Carbon dioxide on the satellites of Saturn: Results from the Cassini VIMS investigation and revisions to the VIMS wavelength scale

Several of the icy satellites of Saturn show the spectroscopic signature of the asymmetric stretching mode of C-O in carbon dioxide (CO₂) at or near the nominal solid-phase laboratory wavelength of 4.2675 μm (2343.3 cm⁻¹), discovered with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft. We report here on an analysis of the variation in wavelength and width of the CO₂ absorption band in the spectra of Phoebe, Iapetus, Hyperion, and Dione. Comparisons are made to laboratory spectra of pure CO₂, CO₂ clathrates, ternary mixtures of CO₂ with other volatiles, implanted and adsorbed CO₂ in non-volatile materials, and ab initio theoretical calculations of CO₂ * nH₂O. At the wavelength resolution of VIMS, the CO₂ on Phoebe is indistinguishable from pure CO₂ ice (each molecule’s nearby neighbors are also CO₂) or type II clathrate of CO₂ in H₂O. In contrast, the CO₂ band on Iapetus, Hyperion, and Dione is shifted to shorter wavelengths (typically ∼4.255 μm (∼2350.2 cm⁻¹)) and broadened. These wavelengths are characteristic of complexes of CO₂ with different near-neighbor molecules that are encountered in other volatile mixtures such as with H₂O and CH₃OH, and non-volatile host materials like silicates, some clays, and zeolites. We suggest that Phoebe’s CO₂ is native to the body as part of the initial inventory of condensates and now exposed on the surface, while CO₂ on the other three satellites results at least in part from particle or UV irradiation of native H₂O plus a source of C, implantation or accretion from external sources, or redistribution of native CO₂ from the interior.The analysis presented here depends on an accurate VIMS wavelength scale. In preparation for this work, the baseline wavelength calibration for the Cassini VIMS was found to be distorted around 4.3 μm, apparently as a consequence of telluric CO₂ gas absorption in the pre-launch calibration. The effect can be reproduced by convolving a sequence of model detector response profiles with a deep atmospheric CO₂ absorption profile, producing distorted detector profile shapes and shifted central positions. In a laboratory blackbody spectrum used for radiance calibration, close examination of the CO₂ absorption profile shows a similar deviation from that expected from a model. These modeled effects appear to be sufficient to explain the distortion in the existing wavelength calibration now in use. A modification to the wavelength calibration for 13 adjacent bands is provided. The affected channels span about 0.2 μm centered on 4.28 μm. The maximum wavelength change is about 10 nm toward longer wavelength. This adjustment has implications for interpretation of some of the spectral features observed in the affected wavelength interval, such as from CO₂, as discussed in this paper.     

Correlations between VIMS and RADAR data over the surface of Titan: Implications for Titan’s surface properties

We apply a multivariate statistical method to Titan data acquired by different instruments onboard the Cassini spacecraft. We have searched through Cassini/VIMS hyperspectral cubes, selecting those data with convenient viewing geometry and that overlap with Cassini/RADAR scatterometry footprints with a comparable spatial resolution. We look for correlations between the infrared and microwave ranges the two instruments cover. Where found, the normalized backscatter cross-section obtained from the scatterometer measurement, corrected for incidence angle, and the calibrated antenna temperature measured along with the scatterometry echoes, are combined with the infrared reflectances, with estimated errors, to produce an aggregate data set, that we process using a multivariate classification method to identify homogeneous taxonomic units in the multivariate space of the samples.In medium resolution data (from 20 to 100 km/pixel), sampling relatively large portions of the satellite’s surface, we find regional geophysical units matching both the major dark and bright features seen in the optical mosaic. Given the VIMS cubes and RADAR scatterometer passes considered in this work, the largest homogeneous type is associated with the dark equatorial basins, showing similar characteristics as each other on the basis of all the considered parameters.On the other hand, the major bright features seen in these data generally do not show the same characteristics as each other. Xanadu, the largest continental feature, is as bright as the other equatorial bright features, while showing the highest backscattering coefficient of the entire satellite. Tsegihi is very bright at 5 μm but it shows a low backscattering coefficient, so it could have a low roughness on a regional scale and/or a different composition. Another well-defined region, located southwest of Xanadu beyond the Tui Regio, seems to be detached from the surrounding terrains, being bright at 2.69, 2.78 and 5 μm but having a low radar brightness. In this way, other units can be found that show correlations or anti-correlations between the scatterometric response and the spectrophotometric behavior, not evident from the optical remote sensing data.     

