Mixed fluid sources involved in diamond growth constrained by Sr–Nd–Pb–C–N isotopes and trace elements

Sub-micrometer inclusions in diamonds carry high-density fluids (HDF) from which the host diamonds have precipitated. The chemistry of these fluids is our best opportunity of characterizing the diamond-forming environment. The trace element patterns of diamond fluids vary within a limited range and are similar to those of carbonatitic/kimberlitic melts that originate from beneath the lithospheric mantle. A convecting mantle origin for the fluid is also implied by C isotopic compositions and by a preliminary Sr isotopic study (Akagi, T., Masuda, A., 1988. Isotopic and elemental evidence for a relationship between kimberlite and Zaire cubic diamonds. Nature 336, 665–667.). Nevertheless, the major element chemistry of HDFs is very different from that of kimberlites and carbonatites, varying widely and being characterized by extreme K enrichment (up to ～ 39 wt.% on a water and carbonate free basis) and high volatile contents. The broad spectrum of major element compositions in diamond-forming fluids has been related to fluid–rock interaction and to immiscibility processes.Elemental signatures can be easily modified by a variety of mantle processes whereas radiogenic isotopes give a clear fingerprint of the time-integrated evolution of the fluid source region. Here we present the results of the first multi radiogenic-isotope (Sr, Nd, Pb) and trace element study on fluid-rich diamonds, implemented using a newly developed off-line laser sampling technique. The data are combined with N and C isotope analysis of the diamond matrix to better understand the possible sources of fluid involved in the formation of these diamonds. Sr isotope ratios vary significantly within single diamonds. The highly varied but unsupported Sr isotope ratios cannot be explained by immiscibility processes or fluid-mineral elemental fractionations occurring at the time of diamond growth. Our results demonstrate the clear involvement of a mixed fluid, with one component originating from ancient incompatible element-enriched parts of the lithospheric mantle while the trigger for releasing this fluid source was probably carbonatitic/kimberlitic melts derived from greater depths. We suggest that phlogopite mica was an integral part of the enriched lithospheric fluid source and that breakdown of this mica releases K and radiogenic Sr into a fluid phase. The resulting fluids operate as a major metasomatic agent in the sub-continental lithospheric mantle as reflected by the isotopic composition and trace element patterns of G10 garnets.     

Synergistic effects of diuron and sedimentation on photosynthesis and survival of crustose coralline algae

Effects of short-term exposure to sedimentation and diuron, separately and in combination, on the photophysiology and survival of crustose coralline algae (CCA) were examined in controlled time-course experiments, using pulse-amplitude modulation (PAM) chlorophyll fluorometry. These experiments indicated that the effects of sediments and diuron, when applied in isolation, were often reversible, with recovery time dependent upon sediment type and diuron concentration. Exposure to fine (<63 microm grain size), nutrient-rich estuarine sediments reduced effective quantum yields (Delta F/F(m')) of photosystem II in CCA species more than exposure to the same amount of fine (<63 microm grain size) calcareous sediments. Significant inhibition of photosynthesis (Delta F/F(m')) was also observed at diuron concentrations > or =2.9 microg L(-1). Fine estuarine sediments in combination with 0.79 microg L(-1) dissolved diuron, caused yields (Delta F/F(m')) to drop by 60% compared with controls after 24 h. The combined exposure to sediments and diuron also retarded recovery, thus Delta F/F(m') values were still only 60% of the controls after 9 days recovery in clean seawater. Mortality of CCA was observed in some fragments treated with combinations of sediment and diuron. Our results suggest that sediment deposition and exposure to diuron can negatively affect the photosynthetic activity of CCA, with sedimentation stress being significantly enhanced by the presence of trace concentrations of diuron.     

Methane and its isotopologues on Saturn from Cassini/CIRS observations

High spectral resolution observations from the Cassini Composite Infrared Spectrometer [Flasar, F.M., and 44 colleagues, 2004. Space Sci. Rev. 115, 169-297] are analysed to derive new estimates for the mole fractions of CH₄, CH₃D and ¹³CH₄ of (4.7±0.2)×¹⁰⁻³, (3.0±0.2)×¹⁰⁻⁷ and (5.1±0.2)×¹⁰⁻⁵ respectively. The mole fractions show no hemispherical asymmetries or latitudinal variability. The analysis combines data from the far-IR methane rotational lines and the mid-IR features of methane and its isotopologues, using both the correlated-k retrieval algorithm of Irwin et al. [Irwin, P., and 9 colleagues, 2008. J. Quant. Spectrosc. Radiat. Trans. 109, 1136-1150] and a line-by-line approach to evaluate the reliability of the retrieved quantities. C/H was found to be enhanced by 10.9±0.5 times the solar composition of Grevesse et al. [Grevesse, N., Asplund, M., Sauval, A., 2007. Space Sci. Rev. 130 (1), 105-114], 2.25±0.55 times larger than the enrichment on Jupiter, and supporting the increasing fractional core mass with distance from the Sun predicted by the core accretion model of planetary formation. A comparison of the jovian and saturnian C/N, C/S and C/P ratios suggests different reservoirs of the trapped volatiles in a primordial solar nebula whose composition varies with distance from the Sun. This is supported by our derived D/H ratio in methane of (1.6±0.2)×¹⁰⁻⁵, which appears to be smaller than the jovian value of Lellouch et al. [Lellouch, E., Bézard, B., Fouchet, T., Feuchtgruber, H., Encrenaz, T., de Graauw, T., 2001. Astron. Astrophys. 370, 610-622]. Mid-IR emission features provided an estimate of , which is consistent with both the terrestrial ratio and jovian ratio, suggesting that carbon was accreted from a shared reservoir for all of the planets.     

