The fidelity of melt inclusions as records of melt composition

A series of experiments created melt inclusions in plagioclase and pyroxene crystals grown from a basaltic melt at 1,150°C, 1.0 GPa to investigate diffusive fractionation during melt inclusion formation; additionally, P diffusion in a basaltic melt was measured at 1.0 GPa. Melt inclusions and melts within a few 100 microns of plagioclase–melt interfaces were analyzed for comparison with melt compositions far from the crystals. Melt inclusions and melt compositions in the boundary layer close to the crystal–melt interface were similar, but both differ significantly in incompatible element concentrations from melt found greater than approximately 200 microns away from the crystals. The compositional profiles of S, Cl, P, Fe, and Al in the boundary layers were successfully reproduced by a two-step model of rapid crystal growth followed by diffusive relaxation toward equilibrium after termination of crystal growth. Applying this model to investigate possible incompatible element enrichment in natural melt inclusions demonstrated that at growth rates high enough to create the conditions for melt inclusion formation, ∼10⁻⁹–10⁻⁸ m s⁻¹, the concentration of water in the boundary layer near the crystal was similar to that of the bulk melt because of its high diffusion coefficient, but sulfur, with a diffusivity similar to major elements and CO₂, was somewhat enriched in the boundary layer melt, and phosphorus, with its low diffusion coefficient similar to other high-field strength elements and rare earth elements, was significantly enriched. Thus, the concentrations of sulfur and phosphorus in melt inclusions may over-estimate their values in the bulk melt, and other elements with similar diffusion coefficients may also be enriched in melt inclusions relative to the bulk melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Neodymium isotopes in seawater from the Barents Sea and Fram Strait Arctic-Atlantic gateways

The neodymium concentration, C_Nd, and isotopic composition, ε_Nd, in seawater have been determined in the water column at five sites in the Barents Sea-Fram Strait area where most of the water exchange between the Arctic Ocean and the North Atlantic takes place. In the main Arctic Ocean inflow branch across the Barents Sea the concentration and isotopic composition (C_Nd = 15.5 pmol/kg and ε_Nd = −10.8) are similar to those reported for the northeastern Nordic Seas, which is consistent with this region being a source area for the Arctic inflow. Due to the addition of Nd from Svalbard shelf sediments, the C_Nd in the surface waters above 150 m, in the Fram Strait inflow branch is higher by a factor of 2 and the ε_Nd is shifted to lower values (−11.8).In the stratified Nansen Basin, where cold low salinity water overlies warmer Atlantic water the C_Nd and ε_Nd do not vary with the vertical temperature-salinity structure but are essentially constant and similar to those of the Atlantic inflow throughout the entire water column, down to 3700 m depth, which indicates that the Nd is to a large extent of Atlantic origin.Compared to the Atlantic inflow water, the Nd in the major Arctic Ocean outflow, the Fram Strait, show higher C_Nd in the surface waters above 150 m, and a higher ε_Nd (−9.8) throughout the entire water column down to 1300 m depth. Sources for the more radiogenic Nd isotopic composition in deep water of the Fram Strait outflow most likely involve boundary exchange with sediments on the shelf and slope as the water passes along the Canadian archipelago. River water is a possible source in the surface water but it also seems likely that Pacific water Nd, modified by interactions on the shelf, is an important component in the Fram Strait surface outflow. Changes in the relative proportions of inflow of river water and flow of Pacific water through the Arctic Ocean could thus influence the isotopic composition of Nd in the North Atlantic.     

An 8-year record of gas geochemistry and isotopic composition of methane during baseline sampling at a groundwater observation well in Alberta (Canada)

