A pressure-jump time-resolved x-ray diffraction study of cubic-cubic transition kinetics in monoolein

In the past two decades, the geometric pathways involved in the transformations between inverse bicontinuous cubic phases in amphiphilic systems have been extensively theoretically modeled. However, little experimental data exists on the cubic-cubic transformation in pure lipid systems. We have used pressure-jump time-resolved X-ray diffraction to investigate the transition between the gyroid Q(II)(G) and double-diamond Q(II)(D) phases in mixtures of 1-monoolein in 30 wt% water. We find for this system that the cubic-cubic transition occurs without any detectable intermediate structures. In addition, we have determined the kinetics of the transition, in both the forward and reverse directions, as a function of pressure-jump amplitude, temperature, and water content. A recently developed model allows (at least in principle) the calculation of the activation energy for lipid phase transitions from such data. The analysis is applicable only if kinetic reproducibility is achieved, at least within one sample, and achievement of such kinetic reproducibility is shown here, by carrying out prolonged pressure-cycling. The rate of transformation shows clear and consistent trends with pressure-jump amplitude, temperature, and water content, all of which are shown to be in agreement with the effect of the shift in the position of the cubic-cubic phase boundary following a change in the thermodynamic parameters.

The effect of vessel diameter on time dependent gas hold-up variations in highly viscous impeller agitated liquids

Time dependent gas hold-up generated in the 0.3 and 0.6 m diameter vessels using high viscosity castor oil and carboxy methyl cellulose (CMC) solution was compared on the basis of impeller speed (N) and gas velocity (V-G). Two types of hold-up were distinguished-the hold-up due to tiny bubbles (epsilon(ft)) and total hold-up (epsilon(f)), which included large and tiny bubbles. It was noted that vessel diameter (i.e. the scale of operation) significantly influences (i) the trends and the values of epsilon(f) and epsilon(ft), and (ii) the values of tau (a constant reflecting the time dependency of hold-up). The results showed that a scale independent correlation for gas hold-up of the form epsilon(f) or epsilon(ft) = A(N or P-G/V)(a) (V-G)(b), where "a" and "b" are positive constants is not appropriate for viscous liquids. This warrants further investigations into the effect of vessel diameter on gas hold-up in impeller agitated high viscosity liquids (mu or mu(a) > 0.4 Pa s). (C) 2003 Elsevier B.V. All rights reserved.

Tropospheric temperature trends: history of an ongoing controversy

Changes in atmospheric temperature have a particular importance in climate research because climate models consistently predict a distinctive vertical profile of trends. With increasing greenhouse gas concentrations, the surface and troposphere are consistently projected to warm, with an enhancement of that warming in the tropical upper troposphere. Hence, attempts to detect this distinct ‘fingerprint’ have been a focus for observational studies. The topic acquired heightened importance following the 1990 publication of an analysis of satellite data which challenged the reality of the projected tropospheric warming. This review documents the evolution over the last four decades of understanding of tropospheric temperature trends and their likely causes. Particular focus is given to the difficulty of producing homogenized datasets, with which to derive trends, from both radiosonde and satellite observing systems, because of the many systematic changes over time. The value of multiple independent analyses is demonstrated. Paralleling developments in observational datasets, increased computer power and improved understanding of climate forcing mechanisms have led to refined estimates of temperature trends from a wide range of climate models and a better understanding of internal variability. It is concluded that there is no reasonable evidence of a fundamental disagreement between tropospheric temperature trends from models and observations when uncertainties in both are treated comprehensively

Long-lived halocarbon trends and budgets from atmospheric chemistry modelling constrained with measurements in polar firn

