Experimental constraints on ureilite petrogenesis

This experimental study explores the petrogenesis of ureilites by a partial melting/smelting process. Experiments have been performed over temperature (1150-1280 °C), pressure (5-12.5 MPa), and low oxygen fugacity (graphite-CO gas) conditions appropriate for a hypothetical ureilite parent body ∼200 km in size. Experimental and modeling results indicate that a partial melting/smelting model of ureilite petrogenesis can explain many of the unique characteristics displayed by this meteorite group. Compositional information preserved in the pigeonite-olivine ureilites was used to estimate the composition of melts in equilibrium with the ureilites. The results of 20 experiments saturated with olivine, pyroxene, metal, and liquid with appropriate ureilite compositions are used to calibrate the phase coefficients and pressure-temperature dependence of the smelting reaction. The calibrated coefficients are used to model the behavior of a hypothetical residue that is experiencing fractional smelting. The residue is initially olivine-rich and smelting progressively depletes the olivine content and enriches the pyroxene and metal contents of the residues. The modeled residue composition at 1260 °C best reproduces the trend of ureilite bulk compositions. The model results also indicate that as a ureilite residue undergoes isothermal decompression smelting over a range of temperatures, Ca/Al values and Cr₂O₃ contents are enriched at lower temperatures (below ∼1240 °C) and tend to decrease at higher temperatures. Therefore, fractional smelting can account for the high Ca/Al and Cr₂O₃ wt% values observed in ureilites. We propose that ureilites were generated from an olivine-rich, cpx-bearing residue. Smelting began when the residue was partially melted and contained liquid, olivine, and carbon. These residues experienced varying degrees of fractional smelting to produce the compositional variability observed within the pigeonite-bearing ureilites. Variations in mineral composition, modal proportions, and isotopic signatures are best described by heterogeneous accretion of the ureilite parent body followed by minimal and variable degrees of igneous processing.     

Trace/minor element:calcium ratios in cultured benthic foraminifera. Part I: Inter-species and inter-individual variability

Trace/minor element signatures (D_Cd, D_Ba, D_Mg, and D_Sr) were measured in the tests (shells) of benthic foraminifera cultured in a trace-metal-concentration-controlled system. The culture system was constructed of inert materials and designed to limit microhabitat effects. This system ensured that variation observed in cultured foraminiferal element:calcium (TE/Ca) signatures was due to biologically mediated (vital) effects only. Two species, Bulimina aculeata and Rosalina vilardeboana, reproduced prolifically during two 4-to-8-month culture periods. In every case (i.e., for both species and each element), the inter-individual variability was larger than the analytical precision. Mean (±1 standard deviation) D_E signatures for B. aculeata were: D_Cd: 1.5 ± 0.4, D_Ba × 10: 2.1 ± 0.7, D_Mg × 1000: 0.62 ± 0.15, and D_Sr × 10: 1.5 ± 0.1. Cultured B. aculeata D_Mg, calibrated from culture and core-top (live) field specimens, predicted temperatures within ±2.0 °C. The observed inter-individual variability from culture specimens was as large or larger than comparable results from core-top investigations. R. vilardeboana D_Cd signatures were significantly lower, while D_Ba, D_Mg, and D_Sr signatures were significantly higher than B. aculeata values. Since our culture system minimizes microhabitat variability, the variation in measured TE/Ca ratios suggests that biological processes are a significant factor in inter-individual and inter-species variability. Comparison of cultured and field-collected foraminiferal D_Ba signatures supports previous findings that pore-water chemistry is a major environmental influence on foraminiferal test chemistry.     

