Hydrocarbon pollution of the Mediterranean coastline of Morocco

Organic geochemical study of hydrocarbon pollution of the Mediterranean coastline of Morocco (Tangier-Nador) was performed during March–April 2002. It corresponds to a preliminary work representing an initial assessment of oil contamination of Moroccan coast.Three coastal sites corresponding to Tangier, Tetouan and Nador, representing the main built-up area of this marine region, were selected for superficial sediments, water and organism sampling. Results showed high contamination levels in these three selected sites, known as the most exposed areas to urban and industrial discharges. The maximal contamination corresponding to the sum of non-aromatic (NAH) and polycyclic aromatic hydrocarbons (PAH) encountered in sediment samples was about 553 μg/g (dw). Nevertheless, even a small city agglomeration without any industrial activity showed high values reaching 370 μg/g (dw), which confirm the important hydrocarbons input coming from discharges of fishing ships and oil transporting tankers.The obtained results from this survey reflecting in part the important amounts drained via effluents toward the Moroccan Mediterranean coasts, presented to the concerned authorities drove to the realization of the project of treatment of the wastewater.They later expect to lower rates by 50%, which is still insufficient for a fragile ecosystem such as the Mediterranean and sensitive to anthropogenic effects.     

The 2013 Ibiza Calibration Campaign of Jason-2 and SARAL Altimeters

This study presents the results of the 2013 Ibiza (Western Mediterranean) calibration campaign of Jason-2 and SARAL altimeters. It took place from 14 to 16 September 2013 and comprised two phases: the calibration of the GNSS (Global Navigation Satellite System) buoys to estimate the antenna height of each of them and the absolute calibration to estimate the altimeter bias (i.e., the difference of sea level measured by radar altimetry and GNSS). The first one was achieved in the Ibiza harbor at a close vicinity of the Ibiza tide gauge and the second one was performed at ～ 40 km at the northwest of Ibiza Island at a crossover point of Jason-2 and SARAL nominal groundtracks. Five buoys were used to delineate the crossover region and their measurements interpolated at the exact location of each overflight. The overflights occurred two consecutive days: 15 and 16 September 2013 for Jason-2 and SARAL, respectively. The GNSS data were processed using precise point positioning technique. The biases found are of (?0.1 ± 0.9) and (?3.1 ± 1.5) cm for Jason-2 and SARAL, respectively.     

Protracted oogenesis and annual reproductive periodicity in the deep‐sea pennatulacean Halipteris finmarchica (Anthozoa,Octocorallia)

Halipteris finmarchica is one of the most common species of deep‐sea pennatulacean corals in the Northwest Atlantic; it was recently determined to act as a biogenic substrate for other species and as a nursery for fish larvae. Its reproductive cycle was investigated in colonies sampled in 2006 and 2007 along the continental slope of Newfoundland and Labrador (Canada). Halipteris finmarchica exhibits large oocytes (maximum diameter of 1000 μm), which are consistent with lecithotrophic larval development. Female potential fecundity based on mature oocytes just before spawning was ~6 oocytes · polyp^?1 (500–6300 oocytes · colony^?1); male potential fecundity was 16 spermatocysts · polyp^?1 (5500–57,400 spermatocysts · colony^?1). Based on statistical analysis of size‐probability frequency distributions, males harboured one cohort of spermatocysts that matured inside 8–11 months, whereas females harboured two distinct cohorts of oocytes; a persistent pool of small ones (≤400 μm) and a small number (~20%) of larger ones that grew from ~400 to >800 μm over a year. Despite this difference in the tempo of oogenesis and spermatogenesis, a synchronic annual spawning was detected. A latitudinal shift in the spawning period occurred from south (April in the Laurentian Channel) to north (May in Grand Banks and July–August in Labrador/Lower Arctic), following the development of the phytoplankton bloom (i.e. sinking of phytodetritus). Prolonged oogenesis with the simultaneous presence of different oocyte classes in a given polyp is likely not uncommon in deep‐sea octocorals and could hamper the detection of annual/seasonal reproduction when sample sizes are low and/or time series discontinued or brief.     

