Experimental and computational study of trace element distribution between orthopyroxene and anhydrous silicate melt: substitution mechanisms and the effect of iron

Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg₂Si₂O₆) and ferrosilite (Fe₂Si₂O₆). Calculated solution energies show that R²⁺ cations are more soluble in Opx than R³⁺ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R³⁺ cations by coupled substitution with Li⁺ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r ₀, maximum partition coefficients D ₀, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r ₀ values for R³⁺ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r ₀ = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r ₀ values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.     

Mineralogical control of rare earth elements in acid sulfate soils

Major, trace and rare earth element concentrations were measured in porewater, surface water and sediments at an acid sulfate soil site. The concentrations of La and Ce in porewater are up to 1-3 ppm. There is a strong correlation between REE concentration and acidity, except that the maximum concentrations were consistently found below the horizon of maximum acidity, associated with an increase in pH (to ca. 4) and change in mineralogy from jarosite-dominated to goethite-dominated mottles. Jarosite replacement by goethite is as expected with the rise in pH, which in turn is due to the occurrence of a fossil shell bed just below. The rare earth element patterns in the porewaters are enriched in the MREE with respect to Post-Archaean Australian Shale (PAAS). Measurements and calculations show that this is in accord with experiments on low-degree partial dissolution of jarosite, even when the jarosite itself is highly enriched in LREE. There is a clear fractionation in the patterns between the clay-rich soil matrix, which is slightly depleted in the LREE when normalized to PAAS (La/Yb_PAAS ∼0.5), and the secondary mineral phase jarosite, which is enriched in the LREE (La/Yb_PAAS = 15-50). The REE pattern in the porewater changes with the transition from jarosite- to goethite-rich mottles, becoming relatively more enriched in the LREE compared to the HREE, which is consistent with the incongruent dissolution of jarosite to form goethite and the release of greater amounts of jarosite REE to solution, including proportionately more of the jarosite-compatible LREE.Maximum surface water REE concentrations in acidic water were 100-200 ppb La and Ce. REE patterns in surface water were very similar to the porewater transition zone, enriched in the MREE, but asymmetric, relatively enriched in the LREE compared to the HREE.     

Length Scales of Scalar Diffusion in the Convective Boundary Layer: Laboratory Observations

A laboratory study of scalar diffusion in the convective boundary layer has found results that are consistent with a 1999 large-eddy simulation (LES) study by Jonker, Duynkerke and Cuijpers. For bottom-up and top-down scalars (introduced as ‘infinite’ area sources of passive tracer at the surface and inversion, respectively) the dominant length scale was found to be much larger than the length scale for density fluctuations, the latter being equal to the boundary-layer depth h. The variance of the normalized passive scalar grew continuously with time and its magnitude was about 3–5 times larger for the top-down case than for the bottom-up case. The vertical profiles of the normalized passive scalar variance were found to be approximately constant through the convective boundary layer (CBL) with a value of about 3–8c_*² for bottom-up and 10–50c_*² for top-down diffusion. Finally, there was some evidence of a minimum in the variance and dominant length scale for scalar flux ratios (top-down to bottom-up flux) close to −0.5. All these convection tank results confirm the LES results and support the hypothesis that there is a distinct difference in behaviour between the dynamic and passive variables in the CBL.     

Boundedness of Turbulent Temperature Probability Distributions,and their Relation to the Vertical Profile in the Convective Boundary Layer

Higher-order moments, minima and maxima of turbulent temperature and water vapour mixing ratio probability density functions measured with an eddy-covariance system near the ground were related to each other and to vertical boundary-layer profiles of the same scalars obtained through airborne soundings. The dependence of kurtosis on squared skewness showed a kurtosis intercept below the Gaussian expectation, suggesting a compression of the probability density function by the presence of natural boundaries. This hypothesis was corroborated by comparing actual minima and maxima of turbulent fluctuations to estimates obtained from the first four sample moments by fitting a four-parameter beta distribution. The most sharply defined boundaries were found for the minima of temperature datasets during the day, indicating that negative temperature fluctuations at the sensor are limited by the availability of lower temperatures in the boundary layer. By comparison to vertical profiles, it could be verified that the turbulent minimum of temperature near the ground is close to the minimum of potential temperature in the boundary layer. The turbulent minimum of water vapour mixing ratio was found to be equal to the mixing ratio at a height above the minimum of the temperature profile. This height roughly agrees with the top of the non-local unstable domain according to bulk Richardson number profiles. We conclude that turbulence statistics measured near the surface cannot be solely explained by local effects, but contain information about the whole boundary layer including the entrainment zone.     

