Background, aim, and scope Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate. Materials and methods The decay of the organics was followed using in situ Fourier transform infrared spectroscopy and the rate coefficients were determined using a relative kinetic method and different hydrocarbon reference compounds. Results The following room temperature rate coefficients (in cm³ molecule⁻¹ s⁻¹) were obtained: k ₁ (Cl + CH₃C(O)OCH=CH₂) = (2.68 ± 0.91) x 10⁻¹⁰, k ₂ (Cl + CH₃C(O)OCH₂CH=CH₂) = (1.30 ± 0.45) x 10⁻¹⁰, and k ₃ (Cl + CH₂=CHC(O)O(CH₂)₃CH₃) = (2.50 ± 0.78) x 10⁻¹⁰, where the uncertainties are a combination of the 2σ statistical errors from linear regression analyses and a contribution to cover uncertainties in the rate coefficients of the reference hydrocarbons. Discussion This is the first kinetic study of the title reactions under atmospheric conditions. The kinetic data were analyzed in terms of reactivity trends and used to estimate the atmospheric lifetimes of the esters and assess their potential importance in the marine atmosphere. Conclusions Although reaction with OH radicals is the major atmospheric sink for the unsaturated esters studied, reaction with Cl atoms can compete in the early morning hours in coastal areas where the Cl concentration can reach peak values as high as 1 x 10⁵ atoms cm⁻³. The calculated residence times show that the chemistry of unsaturated esters will impact air quality locally near their emission sources. Recommendations and perspectives The reactions need to be studied over the range of temperatures and pressures generally encountered in the marine atmosphere. In addition, product studies should also be performed as a function of temperature since this will allow degradation mechanisms to be derived, which are representative for the wide range of conditions occurring in marine environments. Inclusion of the kinetic and product data in tropospheric numerical models will allow an assessment of potential environmental impacts of the esters for different marine pollution scenarios.

Background, aim, and scope The present study focuses on the temporal concentration changes of four common organic pollutants in small freshwater streams of Hesse, Germany. The substances (tris(2-chloroethyl)phosphate (TCEP), the technical isomer mixture of 4-nonylphenol (NP), 2-(t-butylamino)-4-(ethylamino)-6-(methylthio)-s-triazine (terbutryn), and N,N-diethyl-m-toluamide (DEET)) are subject to differing regulations. Whereas the use of NP and the related nonylphenolethoxylates (NPEOs) are almost completely banned under EU directive 2003/53/EC, the herbicide terbutryn is only restricted for use as a herbicide in the majority of member states of the European Union (EU). In contrast, TCEP and DEET are not regulated by legislation, but have been replaced in some products through consumer pressure. The impact of regulation on the environmental concentrations of these pollutants is discussed. Materials and methods The substances were monitored in small freshwater streams in the Hessisches Ried region, Germany, during the period September 2003 to September 2006. The samples were extracted with solid phase extraction (SPE) and analyzed by coupled gas chromatography-mass spectrometry (GC-MS). Results All target compounds were detected frequently within the fresh water streams of the study area. Monitoring in the study area revealed a significant concentration decrease only for NP. For the other three compounds, no significant concentration decrease was observed. Terbutryn concentrations and loads showed a seasonal trend with higher levels in summer and autumn, but were also present in winter and spring. Concentrations of TCEP and DEET were in the range of prior investigations. Discussion The decrease of NP concentrations and loads during the sampling period indicates that the regulation of NP and NP ethoxylates has led to a significant improvement in reducing the occurrence of this compound in the aquatic environment. Furthermore, the ban on agricultural use of terbutryn at the end of 2003 had no discernable influence on terbutryn concentrations in the following years. Conclusions The benefits of national bans or self-regulations by manufacturers on several chemicals appear to be limited. In contrast, the European-wide ban (of NP) revealed to be effective in preventing the substance from entering the aquatic environment on a large scale and reduced the NP concentration to an acceptable level (i.e., below the PNEC). Recommendations and perspectives Further research is needed to investigate diffuse sources and point sources of terbutryn not related to agriculture. Further research is required to find an explanation for the ongoing high concentration of TCEP in river water despite of the supposed replacement of TCEP by TCPP already in the 1990s.

