Mechanisms of ocean heat uptake in a coupled climate model and the implications for tracer based predictions of ocean heat uptake

The distribution of tracers in the ocean is often taken as an indication of the ventilation pathways for oceanic water masses. It has been suggested that under anthropogenic forcing heat will be taken up into the interior of the ocean along isopycnal ventilation pathways. This notion is investigated by examining distributions of potential temperature and a passive anomaly temperature tracer in a coupled climate experiment where CO2 is increased at a rate of 2% per year. We show that interior temperature changes cannot be explained solely by passive tracer transport along isopycnals. Heat uptake is strongly affected by changes in circulation and has a substantial diapycnal component.

Predicting magnetospheric dynamics with a coupled sun-to-Earth model: challenges and first results

Results from the first Sun-to-Earth coupled numerical model developed at the Center for Integrated Space Weather Modeling are presented. The model simulates physical processes occurring in space spanning from the corona of the Sun to the Earth's ionosphere, and it represents the first step toward creating a physics-based numerical tool for predicting space weather conditions in the near-Earth environment. Two 6- to 7-d intervals, representing different heliospheric conditions in terms of the three-dimensional configuration of the heliospheric current sheet, are chosen for simulations. These conditions lead to drastically different responses of the simulated magnetosphere-ionosphere system, emphasizing, on the one hand, challenges one encounters in building such forecasting tools, and on the other hand, emphasizing successes that can already be achieved even at this initial stage of Sun-to-Earth modeling.

ENSO at 6ka and 21ka from ocean–atmosphere coupled model simulations

We analyze how the characteristics of El Niño-Southern Oscillation (ENSO) are changed in coupled ocean–atmosphere simulations of the mid-Holocene (MH) and the Last Glacial Maximum (LGM) performed as part of the Paleoclimate Modeling Intercomparison Project phase 2 (PMIP2). Comparison of the model results with present day observations show that most of the models reproduce the large scale features of the tropical Pacific like the SST gradient, the mean SST and the mean seasonal cycles. All models simulate the ENSO variability, although with different skill. Our analyses show that several relationships between El Niño amplitude and the mean state across the different control simulations are still valid for simulations of the MH and the LGM. Results for the MH show a consistent El Niño amplitude decrease. It can be related to the large scale atmospheric circulation changes. While the Northern Hemisphere receives more insolation during the summer time, the Asian summer monsoon system is strengthened which leads to the enhancement of the Walker circulation. Easterlies prevailing over the central eastern Pacific induce an equatorial upwelling that damps the El Niño development. Results are less conclusive for 21ka. Large scale dynamic competes with changes in local heat fluxes, so that model shows a wide range of responses, as it is the case in future climate projections.

Representing El Niño in coupled ocean–atmosphere GCMs: the dominant role of the atmospheric component

A systematic modular approach to investigate the respective roles of the ocean and atmosphere in setting El Niño characteristics in coupled general circulation models is presented. Several state-of-the-art coupled models sharing either the same atmosphere or the same ocean are compared. Major results include 1) the dominant role of the atmosphere model in setting El Niño characteristics (periodicity and base amplitude) and errors (regularity) and 2) the considerable improvement of simulated El Niño power spectra—toward lower frequency—when the atmosphere resolution is significantly increased. Likely reasons for such behavior are briefly discussed. It is argued that this new modular strategy represents a generic approach to identifying the source of both coupled mechanisms and model error and will provide a methodology for guiding model improvement.

The role of lateral ocean physics in the upper ocean thermal balance of a coupled ocean-atmosphere GCM

The sensitivity of the upper ocean thermal balance of an ocean-atmosphere coupled GCM to lateral ocean physics is assessed. Three 40-year simulations are performed using horizontal mixing, isopycnal mixing, and isopycnal mixing plus eddy induced advection. The thermal adjustment of the coupled system is quite different between the simulations, confirming the major role of ocean mixing on the heat balance of climate. The initial adjustment phase of the upper ocean (SST) is used to diagnose the physical mechanisms involved in each parametrisation. When the lateral ocean physics is modified, significant changes of SST are seen, mainly in the southern ocean. A heat budget of the annual mixed layer (defined as the “bowl”) shows that these changes are due to a modified heat transfer between the bowl and the ocean interior. This modified heat intake of the ocean interior is directly due to the modified lateral ocean physics. In isopycnal diffusion, this heat exchange, especially marked at mid-latitudes, is both due to an increased effective surface of diffusion and to the sign of the isopycnal gradients of temperature at the base of the bowl. As this gradient is proportional to the isopycnal gradient of salinity, this confirms the strong role of salinity in the thermal balance of the coupled system. The eddy induced advection also leads to increased exchanges between the bowl and the ocean interior. This is both due to the shape of the bowl and again to the existence of a salinity structure. The lateral ocean physics is shown to be a significant contributor to the exchanges between the diabatic and the adiabatic parts of the ocean.