The budgets of seven halogenated gases (CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, CCl4 and SF6) are studied by comparing measurements in polar firn air from two Arctic and three Antarctic sites, and simulation results of two numerical models: a 2-D atmospheric chemistry model and a 1-D firn diffusion model. The first one is used to calculate atmospheric concentrations from emission trends based on industrial inventories; the calculated concentration trends are used by the second one to produce depth concentration profiles in the firn. The 2-D atmospheric model is validated in the boundary layer by comparison with atmospheric station measurements, and vertically for CFC-12 by comparison with balloon and FTIR measurements. Firn air measurements provide constraints on historical atmospheric concentrations over the last century. Age distributions in the firn are discussed using a Green function approach. Finally, our results are used as input to a radiative model in order to evaluate the radiative forcing of our target gases. Multi-species and multi-site firn air studies allow to better constrain atmospheric trends. The low concentrations of all studied gases at the bottom of the firn, and their consistency with our model results confirm that their natural sources are small. Our results indicate that the emissions, sinks and trends of CFC-11, CFC-12, CFC-113, CFC-115 and SF6 are well constrained, whereas it is not the case for CFC-114 and CCl4. Significant emission-dependent changes in the lifetimes of halocarbons destroyed in the stratosphere were obtained. Those result from the time needed for their transport from the surface where they are emitted to the stratosphere where they are destroyed. Efforts should be made to update and reduce the large uncertainties on CFC lifetimes.

Trends in the start of the wet season over Africa

A quarter of a century of daily rainfall data from the Global Telecommunications System are used to define the temporal and spatial variability of the start of the wet season over Africa and surrounding extreme south of Europe and parts of the Middle East. From 1978 to 2002, the start of the wet season arrived later in the year for the majority of the region, as time progressed. In some parts of the continent, there was an annual increase in the start date of up to 4 days per year. On average, the start of the wet season arrived 9–21 days later from 1978 to 2002, depending on the threshold used to define the start of the rains (varying from 10–30 mm over 2 days, with no dry period in the following 10 days). It is noted that the inter-annual variability of the start of the wet season is high with the range of start dates varying on average from 116 to 142 days dependent on the threshold used to determine the start date. These results may have important implications for agriculturists on all levels (from the individual farmer to those responsible for regional food supply), as knowledge of potential future climate changes starts to play an increasingly important role in the agricultural decision-making process, such as sowing and harvesting times.

On the evaluation of temperature trends in the tropical troposphere

A series of model experiments with the coupled Max-Planck-Institute ECHAM5/OM climate model have been investigated and compared with microwave measurements from the Microwave Sounding Unit (MSU) and re-analysis data for the period 1979–2008. The evaluation is carried out by computing the Temperature in the Lower Troposphere (TLT) and Temperature in the Middle Troposphere (TMT) using the MSU weights from both University of Alabama (UAH) and Remote Sensing Systems (RSS) and restricting the study to primarily the tropical oceans. When forced by analysed sea surface temperature the model reproduces accurately the time-evolution of the mean outgoing tropospheric microwave radiation especially over tropical oceans but with a minor bias towards higher temperatures in the upper troposphere. The latest reanalyses data from the 25 year Japanese re-analysis (JRA25) and European Center for Medium Range Weather Forecasts Interim Reanalysis are in very close agreement with the time-evolution of the MSU data with a correlation of 0.98 and 0.96, respectively. The re-analysis trends are similar to the trends obtained from UAH but smaller than the trends from RSS. Comparison of TLT, computed from observations from UAH and RSS, with Sea Surface Temperature indicates that RSS has a warm bias after 1993. In order to identify the significance of the tropospheric linear temperature trends we determined the natural variability of 30-year trends from a 500 year control integration of the coupled ECHAM5 model. The model exhibits natural unforced variations of the 30 year tropospheric trend that vary within ±0.2 K/decade for the tropical oceans. This general result is supported by similar results from the Geophysical Fluid Dynamics Laboratory (GFDL) coupled climate model. Present MSU observations from UAH for the period 1979–2008 are well within this range but RSS is close to the upper positive limit of this variability. We have also compared the trend of the vertical lapse rate over the tropical oceans assuming that the difference between TLT and TMT is an approximate measure of the lapse rate. The TLT–TMT trend is larger in both the measurements and in the JRA25 than in the model runs by 0.04–0.06 K/decade. Furthermore, a calculation of all 30 year TLT–TMT trends of the unforced 500-year integration vary between ±0.03 K/decade suggesting that the models have a minor systematic warm bias in the upper troposphere.

