A Pulsed Laser Photolysis-Resonance Fluorescence Kinetic Study of the Atmospheric Cl Atom-Initiated Oxidation of Propene and a Series of 3-Halopropenes at Room Temperature

Absolute rate coefficient measurements have been carried out for the reactions of Cl atoms with propene and a series of 3-halopropenes, at room temperature (298 ± 2) K using a newly constructed laser photolysis-resonance fluorescence (PLP-RF) system. The rate coefficients obtained (in units of cm³ molecule^–1 s^–1) are: propene (1.40± 0.24) ×10^–10, 3-fluoropropene (4.92 ± 0.42) ×10^–11, 3-chloropropene (7.47 ± 1.50) × 10^–11, 3-bromopropene (1.23± 0.14) ×10^–10 and 3-iodopropene (1.29± 0.15) ×10^–10. In order to test this new system, the reactions of Cl atoms with acetone and isoprene have also been studied and compared with data previously reported. The rate coefficients determined at room temperature for these last two reactions are (2.93 ± 0.20) ×10^–12 cm³ molecule^–1 s^{– 1} and (3.64± 0.20)×10^–10 cm³ molecule^–1 s^–1, respectively. The measured values were independent of pressure over the range 20–200 Torr. The influence of the different halogen atoms substituents on the reactivity of these alkenes with Cl atoms as well as the atmospheric implications of these measurements are studied and discussed for the first time in this work and compared with the reactivity with NO₃ and OH radicals.     

Seismic Vulnerability of Historical Constructions: A Contribution

Earthquakes are known to be natural hazards that have affected tremendously historical constructions. Unfortunately, as far as earthquake impacts are concerned, there are no world statistics to compare the suffering of populations or of the building stock and their evolution in time, with the damage inflicted to the stock of historical constructions. Lately, a great effort has been placed on engineering developments: (i) to better understand the seismic behaviour of historical construction and (ii) to assess the benefits of different techniques for reinforcing these structures. However, a great deal of discussion is still going on the type of reinforcement that should be applied, how effective it is and how much it costs. Research is needed for helping in these decisions, by providing a more precise framework in this field. The aim of this review is to make an overall insight on some of the available methods for assessing seismic vulnerability of historical constructions and on how to use them in the case of occurrence of an earthquake. Given this occurrence, the objective is to minimize the effects of aftershocks, avoid hurried demolition made under extreme pressure and help shore-up parts in risk of falling. The final aim is also to help in the definition of strategies for the repair of the damaged patrimony, or as a measure to prevent damage in future earthquakes for the most vulnerable cases. The paper is illustrated with the presentation of several examples published in the literature where the author participated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Seismological Studies of a Fluid Injection in Sedimentary Rocks, East Texas

—?Induced microseismicity data from a large volume fluid injection into sedimentary rock was analyzed to study the fracture system, fluid pathways, and state of stress in the lower Frio formation in east Texas. Seismicity data are from two arrays of 25 3-component geophone packages sited in two monitoring boreholes. From a total of 2,894 event triggers, a subset of 54 microearthquakes was chosen for their high quality seismograms and clear P and S arrivals. Arrival times were picked with a precision of 0.5 to 1.0?ms, and microearthquakes were located with hypocentral uncertainties estimated as less than 10–20?m. Hypocenters farthest from the injection well define a nearly horizontal tube of seismicity approximately aligned in the direction of the injection well. A simultaneous inversion of arrival times for transverse isotropic velocity structure and hypocenters yielded P-wave anisotropy of ?14% and S-wave anisotropy of ?2%. Thus, velocities along vertical ray paths are higher than those along horizontal paths, probably because of lithologic differences. Single-event focal mechanisms were determined for 47 events, and many of them are normal fault type. The minimum principal stress derived from the focal mechanisms is nearly horizontal and trends approximately north-south, consistent with the regional stress state. An imaging analysis of the seismograms shows the presence of strong seismic scatterers at positions that correlate with boundaries seen in the hypocenters; both features probably result from a similar set of heterogeneities. This study demonstrates the abundance of information that can be extracted from induced seismicity data and underscores the value of induced seismicity monitoring for studying the fluid and fracture systems created by fluid injections.     

Organic facies and depositional palaeoenvironment of lignites from Rio Maior Basin (Portugal)