Phosphine on Jupiter and Saturn from Cassini/CIRS

The global distribution of phosphine (PH₃) on Jupiter and Saturn is derived using 2.5 cm⁻¹ spectral resolution Cassini/CIRS observations. We extend the preliminary PH₃ analyses on the gas giants [Irwin, P.G.J., and 6 colleagues, 2004. Icarus 172, 37-49; Fletcher, L.N., and 9 colleagues, 2007a. Icarus 188, 72-88] by (a) incorporating a wider range of Cassini/CIRS datasets and by considering a broader spectral range; (b) direct incorporation of thermal infrared opacities due to tropospheric aerosols and (c) using a common retrieval algorithm and spectroscopic line database to allow direct comparison between these two gas giants.The results suggest striking similarities between the tropospheric dynamics in the 100-1000 mbar regions of the giant planets: both demonstrate enhanced PH₃ at the equator, depletion over neighbouring equatorial belts and mid-latitude belt/zone structures. Saturn's polar PH₃ shows depletion within the hot cyclonic polar vortices. Jovian aerosol distributions are consistent with previous independent studies, and on Saturn we demonstrate that CIRS spectra are most consistent with a haze in the 100-400 mbar range with a mean optical depth of 0.1 at 10 μm. Unlike Jupiter, Saturn's tropospheric haze shows a hemispherical asymmetry, being more opaque in the southern summer hemisphere than in the north. Thermal-IR haze opacity is not enhanced at Saturn's equator as it is on Jupiter.Small-scale perturbations to the mean PH₃ abundance are discussed both in terms of a model of meridional overturning and parameterisation as eddy mixing. The large-scale structure of the PH₃ distributions is likely to be related to changes in the photochemical lifetimes and the shielding due to aerosol opacities. On Saturn, the enhanced summer opacity results in shielding and extended photochemical lifetimes for PH₃, permitting elevated PH₃ levels over Saturn's summer hemisphere.     

The origin and evolution of Saturn’s 2011–2012 stratospheric vortex

The planet-encircling springtime storm in Saturn’s troposphere (December 2010–July 2011, Fletcher, L.N. et al. [2011]. Science 332, 1413–1414; Sánchez-Lavega, A. et al. [2011]. Nature 475, 71–74; Fischer, G. et al. [2011]. Nature 475, 75–77) produced dramatic perturbations to stratospheric temperatures, winds and composition at mbar pressures that persisted long after the tropospheric disturbance had abated. Thermal infrared (IR) spectroscopy from the Cassini Composite Infrared Spectrometer (CIRS), supported by ground-based IR imaging from the VISIR instrument on the Very Large Telescope and the MIRSI instrument on NASA’s IRTF, is used to track the evolution of a large, hot stratospheric anticyclone between January 2011 and March 2012. The evolutionary sequence can be divided into three phases: (I) the formation and intensification of two distinct warm airmasses near 0.5 mbar between 25 and 35°N (B1 and B2) between January–April 2011, moving westward with different zonal velocities, B1 residing directly above the convective tropospheric storm head; (II) the merging of the warm airmasses to form the large single ‘stratospheric beacon’ near 40°N (B0) between April and June 2011, disassociated from the storm head and at a higher pressure (2 mbar) than the original beacons, a downward shift of 1.4 scale heights (approximately 85 km) post-merger; and (III) the mature phase characterised by slow cooling (0.11 ± 0.01 K/day) and longitudinal shrinkage of the anticyclone since July 2011. Peak temperatures of 221.6 ± 1.4 K at 2 mbar were measured on May 5th 2011 immediately after the merger, some 80 K warmer than the quiescent surroundings. From July 2011 to the time of writing, B0 remained as a long-lived stable stratospheric phenomenon at 2 mbar, moving west with a near-constant velocity of 2.70 ± 0.04 deg/day (?24.5 ± 0.4 m/s at 40°N relative to System III longitudes). No perturbations to visible clouds and hazes were detected during this period.With no direct tracers of motion in the stratosphere, we use thermal windshear calculations to estimate clockwise peripheral velocities of 200–400 m/s at 2 mbar around B0. The peripheral velocities of the two original airmasses were smaller (70–140 m/s). In August 2011, the size of the vortex as defined by the peripheral collar was 65° longitude (50,000 km in diameter) and 25° latitude. Stratospheric acetylene (C₂H₂) was uniformly enhanced by a factor of three within the vortex, whereas ethane (C₂H₆) remained unaffected. The passage of B0 generated a new band of warm stratospheric emission at 0.5 mbar at its northern edge, and there are hints of warm stratospheric structures associated with the beacons at higher altitudes (p < 0.1 mbar) than can be reliably observed by CIRS nadir spectroscopy. Analysis of the zonal windshear suggests that Rossby wave perturbations from the convective storm could have propagated vertically into the stratosphere at this point in Saturn’s seasonal cycle, one possible source of energy for the formation of these stratospheric anticyclones.     

Upper limits on hydrogen halides in Jupiter from Cassini/CIRS observations

We have determined the following upper limits for the mole fraction of hydrogen halides in Jupiter's atmosphere from Cassini/CIRS observations: [HF]<2.7×10−11, [HCl]<2.3×10−9, [HBr]<1.0×10−9, [HI]<7.6×10−9. These limits are smaller than solar composition for HF and HCl, and support the halogens' condensation in ammonium salts predicted by thermochemical models for the upper jovian troposphere.