Variability in baseline groundwater methane concentrations and isotopic compositions was assessed while comparing free and dissolved gas sampling approaches for a groundwater monitoring well in Alberta (Canada) over an 8-year period. Methane concentrations in dissolved gas samples (n?=?12) were on average 4,380?±?2,452 μg/L, yielding a coefficient of variation (CV) >50 %. Methane concentrations in free gas samples (n?=?12) were on average 228,756?±?62,498 ppm by volume, yielding a CV of 27 %. Quantification of combined sampling, sample handling and analytical uncertainties was assessed via triplicate sampling (CV of 19 % and 12 % for free gas and dissolved gas methane concentrations, respectively). Free and dissolved gas samples yielded comparable methane concentration patterns and there was evidence that sampling operations and pumping rates had a marked influence on the obtained methane concentrations in free gas. δ¹³C_CH4 and δ²H_CH4 values of methane were essentially constant (?78.6?±?1.3 and ?300?±?3?‰, respectively) throughout the observation period, suggesting that methane was derived from the same biogenic source irrespective of methane concentration variations. The isotopic composition of methane constitutes a robust and highly valuable baseline parameter and increasing δ¹³C_CH4 and δ²H_CH4 values during repeat sampling may indicate influx of thermogenic methane. Careful sampling and analytical procedures with identical and repeatable approaches are required in baseline-monitoring programs to generate methane concentration and isotope data for groundwater that can be reliably compared to repeat measurements once potential impact from oil and gas development, for example, may occur.     

A Study on the Periodicity of Hardness Ratio of the X-ray Binary Cyg X-1 as a Black Hole Candidate

Using the All-Sky Monitor (ASM, 1.5∼12 keV) data of Rossi X-ray Timing Explorer (RXTE) from January 1996 to October 2011, we have analyzed in detail the power spectrum of the hardness ratio (HR) (5∼12 keV/3∼5 keV) of the X-ray binary Cyg X-1 as a black hole candidate. The results show that the HR exhibits the following periodical variations: (1) During MJD = 50087∼55841, the HR presented the the periods T ≈ 5.6 d, T ≈ 40.0 d, T ≈ 78.4 d, T ≈ 173.8 d, and T ≈ 400/800 d; (2) When Cyg X-1 was in the hard state, the HR exhibited the periods T ≈ 5.6 d, T ≈ 33.7/67.6 d, T ≈ 45.3 d, and T ≈ 165.3 d; (3) When Cyg X-1 was in the soft state, the HR exhibited the periods T ≈ 38.5 d, T ≈ d, and T ≈ 128.3 d. Moreover, using the viscosity theory and Zdziarski accretion disk model, we have made a discussion on the physical mechanism of this kind of periodicity.     

Temperature Dependence of Single-Crystal Spinel (MgAl2O4) Elastic Constants from 293 to 423°K Measured by Light-Sound Scattering in the Raman-Nath Region

Summary. The temperature dependence of single-crystal elastic constants of synthetic stoichiometric MgAl₂O₄ spinel has been measured by the light-sound scattering technique in the Raman-Nath region. The crystal is set into forced vibration by a single crystal LiNbO₃ transducer coupled to one crystal face. A He-Ne Laser beam is diffracted by the stress-induced birefringence inside the crystal. The diffraction angle is determined from the distance between two spots exposed on a photographic plate by the first order diffracted beams as measured by a microdensitometer. The sound wavelength inside the crystal is then inferred from the laser diffraction angle. Combining the sound wavelength with the measured transducer frequency, the velocity inside the crystal is determined typically to a precision of 0·05 per cent. In this method, the measurement of velocity is not dependent on either the determination of sample length or on phase shifts at sample-transducer interface. Velocities of four pure modes, L //[001], T //[001], L //[110], and T //[110]( P //[1 1 0] are measured in the temperature range between 293 and 423 °K. A linear temperature dependence is fit to the data by a least square method. Values obtained at 25 °C from this linear fit are
The temperature dependence of the adiabatic elastic constants and bulk and shear (VRH average) moduli is computed using the density and literature value of thermal expansion coefficient. Values obtained are:
A comparison with previous measurements by pulse superposition and ultrasonic interferometry methods is made. Disagreement, when present, is discussed in terms of the separate measuring techniques. Finally, the present method, with its possibility for further improvement, is evaluated as a new method to measure temperature and pressure dependence of elastic constants.     

