Transferring the heterogeneity of surface emissions to variability in pollutant concentrations over urban areas through a chemistry-transport model

Horizontal resolution of grid-based chemistry-transport models is limited to a few square kilometers which has been proved insufficient for assessing human exposure and health impact. We propose a general methodology, applicable on any kind of grid-based air-quality model, that combines subgrid scale information on emission and land-use data in order to disaggregate the grid-averaged emission flux into a set of source-specific components (subgrid-environments). Different subgrid concentrations are calculated inside each one of these environments providing a direct estimate of pollutant variability along with the ‘standard’ grid-averaged model output. The method was first validated over a controlled emissions case by comparing concentrations modeled in the subgrid-environments with concentrations modeled directly at higher model resolution and next over a real case-study, where subgrid concentrations were compared with monitor data from sites representing different types of urban environments (i.e. roads and residential blocks). It was shown that the method is capable to yield accurate estimates of small scale pollutant variability.     

Oxidation of a PAH polluted soil using modified Fenton reaction in unsaturated condition affects biological and physico-chemical properties

A batch experiment was conducted to assess the impact of chemical oxidation using modified Fenton reaction on PAH content and on physico-chemical and biological parameters of an industrial PAH contaminated soil in unsaturated condition. Two levels of oxidant (H₂O₂, 6 and 65 g kg⁻¹) and FeSO₄ were applied. Agronomic parameters, bacterial and fungal density, microbial activity, seed germination and ryegrass growth were assessed. Partial removal of PAHs (14% and 22%) was obtained with the addition of oxidant. The impact of chemical oxidation on PAH removal and soil physico-chemical and biological parameters differed depending on the level of reagent. The treatment with the highest concentration of oxidant decreased soil pH, cation exchange capacity and extractable phosphorus content. Bacterial, fungal, and PAH degrading bacteria densities were also lower in oxidized soil. However a rebound of microbial populations and an increased microbial activity in oxidized soil were measured after 5 weeks of incubation. Plant growth on soil treated by the highest level of oxidant was negatively affected.     

Speciation of five arsenic species (arsenite, arsenate, MMAAV, DMAAV and AsBet) in different kind of water by HPLC-ICP-MS

A method using Ion Chromatography hyphenated to an Inductively Coupled Plasma-Mass Spectrometer has been developed to accurately determine arsenite (As(III)), arsenate (As(V)), mono-methylarsonic acid (MMAA(V)), dimethylarsinic acid (DMAA(V)) and arsenobetaine (AsBet) in different water matrices. The developed method showed a high sensitivity with detection limits for each arsenic species close to 0.4pg injected. Arsenite and arsenate were the major species found in surface and well waters, but AsBet and DMAA(V) were found in some surface waters, which has never been reported before, while in some natural mineral waters located in volcanic region, the arsenic content exceeded the maximal admissible arsenic content by European legislation standards and the predominant form was As(V).     

Concomitant Zn-Cd and Pb retention in a carbonated fluvio-glacial deposit under both static and dynamic conditions

The chemical and physical processes involved in the retention of 10(-2)M Zn, Pb and Cd in a calcareous medium were studied under saturated dynamic (column) and static (batch) conditions. Retention in columns decreased in order: Pb>Cd approximately Zn. In the batch experiments, the same order was observed for a contact time of less than 40h and over, Pb>Cd>Zn. Stronger Pb retention is in accordance with the lower solubility of Pb carbonates. However, the equality of retained Zn and Cd does not fit the solubility constants of carbonated solids. SEM analysis revealed that heavy metals and calcareous particles are associated. Pb precipitated as individualized Zn-Cd-Ca- free carbonated crystallites. All the heavy metals were also found to be associated with calcareous particles, without any change in their porosity, pointing to a surface/lattice diffusion-controlled substitution process. Zn and Cd were always found in concomitancy, though Pb fixed separately at the particle circumferences. The Phreeqc 2.12 interactive code was used to model experimental data on the following basis: flow fractionation in the columns, precipitation of Pb as cerrusite linked to kinetically controlled calcite dissolution, and heavy metal sorption onto proton exchanging sites (presumably surface complexation onto a calcite surface). This model simulates exchanges of metals with surface protons, pH buffering and the prevention of early Zn and Cd precipitation. Both modeling and SEM analysis show a probable significant decrease of calcite dissolution along with its contamination with metals.     