Performance of the OPA/ARPEGE-T21 global ocean-atmosphere coupled model

The climatology of the OPA/ARPEGE-T21 coupled general circulation model (GCM) is presented. The atmosphere GCM has a T21 spectral truncation and the ocean GCM has a 2°×1.5° average resolution. A 50-year climatic simulation is performed using the OASIS coupler, without flux correction techniques. The mean state and seasonal cycle for the last 10 years of the experiment are described and compared to the corresponding uncoupled experiments and to climatology when available. The model reasonably simulates most of the basic features of the observed climate. Energy budgets and transports in the coupled system, of importance for climate studies, are assessed and prove to be within available estimates. After an adjustment phase of a few years, the model stabilizes around a mean state where the tropics are warm and resemble a permanent ENSO, the Southern Ocean warms and almost no sea-ice is left in the Southern Hemisphere. The atmospheric circulation becomes more zonal and symmetric with respect to the equator. Once those systematic errors are established, the model shows little secular drift, the small remaining trends being mainly associated to horizontal physics in the ocean GCM. The stability of the model is shown to be related to qualities already present in the uncoupled GCMs used, namely a balanced radiation budget at the top-of-the-atmosphere and a tight ocean thermocline.

Impact of the Atlantic Ocean on the multidecadal fluctuation of El Nino–Southern Oscillation–South Asian monsoon relationship in a coupled general circulation model

The multidecadal variability of El Niño–Southern Oscillation (ENSO)–South Asian monsoon relationship is elucidated in a 1000 year control simulation of a coupled general circulation model. The results indicate that the Atlantic Multidecadal Oscillation (AMO), resulting from the natural fluctuation of the Atlantic Meridional Overturning Circulation (AMOC), plays an important role in modulating the multidecadal variation of the ENSO-monsoon relationship. The sea surface temperature anomalies associated with the AMO induce not only significant climate impact in the Atlantic but also the coupled feedbacks in the tropical Pacific regions. The remote responses in the Pacific Ocean to a positive phase of the AMO which is resulted from enhanced AMOC in the model simulation and are characterized by statistically significant warming in the North Pacific and in the western tropical Pacific, a relaxation of tropical easterly trades in the central and eastern tropical Pacific, and a deeper thermocline in the eastern tropical Pacific. These changes in mean states lead to a reduction of ENSO variability and therefore a weakening of the ENSO-monsoon relationship. This study suggests a nonlocal mechanism for the low-frequency fluctuation of the ENSO-monsoon relationship, although the AMO explains only a fraction of the ENSO–South Asian monsoon variation on decadal-multidecadal timescale. Given the multidecadal variation of the AMOC and therefore of the AMO exhibit decadal predictability, this study highlights the possibility that a part of the change of climate variability in the Pacific Ocean and its teleconnection may be predictable.

Development and assessment of a coupled crop-climate model

It is well established that crop production is inherently vulnerable to variations in the weather and climate. More recently the influence of vegetation on the state of the atmosphere has been recognized. The seasonal growth of crops can influence the atmosphere and have local impacts on the weather, which in turn affects the rate of seasonal crop growth and development. Considering the coupled nature of the crop-climate system, and the fact that a significant proportion of land is devoted to the cultivation of crops, important interactions may be missed when studying crops and the climate system in isolation, particularly in the context of land use and climate change. To represent the two-way interactions between seasonal crop growth and atmospheric variability, we integrate a crop model developed specifically to operate at large spatial scales (General Large Area Model for annual crops) into the land surface component of a global climate model (GCM; HadAM3). In the new coupled crop-climate model, the simulated environment (atmosphere and soil states) influences growth and development of the crop, while simultaneously the temporal variations in crop leaf area and height across its growing season alter the characteristics of the land surface that are important determinants of surface fluxes of heat and moisture, as well as other aspects of the land-surface hydrological cycle. The coupled model realistically simulates the seasonal growth of a summer annual crop in response to the GCM's simulated weather and climate. The model also reproduces the observed relationship between seasonal rainfall and crop yield. The integration of a large-scale single crop model into a GCM, as described here, represents a first step towards the development of fully coupled crop and climate models. Future development priorities and challenges related to coupling crop and climate models are discussed.

