Understanding mixing efficiency in the oceans. Do the nonlinearities of the equation of state matter?

There exist two central measures of turbulent mixing in turbulent stratified fluids that are both caused by molecular diffusion: 1) the dissipation rate D(APE) of available potential energy APE; 2) the turbulent rate of change Wr, turbulent of background gravitational potential energy GPEr. So far, these two quantities have often been regarded as the same energy conversion, namely the irreversible conversion of APE into GPEr, owing to the well known exact equality D(APE)=Wr, turbulent for a Boussinesq fluid with a linear equation of state. Recently, however, Tailleux (2009) pointed out that the above equality no longer holds for a thermally-stratified compressible, with the ratio ξ=Wr, turbulent/D(APE) being generally lower than unity and sometimes even negative for water or seawater, and argued that D(APE) and Wr, turbulent actually represent two distinct types of energy conversion, respectively the dissipation of APE into one particular subcomponent of internal energy called the "dead" internal energy IE0, and the conversion between GPEr and a different subcomponent of internal energy called "exergy" IEexergy. In this paper, the behaviour of the ratio ξ is examined for different stratifications having all the same buoyancy frequency N vertical profile, but different vertical profiles of the parameter Υ=α P/(ρCp), where α is the thermal expansion coefficient, P the hydrostatic pressure, ρ the density, and Cp the specific heat capacity at constant pressure, the equation of state being that for seawater for different particular constant values of salinity. It is found that ξ and Wr, turbulent depend critically on the sign and magnitude of dΥ/dz, in contrast with D(APE), which appears largely unaffected by the latter. These results have important consequences for how the mixing efficiency should be defined and measured in practice, which are discussed.

Simulated global-mean sea level changes over the last half-millennium

Simulations of the last 500 yr carried out using the Third Hadley Centre Coupled Ocean-Atmosphere GCM (HadCM3) with anthropogenic and natural (solar and volcanic) forcings have been analyzed. Global-mean surface temperature change during the twentieth century is well reproduced. Simulated contributions to global-mean sea level rise during recent decades due to thermal expansion (the largest term) and to mass loss from glaciers and ice caps agree within uncertainties with observational estimates of these terms, but their sum falls short of the observed rate of sea level rise. This discrepancy has been discussed by previous authors; a completely satisfactory explanation of twentieth-century sea level rise is lacking. The model suggests that the apparent onset of sea level rise and glacier retreat during the first part of the nineteenth century was due to natural forcing. The rate of sea level rise was larger during the twentieth century than during the previous centuries because of anthropogenic forcing, but decreasing natural forcing during the second half of the twentieth century tended to offset the anthropogenic acceleration in the rate. Volcanic eruptions cause rapid falls in sea level, followed by recovery over several decades. The model shows substantially less decadal variability in sea level and its thermal expansion component than twentieth-century observations indicate, either because it does not generate sufficient ocean internal variability, or because the observational analyses overestimate the variability.

Understanding projections of sea level rise in a Hadley Centre coupled climate model

Sea level changes resulting from CO2-induced climate changes in ocean density and circulation have been investigated in a series of idealised experiments with the Hadley Centre HadCM3 AOGCM. Changes in the mass of the ocean were not included. In the global mean, salinity changes have a negligible effect compared with the thermal expansion of the ocean. Regionally, sea level changes are projected to deviate greatly from the global mean (standard deviation is 40% of the mean). Changes in surface fluxes of heat, freshwater and wind stress are all found to produce significant and distinct regional sea level changes, wind stress changes being the most important and the cause of several pronounced local features, while heat and freshwater flux changes affect large parts of the North Atlantic and Southern Ocean. Regional change is related mainly to density changes, with a relatively small contribution in mid and high latitudes from change in the barotropic circulation. Regional density change has an important contribution from redistribution of ocean heat content. In general, unlike in the global mean, the regional pattern of sea level change due to density change appears to be influenced almost as much by salinity changes as by temperature changes, often in opposition. Such compensation is particularly marked in the North Atlantic, where it is consistent with recent observed changes. We suggest that density compensation is not a property of climate change specifically, but a general behavior of the ocean.

