Climate model sensitivity to atmospheric CO2 concentrations for the middle Miocene

We present results of the first middle Miocene climate modelling study using the latest NCAR Community Atmosphere Model (CAM v.3.1) and Community Land Model (CLM v.3.0) coupled to a slab ocean. We examine the sensitivity of the middle Miocene climate to varying concentrations of atmospheric carbon dioxide (180, 355 and 700 ppm). Model simulations are forced with realistic Miocene boundary conditions for continental geometry, topography and vegetation. Global annual mean surface temperature increases by 2.2 °C with each successive doubling of CO₂ which is consistent with climate sensitivity of previous paleoclimate studies and estimates for future climate. In addition to growing evidence that tropical sea surface temperatures were higher than suggested by proxy-data, our understanding of middle to high latitude warming mechanisms is still incomplete. We compare our results to the late Miocene study of Steppuhn et al. [Steppuhn, A., Micheels, A., Bruch, A., Uhl, D., Utescher, T., Mosbrugger, V., 2007. The sensitivity of ECHAM4/ML to a double CO₂ scenario for the Late Miocene and the comparison to terrestrial proxy data. Global and Planetary Change, 57, 189–212] to explore the dependence of paleoclimate model sensitivities on different software systems and boundary conditions. Our comparison shows climate sensitivity to be overall quite robust — this is as significant, as it is often unclear to what extent simulation behaviour and outputs are dependent on a particular model implementation and initial/boundary conditions. Some distinct differences in model outputs, such as our reduced latitudinal surface temperature gradient and stronger Asian monsoon system, compared to the late Miocene study of Steppuhn et al. [Steppuhn, A., Micheels, A., Bruch, A., Uhl, D., Utescher, T., Mosbrugger, V., 2007. The sensitivity of ECHAM4/ML to a double CO₂ scenario for the Late Miocene and the comparison to terrestrial proxy data. Global and Planetary Change, 57, 189–212] are shown to be closely linked to the choice of topography, vegetation and ocean heat flux.     

Effects of a 2 × CO2 climate on two large lake systems: Pyramid Lake, Nevada, and Yellowstone Lake, Wyoming

The possible effects of trace-gas induced climatic changes on Pyramid and Yellowstone Lakes are assessed using a model of lake temperature. The model is driven by years of hourly meteorological data obtained directly from the output of double-CO₂ experiments (2 × CO₂) conducted with a regional climate model nested in a general circulation model. The regional atmospheric model is the climate version of the National Center for Atmospheric Research/Pennsylvania State University mesoscale model, MM4.Average annual surface temperature of Pyramid Lake for the 2 × CO₂ climate is 15.5 ± 5.4°C (±1 σ), 2.8°C higher than the control. Annual overturn of the lake ceases as a result of these higher temperatures for the 2 × CO₂ climate. Evaporation increases from 1400 mm yr⁻¹ in the control to 1595 mm yr⁻¹ in the 2 × CO₂ simulation, but net water supplied to the Pyramid Lake basin increases from −6 mm yr⁻¹ in the control to +27 mm yr⁻¹ in the 2 × CO₂ simulation due to increased precipitation.For the open water periods, the average annual surface temperature of Yellowstone Lake is 13.2 ± 5.1°C for the 2 × CO₂ climate, a temperature 1.6°C higher than the control. The annual duration of ice cover on the lake is 152 days in the 2 × CO₂ simulation, a reduction of 44 days relative to the control. Warming of the lake for the 2 × CO₂ climate is mostly confined to the near-surface. Simulated spring overturn for the 2 × CO₂ climate occurs earlier in the year and fall overturn later than in the control. Evaporation increases from 544 mm yr⁻¹ to 600 mm yr⁻¹ in the 2 × CO₂ simulation, but net water supplied to the Yellowstone Lake basin increases from +373 mm yr⁻¹ in the control to +619 mm yr⁻¹ due to increased precipitation. The effects of these climatic changes suggest possible deterioration of water quality and productivity in Pyramid Lake and possible enhancement of productivity in Yellowstone Lake.     

