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.     

Disposition and metabolic profiling of [14C]-decabromodiphenyl ether in pregnant Wistar rats

Fully brominated diphenyl ether, decabromodiphenyl ether (DBDE), is one of the most widely used brominated flame retardants worldwide. Little data is available about the metabolic fate of DBDE in animal models and nothing at all about the extent of foetal exposure. In this work, pregnant Wistar rats were force-fed with 99.8% pure [14C]-DBDE over 96 h at a late stage of gestation (days 16 to 19). More than 19% of the administered dose was recovered in tissues and carcasses, demonstrating efficient absorption of DBDE despite its high molecular weight and low solubility. The highest concentrations of DBDE residues were found in endocrine glands (adrenals, ovaries) and in the liver, with lower values recorded for fat. In all tissue extracts, most of the radioactivity was associated with unchanged DBDE. The use of high-grade purity [14C]-DBDE allowed quantification of several metabolites present both in maternal tissues and in foetuses. These biotransformation products accounted for 9-27% of the extractable radioactivity in tissues and 14% of that in foetuses. Three nona-BDEs and one octa-BDE were identified by LC-APPI/MS. The unequivocal characterisation of a hydroxylated octa-BDE isolated from liver was confirmed by NMR. In rat, the main metabolic pathways of DBDE are debromination and oxidation. DBDE, and very likely most of its metabolites, are able to cross the placental barrier in rat. Metabolic profiles, obtained in vivo for the first time, demonstrated the presence of DBDE and major biotransformation products in endocrine glands as well as in foetuses. The biological activity of these metabolites still needs to be assessed in order to better understand the potential toxicity of DBDE.     

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.     

The Incidence of Tariff Schedules and Price Information on Inattentive Consumers: a Lab Experiment

We design an induced value laboratory consumption choice experiment where complex tariff schemes trigger nonlinear simplification heuristics that lead individuals to over- or underconsume public goods such as electricity, gas, or drinking water. By studying this “schmeduling” bias, we investigate how an informational nudge could reduce it. Participants choose consumption levels repeatedly under different tariff schemes, where the marginal price per unit either remains constant (constant block rate, i.e., CBR) or increases above a certain threshold (increasing block rate, or IBR). We observe that the vast majority of choices are optimal, but a significant number of them reveal overconsumption. To investigate the impact of the informational nudge on these errors, some of our participants received a marginal price reminder. In that case, the learning effect helps to achieve convergence towards the optimal consumption value. To explain these effects, we use econometric models relying on microeconomic behavioral inattention to price to capture the magnitude of consumers’ inattention, observing, in particular, how the informational nudge is decreasing it.

     

A Stochastic Dynamic Game of Carbon Emissions Trading

This paper proposes a computable stochastic equilibrium model to represent the possible competition between Russia and China on the international market of carbon emissions permits. The model includes a representation of the uncertainty concerning the date of entry of developing countries (e.g., China) on this market in the form of an event tree. Assuming that this date of entry is an uncontrolled event, we model the competition as a dynamic game played on an event tree and we look for a solution called S-adapted equilibrium. We compare the solution obtained from realistic data describing the demand curves for permits and the marginal abatement cost curves in different countries, under different market and information structures: (i) Russia's monopoly, (ii) Russia–China competition in a deterministic framework, (iii) Russia–China competition in a stochastic framework. The results show the possible impact of this competition on the pricing of emissions permits and on the effectiveness of Kyoto and post-Kyoto agreements, without a US participation.     

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.     

Characterisation of the physico-mechanical parameters of MSW

Following the basics of soil mechanics, the physico-mechanical behaviour of municipal solid waste (MSW) can be defined through constitutive relationships which are expressed with respect to three physical parameters: the dry density, the porosity and the gravimetric liquid content. In order to take into account the complexity of MSW (grain size distribution and heterogeneity larger than for conventional soils), a special oedometer was designed to carry out laboratory experiments. This apparatus allowed a coupled measurement of physical parameters for MSW settlement under stress. The studied material was a typical sample of fresh MSW from a French landfill. The relevant physical parameters were measured using a gas pycnometer. Moreover, the compressibility of MSW was studied with respect to the initial gravimetric liquid content. Proposed methods to assess the set of three physical parameters allow a relevant understanding of the physico-mechanical behaviour of MSW under compression, specifically, the evolution of the limit liquid content. The present method can be extended to any type of MSW.