Alpine lake sediment records of the impact of glaciation and climate change on the biogeochemical cycling of soil nutrients

Lake sediment cores from the Coast Mountains of British Columbia were analyzed using chemical sequential extractions to partition the dominant geochemical fractions of phosphorus (P). The P fractions include mineral P (the original source of bioavailable P), occluded P (bound to soil oxides), and organic P (remains of organic matter). By comparing P fractions of soil and recent lake sediment samples, these fractions are shown to be a valid proxy for landscape-scale nutrient status. Changes in soil development for an alpine watershed (Lower Joffre Lake) are inferred from the P fractions in the basin's outlet lake sediments. Glacially sourced mineral P dominates at the base of the core, but several rapid shifts in P geochemistry are evident in the first ∼3000 yr of the record. The latter indicates an interval of early and rapid soil nutrient maturation from ∼9600 to 8500 cal yr BP and a significant influx of slope-derived material into Lower Joffre Lake. A substantial increase in mineral P occurs at ca. 8200 cal yr BP, consistent with the cold event in the vicinity of the North Atlantic at that time. The more recent record reveals a continual increase in the proportion of mineral P from glacial sources to the lake, indicating a trend toward cooler conditions in the Coast Mountains.     

Late Barremian to early Aptian calcareous nannofossil paleoceanography and paleoecology from the Ocean Drilling Program Hole 641C (Galicia Margin)

Calcareous nannofossil assemblages at Site 641C (Galicia Margin, North Atlantic) were investigated in order to determine changes in fertility and temperature of surface waters. Taxa such as Zeughrabdotus spp. <3.5 μm, Biscutum constans, Discorhabdus rotatorius and Diazomatolithus lehmanii, which thrived in higher fertility conditions, are particularly abundant across the CM0 interval as opposed to those with oligotrophic affinities such as Watznaueria spp. and Nannoconus spp., which are generally reduced in abundance. The abundances of nannoconids are much lower than those observed in Tethyan sections, indicating higher fertility conditions. Slumpings and low recovery prevent the identification of the onset of the “nannoconid crisis”, but a sharp drop in nannoconid abundances, observed prior to the CM0 interval, correlates with the “nannoconid decline” observed in several Tethys sections.The normalized ratio between low and high fertility taxa (Fertility Index) was used to characterize the nannofossil assemblages in terms of productivity changes. The highest values of the Fertility Index were observed across magnetic chron CM0. The paucity of cold water taxa such as Seribiscutum spp. and Repagulum parvidentatum suggests warm water conditions throughout the deposition of upper Barremian–lower Aptian sediments on the Galicia Margin.     

Organic compounds in produced waters from coalbed natural gas wells in the Powder River Basin,Wyoming, USA

The organic composition of produced water samples from coalbed natural gas (CBNG) wells in the Powder River Basin, WY, sampled in 2001 and 2002 are reported as part of a larger study of the potential health and environmental effects of organic compounds derived from coal. The quality of CBNG produced waters is a potential environmental concern and disposal problem for CBNG producers, and no previous studies of organic compounds in CBNG produced water have been published. Organic compounds identified in the produced water samples included: phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, various non-aromatic compounds, and phthalates. Many of the identified organic compounds (phenols, heterocyclic compounds, PAHs) are probably coal-derived. PAHs represented the group of organic compounds most commonly observed. Concentrations of total PAHs ranged up to 23 μg/L. Concentrations of individual compounds ranged from about 18 to <0.01 μg/L. Temporal variability of organic compound concentrations was documented, as two wells with relatively high organic compound contents in produced water in 2001 had much lower concentrations in 2002.     

Production of carbonic fluids during metamorphism of graphitic pelites in a collisional orogen—An assessment from fluid inclusions

