Gas-phase reactions of NO3 and N2O5 with (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol

The night-time atmospheric chemistry of the biogenic volatile organic compounds (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these stress-induced plant emissions were measured using the discharge-flow technique. We employed off-axis continuous-wave cavity-enhanced absorption spectroscopy (CEAS) for the detection of NO3, which enabled us to work in excess of the hexenol compounds over NO3. The rate coefficients determined were (2.93 +/- 0.58) x 10(-13) cm(3) molecule(-1) s(-1), (2.67 +/- 0.42) x 10(-13) cm(3) molecule(-1) s(-1), (4.43 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1), (1.56 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1), and (1.30 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1) for (Z)-hex-4-en-1-ol, (Z)-hex-3en-1-ol, (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol. The rate coefficient for the reaction of NO3 with (Z)-hex-3-en-1-ol agrees with the single published determination of the rate coefficient using a relative method. The other rate coefficients have not been measured before and are compared to estimated values. Relative-rate studies were also performed, but required modification of the standard technique because N2O5 (used as the source of NO3) itself reacts with the hexenols. We used varying excesses of NO2 to determine simultaneously rate coefficients for reactions of NO3 and N2O5 with (E)-hex-3-en-1-ol of (5.2 +/- 1.8) x 10(-13) cm(3) molecule(-1) s(-1) and (3.1 +/- 2.3) x 10(-18) cm(3) molecule(-1) s(-1). Our new determinations suggest atmospheric lifetimes with respect to NO3-initiated oxidation of roughly 1-4 h for the hexenols, comparable with lifetimes estimated for the atmospheric degradation by OH and shorter lifetimes than for attack by O-3. Recent measurements of [N2O5] suggest that the gas-phase reactions of N2O5 with unsaturated alcohols will not be of importance under usual atmospheric conditions, but they certainly can be in laboratory systems when determining rate coefficients.

The advection of high-resolution tracers by low-resolution winds

The usefulness of any simulation of atmospheric tracers using low-resolution winds relies on both the dominance of large spatial scales in the strain and time dependence that results in a cascade in tracer scales. Here, a quantitative study on the accuracy of such tracer studies is made using the contour advection technique. It is shown that, although contour stretching rates are very insensitive to the spatial truncation of the wind field, the displacement errors in filament position are sensitive. A knowledge of displacement characteristics is essential if Lagrangian simulations are to be used for the inference of airmass origin. A quantitative lower estimate is obtained for the tracer scale factor (TSF): the ratio of the smallest resolved scale in the advecting wind field to the smallest “trustworthy” scale in the tracer field. For a baroclinic wave life cycle the TSF = 6.1 ± 0.3 while for the Northern Hemisphere wintertime lower stratosphere the TSF = 5.5 ± 0.5, when using the most stringent definition of the trustworthy scale. The similarity in the TSF for the two flows is striking and an explanation is discussed in terms of the activity of potential vorticity (PV) filaments. Uncertainty in contour initialization is investigated for the stratospheric case. The effect of smoothing initial contours is to introduce a spinup time, after which wind field truncation errors take over from initialization errors (2–3 days). It is also shown that false detail from the proliferation of finescale filaments limits the useful lifetime of such contour advection simulations to 3σ−1 days, where σ is the filament thinning rate, unless filaments narrower than the trustworthy scale are removed by contour surgery. In addition, PV analysis error and diabatic effects are so strong that only PV filaments wider than 50 km are at all believable, even for very high-resolution winds. The minimum wind field resolution required to accurately simulate filaments down to the erosion scale in the stratosphere (given an initial contour) is estimated and the implications for the modeling of atmospheric chemistry are briefly discussed.