The nature of Cu bonding to natural organic matter

Copper biogeochemistry is largely controlled by its bonding to natural organic matter (NOM) for reasons not well understood. Using XANES and EXAFS spectroscopy, along with supporting thermodynamic equilibrium calculations and structural and steric considerations, we show evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)₂-like ring chelate at 100-300 ppm Cu concentration, and a six-membered Cu(malonate))_1-2-like ring chelate at higher concentration. A “structure fingerprint” is defined for the 5.0-7.0 Å⁻¹ EXAFS region which is indicative of the ring size and number (i.e., mono- vs. bis-chelate), and the distance and bonding of axial oxygens (O_ax) perpendicular to the chelate plane formed by the four equatorial oxygens (O_eq) at 1.94 Å. The stronger malate-type chelate is a C₄ dicarboxylate, and the weaker malonate-type chelate a C₃ dicarboxylate. The malate-type chelate owes its superior binding strength to an -OH for -H substitution on the α carbon, thus offering additional binding possibilities. The two new model structures are consistent with the majority of carboxyl groups being clustered and α-OH substitutions common in NOM, as shown by recent infrared and NMR studies. The high affinity of NOM for Cu(II) is explained by the abundance and geometrical fit of the two types of structures to the size of the equatorial plane of Cu(II). The weaker binding abilities of functionalized aromatic rings also is explained, as malate-type and malonate-type structures are present only on aliphatic chains. For example, salicylate is a monocarboxylate which forms an unfavorable six-membered chelate, because the OH substitution is in the β position. Similarly, phthalate is a dicarboxylate forming a highly strained seven-membered chelate.Five-membered Cu(II) chelates can be anchored by a thiol α-SH substituent instead of an alcohol α-OH, as in thio-carboxylic acids. This type of chelate is seldom present in NOM, but forms rapidly when Cu(II) is photoreduced to Cu(I) at room temperature under the X-ray beam. When the sample is wet, exposure to the beam can reduce Cu(II) to Cu(0). Chelates with an α-amino substituent were not detected, suggesting that malate-like α-OH dicarboxylates are stronger ligands than amino acids at acidic pH, in agreement with the strong electronegativity of the COOH clusters. However, aminocarboxylate Cu(II) chelates may form after saturation of the strongest sites or at circumneutral pH, and could be observed in NOM fractions enriched in proteinaceous material. Overall, our results support the following propositions:

(1)

The most stable Cu-NOM chelates at acidic pH are formed with closely-spaced carboxyl groups and hydroxyl donors in the α-position; oxalate-type ring chelates are not observed.

(2)

Cu(II) bonds the four equatorial oxygens to the heuristic distance of 1.94 ± 0.01 Å, compared to 1.97 Å in water. This shortening increases the ligand field strength, and hence the covalency of the Cu-O_eq bond and stability of the chelate.

(3)

The chelate is further stabilized by the bonding of axial oxygens with intra- or inter-molecular carboxyl groups.

(4)

Steric hindrances in NOM are the main reason for the absence of Cu-Cu interactions, which otherwise are common in carboxylate coordination complexes.

     

Spectroscopic analysis (FTIR, Raman) of water in mafic and intermediate glasses and glass inclusions

Micro-Raman spectroscopy, even though a very promising technique, is not still routinely applied to analyse H₂O in silicate glasses. The accuracy of Raman water determinations critically depends on the capability to predict and take into account both the matrix effects (bulk glass composition) and the analytical conditions on band intensities. On the other hand, micro-Fourier transform infrared spectroscopy is commonly used to measure the hydrous absorbing species (e.g., hydroxyl OH⁻ and molecular H₂O) in natural glasses, but requires critical assumptions for the study of crystal-hosted glasses. Here, we quantify for the first time the matrix effect of Raman external calibration procedures for the quantification of the total H₂O content (H₂O_T = OH⁻ + H₂O_m) in natural silicate glasses. The procedures are based on the calibration of either the absolute (external calibration) or scaled (parameterisation) intensity of the 3550 cm⁻¹ band. A total of 67 mafic (basanite, basalt) and intermediate (andesite) glasses hosted in olivines, having between 0.2 and 4.8 wt% of H₂O, was analysed. Our new dataset demonstrates, for given water content, the height (intensity) of Raman H₂O_T band depends on glass density, reflectance and water environment. Hence this matrix effect must be considered in the quantification of H₂O by Raman spectroscopy irrespective of the procedure, whereas the parameterisation mainly helps to predict and verify the self-consistency of the Raman results. In addition, to validate the capability of the micro-Raman to accurately determine the H₂O content of multicomponent aluminosilicate glasses, a subset of 23 glasses was analysed by both micro-Raman and micro-FTIR spectroscopy using the band at 3550 cm⁻¹. We provide new FTIR absorptivity coefficients (ε₃₅₅₀) for basalt (62.80 ± 0.8 L mol⁻¹ cm⁻¹) and basanite (43.96 ± 0.6 L mol⁻¹ cm⁻¹). These values, together with an exhaustive review of literature data, confirm the non-linear decline of the FTIR absorptivity coefficient (ε₃₅₅₀) as the glass depolymerisation increases. We demonstrate the good agreement between micro-FTIR and micro-Raman determination of H₂O in silicate glasses when the matrix effects are properly considered.     

