Stratospheric water vapor and climate: sensitivity to the representation in radiation codes

There has been considerable interest in the climate impact of trends in stratospheric water vapor (SWV). However, the representation of the radiative properties of water vapor under stratospheric conditions remains poorly constrained across different radiation codes. This study examines the sensitivity of a detailed line-by-line (LBL) code, a Malkmus narrow-band model and two broadband GCM radiation codes to a uniform perturbation in SWV in the longwave spectral region. The choice of sampling rate in wave number space (Δν) in the LBL code is shown to be important for calculations of the instantaneous change in heating rate (ΔQ) and the instantaneous longwave radiative forcing (ΔFtrop). ΔQ varies by up to 50% for values of Δν spanning 5 orders of magnitude, and ΔFtrop varies by up to 10%. In the three less detailed codes, ΔQ differs by up to 45% at 100 hPa and 50% at 1 hPa compared to a LBL calculation. This causes differences of up to 70% in the equilibrium fixed dynamical heating temperature change due to the SWV perturbation. The stratosphere-adjusted radiative forcing differs by up to 96% across the less detailed codes. The results highlight an important source of uncertainty in quantifying and modeling the links between SWV trends and climate.

The roles of aerosol, water vapor and cloud in future global dimming/brightening

Observational evidence indicates significant regional trends in solar radiation at the surface in both all-sky and cloud-free conditions. Negative trends in the downwelling solar surface irradiance (SSI) have become known as ‘dimming’ while positive trends have become known as ‘brightening’. We use the Met Office Hadley Centre HadGEM2 climate model to model trends in cloud-free and total SSI from the pre-industrial to the present-day and compare these against observations. Simulations driven by CMIP5 emissions are used to model the future trends in dimming/brightening up to the year 2100. The modeled trends are reasonably consistent with observed regional trends in dimming and brightening which are due to changes in concentrations in anthropogenic aerosols and, potentially, changes in cloud cover owing to the aerosol indirect effects and/or cloud feedback mechanisms. The future dimming/brightening in cloud-free SSI is not only caused by changes in anthropogenic aerosols: aerosol impacts are overwhelmed by a large dimming caused by increases in water vapor. There is little trend in the total SSI as cloud cover decreases in the climate model used here, and compensates the effect of the change in water vapor. In terms of the surface energy balance, these trends in SSI are obviously more than compensated by the increase in the downwelling terrestrial irradiance from increased water vapor concentrations. However, the study shows that while water vapor is widely appreciated as a greenhouse gas, water vapor impacts on the atmospheric transmission of solar radiation and the future of global dimming/brightening should not be overlooked.

The circulation response to idealized changes in stratospheric water vapor

Observations show that stratospheric water vapor (SWV) concentrations increased by ~30% between 1980 and 2000. SWV has also been projected to increase by up to a factor of two over the 21st century. Trends in SWV impact on stratospheric temperatures, which may lead to changes in the stratospheric circulation. Perturbations in temperature and wind in the stratosphere have been shown to influence the extratropical tropospheric circulation. This study investigates the response to a uniform doubling in SWV from 3 to 6 ppmv in a comprehensive stratosphere-resolving atmospheric-GCM. The increase in SWV causes stratospheric cooling with a maximum amplitude of 5-6 K in the polar lower stratosphere and 2-3 K in the tropical lower stratosphere. The zonal wind on the upper flanks of the subtropical jets is more westerly by up to ~5 m s−1. Changes in resolved wave drag in the stratosphere result in an increase in the strength of tropical upwelling associated with the Brewer-Dobson circulation of ~10% throughout the year. In the troposphere, the increase in SWV causes significant meridional dipole changes in the midlatitude zonal-mean zonal wind of up to 2.8 m s−1 at 850 hPa, which are largest in boreal winter in both hemispheres. This suggests a more poleward storm track under uniformly increased stratospheric water vapor. The circulation changes in both the stratosphere and troposphere are almost entirely due to the increase in SWV at pressures greater than 50 hPa. The results show that long-term trends in SWV may impact on stratospheric temperatures and wind, the strength of the Brewer-Dobson circulation and extratropical surface climate.

