Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

Water vapor variability in the tropics and its links to dynamics and precipitation

The distribution and variability of water vapor and its links with radiative cooling and latent heating via precipitation are crucial to understanding feedbacks and processes operating within the climate system. Column-integrated water vapor (CWV) and additional variables from the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year reanalysis (ERA40) are utilized to quantify the spatial and temporal variability in tropical water vapor over the period 1979–2001. The moisture variability is partitioned between dynamical and thermodynamic influences and compared with variations in precipitation provided by the Climate Prediction Center Merged Analysis of Precipitation (CMAP) and the Global Precipitation Climatology Project (GPCP). The spatial distribution of CWV is strongly determined by thermodynamic constraints. Spatial variability in CWV is dominated by changes in the large-scale dynamics, in particular associated with the El Niño–Southern Oscillation (ENSO). Trends in CWV are also dominated by dynamics rather than thermodynamics over the period considered. However, increases in CWV associated with changes in temperature are significant over the equatorial east Pacific when analyzing interannual variability and over the north and northwest Pacific when analyzing trends. Significant positive trends in CWV tend to predominate over the oceans while negative trends in CWV are found over equatorial Africa and Brazil. Links between changes in CWV and vertical motion fields are identified over these regions and also the equatorial Atlantic. However, trends in precipitation are generally incoherent and show little association with the CWV trends. This may in part reflect the inadequacies of the precipitation data sets and reanalysis products when analyzing decadal variability. Though the dynamic component of CWV is a major factor in determining precipitation variability in the tropics, in some regions/seasons the thermodynamic component cancels its effect on precipitation variability.

Impacts of climate change on in-stream nitrogen in a lowland chalk stream: An appraisal of adaptation strategies

The impacts of climate change on nitrogen (N) in a lowland chalk stream are investigated using a dynamic modelling approach. The INCA-N model is used to simulate transient daily hydrology and water quality in the River Kennet using temperature and precipitation scenarios downscaled from the General Circulation Model (GCM) output for the period 1961-2100. The three GCMs (CGCM2, CSIRO and HadCM3) yield very different river flow regimes with the latter projecting significant periods of drought in the second half of the 21st century. Stream-water N concentrations increase over time as higher temperatures enhance N release from the soil, and lower river flows reduce the dilution capacity of the river. Particular problems are shown to occur following severe droughts when N mineralization is high and the subsequent breaking of the drought releases high nitrate loads into the river system. Possible strategies for reducing climate-driven N loads are explored using INCA-N. The measures include land use change or fertiliser reduction, reduction in atmospheric nitrate and ammonium deposition, and the introduction of water meadows or connected wetlands adjacent to the river. The most effective strategy is to change land use or reduce fertiliser use, followed by water meadow creation, and atmospheric pollution controls. Finally, a combined approach involving all three strategies is investigated and shown to reduce in-stream nitrate concentrations to those pre-1950s even under climate change. (c) 2006 Elsevier B.V. All rights reserved.

Stratospheric temperature and radiative forcing response to 11-year solar cycle changes in irradiance and ozone

The 11-yr solar cycle temperature response to spectrally resolved solar irradiance changes and associated ozone changes is calculated using a fixed dynamical heating (FDH) model. Imposed ozone changes are from satellite observations, in contrast to some earlier studies. A maximum of 1.6 K is found in the equatorial upper stratosphere and a secondary maximum of 0.4 K in the equatorial lower stratosphere, forming a double peak in the vertical. The upper maximum is primarily due to the irradiance changes while the lower maximum is due to the imposed ozone changes. The results compare well with analyses using the 40-yr ECMWF Re-Analysis (ERA-40) and NCEP/NCAR datasets. The equatorial lower stratospheric structure is reproduced even though, by definition, the FDH calculations exclude dynamically driven temperature changes, suggesting an important role for an indirect dynamical effect through ozone redistribution. The results also suggest that differences between the Stratospheric Sounding Unit (SSU)/Microwave Sounding Unit (MSU) and ERA-40 estimates of the solar cycle signal can be explained by the poor vertical resolution of the SSU/MSU measurements. The adjusted radiative forcing of climate change is also investigated. The forcing due to irradiance changes was 0.14 W m−2, which is only 78% of the value obtained by employing the standard method of simple scaling of the total solar irradiance (TSI) change. The difference arises because much of the change in TSI is at wavelengths where ozone absorbs strongly. The forcing due to the ozone change was only 0.004 W m−2 owing to strong compensation between negative shortwave and positive longwave forcings.

