Sensitivity of biogenic isoprene emissions to past, present and future environmental conditions and implications for atmospheric chemistry.

[1] We have implemented a process-based isoprene emission model in the HadGEM2 Earth-system model with coupled atmospheric chemistry in order to examine the feedback between isoprene emission and climate. Isoprene emissions and their impact on atmospheric chemistry and climate are estimated for preindustrial (1860–1869), present-day (2000–2009), and future (2100–2109) climate conditions. The estimate of 460 TgC/yr for present-day global total isoprene emission is consistent with previous estimates. Preindustrial isoprene emissions are estimated to be 26% higher than present-day. Future isoprene emissions using the RCP8.5 scenario are similar to present-day because increased emissions resulting from climate warming are countered by CO2 inhibition of isoprene emissions. The impact of biogenic isoprene emissions on the global O3 burden and CH4 lifetime is small but locally significant, and the impact of changes in isoprene emissions on atmospheric chemistry depends strongly on the state of climate and chemistry.

A Lagrangian model of air-mass photochemistry and mixing using a trajectory ensemble: the Cambridge Tropospheric Trajectory model of Chemistry And Transport (CiTTyCAT) version 4.2

A Lagrangian model of photochemistry and mixing is described (CiTTyCAT, stemming from the Cambridge Tropospheric Trajectory model of Chemistry And Transport), which is suitable for transport and chemistry studies throughout the troposphere. Over the last five years, the model has been developed in parallel at several different institutions and here those developments have been incorporated into one "community" model and documented for the first time. The key photochemical developments include a new scheme for biogenic volatile organic compounds and updated emissions schemes. The key physical development is to evolve composition following an ensemble of trajectories within neighbouring air-masses, including a simple scheme for mixing between them via an evolving "background profile", both within the boundary layer and free troposphere. The model runs along trajectories pre-calculated using winds and temperature from meteorological analyses. In addition, boundary layer height and precipitation rates, output from the analysis model, are interpolated to trajectory points and used as inputs to the mixing and wet deposition schemes. The model is most suitable in regimes when the effects of small-scale turbulent mixing are slow relative to advection by the resolved winds so that coherent air-masses form with distinct composition and strong gradients between them. Such air-masses can persist for many days while stretching, folding and thinning. Lagrangian models offer a useful framework for picking apart the processes of air-mass evolution over inter-continental distances, without being hindered by the numerical diffusion inherent to global Eulerian models. The model, including different box and trajectory modes, is described and some output for each of the modes is presented for evaluation. The model is available for download from a Subversion-controlled repository by contacting the corresponding authors.

Ozone climatology using interactive chemistry: results from the Canadian Middle Atmosphere Model

The climatology of ozone produced by the Canadian Middle Atmosphere Model (CMAM) is presented. This three-dimensional global model incorporates the radiative feedbacks of ozone and water vapor calculated on-line with a photochemical module. This module includes a comprehensive gas-phase reaction set and a limited set of heterogeneous reactions to account for processes occurring on background sulphate aerosols. While transport is global, photochemistry is solved from about 400 hPa to the top of the model at ∼95 km. This approach provides a complete and comprehensive representation of transport, emission, and photochemistry of various constituents from the surface to the mesopause region. A comparison of model results with observations indicates that the ozone distribution and variability are in agreement with observations throughout most of the model domain. Column ozone annual variation is represented to within 5–10% of the observations except in the Southern Hemisphere for springtime high latitudes. The vertical ozone distribution is generally well represented by the model up to the mesopause region. Nevertheless, in the upper stratosphere, the model generally underestimates the amount of ozone as well as the latitudinal tilting of ozone isopleths at high latitude. Ozone variability is analyzed and compared with measurements. The comparison shows that the phase and amplitude of the seasonal variation as well as shorter timescale variations are well represented by the model at various latitudes and heights. Finally, the impact of incorporating ozone radiative feedback on the model climatology is isolated. It is found that the incorporation of ozone radiative feedback results in a cooling of ∼8 K in the summer stratopause region, which corrects a warm bias that results when climatological ozone is used.

