Reformulated O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios

Mass-spectrometric stable isotope measurements of CO₂ use molecular ion currents at mass-to-charge ratios m/z 44, 45 and 46 to derive the elemental isotope ratios n(¹³C)/n(¹²C) and n(¹⁸O)/n(¹⁶O), abbreviated ¹³C/¹²C and ¹⁸O/¹⁶O, relative to a reference. The ion currents have to be corrected for the contribution of ¹⁷O-bearing isotopologues, the so-called ‘¹⁷O correction’. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing ¹³C/¹²C (¹³R), ¹⁷O/¹⁶O (¹⁷R) and ¹⁸O/¹⁶O (¹⁸R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO₂ generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H₃PO₄ at 25 °C (VPDB-CO₂). I find , ¹⁸R_VSMOW/10⁻⁶ = 2005.20 ± 0.45, ¹³R_VPDB-CO2/10^-6= 11124 ± 45, and ¹⁸R_VPDB-CO2/10^-6=2088.37±0.90. I also rephrase the calculation scheme for the ¹⁷O correction completely in terms of relative isotope ratio differences (δ values). This reveals that only ratios of isotope ratios (namely, ¹⁷R/¹³R and ¹³R¹⁷R/¹⁸R) are required for the ¹⁷O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative ¹³C/¹²C difference, but not for¹⁸O/¹⁶O. Even though inter-laboratory differences can be corrected for by a common ‘ratio assumption set’ and/or normalisation, the ultimate accuracy of the ¹⁷O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between ¹⁷O/¹⁶O and ¹⁸O/¹⁶O isotope ratios. For highest accuracy in the ¹³C/¹²C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that allows direct measurement of ¹³R¹⁷R/¹⁸R.     

The contribution of sulphur dioxide from ablating micrometeorites to the atmospheres of Earth and Mars

Atmospheric composition is a key control on climate and the habitability of planetary surfaces. Ablation of infalling micrometeorites has been recognised as one way in which atmospheric chemistry can be changed, especially at times in solar system history when the infall rates of exogenous material were high. Despite its potential to influence climate and habitability, extraterrestrial sulphur dioxide is currently an unquantified contribution to the atmospheres of the terrestrial planets. We have used flash pyrolysis to simulate the atmospheric entry of micrometeorites and Fourier-transform infrared spectroscopy to identify and quantify the sulphur dioxide produced from the carbonaceous meteorites Orgueil (CI1), ALH 88045 (CM1), Cold Bokkeveld (CM2), Murchison (CM2) and Mokoia (CV3). We have used this approach to understand the introduction of sulphur dioxide to the atmospheres of Earth and Mars from infalling micrometeorites. Sulphates, present in carbonaceous chondrites at a few wt.%, are resistant to thermal decomposition, limiting the yields of sulphur dioxide from unmelted micrometeorites. Infalling micrometeorites are a minor source of present-day sulphur dioxide on Earth and Mars, calculated to be up to around 2400 tonnes and about 350 tonnes, respectively. During the Late Heavy Bombardment (LHB), the much greater infall rates of micrometeoritic dust are calculated to be associated with average production rates of sulphur dioxide of around 20 Mt yr⁻¹ for the early Earth and 0.5 Mt yr⁻¹ for early Mars, for a LHB of 100 Myr. These rates of delivery of sulphur dioxide at high altitudes would have reduced the solar energy reaching the surfaces of these planets, via scattering of sunlight by stratospheric sulphate aerosols, and may have had detrimental effects on developing biospheres by promoting cooler climates and reducing the probability of liquid water on planetary surfaces.     

The measurement and extraction of the <nu>6 atmospheric emission band of CFC-12 from interfering emission features

Ground-based thermal emission measurements of the zenith sky have been made at Peterborough, Ontario since January 1993. In this paper, the measurement of the ₆ band of atmospheric CFC-12, an important greenhouse gas, is presented for a cold, clear day in January 1994. A spectrum of the non-CFC-12 emission features has been simulated using the FASCD3P radiation code and measured radiosonde profiles of temperature, pressure and humidity. This has enabled a satisfactory subtraction of the interfering emission features from the CFC-12 emission spectrum. A comparison of the observed and simulated ₆-bands of CFC-12 shows good agreement at all frequencies of emission. From these spectra the total downward greenhouse radiative flux from the CFC-12 ₆ emission based for a very cold day has been estimated to be 0.27 W m⁻²±10%.     

Modeling preferential flow in reactive barriers: implications for performance and design

Reactive barriers are passive and in situ ground water treatment systems. Heterogeneities in hydraulic conductivity (K) within the aquifer-reactive barrier system will result in higher flux rates, and reduced residence times, through portions of the barrier. These spatial variations in residence time will affect the treatment capacity of the barrier. A numerical flow model was used to evaluate the effects of spatial variations in K on preferential flow through barriers. The simulations indicate that the impact of heterogeneities in K will be a function of their location and distribution; the more localized the high K zone, the greater the preferential flow. The geometry of the reactive barrier will also strongly influence flow distribution. Aquifer heterogeneities will produce greater preferential flow in thinner barriers compared to thicker barriers. If the barrier K is heterogeneous, greater preferential flow will occur in thicker barriers. The K of the barrier will affect the flow distribution; decreasing the K of the barrier can result in more even distribution of flow. Results indicate that less variable flow will be attained utilizing thicker, homogeneous barriers. The addition of homogeneous zones to thinner barriers will be effective at redistributing flow only if installed immediately adjacent to both the up- and downgradient faces of the barrier.     

