The kinetics of the gas-phase reactions of selected monoterpenes and cyclo-alkenes with ozone and the NO3 radical

The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere.

A feasible study of EEG-driven assistive robotic system for stroke rehabilitation

Stroke is a medical emergency and can cause a neurological damage, affecting the motor and sensory systems. Harnessing brain plasticity should make it possible to reconstruct the closed loop between the brain and the body, i.e., association of the generation of the motor command with the somatic sensory feedback might enhance motor recovery. In order to aid reconstruction of this loop with a robotic device it is necessary to assist the paretic side of the body at the right moment to achieve simultaneity between motor command and feedback signal to somatic sensory area in brain. To this end, we propose an integrated EEG-driven assistive robotic system for stroke rehabilitation. Depending on the level of motor recovery, it is important to provide adequate stimulation for upper limb motion. Thus, we propose an assist arm incorporating a Magnetic Levitation Joint that can generate a compliant motion due to its levitation and mechanical redundancy. This paper reports on a feasibility study carried out to verify the validity of the robot sensing and on EEG measurements conducted with healthy volunteers while performing a spontaneous arm flexion/extension movement. A characteristic feature was found in the temporal evolution of EEG signal in the single motion prior to executed motion which can aid in coordinating timing of the robotic arm assistance onset.

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.

Multi-vehicle planning using RRT-connect

The problem of planning multiple vehicles deals with the design of an effective algorithm that can cause multiple autonomous vehicles on the road to communicate and generate a collaborative optimal travel plan. Our modelling of the problem considers vehicles to vary greatly in terms of both size and speed, which makes it suboptimal to have a faster vehicle follow a slower vehicle or for vehicles to drive with predefined speed lanes. It is essential to have a fast planning algorithm whilst still being probabilistically complete. The Rapidly Exploring Random Trees (RRT) algorithm developed and reported on here uses a problem specific coordination axis, a local optimization algorithm, priority based coordination, and a module for deciding travel speeds. Vehicles are assumed to remain in their current relative position laterally on the road unless otherwise instructed. Experimental results presented here show regular driving behaviours, namely vehicle following, overtaking, and complex obstacle avoidance. The ability to showcase complex behaviours in the absence of speed lanes is characteristic of the solution developed.

Experimental analysis of the Reynolds flocking model

The classic Reynolds flocking model is formally analysed, with results presented and discussed. Flocking behaviour was investigated through the development of two measurements of flocking, flock area and polarisation, with a view to applying the findings to robotic applications. Experiments varying the flocking simulation parameters individually and simultaneously provide new insight into the control of flock behaviour.

A 45 kyr palaeoclimate record from the lowland interior of tropical South America

We present a well-dated, high-resolution, ~ 45 kyr lake sediment record reflecting regional temperature and precipitation change in the continental interior of the Southern Hemisphere (SH) tropics of South America. The study site is Laguna La Gaiba (LLG), a large lake (95 km2) hydrologically-linked to the Pantanal, an immense, seasonally-flooded basin and the world's largest tropical wetland (135,000 km2). Lake-level changes at LLG are therefore reflective of regional precipitation. We infer past fluctuations in precipitation at this site through changes in: i) pollen-inferred extent of flood-tolerant forest; ii) relative abundance of terra firme humid tropical forest versus seasonally-dry tropical forest pollen types; and iii) proportions of deep- versus shallow-water diatoms. A probabilistic model, based on plant family and genus climatic optima, was used to generate quantitative estimates of past temperature from the fossil pollen data. Our temperature reconstruction demonstrates rising temperature (by 4 °C) at 19.5 kyr BP, synchronous with the onset of deglacial warming in the central Andes, strengthening the evidence that climatic warming in the SH tropics preceded deglacial warming in the Northern Hemisphere (NH) by at least 5 kyr. We provide unequivocal evidence that the climate at LLG was markedly drier during the last glacial period (45.0–12.2 kyr BP) than during the Holocene, contrasting with SH tropical Andean and Atlantic records that demonstrate a strengthening of the South American summer monsoon during the global Last Glacial Maximum (~ 21 kyr BP), in tune with the ~ 20 kyr precession orbital cycle. Holocene climate conditions occurred as early as 12.8–12.2 kyr BP, when increased precipitation in the Pantanal catchment caused heightened flooding and rising lake levels in LLG. In contrast to this strong geographic variation in LGM precipitation across the continent, expansion of tropical dry forest between 10 and 3 kyr BP at LLG strengthens the body of evidence for widespread early–mid Holocene drought across tropical South America.