Background, aim, and scope Improving the parameterization of processes in the atmospheric boundary layer (ABL) and surface layer, in air quality and chemical transport models. To do so, an asymmetrical, convective, non-local scheme, with varying upward mixing rates is combined with the non-local, turbulent, kinetic energy scheme for vertical diffusion (COM). For designing it, a function depending on the dimensionless height to the power four in the ABL is suggested, which is empirically derived. Also, we suggested a new method for calculating the in-canopy resistance for dry deposition over a vegetated surface. Materials and methods The upward mixing rate forming the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. The vertical eddy diffusivity is parameterized using the mean turbulent velocity scale that is obtained by the vertical integration within the ABL. In-canopy resistance is calculated by integration of inverse turbulent transfer coefficient inside the canopy from the effective ground roughness length to the canopy source height and, further, from its the canopy height. Results This combination of schemes provides a less rapid mass transport out of surface layer into other layers, during convective and non-convective periods, than other local and non-local schemes parameterizing mixing processes in the ABL. The suggested method for calculating the in-canopy resistance for calculating the dry deposition over a vegetated surface differs remarkably from the commonly used one, particularly over forest vegetation. Discussion In this paper, we studied the performance of a non-local, turbulent, kinetic energy scheme for vertical diffusion combined with a non-local, convective mixing scheme with varying upward mixing in the atmospheric boundary layer (COM) and its impact on the concentration of pollutants calculated with chemical and air-quality models. In addition, this scheme was also compared with a commonly used, local, eddy-diffusivity scheme. Simulated concentrations of NO₂ by the COM scheme and new parameterization of the in-canopy resistance are closer to the observations when compared to those obtained from using the local eddy-diffusivity scheme. Conclusions Concentrations calculated with the COM scheme and new parameterization of in-canopy resistance, are in general higher and closer to the observations than those obtained by the local, eddy-diffusivity scheme (on the order of 15-22%). Recommendations and perspectives To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO₂) were compared for the years 1999 and 2002. The comparison was made for the entire domain used in simulations performed by the chemical European Monitoring and Evaluation Program Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.

The Institute of Environmental Engineering at the University of Pannonia has undertaken the challenge to develop an online environmental information system. This system is able to receive and process the collected environmental data via Internet. The authors have attached importance to the presentation of the data and have included other comprehensible information for laymen as well in order to work out visualisation techniques that are expressive and attract attention for environmental questions through the developed information system. The ways of visualizing physical and chemical parameters of surface water and the effects of motorway construction were examined.

National audience | Given the good performance of geosynthetic material for drainage, it seems interesting to use these products to replace part or all of the drainage layer commonly used in landfill cells (silicate materials). The calculation showed that the replacement of a granular layer of 0.50 m by a drainage geosynthetic product is not always as easy as it seems: the maximum water head legally acceptable decreases with the thickness of the studied equivalent solution, which limits its ability to flow. ARCADIS and SITA DECTRA present here a case study on the Romagne-sous-Montfaucon landfill site for which a hybrid (solid granular + geosynthetic) was called. | Compte tenu des bonnes performances des géosynthétiques de drainage, il semble intéressant d'utiliser ces produits pour remplacer tout ou partie du massif drainant généralement utilisé en fond de casier d'installations de stockage de déchets. Le calcul montre que le remplacement d'une couche granulaire de 0,50 m par un géosynthétique de drainage n'est pas toujours aussi aisé qu'il y paraît : la charge maximale réglementairement acceptable diminue avec l'épaisseur du dispositif équivalent considéré, ce qui limite sa capacité de débit. Arcadis et Sita Dectra présentent ici une étude de cas sur le site de Romagne-sous-Montfaucon pour lequel un dispositif hybride (massif granulaire + géosynthétique) a été préconisé.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]RIVAGE | National audience | The paper presents parts of the recent guide of recommendations "Mountain reservoirs". It makes a synthesis of a feedback on the behaviour and the pathology of geomembrane lining systems and gives the strong recommendations of the guide relative to these systems, in particular onto the structure support, the drainage inherent to the DEG and the covering structure. A general description of the guide ends the article. | L'article présente, à travers le récent guide de recommandations « Retenues d'altitude », la synthèse d'un retour d'expérience sur le comportement et la pathologie des dispositifs d'étanchéité par géomembrane (DEG) en altitude. Il donne les recommandations fortes du guide relatives à ces dispositifs, en particulier sur la structure support, le drainage inhérent au DEG et la structure de recouvrement. Un descriptif général du guide termine l'article.