Stratospheric temperature trends: our evolving understanding

We review the scientific literature since the 1960s to examine the evolution of modeling tools and observations that have advanced understanding of global stratospheric temperature changes. Observations show overall cooling of the stratosphere during the period for which they are available (since the late 1950s and late 1970s from radiosondes and satellites, respectively), interrupted by episodes of warming associated with volcanic eruptions, and superimposed on variations associated with the solar cycle. There has been little global mean temperature change since about 1995. The temporal and vertical structure of these variations are reasonably well explained bymodels that include changes in greenhouse gases, ozone, volcanic aerosols, and solar output, although there are significant uncertainties in the temperature observations and regarding the nature and influence of past changes in stratospheric water vapor. As a companion to a recent WIREs review of tropospheric temperature trends, this article identifies areas of commonality and contrast between the tropospheric and stratospheric trend literature. For example, the increased attention over time to radiosonde and satellite data quality has contributed to better characterization of uncertainty in observed trends both in the troposphere and in the lower stratosphere, and has highlighted the relative deficiency of attention to observations in the middle and upper stratosphere. In contrast to the relatively unchanging expectations of surface and tropospheric warming primarily induced by greenhouse gas increases, stratospheric temperature change expectations have arisen from experiments with a wider variety of model types, showingmore complex trend patterns associated with a greater diversity of forcing agents.

Clear-sky biases in satellite infrared estimates of upper tropospheric humidity and its trends

We use microwave retrievals of upper tropospheric humidity (UTH) to estimate the impact of clear-sky-only sampling by infrared instruments on the distribution, variability and trends in UTH. Our method isolates the impact of the clear-sky-only sampling, without convolving errors from other sources. On daily time scales IR-sampled UTH contains large data gaps in convectively active areas, with only about 20-30 % of the tropics (30 S­ 30 N) being sampled. This results in a dry bias of about -9 %RH in the area-weighted tropical daily UTH time series. On monthly scales, maximum clear-sky bias (CSB) is up to -30 %RH over convectively active areas. The magnitude of CSB shows significant correlations with UTH itself (-0.5) and also with the variability in UTH (-0.6). We also show that IR-sampled UTH time series have higher interannual variability and smaller trends compared to microwave sampling. We argue that a significant part of the smaller trend results from the contrasting influence of diurnal drift in the satellite measurements on the wet and dry regions of the tropics.

An analysis of long-term trends, seasonality and short-term dynamics in water quality data from Plynlimon, Wales

This paper examines two hydrochemical time-series derived from stream samples taken in the Upper Hafren catchment, Plynlimon, Wales. One time-series comprises data collected at 7-hour intervals over 22 months (Neal et al., submitted, this issue), while the other is based on weekly sampling over 20 years. A subset of determinands: aluminium, calcium, chloride, conductivity, dissolved organic carbon, iron, nitrate, pH, silicon and sulphate are examined within a framework of non-stationary time-series analysis to identify determinand trends, seasonality and short-term dynamics. The results demonstrate that both long-term and high-frequency monitoring provide valuable and unique insights into the hydrochemistry of a catchment. The long-term data allowed analysis of long-termtrends, demonstrating continued increases in DOC concentrations accompanied by declining SO4 concentrations within the stream, and provided new insights into the changing amplitude and phase of the seasonality of the determinands such as DOC and Al. Additionally, these data proved invaluable for placing the short-term variability demonstrated within the high-frequency data within context. The 7-hour data highlighted complex diurnal cycles for NO3, Ca and Fe with cycles displaying changes in phase and amplitude on a seasonal basis. The high-frequency data also demonstrated the need to consider the impact that the time of sample collection can have on the summary statistics of the data and also that sampling during the hours of darkness provides additional hydrochemical information for determinands which exhibit pronounced diurnal variability. Moving forward, this research demonstrates the need for both long-term and high-frequency monitoring to facilitate a full and accurate understanding of catchment hydrochemical dynamics.