Glacier shrinkage and climatic change in the Russian Altai from the mid-20th century: An assessment using remote sensing and PRECIS regional climate model

This paper examines changes in the surface area of glaciers in the North and South Chuya Ridges, Altai Mountains in 1952-2004 and their links with regional climatic variations. The glacier surface areas for 2004 were derived from the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) imagery. Data from the World Glacier Inventory (WGI)dating to 1952 and aerial photographs from 1952 were used to estimate the changes. 256 glaciers with a combined area of 253±5.1 km2 have been identified in the region in 2004. Estimation of changes in extent of 126 glaciers with the individual areas not less than 0.5 km2 in 1952 revealed a 19.7±5.8% reduction. The observed glacier retreat is primarily driven by an increase in summer temperatures since the 1980s when air temperatures were increasing at a rate of 0.10 - 0.13oC a-1 at the glacier tongue elevation. The regional climate projections for A2 and B2 CO2 emission scenarios developed using PRECIS regional climate model indicate that summer temperatures will increase in the Altai in 2071-2100 by 6-7oC and 3-5oC respectively in comparison with 1961-1990 while annual precipitation will increase by 15% and 5%. The length of the ablation season will extend from June-August to the late April – early October. The projected increases in precipitation will not compensate for the projected warming and glaciers will continue to retreat in the 21st century under both B2 and A2 scenarios.

Associations between elevated atmospheric temperature and human mortality: a critical review of the literature

The effects of the anomalously warm European summer of 2003 highlighted the importance of understanding the relationship between elevated atmospheric temperature and human mortality. This review is an extension of the brief evidence examining this relationship provided in the IPCC’s Assessment Reports. A comprehensive and critical review of the literature is presented, which highlights avenues for further research, and the respective merits and limitations of the methods used to analyse the relationships. In contrast to previous reviews that concentrate on the epidemiological evidence, this review acknowledges the inter-disciplinary nature of the topic and examines the evidence presented in epidemiological, environmental health, and climatological journals. As such, present temperature–mortality relationships are reviewed, followed by a discussion of how these are likely to change under climate change scenarios. The importance of uncertainty, and methods to include it in future work, are also considered.

Vascular plant diversity and climate change in the alpine zone of the Lefka Ori, Crete

The aim of this study is to analyse the vascular flora and the local climate along an altitudinal gradient in the Lefka Ori massif Crete and to evaluate the potential effects of climate change on the plant diversity of the sub-alpine and alpine zones. It provides a quantitative/qualitative analysis of vegetation-environment relationships for four summits along an altitude gradient on the Lefka Ori massif Crete (1664-2339 m). The GLORIA multi-summit approach was used to provide vegetation and floristic data together with temperature records for every summit. Species richness and species turnover was calculated together with floristic similarity between the summits. 70 species were recorded, 20 of which were endemic, belonging to 23 different families. Cretan endemics dominate at these high altitudes. Species richness and turnover decreased with altitude. The two highest summits showed greater floristic similarity. Only 20% of the total flora recorded reaches the highest summit while 10% is common among summits. Overall there was a 4.96 degrees C decrease in temperature along the 675 m gradient. Given a scenario of temperature increase the ecotone between the sub-alpine and alpine zone would be likely to have the greatest species turnover. Southern exposures are likely to be invaded first by thermophilous species while northern exposures are likely to be more resistant to changes. Species distribution shifts will also depend on habitat availability. Many, already threatened, local endemic species will be affected first.

