Modeling the Effect of Vapor Wall Deposition on the Formation of Secondary Organic Aerosol in Chamber Studies

Laboratory chamber experiments are used to investigate formation of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors under a variety of environmental conditions. Simulations of these experiments test our understanding of the prevailing chemistry of SOA formation as well as the dynamic processes occurring in the chamber itself. One dynamic process occurring in the chamber that was only recently recognized is the deposition of vapor species to the Teflon walls of the chamber. Low-volatility products formed from the oxidation of volatile organic compounds (VOCs) deposit on the walls rather than forming SOA, decreasing the amount of SOA formed (quantified as the SOA yield: mass of SOA formed per mass of VOC reacted). In this work, several modeling studies are presented that address the effect of vapor wall deposition on SOA formation in chambers.

A coupled vapor-particle dynamics model is used to examine the competition among the rates of gas-phase oxidation to low volatility products, wall deposition of these products, and mass transfer to the particle phase. The relative time scales of these rates control the amount of SOA formed by affecting the influence of vapor wall deposition. Simulations show that an effect on SOA yield of changing the vapor-particle mass transfer rate is only observed when SOA formation is kinetically limited. For systems with kinetically limited SOA formation, increasing the rate of vapor-particle mass transfer by increasing the concentration of seed particles is an effective way to minimize the effect of vapor wall deposition.

This coupled vapor-particle dynamics model is then applied to α-pinene ozonolysis SOA experiments. Experiments show that the SOA yield is affected when changing the oxidation rate but not when changing the rate of gas-particle mass transfer by changing the concentration of seed particles. Model simulations show that the absence of an effect of changing the seed particle concentration is consistent with SOA formation being governed by quasi-equilibrium growth, in which gas-particle equilibrium is established much faster than the rate of change of the gas-phase concentration. The observed effect of oxidation rate on SOA yield arises due to the presence of vapor wall deposition: gas-phase oxidation products are produced more quickly and condense preferentially onto seed particles before being lost to the walls. Therefore, for α-pinene ozonolysis, increasing the oxidation rate is the most effective way to mitigate the influence of vapor wall deposition.

Finally, the detailed model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to simulate α-pinene photooxidation SOA experiments. Unexpectedly, α-pinene OH oxidation experiments show no effect when changing either the oxidation rate or the vapor-particle mass transfer rate, whereas GECKO-A predicts that changing the oxidation rate should drastically affect the SOA yield. Sensitivity studies show that the assumed magnitude of the vapor wall deposition rate can greatly affect conclusions drawn from comparisons between simulations and experiments. If vapor wall loss in the Caltech chamber is of order 10^-5 s^-1, GECKO-A greatly overpredicts SOA during high UV experiments, likely due to an overprediction of second-generation products. However, if instead vapor wall loss in the Caltech chamber is of order 10^-3 s^-1, GECKO-A greatly underpredicts SOA during low UV experiments, possibly due to missing autoxidation pathways in the α-pinene mechanism.

Heat fluxes between the Guadalquivir river and the Gulf of Cádiz Continental Shelf

An 18-year time series of daily sea surface temperature of Gulf of Cadiz and an 18-month time series of temperature collected in the vicinity of the Guadalquivir estuary mouth have been analyzed to investigate the heat exchange between the estuary and the adjacent continental shelf. The first time identifies a continental shelf area where seasonal thermal oscillation signal (amplitudes and phase) changes abruptly. In order to explain this anomaly, the second data set allows a description of thermal fluctuations in a wide range of frequencies and an estimation of the upstream heat budget of the Guadalquivir estuary. Results show that high frequency thermal signal, diurnal and semidiurnal, and water flux signal through Guadalquivir mouth, mainly semidiurnal, apparently interact randomly to give a small exchange of thermal energy at high frequency. There is no trace, at the estuary's mouth, of daily heat exchanges with intertidal mudflats probably because it tends to cancel on daily time scales. Results also show that fluctuations of estimated air-sea fluxes force fluctuations of temperature in a quite homogeneous estuarine, with a delay of 20 days. The along-channel thermal energy gradient reaches magnitudes of 300-400 J m-4 near the mouth during the summer and winter and drives the estuary-shelf exchange of thermal energy at seasonal scale. Particularly, the thermal heat imported by the estuary from the shelf area during late fall-winter-early spring of 2008/2009 is balanced by the thermal heat that the estuary exports to the shelf area during late spring-summer of 2008. In summary, Guadalquivir river removes/imports excess of thermal energy towards/from the continental shelf seasonally, as a mechanism to accommodate excess of heat from one side respect to the other side.