Aperiodicity, structure, and dynamics in Ni(CN)(2)

By combining the results of both x-ray diffraction and neutron total-scattering experiments, we show that Ni(CN)(2) exhibits long-range structural order only in two dimensions, with no true periodicity perpendicular to its gridlike layers. Reverse Monte Carlo analysis gives an experimental distinction between M-C and M-N bond lengths in a homometallic cyanide framework and identifies the vibrational modes responsible for anomalous positive and negative thermal expansion in the title compound.

Structure of AuCN determined from total neutron diffraction

The structure of gold cyanide, AuCN, has been determined at 10 and 300 K using total neutron diffraction. The structure consists of infinite -Au-(CN)-Au-(CN)-Au-(CN)- linear chains, hexagonally packed, with the gold atoms in sheets. The Au-C and Au-N bond lengths are found to be identical, with d(Au-C/N) = 1.9703(5) Angstrom at 300 K. This work supersedes a previous study, by others, which used Rietveld analysis of neutron Bragg diffraction in isolation, and found these bonds to have significantly different lengths (Deltad = 0.24 Angstrom) at 300 K. The total correlation function, T(r), at 10 and 300 K, has been modeled using information derived from total diffraction. The broadening of inter- and intrachain correlations differs markedly due to random displacements of the chains in the direction of the chain axes. This is a consequence of the relatively weak bonding between the chains. An explanation for the negative thermal expansion in the c-direction, which occurs between 10 and 300 K, is presented.

Comparison of results from several AOGCMs for global and regional sea-level change 1900-2100

Sea-level rise is an important aspect of climate change because of its impact on society and ecosystems. Here we present an intercomparison of results from ten coupled atmosphere-ocean general circulation models (AOGCMs) for sea-level changes simulated for the twentieth century and projected to occur during the twenty first century in experiments following scenario IS92a for greenhouse gases and sulphate aerosols. The model results suggest that the rate of sea-level rise due to thermal expansion of sea water has increased during the twentieth century, but the small set of tide gauges with long records might not be adequate to detect this acceleration. The rate of sea-level rise due to thermal expansion continues to increase throughout the twenty first century, and the projected total is consequently larger than in the twentieth century; for 1990-2090 it amounts to 0.20-0.37 in. This wide range results from systematic uncertainty in modelling of climate change and of heat uptake by the ocean. The AOGCMs agree that sea-level rise is expected to be geographically non-uniform, with some regions experiencing as much as twice the global average, and others practically zero, but they do not agree about the geographical pattern. The lack of agreement indicates that we cannot currently have confidence in projections of local sea- level changes, and reveals a need for detailed analysis and intercomparison in order to understand and reduce the disagreements.

Understanding and projecting sea level change

There is intense scientific and public interest in the Intergovernmental Panel on Climate Change (IPCC) projections of sea level for the twenty-first century and beyond. The Fourth Assessment Report (AR4) projections, obtained by applying standard methods to the results of the World Climate Research Programme Coupled Model Experiment, includes estimates of ocean thermal expansion, the melting of glaciers and ice caps (G&ICs), increased melting of the Greenland Ice Sheet, and increased precipitation over Greenland and Antarctica, partially offsetting other contributions. The AR4 recognized the potential for a rapid dynamic ice sheet response but robust methods for quantifying it were not available. Illustrative scenarios suggested additional sea level rise on the order of 10 to 20 cm or more, giving a wide range in the global averaged projections of about 20 to 80 cm by 2100. Currently, sea level is rising at a rate near the upper end of these projections. Since publication of the AR4 in 2007, biases in historical ocean temperature observations have been identified and significantly reduced, resulting in improved estimates of ocean thermal expansion. Models that include all climate forcings are in good agreement with these improved observations and indicate the importance of stratospheric aerosol loadings from volcanic eruptions. Estimates of the volumes of G&ICs and their contributions to sea level rise have improved. Results from recent (but possibly incomplete) efforts to develop improved ice sheet models should be available for the 2013 IPCC projections. Improved understanding of sea level rise is paving the way for using observations to constrain projections. Understanding of the regional variations in sea level change as a result of changes in ocean properties, wind-stress patterns, and heat and freshwater inputs into the ocean is improving. Recently, estimates of sea level changes resulting from changes in Earth's gravitational field and the solid Earth response to changes in surface loading have been included in regional projections. While potentially valuable, semi-empirical models have important limitations, and their projections should be treated with caution