Historical and idealized climate model experiments: an intercomparison of Earth system models of intermediate complexity

Both historical and idealized climate model experiments are performed with a variety of Earth system models of intermediate complexity (EMICs) as part of a community contribution to the Intergovernmental Panel on Climate Change Fifth Assessment Report. Historical simulations start at 850 CE and continue through to 2005. The standard simulations include changes in forcing from solar luminosity, Earth's orbital configuration, CO2, additional greenhouse gases, land use, and sulphate and volcanic aerosols. In spite of very different modelled pre-industrial global surface air temperatures, overall 20th century trends in surface air temperature and carbon uptake are reasonably well simulated when compared to observed trends. Land carbon fluxes show much more variation between models than ocean carbon fluxes, and recent land fluxes appear to be slightly underestimated. It is possible that recent modelled climate trends or climate–carbon feedbacks are overestimated resulting in too much land carbon loss or that carbon uptake due to CO2 and/or nitrogen fertilization is underestimated. Several one thousand year long, idealized, 2 × and 4 × CO2 experiments are used to quantify standard model characteristics, including transient and equilibrium climate sensitivities, and climate–carbon feedbacks. The values from EMICs generally fall within the range given by general circulation models. Seven additional historical simulations, each including a single specified forcing, are used to assess the contributions of different climate forcings to the overall climate and carbon cycle response. The response of surface air temperature is the linear sum of the individual forcings, while the carbon cycle response shows a non-linear interaction between land-use change and CO2 forcings for some models. Finally, the preindustrial portions of the last millennium simulations are used to assess historical model carbon-climate feedbacks. Given the specified forcing, there is a tendency for the EMICs to underestimate the drop in surface air temperature and CO2 between the Medieval Climate Anomaly and the Little Ice Age estimated from palaeoclimate reconstructions. This in turn could be a result of unforced variability within the climate system, uncertainty in the reconstructions of temperature and CO2, errors in the reconstructions of forcing used to drive the models, or the incomplete representation of certain processes within the models. Given the forcing datasets used in this study, the models calculate significant land-use emissions over the pre-industrial period. This implies that land-use emissions might need to be taken into account, when making estimates of climate–carbon feedbacks from palaeoclimate reconstructions.

Late Holocene methane rise caused by orbitally controlled increase in tropical sources

Considerable debate surrounds the source of the apparently ‘anomalous’1 increase of atmospheric methane concentrations since the mid-Holocene (5,000 years ago) compared to previous interglacial periods as recorded in polar ice core records2. Proposed mechanisms for the rise in methane concentrations relate either to methane emissions from anthropogenic early rice cultivation1, 3 or an increase in natural wetland emissions from tropical4 or boreal sources5, 6. Here we show that our climate and wetland simulations of the global methane cycle over the last glacial cycle (the past 130,000 years) recreate the ice core record and capture the late Holocene increase in methane concentrations. Our analyses indicate that the late Holocene increase results from natural changes in the Earth's orbital configuration, with enhanced emissions in the Southern Hemisphere tropics linked to precession-induced modification of seasonal precipitation. Critically, our simulations capture the declining trend in methane concentrations at the end of the last interglacial period (115,000–130,000 years ago) that was used to diagnose the Holocene methane rise as unique. The difference between the two time periods results from differences in the size and rate of regional insolation changes and the lack of glacial inception in the Holocene. Our findings also suggest that no early agricultural sources are required to account for the increase in methane concentrations in the 5,000 years before the industrial era.