Rapid topographic change measured by high-resolution satellite radar at Soufriere Hills Volcano, Montserrat, 2008-2010

High-resolution satellite radar observations of erupting volcanoes can yield valuable information on rapidly changing deposits and geomorphology. Using the TerraSAR-X (TSX) radar with a spatial resolution of about 2 m and a repeat interval of 11-days, we show how a variety of techniques were used to record some of the eruptive history of the Soufriere Hills Volcano, Montserrat between July 2008 and February 2010. After a 15-month pause in lava dome growth, a vulcanian explosion occurred on 28 July 2008 whose vent was hidden by dense cloud. We were able to show the civil authorities using TSX change difference images that this explosion had not disrupted the dome sufficient to warrant continued evacuation. Change difference images also proved to be valuable in mapping new pyroclastic flow deposits: the valley-occupying block-and-ash component tending to increase backscatter and the marginal surge deposits reducing it, with the pattern reversing after the event. By comparing east- and west-looking images acquired 12 hours apart, the deposition of some individual pyroclastic flows can be inferred from change differences. Some of the narrow upper sections of valleys draining the volcano received many tens of metres of rockfall and pyroclastic flow deposits over periods of a few weeks. By measuring the changing shadows cast by these valleys in TSX images the changing depth of infill by deposits could be estimated. In addition to using the amplitude data from the radar images we also used their phase information within the InSAR technique to calculate the topography during a period of no surface activity. This enabled areas of transient topography, crucial for directing future flows, to be captured.

Kinetics of layer hopping in a diblock copolymer lamellar phase

In the ordered state, symmetric diblock copolymers self-assemble into an anisotropic lamellar morphology. The equilibrium thickness of the lamellae is the result of a delicate balance between enthalpic and entropic energies, which can be tuned by controlling the temperature. Here we devise a simple yet powerful method of detecting tiny changes in the lamellar thickness using optical microscopy. From such measurements we characterize the enthalpic interaction as well as the kinetics of molecules as they hop from one layer to the next in order to adjust the lamellar thickness in response to a temperature jump. The resolution of the measurements facilitate a direct comparison to predictions from self-consistent field theory.

Synoptic scale disturbances of the Indian Summer Monsoon as simulated in a high resolution climate model

Hamburg atmospheric general circulation model ECHAM3 at T106 resolution (1.125' lat.Aon.) has considerable skill in reproducing the observed seasonal reversal of mean sea level pressure, the location of the summer heat low as well as the position of the monsoon trough over the Indian subcontinent. The present-day climate and its seasonal cycle are realistically simulated by the model over this region. The model simulates the structure, intensity, frequency, movement and lifetime of monsoon depressions remarkably well. The number of monsoon depressions/storms simulated by the model in a year ranged from 5 to 12 with an average frequency of 8.4 yr-', not significantly different from the observed climatology. The model also simulates the interannual variability in the formation of depressions over the north Bay of Bengal during the summer monsoon season. In the warmer atmosphere under doubled CO2 conditions, the number of monsoon depressions/cyclonic storms forming in Indian seas in a year ranged from 5 to 11 with an average frequency of 7.6 yr-', not significantly different from those inferred in the control run of the model. However, under doubled CO2 conditions, fewer depressions formed in the month of June. Neither the lowest central pressure nor the maximum wind speed changes appreciably in monsoon depressions identified under simulated enhanced greenhouse conditions. The analysis suggests there will be no significant changes in the number and intensity of monsoon depressions in a warmer atmosphere.

Wavelet-based ULF wave diagnosis of substorm expansion phase onset

Using a discrete wavelet transform with a Meyer wavelet basis, we present a new quantitative algorithm for determining the onset time of Pi1 and Pi2 ULF waves in the nightside ionosphere with ∼20- to 40-s resolution at substorm expansion phase onset. We validate the algorithm by comparing both the ULF wave onset time and location to the optical onset determined by the Imager for Magnetopause-to-Aurora Global Exploration (IMAGE)–Far Ultraviolet Imager (FUV) instrument. In each of the six events analyzed, five substorm onsets and one pseudobreakup, the ULF onset is observed prior to the global optical onset observed by IMAGE at a station closely conjugate to the optical onset. The observed ULF onset times expand both latitudinally and longitudinally away from an epicenter of ULF wave power in the ionosphere. We further discuss the utility of the algorithm for diagnosing pseudobreakups and the relationship of the ULF onset epicenter to the meridians of elements of the substorm current wedge. The importance of the technique for establishing the causal sequence of events at substorm onset, especially in support of the multisatellite Time History of Events and Macroscale Interactions During Substorms (THEMIS) mission, is also described.