Role of H2O and CO2 Ices in Martian Climate Changes

In order to study the stability of martian climate, we constructed a two-dimensional (horizontal-vertical) energy balance model. The long-term CO₂ mass exchange process between the atmosphere and CO₂ ice caps is investigated with particular attention to the effect of planetary ice distribution on the climate stability. Our model calculation suggests that high atmospheric pressure presumed for past Mars would be unstabilized if H₂O ice widely prevailed. As a result, a cold climate state might have been achieved by the condensation of atmospheric CO₂ onto ice caps. On the other hand, the low atmospheric pressure, which is buffered by the CO₂ ice cap and likely close to the present pressure, would be unstabilized if the CO₂ ice albedo decreased. This may have led the climate into a warm state with high atmospheric pressure owing to complete evaporation of CO₂ ice cap. Through the albedo feedback mechanisms of H₂O and CO₂ ices in the atmosphere-ice cap system, Mars may have experienced warm and cold climates episodically in its history.     

Simulated responses of Pinus halepensis forest productivity to climatic change and CO2 increase using a statistical model

Tree ring chronologies provide long-term records of growth in natural environmental conditions and may be used to evaluate impacts of climatic change and CO₂ increase on forest productivity. This study focuses on 21 Pinus halepensis forest stands in calcareous Provence (in the south-east of France). A chronology of net primary productivity (NPP) both for the 20th century and for each stand was estimated using tree ring data (width and density). The response of each stand to climate in terms of NPP was statistically modelled using response functions. Anomalies between estimated NPP and NPP reconstructed by response functions were calculated to evaluate the fertilising effect of CO₂ increase on tree growth. The changes in anomalies during the 20th century were attributed to the effect of CO₂ increase. A multiplying factor (β) linking CO₂ concentration and stand productivity was then calculated, on the basis of the trend observed during the 20th century. In this study, the value of the β factor obtained under natural conditions (β=0.50) is consistent with those from controlled CO₂ enrichment experiments. Both response functions and the β factor were used to predict NPP changes for a 2×CO₂ scenario. The 2×CO₂ climate was obtained using predictions from Météo France's ARPEGE atmospheric general circulation model (AGCM) downscaled to Marseilles meteorological station. NPP increased significantly for nine stands solely when the climatic effect was taken into account. The main factors responsible for this enhancement were increased winter and early spring temperatures. When the fertilising effect of the CO₂ increase was added, NPP was significantly enhanced for 14 stands (i.e. NPP enhancement ranged from 8% to 55%). Although the effects of global change were slightly detectable during the 20th century, their acceleration is likely to lead to great changes in the future productivity of P. halepensis forests.     

Carbon dioxide on the satellites of Saturn: Results from the Cassini VIMS investigation and revisions to the VIMS wavelength scale

Several of the icy satellites of Saturn show the spectroscopic signature of the asymmetric stretching mode of C-O in carbon dioxide (CO₂) at or near the nominal solid-phase laboratory wavelength of 4.2675 μm (2343.3 cm⁻¹), discovered with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft. We report here on an analysis of the variation in wavelength and width of the CO₂ absorption band in the spectra of Phoebe, Iapetus, Hyperion, and Dione. Comparisons are made to laboratory spectra of pure CO₂, CO₂ clathrates, ternary mixtures of CO₂ with other volatiles, implanted and adsorbed CO₂ in non-volatile materials, and ab initio theoretical calculations of CO₂ * nH₂O. At the wavelength resolution of VIMS, the CO₂ on Phoebe is indistinguishable from pure CO₂ ice (each molecule’s nearby neighbors are also CO₂) or type II clathrate of CO₂ in H₂O. In contrast, the CO₂ band on Iapetus, Hyperion, and Dione is shifted to shorter wavelengths (typically ∼4.255 μm (∼2350.2 cm⁻¹)) and broadened. These wavelengths are characteristic of complexes of CO₂ with different near-neighbor molecules that are encountered in other volatile mixtures such as with H₂O and CH₃OH, and non-volatile host materials like silicates, some clays, and zeolites. We suggest that Phoebe’s CO₂ is native to the body as part of the initial inventory of condensates and now exposed on the surface, while CO₂ on the other three satellites results at least in part from particle or UV irradiation of native H₂O plus a source of C, implantation or accretion from external sources, or redistribution of native CO₂ from the interior.The analysis presented here depends on an accurate VIMS wavelength scale. In preparation for this work, the baseline wavelength calibration for the Cassini VIMS was found to be distorted around 4.3 μm, apparently as a consequence of telluric CO₂ gas absorption in the pre-launch calibration. The effect can be reproduced by convolving a sequence of model detector response profiles with a deep atmospheric CO₂ absorption profile, producing distorted detector profile shapes and shifted central positions. In a laboratory blackbody spectrum used for radiance calibration, close examination of the CO₂ absorption profile shows a similar deviation from that expected from a model. These modeled effects appear to be sufficient to explain the distortion in the existing wavelength calibration now in use. A modification to the wavelength calibration for 13 adjacent bands is provided. The affected channels span about 0.2 μm centered on 4.28 μm. The maximum wavelength change is about 10 nm toward longer wavelength. This adjustment has implications for interpretation of some of the spectral features observed in the affected wavelength interval, such as from CO₂, as discussed in this paper.     

