On the practice of estimating fractal dimension

Coastlines epitomize deterministic fractals and fractal (Hausdorff-Besicovitch) dimensions; a divider [compass] method can be used to calculate fractal dimensions for these features. Noise models are used to develop another notion of fractals, a stochastic one. Spectral and variogram methods are used to estimate fractal dimensions for stochastic fractals. When estimating fractal dimension, the objective of the analysis must be consistent with the method chosen for fractal dimension calculation. Spectal and variogram methods yield fractal dimensions which indicate the similarity of the feature under study to noise (e.g., Brownian noise). A divider measurement method yields a fractal dimension which is a measure of complexity of shape.     

Observations of interstellar HOCO+: abundance enhancements toward the galactic center

A survey of the 4(04)-3(03) and 1(01)-0(00) transitions of HOCO+ has been made toward several molecular clouds. The HOCO+ molecule was not observed in any sources except Sgr B2 and Sgr A. The 5(05)-4(04) and 4(14)-3(13) transitions were also detected toward Sgr B2. The results indicate that gas phase CO2 is not a major carbon reservoir in typical molecular clouds. In Sgr B2, the HOCO+ antenna temperature exhibits a peak approximately 2' north of the Sgr B2 central position (Sgr B2[M]) and the 4(04)-3(03) line emission is extended over a approximately 10' x 10' region. The column density of HOCO+ at the northern peak in Sgr B2 is approximately 3 x 10(14) cm-2, and the fractional abundance relative to H2 > or = 3 x 10(-10), which is about 2 orders of magnitude greater than recent predictions of quiescent cloud ion-molecule chemistry.     

Identification of the interstellar cyanomethyl radical (CH2CN) in the molecular clouds TMC-1 and Sagittarius B2

We report the astronomical identification of the cyanomethyl radical, CH2CN, the heaviest nonlinear molecular radical to be identified in interstellar clouds. The complex fine and hyperfine structures of the lowest rotational transitions at about 20.12 and 40.24 GHz are resolved in TMC-1, where the abundance appears to be about 5 x 10(-9) relative to that of H2. This is significantly greater than the observed abundance of CH3CN (methyl cyanide) in TMC-1. In Sgr B2 the hyperfine structure is blended in the higher frequency transitions at 40, 80, and 100 GHz, although the spin-rotation doubling is clearly evident. Preliminary searches in other sources indicate that the distribution of CH2CN is similar to that for such carbon chain species as HC3N or C4H.     

Variations in the HCN/HNC abundance ratio in the Orion molecular cloud

We have used observations of the rare isotopes of HCN and HNC to determine the relative abundance of these two chemical isomers along the central ridge of the Orion molecular cloud. The abundance ratio [HCN]/[HNC] decreases by more than an order of magnitude from the relatively warm plateau and hot core sources toward the KL nebula to the colder, more quiescent clouds to the north and south. Even in the cooler regions, however, the ratio is an order of magnitude larger than that found in previous investigations of cold dark clouds. We determine the kinetic temperature in the regions we have studied from new observations of methylacetylene (CH3CCH), together with other recent estimates of the gas temperature near KL. The results suggest that the warmer portions of the cloud are dominated by different chemical pathways than those in the general interstellar cloud material.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Solar wind helium, neon, and argon isotopic and elemental composition: Data from the metallic glass flown on NASA’s Genesis mission

Solar wind (SW) helium, neon, and argon trapped in a bulk metallic glass (BMG) target flown on NASA’s Genesis mission were analyzed for their bulk composition and depth-dependent distribution. The bulk isotopic and elemental composition for all three elements is in good agreement with the mean values observed in the Apollo Solar Wind Composition (SWC) experiment. Conversely, the He fluence derived from the BMG is up to 30% lower than values reported from other Genesis bulk targets or in-situ measurements during the exposure period. SRIM implantation simulations using a uniform isotopic composition and the observed bulk velocity histogram during exposure reproduces the Ne and Ar isotopic variations with depth within the BMG in a way which is generally consistent with observations. The similarity of the BMG release patterns with the depth-dependent distributions of trapped solar He, Ne, and Ar found in lunar and asteroidal regolith samples shows that also the solar noble gas record of extraterrestrial samples can be explained by mass separation of implanted SW ions with depth. Consequently, we conclude that a second solar noble gas component in lunar samples, referred to as the “SEP” component, is not needed. On the other hand, a small fraction of the total solar gas in the BMG released from shallow depths is markedly enriched in the light isotopes relative to predictions from implantation simulations with a uniform isotopic composition. Contributions from a neutral solar or interstellar component are too small to explain this shallow sited gas. We tentatively attribute this superficially implanted gas to low-speed, current-sheet related SW, which was fractionated in the corona due to inefficient Coulomb drag. This fractionation process could also explain relatively high Ne/Ar elemental ratios in the same initial gas fraction.     

