Changes in stream water quality due to logging of the boreal forest in the Montmorency Forest,Québec

Summer stream water quality was monitored before and following the logging of 50% of the boreal forest within three small watersheds (<50 ha) nested in the ‘Ruisseau des Eaux‐Volées’ Experimental Watershed, Montmorency Forest (Québec, Canada). Logging was conducted in winter, on snow cover according to recommended best management practices (BMPs) to minimize soil disturbance and protect advance growth. A 20‐m forest buffer was maintained along perennial streams. In watershed 7·2, cut‐blocks were located near the stream network and logging was partially allowed within the riparian buffer zone. In watersheds 7·5 and 7·7, logging occurred farther away from the stream network. Observations were also made for watershed 7·3 that collected the runoff from watersheds 7·2 and 7·5, and watershed 7·6, the uproad portion of watershed 7·7. The control watershed 0·2 was contiguous to the impacted watersheds and remained undisturbed. Following clearcutting, changes in summer daily maximum and minimum stream temperatures remained within ± 1 °C while changes in diurnal variation did not decrease by more than 0·5 °C. Concentrations of NO₃^? greatly increased by up to 6000% and concentrations of K⁺ increased by up to 300% during the second summer after logging. Smaller increases were observed for Fe_total (up to 71%), specific conductance (up to 26%), and Mg²⁺ (up to 19%). Post‐logging pH decreased slightly by no more than 7% while PO₄^3? concentration remained relatively constant. Suspended sediment concentrations appeared to increase during post‐logging, but there was not enough pre‐logging data to statistically confirm this result. Logging of moderate intensity and respecting established BMPs may account for the limited changes of water quality parameters and the low exceedances of the criteria for the protection of aquatic life. The proximity of the cutover to the stream network and logging within the riparian zone did not appear to affect water quality. Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Meteorites at Meridiani Planum provide evidence for significant amounts of surface and near‐surface water on early Mars

Abstract– Six large iron meteorites have been discovered in the Meridiani Planum region of Mars by the Mars Exploration Rover Opportunity in a nearly 25 km‐long traverse. Herein, we review and synthesize the available data to propose that the discovery and characteristics of the six meteorites could be explained as the result of their impact into a soft and wet surface, sometime during the Noachian or the Hesperian, subsequently to be exposed at the Martian surface through differential erosion. As recorded by its sediments and chemical deposits, Meridiani has been interpreted to have undergone a watery past, including a shallow sea, a playa, an environment of fluctuating ground water, and/or an icy landscape. Meteorites could have been encased upon impact and/or subsequently buried, and kept underground for a long time, shielded from the atmosphere. The meteorites apparently underwent significant chemical weathering due to aqueous alteration, as indicated by cavernous features that suggest differential acidic corrosion removing less resistant material and softer inclusions. During the Amazonian, the almost complete disappearance of surface water and desiccation of the landscape, followed by induration of the sediments and subsequent differential erosion and degradation of Meridiani sediments, including at least 10–80 m of deflation in the last 3–3.5 Gy, would have exposed the buried meteorites. We conclude that the iron meteorites support the hypothesis that Mars once had a denser atmosphere and considerable amounts of water and/or water ice at and/or near the surface.     

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.

     

Controlling factors of volumetrically important marine carbonate cementation in deep slope settings

The controlling parameters of early marine carbonate cementation in shoal water and hemipelagic to pelagic domains are well‐studied. In contrast, the mechanisms driving the precipitation of early marine carbonate cements at deeper slope settings have received less attention, despite the fact that considerable volumes of early marine cement are present at recent and fossil carbonate slopes in water depths of several hundreds of metres. In order to better understand the controlling factors of pervasive early marine cementation at greater water depths, marine carbonate cements observed along time‐parallel platform to basin transects of two intact Pennsylvanian carbonate slopes are compared with those present in the slope deposits of the Permian Capitan Reef and Neogene Mururoa Atoll. In all four settings, significant amounts of marine cements occlude primary pore spaces downslope into thermoclinal water depths, i.e. in a bathymetric range between some tens and several hundreds of metres. Radial, radiaxial and fascicular optic fibrous calcites, and radiaxial prismatic calcites are associated with re‐deposited facies, boundstones and rudstones. Botryoidal (formerly) aragonitic precipitates are common in microbially induced limestones. From these case studies, it is tentatively concluded that sea water circulation in an extensive, near‐sea floor pore system is a first‐order control on carbonate ion supply and marine cementation. Coastal upwelling and internal or tidal currents are the most probable mechanisms driving pore water circulation at these depths. Carbonate cements precipitated under conditions of normal to elevated alkalinity, locally elevated nutrient levels and variable sea water temperatures. The implications of these findings and suggestions for future work are discussed.     

An EPR study of native radiation-induced paramagnetic defects in sudoite (di–trioctahedral Al–Mg chlorite) from the alteration halo related to unconformity-type uranium deposits

Natural radiation-induced defects were identified in specimens of sudoite (Al–Mg di-trioctahedral chlorite) related to unconformity-type uranium deposits at the base of the Athabasca Group (Saskatchewan, Canada), using electron paramagnetic resonance (EPR) spectroscopy at X- and Q-band frequencies. X-band spectra indicate the presence of a main native defect, named the A_s-center, whose EPR signal is dominated by an axially distorted spectrum with apparent principal components as follows: g _// = 2,051 and g _⊥ = 2,005, and a secondary defect with apparent component g = 2,025. The study of oriented specimens shows that the main defect has its g _// component perpendicular to the (ab) plane of sudoite. The A_s-center corresponds to an electron hole located on oxygen atoms of the structure and is likely associated with Si, according to the lack of hyperfine structure. The A_s-center in sudoite has EPR parameters similar to the A-center in kaolinite and dickite, and the A_i-center in illite. The saturation behavior of EPR spectra as a function of power demonstrates that native defects of sudoite are different from those known in other clays, such as kaolinite, dickite or smectite, but are similar to those of illite. The isochronal annealing data suggest that the main defect in sudoite is stable to more than 300°C. The corresponding defects characterized in sudoite may have the potential for tracing past radionuclide migration around unconformity-type uranium deposits.     

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.