Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Combining satellite data and models to estimate cloud radiative effect at the surface and in the atmosphere

Satellite measurements and numerical forecast model reanalysis data are used to compute an updated estimate of the cloud radiative effect on the global multi-annual mean radiative energy budget of the atmosphere and surface. The cloud radiative cooling effect through reflection of shortwave radiation dominates over the longwave heating effect, resulting in a net cooling of the climate system of –21 Wm-2. The shortwave radiative effect of cloud is primarily manifest as a reduction in the solar radiation absorbed at the surface of -53 Wm-2. Clouds impact longwave radiation by heating the moist tropical atmosphere (up to around 40 Wm-2 for global annual means) while enhancing the radiative cooling of the atmosphere over other regions, in particular higher latitudes and sub-tropical marine stratocumulus regimes. While clouds act to cool the climate system during the daytime, the cloud greenhouse effect heats the climate system at night. The influence of cloud radiative effect on determining cloud feedbacks and changes in the water cycle are discussed.

Objective detection of sting jets in low-resolution datasets

Sting jets are transient coherent mesoscale strong wind features that can cause damaging surface wind gusts in extratropical cyclones. Currently, we have only limited knowledge of their climatological characteristics. Numerical weather prediction models require enough resolution to represent slantwise motions with horizontal scales of tens of kilometres and vertical scales of just a few hundred metres to represent sting jets. Hence, the climatological characteristics of sting jets and the associated extratropical cyclones can not be determined by searching for sting jets in low-resolution datasets such as reanalyses. A diagnostic is presented and evaluated for the detection in low-resolution datasets of atmospheric regions from which sting jets may originate. Previous studies have shown that conditional symmetric instability (CSI) is present in all storms studied with sting jets, while other, rapidly developing storms of a similar character but no CSI do not develop sting jets. Therefore, we assume that the release of CSI is needed for sting jets to develop. While this instability will not be released in a physically realistic way in low-resolution models (and hence sting jets are unlikely to occur), it is hypothesized that the signature of this instability (combined with other criteria that restrict analysis to moist mid-tropospheric regions in the neighbourhood of a secondary cold front) can be used to identify cyclones in which sting jets occurred in reality. The diagnostic is evaluated, and appropriate parameter thresholds defined, by applying it to three case studies simulated using two resolutions (with CSI-release resolved in only the higher-resolution simulation).

Predictability of the western North Pacific summer climate demonstrated by the coupled models of ENSEMBLES

The Asian monsoon system, including the western North Pacific (WNP), East Asian, and Indian monsoons, dominates the climate of the Asia-Indian Ocean-Pacific region, and plays a significant role in the global hydrological and energy cycles. The prediction of monsoons and associated climate features is a major challenge in seasonal time scale climate forecast. In this study, a comprehensive assessment of the interannual predictability of the WNP summer climate has been performed using the 1-month lead retrospective forecasts (hindcasts) of five state-of-the-art coupled models from ENSEMBLES for the period of 1960–2005. Spatial distribution of the temporal correlation coefficients shows that the interannual variation of precipitation is well predicted around the Maritime Continent and east of the Philippines. The high skills for the lower-tropospheric circulation and sea surface temperature (SST) spread over almost the whole WNP. These results indicate that the models in general successfully predict the interannual variation of the WNP summer climate. Two typical indices, the WNP summer precipitation index and the WNP lower-tropospheric circulation index (WNPMI), have been used to quantify the forecast skill. The correlation coefficient between five models’ multi-model ensemble (MME) mean prediction and observations for the WNP summer precipitation index reaches 0.66 during 1979–2005 while it is 0.68 for the WNPMI during 1960–2005. The WNPMI-regressed anomalies of lower-tropospheric winds, SSTs and precipitation are similar between observations and MME. Further analysis suggests that prediction reliability of the WNP summer climate mainly arises from the atmosphere–ocean interaction over the tropical Indian and the tropical Pacific Ocean, implying that continuing improvement in the representation of the air–sea interaction over these regions in CGCMs is a key for long-lead seasonal forecast over the WNP and East Asia. On the other hand, the prediction of the WNP summer climate anomalies exhibits a remarkable spread resulted from uncertainty in initial conditions. The summer anomalies related to the prediction spread, including the lower-tropospheric circulation, SST and precipitation anomalies, show a Pacific-Japan or East Asia-Pacific pattern in the meridional direction over the WNP. Our further investigations suggest that the WNPMI prediction spread arises mainly from the internal dynamics in air–sea interaction over the WNP and Indian Ocean, since the local relationships among the anomalous SST, circulation, and precipitation associated with the spread are similar to those associated with the interannual variation of the WNPMI in both observations and MME. However, the magnitudes of these anomalies related to the spread are weaker, ranging from one third to a half of those anomalies associated with the interannual variation of the WNPMI in MME over the tropical Indian Ocean and subtropical WNP. These results further support that the improvement in the representation of the air–sea interaction over the tropical Indian Ocean and subtropical WNP in CGCMs is a key for reducing the prediction spread and for improving the long-lead seasonal forecast over the WNP and East Asia.