Still feeling it: the time course of emotional recovery from an attentional perspective

Emotional reactivity and the time taken to recover, particularly from negative, stressful, events, are inextricably linked, and both are crucial for maintaining well-being. It is unclear, however, to what extent emotional reactivity during stimulus onset predicts the time course of recovery after stimulus offset. To address this question, 25 participants viewed arousing (negative and positive) and neutral pictures from the International Affective Picture System (IAPS) followed by task-relevant face targets, which were to be gender categorized. Faces were presented early (400–1500 ms) or late (2400–3500 ms) after picture offset to capture the time course of recovery from emotional stimuli. Measures of reaction time (RT), as well as face-locked N170 and P3 components were taken as indicators of the impact of lingering emotion on attentional facilitation or interference. Electrophysiological effects revealed negative and positive images to facilitate face-target processing on the P3 component, regardless of temporal interval. At the individual level, increased reactivity to: (1) negative pictures, quantified as the IAPS picture-locked Late Positive Potential (LPP), predicted larger attentional interference on the face-locked P3 component to faces presented in the late time window after picture offset. (2) Positive pictures, denoted by the LPP, predicted larger facilitation on the face-locked P3 component to faces presented in the earlier time window after picture offset. These results suggest that subsequent processing is still impacted up to 3500 ms after the offset of negative pictures and 1500 ms after the offset of positive pictures for individuals reacting more strongly to these pictures, respectively. Such findings emphasize the importance of individual differences in reactivity when predicting the temporality of emotional recovery. The current experimental model provides a novel basis for future research aiming to identify profiles of adaptive and maladaptive recovery.

The physical pendulum in an advanced undergraduate course in mechanics

The physical pendulum treated with a Hamiltonian formulation is a natural topic for study in a course in advanced classical mechanics. For the past three years, we have been offering a series of problem sets studying this system numerically in our third-year undergraduate courses in mechanics. The problem sets investigate the physics of the pendulum in ways not easily accessible without computer technology and explore various algorithms for solving mechanics problems. Our computational physics is based on Mathematica with some C communicating with Mathematica, although nothing in this paper is dependent on that choice. We have nonetheless found this system, and particularly its graphics, to be a good one for use with undergraduates.

Synthesis of thiolated and acrylated nanoparticles using thiol-ene click chemistry: towards novel mucoadhesive materials for drug delivery

Thiol- and acrylate-functionalized nanoparticles have been synthesized from pentaerythritol tetrakis(3-mercapto-propionate) and pentaerythritol tetraacrylate using thiol-ene click chemistry. Using Raman and 1H NMR spectroscopy as well as Ellman's assay, it was demonstrated that excess pentaerythritol tetraacrylate in the feed mixture led to nanoparticles with free acrylate groups on their surface, whereas nanoparticles with thiolated surfaces could be synthesized using feed mixtures with excess pentaerythritol tetrakis(3-mercapto-propionate). The possibility of fluorescent labelling of thiolated nanoparticles has been demonstrated through their reaction with fluorescein-5-maleimide. The thiolated nanoparticles were found to be mucoadhesive and exhibited retention on mucosal surface of porcine urinary bladder.

Wave activity in the tropical tropopause layer in seven reanalysis and four chemistry climate model data sets

Sub-seasonal variability including equatorial waves significantly influence the dehydration and transport processes in the tropical tropopause layer (TTL). This study investigates the wave activity in the TTL in 7 reanalysis data sets (RAs; NCEP1, NCEP2, ERA40, ERA-Interim, JRA25, MERRA, and CFSR) and 4 chemistry climate models (CCMs; CCSRNIES, CMAM, MRI, and WACCM) using the zonal wave number-frequency spectral analysis method with equatorially symmetric-antisymmetric decomposition. Analyses are made for temperature and horizontal winds at 100 hPa in the RAs and CCMs and for outgoing longwave radiation (OLR), which is a proxy for convective activity that generates tropopause-level disturbances, in satellite data and the CCMs. Particular focus is placed on equatorial Kelvin waves, mixed Rossby-gravity (MRG) waves, and the Madden-Julian Oscillation (MJO). The wave activity is defined as the variance, i.e., the power spectral density integrated in a particular zonal wave number-frequency region. It is found that the TTL wave activities show significant difference among the RAs, ranging from ∼0.7 (for NCEP1 and NCEP2) to ∼1.4 (for ERA-Interim, MERRA, and CFSR) with respect to the averages from the RAs. The TTL activities in the CCMs lie generally within the range of those in the RAs, with a few exceptions. However, the spectral features in OLR for all the CCMs are very different from those in the observations, and the OLR wave activities are too low for CCSRNIES, CMAM, and MRI. It is concluded that the broad range of wave activity found in the different RAs decreases our confidence in their validity and in particular their value for validation of CCM performance in the TTL, thereby limiting our quantitative understanding of the dehydration and transport processes in the TTL.