SLOPE STABILITY ANALYSIS OF MOUNT MEAGER, SOUTH-WESTERN BRITISH COLUMBIA, CANADA

The Mount Meager Volcanic Complex (MMVC) in south-western British Columbia is a potentially active, hydrothermally altered massif comprising a series of steep, glaciated peaks. Climatic conditions and glacial retreat has led to the further weathering, exposure and de-buttressing of steep slopes composed of weak, unconsolidated material. This has resulted in an increased frequency of landslide events over the past few decades, many of which have dammed the rivers bordering the Complex. The breach of these debris dams presents a risk of flooding to the downstream communities. Preliminary mapping showed there are numerous sites around the Complex where future failure could occur. Some of these areas are currently undergoing progressive slope movement and display features to support this such as anti-scarps and tension cracks. The effect of water infiltration on stability was modelled using the Rocscience program Slide 6.0. The main site of focus was Mount Meager in the south- east of the Complex where the most recent landslide took place. Two profiles through Mount Meager were analysed along with one other location in the northern section of the MMVC, where instability had been detected. The lowest Factor of Safety (FOS) for each profile was displayed and an estimate of the volume which could be generated was deduced. A hazard map showing the inundation zones for various volumes of debris flows was created from simulations using LAHARZ. Results showed the massif is unstable, even before infiltration. Varying the amount of infiltration appears to have no significant impact on the FOS annually implying that small changes of any kind could also trigger failure. Further modelling could be done to assess the impact of infiltration over shorter time scales. The Slide models show the volume of material that could be delivered to the Lillooet River Valley to be of the order of 109 m3 which, based on the LAHARZ simulations, would completely inundate the valley and communities downstream. A major hazard of this is that the removal of such a large amount of material has the potential to trigger an explosive eruption of the geothermal system and renew volcanic activity. Although events of this size are infrequent, there is a significant risk to the communities downstream of the complex.

Documentary sources to investigate multidecadal variability of droughts

Droughts are probably the natural hazard with the highest socioeconomic impact. Simultaneously, they are a very complex phenomenon; they are triggered by a diversity of physical factors and occur at a variety of time scales. Consequently, the instrumental record currently available is too short and the characterization of its multidecadal variability requires the use of natural proxies (tree rings, sedimentary records) or documentary sources. In this paper we analyse three documentary sources with potential to analyse the long-term variability of droughts: chapter acts, logbooks and chronicles. The chapter acts recorded discussions and decisions made during the assemblies of the local authorities and provide continuous and direct evidence on drought impacts. They are especially useful to study droughts between the 15th and the 19th centuries in Europe and the 17th to 18th in the former colonies. Logbooks recorded the meteorological conditions and the incidents occurred during navigation. They provide indirect information through the circulation indices that can be very helpful to understand the mechanisms and teleconnections associated to droughts. Finally, the chronicles are historiographical documents describing political and social events. They are secondary sources and the references to climatic events are discontinuous, thus their analysis must be extremely careful, but they are especially useful to study specific drought events especially prior to 15th century when no other sources are available.

