarus》2008,196(1):258-273

We explore the origin and orbital evolution of the Kuiper belt in the framework of a recent model of the dynamical evolution of the giant planets, sometimes known as the Nice model. This model is characterized by a short, but violent, instability phase, during which the planets were on large eccentricity orbits. It successfully explains, for the first time, the current orbital architecture of the giant planets [Tsiganis, K., Gomes, R., Morbidelli, A., Levison, H.F., 2005. Nature 435, 459-461], the existence of the Trojans populations of Jupiter and Neptune [Morbidelli, A., Levison, H.F., Tsiganis, K., Gomes, R., 2005. Nature 435, 462-465], and the origin of the late heavy bombardment of the terrestrial planets [Gomes, R., Levison, H.F., Tsiganis, K., Morbidelli, A., 2005. Nature 435, 466-469]. One characteristic of this model is that the proto-planetary disk must have been truncated at roughly 30 to 35 AU so that Neptune would stop migrating at its currently observed location. As a result, the Kuiper belt would have initially been empty. In this paper we present a new dynamical mechanism which can deliver objects from the region interior to ∼35 AU to the Kuiper belt without excessive inclination excitation. In particular, we show that during the phase when Neptune's eccentricity is large, the region interior to its 1:2 mean motion resonance becomes unstable and disk particles can diffuse into this area. In addition, we perform numerical simulations where the planets are forced to evolve using fictitious analytic forces, in a way consistent with the direct N-body simulations of the Nice model. Assuming that the last encounter with Uranus delivered Neptune onto a low-inclination orbit with a semi-major axis of ∼27 AU and an eccentricity of ∼0.3, and that subsequently Neptune's eccentricity damped in ∼1 My, our simulations reproduce the main observed properties of the Kuiper belt at an unprecedented level. In particular, our results explain, at least qualitatively: (1) the co-existence of resonant and non-resonant populations, (2) the eccentricity-inclination distribution of the Plutinos, (3) the peculiar semi-major axis—eccentricity distribution in the classical belt, (4) the outer edge at the 1:2 mean motion resonance with Neptune, (5) the bi-modal inclination distribution of the classical population, (6) the correlations between inclination and physical properties in the classical Kuiper belt, and (7) the existence of the so-called extended scattered disk. Nevertheless, we observe in the simulations a deficit of nearly-circular objects in the classical Kuiper belt.  相似文献