CO2 production by ion irradiation of H2O ice on top of carbonaceous materials and its relevance to the Galilean satellites

In this work we report on new experiments of ion irradiation of water ice deposited on top of solid carbonaceous materials to study the production of CO₂ at the interface ice/refractory material and discuss the possibility that this mechanism accounts for the quantity of CO₂ ice detected on the surfaces of the Galilean satellites. The used experimental technique has been in situ infrared spectroscopy. We have irradiated thin films of H₂O frost on carbonaceous layers with 200 keV of He⁺ and Ar⁺, and 30 keV of He⁺ at 16 and 80 K. The used carbonaceous layers have been asphaltite, a natural bitumen, and solid organic residues obtained by irradiation of frozen benzene. In both cases the results show that CO₂ is produced very efficiently after irradiation obtaining a maximum quantity of the order of . These results are, also quantitatively similar, to those recently obtained for water ice deposited on amorphous carbon films [Mennella, V., Palumbo, M.E., Baratta, G.A., 2004. Formation of CO and CO₂ molecules by ion irradiation of water ice covered hydrogenated carbon grains. Astrophys. J. 615, 1073-1080]. Thus we suggest that, whatever is the carbonaceous residue, CO₂ will be produced efficiently by the studied process. These results have interest in the context of the surfaces of the icy Galilean satellites in which CO₂ has been detected mainly trapped in the non-ice material, not in the pure water ice. We suggest that radiolysis of mixtures of water ice and refractory carbonaceous materials is the primary formation mechanism responsible for the CO₂ formation on the surfaces of the Galilean satellites.     

Eocene–Miocene carbon-isotope and floral record from brown coal seams in the Gippsland Basin of southeast Australia

The carbon-isotope and palynological record through 580 m thick almost continuous brown coal in southeast Australia's Gippsland Basin is a relatively comprehensive southern hemisphere Middle Eocene to Middle Miocene record for terrestrial change. The carbon isotope δ¹³C_coal values of these coals range from ? 27.7‰ to ? 23.2. This isotopic variability follows gymnosperm/angiosperm fluctuations, where higher ratios coincide with heavier δ¹³C values. There is also long-term variability in carbon isotopes through time. From the Eocene greenhouse world of high gymnosperm-heavier δ¹³C_coal values, there is a progressive shift to lighter δ¹³C_coal values that follows the earliest (Oi1?) glacial events around 33 Ma (Early Oligocene). The overlying Oligocene–Early Miocene brown coals have lower gymnosperm abundance, associated with increased %Nothofagus (angiosperm), and lightening of isotopes during Oligocene cooler conditions.The Miocene palynological and carbon-isotope record supports a continuation to the Oligocene trends until around the late Early Miocene (circa 19 Ma) when a warming commenced, followed by an even stronger isotope shift around 16 Ma that peaked in the Middle Miocene when higher gymnosperm abundance and heavier isotopes prevailed. The cycle between the two major warm peaks of Middle Eocene and Middle Miocene was circa 30 Ma long. This change corresponds to a fall in inferred pCO₂ levels for the same period. The Gippsland data suggest a link between gymnosperm abundance, long-term plant δ¹³C composition, climatic change, and atmospheric pCO₂. Climatic deterioration in the Late Miocene terminated peat accumulation in the Gippsland Basin and no further significant coals formed in southeast Australia.The poor correspondence between this terrestrial isotope data and the marine isotope record is explained by the dominant control on δ¹³C by the gymnosperm/angiosperm abundance, although in turn this poor correspondence may reflect palaeoclimate control. From the brown coal seam dating, the coal appears to have accumulated during a considerable part of the allocated 30 Ma Cenozoic time period. These brown coal carbon isotope and palynological data appear to record a more gradual atmospheric carbon isotope change compared to the marine record.     