The Rio Maior Basin (Portugal) is a tectonic depression, filled by a Pliocene sequence that comprises, from floor to roof: (i) kaoliniferous fine sands, (ii) diatomites and lignites, (iii) recent deposits of sandstone and clay. The diatomites and lignites form a small dissimetric syncline with alternating seams. Ten lignite seams were identified and named from floor to roof as F, E, D, C.2, C.1, C, B, A, a and a′. Seams A, D, E and F are considered to be the main seams.The organic fraction consists mainly of macerals of the huminite group, with small percentages of inertinite and liptinite groups. However, the petrographic composition of each seam is distinct, particularly with regards to macerals of the huminite and liptinite groups.Calculation of petrographic indices permitted to plot the coals in facies and palaeoenvironment diagrams. Five facies have been defined: (i) aquatic, (ii) herbaceous swamp, (iii) mixed swamp with forest and herbaceous vegetation, (vi) forest swamp (wetter) and (v) forest swamp (drier).These lignites are humic coals formed from organic matter of terrestrial origin. The peat biomass at the origin of these coals formed from a very diverse vegetation comprising gymnosperms and angiosperms. In seams F, and occasionally in seams E and D, Botryococcus algae have also contributed to the biomass. Peat deposition corresponded to a rheotrophic hydrological regime: the water level always remained above the topographic surface of the basin. Nevertheless, during the deposition of seam A in the northern part of the basin, the water level was slightly below the topographic surface. The organic matter was preserved in anaeorobic conditions.     

Catastrophic floods as a possible cause of organic matter accumulation giving rise to coal, Paraná Basin, Brazil

Gondwana coals of the Rio Bonito Formation (Paraná Basin) in Southern Brazil have generally large ash yields, so they could be better called coaly siltstones than coal. In addition, hummocky cross stratification (HCS) was found in several coal beds of the Rio Bonito Formation throughout the basin. In this formation, the frequent and close relationship between facies involving rocks generated by subaqueous gravity flows (diamictites) and coal itself provides an excellent depositional model based on resedimentary processes acting during deposition, as well as a stratigraphic rearrangement of the present units.In the State of Rio Grande do Sul (southern part of Paraná Basin), coals are actually prodelta deposits related to delta-front diamictite and conglomeratic sandstone with sigmoidal bedding. Coal-forming organic sediments would come from trees plucked by the floods, as indicated by the wood logs floating in the diamictite, and reworking of previous peat accumulations. Every coal layer is covered generally by paleosoil siltstones, which represent colonization at the top of the catastrophic flood deposit, ending a sedimentary cycle.In case of Brazilian coal settings, several authors recognized deltas (fan deltas or braid deltas). Here is particularly considered the general environment as a salted interior sea (lago mare, Hsü et al. sense).The present study will refer to three important lithostratigraphic units in the Carboniferous–Early Triassic cycle: the Itararé Group, the Rio Bonito Formation, and the Palermo Formation.Although the preferential mode of occurrence of HCS in shallow marine environments indicates a genesis attributed to storm action, other causes, such as catastrophic flooding, have been advanced. Mutti et al. [Mem. Sci. Geol. 48 (1996) 233] described flood-dominated deltaic systems with thick conglomerate, sandstone, and pelitic deposits, derived from small- to medium-scale fluvial systems and mountain-bordered drainage basins adjacent to the sea. In such settings, seaward sediment flow can increase dramatically when weather conditions can supply water in such amounts to produce catastrophic floods. Thick and laterally extensive sandstone lobes with HCS are the fundamental depositional elements of fan deltas and other river-dominated delta systems.Diamictites and coal together could be a result from Jökullhlaups—an Icelandic term for glacial outburst flood—in case of catastrophic floods coming from a melting mountain glacier, similar to the Columbia River Valley Scablands (15,000 BP) and in modern Iceland examples.     

Evidence of direct particle trapping by a tropical seagrass meadow

The capacity of seagrass canopies to directly retain sestonic particles was tested by quantifying the rate at which suspended fluorescent tracer particles were retained within a tropical Philippine seagrass meadow and by examining whether the test particles lost from the water column were later bound to seagrass leaves or inside epibionts. The particle loss rates in the presence of seagrass canopies were up to 4 times higher than those in unvegetated and plankton controls. The seagrass canopies trapped particles with a maximum rate of 0.73 (±0.24) h^?1. As much as 5% of the particles trapped by the seagrass leaves were physically adhered to the leaf surfaces following rinsing. Particles were also observed to be ingested by protozoa (ciliates and amoeba-like organisms), residing on the surface of the leaves, and may be the dominant particle trapping mechanism by seagrass leaves. These processes should provide an efficient mechanism for the transfer of planktonic production to the benthos, adding to the high organic carbon input maintained by the high production of the seagrass themselves.     

Depositional controls on coal distribution and quality in the Eocene Brunner Coal Measures, Buller Coalfield, South Island, New Zealand