Eulerian-Lagrangian definition of coarse bed-load transport: Theory and verification with low-cost inertial measurement units

Fluvial sediment transport is controlled by hydraulics, sediment properties and arrangement, and flow history across a range of time scales. This physical complexity has led to ambiguous definition of the reference frame (Lagrangian or Eulerian) in which sediment transport is analysed. A general Eulerian-Lagrangian approach accounts for inertial characteristics of particles in a Lagrangian (particle fixed) frame, and for the hydrodynamics in an independent Eulerian frame. The necessary Eulerian-Lagrangian transformations are simplified under the assumption of an ideal Inertial Measurement Unit (IMU), rigidly attached at the centre of the mass of a sediment particle. Real, commercially available IMU sensors can provide high frequency data on accelerations and angular velocities (hence forces and energy) experienced by grains during entrainment and motion, if adequately customized. IMUs are subjected to significant error accu- mulation but they can be used for statistical parametrisation of an Eulerian-Lagrangian model, for coarse sediment particles and over the temporal scale of individual entrainment events. In this thesis an Eulerian-Lagrangian model is introduced and evaluated experimentally. Absolute inertial accelerations were recorded at a 4 Hz frequency from a spherical instrumented particle (111 mm diameter and 2383 kg/m3 density) in a series of entrainment threshold experiments on a fixed idealised bed. The grain-top inertial acceleration entrainment threshold was approximated at 44 and 51 mg for slopes 0.026 and 0.037 respectively. The saddle inertial acceleration entrainment threshold was at 32 and 25 mg for slopes 0.044 and 0.057 respectively. For the evaluation of the complete Eulerian-Lagrangian model two prototype sensors are presented: an idealised (spherical) with a diameter of 90 mm and an ellipsoidal with axes 100, 70 and 30 mm. Both are instrumented with a complete IMU, capable of sampling 3D inertial accelerations and 3D angular velocities at 50 Hz. After signal analysis, the results can be used to parametrize sediment movement but they do not contain positional information. The two sensors (spherical and ellipsoidal) were tested in a series of entrainment experiments, similar to the evaluation of the 111 mm prototype, for a slope of 0.02. The spherical sensor entrained at discharges of 24.8 ± 1.8 l/s while the same threshold for the ellipsoidal sensor was 45.2 ± 2.2 l/s. Kinetic energy calculations were used to quantify the particle-bed energy exchange under fluvial (discharge at 30 l/s) and non-fluvial conditions. All the experiments suggest that the effect of the inertial characteristics of coarse sediments on their motion is comparable to the effect hydrodynamic forces. The coupling of IMU sensors with advanced telemetric systems can lead to the tracking of Lagrangian particle trajectories, at a frequency and accuracy that will permit the testing of diffusion/dispersion models across the range of particle diameters.

A multiscale multisurface constitutive model for the thermo-plastic behavior of polyethylene

We present a multiscale model bridging length and time scales from molecular to continuum levels with the objective of predicting the yield behavior of amorphous glassy polyethylene (PE). Constitutive pa- rameters are obtained from molecular dynamics (MD) simulations, decreasing the requirement for ad- hoc experiments. Consequently, we achieve: (1) the identification of multisurface yield functions; (2) the high strain rate involved in MD simulations is upscaled to continuum via quasi-static simulations. Validation demonstrates that the entire multisurface yield functions can be scaled to quasi-static rates where the yield stresses are possibly predicted by a proposed scaling law; (3) a hierarchical multiscale model is constructed to predict temperature and strain rate dependent yield strength of the PE.

An Approach to Tactical Performance Optimization in a Big Data World

The amount of data collected from an individual player during a football match has increased significantly in recent years, following technological evolution in positional tracking. However, given the short time that separates competitions, the common analysis of these data focuses on the magnitude of actions of each player, while considering either technical or physical perform- ance. This focus leads to a considerable amount of information not being taken into account in performance optimization, particularly while considering a sequence of different matches of the same team. In this presentation, we will present a tactical performance indicator that considers players’ overall positioning and their level of coordination during the match. This performance indicator will be applied in different time scales, with a particular focus on possible practical applications.