On the OH initiated oxidation of C2-C5 aliphatic aldehydes in the presence of mineral aerosols

Clay particles are present in large quantities in mineral dust of atmospheric aerosols, and their interaction with organic species may influence atmospheric reactions and the prediction of environmental risks. However, the kinetics and mechanisms of adsorption and reaction of atmospheric volatile organic compounds on aerosol surfaces are not well understood.In this work, quantum chemical methods are used to study the adsorption of C2-C5 aliphatic aldehydes on silicate clusters active sites, and their subsequent reaction with OH radicals. It is shown that adsorption may occur in two different ways, and that the adsorption complex structure determines the subsequent path of its reaction with OH. The initial step in the OH reaction with acetaldehyde occurs according to the same mechanism as in the gas phase, i.e., the aldehydic hydrogen abstraction. Starting from propanal, another abstraction channel becomes increasingly important, involving mainly the abstraction of a β-hydrogen of the aliphatic chain. In the presence of a silica monomer model surface, the reaction rate of aldehydes with OH free-radicals is smaller than in the gas phase. Furthermore silicates are good sinks for trapping these aldehydes. Thus, our results may have implications in the study of tropospheric chemistry and cosmochemistry.     

Influence of size on the constitutive equations of concrete or rock dowels

The numerical fracture analysis of non‐homogeneous rock or concrete dowels subjected to shear and compression is described in detail. The method of analysis allows the consideration of scale and rate effects due to material non‐homogeneity and fracture. The proposed approach is verified by comparing numerical predictions with experimental results reported in the literature for a series of small rock samples, since experimental evidence for large bodies is not yet available (2007). Results generated by Monte Carlo simulation using the so‐called discrete element method to model the dowels suggest that a simple three parameters law can be used to predict the relationship between tangential stress at the base and lateral distortion. It is observed that the larger the size of the cubes, the smaller both the peak tangential stress and the rupture distortion. Size effects are also evaluated in samples with vertical restraint. The influence of loading rate is likewise numerically assessed for two sample sizes. The effect is compatible with experimental evidence available for concrete using small samples. Copyright © 2008 John Wiley & Sons, Ltd.     

Understanding carbonate factories through palaeoecological and sedimentological signals – Tribute to Luis Pomar

The carbonate factories, their controlling factors and their palaeoecological and sedimentological signals recorded in sedimentary successions are key elements for understanding the evolution of carbonate platform systems. Luis Pomar has dedicated most of his academic life to the study of carbonate rocks and carbonate factories. The idea for this special issue to celebrate Pomar’s career arose during a session at the 34^th International Association of Sedimentologists meeting held in Rome, entitled ‘Understanding carbonate factories through palaeoecological and geochemical signals’. The proposal encountered great response among participants, and additional contributions followed an email invitation to other specialists. This issue contains a variety of papers on carbonate sedimentology and carbonate factories. Here, an introduction that contextualizes the papers and key concepts discussed in this thematic issue is provided. It reviews Luis Pomar’s major achievements in carbonate sedimentology and discusses the evolution of the concept of the carbonate factory and the series of palaeoecological and sedimentological signals used to characterize the wide spectrum of carbonate depositional systems found in the natural world.     

Jupiter's obliquity and a long-lived circumplanetary disk

It has been claimed [Canup, R.M., Ward, W.R., 2002. Astron. J. 124, 3404-3423; Ward, W.R., 2003. In: AGU, Fall Meeting 2003] that a long-lived minimum mass circumplanetary gas disk is inconsistent with Jupiter's low obliquity. Here we find that while Jupiter's obliquity may constrain its characteristics it does not rule out a long-lived massive (compared to the mass of the Galilean satellites) disk. This is because the argument assumes a Solar System much like that of the present day with the one exception of a circumjovian disk which is then allowed to dissipate on a long timescale (¹⁰⁶-¹⁰⁷ yr). Given that the sequence of events in Solar System history that fit known constraints is non-unique, we choose for the sake of clarity of exposition the orbital architecture framework of Tsiganis et al. [Tsiganis, K., Gomes, R., Morbidelli, A., Levison, H.F., 2005. Nature 435, 459-461], in which Jupiter and Saturn were once in compact, nearly coplanar orbits, and show that in this case Jupiter's low obliquity is consistent with the SEMM (solids-enhanced minimum mass) satellite formation model of Mosqueira and Estrada [Mosqueira, I., Estrada, P.R., 2003a. Icarus 163, 198-231; Mosqueira, I., Estrada, P.R., 2003b. Icarus 163, 232-255]. We suggest that a low inclination starting condition may apply, but stress that our SEMM satellite formation model could be compatible with Jupiter's obliquity even for mutually inclined giant planets.     

