Prediction of the abiotic degradability of organic compounds in the troposphere

A statistically relevant correlation between the reaction rate coefficient, k _OH, for the OH radical reaction with 161 organic compounds in the gas phase at 300 K, and the corresponding vertical ionisation energies E _i,v, reveals two classes of compounds: aromatics where –log(k _OH/cm³s^-1)3/2E _i,v(eV)–2 and aliphatics where –log(k _OH/cm³s^-1)4/5E _i,v(eV)+3. The prediction of the rate coefficient, k _OH, for the reaction of OH with organic molecules from the above equations has a probability of about 90%. Assuming a global diurnal mean of the OH radical concentration of 5×10⁵ cm³, the upper limit of the tropospheric half-life of organic compounds and their persistence can be estimated.     

Using low-density discrete Airborne Laser Scanning data to assess the potential carbon dioxide emission in case of a fire event in a Mediterranean pine forest

The aim of study is to map the carbon dioxide (CO₂) emission of the aboveground tree biomass (AGB) in case of a fire event. The suitability of low point density, discrete, multiple-return, Airborne Laser Scanning (ALS) data and the influence of several characteristics of these data and the study area on the results obtained have been evaluated. A sample of 45 circular plots representative of Pinus halepensis Miller stands were used to fit and validate the model of AGB. The ALS point clouds were processed to obtain the independent variables and a multivariate linear regression analysis between field data and ALS-derived variables allowed estimation of AGB. Then, the influence of several characteristics on the residuals of the model was analyzed. Finally, conversion factors were applied to obtain the CO₂ values. The AGB model presented a R² value of 0.84 with a relative root-mean-square error of 27.35%. This model included ALS variables related to vegetation height variability and to canopy density. Terrain slope, aspect, canopy cover, scan angle and the number of laser returns did not influence AGB estimations at plot level.     

Role of land-surface temperature feedback on model performance for the stable boundary layer

At present a variety of boundary-layer schemes is in use in numerical models and often a large variation of model results is found. This is clear from model intercomparisons, such as organized within the GEWEX Atmospheric Boundary Layer Study (GABLS). In this paper we analyze how the specification of the land-surface temperature affects the results of a boundary-layer scheme, in particular for stable conditions. As such we use a well established column model of the boundary layer and we vary relevant parameters in the turbulence scheme for stable conditions. By doing so, we can reproduce the outcome for a variety of boundary-layer models. This is illustrated with the original set-up of the second GABLS intercomparison study using prescribed geostrophic winds and land-surface temperatures as inspired by (but not identical to) observations of CASES-99 for a period of more than two diurnal cycles. The model runs are repeated using a surface temperature that is calculated with a simple land-surface scheme. In the latter case, it is found that the range of model results in stable conditions is reduced for the sensible heat fluxes, and the profiles of potential temperature and wind speed. However, in the latter case the modelled surface temperatures are rather different than with the original set-up, which also impacts on near-surface air temperature and wind speed. As such it appears that the model results in stable conditions are strongly influenced by non-linear feedbacks in which the magnitude of the geostrophic wind speed and the related land-surface temperature play an important role.     

Spectral density regression for bivariate extremes

We introduce a density regression model for the spectral density of a bivariate extreme value distribution, that allows us to assess how extremal dependence can change over a covariate. Inference is performed through a double kernel estimator, which can be seen as an extension of the Nadaraya–Watson estimator where the usual scalar responses are replaced by mean constrained densities on the unit interval. Numerical experiments with the methods illustrate their resilience in a variety of contexts of practical interest. An extreme temperature dataset is used to illustrate our methods.     

Coupling hydrogeological with surface runoff model in a Poltva case study in Western Ukraine

This paper presents the hydrological coupling of the software framework OpenGeoSys (OGS) with the EPA Storm Water Management Model (SWMM). Conceptual models include the Saint Venant equation for river flow, the 2D Darcy equations for confined and unconfined groundwater flow, a two-way hydrological coupling flux in a compartment coupling approach (conductance concept), and Lagrangian particles for solute transport in the river course. A SWMM river–OGS aquifer inter-compartment coupling flux is examined for discharging groundwater in a systematic parameter sensitivity analysis. The parameter study involves a small perturbation (first-order) sensitivity analysis and is performed for a synthetic test example base-by-base through a comprehensive range of aquifer parametrizations. Through parametrization, the test cases enables to determine the leakance parameter for simulating streambed clogging and non-ocillatory river-aquifer water exchange rates with the sequential (partitioned) coupling scheme. The implementation is further tested with a hypothetical but realistic 1D river–2D aquifer model of the Poltva catchment, where discharging groundwater in the upland area affects the river–aquifer coupling fluxes downstream in the river course (propagating feedbacks). Groundwater contribution in the moving river water is numerically determined with Lagrangian particles. A numerical experiment demonstrates that the integrated river–aquifer model is a serviceable and realistic constituent in a complete compartment model of the Poltva catchment.     