High-latitude climate sensitivity to ice-sheet forcing over the last 120kyr

Interpretation of ice-core records is currently limited by paucity of modelling at adequate temporal and spatial resolutions. Several key questions relate to mechanisms of polar amplification and inter-hemispheric coupling on glacial/interglacial timescales. Here, we present the first results from a large set of global ocean–atmosphere climate model ‘snap-shot’ simulations covering the last 120 000 years using the Hadley Centre climate model (HadCM3) at up to 1 kyr temporal resolution. Two sets of simulations were performed in order to examine the roles of orbit and greenhouse gases versus ice-sheet forcing of orbital-scale climate change. A series of idealised Heinrich events were also simulated, but no changes to aerosols or vegetation were prescribed. This paper focuses on high latitudes and inter-hemispheric linkages. The simulations reproduce polar temperature trends well compared to ice-core reconstructions, although the magnitude is underestimated. Polar amplification varies with obliquity, but this variability is dampened by including variations in land ice coverage, while the overall amplification factor increases. The relatively constant amplification of Antarctic temperatures (with ice-sheet forcing included) suggests it is possible to use Antarctic temperature reconstructions to estimate global changes (which are roughly half the magnitude). Atlantic Ocean overturning circulation varies considerably only with the introduction of Northern Hemisphere ice sheets, but only weakens in the North Atlantic in the deep glacial, when ocean–sea-ice feedbacks result in the movement of the region of deep convection to lower latitudes and with the introduction of freshwater to the surface North Atlantic in order to simulate Heinrich events.

Late Quaternary fire regimes of Australasia

We have compiled 223 sedimentary charcoal records from Australasia in order to examine the temporal and spatial variability of fire regimes during the Late Quaternary. While some of these records cover more than a full glacial cycle, here we focus on the last 70,000 years when the number of individual records in the compilation allows more robust conclusions. On orbital time scales, fire in Australasia predominantly reflects climate, with colder periods characterized by less and warmer intervals by more biomass burning. The composite record for the region also shows considerable millennial-scale variability during the last glacial interval (73.5–14.7 ka). Within the limits of the dating uncertainties of individual records, the variability shown by the composite charcoal record is more similar to the form, number and timing of Dansgaard–Oeschger cycles as observed in Greenland ice cores than to the variability expressed in the Antarctic ice-core record. The composite charcoal record suggests increased biomass burning in the Australasian region during Greenland Interstadials and reduced burning during Greenland Stadials. Millennial-scale variability is characteristic of the composite record of the sub-tropical high pressure belt during the past 21 ka, but the tropics show a somewhat simpler pattern of variability with major peaks in biomass burning around 15 ka and 8 ka. There is no distinct change in fire regime corresponding to the arrival of humans in Australia at 50 ± 10 ka and no correlation between archaeological evidence of increased human activity during the past 40 ka and the history of biomass burning. However, changes in biomass burning in the last 200 years may have been exacerbated or influenced by humans.

Updating existing emotional memories involves the frontopolar/orbitofrontal cortex in ways that acquiring new emotional memories does not

In life, we must often learn new associations to people, places, or things we already know. The current fMRI study investigated the neural mechanisms underlying emotional memory updating. Nineteen participants first viewed negative and neutral pictures and learned associations between those pictures and other neutral stimuli, such as neutral objects and encoding tasks. This initial learning phase was followed by a memory updating phase, during which participants learned picture-location associations for old pictures (i.e., pictures previously associated with other neutral stimuli) and new pictures (i.e., pictures not seen in the first phase). There was greater frontopolar/orbito-frontal (OFC) activity when people learned picture–location associations for old negative pictures than for new negative pictures, but frontopolar OFC activity did not significantly differ during learning locations of old versus new neutral pictures. In addition, frontopolar activity was more negatively correlated with the amygdala when participants learned picture–location associations for old negative pictures than for new negative or old neutral pictures. Past studies revealed that the frontopolar OFC allows for updating the affective values of stimuli in reversal learning or extinction of conditioning [e.g., Izquierdo, A., & Murray, E. A. Opposing effects of amygdala and orbital PFC lesions on the extinction of instrumental responding in macaque monkeys. European Journal of Neuroscience, 22, 2341–2346, 2005]; our findings suggest that it plays a more general role in updating associations to emotional stimuli.

