Preliminary report on a dinosaur tracksite from Lower Cretaceous strata in Mount Lebanon

A dinosaur tracksite was discovered in Batha on the side of the road from Harissa to Ghosta (Keserwan, Lebanon). About ten trackways are exposed at the top of two beds of Lower Cretaceous limestones over an area of approximately 1000 m². These footprints were probably made by at least two dinosaur species, Sauropoda and either Theropoda or Ornithopoda. The site, which is the first record from Lebanon, should be protected to allow further scientific investigations.     

Assessing the origin of old apparent ages derived by Pb stepwise leaching of vein-hosted epidote from Mount Isa,northwest Queensland,Australia

Epidote metasomatism affected large areas of tholeiitic metabasalts of the ~1,780 Ma Eastern Creek Volcanics in the Western Fold Belt of the Proterozoic Mount Isa inlier. Hydrothermal epidote generally occurs in quartz veins parallel to or boudinaged within the dominant S₂ fabrics which formed during the regional metamorphic peak at ~1,570 Ma associated with the Isan orogeny. Previously published stable isotopic and halogen data suggest that the fluids responsible for epidote formation are metamorphic in origin (with an evaporitic component). Application of the Pb stepwise leaching technique to the epidote does not separate radiogenic Pb⁴⁺ and common Pb²⁺, generating little spread in ²⁰⁶Pb/²⁰⁴Pb (between 16.0 and 30.5). The causes for this relatively low range are twofold: There is little radiogenic Pb in the epidotes (the most radiogenic steps account for <1 % of Pb released) and both Pb²⁺ and uranogenic Pb⁴⁺ substitute into the same site in the epidote crystal lattice. Consequently, age regressions using the Pb stepwise leaching data give ages between 150 and 1,500 myrs older than the host rocks and over 450 myrs older than the thermal metamorphic peak. These old ages are attributed to chemical inheritance from the host metabasalts, via radiogenic Pb release by breakdown of phases such as zircon, monazite, titanomagnetite, and ilmenite during metamorphism. This idea is supported by trace element data and chrondrite-normalized rare earth element patterns that are similar to both the metabasalts and epidotes (except for a variable Eu anomaly in the latter). Relatively high fO₂ during vein formation (Fe³⁺ dominates in the epidote crystal lattice) would allow the incorporation of Th⁴⁺ and exclusion of U⁶⁺ and would explain elevated Th/U ratios (up to 12) in epidote compared with the host metabasalts. Non-incorporation of U would explain the relatively low U/Pb ratios and non-radiogenic character of the epidote. This process may provide a source of metal for the small U deposits around Mount Isa and may also suggest a relationship between U mineralization and regional Cu mobilization during the Isan orogeny. Our work suggests that non-conventional geochronometers should be used only if additional geological information and geochemical data (e.g., mineral chemistry, trace elements) are available to evaluate any resulting age calculations.     

Evaluation of the third- and fourth-generation GOCE Earth gravity field models with Australian terrestrial gravity data in spherical harmonics

In March 2013, the fourth generation of European Space Agency’s (ESA) global gravity field models, DIR4 (Bruinsma et al. in Proceedings of the ESA living planet symposium, 28 June–2 July, Bergen, ESA, Publication SP-686, 2010b) and TIM4 (Migliaccio et al. in Proceedings of the ESA living planet symposium, 28 June–2 July, Bergen, ESA, Publication SP-686, 2010), generated from the Gravity field and steady-state Ocean Circulation Explorer (GOCE) gravity observation satellite was released. We evaluate the models using an independent ground truth data set of gravity anomalies over Australia. Combined with Gravity Recovery and Climate Experiment (GRACE) satellite gravity, a new gravity model is obtained that is used to perform comparisons with GOCE models in spherical harmonics. Over Australia, the new gravity model proves to have significantly higher accuracy in the degrees below 120 as compared to EGM2008 and seems to be at least comparable to the accuracy of this model between degree 150 and degree 260. Comparisons in terms of residual quasi-geoid heights, gravity disturbances, and radial gravity gradients evaluated on the ellipsoid and at approximate GOCE mean satellite altitude ( $h=250$  km) show both fourth generation models to improve significantly w.r.t. their predecessors. Relatively, we find a root-mean-square improvement of 39 % for the DIR4 and 23 % for TIM4 over the respective third release models at a spatial scale of 100 km (degree 200). In terms of absolute errors, TIM4 is found to perform slightly better in the bands from degree 120 up to degree 160 and DIR4 is found to perform slightly better than TIM4 from degree 170 up to degree 250. Our analyses cannot confirm the DIR4 formal error of 1 cm geoid height (0.35 mGal in terms of gravity) at degree 200. The formal errors of TIM4, with 3.2 cm geoid height (0.9 mGal in terms of gravity) at degree 200, seem to be realistic. Due to combination with GRACE and SLR data, the DIR models, at satellite altitude, clearly show lower RMS values compared to TIM models in the long wavelength part of the spectrum (below degree and order 120). Our study shows different spectral sensitivity of different functionals at ground level and at GOCE satellite altitude and establishes the link among these findings and the Meissl scheme (Rummel and van Gelderen in Manusrcipta Geodaetica 20:379–385, 1995).     