Improvement of 3D protein models using multiple templates guided by single-template model quality assessment

Motivation: Modelling the 3D structures of proteins can often be enhanced if more than one fold template is used during the modelling process. However, in many cases, this may also result in poorer model quality for a given target or alignment method. There is a need for modelling protocols that can both consistently and significantly improve 3D models and provide an indication of when models might not benefit from the use of multiple target-template alignments. Here, we investigate the use of both global and local model quality prediction scores produced by ModFOLDclust2, to improve the selection of target-template alignments for the construction of multiple-template models. Additionally, we evaluate clustering the resulting population of multi- and single-template models for the improvement of our IntFOLD-TS tertiary structure prediction method. Results: We find that using accurate local model quality scores to guide alignment selection is the most consistent way to significantly improve models for each of the sequence to structure alignment methods tested. In addition, using accurate global model quality for re-ranking alignments, prior to selection, further improves the majority of multi-template modelling methods tested. Furthermore, subsequent clustering of the resulting population of multiple-template models significantly improves the quality of selected models compared with the previous version of our tertiary structure prediction method, IntFOLD-TS.

Trends in Austral jet position in ensembles of high- and low-top CMIP5 models

Trends in the position of the DJF Austral jet have been analysed for multi-model ensemble simulations of a subset of high- and low-top models for the periods 1960-2000, 2000-2050, and 2050-2098 under the CMIP5 historical, RCP4.5, and RCP8.5 scenarios. Comparison with ERA-Interim, CFSR and the NCEP/NCAR reanalysis shows that the DJF and annual mean jet positions in CMIP5 models are equatorward of reanalyses for the 1979-2006 mean. Under the RCP8.5 scenario, the mean jet position in the high-top models moves 3 degrees poleward of its 1860-1900 position by 2098, compared to just over 2 degrees for the low-top models. Changes in jet position are linked to changes in the meridional temperature gradient. Compared to low-top models, the high-top models predict greater warming in the tropical upper troposphere due to increased greenhouse gases for all periods considered: up to 0.28 K/decade more in the period 2050-2098 under the RCP8.5 scenario. Larger polar lower-stratospheric cooling is seen in high-top models: -1.64 K/decade compared to -1.40 K/decade in the period 1960-2000, mainly in response to ozone depletion, and -0.41 K/decade compared to -0.12 K/decade in the period 2050-2098, mainly in response to increases in greenhouse gases. Analysis suggests that there may be a linear relationship between the trend in jet position and meridional temperature gradient, even under strong forcing. There were no clear indications of an approach to a geometric limit on the absolute magnitude of the poleward shift by 2100.

Sources of multi-decadal variability in Arctic sea ice extent

The observed dramatic decrease in September sea ice extent (SIE) has been widely discussed in the scientific literature. Though there is qualitative agreement between observations and ensemble members of the Third Coupled Model Intercomparison Project (CMIP3), it is concerning that the observed trend (1979–2010) is not captured by any ensemble member. The potential sources of this discrepancy include: observational uncertainty, physical model limitations and vigorous natural climate variability. The latter has received less attention and is difficult to assess using the relatively short observational sea ice records. In this study multi-centennial pre-industrial control simulations with five CMIP3 climate models are used to investigate the role that the Arctic oscillation (AO), the Atlantic multi-decadal oscillation (AMO) and the Atlantic meridional overturning circulation (AMOC) play in decadal sea ice variability. Further, we use the models to determine the impact that these sources of variability have had on SIE over both the era of satellite observation (1979–2010) and an extended observational record (1953–2010). There is little evidence of a relationship between the AO and SIE in the models. However, we find that both the AMO and AMOC indices are significantly correlated with SIE in all the models considered. Using sensitivity statistics derived from the models, assuming a linear relationship, we attribute 0.5–3.1%/decade of the 10.1%/decade decline in September SIE (1979–2010) to AMO driven variability.