Analysis of precipitation climatology simulated by high resolution coupled global models over the South America

The results of coupled high resolution global models (CGCMs) over South America are discussed. HiGEM1.2 and HadGEM1.2 simulations, with horizontal resolution of ~90 and 135 km, respectively, are compared. Precipitation estimations from CMAP (Climate Prediction Center—Merged Analysis of Precipitation), CPC (Climate Prediction Center) and GPCP (Global Precipitation Climatology Project) are used for validation. HiGEM1.2 and HadGEM1.2 simulated seasonal mean precipitation spatial patterns similar to the CMAP. The positioning and migration of the Intertropical Convergence Zone and of the Pacific and Atlantic subtropical highs are correctly simulated by the models. In HiGEM1.2 and HadGEM1.2, the intensity and locations of the South Atlantic Convergence Zone are in agreement with the observed dataset. The simulated annual cycles are in phase with estimations of rainfall for most of the six regions considered. An important result is that HiGEM1.2 and HadGEM1.2 eliminate a common problem of coarse resolution CGCMs, which is the simulation of a semiannual cycle of precipitation due to the semiannual solar forcing. Comparatively, the use of high resolution in HiGEM1.2 reduces the dry biases in the central part of Brazil during austral winter and spring and in most part of the year over an oceanic box in eastern Uruguay.

The vertical structure of oceanic Rossby waves: a comparison of high-resolution model data to theoretical vertical structures

Tests of the new Rossby wave theories that have been developed over the past decade to account for discrepancies between theoretical wave speeds and those observed by satellite altimeters have focused primarily on the surface signature of such waves. It appears, however, that the surface signature of the waves acts only as a rather weak constraint, and that information on the vertical structure of the waves is required to better discriminate between competing theories. Due to the lack of 3-D observations, this paper uses high-resolution model data to construct realistic vertical structures of Rossby waves and compares these to structures predicted by theory. The meridional velocity of a section at 24° S in the Atlantic Ocean is pre-processed using the Radon transform to select the dominant westward signal. Normalized profiles are then constructed using three complementary methods based respectively on: (1) averaging vertical profiles of velocity, (2) diagnosing the amplitude of the Radon transform of the westward propagating signal at different depths, and (3) EOF analysis. These profiles are compared to profiles calculated using four different Rossby wave theories: standard linear theory (SLT), SLT plus mean flow, SLT plus topographic effects, and theory including mean flow and topographic effects. Our results support the classical theoretical assumption that westward propagating signals have a well-defined vertical modal structure associated with a phase speed independent of depth, in contrast with the conclusions of a recent study using the same model but for different locations in the North Atlantic. The model structures are in general surface intensified, with a sign reversal at depth in some regions, notably occurring at shallower depths in the East Atlantic. SLT provides a good fit to the model structures in the top 300 m, but grossly overestimates the sign reversal at depth. The addition of mean flow slightly improves the latter issue, but is too surface intensified. SLT plus topography rectifies the overestimation of the sign reversal, but overestimates the amplitude of the structure for much of the layer above the sign reversal. Combining the effects of mean flow and topography provided the best fit for the mean model profiles, although small errors at the surface and mid-depths are carried over from the individual effects of mean flow and topography respectively. Across the section the best fitting theory varies between SLT plus topography and topography with mean flow, with, in general, SLT plus topography performing better in the east where the sign reversal is less pronounced. None of the theories could accurately reproduce the deeper sign reversals in the west. All theories performed badly at the boundaries. The generalization of this method to other latitudes, oceans, models and baroclinic modes would provide greater insight into the variability in the ocean, while better observational data would allow verification of the model findings.