Revisiting the Earth's sea-level and energy budgets from 1961 to 2008

We review the sea-level and energy budgets together from 1961, using recent and updated estimates of all terms. From 1972 to 2008, the observed sea-level rise (1.8 ± 0.2 mm yr−1 from tide gauges alone and 2.1 ± 0.2 mm yr−1 from a combination of tide gauges and altimeter observations) agrees well with the sum of contributions (1.8 ± 0.4 mm yr−1) in magnitude and with both having similar increases in the rate of rise during the period. The largest contributions come from ocean thermal expansion (0.8 mm yr−1) and the melting of glaciers and ice caps (0.7 mm yr−1), with Greenland and Antarctica contributing about 0.4 mm yr−1. The cryospheric contributions increase through the period (particularly in the 1990s) but the thermosteric contribution increases less rapidly. We include an improved estimate of aquifer depletion (0.3 mm yr−1), partially offsetting the retention of water in dams and giving a total terrestrial storage contribution of −0.1 mm yr−1. Ocean warming (90% of the total of the Earth's energy increase) continues through to the end of the record, in agreement with continued greenhouse gas forcing. The aerosol forcing, inferred as a residual in the atmospheric energy balance, is estimated as −0.8 ± 0.4 W m−2 for the 1980s and early 1990s. It increases in the late 1990s, as is required for consistency with little surface warming over the last decade. This increase is likely at least partially related to substantial increases in aerosol emissions from developing nations and moderate volcanic activity

Ocean heat uptake and its consequences for the magnitude of sea level rise and climate change

Under increasing greenhouse gas concentrations, ocean heat uptake moderates the rate of climate change, and thermal expansion makes a substantial contribution to sea level rise. In this paper we quantify the differences in projections among atmosphere-ocean general circulation models of the Coupled Model Intercomparison Project in terms of transient climate response, ocean heat uptake efficiency and expansion efficiency of heat. The CMIP3 and CMIP5 ensembles have statistically indistinguishable distributions in these parameters. The ocean heat uptake efficiency varies by a factor of two across the models, explaining about 50% of the spread in ocean heat uptake in CMIP5 models with CO2 increasing at 1%/year. It correlates with the ocean global-mean vertical profiles both of temperature and of temperature change, and comparison with observations suggests the models may overestimate ocean heat uptake and underestimate surface warming, because their stratification is too weak. The models agree on the location of maxima of shallow ocean heat uptake (above 700 m) in the Southern Ocean and the North Atlantic, and on deep ocean heat uptake (below 2000 m) in areas of the Southern Ocean, in some places amounting to 40% of the top-to-bottom integral in the CMIP3 SRES A1B scenario. The Southern Ocean dominates global ocean heat uptake; consequently the eddy-induced thickness diffusivity parameter, which is particularly influential in the Southern Ocean, correlates with the ocean heat uptake efficiency. The thermal expansion produced by ocean heat uptake is 0.12 m YJ−1, with an uncertainty of about 10% (1 YJ = 1024 J).