Preliminary study of ballistic impact on an industrial tank: Projectile velocity decay

Since the events of September 11, 2001, the possibility of an intentional act targeting the chemical process industry has become realistic. It is, therefore, a great concern to be able to predict the immediate consequences of such an act. This study is intended to improve our knowledge about the sequence of events that occurs when a high-speed bullet (>1000 m s⁻¹) penetrates a vessel filled with toxic liquid. We find that, prior to liquid ejection, several well-defined phases occur, including the phenomenon known as the “hydraulic ram.” This paper focuses on projectile–target interactions and explains how the decay of projectile velocity is related to the initial conditions of the target.     

New remains of the enigmatic cetartiodactyl Bugtitherium grandincisivum Pilgrim, 1908, from the upper Oligocene of the Bugti Hills (Balochistan, Pakistan)

Newly discovered fossil material of the enigmatic cetartiodactyl Bugtitherium grandincisivum from the upper Oligocene of the Bugti Member of the Chitarwata Formation in the Bugti Hills (Balochistan, Pakistan) is reported. These new specimens consist of two fragmentary muzzles (one preserving the first incisors and belonging to a juvenile) and a fragmentary right mandible with m3. The morphologies of the anterior dentition and m3 provided by these new specimens confirm the validity of the genus Bugtitherium and advocate probable anthracotheriid affinity for the genus rather than entelodontid or suoid affinities, but do not definitively close the debate about Bugtitherium’s familial affinities within Cetartiodactyla. Although still poorly documented, this large-sized anthracotheriid-like cetartiodactyl is a possible key form for understanding the early evolution of hippos, and, in turn, the ancestry of whales, because of both its morphological similarities with hippos and primitive Paleogene whales and its Tethysian distribution.     

A three-dimensional experimental investigation of the structure of the spanwise vortex generated by a shallow vortex dipole

The three-dimensional dynamics of shallow vortex dipoles is investigated by means of an innovative three-dimensional, three-component (3D-3C) scanning PIV technique. In particular, the three-dimensional structure of a frontal spanwise vortex is characterized. The technique allows the computation of the three-dimensional pressure field and the planar (x, y) distribution of the wall shear stress, which are not available using standard 2D PIV measurements. The influence of such a complex vortex structure on mass transport is discussed in the context of the available pressure and wall shear stress fields.     

Inclusion of the variability of diffuse pollutions in LCA for agriculture: the case of slurry application techniques

LCAs (life cycle assessments) are often based on average data to produce a generic evaluation of a good or service. However, ignoring variability and induced uncertainty of LCA results reduces their significance, especially when dealing with agricultural processes that present high natural fluctuations. The objective of the study was to explore the robustness of LCA results when accounting for variable emissions data, illustrated by the case of slurry application techniques. Four application techniques were compared: band spreading, broadcast spreading, harrowing after surface application and direct injection.On the basis of the normalisation results, acidification, eutrophication and global warming potentials were selected. To estimate field nitrogen emissions, an original approach was developed based on relative nitrogen loss factors for each technique from a literature review. The calculated field emissions from different soil and climate conditions were considered equally probable and were propagated into a range of LCA result using the Monte Carlo method. Injection and harrowing both showed reduced acidification and eutrophication potentials compared to band spreading and broadcast spreading but had larger global warming potentials, which could be particularly important with injection. Harrowing consequently appeared as the best compromise. Despite the large range of LCA results, robust conclusions could be drawn. To achieve a more refined comparison between the techniques, the use of process-based models in contrasted situations is suggested.