Calculating the two-dimensional magnetotelluric Jacobian in finite elements using reciprocity

To speed up the calculation of the field Jacobian for 2-D magnetoteliuric inversion using finite elements, the principle of electromagnetic reciprocity is applied. The governing relationship for the Jacobian of the field along strike is obtained by differentiating the Helmholtz equation with respect to the resistivity of each region in the finite-element mesh. The result is a similar Helmholtz equation for the Jacobian, with new sources distributed over all nodes within the parameter medium. However, according to the principle of electromagnetic reciprocity, the roles of sources and receivers are interchangeable. Utilizing reciprocity, the field values obtained from the original forward problem and for new unit sources imposed at the receivers are then utilized in the calculation of the Jacobian by simple multiplication and summation with finite-element terms at each rectangle in the mesh. For the auxiliary (across-strike) fields, the Jacobian terms are obtained by solving source vectors loaded with parabola coefficients used in the approximation to Maxwell's equations. Jacobian terms for the apparent resistivity ( p _a), the impedance phase (φ) and the vertical magnetic field ( K _zy) are then calculated utilizing the parallel- and auxiliary-field Jacobians. Comparison of Jacobian values obtained from reciprocity calculations and by differencing two forward solutions show that the reciprocity method is accurate and can be used to decrease the number of calculations required to obtain sensitivities by one to two orders of magnitude.     

Comparative study of sampling methods and in situ and laboratory analysis for shallow-water submarine hydrothermal systems

A primary aim for sampling of submarine hydrothermal vents is to minimize inclusion of ambient seawater. Here, we compare the results of three different sampling methods (air displacement, two-valve bottle, and syringes) for shallow submarine systems. Mixing of hydrothermal fluid with seawater is unavoidable; however, calculations based on linear mixing models allow estimation of the hydrothermal fluid end-member composition. The results show that sampling with a two-valve bottle and syringes are the best options because they allow collection of samples with a large proportion of hydrothermal fluid. Additionally, we compare the results of in situ and laboratory analyses of the fluid samples, and demonstrate that determination of chemical composition in situ is the best option for some components, as re-equilibration affects some component concentrations (i.e. bicarbonate). Conversely, silica determination in situ usually underestimates the concentration in the fluid, as it does not account for polymeric silica. Other components can be measured either in the field or in the laboratory.     

Syntectonic emplacement of the Middle Jurassic Concón Mafic Dike Swarm, Coastal Range, central Chile (33° S)

The Concón Mafic Dike Swarm (CMDS) consists of basaltic to andesitic dikes emplaced into deformed Late Paleozoic granitoids during the development of the Jurassic arc of central Chile. The dikes are divided into an early group of thick dikes (5–12 m) and a late group of thin dikes (0.5–3 m). Two new amphibole ⁴⁰Ar/³⁹Ar dates obtained from undeformed and deformed dikes, constrain the age of emplacement and deformation of the CMDS between 163 and 157 Ma. Based on radiometric ages, field observations, AMS studies and petrographic data, we conclude that the emplacement of the CMDS was syntectonic with the Jurassic arc extension and associated with sinistral displacements along the NW-trending structures that host the CMDS. The common occurrence of already deformed and rotated xenoliths in the dikes indicates that deformation in the granitoids started previously.The early thick dikes and country rocks appear to have been remagnetized during the exhumation of deep-seated coastal rocks in the Early Cretaceous (around 100 Ma). The remanent magnetization in late thin dikes is mainly retained by small amounts of low-Ti magnetite at high temperature and pyrrhotite at low temperature. The magnetization in these dikes appears to be primary in origin. Paleomagnetic results from the thin dikes also indicate that the whole area was tilted  23° to the NNW during cooling of the CMDS.The NNW–SSE extension vectors deduced from the paleomagnetic data and internal fabric of dikes are different with respect to extension direction deduced for the Middle–Late Jurassic of northern Chile, pointing to major heterogeneities along the margin of the overriding plate during the Mesozoic or differences in the mechanisms driving extension during such period.