The Late Miocene climate response to a modern Sahara desert

The climate cooling and vegetation changes in the Miocene/Pliocene are generally well documented by various proxy data. Some important ecosystem changes occurred at that time. Palaeobotanical evidence suggests that the Sahara desert first appeared in the Pliocene, whereas in the Miocene North Africa was green. In the present study, we investigate the Late Miocene climate response to the appearance of the Sahara desert from a climate modelling sensitivity experiment. We compare a model experiment, which includes a full set of Late Miocene boundary conditions, with another one using the same boundary conditions except that the North African vegetation refers to the present-day situation. Our sensitivity study demonstrates that the introduction of the Sahara desert leads to a cooling and an aridification in Africa. In addition, we observe teleconnection patterns related to the North African desertification at around the Miocene/Pliocene boundary. From our sensitivity experiment, we observe that the Sahara contributes to a cooling in Central Asia and in North America. As compared to hypsodonty data for Central Asia, an increased aridity is underestimated in the Sahara experiment. Finally, we observe that the introduction of the Sahara leads to a cooling in the northern high latitudes. Hence, our sensitivity experiment indicates that the appearance of the Sahara desert is one piece to better understand Late Cenozoic climate cooling being most pronounced in the high latitudes.     

CO2 clouds, CAPE and convection on Mars: Observations and general circulation modeling

The thermal emission spectrometer (TES) and the radio science (RS) experiment flying on board the Mars Global Surveyor (MGS) spacecraft have made observations of atmospheric temperatures below the saturation temperature of carbon dioxide (CO₂). This supersaturated air provides a source of convective available potential energy (CAPE), which, when realized may result in vigorous convective mixing. To this point, most Mars atmospheric models have assumed vertical mixing only when the dry adiabatic lapse rate is exceeded. Mixing associated with the formation of CO₂ clouds could have a profound effect on the vertical structure of the polar night, altering the distribution of temperature, aerosols, and gasses.Presented in this work are estimates of the total planetary inventory of CAPE and the potential convective energy flux (PCEF) derived from RS and TES temperature profiles. A new Mars Global Circulation Model (MGCM) CO₂ cloud model is developed to better understand the distribution of observed CAPE and its potential effect on Martian polar dynamics and heat exchange, as well as effects on the climate as a whole. The new CO₂ cloud model takes into account the necessary cloud microphysics that allow for supersaturation to occur and includes a parameterization for CO₂ cloud convection. It is found that when CO₂ cloud convective mixing is included, model results are in much better agreement with the observations of the total integrated CAPE as well as total column non-condensable gas concentrations presented by Sprague et al. [2005a, GRS measurements of Ar in Mars’ atmosphere, American Astronomical Society, DPS meeting #37, #24.08, and 2005b, Distribution and Abundance of Mars’ Atmospheric Argon, 36th Annual Lunar and Planetary Science Conference, #2085] When the radiative effects of water ice clouds are included the agreement is further improved.     

