A plume tectonics model for the Tharsis province, Mars

Morphological and structural data from the whole Tharsis province suggest that a number of shallow grabens radially oriented about the Tharsis bulge on Mars are underlain by dykes, which define giant radiating swarms similar to, e.g. the Mackenzie dyke swarm of the Canadian shield. Mechanisms for graben formation are proposed, and the depth, width, and height of the associated dykes are estimated. Structural mapping leads to define successive stages of dyke emplacement, and provide stress-trajectory maps that indicate a steady source of the regional stress during the whole history of the Tharsis province. A new tectonic model of Tharsis is presented, based on an analogy with dyke swarms on the Earth that form inside hot spots. This model successfully matches the following features: (1) the geometry of the South Tharsis Ridge Belt, which may have been a consequence of the compressional stress field at the boundary between the uplifted and non-uplifted areas in the upper part of the lithosphere at the onset of hot spot activity; (2) extensive lava flooding, interpreted as a consequence of the high thermal anomaly at the onset of plume (hot spot) activity; (3) wrinkle ridge geometry in the Tharsis hemisphere, the formation of which is interpreted as a consequence of buoyant subsidence of the brittle crust in response to the lava load; (4) Valles Marineris limited stretching by preliminary passive rifting, and uplift, viewed as a necessary consequence of adiabatic mantle decompression induced by stretching. The geometrical analysis of dyke swarms suggests the existence of a large, Tharsis-independent extensional state of stress during all the period of tectonic activity, in which the minimum compressive stress is roughly N---S oriented. Although magmatism must have loaded the lithosphere significantly after the plume activity ceased and be responsible for additional surface deformations, there is no requirement for further loading stress to explain surficial features. Comparison with succession of magmatic and tectonic events related to hot spots on the Earth suggests that the total time required to produce all the surface deformation observed in the Tharsis province over the last 3.8 Ga does probably not exceed 10 or 15 Ma.     

Sensitivity analysis of a deterministic water temperature model to forest canopy and soil temperature in Catamaran Brook (New Brunswick,Canada)

A coupled deterministic hydrological and water temperature model, CEQUEAU, was modified to include soil temperature and crown closure in its calculation of local advective terms in the heat budget. The modified model was than tested to verify its sensitivity to these modifications. An analysis of the heat budget of a small forested catchment in eastern Canada revealed that the advective term related to interflow plays a significant role in the daily water heat budget, providing on average 28% of the local advective budget (which also includes advective heat terms from surface runoff and groundwater) and nearly 14% of the total heat budget (which includes all radiative terms at the water surface, convection and evaporation, as well as the local advective terms). Relative sensitivity indices (RSIs) were used to verify the impact of the newly introduced parameters and variables. Among them, parameters related to the forest cover (crown closure and leaf area index) have a maximum RSI of ?0·6; i.e. a 100% increase in value produces a 60% decrease in the local advective term. Parameters with the greatest influence are the volume of water contributing to interflow and the amplitude of the net radiative flux at the soil surface, which, if doubled, would double the contribution of the local interflow advective term to the heat budget. Copyright © 2003 John Wiley & Sons, Ltd.     

Pressures of Crystallization of Icelandic Magmas

Iceland lies astride the Mid-Atlantic Ridge and was createdby seafloor spreading that began about 55 Ma. The crust is anomalouslythick (20–40 km), indicating higher melt productivityin the underlying mantle compared with normal ridge segmentsas a result of the presence of a mantle plume or upwelling centeredbeneath the northwestern edge of the Vatnajökull ice sheet.Seismic and volcanic activity is concentrated in 50 km wideneovolcanic or rift zones, which mark the subaerial Mid-AtlanticRidge, and in three flank zones. Geodetic and geophysical studiesprovide evidence for magma chambers located over a range ofdepths (1·5–21 km) in the crust, with shallow magmachambers beneath some volcanic centers (Katla, Grimsvötn,Eyjafjallajökull), and both shallow and deep chambers beneathothers (e.g. Krafla and Askja). We have compiled analyses ofbasalt glass with geochemical characteristics indicating crystallizationof ol–plag–cpx from 28 volcanic centers in the Western,Northern and Eastern rift zones as well as from the SouthernFlank Zone. Pressures of crystallization were calculated forthese glasses, and confirm that Icelandic magmas crystallizeover a wide range of pressures (0·001 to 1 GPa), equivalentto depths of 0–35 km. This range partly reflects crystallizationof melts en route to the surface, probably in dikes and conduits,after they leave intracrustal chambers. We find no evidencefor a shallow chamber beneath Katla, which probably indicatesthat the shallow chamber identified in other studies containssilica-rich magma rather than basalt. There is reasonably goodcorrelation between the depths of deep chambers (> 17 km)and geophysical estimates of Moho depth, indicating that magmaponds at the crust–mantle boundary. Shallow chambers (<7·1 km) are located in the upper crust, and probablyform at a level of neutral buoyancy. There are also discretechambers at intermediate depths (11 km beneath the rift zones),and there is strong evidence for cooling and crystallizing magmabodies or pockets throughout the middle and lower crust thatmight resemble a crystal mush. The results suggest that themiddle and lower crust is relatively hot and porous. It is suggestedthat crustal accretion occurs over a range of depths similarto those in recent models for accretionary processes at mid-oceanridges. The presence of multiple stacked chambers and hot, porouscrust suggests that magma evolution is complex and involvespolybaric crystallization, magma mixing, and assimilation. KEY WORDS: Iceland rift zones; cotectic crystallization; pressure; depth; magma chamber; volcanic glass     

Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Up to what temperature is petroleum stable? New insights from a 5200 free radical reactions model

The discovery of crude oils and condensates at ever higher temperatures casts doubt on the validity of the usual geochemical modelling approach, that uses empirical reactions and rate constants. The solution used to account for such a high thermal stability is presently to adjust the rate parameters, but the physical meaning and scientific value of such a strategy can be questioned. We have developed a mechanistic model consisting of 5200 lumped free radical reactions to describe the thermal evolution of a mixture of 52 organic species meant to represent light petroleum. Rate constants used are those available in the literature or estimated using well established thermochemistry-reactivity correlations. Chemical structures included in the model are linear, branched and cyclic hydrocarbons, hydro- and alkyl-aromatics, PAHs, and three heteroatomic compounds. Reactions include cracking and alkylation chains and inhibiting and accelerating reactions from the various reactants. This model has been applied to several mixtures with various proportions of reaction inhibitors and accelerators, and to a composition representing a light mature oil. From the results obtained, we conclude that mature oils will be stable up to 240–260 °C, depending on their composition, and that the thermal cracking of oil to gas is not possible under reasonable basin conditions. The kinetics of petroleum cracking are thus much slower than generally recognized.