Fluid inclusions in quartz veins within Proterozoic metamorphic rocks in the Black Hills, South Dakota, were examined by microthermometry and Raman spectroscopy to assess the evolution of fluid compositions during regional metamorphism of organic-rich shales and late-orogenic magmatism, both of which were related to the collision of the Wyoming and Superior crustal blocks. Fluid inclusions occur in veins that began to be generated before or during regional compression and metamorphism that reached at least garnet-grade conditions, and in veins within the aureole of the Harney Peak Granite (HPG), where temperatures reached second-sillimanite grade conditions. Early veins in the schists have undergone recrystallization during heating and deformation that modified the composition of early CH₄ or CO₂ and N₂-dominated inclusions. These fluids were apparently trapped under conditions of immiscibility with a saline aqueous fluid phase. They are interpreted to represent components generated during maturation of organic matter and dehydration of phyllosilicates during incipient metamorphism at reducing fO₂ conditions. Most inclusions in the quartz veins are, however, secondary CO₂-bearing. They imply a transition to higher fO₂ conditions with increasing temperature of regional metamorphism. The fO₂ conditions may have been controlled by the mineral assemblage in the host metapelites. The prevalence of bimodal distributions of trapped CO₂-N₂ and aqueous endmembers in the biotite and garnet zones also suggests that two immiscible fluid phases existed during the regional metamorphism.In the aureole of the HPG, graphite was evidently consumed by influx of magmatic fluids. CO₂-H₂O fluid inclusions dominate, but they have significantly less N₂ than inclusions at lower metamorphic grades. All inclusions define secondary trails in mostly unstrained quartz. The bimodality of inclusion compositions is not as well defined as at lower grades, with many inclusions containing intermediate CO₂-H₂O compositions. This suggests that a single fluid phase existed at the high temperatures in the granite aureole, but then unmixed during cooling. A set of late quartz veins with graphitized and tourmalinized selvages in the granite aureole contains CH₄-bearing inclusions with little N₂. The existence of CH₄ in these inclusions is attributed to complexing of magmatic B with hydroxyl anions taken from the CO₂-H₂O fluid phase, effectively causing reduction in fO₂ and promoting precipitation of graphite.     

Rare earth element diffusion in diopside: influence of temperature, pressure, and ionic radius, and an elastic model for diffusion in silicates

Volume diffusion rates for five rare earth elements (La, Ce, Nd, Dy, and Yb) have been measured in single crystals of natural diopside at pressures of 0.1 MPa to 2.5 GPa and temperatures of 1,050 to1,450 °C. Polished, pre-annealed crystals were coated with a thin film of rare earth element oxides, then held at constant temperature and pressure for times ranging from 20 to 882 h. Diffusion profiles in quenched samples were measured by SIMS (secondary ion mass spectrometry) depth profiling. At 1 atm pressure, with the oxygen fugacity controlled near the quartz-fayalite-magnetite buffer, the following Arrhenius relations were obtained for diffusion normal to (001) (diffusion coefficient D in m²/s): log₁₀D_Yb=(-4.64ǂ.42)-(411ᆠ kJ/mol/2.303RT); log₁₀D_Dy=(-3.31ǃ.44)-(461ᆽ kJ/mol/2.303RT); log₁₀D_Nd=(-2.95DŽ.64)-(496ᇡ kJ/mol/2.303RT); log₁₀D_Ce=(-4.10ǃ.08)-(463ᆳ kJ/mol/2.303RT); log₁₀D_Lu=(-4.22DŽ.66)-(466ᇢ kJ/mol/2.303RT). Diffusion rates decrease significantly with increasing ionic radius, with La a factor of ~35 slower than Yb. The relationship between diffusivity and ionic radius is consistent with a model in which elastic strain plays a critical role in governing the motion of an ion through the crystal lattice. Activation volumes for Yb and Ce diffusion, at constant temperature and oxygen fugacity, are 9.0DŽ.0 cm³/mol and 8.9Dž.2 cm³/mol, respectively, corresponding to an order of magnitude decrease in diffusivity as pressure is increased from 0 to 3 GPa at 1,200 °C. Diffusion of Nd is such that grain-scale isotopic equilibrium in the mantle can be achieved in ~1 My under conditions near the peridotite solidus (~1,450 °C at 2.5 GPa). The equilibration time is much longer under P, T conditions of the lithospheric mantle or at the eclogite solidus (~1 Gy at 1.5 GPa and 1,150 °C). Because of the relatively strong decrease in diffusivity with pressure (two orders of magnitude between 2.5 and 15 GPa along an adiabatic temperature gradient), Nd transport in clinopyroxene will be effectively frozen at pressures approaching the transition zone, on time scales less than 100 My. Rare earth element diffusion rates are slow enough that significant disequilibrium uptake of REE by growing clinopyroxene phenocrysts may be preserved under natural conditions of basalt crystallization. The relative abundances and spatial distributions of REE in such crystals may provide a sensitive record of the cooling and crystallization history of the host lava.