Automated mechanism generation. Part 1: mechanism development and rate constant estimation for VOC chemistry in the atmosphere

A framework for automated mechanism generation for modeling atmospheric chemistry at the mechanistic level was developed. In part 1, categorization of reactions into reaction families and determination of rate coefficients using a hierarchical approach that uses experimental data and kinetic correlations are described. The main focus was to develop kinetic correlations for estimating rate coefficients that are not available experimentally, and the main correlation used was the Evans–Polanyi relationship that relates the activation energy to the heat of reaction. A hierarchical scheme for calculating heats of reaction and other thermodynamic properties was developed. The rate constants calculated using the proposed correlations are in most cases within an order of magnitude of available experimental values, and 82% are within a factor of five.     

A multi-perspective examination of heat waves affecting Metro Vancouver: now into the future

Using studies of places where heat waves are common, projected changes in heat waves in Metro Vancouver are assessed from a multi-disciplinary perspective with respect to the potential impacts of the physical change on the people and infrastructure with the intention of being better prepared for future events. Trends in maximum temperature parameters for Metro Vancouver for the past 75 years are generally not statistically significant; however, projections for 2041–2060 and 2081–2100 suggest that the region will experience such events more frequently in the future due to climate change. While Metro Vancouver, British Columbia (BC) generally does not typically experience heat waves it was strongly affected by a major heat event in July 2009, with temperature records being broken at Vancouver (≥31 °C) on the coast and at Abbotsford (≥36 °C) 65-km inland. A lack of sea breeze during this event meant that there was no cooling effect, and land surface temperatures over the downtown area approached 40 °C and excess deaths occurred. Many victims were either in the 65–74 age category, the vulnerable poor, or people with mental health issues. Because these events are rare, many buildings lack air-conditioning, and residents of Metro Vancouver under-anticipate their vulnerability. The costs of health-related impacts outweighed those related to higher electricity usage.     

Empirical spatial econometric modelling of small scale neighbourhood

The aim of the paper is to model small scale neighbourhood in a house price model by implementing the newest methodology in spatial econometrics. A common problem when modelling house prices is that in practice it is seldom possible to obtain all the desired variables. Especially variables capturing the small scale neighbourhood conditions are hard to find. If there are important explanatory variables missing from the model, the omitted variables are spatially autocorrelated and they are correlated with the explanatory variables included in the model, it can be shown that a spatial Durbin model is motivated. In the empirical application on new house price data from Helsinki in Finland, we find the motivation for a spatial Durbin model, we estimate the model and interpret the estimates for the summary measures of impacts. By the analysis we show that the model structure makes it possible to model and find small scale neighbourhood effects, when we know that they exist, but we are lacking proper variables to measure them.     

High-resolution chronology for the Mesoamerican urban center of Teotihuacan derived from Bayesian statistics of radiocarbon and archaeological data

A high-resolution ¹⁴C chronology for the Teopancazco archaeological site in the Teotihuacan urban center of Mesoamerica was generated by Bayesian analysis of 33 radiocarbon dates and detailed archaeological information related to occupation stratigraphy, pottery and archaeomagnetic dates. The calibrated intervals obtained using the Bayesian model are up to ca. 70% shorter than those obtained with individual calibrations. For some samples, this is a consequence of plateaus in the part of the calibration curve covered by the sample dates (2500 to 1450 ¹⁴C yr BP). Effects of outliers are explored by comparing the results from a Bayesian model that incorporates radiocarbon data for two outlier samples with the same model excluding them. The effect of outliers was more significant than expected. Inclusion of radiocarbon dates from two altered contexts, 500 ¹⁴C yr earlier than those for the first occupational phase, results in ages calculated by the model earlier than the archaeological records. The Bayesian chronology excluding these outliers separates the first two Teopancazco occupational phases and suggests that ending of the Xolalpan phase was around cal AD 550, 100 yr earlier than previously estimated and in accordance with previously reported archaeomagnetic dates from lime plasters for the same site.     