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.     

Dissolution kinetics of diopside as a function of solution saturation state: Macroscopic measurements and implications for modeling of geological storage of CO2

Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔG_r) in a continuously stirred flow-through reactor at 90 °C and pH_90 °C = 5.05. The overall relation between r and ΔG_r was determined over a free energy range of −130.9 < ΔG_r < −47.0 kJ mo1⁻¹. The data define a highly non-linear, sigmoidal relation between r and ΔG_r. At far-from-equilibrium conditions (ΔG_r ? −76.2 kJ mo1⁻¹), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔG_r. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔG_r region defined by −76.2 < ΔG_r ? −61.5 kJ mo1⁻¹. Dissolution closer to equilibrium (ΔG_r > −61.5 kJ mo1⁻¹) is characterised by a much weaker inverse dependence of the rates on ΔG_r. Modeling the experimental r-ΔG_r data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔG_r relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO₂ over long time spans. In order to take into account the actual experimental r-ΔG_r relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO₂ interactions performed with classical geochemical codes should be evaluated with great caution.     

Pressure–temperature evolution of lawsonite eclogite in Sivrihisar; Tavşanlı Zone–Turkey

The Cretaceous blueschist belt, Tavşanlı Zone, representing the subducted and exhumed northern continental margin of the Anatolide–Tauride platform is exposed in Western Anatolia. The Sivrihisar area east of Tavşanlı is made up of tectonic units consisting of i) metaclastics and conformably overlying massive marbles (coherent blueschist unit), ii) blueschist-eclogite unit, iii) marble–calcschist intercalation and iv) metaperidotite slab. The metaclastics are composed of jadeite–lawsonite–glaucophane and jadeite–glaucophane–chloritoid schists, phengite phyllites, and calcschists with glaucophane–lawsonite metabasite layers. The blueschist-eclogite unit representing strongly sheared, deeply buried and imbricated tectonic slices of accreted uppermost levels of the oceanic crust with minor metamorphosed serpentinite bodies consists of lawsonite-bearing eclogitic metabasites (approximately 90% of the field), lawsonite eclogites, metagabbros, serpentinites, pelagic marbles, omphacite–glaucophane–lawsonite metapelites and metacherts. The mineral assemblage of the lawsonite eclogite (garnet + omphacite > 70%) is omphacite, garnet, lawsonite, glaucophane, phengite and rutile. Lawsonite eclogite lenses are enclosed by garnet–lawsonite blueschist envelopes.Textural evidence from lawsonite eclogites and country rocks reveals that they did not leave the stability field of lawsonite during subduction and exhumation. The widespread preservation of lawsonite in eclogitic metabasites and eclogites can be attributed to rapid subduction and subsequent exhumation in a low geothermal gradient of the oceanic crust material without experiencing a thermal relaxation. Peak P–T conditions of lawsonite eclogites are estimated at 24 ± 1 kbar and 460 ± 25 °C. These P–T conditions indicate a remarkably low geotherm of 6.2 °C/km corresponding to a burial depth of 74 km.     