Comparative studies on compounds occluded inside asphaltenes hierarchically released by increasing amounts of H2O2/CH3COOH

Being the heaviest fraction of crude oils, asphaltenes are liable to aggregate, and other molecules in the oils can be steadily adsorbed onto, and even occluded inside the macromolecular structures of the asphaltenes. These occluded compounds inside the asphaltenes can survive over geological time in oil reservoirs owing to effective protection by the macromolecular structures of the asphaltenes. The asphaltenes of a crude oil (ZG31) from the central Tarim Basin, NW China, were hierarchically degraded by increasing the amount of H₂O₂/CH₃COOH to release the occluded compounds. Besides the common components, series of even numbered n-alk-1-enes and 3-ethylalkanes were detected among the occluded compounds. Comparison of the biomarker distributions and the compound-specific C isotopic results between the compounds from the maltenes and those from the occluded fraction, the ZG31 reservoir was suggested to have been charged multiple times, with different charges being derived from different strata of source rocks.     

Middle Carboniferous crustal melting in the Variscan Belt: New insights from U–Th–Pbtot. monazite and U–Pb zircon ages of the Montagne Noire Axial Zone (southern French Massif Central)

In France, the Devonian–Carboniferous Variscan orogeny developed at the expense of continental crust belonging to the northern margin of Gondwana. A Visean–Serpukhovian crustal melting has been recently documented in several massifs. However, in the Montagne Noire of the Variscan French Massif Central, which is the largest area involved in this partial melting episode, the age of migmatization was not clearly settled. Eleven U–Th–Pb_tot. ages on monazite and three U–Pb ages on associated zircon are reported from migmatites (La Salvetat, Ourtigas), anatectic granitoids (Laouzas, Montalet) and post-migmatitic granites (Anglès, Vialais, Soulié) from the Montagne Noire Axial Zone are presented here for the first time. Migmatization and emplacement of anatectic granitoids took place around 333–326 Ma (Visean) and late granitoids emplaced around 325–318 Ma (Serpukhovian). Inherited zircons and monazite date the orthogneiss source rock of the Late Visean melts between 560 Ma and 480 Ma. In migmatites and anatectic granites, inherited crystals dominate the zircon populations. The migmatitization is the middle crust expression of a pervasive Visean crustal melting event also represented by the “Tufs anthracifères” volcanism in the northern Massif Central. This crustal melting is widespread in the French Variscan belt, though it is restricted to the upper plate of the collision belt. A mantle input appears as a likely mechanism to release the heat necessary to trigger the melting of the Variscan middle crust at a continental scale.     

HydroCube: an entity-relationship hydrogeological data model

Managing, handling and accessing hydrogeological information depends heavily on the applied hydrogeological data models, which differ between institutions and countries. The effective dissemination of hydrogeological information requires the convergence of such models to make hydrogeological information accessible to multiple users such as universities, water suppliers, and administration and research organisations. Furthermore, because hydrogeological studies are complex, they require a wide variety of high-quality hydrogeological data with appropriate metadata in clearly designed and coherent structures. A need exists, therefore, to develop and implement hydrogeological data models that cover, as much as possible, the full hydrogeological domain. A new data model, called HydroCube, was developed for the Walloon Region in Belgium in 2005. The HydroCube model presents an innovative holistic project-based approach which covers a full set of hydrogeological concepts and features, allowing for effective hydrogeological project management. The model stores data relating to the project locality, hydrogeological equipment, and related observations and measurements. In particular, it focuses on specialized hydrogeological field experiments such as pumping and tracer tests. This logical data model uses entity-relationship diagrams and it has been implemented in the Microsoft Access environment. It has been enriched with a fully functional user interface.     

Observing the atmospheric wind from space

Among the basic variables that characterize the thermodynamic state of the atmosphere, wind is relatively poorly observed. Surface measurements by in situ sensors are numerous, but irregularly distributed over the globe. Upper level winds are characterized by radiosoundings that are reliable and accurate, but in a very limited number due to their expensive cost. They are complemented by wind measurements performed by commercial aircrafts, but these data are mostly acquired along the major flight routes at a cruising altitude of ～10 km. Radio sondes and aircrafts leave large gaps in the observation network that have been partly complemented for 10 years by an increasing amount of wind information derived from cloud tracking in satellite images, and more recently, surface winds by scatterometers. However, the observation capacity still suffers deficiencies as there is still no information in cloud-free parts of the atmosphere, and no complete vertical profiles except for the radiosoundings. They should be overcome with the launch in 2011 of the European satellite ADM-Aeolus, a space-based Doppler lidar currently under development at the European Space Agency.