H2O2 production by high-energy electrons on icy satellites as a function of surface temperature and electron flux

Chemistry on the icy surface of Europa is heavily influenced by the incident energetic particle flux from the jovian magnetosphere. The majority (>75%) of this energy is in the form of high energy electrons (extending to >10 MeV). We have simulated the electron irradiation environment of Europa with a vacuum system containing a high-energy electron gun for irradiation of ice samples formed on a gold mirror cooled with a cryostat. Pure water films of ∼2.6 μm thickness were grown at 100 K and then either cooled (to 80 K), warmed (to 120 K) or left at 100 K and subsequently irradiated with 10 keV electrons. The production of hydrogen peroxide (H₂O₂) was monitored by observation of the 2850 cm⁻¹ (3.5 μm) band. Equilibrium concentrations of H₂O₂, in units of percent by number H₂O₂ relative to water, were found to be 0.043% (80 K), 0.029% (100 K), and 0.0063% (120 K). These values are 33%, 22%, and 5%, respectively, that of the reported surface concentration on the leading hemisphere of Europa (Carlson, R.W., Anderson, M.S., Johnson, R.E., Smythe, W.D., Hendrix, A.R., Barth, C.A., et al. [1999]. Science 283(5410), 2062-2064) and less than the equilibrium concentrations formed by ion irradiation. In addition to the ice film temperature, the current of electrons was varied between different experiments to determine the production and destruction of H₂O₂ as a function of both electron flux and ice temperature. Variation in current was found to have little effect on the results other than accelerating arrival at radiolytic equilibrium.     

PFS/MEX observations of the condensing CO2 south polar cap of Mars

The condensing CO₂ south polar cap of Mars and the mechanisms of the CO₂ ice accumulation have been studied through the analysis of spectra acquired by the Planetary Fourier Spectrometer (PFS) during the first two years of ESA's Mars Express (MEX) mission. This dataset spans more than half a martian year, from Ls∼330° to Ls∼194°, and includes the southern fall season which is found to be extremely important for the study of the residual south polar cap asymmetry. The cap expands symmetrically and with constant speed during the fall season. The maximum extension occurs sometime in the 80°-90° Ls range, when the cap edges are as low as −40° latitude. Inside Hellas and Argyre basins, frost can be stable at lower latitudes due to the higher pressure values, causing the seasonal cap to be asymmetric. Within the seasonal range considered in this paper, the cap edge recession rate is approximately half the rate at which the cap edge expanded. The longitudinal asymmetries reduce during the cap retreat, and disappear around Ls∼145°. Two different mechanisms are responsible for CO₂ ice accumulation during the fall season, especially in the 50°-70° Ls range. Here, CO₂ condensation in the atmosphere, and thus precipitation, is allowed exclusively in the western hemisphere, and particularly in the longitudinal corridor of the perennial cap. In the eastern hemisphere, the cap consists mainly of CO₂ frost deposits, as a consequence of direct vapor deposition. The differences in the nature of the surface ice deposits are the main cause for the residual south polar cap asymmetry. Results from selected PFS orbits have also been compared with the results provided by the martian general circulation model (GCM) of the Laboratoire de Météorologie dynamique (LMD) in Paris, with the aim of putting the observations in the context of the global circulation. This first attempt of cross-validation between PFS measurements and the LMD GCM on the one hand confirms the interpretation of the observations, and on the other hand shows that the climate modeling during the southern polar night on Mars is extremely sensitive to the dynamical forcing.     

Use of a land-surface-transfer scheme (LSX) in a global climate model: the response to doubling stomatal resistance

One response of vegetation to future increases in atmospheric CO₂ may be a widespread increase in stomatal resistance. Such a response would increase plant water usage efficiency while still allowing CO₂ assimilation at current rates. The associated reduction in transpiration rates has the potential of causing significant modifications in climate on regional and global scales.This paper describes the effects of a uniform doubling of the stomatal resistance parameterization in a global climate model (GENESIS). The model includes a land-surface transfer scheme (LSX) that accounts for the physical effects of vegetation, including stomatal resistance and transpiration, which is described in detail in an appendix. The atmospheric general circulation model is a heavily modified version of the NCAR Community Climate Model version 1 with new treatments of clouds, penetrative convection, planetary boundary layer mixing, solar radiation, the diurnal cycle, and semi-Lagrangian transport of water vapor. The other surface models include multi-layer models of soil, snow and sea ice, and a 50-m slab ocean mixed layer.The effects of doubling the stomatal resistance parameterization are largest in heavily forested regions: tropical South America, and parts of the Northern Hemispheric boreal forests in Canada, Russia and Siberia in summer. The primary surface changes are a decrease in evapotranspiration, an increase in upward sensible heat flux, and a surface-air warming. Secondary effects include shifts in the ITCZ which cause large increases in precipitation, soil moisture and runoff in western tropical South America, and decreases in these quantities in northern subtropical Africa. Noticeable changes in relative humidity, cloudiness and meridional circulation occur throughout the troposphere. The global effects on atmospheric temperature and specific humidity are small fractions of those found in other doubled CO₂ experiments. However, unlike doubled CO₂ the signs of those changes combine to give relatively large reductions in relative humidity and cloudiness. It is suggested that the stomatal-resistance effect and other plant responses to large-scale environmental perturbations should be included in models of future climate.     

Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO₂ in H₂O and CH₃OH, and find they are significantly different from that of pure solid CO₂. Peaks not present in either pure H₂O or pure CO₂ spectra become evident when the two are mixed. First, the putative theoretically forbidden CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹), that is absent from our spectrum of pure solid CO₂, is prominent in the spectra of H₂O/CO₂=5 and 25 mixtures. Second, a 2.74-μm (3650 cm⁻¹) dangling OH feature of H₂O (and a potentially related peak at 1.89 μm) appear in the spectra of CO₂-H₂O ice mixtures, but are probably not diagnostic of the presence of CO₂. Other CO₂ peaks display shifts in position and increased width because of intermolecular interactions with H₂O. Warming causes some peak positions and profiles in the spectrum of a H₂O/CO₂=5 mixture to take on the appearance of pure CO₂. Absolute strengths for absorptions of CO₂ in solid H₂O are estimated. Similar results are observed for CO₂ in solid CH₃OH. Since the CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹) is not present in pure CO₂ but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO₂ is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.     

Effects of scattered solar radiation and absorption by SO2 on the photodissociation processes in the stratosphere of Venus

In the stratosphere of Venus, the available luminous flux which locally produces the photodissociation processes at a given altitude may be divided into three parts: direct incoming downward flux, flux resulting from the reflection on the surface of the clouds, and flux due to molecular scattering. A relatively simple computation method has been used to evaluate the relative importance of these three parts at altitudes between 65 and 100 km. It is shown that the extra contribution of the reflected and scattered fluxes to photodissociation processes cannot be neglected in the uv and visible regions. In the case of SO₂, for instance, which presents an absorption band in the uv, the photodissociation coefficient is increased 30% due to these effects. Calculations of the photodissociation coefficients of CO₂, O₃, H₂S, and SO₂ are presented. As a result of the increase by 60% in the ozone photolysis rate, the calculated O₂ infrared band at 1.27 μm is larger by a factor of nearly 2 than is expected from a calculation without taking albedo or scattering into account.     

Liquid water on Mars: An energy balance climate model for CO2/H2O atmospheres

Geologic evidence of the prior existence of liquid water on Mars suggests surface temperatures T_s were once considerably warmer than at present; and that such a condition may have arisen from a larger atmospheric greenhouse. Here we develop a simple climate model for a CO₂/H₂O Mars atmosphere including water vapor-longwave opacity feedback in the atmosphere and temperature-albedo feedback at surface icecaps, under the assumption that once the Martian surface pressure was p_s ≥ 1 atm CO₂. Longwave flux to space is computed as a function of T_s and p_s using band-absorption models for the effect of the 15-μm fundamental, and the 10- and 15-μm hot bands, of the CO₂ molecule; as well as the pure rotation bands and e continuum of H₂O. The derived global radiative balance predicts a global mean surface temperature of 283°K at 1 atm CO₂. When the emission model is coupled to a latitudinally resolved energy balance climate model, including the effect of poleward heat transfer by atmospheric baroclinic eddies, the solutions vary, depending on p_s. We considered two cases: (1) the present Mars (p_s ? 0.007 atm) with pressure-buffering by solid CO₂ icecaps, and limited poleward heat flux by the atmosphere; and (2) a hypothetical “hot Mars” (p_s ? 1.0 atm), whose much higher CO₂ amount augmented by H₂O evaporative feedback yields a theoretical T_s distribution with latitude admitting liquid water over 95% of the surface, water icecaps at the poles, and a diminished equator-to-pole temperature gradient relative to the present.     

