Influence of chemistry on the flux-gradient relationships for the NO-O3-NO2 system

It is shown that K-theory has to be modified for chemical systems that react with time scales similar to the turbulence time scale. In such systems, the value of the exchange coefficient depends not only on the turbulence parameters, but also on the chemical reaction rates. As an example, the NO-O₃-NO₂ chemical system is studied. Using second-moment equations, new flux-gradient relationships for the neutral atmospheric surface layer are obtained which depend on the time scale ratios of turbulence ( _t ) and chemical reactions ( _ch), i.e., reactive K-theory. Within the framework of this reactive K-theory, the flux of a chemical species is both a function of the concentration gradients of the three chemical species involved and of the ratio of the time scale of turbulence to the time scale of chemistry. In the special case of slow chemistry ( _{t ch}) inert K-theory is applicable.The reactive exchange coefficients are implemented in a surface-layer model that calculates the flux and concentration profiles of the three chemical species. The results of the calculations of the effective exchange coefficients are different for reactive K-theory and inert K-theory; the differences are largest for nitric oxide, but smaller for ozone and nitrogen dioxide.     

Integrated modelling of Polycyclic Aromatic Hydrocarbons in the marine environment: Coupling of hydrodynamic, fate and transport, bioaccumulation and planktonic food-web models

Spatio-temporal variability of pollutants in the environment is a complex phenomenon that requires a combined approach for its analysis. Whereas data on measured levels of contaminants in various environmental compartments is essential, it is not always possible to monitor at the necessary frequency and with the adequate spatial sampling distribution to capture this variability. Therefore a modelling approach able to complement experimental data and close the gaps in the monitoring programs is useful for assessing the contaminant dynamics occurring at different time scales. In this work a 1D water column fate model has been developed and tested for Polycyclic Aromatic Hydrocarbons (PAHs). The model has been coupled with a simple ecological model that includes a bioaccumulation module. Afterwards, the model has been used to study the temporal variability of contaminant concentrations as well as the fluxes between compartments. The results evidence the complex coupling between spatio-temporal scales and its influence on environmental concentration levels.     

The origin of presolar nova grains

Abstract— Infrared observations reveal that classical novae often form dust in their expanding shells ejected into the interstellar medium as a consequence of violent outbursts. Recent experimental efforts have led to the identification of presolar nova candidate grains from the Acfer 094 and Murchison meteorites. Recently, however, concerns have been raised about the stellar paternity of these grains by new measurements on another sample of SiC grains: these grains are characterized by ¹²C/¹³C and ¹⁴N/¹⁵N ratios similar to the ones reported for the nova grains, but a number of different imprints suggest that a possible supernova origin cannot be excluded. Here we review the predicted nucleosynthetic imprints accompanying nova explosions and discuss the chances to synthesize heavier species, such as titanium, in nova‐like events.     

Identification of groundwater quality trends in a chalk aquifer threatened by intensive agriculture in Belgium

The European Union (EU) has adopted directives requiring that Member States take measures to reach a “good” chemical status of water resources by the year 2015 (Water Framework Directive: WFD). In order to achieve the environmental objectives for groundwater, the identification and reversal of significant upward trends in pollutant concentrations are required. A very detailed dataset available for the Hesbaye chalk aquifer in Belgium is used to evaluate tools and to propose efficient methodologies for identifying and quantifying nitrate trends in groundwater. Results indicate that the parametric linear regression and the non-parametric Mann-Kendall tests are robust; however, the latter test seems more adequate as it does not require verification of the normality of the dataset and it provides calculated nitrate trends very comparable to those obtained using linear regression. From a hydrogeological point of view, results highlight a general upward trend in the whole groundwater basin. The extrapolation of the trend analysis results indicates that measures have to be taken urgently in order to avoid further major degradation of groundwater quality within the next 10–70 years. However, a good groundwater quality status cannot be expected in the Hesbaye aquifer for the 2015 EU WFD deadline.     

Preuves de la discordance de l'Ordovicien supérieur dans la zone axiale des Pyrénées : exemple du dôme de la Garonne (Espagne,France)

The geological mapping of the Garonne Dome had already shown an angular unconformity between the Upper Ordovician and the underlying series. This paper presents data from a nearby location, Planelh deth Pas Estret, southeast of the Garonne Dome, where the unconformity can be seen at outcrop scale. The unconformity angles amount to up to 20°. This unconformity is interpreted as a result of an extensional event of pre-Upper Ordovician age. To cite this article: J. Garc??a-Sansegundo et al., C. R. Geoscience 336 (2004).     

Fluorite dissolution at acidic pH: In situ AFM and ex situ VSI experiments and Monte Carlo simulations

Dissolution of the fluorite (1 1 1) cleavage surface was investigated by means of in situ atomic force microscopy (AFM) and ex situ vertical scanning interferometry (VSI) experiments at pH range 1-3 in HCl solutions. Surface retreat was quantified at different pH values, yielding dissolution rates that were used to derive an empirical rate law for fluorite dissolution:

     

The applicability and limitations of thermodynamic geochemical models to simulate trace element behaviour in natural waters. Lessons learned from natural analogue studies

Natural analogue investigations aim to understand key phenomena and processes in natural systems related to those expected to occur in radioactive waste repositories. One of the key applications of natural analogue studies has been the possibility to test the geochemical models to be used to describe the migration of radionuclides in a future radioactive waste repository system. To this end, several geochemical modelling testing exercises (commonly denoted as blind predictive modelling, BPM) have formed an integral part of these studies over the last decade.

