Observation of lattice defects in orthorhombic iron disulfide (marcasite)

Different types of lattice defects have been studied by transmission electron microscopy (TEM) at 100 and 200 kV in a sample of natural marcasite. The most frequently occurring Burgers vectors are b=[001], [100] and 〈101〉. Dislocations with large Burgers vectors (b=〈110〉 and 〈111〉) have also been characterized: these are possibly split. Interactions between the different dislocations result in a build-up of dislocation networks. Dislocation structures show that the sample has undergone a strong recovery. These observations are confirmed by metallographic and scanning electron microscopy (SEM) observations after chemical etching.     

Rate constant measurement for the reactions of OH and Cl with peroxyacetyl nitrate at 298 K

The gas phase reactions of peroxyacetyl nitrate (PAN) with OH and Cl have been studied using the discharge-flow EPR method. The rate constants are found to be k ₃=(7.5±1.4)×10^-14 and k ₄=(3.7±1.7)×10^-13 cm³ molecule^-1 s^-1 at 298 K, respectively. These results confirm that the OH+PAN reaction will be the dominant sink of PAN in the middle and upper troposphere, whereas the reaction Cl+PAN will be negligible in contrast with previous estimations.     

Kinetic Studies of OH and O3 Reactions with Allyl and Isopropenyl Acetate

Rate coefficients have been measured for the gas phasereactions of hydroxyl (OH) radicals and ozone with twounsaturated esters, allyl acetate(CH₃C(O)OCH₂CH=CH₂) and isopropenylacetate (CH₃C(O)OC(CH₃)=CH₂). The OHexperiments were carried out using the pulsed laserphotolysis – laser induced fluorescence technique overthe temperature range 243–372 K and the kinetic dataused to derive the following Arrhenius expressions (inunits of cm³ molecule^-1 s^-1): allylacetate, k ₁ = (2.33 ± 0.27) ×10^-12 exp[(732 ± 34)/T]; and isopropenyl acetate,k ₂ = (4.52 ± 0.62) × 10^-12exp[(809 ± 39)/T]. At 298 K, the rate coefficients obtained (inunits of 10^-12 cm³ molecule^-1 s^-1)are: k ₁ = (27.1 ± 3.0) and k ₂= (69.6± 9.4). The relative rate technique has been usedto determine rate coefficients for the reaction ofozone with the acetates. Using methyl vinyl ketone asthe reference compound and a value of4.8 × 10^-18 cm³ molecule^-1s^-1 asthe rate coefficient for its reaction with O₃,the following rate coefficients were derived at 298 ± 4 K (in units of10^-18 cm³molecule^-1 s^-1): allyl acetate, (2.4 ± 0.7) andisopropenyl acetate (0.7 ± 0.2). Theresults are discussed in terms of structure-activityrelationships and used to derive atmospheric lifetimesfor the acetates.     

Spectres d'absorption dans le proche ultraviolet de CS2 et SO2 entre 200 et 300K

The near U.V. absorption cross-sections of CS₂ and SO₂ have been measured, at a 0.2 nm resolution, at different temperatures ranging from 200 to 300 K. These data will be used to interpret absorption measurements of the stratosphere of Venus.     

Network‐scale dynamics of grain‐size sorting: implications for downstream fining,stream‐profile concavity,and drainage basin morphology

We explore the link between channel‐bed texture and river basin concavity in equilibrium catchments using a numerical landscape evolution model. Theory from homogeneous sediment transport predicts that river basin concavity directly increases with bed sediment size. If the effective grain size on a river bed governs its concavity, then natural phenomena such as grain‐size sorting and channel armouring should be linked to concavity. We examine this hypothesis by allowing the bed sediment texture to evolve in a transport‐limited regime using a two grain‐size mixture of sand and gravel. Downstream ?ning through selective particle erosion is produced in equilibrium. As the channel‐bed texture adjusts downstream so does the local slope. Our model predicts that it is not the texture of the original sediment mixture that governs basin concavity. Rather, concavity is linked to the texture of the sorted surface layer. Two different textural regimes are produced in the experiments: a transitional regime where the mobility of sand and gravel changes with channel‐bed texture, and a sand‐dominated region where the mobility of sand and gravel is constant. The concavity of these regions varies depending on the median gravel‐ or sand‐grain size, erosion rate, and precipitation rate. The results highlight the importance of adjustments in both surface texture and slope in natural rivers in response to changes in ?uvial and sediment inputs throughout a drainage network. This adjustment can only be captured numerically using multiple grain sizes or empirical downstream ?ning rules. Copyright © 2004 John Wiley & Sons, Ltd.     

Rainfall-induced landslide susceptibility zonation of Puerto Rico

Landslides are a major geologic hazard with estimated tens of deaths and $1–2 billion in economic losses per year in the US alone. The island of Puerto Rico experiences one or two large events per year, often triggered in steeply sloped areas by prolonged and heavy rainfall. Identifying areas susceptible to landslides thus has great potential value for Puerto Rico and would allow better management of its territory. Landslide susceptibility zonation (LSZ) procedures identify areas prone to failure based on the characteristics of past events. LSZs are here developed based on two widely applied methodologies: bivariate frequency ratio (FR method) and logistic regression (LR method). With these methodologies, the correlations among eight possible landslide-inducing factors over the island have been investigated in detail. Both methodologies indicate aspect, slope, elevation, geological discontinuities, and geology as highly significant landslide-inducing factors, together with land-cover for the FR method and distance from road for the LR method. The LR method is grounded in rigorous statistical testing and model building but did not improve results over the simpler FR method. Accordingly, the FR method has been selected to generate a landslide susceptibility map for Puerto Rico. The landslide susceptibility predictions were tested against previous landslide analyses and other landslide inventories. This independent evaluation demonstrated that the two methods are consistent with landslide susceptibility zonation from those earlier studies and showed this analysis to have resulted in a robust and verifiable landslide susceptibility zonation map for the whole island of Puerto Rico.     