New atmospheric pCO2 estimates from palesols during the late Paleocene/early Eocene global warming interval

The late Paleocene to early Eocene was one of the warmest intervals in Earth's history. Superimposed on this long-term warming was an abrupt short-term extreme warm event at or near the Paleocene/Eocene boundary and centered in the higher latitudes. This short-term climate warming was associated with a major benthic foraminiferal extinction and a dramatic 3–4% drop in the ocean's carbon isotopic composition. It has been suggested that the late paleocene/early Eocene global warming was caused by an enhanced greenhouse effect associated with higher levels of atmospheric CO₂ relative to present levels. We present carbon isotopic data from the co-existing paleosols organic matter and carbonates from a terrestrial sequence in the Paris Basin, France that contradict the notion that an increase in atmospheric CO₂ level was the cause of extreme warming for this time interval. Atmospheric pCO₂ estimates for the Late Paleocene/early Eocene estimated from the terrestrial carbon isotopic record spanning the Paleocene/Eocene transition, are indistinguishable from each other and were generally between 300 and 700 ppm.     

Thick and thin models of the evolution of carbon dioxide on Mars

We present results from a new simulation code that accounts for the evolution of the reservoirs of carbon dioxide on Mars, from its early years to the present. We establish a baseline model parameter set that produces results compatible with the present (i.e., Patm?6.5 mbar with permanent CO₂ ice cap) for a wide range of initial inventories. We find that the initial inventory of CO₂ broadly determines the evolutionary course of the reservoirs of CO₂. The reservoirs include the atmosphere, ice cap, adsorbed CO₂ in the regolith, and carbonate rocks. We track the evolution of the free inventory: the atmosphere, ice cap and regolith. Simulations begin at 4.53 Gyr before present with a rapid loss of free inventory to space in the early Noachian. Models that assume a relatively small initial inventory (?5 bar) have pronounced minima in the free inventory of CO₂ toward the end of the Noachian. Under baseline parameters, initial inventories below ∼4.5 bar result in a catastrophic loss of the free inventory to space. The current free inventory would be then determined by the balance between outgassing, sputtering losses and chemical weathering following the end of the late bombardment. We call these “thin” models. They generically predict small current free inventories in line with expectations of a small present CO₂ ice cap. For “thick” models, with initial inventories ?5 bar, a surplus of 300-700 mbar of free CO₂ remains during the late-Noachian. The histories of free inventory in time for thick models tend to converge within the last 3.5 Gyr toward a present with an ice cap plus atmospheric inventory of about 100 mbar. For thick models, the convergence is largely due to the effects of chemical weathering, which draws down higher free inventories more rapidly than the low. Thus, thick models have ?450 mbar carbonate reservoirs, while thin models have ?200 mbar. Though both thick and thin scenarios can reproduce the current atmospheric pressure, the thick models imply a relatively large current CO₂ ice cap and thin models, little or none. While the sublimation of a massive cap at a high obliquity would create a climate swing of greenhouse warming for thick models, under the thin model, mean temperatures and pressures would be essentially unaffected by increases in obliquity.     

Phytochemical changes in leaves of subtropical grasses and fynbos shrubs at elevated atmospheric CO2 concentrations

