Mesozoic climates: General circulation models and the rock record

General circulation models (GCMs) use the laws of physics and an understanding of past geography to simulate climatic responses. They are objective in character. However, they tend to require powerful computers to handle vast numbers of calculations. Nevertheless, it is now possible to compare results from different GCMs for a range of times and over a wide range of parameterisations for the past, present and future (e.g. in terms of predictions of surface air temperature, surface moisture, precipitation, etc.). GCMs are currently producing simulated climate predictions for the Mesozoic, which compare favourably with the distributions of climatically sensitive facies (e.g. coals, evaporites and palaeosols). They can be used effectively in the prediction of oceanic upwelling sites and the distribution of petroleum source rocks and phosphorites. Models also produce evaluations of other parameters that do not leave a geological record (e.g. cloud cover, snow cover) and equivocal phenomena such as storminess. Parameterisation of sub-grid scale processes is the main weakness in GCMs (e.g. land surfaces, convection, cloud behaviour) and model output for continental interiors is still too cold in winter by comparison with palaeontological data. The sedimentary and palaeontological record provides an important way that GCMs may themselves be evaluated and this is important because the same GCMs are being used currently to predict possible changes in future climate. The Mesozoic Earth was, by comparison with the present, an alien world, as we illustrate here by reference to late Triassic, late Jurassic and late Cretaceous simulations. Dense forests grew close to both poles but experienced months-long daylight in warm summers and months-long darkness in cold snowy winters. Ocean depths were warm (8 degrees C or more to the ocean floor) and reefs, with corals, grew 10 degrees of latitude further north and south than at the present time. The whole Earth was warmer than now by 6 degrees C or more, giving more atmospheric humidity and a greatly enhanced hydrological cycle. Much of the rainfall was predominantly convective in character, often focused over the oceans and leaving major desert expanses on the continental areas. Polar ice sheets are unlikely to have been present because of the high summer temperatures achieved. The model indicates extensive sea ice in the nearly enclosed Arctic seaway through a large portion of the year during the late Cretaceous, and the possibility of sea ice in adjacent parts of the Midwest Seaway over North America. The Triassic world was a predominantly warm world, the model output for evaporation and precipitation conforming well with the known distributions of evaporites, calcretes and other climatically sensitive facies for that time. The message from the geological record is clear. Through the Phanerozoic, Earth's climate has changed significantly, both on a variety of time scales and over a range of climatic states, usually baldly referred to as "greenhouse" and "icehouse", although these terms disguise more subtle states between these extremes. Any notion that the climate can remain constant for the convenience of one species of anthropoid is a delusion (although the recent rate of climatic change is exceptional). (c) 2006 Elsevier B.V. All rights reserved.

Selectivity of bis(calix[4]diquinone) ionophores towards metal ions in solvent dimethylsulfoxide: a molecular mechanics and molecular dynamics study

Molecular modelling studies have been carried out on two bis(calix[4]diqu(inone) ionophores, each created from two (calix[4]diquinone)arenes bridged at their bottom rims via alkyl chains (CH2)(n), 1: n = 3, 2; n = 4, in order to understand the reported selectivity of these ligands towards different sized metal ions such as Na+, K+, Rb+, and Cs+ in dmso solution. Conformational. analyses have been carried out which show that in the lowest energy conformations of the two macrocycles, the individual calix[4]diquinones exhibit a combination of partial cone, 1,3-alternate and cone conformations. The interactions of these alkali metals with the macrocycles have been studied in the gas phase and in a periodic box of solvent dmso by molecular mechanics and molecular dynamics calculations. Molecular mechanics calculations have been carried out on the mode of entry of the ions into the macrocycles and suggest that this is likely to occur from the side of the central cavity, rather than through the main axis of the calix[4]diquinones. There are energy barriers of ca. 19 kcal mol(-1) for this entry path in the gas phase, but in solution no energy barrier is found. Molecular dynamics simulations show that in both 1 and 2, though particularly in the latter macrocycle, one or two solvent molecules are bonded to the metal throughout the course of the simulation, often to the exclusion, of one or more of the ether oxygen atoms. By contrast the carbonyl oxygen atoms remain bonded to the metal atoms throughout with bond lengths that remain significantly less than those to the ether oxygen atoms. Free energy perturbation studies have been carried out in dmso and indicate that for 1, the selectivity follows the order Rb+ approximate to K+ > Cs+ >> Na+, which is partially in agreement with the experimental results. The energy differences are small and indeed the ratio between stability constants found for Cs+ and K+ complexes is only 0.60, showing that 1 has only a slight preference for K+. For the larger receptor 2, which is better suited to metal complexation, the binding affinity follows the pattern Cs+ >> Rb+ >> K+ >> Na+, with energy differences of 5.75, 2.61, 2.78 kcal mol(-1) which is perfectly consistent with experimental results.

Quantum mechanics studies of the tautomers of dlhydrodiacetylformoin, an important Maillard intermediate and the synthesis of furaneol

Conformational analyses have been carried out on the acyclic and cyclic forms of dihydrodiacetylformoin, an important Maillard intermediate and precursor for furaneol. For the acyclic forms, the 2,5-dicarbonyl isomers have the lowest energy, while for the cyclic forms, the 3-carbonyl are favoured over the 4-carbonyl isomers. The likely path for cyclisation is investigated and it is shown that the favoured path is dependent upon the relative chiralities of the carbon atoms and in particular that the reaction proceeds more readily if C2 and C3 have different chiralities. After cyclisation, the reaction path to produce furaneol proceeds via the loss of a water molecule. This reaction has been studied with a model including two water molecules and a hydroxide anion and shows relatively low-energy barriers. (C) 2008 Published by Elsevier B.V.