Measuring large topographic change with InSAR: lava thicknesses, extrusion rate and subsidence rate at Santiaguito volcano, Guatemala

Lava flows can produce changes in topography on the order of 10s-100s of metres. A knowledge of the resulting volume change provides evidence about the dynamics of an eruption. We present a method to measure topographic changes from the differential InSAR phase delays caused by the height differences between the current topography and a Digital Elevation Model (DEM). This does not require a pre-event SAR image, so it does not rely on interferometric phase remaining coherent during eruption and emplacement. Synthetic tests predicts that we can estimate lava thickness of as little as �9 m, given a minimum of 5 interferograms with suitably large orbital baseine separations. In the case of continuous motion, such as lava flow subsidence, we invert interferometric phase simultaneously for topographic change and displacement. We demonstrate the method using data from Santiaguito volcano, Guatemala, and measure increases in lava thickness of up to 140 m between 2000 and 2009, largely associated with activity between 2000 and 2005. We find a mean extrusion rate of 0.43 +/- 0.06 m3/s, which lies within the error bounds of the longer term extrusion rate between 1922-2000. The thickest and youngest parts of the flow deposit were shown to be subsiding at an average rate of �-6 cm/yr. This is the first time that flow thickness and subsidence have been measured simultaneously. We expect this method to be suitable for measurment of landslides and other mass flow deposits as well as lava flows.

Infrared Observations of XTE J1118+480

Infrared observations of the outbursting black hole XTE J1118+480 (ATEL #383) were performed using SQIID on the Kitt Peak National Observatory 2.1m telescope. Observations spanning 2005 January 15.42-15.58 found it somewhat fainter than the previous outburst (IAUC # 7394 , # 7407 ), at average brightness J=12.91+/-0.03, H=12.50+/-0.03, K=11.95+/-0.03. The colors again correspond to an approximately flat spectrum in F_nu. No orbital variation is apparent, but there is substantial unresolved rapid variability with rms amplitude 22% in K (between 2s exposures). Further observations are planned nightly until Jan 21.

The Mid-Brunhes Event and West Antarctic ice sheet stability

The complex cyclical nature of Pleistocene climate, driven by the evolving orbital configuration of the Earth, is well known but not well understood. A major climatic transition took place at the Mid-Brunhes Event (MBE), ca. 430 ka ago after which the amplitude of the ca.100 ka climate oscillations increased, with substantially warmer interglacials, including periods warmer than present. Recent modelling has indicated that while the timing of these warmer-than-present transient (WPT) events is consistent with southern warming due to a deglaciation-forced slowdown of the Atlantic Meridional Overturning Circulation, the magnitude of warming requires a local amplification, for which a candidate is the feedback of significant West Antarctic Ice Sheet (WAIS) retreat. We here extend this argument, based on the absence of WPTs in the early ice core record (450–800 ka ago), to hypothesize that the MBE could be a manifestation of decreased WAIS stability, triggered by ongoing subglacial erosion.

Fire history and the Global Charcoal Database: a new tool for hypothesis testing and data exploration

Version 1 of the Global Charcoal Database is now available for regional fire history reconstructions, data exploration, hypothesis testing, and evaluation of coupled climate–vegetation–fire model simulations. The charcoal database contains over 400 radiocarbon-dated records that document changes in charcoal abundance during the Late Quaternary. The aim of this public database is to stimulate cross-disciplinary research in fire sciences targeted at an increased understanding of the controls and impacts of natural and anthropogenic fire regimes on centennial-to-orbital timescales. We describe here the data standardization techniques for comparing multiple types of sedimentary charcoal records. Version 1 of the Global Charcoal Database has been used to characterize global and regional patterns in fire activity since the last glacial maximum. Recent studies using the charcoal database have explored the relation between climate and fire during periods of rapid climate change, including evidence of fire activity during the Younger Dryas Chronozone, and during the past two millennia.