Cannabidivarin is anticonvulsant in mouse and rat in vitro and in seizure models

Summary Background and purpose: Phytocannabinoids in Cannabis sativa have diverse pharmacological targets extending beyond cannabinoid receptors and several exert notable anticonvulsant effects. For the first time, we investigated the anticonvulsant profile of the phytocannabinoid cannabidivarin (CBDV) in vitro and in in vivo seizure models. Experimental approach: The effect of CBDV (1-100μM) on epileptiform local field potentials (LFPs) induced in rat hippocampal brain slices by 4-AP application or Mg2+-free conditions was assessed by in vitro multi-electrode array recordings. Additionally, the anticonvulsant profile of CBDV (50-200 mg kg-1) in vivo was investigated in four rodent seizure models: maximal electroshock (mES) and audiogenic seizures in mice, and pentylenetetrazole (PTZ) and pilocarpine-induced seizures in rat. CBDV effects in combination with commonly-used antiepileptic drugs were investigated in rat seizures. Finally, the motor side effect profile of CBDV was investigated using static beam and gripstrength assays. Key results: CDBV significantly attenuated status epilepticus-like epileptiform LFPs induced by 4-AP and Mg2+-free conditions. CBDV had significant anticonvulsant effects in mES (≥100 mg kg-1), audiogenic (≥50 mg kg-1) and PTZ-induced seizures (≥100 mg kg-1). CBDV alone had no effect against pilocarpine-induced seizures, but significantly attenuated these seizures when administered with valproate or phenobarbital at 200 mg kg-1 CBDV. CBDV had no effect on motor function. Conclusions and Implications: These results indicate that CBDV is an effective anticonvulsant across a broad range of seizure models, does not significantly affect normal motor function and therefore merits further investigation in chronic epilepsy models to justify human trials.

Fingerprints of changes in annual and seasonal precipitation from CMIP5 models over land and ocean

By comparing annual and seasonal changes in precipitation over land and ocean since 1950 simulated by the CMIP5 (Coupled Model Intercomparison Project, phase 5) climate models in which natural and anthropogenic forcings have been included, we find that clear global-scale and regional-scale changes due to human influence are expected to have occurred over both land and ocean. These include moistening over northern high latitude land and ocean throughout all seasons and over the northern subtropical oceans during boreal winter. However we show that this signal of human influence is less distinct when considered over the relatively small area of land for which there are adequate observations to make assessments of multi-decadal scale trends. These results imply that extensive and significant changes in precipitation over the land and ocean may have already happened, even though, inadequacies in observations in some parts of the world make it difficult to identify conclusively such a human fingerprint on the global water cycle. In some regions and seasons, due to aliasing of different kinds of variability as a result of sub sampling by the sparse and changing observational coverage, observed trends appear to have been increased, underscoring the difficulties of interpreting the apparent magnitude of observed changes in precipitation.

Real-time multi-model decadal climate predictions

We present the first climate prediction of the coming decade made with multiple models, initialized with prior observations. This prediction accrues from an international activity to exchange decadal predictions in near real-time, in order to assess differences and similarities, provide a consensus view to prevent over-confidence in forecasts from any single model, and establish current collective capability. We stress that the forecast is experimental, since the skill of the multi-model system is as yet unknown. Nevertheless, the forecast systems used here are based on models that have undergone rigorous evaluation and individually have been evaluated for forecast skill. Moreover, it is important to publish forecasts to enable open evaluation, and to provide a focus on climate change in the coming decade. Initialized forecasts of the year 2011 agree well with observations, with a pattern correlation of 0.62 compared to 0.31 for uninitialized projections. In particular, the forecast correctly predicted La Niña in the Pacific, and warm conditions in the north Atlantic and USA. A similar pattern is predicted for 2012 but with a weaker La Niña. Indices of Atlantic multi-decadal variability and Pacific decadal variability show no signal beyond climatology after 2015, while temperature in the Niño3 region is predicted to warm slightly by about 0.5 °C over the coming decade. However, uncertainties are large for individual years and initialization has little impact beyond the first 4 years in most regions. Relative to uninitialized forecasts, initialized forecasts are significantly warmer in the north Atlantic sub-polar gyre and cooler in the north Pacific throughout the decade. They are also significantly cooler in the global average and over most land and ocean regions out to several years ahead. However, in the absence of volcanic eruptions, global temperature is predicted to continue to rise, with each year from 2013 onwards having a 50 % chance of exceeding the current observed record. Verification of these forecasts will provide an important opportunity to test the performance of models and our understanding and knowledge of the drivers of climate change.

Multi-year droughts in Europe: analysis of development and causes

Whilst hydrological systems can show resilience to short-term streamflow deficiencies during within-year droughts, prolonged deficits during multi-year droughts are a significant threat to water resources security in Europe. This study uses a threshold-based objective classification of regional hydrological drought to qualitatively examine the characteristics, spatio-temporal evolution and synoptic climatic drivers of multi-year drought events in 1962–64, 1975–76 and 1995–97, on a European scale but with particular focus on the UK. Whilst all three events are multi-year, pan-European phenomena, their development and causes can be contrasted. The critical factor in explaining the unprecedented severity of the 1975–76 event is the consecutive occurrence of winter and summer drought. In contrast, 1962–64 was a succession of dry winters, mitigated by quiescent summers, whilst 1995–97 lacked spatial coherence and was interrupted by wet interludes. Synoptic climatic conditions vary within and between multi-year droughts, suggesting that regional factors modulate the climate signal in streamflow drought occurrence. Despite being underpinned by qualitatively similar climatic conditions and commonalities in evolution and characteristics, each of the three droughts has a unique spatio-temporal signature. An improved understanding of the spatio-temporal evolution and characteristics of multi-year droughts has much to contribute to monitoring and forecasting capability, and to improved mitigation strategies.