Ground-based aerosol optical depth trends at three high-altitude sites in Switzerland and Southern Germany from 1995–2010

Ground-based aerosol optical depth (AOD) climatologies at three high-altitude sites in Switzerland (Jungfraujoch and Davos) and Southern Germany (Hohenpeissenberg) are updated and re-calibrated for the period 1995 – 2010. In addition, AOD time-series are augmented with previously unreported data, and are homogenized for the first time. Trend analysis revealed weak AOD trends (λ = 500 nm) at Jungfraujoch (JFJ; +0.007 decade-1), Davos (DAV; +0.002 decade-1) and Hohenpeissenberg (HPB; -0.011 decade-1) where the JFJ and HPB trends were statistically significant at the 95% and 90% confidence levels. However, a linear trend for the JFJ 1995 – 2005 period was found to be more appropriate than for 1995 – 2010 due to the influence of stratospheric AOD which gave a trend -0.003 decade-1 (significant at 95% level). When correcting for a recently available stratospheric AOD time-series, accounting for Pinatubo (1991) and more recent volcanic eruptions, the 1995 – 2010 AOD trends decreased slightly at DAV and HPB but remained weak at +0.000 decade-1 and -0.013 decade-1 (significant at 95% level). The JFJ 1995 – 2005 AOD time-series similarly decreased to -0.003 decade-1 (significant at 95% level). We conclude that despite a more detailed re40 analysis of these three time-series, which have been extended by five years to the end of 2010, a significant decrease in AOD at these three high-altitude sites has still not been observed.

A framework for adapting survey design through time for wildlife population assessment

Sampling strategies for monitoring the status and trends in wildlife populations are often determined before the first survey is undertaken. However, there may be little information about the distribution of the population and so the sample design may be inefficient. Through time, as data are collected, more information about the distribution of animals in the survey region is obtained but it can be difficult to incorporate this information in the survey design. This paper introduces a framework for monitoring motile wildlife populations within which the design of future surveys can be adapted using data from past surveys whilst ensuring consistency in design-based estimates of status and trends through time. In each survey, part of the sample is selected from the previous survey sample using simple random sampling. The rest is selected with inclusion probability proportional to predicted abundance. Abundance is predicted using a model constructed from previous survey data and covariates for the whole survey region. Unbiased design-based estimators of status and trends and their variances are derived from two-phase sampling theory. Simulations over the short and long-term indicate that in general more precise estimates of status and trends are obtained using this mixed strategy than a strategy in which all of the sample is retained or all selected with probability proportional to predicted abundance. Furthermore the mixed strategy is robust to poor predictions of abundance. Estimates of status are more precise than those obtained from a rotating panel design.

Multimodel assessment of the upper troposphere and lower stratosphere: tropics and global trends

The performance of 18 coupled Chemistry Climate Models (CCMs) in the Tropical Tropopause Layer (TTL) is evaluated using qualitative and quantitative diagnostics. Trends in tropopause quantities in the tropics and the extratropical Upper Troposphere and Lower Stratosphere (UTLS) are analyzed. A quantitative grading methodology for evaluating CCMs is extended to include variability and used to develop four different grades for tropical tropopause temperature and pressure, water vapor and ozone. Four of the 18 models and the multi-model mean meet quantitative and qualitative standards for reproducing key processes in the TTL. Several diagnostics are performed on a subset of the models analyzing the Tropopause Inversion Layer (TIL), Lagrangian cold point and TTL transit time. Historical decreases in tropical tropopause pressure and decreases in water vapor are simulated, lending confidence to future projections. The models simulate continued decreases in tropopause pressure in the 21st century, along with ∼1K increases per century in cold point tropopause temperature and 0.5–1 ppmv per century increases in water vapor above the tropical tropopause. TTL water vapor increases below the cold point. In two models, these trends are associated with 35% increases in TTL cloud fraction. These changes indicate significant perturbations to TTL processes, specifically to deep convective heating and humidity transport. Ozone in the extratropical lowermost stratosphere has significant and hemispheric asymmetric trends. O3 is projected to increase by nearly 30% due to ozone recovery in the Southern Hemisphere (SH) and due to enhancements in the stratospheric circulation. These UTLS ozone trends may have significant effects in the TTL and the troposphere.