Impact of stratospheric variability on tropospheric climate change

An improved stratospheric representation has been included in simulations with the Hadley Centre HadGEM1 coupled ocean atmosphere model with natural and anthropogenic forcings for the period 1979–2003. An improved stratospheric ozone dataset is employed that includes natural variations in ozone as well as the usual anthropogenic trends. In addition, in a second set of simulations the quasi biennial oscillation (QBO) of stratospheric equatorial zonal wind is also imposed using a relaxation towards ERA-40 zonal wind values. The resulting impact on tropospheric variability and trends is described. We show that the modelled cooling rate at the tropopause is enhanced by the improved ozone dataset and this improvement is even more marked when the QBO is also included. The same applies to warming trends in the upper tropical troposphere which are slightly reduced. Our stratospheric improvements produce a significant increase of internal variability but no change in the positive trend of annual mean global mean near-surface temperature. Warming rates are increased significantly over a large portion of the Arctic Ocean. The improved stratospheric representation, especially the QBO relaxation, causes a substantial reduction in near-surface temperature and precipitation response to the El Chichón eruption, especially in the tropical region. The winter increase in the phase of the northern annular mode observed in the aftermath of the two major recent volcanic eruptions is partly captured, especially after the El Chichón eruption. The positive trend in the southern annular mode (SAM) is increased and becomes statistically significant which demonstrates that the observed increase in the SAM is largely subject to internal variability in the stratosphere. The possible inclusion in simulations for future assessments of full ozone chemistry and a gravity wave scheme to internally generate a QBO is discussed.

Bioclimatic envelope model of climate change impacts on blanket peatland distribution in Great Britain

Blanket peatlands are rain-fed mires that cover the landscape almost regardless of topography. The geographical extent of this type of peatland is highly sensitive to climate. We applied a global process-based bioclimatic envelope model, PeatStash, to predict the distribution of British blanket peatlands. The model captures the present areal extent (Kappa = 0.77) and is highly sensitive to both temperature and precipitation changes. When the model is run using the UKCIP02 climate projections for the time periods 2011–2040, 2041–2070 and 2071–2100, the geographical distribution of blanket peatlands gradually retreats towards the north and the west. In the UKCIP02 high emissions scenario for 2071–2100, the blanket peatland bioclimatic space is ~84% smaller than contemporary conditions (1961–1990); only parts of the west of Scotland remain inside this space. Increasing summer temperature is the main driver of the projected changes in areal extent. Simulations using 7 climate model outputs resulted in generally similar patterns of declining aereal extent of the bioclimatic space, although differing in degree. The results presented in this study should be viewed as a first step towards understanding the trends likely to affect the blanket peatland distribution in Great Britain. The eventual fate of existing blanket peatlands left outside their bioclimatic space remains uncertain.

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).

Dynamics, stratospheric ozone, and climate change

Dynamics affects the distribution and abundance of stratospheric ozone directly through transport of ozone itself and indirectly through its effect on ozone chemistry via temperature and transport of other chemical species. Dynamical processes must be considered in order to understand past ozone changes, especially in the northern hemisphere where there appears to be significant low-frequency variability which can look “trend-like” on decadal time scales. A major challenge is to quantify the predictable, or deterministic, component of past ozone changes. Over the coming century, changes in climate will affect the expected recovery of ozone. For policy reasons it is important to be able to distinguish and separately attribute the effects of ozone-depleting substances and greenhouse gases on both ozone and climate. While the radiative-chemical effects can be relatively easily identified, this is not so evident for dynamics — yet dynamical changes (e.g., changes in the Brewer-Dobson circulation) could have a first-order effect on ozone over particular regions. Understanding the predictability and robustness of such dynamical changes represents another major challenge. Chemistry-climate models have recently emerged as useful tools for addressing these questions, as they provide a self-consistent representation of dynamical aspects of climate and their coupling to ozone chemistry. We can expect such models to play an increasingly central role in the study of ozone and climate in the future, analogous to the central role of global climate models in the study of tropospheric climate change.