Measurements of NO, NOy, N2O, and O3 during SPURT: implications for transport and chemistry in the lowermost stratosphere

We present measurements of NO, NOy, O3, and N2O within the lowermost stratosphere (LMS) over Europe obtained during the SPURT project. The measurements cover all seasons between November 2001 and July 2003. They span a broad band of latitudes from 30° N to 75° N and a potential temperature range from 290 to 380 K. The measurements represent a comprehensive data set of these tracers and reveal atmospheric transport processes that influence tracer distributions in the LMS. Median mixing ratios of stratospheric tracers in equivalent latitude-potential temperature coordinates show a clear seasonal cycle related to the Brewer-Dobson circulation, with highest values in spring and lowest values in autumn. Vertical tracer profiles show strong gradients at the extratropical tropopause, suggesting that vertical (cross-isentropic) mixing is reduced above the tropopause. Pronounced meridional gradients in the tracer mixing ratios are found on potential temperature surfaces in the LMS. This suggests strongly reduced mixing along isentropes. Concurrent large gradients in static stability in the vertical direction, and of PV in the meridional direction, suggest the presence of a mixing barrier. Seasonal cycles were found in the correlation slopes ΔO3/ΔN2O and ΔNOy/ΔN2O well above the tropopause. Absolute slope values are smallest in spring indicating chemically aged stratospheric air originating from high altitudes and latitudes. Larger values were measured in summer and autumn suggesting that a substantial fraction of air takes a "short-cut" from the tropical tropopause region into the extratropical LMS. The seasonal change in the composition of the LMS has direct implications for the ozone chemistry in this region. Comparisons of measured NO with the critical NO value at which net ozone production changes from negative to positive, imply ozone production up to 20 K above the local tropopause in spring, up to 30 K in summer, and up to 40 K in autumn. Above these heights, and in winter, net ozone production is negative.

The time-course of morphological constraints: Evidence from eye-movements during reading

Lexical compounds in English are constrained in that the non-head noun can be an irregular but not a regular plural (e.g. mice eater vs. *rats eater), a contrast that has been argued to derive from a morphological constraint on modifiers inside compounds. In addition, bare nouns are preferred over plural forms inside compounds (e.g. mouse eater vs. mice eater), a contrast that has been ascribed to the semantics of compounds. Measuring eyemovements during reading, this study examined how morphological and semantic information become available over time during the processing of a compound. We found that the morphological constraint affected both early and late eye-movement measures, whereas the semantic constraint for singular non-heads only affected late measures of processing. These results indicate that morphological information becomes available earlier than semantic information during the processing of compounds.

The time-course of morphological constraints: a study of plurals inside derived words

The avoidance of regular but not irregular plurals inside compounds (e.g. *rats eater vs. mice eater) has been one of the most widely studied morphological phenomena in the psycholinguistics literature. To examine whether the constraints that are responsible for this contrast have any general significance beyond compounding, we investigated derived word forms containing regular and irregular plurals in two experiments. Experiment 1 was an offline acceptability judgment task, and experiment 2 measured eye movements during reading derived words containing regular and irregular plurals and uninflected base nouns. The results from both experiments show that the constraint against regular plurals inside compounds generalizes to derived words. We argue that this constraint cannot be reduced to phonological properties, but is instead morphological in nature. The eye-movement data provide detailed information on the time-course of processing derived word forms indicating that early stages of processing are affected by a general constraint that disallows inflected words from feeding derivational processes, and that the more specific constraint against regular plurals comes in at a subsequent later stage of processing. We argue that these results are consistent with stage-based models of language processing.

The time-course of morphological processing in a second language

We report findings from psycholinguistic experiments investigating the detailed timing of processing morphologically complex words by proficient adult second (L2) language learners of English in comparison to adult native (L1) speakers of English. The first study employed the masked priming technique to investigate -ed forms with a group of advanced Arabic-speaking learners of English. The results replicate previously found L1/L2 differences in morphological priming, even though in the present experiment an extra temporal delay was offered after the presentation of the prime words. The second study examined the timing of constraints against inflected forms inside derived words in English using the eye-movement monitoring technique and an additional acceptability judgment task with highly advanced Dutch L2 learners of English in comparison to adult L1 English controls. Whilst offline the L2 learners performed native-like, the eye-movement data showed that their online processing was not affected by the morphological constraint against regular plurals inside derived words in the same way as in native speakers. Taken together, these findings indicate that L2 learners are not just slower than native speakers in processing morphologically complex words, but that the L2 comprehension system employs real-time grammatical analysis (in this case, morphological information) less than the L1 system.