纤磷钙铝石类化合物:来自地球具工艺用途的材料(英文)

纤磷钙铝石类化合物系由自纤磷钙铝石CaAl3 (OH) 6(HPO4) (PO4)本身、经磷钙铝石CaAl3 (OH) 6(SO4) (PO4)到钾明矾石KAl3 (OH ) 6(SO4) 2 等的天然矿物族所组成的。它们表现出具有很大范围的阳离子置换系列 ,其中以Sr2 +和Ba2 +置换Ca2 +,REEs3 +置换Ca2 +和H+,As5 +置换P5 +,S6+/Se6+置换H+P5 +最为重要。随着置换的进行 ,其热动力学稳定性也逐渐增加。由此 ,纤磷钙铝石类化合物成为很能抗风化的矿物 ,在红土中尤其如此。厚的纤磷钙铝石层形成在闪长岩 (富Sr) ,碳酸盐岩 (富REEs)和含金石英脉 (富As)之上 ,从而保护整个磷酸盐红土 ,使之免受风化。以此方式 ,形成了桌状山脉或岛屿 ,他们具有未受覆盖的表面。这些“纤磷钙铝”石化合物为上述及其它元素形成一有效的地球化学障。“纤磷钙铝石”的这种天然地球化学固定作用可以用适当的母体或人工合成晶体来进行模拟 ,即通过金属阳离子交换或就地反应来模拟。这种固定作用还可用于处理天然和人造的放射性裂变产物、有毒的重金属元素、砷酸盐和硒酸盐、硫酸盐等。     

The Budget of Turbulent Kinetic Energy in the Urban Roughness Sublayer

Full-scale observations from two urban sites in Basel, Switzerland were analysed to identify the magnitude of different processes that create, relocate, and dissipate turbulent kinetic energy (TKE) in the urban atmosphere. Two towers equipped with a profile of six ultrasonic anemometers each sampled the flow in the urban roughness sublayer, i.e. from street canyon base up to roughly 2.5 times the mean building height. This observational study suggests a conceptual division of the urban roughness sublayer into three layers: (1) the layer above the highest roofs, where local buoyancy production and local shear production of TKE are counterbalanced by local viscous dissipation rate and scaled turbulence statistics are close to to surface-layer values; (2) the layer around mean building height with a distinct inflexional mean wind profile, a strong shear and wake production of TKE, a more efficient turbulent exchange of momentum, and a notable export of TKE by transport processes; (3) the lower street canyon with imported TKE by transport processes and negligible local production. Averaged integral velocity variances vary significantly with height in the urban roughness sublayer and reflect the driving processes that create or relocate TKE at a particular height. The observed profiles of the terms of the TKE budget and the velocity variances show many similarities to observations within and above vegetation canopies.     

Iodine Chemistry and its Role in Halogen Activation and Ozone Loss in the Marine Boundary Layer: A Model Study

A detailed set of reactions treating the gas and aqueous phase chemistry of the most important iodine species in the marine boundary layer (MBL) has been added to a box model which describes Br and Cl chemistry in the MBL. While Br and Cl originate from seasalt, the I compounds are largely derived photochemically from several biogenic alkyl iodides, in particular CH2I2, CH2ClI, C2H5I, C3H7I, or CH3I which are released from the sea. Their photodissociation produces some inorganic iodine gases which can rapidly react in the gas and aqueous phase with other halogen compounds. Scavenging of the iodine species HI, HOI, INO2, and IONO2 by aerosol particles is not a permanent sink as assumed in previous modeling studies. Aqueous-phase chemical reactions can produce the compounds IBr, ICl, and I2, which will be released back into the gas phase due to their low solubility. Our study, although highly theoretical, suggests that almost all particulate iodine is in the chemical form of IO-3. Other aqueous-phase species are only temporary reservoirs and can be re-activated to yield gas phase iodine. Assuming release rates of the organic iodine compounds which yield atmospheric concentrations similar to some measurements, we calculate significant concentrations of reactive halogen gases. The addition of iodine chemistry to our reaction scheme has the effect of accelerating photochemical Br and Cl release from the seasalt. This causes an enhancement in ozone destruction rates in the MBL over that arising from the well established reactions O(1D) + H2O 2OH, HO2 + O3 OH + 2O2, and OH + O3 HO2 + O2. The given reaction scheme accounts for the formation of particulate iodine which is preferably accumulated in the smaller sulfate aerosol particles.