We have reviewed, discussed and compared the results obtained from geochemical modelling BPM exercises carried out within six natural analogue studies: Poços de Caldas, Cigar Lake, Maqarin, El Berrocal, Oklo and Palmottu. To make this comparison meaningful, we present the main geochemical characteristics of each site in order to highlight the most relevant mineralogical and hydrochemical differences. The elements selected for discussion are: Sr, Ba, Sn, Pb, Se, Ni, Zn, REEs, Th and U. We have based our discussion on the results obtained from the calculated aqueous speciation as well as by comparing solubility calculations with the actually observed concentrations.

Results can be differentiated into two categories of elemental behaviour:

1. those elements like Th and U under reducing conditions that can be fairly well described by assuming solubility control exerted by pure solid phases as their oxyhydroxides;

2. elements such as Sr, Zn, REEs and U under oxidising conditions for which the association to major geochemical components of the system must be considered in order to explain their concentrations in groundwaters.

Additionally, we discuss the main improvements made to the thermodynamic databases and the geochemical calculation methodologies due to the BPM exercises. Furthermore, the most important characterisation geochemical data needed to complete predictive solubility and speciation calculations are identified.     

Deciphering chrysophyte responses to climate seasonality

Climate change involves alterations in seasonality as well as shifts in mean annual temperature. Cold temperate lakes show strong seasonality, with winter ice cover and alternating mixing and stratification periods during the ice-free season. These physical changes are ultimately related to seasonal weather variation and also drive annual phytoplankton succession. Therefore, phytoplankton remains in lake sediment records are potentially useful for reconstructing past seasonal climate signals. With the exception of investigations on varved sediments, however, little research has been carried out on the subject. Here we present two lines of evidence demonstrating that chrysophyte stomatocysts can be useful for inferring past climatic seasonality. First, we show that marked seasonal stomatocyst replacement is related to periods of the main physical processes in the lake. Second, using instrumental climate data and microfossils in sediment cores, we show that two main components of stomatocyst variability over the last ~150 years are related to seasonal fluctuations. The first of these components is related to stomatocysts present during summer stratification that respond to general warming trends, particularly in July and August. The second component relates to stomatocysts typically present in the spring and autumn mixing periods. Numbers of these two stomatocyst types vary inversely in response to variation in spring (April–May) temperatures. The number of stomatocyst types affected by spring temperatures is much greater than those related to summer temperatures. We provide evidence that chrysophyte stomatocysts are an excellent proxy for spring air temperature reconstructions, with little influence from summer or general annual trends. We also show that with relatively little effort, it is possible to categorise the chrysophyte stomatocyst assemblage of a lake to carry out detailed investigation of the record of seasonal changes preserved within the sediment.     

Scientific management of Mediterranean coastal zone: a hybrid ocean forecasting system for oil spill and search and rescue operations

The oil spill from Prestige tanker showed the importance of scientifically based protocols to minimize the impacts on the environment. In this work, we describe a new forecasting system to predict oil spill trajectories and their potential impacts on the coastal zone. The system is formed of three main interconnected modules that address different capabilities: (1) an operational circulation sub-system that includes nested models at different scales, data collection with near-real time assimilation, new tools for initialization or assimilation based on genetic algorithms and feature-oriented strategic sampling; (2) an oil spill coastal sub-system that allows simulation of the trajectories and fate of spilled oil together with evaluation of coastal zone vulnerability using environmental sensitivity indexes; (3) a risk management sub-system for decision support based on GIS technology. The system is applied to the Mediterranean Sea where surface currents are highly variable in space and time, and interactions between local, sub-basin and basin scale increase the non-linear interactions effects which need to be adequately resolved at each one of the intervening scales. Besides the Mediterranean Sea is a complex reduced scale ocean representing a real scientific and technological challenge for operational oceanography and particularly for oil spill response and search and rescue operations.     

Acoustic emission processes occurring during high-pressure sand compaction

Granular materials submitted to uniaxial compression undergo pore space reduction due to mechanisms such as particle rearrangement and grain crushing. These changes in the internal structure of the material release energy in the form of elastic waves that can be detected by sensors sensitive to acoustic emission. In this study, Acoustic emission monitoring with a wavelet-based signal processing technique is used to identify the various mechanisms occurring during high-pressure sand compaction. Particle movement, grain failure, friction between grains and the surface of the compression cell and intergranular friction are studied. Acoustic emission data recorded during these simplified tests are used to characterize each phenomenon. Wavelet transform analyses allow the identification of useful features, making possible frequency discrimination among sliding, rolling, friction and grain fragmentation processes. For instance, we observe that at low stress, grain flow is characterized by the lowest centroid and peak frequencies, while at greater stresses, intergranular friction and grain fragmentation have the higher values. In the tests performed, the stress–strain evolution and final condition of the tested sand are broadly consistent, irrespective of the condition employed: continuous, stepwise or even variable loading rate or temperature. However, Acoustic emission data manifest much more complex behaviour (including thermal, load-rate dependency and delayed fragmentation phenomena) than that suggested by stress–strain relationships. At low stress levels, grain flow (sliding/rolling) is a relevant strain-accommodation mechanism, but so is crushing due to the effect of concentrated forces at the grain contact level. At high stresses, when crushing is generalized, intergranular friction is also a relevant phenomenon due to the increase in the coordination number produced by previous fragmentation.