Mixed copper, silver, and gold cyanides, (MxM′1–x)CN: tailoring chain structures to influence physical properties

Binary mixed-metal variants of the one-dimensional MCN compounds (M = Cu, Ag, and Au) have been prepared and characterized using powder X-ray diffraction, vibrational spectroscopy, and total neutron diffraction. A solid solution with the AgCN structure exists in the (CuxAg1–x)CN system over the range (0 ≤ x ≤ 1). Line phases with compositions (Cu1/2Au1/2)CN, (Cu7/12Au5/12)CN, (Cu2/3Au1/3)CN, and (Ag1/2Au1/2)CN, all of which have the AuCN structure, are found in the gold-containing systems. Infrared and Raman spectroscopies show that complete ordering of the type [M–C≡N–M′–N≡C−]n occurs only in (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN. The sense of the cyanide bonding was determined by total neutron diffraction to be [Ag–NC–Au–CN−]n in (Ag1/2Au1/2)CN and [Cu–NC–Au–CN−]n in (Cu1/2Au1/2)CN. In contrast, in (Cu0.50Ag0.50)CN, metal ordering is incomplete, and strict alternation of metals does not occur. However, there is a distinct preference (85%) for the N end of the cyanide ligand to be bonded to copper and for Ag–CN–Cu links to predominate. Contrary to expectation, aurophilic bonding does not appear to be the controlling factor which leads to (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN adopting the AuCN structure. The diffuse reflectance, photoluminescence, and 1-D negative thermal expansion (NTE) behaviors of all three systems are reported and compared with those of the parent cyanide compounds. The photophysical properties are strongly influenced both by the composition of the individual chains and by how such chains pack together. The NTE behavior is also controlled by structure type: the gold-containing mixed-metal cyanides with the AuCN structure show the smallest contraction along the chain length on heating.

Extending Murty interferometry to the Terahertz part of the spectrum

We discuss some novel technologies that enable the implementation of shearing interferometry at the terahertz part of the spectrum. Possible applications include the direct measurement of lens parameters, the measurement of refractive index of materials that are transparent to terahertz frequencies, determination of homogeneity of samples, measurement of optical distortions and the non-contact evaluation of thermal expansion coefficient of materials buried inside media that are opaque to optical or infrared frequencies but transparent to THz frequencies. The introduction of a shear to a Gaussian free-space propagating terahertz beam in a controlled manner also makes possible a range of new encoding and optical signal processing modalities.

A Possible Change in Mass Balance of Greenland and Antarctic Ice Sheets in the Coming Century

A high-resolution GCM is found to simulate precipitation and surface energy balance of high latitudes with high accuracy. This opens new possibilities to investigate the future mass balance of polar glaciers and its effect on sea level. The surface mass balance of the Greenland and the Antarctic ice sheets is simulated using the ECHAM3 GCM with TI06 horizontal resolution. With this model, two 5-year integrations for the present and doubled carbon dioxide conditions based on the boundary conditions provided by the ECHAM1/T21 transient experiment have been conducted. A comparison of the two experiments over Greenland and Antarctica shows to what extent the effect of climate change on the mass balance on the two largest glaciers of the world can differ. On Greenland one sees a slight decrease in accumulation and a substantial increase in melt, while on Antarctica a large increase in accumulation without melt is projected. Translating the mass balances into terms of sea-level equivalent. the Greenland discharge causes a sea level rise of 1.1 mm yr−1, while the accumulation on Antarctica tends to lower it by 0.9 mm yr−1. The change in the combined mass balance of the two continents is almost zero. The sea level change of the next century can be affected more effectively by the thermal expansion of seawater and the mass balance of smaller glaciers outside of Greenland and Antarctica.