The petrogenesis of the Lac Guyer komatiites and basalts and the nature of the komatiite-komatiitic basalt compositional gap

A sequence of ultramafic rocks in the Lac Guyer Archean greenstone belt exhibit brecciated flow tops, pillow structures, and spinifex textures testifying to their volcanic origin. Massive, spinifex-textured and differentiated flows in the sequence have the chemical characteristics of peridotitic komatiite, with MgO ranging from 19–25 wt.%. Associated pillowed flows have compositions that straddle the conventional boundary between komatiite and komatiitic basalt with MgO contents ranging from 16 to 19 wt.% MgO and are best termed pyroxenitic komatiites. Unlike other komatiitic occurrences, the peridotitic and pyroxenitic komatiites at Lac Guyer constitute a continuous chemical spectrum with no evidence of population minimum near 18 wt.% MgO. The contrasting behaviour of highly compatible elements, such as Ni and Cr, versus incompatible elements, such as Zr, indicate that this compositional spectrum was produced by a variation in the extent of partial melting (10–40%) of a garnet lherzolite source in the Archean mantle. The pyroxenitic komatiites represent liquids produced during lower (10–20%) degrees of melting during which garnet remained in the mantle residue. However, a change in slope in the distribution of Zr vs. Y between the pyroxenitic and the peridotitic komatiites indicates that garnet was completely consumed at the more extensive degrees of melting which produced the peridotitic komatiites. The Lac Guyer volcanic rocks display a population minimum at 15 wt.% MgO separating komatiitic magmas whose compositions are controlled by partial melting from basalts whose composition is controlled by crystal fractionation. The population minimum near 18 wt.% MgO which is taken as the boundary between komatiite and komatiitic basalt may have a similar origin.     

Basic lavas of the Archean La Grande Greenstone belt: Products of polybaric fractionation and crustal contamination

Despite the fact that some greenstone belts preserve the record of contemporaneous komatiitic and tholeiitic volcanism, a genetic link between the two is not widely accepted. The significance of a compositional gap seperating these magma types and differences in their respective degree of light rare earth element (LREE) enrichment, cited as evidence against a derivative relationship, are complicated by the possibility of crustal assimilation by magmas of komatiitic affinity. In the Archean La Grande Greenstone belt of northern Quebec a succession of metamorphosed tholeiitic basalts and younger, high-Mg, LREE-enriched andesites are preserved. The tholeiites are differentiated basaltic rocks whose chemical compositions appear to have been controlled by low pressure, gabbroic fractional crystallization and are similar to Type 1 MORB. Parental magmas were probably high-Mg liquids of compositions similar to komatiitic basalts which also occur in the greenstone belt. These high-Mg liquids are believed to be themselves the product of high pressure, OLIV+OPX fractional crystallization of more magnesian primary liquids of komatiitic composition. The higher La/Sm ratios of komatiitic basalts and tholeiites relative to komatiites in this belt, can be explained by small degrees of crustal assimilation. In the central part of the belt, late-stage, mafic igneous rocks have chemical compositions similar to Archean examples of contaminated volcanic rocks (e.g., Kambalda, Australia). These late-stage lavas consist of basalts and andesites with high-Mg, Ni and Cr abundances, LREE-enriched profiles and low Ti abundances. They are believed to be the products of crustal assimilation and crystallization of OPX-PLAG-CPX from high-Mg liquids of komatiitic affinity. The volcanic stratigraphy records the progressive effects of crustal contamination through time. A light sialic crust may have initially acted as a density barrier, preventing the eruption of primary high-Mg liquids and forcing fractionation at depth which produced more buoyant compositions. With subsequent thinning of the crust, the density barrier presumably failed, and primary liquids migrated directly toward the surface. Reaction of these liquids with tonalitic crust produced contaminated differentiates.     

Serpentinization of cumulate ultramafic rocks from the North Arm Mountain massif of the Bay of Islands ophiolite

Partially serpentinized dunites and wehrlites comprise the bulk of the cumulate ultramafic unit at the North Arm Mountain massif of the Bay of Islands ophiolite complex, Newfoundland. In a suite of 59 dunites and werhlites from the base of the unit, the serpentinized portions consist of lizardite + chrysotile + brucite + (accessory) magnetite. The ratio of $\text{(}\text{lizardite}\text{+}\text{chrysotile}\text{)}\text{to brucite}\text{= ~8:2 (}\text{weight percent}\text{)}$. Petrographic observations show that most serpentinization occurred at the expense of olivine; only limited amounts of clinopyroxene were serpentized. An estimated volume increase of 32% accompanied serpentinization of the peridotites. Reconstructions of the primary modal proportions of wehrlites (made taking this volume increase into account) contain an average of 6% more clinopyroxene and 6% less olivine than do modal reconstructions that ignore the volume increase. Mass balance calculations provide no clear evidence for appreciable metasomatism of Al₂O₃, CaO, FeO, MgO, or SiO₂ during Serpentinization. The presence of brucite, the evidence that most serpentinization occurred at the expense of olivine, and the lack of appreciable metasomatism, suggest that the primary reaction that controlled serpentinization of the peridotites is: $\text{2Mg}{}_2\text{SiO}{}_2\text{+ 3H}{}_2\text{O ? Mg}{}_3\text{Si}{}_2\text{O}{}_5\text{(OH)}{}_4\text{+ Mg(OH)}{}_2$. olivine added serpentine brucite     