Liquid-vapour homogenisation of fluid inclusions in stalagmites: Evaluation of a new thermometer for paleoclimate research

We present a new approach to determine palaeotemperatures (mean annual surface temperatures) based on measurements of the liquid–vapour homogenisation temperature of fluid inclusions in stalagmites. The aim of this study is to explore the potential and the limitations of this new palaeothermometer and to develop a reliable methodology for routine applications in palaeoclimate research. Therefore, we have investigated recent fluid inclusions from the top part of actively growing stalagmites that have formed at temperatures close to the present-day cave air temperature. A precondition for measuring homogenisation temperatures of originally monophase inclusions is the nucleation of a vapour bubble by means of single ultra-short laser pulses. Based on the observed homogenisation temperatures (Th(obs)) and measurements of the vapour bubble diameter at a known temperature, we calculated stalagmite formation temperatures (Tf) by applying a thermodynamic model that takes into account the effect of surface tension on liquid–vapour homogenisation. Results from recent stalagmite samples demonstrate that calculated stalagmite formation temperatures match the present-day cave air temperature within ± 0.2 °C. To avoid artificially induced changes of the fluid density we defined specific demands on the selection, handling and preparation of the stalagmite samples. Application of the method is restricted to stalagmites that formed at cave temperatures greater than ~ 9–11 °C.

Detection of gyrA mutations in quinolone-resistant Salmonella enterica by denaturing high-performance liquid chromatography

Denaturing high-performance liquid chromatography (DHPLC) was evaluated as a rapid screening and identification method for DNA sequence variation detection in the quinolone resistance-determining region of gyrA from Salmonella serovars. A total of 203 isolates of Salmonella were screened using this method. DHPLC analysis of 14 isolates representing each type of novel or multiple mutations and the wild type were compared with LightCycler-based PCR-gyrA hybridization mutation assay (GAMA) and single-strand conformational polymorphism (SSCP) analyses. The 14 isolates gave seven different SSCP patterns, and LightCycler detected four different mutations. DHPLC detected 11 DNA sequence variants at eight different codons, including those detected by LightCycler or SSCP. One of these mutations was silent. Five isolates contained multiple mutations, and four of these could be distinguished from the composite sequence variants by their DHPLC profile. Seven novel mutations were identified at five different loci not previously described in quinolone-resistant salmonella. DHPLC analysis proved advantageous for the detection of novel and multiple mutations. DHPLC also provides a rapid, high-throughput alternative to LightCycler and SSCP for screening frequently occurring mutations.

Detection of mutations in Salmonella enterica gyrA, gyrB, parC and parE genes by denaturing high performance liquid chromatography (DHPLC) using standard HPLC instrumentation

Aims: Quinolone antibiotics are the agents of choice for treating systemic Salmonella infections. Resistance to quinolones is usually mediated by mutations in the DNA gyrase gene gyrA. Here we report the evaluation of standard HPLC equipment for the detection of mutations (single nucleotide polymorphisms; SNPs) in gyrA, gyrB, parC and parE by denaturing high performance liquid chromatography (DHPLC). Methods: A panel of Salmonella strains was assembled which comprised those with known different mutations in gyrA (n = 8) and fluoroquinolone-susceptible and -resistant strains (n = 50) that had not been tested for mutations in gyrA. Additionally, antibiotic-susceptible strains of serotypes other than Salmonella enterica serovar Typhimurium strains were examined for serotype-specific mutations in gyrB (n = 4), parC (n = 6) and parE (n = 1). Wild-type (WT) control DNA was prepared from Salmonella Typhimurium NCTC 74. The DNA of respective strains was amplified by PCR using Optimase (R) proofreading DNA polymerase. Duplex DNA samples were analysed using an Agilent A1100 HPLC system with a Varian Helix (TM) DNA column. Sequencing was used to validate mutations detected by DHPLC in the strains with unknown mutations. Results: Using this HPLC system, mutations in gyrA, gyrB, parC and parE were readily detected by comparison with control chromatograms. Sequencing confirmed the gyrA predicted mutations as detected by DHPLC in the unknown strains and also confirmed serotype-associated sequence changes in non-Typhimurium serotypes. Conclusions: The results demonstrated that a non-specialist standard HPLC machine fitted with a generally available column can be used to detect SNPs in gyrA, gyrB, parC and parE genes by DHPLC. Wider applications should be possible.