Modelling metal cutting using modern ductile fracture mechanics: Quantitative explanations for some longstanding problems

The assumption that negligible work is involved in the formation of new surfaces in the machining of ductile metals, is re-examined in the light of both current Finite Element Method (FEM) simulations of cutting and modern ductile fracture mechanics. The work associated with separation criteria in FEM models is shown to be in the kJ/m2 range rather than the few J/m2 of the surface energy (surface tension) employed by Shaw in his pioneering study of 1954 following which consideration of surface work has been omitted from analyses of metal cutting. The much greater values of surface specific work are not surprising in terms of ductile fracture mechanics where kJ/m2 values of fracture toughness are typical of the ductile metals involved in machining studies. This paper shows that when even the simple Ernst–Merchant analysis is generalised to include significant surface work, many of the experimental observations for which traditional ‘plasticity and friction only’ analyses seem to have no quantitative explanation, are now given meaning. In particular, the primary shear plane angle φ becomes material-dependent. The experimental increase of φ up to a saturated level, as the uncut chip thickness is increased, is predicted. The positive intercepts found in plots of cutting force vs. depth of cut, and in plots of force resolved along the primary shear plane vs. area of shear plane, are shown to be measures of the specific surface work. It is demonstrated that neglect of these intercepts in cutting analyses is the reason why anomalously high values of shear yield stress are derived at those very small uncut chip thicknesses at which the so-called size effect becomes evident. The material toughness/strength ratio, combined with the depth of cut to form a non-dimensional parameter, is shown to control ductile cutting mechanics. The toughness/strength ratio of a given material will change with rate, temperature, and thermomechanical treatment and the influence of such changes, together with changes in depth of cut, on the character of machining is discussed. Strength or hardness alone is insufficient to describe machining. The failure of the Ernst–Merchant theory seems less to do with problems of uniqueness and the validity of minimum work, and more to do with the problem not being properly posed. The new analysis compares favourably and consistently with the wide body of experimental results available in the literature. Why considerable progress in the understanding of metal cutting has been achieved without reference to significant surface work is also discussed.

An investigation into the mechanics of cutting using data from orthogonally cutting Nylon 66

Cutting force data for Nylon 66 has been examined in terms of various different models of cutting. Theory that includes significant work of separation at the tool tip was found to give the best correlation with experimental data over a wide range of rake angles for derived primary shear plane angle. A fracture toughness parameter was used as the measure of the specific work of separation. Variation in toughness with rake angle determined from cutting is postulated to be caused by mixed mode separation at the tool tip. A rule of mixtures using independently determined values of toughness in tension (mode 1) and shear (mode 11) is found to describe well the variation with rake angle. The ratio of modes varies with rake angle and, in turn, with the primary shear plane angle. Previous suggestions that cutting is a means of experimentally determining fracture toughness are now seen to be extended to identify the mode of fracture toughness as well.

Age relationships beteen low level rock platforms and the high coastal slopes in Jersey and the surrounding area.

Recent research along the coastal cliffs and embayments of Jersey has revealed new aspects of the geomorphology of the rocky shore platform and its relationship with the steep slopes that link it to the island plateau above. Specifically, a rockhead platform meets a 10-30 m high, near vertical cliff at approximately 8-10 m above Jersey Datum (J.D.= ±0 m Ordnance Datum; likewise Guernsey Datum: G.D.), slopes down-towards mid-tide levels becoming ever more deeply dissected. Generalised contours of this platform show it to be distinct from a lower tidal rockhead platform which is comparatively smooth over large areas as it undergoes continuing contemporary abrasion. This lower platform is generally separated from the higher one by low cliffs, less than a metre high at mid-tidal levels, but two to three metres at the base of the backing cliffs. Both of these platforms are shown to antedate the Last Cold Stage (Devensian) head at a number of localities and this relationship is taken to represent the general situation, not only in Jersey, but throughout the other Channel Islands and adjacent coasts of Armorica. Whether either, or both, of these two platforms are older than Marine Oxygen Isotope Substage (MOIS) 5e (Ipswichian) as well is not known. However the considerable age of the numerous and wide intertidal shore platforms of the Channel Islands and adjacent coasts of Amorica makes a greater age quite possible.

Quantum mechanics studies of the tautomers of diacetylformoin, an important maillard product and odorant

Diacetylformoin (3,4-dihydroxy-3-hexene-2,5-dione) has 16 tautomers, many with several possible conformations and all have been geometry optimised using quantum mechanics at the HF/6-31+G* level. Eleven structures have been identified with energies within 10 kcal mol(-1) of the minimum energy structure. Of these eight are acyclic and three cyclic. Calculations of NMR spectra have clarified the identity of the acyclic and cyclic structures found experimentally. The mechanism for cyclisation has been investigated and transition states obtained. The lowest energy reaction path requires the loss and gain of a proton during cyclisation. (c) 2006 Elsevier B.V. All rights reserved.