Multi-season eddy covariance observations of energy, water and carbon fluxes over a suburban area in Swindon, UK

Eddy covariance measurements of the turbulent sensible heat, latent heat and carbon dioxide fluxes for 12 months (2011–2012) are reported for the first time for a suburban area in the UK. The results from Swindon are comparable to suburban studies of similar surface cover elsewhere but reveal large seasonal variability. Energy partitioning favours turbulent sensible heat during summer (midday Bowen ratio 1.4–1.6) and latent heat in winter (0.05–0.7). A significant proportion of energy is stored (and released) by the urban fabric and the estimated anthropogenic heat flux is small but non-negligible (0.5–0.9 MJ m−2 day−1). The sensible heat flux is negative at night and for much of winter daytimes, reflecting the suburban nature of the site (44% vegetation) and relatively low built fraction (16%). Latent heat fluxes appear to be water limited during a dry spring in both 2011 and 2012, when the response of the surface to moisture availability can be seen on a daily timescale. Energy and other factors are more relevant controls at other times; at night the wind speed is important. On average, surface conductance follows a smooth, asymmetrical diurnal course peaking at around 6–9 mm s−1, but values are larger and highly variable in wet conditions. The combination of natural (vegetative) and anthropogenic (emission) processes is most evident in the temporal variation of the carbon flux: significant photosynthetic uptake is seen during summer, whilst traffic and building emissions explain peak release in winter (9.5 g C m−2 day−1). The area is a net source of CO2 annually. Analysis by wind direction highlights the role of urban vegetation in promoting evapotranspiration and offsetting CO2 emissions, especially when contrasted against peak traffic emissions from sectors with more roads. Given the extent of suburban land use, these results have important implications for understanding urban energy, water and carbon dynamics.

Technical note: a simple procedure for removing temporal discontinuities in ERA-Interim upper stratospheric temperatures for use in nudged chemistry-climate model simulations

This note describes a simple procedure for removing unphysical temporal discontinuities in ERA-Interim upper stratospheric global mean temperatures in March 1985 and August 1998 that have arisen due to changes in satellite radiance data used in the assimilation. The derived temperature adjustments (offsets) are suitable for use in stratosphere-resolving chemistry-climate models that are nudged (relaxed) to ERA-Interim winds and temperatures. Simulations using a nudged version of the Canadian Middle Atmosphere Model (CMAM) show that the inclusion of the temperature adjustments produces temperature time series that are devoid of the large jumps in 1985 and 1998. Due to its strong temperature dependence, the simulated upper stratospheric ozone is also shown to vary smoothly in time, unlike in a nudged simulation without the adjustments where abrupt changes in ozone occur at the times of the temperature jumps. While the adjustments to the ERA-Interim temperatures remove significant artefacts in the nudged CMAM simulation, spurious transient effects that arise due to water vapour and persist for about 5 yr after the 1979 switch to ERA-Interim data are identified, underlining the need for caution when analysing trends in runs nudged to reanalyses.

Postpartum GAD is a risk factor for postpartum MDD: the course and longitudinal relationships of postpartum GAD and MDD

Background The objective was to examine the course and longitudinal associations of generalized anxiety disorder (GAD) and major depressive disorder (MDD) in mothers over the postpartum 2 years. Method Using a prospective naturalistic design, 296 mothers recruited from a large community pool were assessed for GAD and MDD at 3, 6, 10, 14, and 24 months postpartum. Structured clinical interviews were used for diagnoses, and symptoms were assessed using self-report questionnaires. Logistic regression analyses were used to examine diagnostic stability and longitudinal relations, and latent variable modeling was employed to examine change in symptoms. Results MDD without co-occurring GAD, GAD without co-occurring MDD, and co-occurring GAD and MDD, displayed significant stability during the postpartum period. Whereas MDD did not predict subsequent GAD, GAD predicted subsequent MDD (in the form of GAD + MDD). Those with GAD + MDD at 3 months postpartum were significantly less likely to be diagnosis free during the follow-up period than those in other diagnostic categories. At the symptom level, symptoms of GAD were more trait-like than those of depression. Conclusions Postpartum GAD and MDD are relatively stable conditions, and GAD is a risk factor for MDD but not vice versa. Given the tendency of MDD and GAD to be persistent, especially when comorbid, and the increased risk for MDD in mothers with GAD, as well as the potential negative effects of cumulative exposure to maternal depression and anxiety on child development, the present findings clearly highlight the need for screening and treatment of GAD in addition to MDD during the postpartum period.