Cloud droplet size and liquid water path retrievals from zenith radiance measurements: examples from the Atmospheric Radiation Measurement Program and the Aerosol Robotic Network

The ground-based Atmospheric Radiation Measurement Program (ARM) and NASA Aerosol Robotic Net- work (AERONET) routinely monitor clouds using zenith ra- diances at visible and near-infrared wavelengths. Using the transmittance calculated from such measurements, we have developed a new retrieval method for cloud effective droplet size and conducted extensive tests for non-precipitating liquid water clouds. The underlying principle is to combine a liquid-water-absorbing wavelength (i.e., 1640 nm) with a non-water-absorbing wavelength for acquiring information on cloud droplet size and optical depth. For simulated stratocumulus clouds with liquid water path less than 300 g m−2 and horizontal resolution of 201 m, the retrieval method underestimates the mean effective radius by 0.8μm, with a root-mean-squared error of 1.7 μm and a relative deviation of 13%. For actual observations with a liquid water path less than 450 g m−2 at the ARM Oklahoma site during 2007– 2008, our 1.5-min-averaged retrievals are generally larger by around 1 μm than those from combined ground-based cloud radar and microwave radiometer at a 5-min temporal resolution. We also compared our retrievals to those from combined shortwave flux and microwave observations for relatively homogeneous clouds, showing that the bias between these two retrieval sets is negligible, but the error of 2.6 μm and the relative deviation of 22 % are larger than those found in our simulation case. Finally, the transmittance-based cloud effective droplet radii agree to better than 11 % with satellite observations and have a negative bias of 1 μm. Overall, the retrieval method provides reasonable cloud effective radius estimates, which can enhance the cloud products of both ARM and AERONET.

Liquid AP-UV-MALDI enables stable ion yields of multiply charged peptide and protein ions for sensitive analysis by mass spectrometry

In biological mass spectrometry (MS), two ionization techniques are predominantly employed for the analysis of larger biomolecules, such as polypeptides. These are nano-electrospray ionization [1, 2] (nanoESI) and matrix-assisted laser desorption/ionization [3, 4] (MALDI). Both techniques are considered to be “soft”, allowing the desorption and ionization of intact molecular analyte species and thus their successful mass-spectrometric analysis. One of the main differences between these two ionization techniques lies in their ability to produce multiply charged ions. MALDI typically generates singly charged peptide ions whereas nanoESI easily provides multiply charged ions, even for peptides as low as 1000 Da in mass. The production of highly charged ions is desirable as this allows the use of mass analyzers, such as ion traps (including orbitraps) and hybrid quadrupole instruments, which typically offer only a limited m/z range (< 2000–4000). It also enables more informative fragmentation spectra using techniques such as collisioninduced dissociation (CID) and electron capture/transfer dissociation (ECD/ETD) in combination with tandem MS (MS/MS). [5, 6] Thus, there is a clear advantage of using ESI in research areas where peptide sequencing, or in general, the structural elucidation of biomolecules by MS/MS is required. Nonetheless, MALDI with its higher tolerance to contaminants and additives, ease-of-operation, potential for highspeed and automated sample preparation and analysis as well as its MS imaging capabilities makes it an ionization technique that can cover bioanalytical areas for which ESI is less suitable. [7, 8] If these strengths could be combined with the analytical power of multiply charged ions, new instrumental configurations and large-scale proteomic analyses based on MALDI MS(/MS) would become feasible.

On the determination of atmospheric water vapor from GPS measurements

Surface-based GPS measurements of zenith path delay (ZPD) can be used to derive vertically integrated water vapor (IWV) of the atmosphere. ZPD data are collected in a global network presently consisting of 160 stations as part of the International GPS Service. In the present study, ZPD data from this network are converted into IWV using observed surface pressure and mean atmospheric water vapor column temperature obtained from the European Centre for Medium-Range Weather Forecasts' (ECMWF) operational analyses (OA). For the 4 months of January/July 2000/2001, the GPS-derived IWV values are compared to the IWV from the ECMWF OA, with a special focus on the monthly averaged difference (bias) and the standard deviation of daily differences. This comparison shows that the GPS-derived IWV values are well suited for the validation of OA of IWV. For most GPS stations, the IWV data agree quite well with the analyzed data indicating that they are both correct at these locations. Larger differences for individual days are interpreted as errors in the analyses. A dry bias in the winter is found over central United States, Canada, and central Siberia, suggesting a systematic analysis error. Larger differences were mainly found in mountain areas. These were related to representation problems and interpolation difficulties between model height and station height. In addition, the IWV comparison can be used to identify errors or problems in the observations of ZPD. This includes errors in the data itself, e.g., erroneous outlier in the measured time series, as well as systematic errors that affect all IWV values at a specific station. Such stations were excluded from the intercomparison. Finally, long-term requirements for a GPS-based water vapor monitoring system are discussed.