Sea surface temperature datasets for climate applications from Phase 1 of the European Space Agency Climate Change Initiative (SST CCI)

Sea surface temperature (SST) datasets have been generated from satellite observations for the period 1991–2010, intended for use in climate science applications. Attributes of the datasets specifically relevant to climate applications are: first, independence from in situ observations; second, effort to ensure homogeneity and stability through the time-series; third, context-specific uncertainty estimates attached to each SST value; and, fourth, provision of estimates of both skin SST (the fundamental measure- ment, relevant to air-sea fluxes) and SST at standard depth and local time (partly model mediated, enabling comparison with his- torical in situ datasets). These attributes in part reflect requirements solicited from climate data users prior to and during the project. Datasets consisting of SSTs on satellite swaths are derived from the Along-Track Scanning Radiometers (ATSRs) and Advanced Very High Resolution Radiometers (AVHRRs). These are then used as sole SST inputs to a daily, spatially complete, analysis SST product, with a latitude-longitude resolution of 0.05°C and good discrimination of ocean surface thermal features. A product user guide is available, linking to reports describing the datasets’ algorithmic basis, validation results, format, uncer- tainty information and experimental use in trial climate applications. Future versions of the datasets will span at least 1982–2015, better addressing the need in many climate applications for stable records of global SST that are at least 30 years in length.

Phase calibration of the EISCAT Svalbard Radar interferometer using optical satellite signatures

The link between natural ion-line enhancements in radar spectra and auroral activity has been the subject of recent studies but conclusions have been limited by the spatial and temporal resolution previously available. The next challenge is to use shorter sub-second integration times in combination with interferometric programmes to resolve spatial structure within the main radar beam, and so relate enhanced filaments to individual auroral rays. This paper presents initial studies of a technique, using optical and spectral satellite signatures, to calibrate the received phase of a signal with the position of the scattering source along the interferometric baseline of the EISCAT Svalbard Radar. It is shown that a consistent relationship can be found only if the satellite passage through the phase fringes is adjusted from the passage predicted by optical tracking. This required adjustment is interpreted as being due to the vector between the theoretical focusing points of the two antennae, i.e. the true radar baseline, differing from the baseline obtained by survey between the antenna foot points. A method to obtain a measurement of the true interferometric baseline using multiple satellite passes is outlined.

The DYMECS project: a statistical approach for the evaluation of convective storms in high-resolution NWP models

A new frontier in weather forecasting is emerging by operational forecast models now being run at convection-permitting resolutions at many national weather services. However, this is not a panacea; significant systematic errors remain in the character of convective storms and rainfall distributions. The DYMECS project (Dynamical and Microphysical Evolution of Convective Storms) is taking a fundamentally new approach to evaluate and improve such models: rather than relying on a limited number of cases, which may not be representative, we have gathered a large database of 3D storm structures on 40 convective days using the Chilbolton radar in southern England. We have related these structures to storm life-cycles derived by tracking features in the rainfall from the UK radar network, and compared them statistically to storm structures in the Met Office model, which we ran at horizontal grid length between 1.5 km and 100 m, including simulations with different subgrid mixing length. We also evaluated the scale and intensity of convective updrafts using a new radar technique. We find that the horizontal size of simulated convective storms and the updrafts within them is much too large at 1.5-km resolution, such that the convective mass flux of individual updrafts can be too large by an order of magnitude. The scale of precipitation cores and updrafts decreases steadily with decreasing grid lengths, as does the typical storm lifetime. The 200-m grid-length simulation with standard mixing length performs best over all diagnostics, although a greater mixing length improves the representation of deep convective storms.

Propagation of the Madden–Julian Oscillation and scale interaction with the diurnal cycle in a high-resolution GCM