Assessing levels of uncertainty in recent temperature time series

We examine to what degree we can expect to obtain accurate temperature trends for the last two decades near the surface and in the lower troposphere. We compare temperatures obtained from surface observations and radiosondes as well as satellite-based measurements from the Microwave Soundings Units (MSU), which have been adjusted for orbital decay and non-linear instrument-body effects, and reanalyses from the European Centre for Medium-Range Weather Forecasts (ERA) and the National Centre for Environmental Prediction (NCEP). In regions with abundant conventional data coverage, where the MSU has no major influence on the reanalysis, temperature anomalies obtained from microwave sounders, radiosondes and from both reanalyses agree reasonably. Where coverage is insufficient, in particular over the tropical oceans, large differences are found between the MSU and either reanalysis. These differences apparently relate to changes in the satellite data availability and to differing satellite retrieval methodologies, to which both reanalyses are quite sensitive over the oceans. For NCEP, this results from the use of raw radiances directly incorporated into the analysis, which make the reanalysis sensitive to changes in the underlying algorithms, e.g. those introduced in August 1992. For ERA, the bias-correction of the one-dimensional variational analysis may introduce an error when the satellite relative to which the correction is calculated is biased itself or when radiances change on a time scale longer than a couple of months, e.g. due to orbit decay. ERA inhomogeneities are apparent in April 1985, October/November 1986 and April 1989. These dates can be identified with the replacements of satellites. It is possible that a negative bias in the sea surface temperatures (SSTs) used in the reanalyses may have been introduced over the period of the satellite record. This could have resulted from a decrease in the number of ship measurements, a concomitant increase in the importance of satellite-derived SSTs, and a likely cold bias in the latter. Alternately, a warm bias in SSTs could have been caused by an increase in the percentage of buoy measurements (relative to deeper ship intake measurements) in the tropical Pacific. No indications for uncorrected inhomogeneities of land surface temperatures could be found. Near-surface temperatures have biases in the boundary layer in both reanalyses, presumably due to the incorrect treatment of snow cover. The increase of near-surface compared to lower tropospheric temperatures in the last two decades may be due to a combination of several factors, including high-latitude near-surface winter warming due to an enhanced NAO and upper-tropospheric cooling due to stratospheric ozone decrease.

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.

Evidence for a climate signal in trends of global crop yield variability over the past 50 years

Low variability of crop production from year to year is desirable for many reasons, including reduced income risk and stability of supplies. Therefore, it is important to understand the nature of yield variability, whether it is changing through time, and how it varies between crops and regions. Previous studies have shown that national crop yield variability has changed in the past, with the direction and magnitude dependent on crop type and location. Whilst such studies acknowledge the importance of climate variability in determining yield variability, it has been assumed that its magnitude and its effect on crop production have not changed through time and, hence, that changes to yield variability have been due to non-climatic factors. We address this assumption by jointly examining yield and climate variability for three major crops (rice, wheat and maize) over the past 50 years. National yield time series and growing season temperature and precipitation were de-trended and related using multiple linear regression. Yield variability changed significantly in half of the crop–country combinations examined. For several crop–country combinations, changes in yield variability were related to changes in climate variability.