Potential role of the quasi-biennial oscillation in the stratosphere-troposphere exchange as found in water vapor in general circulation model experiments

The tropical tropopause is considered to be the main region of upward transport of tropospheric air carrying water vapor and other tracers to the tropical stratosphere. The lower tropical stratosphere is also the region where the quasi-biennial oscillation (QBO) in the zonal wind is observed. The QBO is positioned in the region where the upward transport of tropospheric tracers to the overworld takes place. Hence the QBO can in principle modulate these transports by its secondary meridional circulation. This modulation is investigated in this study by an analysis of general circulation model (GCM) experiments with an assimilated QBO. The experiments show, first, that the temperature signal of the QBO modifies the specific humidity in the air transported upward and, second, that the secondary meridional circulation modulates the velocity of the upward transport. Thus during the eastward phase of the QBO the upward moving air is moister and the upward velocity is less than during the westward phase of the QBO. It was further found that the QBO period is too short to allow an equilibration of the moisture in the QBO region. This causes a QBO signal of the moisture which is considerably smaller than what could be obtained in the limiting case of indefinitely long QBO phases. This also allows a high sensitivity of the mean moisture over a QBO cycle to the El Niño-Southern Oscillation (ENSO) phenomena or major tropical volcanic eruptions. The interplay of sporadic volcanic eruptions, ENSO, and QBO can produce low-frequency variability in the water vapor content of the tropical stratosphere, which renders the isolation of the QBO signal in observational data of water vapor in the equatorial lower stratosphere difficult.

Chapter 17: X-Ray rheology of liquid crystal polymers

X-ray Rheology is an experimental technique which uses time-ressolved x-ray scattering as probe of the molecular level structural reorganisation which accompanies flow. It provides quantitative information on the direction alignment and on the level of global orientation. This information is very helpful in interpreting the classic rheological data on liquid crystal polymers. In this research we use data obtained from a cellulose derivate which exhibits a thermotropic liquid crystal phase. We show how increased shear rates lead to a rapid rise in the global orientation and we related this to therories of flow in liquid crystal polymers from the literature. We show that the relaxation time is independent of the prior shear rate.

Climate determinism revisited: multiple equilibria in a complex climate model

Multiple equilibria in a coupled ocean–atmosphere–sea ice general circulation model (GCM) of an aquaplanet with many degrees of freedom are studied. Three different stable states are found for exactly the same set of parameters and external forcings: a cold state in which a polar sea ice cap extends into the midlatitudes; a warm state, which is ice free; and a completely sea ice–covered “snowball” state. Although low-order energy balance models of the climate are known to exhibit intransitivity (i.e., more than one climate state for a given set of governing equations), the results reported here are the first to demonstrate that this is a property of a complex coupled climate model with a consistent set of equations representing the 3D dynamics of the ocean and atmosphere. The coupled model notably includes atmospheric synoptic systems, large-scale circulation of the ocean, a fully active hydrological cycle, sea ice, and a seasonal cycle. There are no flux adjustments, with the system being solely forced by incoming solar radiation at the top of the atmosphere. It is demonstrated that the multiple equilibria owe their existence to the presence of meridional structure in ocean heat transport: namely, a large heat transport out of the tropics and a relatively weak high-latitude transport. The associated large midlatitude convergence of ocean heat transport leads to a preferred latitude at which the sea ice edge can rest. The mechanism operates in two very different ocean circulation regimes, suggesting that the stabilization of the large ice cap could be a robust feature of the climate system. Finally, the role of ocean heat convergence in permitting multiple equilibria is further explored in simpler models: an atmospheric GCM coupled to a slab mixed layer ocean and an energy balance model