Operational Processing of Hydroacoustics at the Prototype International Data Center

— The Prototype International Data Center (PIDC) has designed and implemented a system to process data from the International Monitoring System's hydroacoustic network. The automatic system detects and measures various signal characteristics that are then used to classify the signal into one of three categories. The detected signals are combined with the seismic and infrasonic detections to automatically form event hypotheses. The automatic results are reviewed by human analysts to form the Reviewed Event Bulletin (REB). Continuous processing of hydroacoustic data has been in place since May 1997 and during that time a large database of hydroacoustic signals has been accumulated. For a two-year period, the REB contains 13,582 T phases that are associated to 8,437 events. This is roughly 25% of REB events after taking station downtime into account. Predicted travel times used in locations are based on the arrival time of the peak a mplitude mode calculated from a normal mode propagation model. Global sound velocity and bathymetry databases are used to obtain reliable 2-D, seasonally dependent, travel-time tables for each hydroacoustic station in the PIDC. A limited number of ground-truth observations indicate that the predicted travel times are good to within 5 seconds for paths extending to over 7,000?km – corresponding to a relative error of less than 0.1%. The ground truth indicates that the random errors in measuring arrival times for impulsive signals are between 1 and 6 seconds. This paper describes and evaluates the automatic hydroacoustic processing compared to the analyst reviewed results. In addition, special studies help characterize the overall performance of the hydroacoustic network.     

Atmospheric Loss Processes of Dimethyl and Diethyl Carbonate

A combined study of the OH gas phase reaction and uptake on aqueous surfacesof two carbonates, dimethyl and diethyl carbonate has been carried out todetermine the atmospheric lifetimes of these compounds. Rate coefficients havebeen measured for gas phase reactions of OH radicals with dimethyl and diethylcarbonate. The experiments were carried out using pulsed laser photolysis– laser induced fluorescence over the temperature range 263–372K and the kinetic data were used to derive the following Arrhenius expressions(in units of cm³ molecule^–1 s^–1):for dimethyl carbonate, k₁ = (0.83±0.27)×10^–12 exp [–(247± 98)/T] and fordiethyl carbonate, k₂ = (0.46±0.15)×10^–12 exp [(503± 203)/T]. At 298 K, therate coefficients obtained (in units of 10^–12 cm³molecule^–1 s^–1) are: k₁ =(0.35± 0.04) and k₂ = (2.31± 0.29). The results arediscussed in terms of structure-activity relationships.The uptake coefficients of both carbonates on aqueous surfaces were measuredas a function of temperature and composition of the liquid phase, using thedroplet train technique coupled to a mass spectrometric detection. Dimethyland diethyl carbonate show very similar results. For both carbonates, themeasured uptake kinetics were found to be independent of the aqueous phasecomposition (pure water, NaOH solutions) but dependent on gas-liquid contacttime which characterises a surface saturation effect. The uptake coefficientvalues show a slight negative temperature dependence for both carbonates.These values vary from 1.4×10^–2 to0.6×10^–2 in the temperature range of 265–279 Kfor dimethyl carbonate, from 2.4×10^–2 to0.9×10^–2 in the temperature range of 270–279 Kfor diethyl carbonate. From the kinetic data, the following Henry's lawconstants were derived between 279 and 265 K: dimethyl carbonate,H₁ = 20–106 M atm^–1; and diethyl carbonate,H₂ = 30–98 M atm^–1. The reported data showthat the OH reaction is the major atmospheric loss process of these twocarbonates with lifetimes of 33 and 5 days, respectively, while the wetdeposition is a negligible process.     

Chemical ionisation mass spectrometer for measurements of OH and Peroxy radical concentrations in moderately polluted atmospheres

A new version of an atmospheric pressure chemical ionisation mass spectrometer has been developed for ground based in situ atmospheric measurements of OH and total peroxy (HO₂ + organic peroxy) radicals. Based on the previously developed principle of chemical conversion of OH radicals to H₂SO₄ in reaction with SO₂ and detection of H₂SO₄ using an ion molecule reaction with NO₃^─, the new instrument is equipped with a turbulent chemical conversion reactor allowing for measurements in moderately polluted atmosphere at NO concentrations up to several ppb. Unlike other similar devices, where the primary NO₃^─ ions are produced using radioactive ion sources, the new instrument is equipped with a specially developed corona discharge ion source. According to laboratory measurements, the overall accuracy and detection limits are estimated to be, respectively, 25% and 2 × 10⁵ molecule cm^-3 for OH and 30% and 1 × 10⁵ molecule cm^-3 for HO₂ at 10 min integration times. The detection limit for measurements of OH radicals under polluted conditions is 5 × 10⁵ molecules cm^-3 at 10 min integration times. Examples of ambient air measurements during a field campaign near Paris in July 2007 are presented demonstrating the capability of the new instrument, although with reduced performance due to the employment of non isotopic SO₂.