Hydrolytic enzymes of the paua Haliotis iris,a marine gastropod (note).

Extracts of the viscera of Haliotis iris (Martyn, 1784) were shown to hydrolyse 2‐hydroxy‐5‐nitrophenyl sulphate at pH 5.5, and the p‐nitrophenyl derivatives of α‐ and β‐D‐galactose, α‐ and β‐D‐mannose, α‐L‐lucose, β‐D‐glucuronic acid, β‐N‐acetyl glucosamine and phosphate at pH 4.0 and 5.5: p‐nitrophenyl‐β‐L‐fucose was not hydrolysed.     

Copper speciation survey from UK marinas, harbours and estuaries

The use of copper in antifouling paints has increased in the UK in the last 20 years as TBT and several other organic biocides have been phased out. To assess the probable impact of copper on estuarine systems a survey was undertaken to measure the different fractions of copper present in the water column at current usage. The different fractions measured were; labile copper, (LCu) considered as both the free copper ions and inorganically bound copper, the total dissolved copper (TDCu) present, and the difference between them taken as the organically bound likely non-toxic copper fraction. The survey considered sites with different levels of boat use, namely marinas, harbours and estuaries, differing physical parameters of suspended and dissolved organic matter, different seasons of the year and different depths in the water column all of which control speciation behaviour. Suspended particulate matter (SPM) values were measured at all sites and increased from West to East coast locations (5.7-34.4 mg/l). Dissolved organic matter (DOM) values ranged from 0.58 to 2.2mg/l C. The total dissolved copper concentrations ranged from 0.30 to 6.68 microg/l, with labile fraction ranging from 0.02 to 2.69 microg/l, and most labile copper concentrations below 1 microg/l. None of the yearly mean copper measurements exceeded the 76/464/EEC EQS of 5 microg/l. Of the 306 measurements, only one dissolved copper value in one season was above 5 microg/l. This ratio of labile to total copper was between 10 and 30%. The results from this survey suggest that if toxicity of copper is due to the labile fraction then using the total dissolved copper concentrations as an indicator of impact overestimate the risk by a factor of four times.     

On the Measurement of Dewfall and Fog-Droplet Deposition

An observational study has been conducted concerning atmospheric dewfall and fog-droplet deposition with application to the formation and maintenance of fog layers. The relationship between dew and fog is discussed together with the challenges and requirements to measure representative values of their deposition to the surface. A practical instrument developed at the UK Met Office Research Unit, Cardington, is described. The instrument is a small portable device that uses a load cell to measure the weight of a pan upon which various types of natural and artificial canopies can be placed, and can measure dewfall and fog-droplet deposition to an accuracy of 0.0005 mm. Dewfall results from this device are shown for a selection of nights under varying conditions. On a given night the overriding factor determining the amount of dew deposition appears to be location. Several dewmeter devices were placed at different locations around the 18 ha Cardington field site for various clear nights and it was found that dew amounts varied significantly, depending on location: canopies with a more open aspect experienced more deposition by up to a factor of two. The results also suggest that the hygroscopic effect of a canopy, whereby water is absorbed into the canopy and topsoil layer before dew formation begins, is also important for the removal of atmospheric water vapour. Results indicate this effect can be of a similar magnitude to dew deposition. Measurements of fog-droplet deposition showed total water deposition rates did not change when thin radiation fog formed. When optically thick adiabatic fog formed, deposition rates were seen to decrease with time or be generally lower than for thinner radiation fog. Further observations are required to establish if the behaviours found are typical for all fogs.     

Post-peak,fluid-mediated modification of granulite facies zircon and monazite in the Trivandrum Block,southern India

The quarry at Kottavattom in the Trivandrum Block of southern India contains spectacular examples of fluid-assisted alteration of high-grade metamorphic rocks. Garnet-biotite gneiss has undergone a change in mineral assemblage to form submetre scale orthopyroxene-bearing patches, later retrogressed to form an amphibole-bearing lithology. These patches, often referred to as arrested or incipient charnockite, crosscut the original metamorphic foliation and are typically attributed to passage of a low aH₂O fluid through the rock. Whilst this conversion is recognised as a late stage process, little detailed chronological work exists to link it temporally to metamorphism in the region. Zircon and monazite analysed from Kottavattom not only record metamorphism in the Trivandrum Block but also show internal, lobate textures crosscutting the original zoning, consistent with fluid-aided coupled dissolution-reprecipitation during formation of the orthopyroxene-bearing patches. High-grade metamorphism at the quarry occurred between the formation of metamorphic monazite at ~585 Ma and the growth of metamorphic zircon at ~523 Ma. The fluid-assisted alteration of the garnet-biotite gneiss is poorly recorded by altered zircon with only minimal resetting of the U–Pb system, whereas monazite has in some cases undergone complete U–Pb resetting and records an age for fluid infiltration at ~495 Ma. The fluid event therefore places the formation of the altered patches at least 25 Myr after the zircon crystallisation in the garnet-biotite gneiss. The most likely fluid composition causing the modification and U–Pb resetting of zircon and monazite is locally derived hypersaline brine.     