Ocean heat transport and water vapor greenhouse in a warm equable climate: a new look at the low gradient paradox

The authors study the role of ocean heat transport (OHT) in the maintenance of a warm, equable, ice-free climate. An ensemble of idealized aquaplanet GCM calculations is used to assess the equilibrium sensitivity of global mean surface temperature and its equator-to-pole gradient (ΔT) to variations in OHT, prescribed through a simple analytical formula representing export out of the tropics and poleward convergence. Low-latitude OHT warms the mid- to high latitudes without cooling the tropics; increases by 1°C and ΔT decreases by 2.6°C for every 0.5-PW increase in OHT across 30° latitude. This warming is relatively insensitive to the detailed meridional structure of OHT. It occurs in spite of near-perfect atmospheric compensation of large imposed variations in OHT: the total poleward heat transport is nearly fixed. The warming results from a convective adjustment of the extratropical troposphere. Increased OHT drives a shift from large-scale to convective precipitation in the midlatitude storm tracks. Warming arises primarily from enhanced greenhouse trapping associated with convective moistening of the upper troposphere. Warming extends to the poles by atmospheric processes even in the absence of high-latitude OHT. A new conceptual model for equable climates is proposed, in which OHT plays a key role by driving enhanced deep convection in the midlatitude storm tracks. In this view, the climatic impact of OHT depends on its effects on the greenhouse properties of the atmosphere, rather than its ability to increase the total poleward energy transport.

Spectral nonlocality, absolute equilibria and Kraichnan-Leith-Batchelor phenomenology in two-dimensional turbulent energy cascades

We study the degree to which Kraichnan–Leith–Batchelor (KLB) phenomenology describes two-dimensional energy cascades in α turbulence, governed by ∂θ/∂t+J(ψ,θ)=ν∇2θ+f, where θ=(−Δ)α/2ψ is generalized vorticity, and ψ^(k)=k−αθ^(k) in Fourier space. These models differ in spectral non-locality, and include surface quasigeostrophic flow (α=1), regular two-dimensional flow (α=2) and rotating shallow flow (α=3), which is the isotropic limit of a mantle convection model. We re-examine arguments for dual inverse energy and direct enstrophy cascades, including Fjørtoft analysis, which we extend to general α, and point out their limitations. Using an α-dependent eddy-damped quasinormal Markovian (EDQNM) closure, we seek self-similar inertial range solutions and study their characteristics. Our present focus is not on coherent structures, which the EDQNM filters out, but on any self-similar and approximately Gaussian turbulent component that may exist in the flow and be described by KLB phenomenology. For this, the EDQNM is an appropriate tool. Non-local triads contribute increasingly to the energy flux as α increases. More importantly, the energy cascade is downscale in the self-similar inertial range for 2.5<α<10. At α=2.5 and α=10, the KLB spectra correspond, respectively, to enstrophy and energy equipartition, and the triad energy transfers and flux vanish identically. Eddy turnover time and strain rate arguments suggest the inverse energy cascade should obey KLB phenomenology and be self-similar for α<4. However, downscale energy flux in the EDQNM self-similar inertial range for α>2.5 leads us to predict that any inverse cascade for α≥2.5 will not exhibit KLB phenomenology, and specifically the KLB energy spectrum. Numerical simulations confirm this: the inverse cascade energy spectrum for α≥2.5 is significantly steeper than the KLB prediction, while for α<2.5 we obtain the KLB spectrum.

Electro-active nanofibres electrospun from blends of poly-vinyl cinnamate and a cholesteric liquid crystalline silicone polymer

Electrospinning was used to generate polymer nanofibres from blends of poly-vinyl cinnamate (PVCN) and a cholesteric silicone polymer. Only blends that contained at least 40 % of PVCN produced fibres. Both differential scanning calorimetry and electron dispersion spectroscopy data indicate that the samples are miscible over a wide temperature interval. The variation of fibre diameter with concentration is nonlinear with a well-defined minimum corresponding to an 80 % PVCN blend. The fibres are birefringent with Kerr constants similar to that of cholesteric liquid crystals. Although not significant, the Kerr constant increases with increasing silicone polymer concentration.