The Madden–Julian Oscillation (MJO) is the chief source of tropical intra-seasonal variability, but is simulated poorly by most state-of-the-art GCMs. Common errors include a lack of eastward propagation at the correct frequency and zonal extent, and too small a ratio of eastward- to westward-propagating variability. Here it is shown that HiGEM, a high-resolution GCM, simulates a very realistic MJO with approximately the correct spatial and temporal scale. Many MJO studies in GCMs are limited to diagnostics which average over a latitude band around the equator, allowing an analysis of the MJO’s structure in time and longitude only. In this study a wider range of diagnostics is applied. It is argued that such an approach is necessary for a comprehensive analysis of a model’s MJO. The standard analysis of Wheeler and Hendon (Mon Wea Rev 132(8):1917–1932, 2004; WH04) is applied to produce composites, which show a realistic spatial structure in the MJO envelopes but for the timing of the peak precipitation in the inter-tropical convergence zone, which bifurcates the MJO signal. Further diagnostics are developed to analyse the MJO’s episodic nature and the “MJO inertia” (the tendency to remain in the same WH04 phase from one day to the next). HiGEM favours phases 2, 3, 6 and 7; has too much MJO inertia; and dies out too frequently in phase 3. Recent research has shown that a key feature of the MJO is its interaction with the diurnal cycle over the Maritime Continent. This interaction is present in HiGEM but is unrealistically weak.

A mechanism of internal decadal atlantic ocean variability in a high-resolution coupled climate model

The North Atlantic Ocean subpolar gyre (NA SPG) is an important region for initialising decadal climate forecasts. Climate model simulations and palaeo climate reconstructions have indicated that this region could also exhibit large, internally generated variability on decadal timescales. Understanding these modes of variability, their consistency across models, and the conditions in which they exist, is clearly important for improving the skill of decadal predictions — particularly when these predictions are made with the same underlying climate models. Here we describe and analyse a mode of internal variability in the NA SPG in a state-of-the-art, high resolution, coupled climate model. This mode has a period of 17 years and explains 15–30% of the annual variance in related ocean indices. It arises due to the advection of heat content anomalies around the NA SPG. Anomalous circulation drives the variability in the southern half of the NA SPG, whilst mean circulation and anomalous temperatures are important in the northern half. A negative feedback between Labrador Sea temperatures/densities and those in the North Atlantic Current is identified, which allows for the phase reversal. The atmosphere is found to act as a positive feedback on to this mode via the North Atlantic Oscillation which itself exhibits a spectral peak at 17 years. Decadal ocean density changes associated with this mode are driven by variations in temperature, rather than salinity — a point which models often disagree on and which we suggest may affect the veracity of the underlying assumptions of anomaly-assimilating decadal prediction methodologies.

Phase-transition studies of Ba(0.90)Ca(0.10)(Ti(1-x)Zr(x))O(3) ferroelectric ceramic compounds

Perovskite-structured Ba(0.90)Ca(0.10)(Ti(1-x)Zr(x))O(3) ceramics were prepared in this work and subsequently studied in terms of composition-dependent dielectric and high-resolution long-range order structural properties from 30 to 450 K. The dielectric response of these materials was measured at several frequencies in the range from 1 kHz to 1 MHz. Combining both techniques, including Rietveld refinement of the X-ray diffraction data, allowed observing that, when increasing Zr(4+) content, the materials change from conventional to diffuse and relaxor ferroelectric compounds, the transition occurring spontaneously at the x = 0.18 composition. Interestingly, this spontaneous transition turned out to be prevented for a further increase of Zr(4+). On the basis of all the dielectric and structural results processed, a phase diagram of this system is presented. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Insights into the dynamics and sources of atmospheric lead and particulate matter in Sao Paulo, Brazil, from high temporal resolution sampling

We present the first results of a study investigating the processes that control concentrations and sources of Pb and particulate matter in the atmosphere of Sao Paulo City Brazil Aerosols were collected with high temporal resolution (3 hours) during a four-day period in July 2005 The highest Pb concentrations measured coincided with large fireworks during celebration events and associated to high traffic occurrence Our high-resolution data highlights the impact that a singular transient event can have on air quality even in a megacity Under meteorological conditions non-conducive to pollutant dispersion Pb and particulate matter concentrations accumulated during the night leading to the highest concentrations in aerosols collected early in the morning of the following day The stable isotopes of Pb suggest that emissions from traffic remain an Important source of Pb in Sao Paulo City due to the large traffic fleet despite low Pb concentrations in fuels (C) 2010 Elsevier BV All rights reserved