Thermal observations of Saturn's main rings by Cassini CIRS: Phase, emission and solar elevation dependence

Two and a half years after Saturn orbit insertion (SOI) the Cassini composite infrared spectrometer (CIRS) has acquired an extensive set of thermal measurements (including physical temperature and filling factor) of Saturn's main rings for a number of different viewing geometries, most of which are not available from Earth. Thermal mapping of both the lit and unlit faces of the rings is being performed within a multidimensional observation space that includes solar phase angle, spacecraft elevation and solar elevation. Comprehensive thermal mapping is a key requirement for detailed modeling of ring thermal properties.To first order, the largest temperature changes on the lit face of the rings are driven by variations in phase angle while differences in temperature with changing spacecraft elevation are a secondary effect. Ring temperatures decrease with increasing phase angle suggesting a population of slowly rotating ring particles [Spilker, L.J., Pilorz, S.H., Wallis, B.D., Pearl, J.C., Cuzzi, J.N., Brooks, S.M., Altobelli, N., Edgington, S.G., Showalter, M., Michael Flasar, F., Ferrari, C., Leyrat, C. 2006. Cassini thermal observations of Saturn's main rings: implications for particle rotation and vertical mixing. Planet. Space Sci. 54, 1167-1176, doi: 10.1016/j.pss.2006.05.033]. Both lit A and B rings show that temperature decreases with decreasing rings solar elevation while temperature changes in the C ring and Cassini Division are more muted. Variations in the geometrical filling factor, β, are primarily driven by changes in spacecraft elevation. For the optically thinnest region of the C ring, β variations are found to be nearly exclusively determined by spacecraft elevation. Both a multilayer and a monolayer model provide an excellent fit to the data in this region. In both cases, a ring infrared emissivity >0.9 is required, together with a random and homogeneous distribution of the particles. The interparticle shadowing function required for the monolayer model is very well constrained by our data and matches experimental measurements performed by Froidevaux [1981a. Saturn's rings: infrared brightness variation with solar elevation. Icarus 46, 4-17].     

Evidence for plunging river plume deposits in the Pahrump Hills member of the Murray formation,Gale crater,Mars

Recent robotic missions to Mars have offered new insights into the extent, diversity and habitability of the Martian sedimentary rock record. Since the Curiosity rover landed in Gale crater in August 2012, the Mars Science Laboratory Science Team has explored the origins and habitability of ancient fluvial, deltaic, lacustrine and aeolian deposits preserved within the crater. This study describes the sedimentology of a ca 13 m thick succession named the Pahrump Hills member of the Murray formation, the first thick fine‐grained deposit discovered in situ on Mars. This work evaluates the depositional processes responsible for its formation and reconstructs its palaeoenvironmental setting. The Pahrump Hills succession can be sub‐divided into four distinct sedimentary facies: (i) thinly laminated mudstone; (ii) low‐angle cross‐stratified mudstone; (iii) cross‐stratified sandstone; and (iv) thickly laminated mudstone–sandstone. The very fine grain size of the mudstone facies and abundant millimetre‐scale and sub‐millimetre‐scale laminations exhibiting quasi‐uniform thickness throughout the Pahrump Hills succession are most consistent with lacustrine deposition. Low‐angle geometric discordances in the mudstone facies are interpreted as ‘scour and drape’ structures and suggest the action of currents, such as those associated with hyperpycnal river‐generated plumes plunging into a lake. Observation of an overall upward coarsening in grain size and thickening of laminae throughout the Pahrump Hills succession is consistent with deposition from basinward progradation of a fluvial‐deltaic system derived from the northern crater rim into the Gale crater lake. Palaeohydraulic modelling constrains the salinity of the ancient lake in Gale crater: assuming river sediment concentrations typical of floods on Earth, plunging river plumes and sedimentary structures like those observed at Pahrump Hills would have required lake densities near freshwater to form. The depositional model for the Pahrump Hills member presented here implies the presence of an ancient sustained, habitable freshwater lake in Gale crater for at least ca 10³ to 10⁷ Earth years.     

Incorporating inland flooding into hurricane evacuation decision support modeling

Natural Hazards - Formal engineering hurricane evacuation studies have not typically considered inland flooding explicitly, though it has been shown repeatedly to be a major cause of damage and...     

An estuarine benthic index of biotic integrity (B-IBI) for Chesapeake Bay

A multimetric benthic index of biotic integrity (B-IBI) was developed using data from five Chesapeake Bay sampling programs conducted between 1972 and 1991. Attributes of the index were selected by comparing the response of 17 candidate measures of benthic condition (metrics) between a set of minimally affected reference sites and at all other sites for which data were available. This procedure was conducted independently for each of seven habitats defined by salinity and substrate. Fifteen of the 17 candidate metrics differed significantly between reference sites and other sites for at least one habitat. No metric differed significantly in all seven habitats; however, four metrics, species diversity, abundance, biomass, and percent of abundance as pollution-indicative taxa, differed in six habitats. The index was calculated by scoring each selected metric as 5, 3, or 1 depending on whether its value at a site approximated, deviated slightly from, or deviated greatly from conditions at the best reference sites. Validation based on independent data collected between 1992 and 1994 indicated that the index correctly distinguished stressed sites from reference sites 93% of the time, with the highest validation rates occurring in high salinity habitats.