The reversibility of sea level rise

During the last century, global climate has been warming, and projections indicate that such a warming is likely to continue over coming decades. Most of the extra heat is stored in the ocean, resulting in thermal expansion of seawater and global mean sea level rise. Previous studies have shown that after CO2 emissions cease or CO2 concentration is stabilized, global mean surface air temperature stabilizes or decreases slowly, but sea level continues to rise. Using idealized CO2 scenario simulations with a hierarchy of models including an AOGCM and a step-response model, the authors show how the evolution of thermal expansion can be interpreted in terms of the climate energy balance and the vertical profile of ocean warming. Whereas surface temperature depends on cumulative CO2 emissions, sea level rise due to thermal expansion depends on the time profile of emissions. Sea level rise is smaller for later emissions, implying that targets to limit sea level rise would need to refer to the rate of emissions, not only to the time integral. Thermal expansion is in principle reversible, but to halt or reverse it quickly requires the radiative forcing to be reduced substantially, which is possible on centennial time scales only by geoengineering. If it could be done, the results indicate that heat would leave the ocean more readily than it entered, but even if thermal expansion were returned to zero, the geographical pattern of sea level would be altered. Therefore, despite any aggressive CO2 mitigation, regional sea level change is inevitable.

Twentieth-century global-mean sea-level rise: is the whole greater than the sum of the parts?

Confidence in projections of global-mean sea level rise (GMSLR) depends on an ability to account for GMSLR during the twentieth century. There are contributions from ocean thermal expansion, mass loss from glaciers and ice sheets, groundwater extraction, and reservoir impoundment. Progress has been made toward solving the “enigma” of twentieth-century GMSLR, which is that the observed GMSLR has previously been found to exceed the sum of estimated contributions, especially for the earlier decades. The authors propose the following: thermal expansion simulated by climate models may previously have been underestimated because of their not including volcanic forcing in their control state; the rate of glacier mass loss was larger than previously estimated and was not smaller in the first half than in the second half of the century; the Greenland ice sheet could have made a positive contribution throughout the century; and groundwater depletion and reservoir impoundment, which are of opposite sign, may have been approximately equal in magnitude. It is possible to reconstruct the time series of GMSLR from the quantified contributions, apart from a constant residual term, which is small enough to be explained as a long-term contribution from the Antarctic ice sheet. The reconstructions account for the observation that the rate of GMSLR was not much larger during the last 50 years than during the twentieth century as a whole, despite the increasing anthropogenic forcing. Semiempirical methods for projecting GMSLR depend on the existence of a relationship between global climate change and the rate of GMSLR, but the implication of the authors' closure of the budget is that such a relationship is weak or absent during the twentieth century.

The interplay of metal-atom ordering, Fermi leveltuning and thermoelectric properties in cobalt shandites Co3M2S2 (M = Sn, In)

A combination of structural, physical and computational techniques including powder X-ray and neutron diffraction, SQUID magnetometry, electrical and thermal transport measurements, DFT calculations and 119Sn Mössbauer and X-ray photoelec-tron spectroscopies has been applied to Co3Sn2-xInxS2 (0 ≤ x ≤ 2) in an effort to understand the relationship between metal-atom ordering and physical properties as the Fermi level is systematically varied. Whilst solid solution behavior is found throughout the composition region, powder neutron diffraction reveals that indium preferentially occupies an inter-layer site over an alternative kagome-like intra-layer site. DFT calculations indicate that this ordering, which leads to a lowering of energy, is related to the dif-fering bonding properties of tin and indium. Spectroscopic data suggest that throughout the composition range 0 ≤ x ≤ 2, all ele-ments adopt oxidation states that are significantly reduced from expectations based on formal charges. Chemical substitution ena-bles the electrical transport properties to be controlled through tuning of the Fermi level within a region of the density of states, which comprises narrow bands of predominantly Co d-character. This leads to a compositionally-induced double metal-to-semiconductor-to-metal transition. The marked increase in the Seebeck coefficient as the semiconducting region is approached leads to a substantial improvement in the thermoelectric figure of merit, ZT, which exhibits a maximum of ZT = 0.32 at 673 K. At 425 K, the figure of merit for phases in the region 0.8 ≤ x ≤ 0.85 is amongst the highest reported for sulphide phases, suggesting these materials may have applications in low-grade waste heat recovery.