The Buller Coalfield on the West Coast of the South Island, New Zealand, contains the Eocene Brunner Coal Measures. The coal measures unconformably overlie Paleozoic-Cretaceous basement rocks and are conformably overlain by, and laterally interfinger with, the Eocene marine Kaiata Formation. This study examines the lithofacies frameworks of the coal measures in order to interpret their depositional environments. The lower part of the coal measures is dominated by conglomeratic lithofacies that rest on a basal erosional surface and thicken in paleovalleys incised into an undulating peneplain surface. These lithofacies are overlain by sandstone, mudstone and organic-rich lithofacies of the upper part of the coal measures. The main coal seam of the organic-rich lithofacies is thick (10–20 m), extensive, locally split, and locally absent. This seam and associated coal seams in the Buller Coalfield are of low- to high-volatile bituminous rank (vitrinite reflectance between 0.65% and 1.75%). The main seam contains a variable percentage of ash and sulphur. These values are related to the thickening and areal distribution of the seam, which in turn, were controlled by the nature of clastic deposition and peat-forming mire systems, marine transgression and local tidal incursion. The conglomeratic lithofacies represent deposits of trunk and tributary braided streams that rapidly aggraded incised paleovalleys during sea-level stillstands. The main seam represents a deposit of raised mires that initially developed as topogenous mires on abandoned margins of inactive braidbelts. Peat accumulated in mires as a response to a rise in the water table, probably initially due to gradual sea-level rise and climate, and the resulting raised topography served as protection from floods.The upper part of the coal measures consists of sandstone lithofacies of fluvial origin and bioturbated sandstone, mudstone and organic-rich lithofacies, which represent deposits of paralic (deltaic, barrier shoreface, tidal and mire) and marine environments. The fluvial sandstone lithofacies accumulated in channels during a sea-level stillstand. The channels were infilled by coeval braided and meandering streams prior to transgression. Continued transgression, ranging from tidal channel-estuarine incursions to widespread but uneven paleoshoreline encroachment, accompanied by moderate basin subsidence, is marked by a stacked, back-stepping geometry of bioturbated sandstone and marine mudstone lithofacies. Final retrogradation (sea-level highstand) is marked by backfilling of estuaries and by rapid landward deposition of the marine Kaiata Formation in the late Eocene.     

Advances in discrete element modelling of underground excavations

The paper presents advances in the discrete element modelling of underground excavation processes extending modelling possibilities as well as increasing computational efficiency. Efficient numerical models have been obtained using techniques of parallel computing and coupling the discrete element method with finite element method. The discrete element algorithm has been applied to simulation of different excavation processes, using different tools, TBMs and roadheaders. Numerical examples of tunnelling process are included in the paper, showing results in the form of rock failure, damage in the material, cutting forces and tool wear. Efficiency of the code for solving large scale geomechanical problems is also shown.     

The ratio between chrysophycean cysts and diatoms in temperate,mountain lakes: some recommendations for its use in paleolimnology

The ratio between chrysophycean cysts and diatom valves (CD ratio) in lake sediments has been suggested as a useful indicator of changing trophic state conditions in oligotrophic lakes. Other environmental factors, however, may influence the CD ratio because chrysophycean cysts usually reflect conditions in the planktonic environment and diatoms reflect benthic conditions. We investigated the CD ratio in 76 mountain lakes in the Pyrenees to determine the environmental drivers that influence the ratio and assess its value for paleoenvironmental inference. The lakes surveyed included a broad range with respect to bedrock type, altitude and surface area, characteristics that cover much of the variability that can be found in cold, oligotrophic mountain lakes. Lake depth and Ca²⁺ concentration explain most of the variation in the CD ratio. Trophic state factors (e.g. total phosphorus, TP) play a secondary role. As a predictor, CD ratio performs primarily as a lake depth indicator. The predictive models can be improved if trophic state (i.e. TP) and chemical conditions (Ca²⁺) are known or can be estimated independently. Use of the CD ratio for inferring Ca²⁺ oscillations only makes sense in lakes with Ca²⁺ <200 µeq/L or in those that oscillate below and above this threshold through time. Other interpretations of the CD ratio (e.g. lake trophic state changes, ice-cover duration) make sense if complementary paleolimnological evidence indicates that neither water depth nor Ca²⁺ concentration changed significantly. Indeed, paleolimnological interpretation of the CD ratio requires considering the particular characteristics of the lake and may vary depending on the temporal scale considered. This study provides some guidelines for evaluating critically the use of the CD ratio.     

Geomorphological evolution of the Tilcara alluvial fan (Jujuy Province, NW Argentina): Tectonic implications and palaeoenvironmental considerations

The development and evolution of the Tilcara alluvial fan, in the Quebrada de Humahuaca (Andean Eastern Cordillera, NW Argentina), has been analysed by using geomorphological mapping techniques, sedimentological characterisation of the deposits and OSL chronological methods. It is a complex segmented alluvial fan made up of five evolutionary stages (units Qf1, Qf2, Qf3, Qf4 and Qf5) developed under arid climatic environments as well as compressive tectonic conditions. Segmentation processes, including aggradation/entrenchment cycles and changes in the location of the depositional lobe, are mainly controlled by climatic and/or tectonic changes as well as channel piracy processes in the drainage system. Alluvial fan deposits include debris flows, sheet flows and braided channel facies associated with high water discharge events in an arid environment. The best mean OSL age estimated for stage Qf2 is 84.5 ± 7 ka BP. In addition, a thrust fault affecting these deposits has been recognized and, as a consequence, the compressive tectonics must date from the Upper Pleistocene in this area of the Andean Eastern Cordillera.