The effects of elevated atmospheric CO₂ concentrations on plant polyphenolic, tannin, nitrogen, phosphorus and total nonstructural carbohydrate concentrations were investigated in leaves of subtropical grass and fynbos shrub species. The hypothesis tested was that carbon-based secondary compounds would increase when carbon gain is in excess of growth requirements. This premise was tested in two ecosystems involving plants with different photosynthetic mechanisms and growth strategies. The first ecosystem comprised grasses from a C₄-dominated, subtropical grassland, where three plots were subjected to three different free air CO₂ enrichment treatments, i.e., elevated (600 to 800 μmol mol⁻¹), intermediate (400 μmol mol⁻¹) and ambient atmospheric CO₂. One of the seven grass species, Alloteropsis semialata, had a C₃ photosynthetic pathway while the other grasses were all C₄. The second ecosystem was simulated in a microcosm experiment where three fynbos species were grown in open-top chambers at ambient and 700 μmol mol⁻¹ atmospheric CO₂ in low nutrient acid sands typical of south western coastal and mountain fynbos ecosystems. Results showed that polyphenolics and tannins did not increase in the grass species under elevated CO₂ and only in Leucadendron laureolum among the fynbos species. Similarly, foliar nitrogen content of grasses was largely unaffected by elevated CO₂, and among the fynbos species, only L. laureolum and Leucadendron xanthoconus showed changes in foliar nitrogen content under elevated CO₂, but these were of different magnitude. The overall decrease in nitrogen and phosphorus and consequent increase in C:N and C:P ratio in both ecosystems, along with the increase in polyphenolics and tannins in L. laureolum in the fynbos ecosystem, may negatively affect forage quality and decomposition rates. It is concluded that fast growing grasses do not experience sink limitation and invest extra carbon into growth rather than polyphenolics and tannins and show small species-specific chemical changes at elevated atmospheric CO₂ concentrations. Responses of fynbos species are varied and were species-specific.     

Climate and carbon cycle changes under the overshoot scenario

The “overshoot scenario” is an emissions scenario in which CO₂ concentration in the atmosphere temporarily exceeds some pre-defined, “dangerous” threshold (before being reduced to non-dangerous levels). Support for this idea comes from its potential to achieve a balance between the burdens of current and future generations in dealing with global warming. Before it can be considered a viable policy, the overshoot scenario needs to be examined in terms of its impacts on the global climate and the environment. In, particular, it must be determined if climate change cause by the overshoot scenario is reversible or not, since crossing that “dangerous” CO₂ threshold could result in climate change from which we might not be able to recover. In this study, we quantify the change in several climatic and environmental variables under the overshoot scenario using a global climate model of intermediate complexity. Compared to earlier studies on the overshoot scenario, we have an explicit carbon cycle model that allows us to represent carbon-climate feedbacks and force the climate model more realistically with CO₂ emissions rates rather than with prescribed atmospheric pCO₂. Our standard CO₂ emissions rate is calculated on the basis of historical atmospheric pCO₂ data and the WRE S650 non-overshoot stabilization profile. It starts from the preindustrial year 1760, peaks in the year 2056, and ends in the year 2300. A variety of overshoot scenarios were constructed by increasing the amplitude of the control emissions peak but decreasing the peak duration so that the cumulative emissions remain essentially constant. Sensitivity simulations of various overshoot scenarios in our model show that many aspects of the global climate are largely reversible by year 2300. The significance of the reversibility, which takes roughly 200 years in our experiments, depends on the time horizon with which it is viewed or the number of future generations for whom equity is sought. At times when the overshoot scenario has emissions rates higher then the control scenario, the transient changes in atmospheric and oceanic temperatures and surface ocean pH can be significant, even for moderate overshoot scenarios that remain within IPCC SRES emissions scenarios. The large transient changes and the centennial timescale of climate reversibility suggest that the overshoot might not be the best mitigation approach, even if it technically follows the optimal economic path.     

Quantum chemical calculation on the potential energy surface of H2CO3 and its implication for martian chemistry

A detailed theoretical study of the potential energy surface of H₂CO₃ is explored at the CCSD(T)//B3LYP/aug-cc-pVTZ level. On the potential energy surface, 12 isomers of H₂CO₃ are located. Their molecular properties such as geometries, vibrational frequencies, rotational constants, dipole moments, gas-phase acidities, and relative energies are calculated. Various reaction pathways and decomposition products have also been discussed. Among these products, CO₂ and H₂O are definitely the most favorable products with predominant abundance. Large energy barriers are predicted for other dissociation channels leading to the formation of oxygen, formaldehyde, and so on. These high energy channels are not important thermodynamically and kinetically, but they might occur in the presence of cosmic rays in astronomic environments. From the present work we suggest that chemical reactions between CO₂ and H₂O at the polar ice caps could be a potential source of H₂CO and O₂, in addition to the previously proposed mechanisms, i.e., the oxidation of methane and cosmic-ray-mediated production through the intermediate H₂CO₃. The results of the present work may provide useful data to improve our understanding of icy chemistry at the polar caps on Mars.