Reliability of regional climate model trends

A necessary condition for a good probabilistic forecast is that the forecast system is shown to be reliable: forecast probabilities should equal observed probabilities verified over a large number of cases. As climate change trends are now emerging from the natural variability, we can apply this concept to climate predictions and compute the reliability of simulated local and regional temperature and precipitation trends (1950–2011) in a recent multi-model ensemble of climate model simulations prepared for the Intergovernmental Panel on Climate Change (IPCC) fifth assessment report (AR5). With only a single verification time, the verification is over the spatial dimension. The local temperature trends appear to be reliable. However, when the global mean climate response is factored out, the ensemble is overconfident: the observed trend is outside the range of modelled trends in many more regions than would be expected by the model estimate of natural variability and model spread. Precipitation trends are overconfident for all trend definitions. This implies that for near-term local climate forecasts the CMIP5 ensemble cannot simply be used as a reliable probabilistic forecast.

Past and recent changes in the North Atlantic oscillation

The North Atlantic oscillation (NAO) is under current climate conditions the leading mode of atmospheric circulation variability over the North Atlantic region. While the pattern is present during the entire year, it is most important during winter, explaining a large part of the variability of the large-scale pressure field, being thus largely determinant for the weather conditions over the North Atlantic basin and over Western Europe. In this study, a review of recent literature on the basic understanding of the NAO, its variability on different time scales and driving physical mechanisms is presented. In particular, the observed NAO variations and long-term trends are put into a long term perspective by considering paleo-proxy evidence. A representative number of recently released NAO reconstructions are discussed. While the reconstructions agree reasonably well with observations during the instrumental overlapping period, there is a rather high uncertainty between the different reconstructions for the pre-instrumental period, which leads to partially incoherent results, that is, periods where the NAO reconstructions do not agree even in sign. Finally, we highlight the future need of a broader definition of the NAO, the assessment of the stability of the teleconnection centers over time, the analysis of the relations to other relevant variables like temperature and precipitation, as well as on the relevant processes involved

Climate change scenarios applied to viticultural zoning in Europe

Climate is one of the main factors controlling winegrape production. Bioclimatic indices describing the suitability of a particular region for wine production are a widely used zoning tool. Seven suitable bioclimatic indices characterize regions in Europe with different viticultural suitability, and their possible geographical shifts under future climate conditions are addressed using regional climate model simulations. The indices are calculated from climatic variables (daily values of temperature and precipitation) obtained from transient ensemble simulations with the regional model COSMO-CLM. Index maps for recent decades (1960–2000) and for the 21st century (following the IPCC-SRES B1 and A1B scenarios) are compared. Results show that climate change is projected to have a significant effect on European viticultural geography. Detrimental impacts on winegrowing are predicted in southern Europe, mainly due to increased dryness and cumulative thermal effects during the growing season. These changes represent an important constraint to grapevine growth and development, making adaptation strategies crucial, such as changing varieties or introducing water supply by irrigation. Conversely, in western and central Europe, projected future changes will benefit not only wine quality, but might also demarcate new potential areas for viticulture, despite some likely threats associated with diseases. Regardless of the inherent uncertainties, this approach provides valuable information for implementing proper and diverse adaptation measures in different European regions.

Flood risk and climate change: global and regional perspectives

A holistic perspective on changing rainfall-driven flood risk is provided for the late 20th and early 21st centuries. Economic losses from floods have greatly increased, principally driven by the expanding exposure of assets at risk. It has not been possible to attribute rain-generated peak streamflow trends to anthropogenic climate change over the past several decades. Projected increases in the frequency and intensity of heavy rainfall, based on climate models, should contribute to increases in precipitation-generated local flooding (e.g. flash flooding and urban flooding). This article assesses the literature included in the IPCC SREX report and new literature published since, and includes an assessment of changes in flood risk in seven of the regions considered in the recent IPCC SREX report—Africa, Asia, Central and South America, Europe, North America, Oceania and Polar regions. Also considering newer publications, this article is consistent with the recent IPCC SREX assessment finding that the impacts of climate change on flood characteristics are highly sensitive to the detailed nature of those changes and that presently we have only low confidence1 in numerical projections of changes in flood magnitude or frequency resulting from climate change.