A crustal suture and lineament in North Africa

A possible suture between an old craton in West Africa and the Arabian—Nubian shield is marked by a persistent zone of Phanerozoic weakness. This zone extends between the Nile and Niger deltas and passes through the Qattara embayment, along the Bahariya fault, through the Kufra basin, between the Tibesti and Jabal al Uwaynat massifs, through the Bahr el Ghazal and Lake Chad areas, and along the Benoue trough.     

Automated mapping of rock slope geometry,kinematics and stability with RSS-GIS

A GIS-implemented, deterministic approach for the automated spatial evaluation of geometrical and kinematical properties of rock slope terrains is presented. Based on spatially distributed directional information on planar geological fabrics and DEM-derived topographic attribute data, the internal geometry of rock slopes can be characterized on a grid cell basis. For such computations, different approaches for the analysis and regionalization of available structural directional information applicable in specific tectonic settings are demonstrated and implemented in a GIS environment. Simple kinematical testing procedures based on feasibility criteria can be conducted on a pixel basis to determine which failure mechanisms are likely to occur at particular terrain locations. In combination with hydraulic and strength data on geological discontinuities, scenario-based rock slope stability evaluations can be performed. For conceptual investigations on rock slope failure processes, a GIS-based specification tool for a 2-D distinct element code (UDEC) was designed to operate with the GIS-encoded spatially distributed rock slope data. The concepts of the proposed methodology for rock slope hazard assessments are demonstrated at three different test sites in Germany.     

Sea‐level and ocean‐current control on carbonate‐platform growth,Maldives, Indian Ocean

Multichannel high‐resolution seismic and multibeam data were acquired from the Maldives‐isolated carbonate platform in the Indian Ocean for a detailed characterization of the Neogene bank architecture of this edifice. The goal of the research is to decipher the controlling factors of platform evolution, with a special emphasis on sea‐level changes and changes of the oceanic currents. The stacking pattern of Lower to Middle Miocene depositional sequences, with an evolution of a ramp geometry to a flat‐topped platform, reflects variations of accommodation, which here are proposed to be primarily governed by fluctuations of relative sea level. Easterly currents during this stage of bank growth controlled an asymmetric east‐directed progradation of the bank edge. During the late middle Miocene, this system was replaced by a twofold configuration of bank development. Bank growth continued synchronously with partial bank demise and associated sediment‐drift deposition. This turnover is attributed to the onset and/or intensification of the Indian monsoon and related upwelling and occurrence of currents, locally changing environmental conditions and impinging upon the carbonate system. Mega spill over lobes, shaped by reversing currents, formed as large‐scale prograding complexes, which have previously been interpreted as deposits formed during a forced regression. On a regional scale, a complex carbonate‐platform growth can occur, with a coexistence of bank‐margin progradation and aggradation, as well as partial drowning. It is further shown that a downward shift of clinoforms and offlapping geometries in carbonate platforms are not necessarily indicative for a sea‐level driven forced regression. Findings are expected to be applicable to other examples of Cenozoic platforms in the Indo‐Pacific region.     

Resolving mechanisms of toxicity while pursuing ecotoxicological relevance?

In this age of modern biology, aquatic toxicological research has pursued mechanisms of action of toxicants. This has provided potential tools for ecotoxicologic investigations. However, problems of biocomplexity and issues at higher levels of biological organization remain a challenge. In the 1980s and 1990s and continuing to a lesser extent today, organisms residing in highly contaminated field sites or exposed in the laboratory to calibrated concentrations of individual compounds were carefully analyzed for their responses to priority pollutants. Correlation of biochemical and structural analyses in cultured cells and tissues, as well as the in vivo exposures led to the production and application of biomarkers of exposure and effect and to our awareness of genotoxicity and its chronic manifestations, such as neoplasms, in wild fishes. To gain acceptance of these findings in the greater environmental toxicology community, “validation of the model” versus other, better-established often rodent models, was necessary and became a major focus. Resultant biomarkers were applied to heavily contaminated and reference field sites as part of effects assessment and with investigations following large-scale disasters such as oil spills or industrial accidents.

Over the past 15 years, in the laboratory, small aquarium fish models such as medaka (Oryzias latipes), zebrafish (Danio rerio), platyfish (Xiphophorus species), fathead minnow (Pimephales promelas), and sheepshead minnow (Cyprinodon variegatus) were increasingly used establishing mechanisms of toxicants. Today, the same organisms provide reliable information at higher levels of biological organization relevant to ecotoxicology. We review studies resolving mechanisms of toxicity and discuss ways to address biocomplexity, mixtures of contaminants, and the need to relate individual level responses to populations and communities.     

Searches for very high energy gamma rays from blazars with CANGAROO-III telescope in 2005-2009

We have searched for very high energy (VHE) gamma rays from four blazars using the CANGAROO-III imaging atmospheric Cherenkov telescope. We report the results of the observations of H 2356-309, PKS 2155-304, PKS 0537-441, and 3C 279, performed from 2005 to 2009, applying a new analysis to suppress the effects of the position dependence of Cherenkov images in the field of view. No significant VHE gamma ray emission was detected from any of the four blazars. The GeV gamma-ray spectra of these objects were obtained by analyzing Fermi/LAT archival data. Wide range (radio to VHE gamma-ray bands) spectral energy distributions (SEDs) including CANGAROO-III upper limits, GeV gamma-ray spectra, and archival data, even though they are non-simultaneous, are discussed using a one-zone synchrotron self-Compton (SSC) model in combination with a external Compton (EC) radiation. The HBLs (H 2356-309 and PKS 2155-304) can be explained by a simple SSC model, and PKS 0537-441 and 3C 279 are well modeled by a combination of SSC and EC model. We find a consistency with the blazar sequence in terms of strength of magnetic field and component size.