Xenon isotope systematics, giant impacts, and mantle degassing on the early Earth

The relationships between the major terrestrial volatile reservoirs are explored by resolving the different components in the Xe isotope signatures displayed by Harding County and Caroline CO₂ well gases and mid-ocean ridge basalts (MORB). For the nonradiogenic isotopes, there is evidence for the presence of components enhanced in the light ^124–128Xe/¹³⁰Xe isotope ratios with respect to the terrestrial atmosphere. The observation of small but significant elevations of these ratios in the MORB and well gas reservoirs means that the nonradiogenic Xe in the atmosphere cannot be the primordial base composition in the mantle. The presence of solar-like components, for example U–Xe, solar wind Xe, or both, is required.For radiogenic Xe generated by decay of short-lived ¹²⁹I and ²⁴⁴Pu, the ¹²⁹Xe_rad/¹³⁶Xe₂₄₄ ratios are indistinguishable in MORB and the present atmosphere, but differ by approximately an order of magnitude between the MORB and well gas sources. Correspondence of these ratios in MORB and the atmosphere within the relatively small uncertainties found here significantly constrains possible mantle degassing scenarios. The widely held view that substantial early degassing of ¹²⁹Xe_rad and ¹³⁶Xe₂₄₄ from the MORB reservoir to the atmosphere occurred and then ended while ¹²⁹I was still alive is incompatible with equal ratios, and so is not a possible explanation for observed elevations of ¹²⁹Xe/¹³⁰Xe in MORB compared to the atmosphere. Detailed degassing chronologies constructed from the isotopic composition of MORB Xe are therefore questionable.If the present estimate for the uranium/iodine ratio in the bulk silicate Earth (BSE) is taken to apply to all interior volatile reservoirs, the differing ¹²⁹Xe_rad/¹³⁶Xe₂₄₄ ratios in MORB and the well gases point to two episodes of major mantle degassing, presumably driven by giant impacts, respectively  20–50 Ma and  95–100 Ma after solar system origin assuming current values for initial ¹²⁹I/¹²⁷I and ²⁴⁴Pu/²³⁸U. The earlier time range, for degassing of the well gas source, spans Hf–W calculations for the timing of a moon-forming impact. The second, later impact further outgassed the upper mantle and MORB source. A single event that degassed both the MORB and gas well reservoirs at the time of the moon-forming collision would be compatible with their distinct ¹²⁹Xe_rad/¹³⁶Xe₂₄₄ ratios only if the post-impact iodine abundance in the MORB reservoir was about an order of magnitude lower than current estimates. In either case, such late dates require large early losses of noble gases, so that initial inventories acquired throughout the Earth must have been substantially higher.The much larger ¹²⁹Xe_rad/¹³⁶Xe₂₄₄ ratio in the well gases compared to MORB requires that these two Xe components evolve from separate interior reservoirs that have been effectively isolated from each other for most of the age of the planet, but are now seen within the upper mantle. These reservoirs have maintained distinct Xe isotope signatures despite having similar Ne isotope compositions that reflect similar degassing histories. This suggests that the light noble gas and radiogenic Xe isotopes are decoupled, with separate long-term storage of the latter. However, without data on the extent of heterogeneities within the upper mantle, this conclusion cannot be easily reconciled with geophysical observations without significant re-evaluation of present noble gas models. Nevertheless the analytic evidence that two different values of ¹²⁹Xe_rad/¹³⁶Xe₂₄₄ exist in the Earth appears firm. If the uranium/iodine ratio is approximately uniform throughout the BSE, it follows that degassing events from separate reservoirs at different times are recorded in the currently available terrestrial Xe data.