Gas phase kinetic and quantum chemical studies of the reactions of silylene with the methylsilanes. Absolute rate constants, temperature dependences, RRKM modelling and potential energy surfaces

Time resolved studies of silylene, SiH2, generated by the 193 nm laser. ash photolysis of phenylsilane, have been carried out to obtain rate coefficients for its bimolecular reactions with methyl-, dimethyl- and trimethyl-silanes in the gas phase. The reactions were studied over the pressure range 3 - 100 Torr with SF6 as bath gas and at five temperatures in the range 300 - 625 K. Only slight pressure dependences were found for SiH2 + MeSiH3 ( 485 and 602 K) and for SiH2 + Me2SiH2 ( 600 K). The high pressure rate constants gave the following Arrhenius parameters: [GRAPHICS] These are consistent with fast, near to collision-controlled, association processes. RRKM modelling calculations are consistent with the observed pressure dependences ( and also the lack of them for SiH2 + Me3SiH). Ab initio calculations at both second order perturbation theory (MP2) and coupled cluster (CCSD(T)) levels, showed the presence of weakly-bound complexes along the reaction pathways. In the case of SiH2 + MeSiH3 two complexes, with different geometries, were obtained consistent with earlier studies of SiH2 + SiH4. These complexes were stabilised by methyl substitution in the substrate silane, but all had exceedingly low barriers to rearrangement to product disilanes. Although methyl groups in the substrate silane enhance the intrinsic SiH2 insertion rates, it is doubtful whether the intermediate complexes have a significant effect on the kinetics. A further calculation on the reaction MeSiH + SiH4 shows that the methyl substitution in the silylene should have a much more significant kinetic effect ( as observed in other studies).

Facile synthesis of Cu(II) complexes of monocondensed N,N,N donor Schiff base ligands: crystal structure, spectroscopic and magnetic properties

Four new copper(II) complexes, [((CuLN3)-N-1)(2)](ClO4)(2) (1), [(CuL2 N-3)(2)](ClO4)(2) (2), [CuL3(N-3)ClO4)](n) (3) and [CuL4(mu-1,1-N-3)(mu-1,3-N-3)(ClO4)](n) (4) where L-1 = N-1-pyridin-2-yl-methylene-propane-1,3-diamine, L-2 = N-1-(1-pyridin-2-yl-ethylidene)propane-1,3-diamine, L-3 =N-1-(1-pyridin-2-yl-ethylidene)ethane-1,2-diamine and L-4=N-1-(1-pyridin-2-yl-ethylidene)propane-1,2-diamine are four tridentate N,N,N donor Schiff base ligands, have been derived and structurally characterized by X-ray crystallography. Compounds 1 and 2 consist of double basal-apical end-on (EO) azide bridged dinuclear Cu-II complexes with square-pyramidal geometry. In complex 3 the square planar mononuclear [CuL3 (N-3)] units are linked by weakly coordinated perchlorate ions in the axial positions of Cu-II to form a one-dimensional chain. Two such chains are connected by hydrogen bonds involving perchlorate ions and azide groups. Compound 4 consists of 1-D chains in which the Cu-II ions with a square-pyramidal geometry are alternately bridged by single EO and end-to-end (EE) azido ligands, both adopting a basal-apical disposition. Variable temperature (300-2 K) magnetic susceptibility measurements and magnetization measurements at 2 K have been performed. The results reveal that complexes 1 and 2 are antiferromagnetically coupled through azido bridges (J= -12.18 +/- 0.09 and -4.43 +/- 0.1 cm(-1) for 1 and 2, respectively). Complex 3 shows two different magnetic interactions through the two kinds of hydrogen bonds; one is antiferromagnetic (J(1) = - 9.69 +/- 0.03 cm(-1)) and the other is ferromagnetic (J(2) = 1.00 +/- 0.01 cm(-1)). From a magnetic point of view complex 4 is a ferromagnetic dinuclear complex (J= 1.91 +/- 0.01 cm(-1)) coupled through the EO bridge only. The coupling through the EE bridge is practically nil as the N(azido)-Cu-II (axial) distance (2.643 angstrom) is too long. (C) 2006 Elsevier Ltd. All rights reserved.

Concomitant polymorphism of an antiferromagnetically coupled dicopper(II,II) complex with single strand helical assembly: synthesis, structure, DSC, magnetic and heterogeneous catalytic studies

Two concomitant polymorphic coordination complexes (dark blue - I and black - II) with the formula (Cu2C44H60N4O4) have been synthesized and characterized crystallographically. Magnetic measurements show the presence of a strong antiferromagnetic interaction and the 2J value corresponds extremely well to the theoretically calculated one, indicating the fact that it follows nicely the magneto-structural relationship. Immobilization of the copper(II) complex I on a 2D-hexagonal mesoporous silica showed good catalytic efficiency in the liquid phase partial oxidation of olefins in the presence of TBHP as an oxidant. (C) 2009 Elsevier Ltd. All rights reserved.

A diphenoxo bridged antiferromagnetically coupled dimer of copper(II) having bridging methanol

A dinuclear copper(II) complex, (mu2-MeOH)bis(mu(2)-phenoxide)dicopper complex with N-(3-aminopropyl)salicylaidimine, has been synthesised and characterised by X-ray structure determination. Variable temperature magnetic susceptibility measurement shows that it is strongly antiferromagnetically coupled. (C) 2003 Elsevier Science B.V. All rights reserved.