Computer-controlled scanning electron microscopy: A fast and reliable tool for diamond prospecting

Computer-controlled scanning electron microscopy is introduced as a faster, reliably and cost-reducing alternative to conventional electron microprobe analyses on kimberlite indicator minerals. The method is based on conventional scanning electron microscopy and energy dispersive X-ray spectrometry, but due to extended counting times, optimised settings and computer-controlled particle recognition valid data can be obtained on a low amount of operator and machine time. A comparison of the results between both methods yields that computer-controlled scanning electron microscopy is able to investigate major and minor element concentrations in indicator minerals with almost the same precision as the electron microprobe.     

Ancient charcoal as a natural archive for paleofire regime and vegetation change in the Mayumbe,Democratic Republic of the Congo

Charcoal was sampled in four soil profiles at the Mayumbe forest boundary (DRC). Five fire events were recorded and 44 charcoal types were identified. One stratified profile yielded charcoal assemblages around 530 cal yr BP and > 43.5 cal ka BP in age. The oldest assemblage precedes the period of recorded anthropogenic burning, illustrating occasional long-term absence of fire but also natural wildfire occurrences within tropical rainforest. No other charcoal assemblages older than 2500 cal yr BP were recorded, perhaps due to bioturbation and colluvial reworking. The recorded paleofires were possibly associated with short-lived climate anomalies. Progressively dry climatic conditions since ca. 4000 cal yr BP onward did not promote paleofire occurrence until increasing seasonality affected vegetation at the end of the third millennium BP, as illustrated by a fire occurring in mature rainforest that persisted until around 2050 cal yr BP. During a drought episode coinciding with the ‘Medieval Climate Anomaly’, mature rainforest was locally replaced by woodland savanna. Charcoal remains from pioneer forest indicate that fire hampered forest regeneration after climatic drought episodes. The presence of pottery shards and oil-palm endocarps associated with two relatively recent paleofires suggests that the effects of climate variability were amplified by human activities.     

Seismic velocities from the Yaquina forearc basin off Peru: evidence for free gas within the gas hydrate stability zone

Multichannel seismic (MCS) data from the Yaquina forearc basin off Peru reveal a complex distribution of gas and gas hydrate related reflections. Lateral variations of the reflection pattern at the assumed base of the gas hydrate stability zone in terms of continuity, amplitude, and signal attenuation underneath are observed, as well as the possible occurrence of paleo-bottom simulating reflectors (BSRs). Phase reversed reflections above the bottom simulating reflector point to free gas within the gas hydrate stability zone (GHSZ). To constrain the interpretation of the observed reflection pattern we calculated the velocity distribution along the MCS line from high-resolution ocean bottom hydrophone recordings with two independent methods. Heat flux values estimated on the basis of the velocity-depth functions increase with decreasing amplitude of the BSR and peak near chemoherms. These results suggest a model of the Yaquina Basin where free gas is trapped under parts of the BSR, and within the GHSZ, particularly under the seafloor and under an erosional unconformity. The hypothesis of a paleo-BSR that reflects the uplift of the base of the hydrate stability zone caused by the deposition of a particular sediment sequence is supported by the estimated heat flux values.     

Synsedimentary faults and amalgamated unconformities: Insights from 3D-seismic and core analysis of the Lower Triassic Middle Buntsandstein, Ems Trough, north-western Germany

The Late Permian/Early Triassic succession of the Central European Basin (CEB) was repeatedly affected by the tectonic pulses associated with the earliest phases of Tethyan and Arctic–North Atlantic rifting. Effects of the differential tectonic subsidence are particularly well recorded by unconformities, which form widespread sequence boundaries. Such unconformities are most obvious in areas occupied by fault-controlled intra-basinal highs (swells). In that areas, stratigraphic loss may comprise entire Lower and Middle Buntsandstein formations and in places remnant Middle Buntsandstein successions directly rest on Permian strata. Analysis of 3D-seismic data and well logs combined with high-resolution sedimentological logging of drillcores at the western margin of the Ems Trough (NW Germany) reveals details of synsedimentary tectonic control on sequence development. Early Triassic extensional faulting of basement blocks provided stepwise addition of accommodation space for continental sequences by growth faulting along north–south oriented fault zones blocks on the flanks of the East Netherlands High. This process is most evident during the development of the Hardegsen Unconformity, which is characterised by an amalgamation of succeeding unconformity surfaces in areas of structurally controlled intrabasinal highs.