Sea-level and reef accretion history of Marine Oxygen Isotope Stage 7 and late Stage 5 based on age and facies of submerged late Pleistocene reefs,Oahu, Hawaii

In situ Pleistocene reefs form a gently sloping nearshore terrace around the island of Oahu. TIMS Th–U ages of in situ corals indicate that most of the terrace is composed of reefal limestones correlating to Marine Oxygen Isotope Stage 7 (MIS 7, ~ 190–245 ka). The position of the in situ MIS 7 reef complex indicates that it formed during periods when local sea level was ~ 9 to 20 m below present sea level. Its extensiveness and geomorphic prominence as well as a paucity of emergent in situ MIS 7 reef-framework deposits on Oahu suggest that much of MIS 7 was characterized by regional sea levels below present. Later accretion along the seaward front of the terrace occurred during the latter part of MIS 5 (i.e., MIS 5a–5d, ~ 76–113 ka). The position of the late MIS 5 reefal limestones is consistent with formation during a period when local sea level was below present. The extensiveness of the submerged Pleistocene reefs around Oahu compared to the relative dearth of Holocene accretion is due to the fact that Pleistocene reefs had both more time and more accommodation space available for accretion than their Holocene counterparts.     

Bayesian modelling the retreat of the Irish Sea Ice Stream

We present an 8000‐year history spanning 650 km of ice margin retreat for the largest marine‐terminating ice stream draining the former British–Irish Ice Sheet. Bayesian modelling of the geochronological data shows the ISIS expanded 34.0–25.3 ka, accelerating into the Celtic Sea to reach maximum limits 25.3–24.5 ka before a collapse with rapid marginal retreat to the northern Irish Sea Basin (ISB). This retreat was rapid and driven by climatic warming, sea‐level rise, mega‐tidal amplitudes and reactivation of meridional circulation in the North Atlantic. The retreat, though rapid, is uneven, with the stepped retreat pattern possibly a function of the passage of the ice stream between normal and adverse ice bed gradients and changing ice stream geometry. Initially, wide calving margins and adverse slopes encouraged rapid retreat (～550 m a^?1) that slowed (～100 m a^?1) at the topographic constriction and bathymetric high between southern Ireland and Wales before rates increased (～200 m a^?1) across adverse bed slopes and wider and deeper basin configuration in the northern ISB. These data point to the importance of the ice bed slope and lateral extent in predicting the longer‐term (>1000 a) patterns and rates of ice‐marginal retreat during phases of rapid collapse, which has implications for the modelling of projected rapid retreat of present‐day ice streams. Copyright © 2013 John Wiley & Sons, Ltd.     

Impacts of uncertain river flow data on rainfall‐runoff model calibration and discharge predictions

In order to quantify total error affecting hydrological models and predictions, we must explicitly recognize errors in input data, model structure, model parameters and validation data. This paper tackles the last of these: errors in discharge measurements used to calibrate a rainfall‐runoff model, caused by stage–discharge rating‐curve uncertainty. This uncertainty may be due to several combined sources, including errors in stage and velocity measurements during individual gaugings, assumptions regarding a particular form of stage–discharge relationship, extrapolation of the stage–discharge relationship beyond the maximum gauging, and cross‐section change due to vegetation growth and/or bed movement. A methodology is presented to systematically assess and quantify the uncertainty in discharge measurements due to all of these sources. For a given stage measurement, a complete PDF of true discharge is estimated. Consequently, new model calibration techniques can be introduced to explicitly account for the discharge error distribution. The method is demonstrated for a gravel‐bed river in New Zealand, where all the above uncertainty sources can be identified, including significant uncertainty in cross‐section form due to scour and re‐deposition of sediment. Results show that rigorous consideration of uncertainty in flow data results in significant improvement of the model's ability to predict the observed flow. Copyright © 2010 John Wiley & Sons, Ltd.