Upwelling, species, and depth effects on coral skeletal cadmium-to-calcium ratios (Cd/Ca)

Skeletal cadmium-to-calcium (Cd/Ca) ratios in hermatypic stony corals have been used to reconstruct changes in upwelling over time, yet there has not been a systematic evaluation of this tracer’s natural variability within and among coral species, between depths and across environmental conditions. Here, coral skeletal Cd/Ca ratios were measured in multiple colonies of Pavona clavus, Pavona gigantea and Porites lobata reared at two depths (1 and 7 m) during both upwelling and nonupwelling intervals in the Gulf of Panama (Pacific). Overall, skeletal Cd/Ca ratios were significantly higher during upwelling than during nonupwelling, in shallow than in deep corals, and in both species of Pavona than in P. lobata. P. lobata skeletal Cd/Ca ratios were uniformly low compared to those in the other species, with no significant differences between upwelling and nonupwelling values. Among colonies of the same species, skeletal Cd/Ca ratios were always higher in all shallow P. gigantea colonies during upwelling compared to nonupwelling, though the magnitude of the increase varied among colonies. For P. lobata, P. clavus and deep P. gigantea, changes in skeletal Cd/Ca ratios were not consistent among all colonies, with some colonies having lower ratios during upwelling than during nonupwelling. No statistically significant relationships were found between skeletal Cd/Ca ratios and maximum linear skeletal extension, δ¹³C or δ¹⁸O, suggesting that at seasonal resolution the Cd/Ca signal was decoupled from growth rate, coral metabolism, and ocean temperature and salinity, respectively. These results led to the following conclusions, (1) coral skeletal Cd/Ca ratios are independent of skeletal extension, coral metabolism and ambient temperature/salinity, (2) shallow P. gigantea is the most reliable species for paleoupwelling reconstruction and (3) the average Cd/Ca record of several colonies, rather than of a single coral, is needed to reliably reconstruct paleoupwelling events.     

Phthalic acid complexation and the dissolution of forsteritic glass studied via in situ FTIR and X-ray scattering

Multiple Internal Reflection Fourier Transform Infra-Red (MIR-FTIR) spectroscopy was developed and used for in situ flow-through experiments designed to study the process of organic acid promoted silicate dissolution. In tandem with the FTIR analysis, ex situ X-ray scattering was used to perform detailed analyses of the changes in the surface structure and chemistry resulting from the dissolution process. Phthalic acid and forsteritic glass that had been Chemically Vapour Deposited (CVD) onto an internal reflection element were used as reactants, and the MIR-FTIR results showed that phthalic acid may promote dissolution by directly binding to exposed Mg metal ion centers on the solid surface. Integrated infrared absorption intensity as a function of time shows that phthalic acid attachment apparently follows a t^1/2 dependence, indicating that attachment is a diffusive process. The diffusion coefficient of phthalic acid was estimated to be approximately 7 × 10⁻⁶ cm² s⁻¹ in the solution near the interface with the glass. Shifts in the infrared absorption structure of the phthalate complexed with the surface compared to the solute species indicate that phthalate forms a seven-membered ring chelate complex. This bidentate complex efficiently depletes Mg from the glass surface, such that after reaction as much as 95% of the Mg may be removed. Surface depletion in Mg causes adsorbate density to fall after an initial attachment stage for the organic ligand. In addition, the infrared analysis shows that silica in the near surface polymerizes after Mg removal, presumably to maintain charge balance. X-ray reflectivity shows that the dissolution rate of forsteritic glass at pH 4 based on Mg removal in such flow-through experiments was equal to 4 × 10⁻¹² mol cm⁻² s⁻¹ (geometric surface area normalized). Reflectivity also shows how the surface mass density decreases during reaction from 2.64 g cm⁻³ to 2.2 g cm⁻³, consistent with preferential loss of Mg from the surface. Auxiliary batch experiments with forsteritic glass films deposited onto soda glass were also completed to add further constraints to the mechanism of reaction. By combining reflectivity with diffuse scatter measurements it is shown that the primary interface changes little in terms of atomic-scale roughness even after removal of several hundred angstroms of material. These measurements unequivocally show how a dicarboxylic acid bonds to and may chelate the dissolution of a magnesium-bearing silicate. At the molecular level the solid surface retreat may best be described by a depinning model where Mg is preferentially removed and residual silica tetrahedra polymerize and act to episodically “pin” the surface.     

Uranophane dissolution and growth in CaCl2-SiO2(aq) test solutions

The dissolution and growth of uranophane [Ca(UO₂)₂(SiO₃OH)₂·5H₂O] have been examined in Ca- and Si-rich test solutions at low temperatures (20.5 ± 2.0 °C) and near-neutral pH (∼6.0). Uranium-bearing experimental solutions undersaturated and supersaturated with uranophane were prepared in matrices of ∼10⁻² M CaCl₂ and ∼10⁻³ M SiO₂(aq). The experimental solutions were reacted with synthetic uranophane and analyzed periodically over 10 weeks. Interpretation of the aqueous solution data permitted extraction of a solubility constant for the uranophane dissolution reaction and standard state Gibbs free energy of formation for uranophane ( kJ mol⁻¹).