A gas-poor planetesimal capture model for the formation of giant planet satellite systems

Assuming that an unknown mechanism (e.g., gas turbulence) removes most of the subnebula gas disk in a timescale shorter than that for satellite formation, we develop a model for the formation of regular (and possibly at least some of the irregular) satellites around giant planets in a gas-poor environment. In this model, which follows along the lines of the work of Safronov et al. [1986. Satellites. Univ. of Arizona Press, Tucson, pp. 89-116], heliocentric planetesimals collide within the planet's Hill sphere and generate a circumplanetary disk of prograde and retrograde satellitesimals extending as far out as ∼RH/2. At first, the net angular momentum of this proto-satellite swarm is small, and collisions among satellitesimals leads to loss of mass from the outer disk, and delivers mass to the inner disk (where regular satellites form) in a timescale ?¹⁰⁵ years. This mass loss may be offset by continued collisional capture of sufficiently small <1 km interlopers resulting from the disruption of planetesimals in the feeding zone of the giant planet. As the planet's feeding zone is cleared in a timescale ?¹⁰⁵ years, enough angular momentum may be delivered to the proto-satellite swarm to account for the angular momentum of the regular satellites of Jupiter and Saturn. This feeding timescale is also roughly consistent with the independent constraint that the Galilean satellites formed in a timescale of ¹⁰⁵-¹⁰⁶ years, which may be long enough to accommodate Callisto's partially differentiated state [Anderson et al., 1998. Science 280, 1573; Anderson et al., 2001. Icarus 153, 157-161]. In turn, this formation timescale can be used to provide plausible constraints on the surface density of solids in the satellitesimal disk (excluding satellite embryos for satellitesimals of size ∼1 km), which yields a total disk mass smaller than the mass of the regular satellites, and means that the satellites must form in several ∼10 collisional cycles. However, much more work will need to be conducted concerning the collisional evolution both of the circumplanetary satellitesimals and of the heliocentric planetesimals following giant planet formation before one can assess the significance of this agreement. Furthermore, for enough mass to be delivered to form the regular satellites in the required timescale one may need to rely on (unproven) mechanisms to replenish the feeding zone of the giant planet. We compare this model to the solids-enhanced minimum mass (SEMM) model of Mosqueira and Estrada [2003a. Icarus 163, 198-231; 2003b. Icarus 163, 232-255], and discuss its main consequences for Cassini observations of the saturnian satellite system.     

Intercomparison of measurements of bulk snow density and water equivalent of snow cover with snow core samplers: Instrumental bias and variability induced by observers

Manually collected snow data are often considered as ground truth for many applications such as climatological or hydrological studies. However, there are many sources of uncertainty that are not quantified in detail. For the determination of water equivalent of snow cover (SWE), different snow core samplers and scales are used, but they are all based on the same measurement principle. We conducted two field campaigns with 9 samplers commonly used in observational measurements and research in Europe and northern America to better quantify uncertainties when measuring depth, density and SWE with core samplers. During the first campaign, as a first approach to distinguish snow variability measured at the plot and at the point scale, repeated measurements were taken along two 20 m long snow pits. The results revealed a much higher variability of SWE at the plot scale (resulting from both natural variability and instrumental bias) compared to repeated measurements at the same spot (resulting mostly from error induced by observers or very small scale variability of snow depth). The exceptionally homogeneous snowpack found in the second campaign permitted to almost neglect the natural variability of the snowpack properties and focus on the separation between instrumental bias and error induced by observers. Reported uncertainties refer to a shallow, homogeneous tundra-taiga snowpack less than 1 m deep (loose, mostly recrystallised snow and no wind impact). Under such measurement conditions, the uncertainty in bulk snow density estimation is about 5% for an individual instrument and is close to 10% among different instruments. Results confirmed that instrumental bias exceeded both the natural variability and the error induced by observers, even in the case when observers were not familiar with a given snow core sampler.