Taking the shopping centre online: new models in e-commerce

Purpose – This paper aims to provide a brief re´sume´ of previous research which has analysed the impact of e-commerce on retail real estate in the UK, and to examine the important marketing role of the internet for shopping centre managers, and retail landlords. Design/methodology/approach – Based on the results from a wider study carried out in 2003, the paper uses case studies from two different shopping centres in the UK, and documents the innovative uses of both web-based marketing and online retailing by organisations that historically have not directly been involved in the retailing process. Findings – The paper highlights the importance of considering online sales within a multi-channel approach to retailing. The two types of emerging shopping centre model which are identified are characterised by their ultimate relationship with the physical shopping centre on whose web site they reside. These can be summarised as: the “centre-led” approach, and the “brand-led” or “marketing-led” approach. Research limitations/implications – The research is based on a limited number of in-depth case studies and secondary data. Further research is needed to monitor the continuing impact of e-commerce on retail property and the marketing strategies of shopping centre managers and owners. Practical implications – Internet-based sales provide an important adjunct to conventional retail sales and an important source of potential risk for landlords and tenants in the real estate investment market. Regardless of whether retailers use the internet as a sales channel, as a product-sourcing tool, or merely to provide information to the consumer, the internet has become a keystone within the greater retail marketing mix. The findings have ramifications for understanding the way in which landlords are structuring their retail property to defray potential risks. Originality/value – The paper examines shopping centre online marketing models for the first time in detail, and will be of value to retail occupiers, owners and other stakeholders of shopping centres.

Endogenous cholinergic tone modulates spontaneous network level neuronal activity in primary cortical cultures grown on multi-electrode arrays

Background Cortical cultures grown long-term on multi-electrode arrays (MEAs) are frequently and extensively used as models of cortical networks in studies of neuronal firing activity, neuropharmacology, toxicology and mechanisms underlying synaptic plasticity. However, in contrast to the predominantly asynchronous neuronal firing activity exhibited by intact cortex, electrophysiological activity of mature cortical cultures is dominated by spontaneous epileptiform-like global burst events which hinders their effective use in network-level studies, particularly for neurally-controlled animat (‘artificial animal’) applications. Thus, the identification of culture features that can be exploited to produce neuronal activity more representative of that seen in vivo could increase the utility and relevance of studies that employ these preparations. Acetylcholine has a recognised neuromodulatory role affecting excitability, rhythmicity, plasticity and information flow in vivo although its endogenous production by cortical cultures and subsequent functional influence upon neuronal excitability remains unknown. Results Consequently, using MEA electrophysiological recording supported by immunohistochemical and RT-qPCR methods, we demonstrate for the first time, the presence of intrinsic cholinergic neurons and significant, endogenous cholinergic tone in cortical cultures with a characterisation of the muscarinic and nicotinic components that underlie modulation of spontaneous neuronal activity. We found that tonic muscarinic ACh receptor (mAChR) activation affects global excitability and burst event regularity in a culture age-dependent manner whilst, in contrast, tonic nicotinic ACh receptor (nAChR) activation can modulate burst duration and the proportion of spikes occurring within bursts in a spatio-temporal fashion. Conclusions We suggest that the presence of significant endogenous cholinergic tone in cortical cultures and the comparability of its modulatory effects to those seen in intact brain tissues support emerging, exploitable commonalities between in vivo and in vitro preparations. We conclude that experimental manipulation of endogenous cholinergic tone could offer a novel opportunity to improve the use of cortical cultures for studies of network-level mechanisms in a manner that remains largely consistent with its functional role.

The influence of anthropogenic aerosol on multi-decadal variations of historical global climate

Analysis of single forcing runs from CMIP5 (the fifth Coupled Model Intercomparison Project) simulations shows that the mid-twentieth century temperature hiatus, and the coincident decrease in precipitation, is likely to have been influenced strongly by anthropogenic aerosol forcing. Models that include a representation of the indirect effect of aerosol better reproduce inter-decadal variability in historical global-mean near-surface temperatures, particularly the cooling in the 1950s and 1960s, compared to models with representation of the aerosol direct effect only. Models with the indirect effect also show a more pronounced decrease in precipitation during this period, which is in better agreement with observations, and greater inter-decadal variability in the inter-hemispheric temperature difference. This study demonstrates the importance of representing aerosols, and their indirect effects, in general circulation models, and suggests that inter-model diversity in aerosol burden and representation of aerosol–cloud interaction can produce substantial variation in simulations of climate variability on multi decadal timescales.