Characterization of synthetic hedenbergite (CaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)–petedunnite (CaZnSi<Subscript>2</Subscript>O<Subscript>6</Subscript>) solid solution series by X-ray powder diffraction and <Superscript>57</Superscript>Fe Mössbauer spectroscopy

Clinopyroxenes along the solid solution series hedenbergite (CaFeSi₂O₆)–petedunnite (CaZnSi₂O₆) were synthesized under hydrothermal conditions and different oxygen fugacities at temperatures of 700 to 1200 °C and pressures of 0.2 to 2.5 GPa. Properties were determined by means of X-ray diffraction, electron microprobe analysis and ⁵⁷Fe Mössbauer spectroscopy at 298 K. Unit-cell parameters display a linear dependency with changing composition. Parameters a₀ and b₀ exhibit a linear decrease with increasing Zn content while the monoclinic angle increases linearly. Parameter c₀ is not affected by composition and remains constant at a value of 5.248 Å. The molar volume can be described according to the equation V_mol (ccm mol^–1)=33.963(16)–0.544(31)*Zn pfu. The isomer shifts of ferrous iron on the octahedral M1 site in hedenbergite are not affected by composition along the hedenbergite–petedunnite solid solution series and remain constant at an average value of 1.18 mm s^–1. Quadrupole splittings of Fe²⁺ on the M1 are, however, strongly affected by composition, and they decrease linearly with increasing petedunnite component in hedenbergite, ranging from 2.25 mm s^–1 for pure hedenbergite end member to 1.99 mm s^–1 for a solid solution containing 84 mole% petedunnite. The half-widths of intermediate solid solutions vary between 0.26 and 0.33 mm s^–1, indicating, in accordance with the microprobe analyses and X-ray diffraction, that samples are homogeneous and well-crystallized. The data from this study demonstrate that the crystallinity of hedenbergitic clinopyroxenes can be improved by using oxide mixtures as starting materials. Crystal sizes for intermediate compositions range up to 70 m, suitable for standard single-crystal X-ray analysis.This paper is dedicated to Prof. Dr. Georg Amthauer, Salzburg, on occasion of his 60th birthday     

The biogeochemistry of sorbed methane in marine sediments

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg⁻¹ dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.     

How Well Can We Measure the Vertical Wind Speed? Implications for Fluxes of Energy and Mass

Sonic anemometers are capable of measuring the wind speed in all three dimensions at high frequencies (10–50 Hz), and are relied upon to estimate eddy-covariance-based fluxes of mass and energy over a wide variety of surfaces and ecosystems. In this study, wind-velocity measurement errors from a three-dimensional sonic anemometer with a non-orthogonal transducer orientation were estimated for over 100 combinations of angle-of-attack and wind direction using a novel technique to measure the true angle-of-attack and wind speed within the turbulent atmospheric surface layer. Corrections to the vertical wind speed varied from −5 to 37% for all angles-of-attack and wind directions examined. When applied to eddy-covariance data from three NOAA flux sites, the wind-velocity corrections increased the magnitude of CO₂ fluxes, sensible heat fluxes, and latent heat fluxes by ≈11%, with the actual magnitude of flux corrections dependent upon sonic anemometer, surface type, and scalar. A sonic anemometer that uses vertically aligned transducers to measure the vertical wind speed was also tested at four angles-of-attack, and corrections to the vertical wind speed measured using this anemometer were within ±1% of zero. Sensible heat fluxes over a forest canopy measured using this anemometer were 15% greater than sensible heat fluxes measured using a sonic anemometer with a non-orthogonal transducer orientation. These results indicate that sensors with a non-orthogonal transducer orientation, which includes the majority of the research-grade three-dimensional sonic anemometers currently in use, should be redesigned to minimize sine errors by measuring the vertical wind speed using one pair of vertically aligned transducers.