[Departement_IRSTEA]Ecotechnologies [TR1_IRSTEA]TED [Axe_IRSTEA]TED-SOWASTE | National audience | Protecting geotextiles are used in the design of watertight bottom liners at landfill sites, above the géomembrane, to protect it against puncture during the installation of the drainage layer and, during the service life, to the weight of the waste to be put in place. To date, the results of the 2 standard tests (static and dynamic tests) given by the technical sheets for the protecting geotextiles are not sufficient to choose the good geotextile. The development of an experimental procedure to simulate in the lab the waste loading conditions is presented here; this procedure uses large size static damage tests and follows a previous study concerning the implementation dynamic conditions (Budka & al., 2006). | Les géotextiles sont utilisés dans la constitution des étanchéités des installations de stockage de déchets (ISD) pour protéger la géomembrane contre les effets du poinçonnement liés à la mise en ½uvre de la couche de drainage puis, en service, au poids des déchets sus jacents. À ce jour, les deux essais normalisés de poinçonnement, statique et dynamique, figurant sur les fiches techniques des géotextiles de protection ne permettent pas directement le choix du produit adapté. La mise au point d'une procédure d'étude des effets des sollicitations en service est présentée ici ; elle s'appuie sur des essais d'endommagement de grandes dimensions et fait suite à une étude déjà publiée sur l'effet des sollicitations de mise en ½uvre (Budka et al., 2006).

[Departement_IRSTEA]Ecotechnologies [TR1_IRSTEA]TED [Axe_IRSTEA]TED-SOWASTE | National audience | This papers aims at presenting the various lining and drainage structures including geosynthetics that can be encountered in mining applications like heap leach pads, tailing storage facilities and waste rock storage facilities. The question of design and durability of drainage and lining systems is then discussed as regards the impact of the large loads that can be encountered in mining applications. Then liquid and gas transfers are discussed together with the attenuation of metals in GCLs. | Cet article permet, après une présentation de différentes structures à base de géosynthétiques rencontrées dans les installations minières ,aires de lixiviation, zones de stockage de résidus de lixiviation,ainsi que stockages de stériles, de discuter des structures d'étanchéité et de drainage mises en place dans ces structures. On aborde ensuite la problématique du dimensionnement et de la durabilité des systèmes drainants et d'étanchéité sous les fortes contraintes mécaniques typiquement rencontrées dans les installations minières. Puis on discute les transferts liquides et gazeux ainsi que l'atténuation des métaux dans les géosynthétiques bentonitiques.

Background, aim and scope The external surface of any building in urban polluted environment is unavoidably destined to be covered with layers that assume a grey to black colour and are generally called 'black crusts'. These, according to standard protocols and glossary, are deteriorated surface layers of stone material; they can have variable thickness, are hard and fragile and can detach spontaneously from the substrate, which, in general, is quite decayed. Plain visual examination may lead to consider 'black crusts' all similar, whilst only a careful diagnostic investigation can distinguish 'black crusts' and the consequences of their formation on stone substrates. In this paper, various black layers on marble are studied and compared and the morphological and compositional characteristics discussed according to the related mechanisms of formation. Differences between old (hundred years) and recent crusts (30 years) are investigated and pointed out. Materials and methods Samples of black crusts collected from the Milan Cathedral façade (Candoglia Marble) have been studied and compared with the careful and synergic employ of traditional techniques: optical (transmission and reflected VIS light) and electron microscopy, X-ray spectrometry and micro-Fourier transform infrared spectroscopy. Results Visual examination of loose fragments does not allow to point out outstanding differences amongst the various samples; black layers have similar main mineral components, gypsum and airborne particles, with different spatial distribution. The microscopic studies allowed to point out the porosity differences, the gypsum crystallisation habit, different amount of embedded particles, level and progress of marble decay. Discussion The observations lead to define three main types of black crusts: black crust deriving from marble sulphation, compact deposit and encrustation due to exogenic materials deposition. Black crusts show evidence of sulphation in progress, without a clear continuity solution between crust and marble; the lack of separation is particularly evident in 'recent' crust, where the sulphation process is more active. Black compact deposits show a higher porosity than black crusts because gypsum is not coming from the chemical corrosion of the substrate but from outside; actually, in the former case, the substrate is sound. Encrustations show a highly regular crystal organisation of gypsum (close packed tabular crystals) that cannot be traced back to casual atmospheric deposit or to corrosion of the substrate but rather to the crystallisation of a solution coming from an external source. Also in this case, the marble is sound; evidence of the effect of some protection treatment is pointed out. Conclusions In spite of the apparent similarity of the examined samples, analytical results have evidenced three main types of black crusts: black crust with decayed substrate, compact deposit and black encrustation showing a sound substrate underneath. Experimental evidence of calcite grains sulphation in progress, taking place according to a model recently proposed, has been observed. Sulphation process is prevented where particular conservation treatments had been applied in the past. Recommendations and perspectives New experimental studies can be focussed to understand the specific conditions (measurements of micro-climatic and thermodynamic parameters) and mechanisms for black crusts formation in situ. The problem of the kinetic of the sulphation process of marble, the assessment of black layers formation in the case of different carbonate stone materials and the study of acid attack in presence of surface protecting layers deserve further investigation.