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.

     

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.     

Comparing the patterns of 20–70 days intraseasonal oscillations over Central Africa during the last three decades

In this paper, we used the Outgoing Longwave Radiation (OLR) data to compare the intraseasonal atmospheric variability patterns over Central Africa, during the last three decades. The spectral analysis indicates that for the three decades, the intraseasonal variability is dominated by 20–80 days periods band with the center near 40–50 days. The results of Empirical Orthogonal Functions (EOFs) analysis have shown that the amount of variance explained by the three retained EOFs are 41.6 % for 1981–1990, 44.2 % for 1991–2000 and 42.6 % for 2001–2010. For the three decades, the three leading EOFs retained exhibit high spatial loadings over Northern Congo, Southern Ethiopia, and Southwestern Tanzania. The power spectra of the leading principal components have their peaks near 40 days for the three decades, indicating MJO signal. The PCs time series revealed that the amplitude of intraseasonal oscillations (ISO) globally decreases from decade to another. The plot of ISO and El Niño-Southern Oscillation (ENSO) indices revealed that the lowest values of ISO strength generally correspond to the relatively large values of ENSO indices and inversely. The mean ISO strength and ISO fluctuations were highest during 1981–1990, and this period also corresponds to the highest fluctuations of ENSO signal.     

Multi-scale aquifer characterization and groundwater flow model parameterization using direct push technologies

Direct push (DP) technologies are typically used for cost-effective geotechnical characterization of unconsolidated soils and sediments. In more recent developments, DP technologies have been used for efficient hydraulic conductivity (K) characterization along vertical profiles with sampling resolutions of up to a few centimetres. Until date, however, only a limited number of studies document high-resolution in situ DP data for three-dimensional conceptual hydrogeological model development and groundwater flow model parameterization. This study demonstrates how DP technologies improve building of a conceptual hydrogeological model. We further evaluate the degree to which the DP-derived hydrogeological parameter K, measured across different spatial scales, improves performance of a regional groundwater flow model. The study area covers an area of ~60 km² with two overlying, mainly unconsolidated sand aquifers separated by a 5–7 m thick highly heterogeneous clay layer (in north-eastern Belgium). The hydrostratigraphy was obtained from an analysis of cored boreholes and about 265 cone penetration tests (CPTs). The hydrogeological parameter K was derived from a combined analysis of core and CPT data and also from hydraulic direct push tests. A total of 50 three-dimensional realizations of K were generated using a non-stationary multivariate geostatistical approach. To preserve the measured K values in the stochastic realizations, the groundwater model K realizations were conditioned on the borehole and direct push data. Optimization was performed to select the best performing model parameterization out of the 50 realizations. This model outperformed a previously developed reference model with homogeneous K fields for all hydrogeological layers. Comparison of particle tracking simulations, based either on the optimal heterogeneous or reference homogeneous groundwater model flow fields, demonstrate the impact DP-derived subsurface heterogeneity in K can have on groundwater flow and solute transport. We demonstrated that DP technologies, especially when calibrated with site-specific data, provide high-resolution 3D subsurface data for building more reliable conceptual models and increasing groundwater flow model performance.     

Using Multiple-Point Geostatistics for Tracer Test Modeling in a Clay-Drape Environment with Spatially Variable Conductivity and Sorption Coefficient

This study investigates the effect of fine-scale clay drapes on tracer transport. A tracer test was performed in a sandbar deposit consisting of cross-bedded sandy units intercalated with many fine-scale clay drapes. The heterogeneous spatial distribution of the clay drapes causes a spatially variable hydraulic conductivity and sorption coefficient. A fluorescent tracer (sodium naphthionate) was injected in two injection wells and ground water was sampled and analyzed from five pumping wells. To determine (1) whether the fine-scale clay drapes have a significant effect on the measured concentrations and (2) whether application of multiple-point geostatistics can improve interpretation of tracer tests in media with complex geological heterogeneity, this tracer test is analyzed with a local three-dimensional ground-water flow and transport model in which fine-scale sedimentary heterogeneity is modeled using multiple-point geostatistics. To reduce memory needs and calculation time for the multiple-point geostatistical simulation step, this study uses the technique of direct multiple-point geostatistical simulation of edge properties. Instead of simulating pixel values, model cell edge properties indicating the presence of irregularly shaped surfaces are simulated using multiple-point geostatistical simulations. Results of a sensitivity analysis show under which conditions clay drapes have a significant effect on the concentration distribution. Calibration of the model against measured concentrations from the tracer tests reduces the uncertainty on the clay-drape parameters. The calibrated model shows which features of the breakthrough curves can be attributed to the geological heterogeneity of the aquifer and which features are caused by other processes.     

Cratering and modification of wet‐target craters: Projectile impact experiments and field observations of the Lockne marine‐target crater (Sweden)

Abstract— Marine impacts are one category of crater formation in volatile targets. At target water depths exceeding the diameter of the impactor, the zones of vaporization, melting, and excavation of the standard land‐target cratering model develop partially or entirely in the water column. The part of the crater that has a potential of being preserved (seafloor crater) may to a great extent be formed by material emplacement and excavation processes that are very different from land‐target craters. These processes include a high‐energy, water‐jet‐driven excavation flow. At greater water depths, the difference in strength of the target layers causes a concentric crater to evolve. The crater consists of a wide water cavity with a shallow excavation flow along the seabed surrounding a nested, deeper crater in the basement. The modification of the crater is likewise influenced by the water through its forceful resurge to fill the cavity in the water mass and the seafloor. The resurge flow is strongly erosive and incorporates both ejecta and rip‐up material from the seabed surrounding the excavated crater. A combination of field observations and impact experiments has helped us analyze the processes affecting the zone between the basement crater and the maximum extent of the water cavity. The resurge erosion is facilitated by fragmentation of the upper parts of the solid target caused by a) spallation and b) vibrations from the shallow excavation flow and, subsequently, c) the vertical collapse of the water cavity rim wall. In addition, poorly consolidated and saturated sediments may collapse extensively, possibly aided by a violent expansion of the pore water volume when it turns into a spray during passage of the rarefaction wave. This process may also occur at impacts into water‐saturated targets without an upper layer of seawater present. Our results have implications for impacts on both Earth and Mars, and possibly anywhere in the solar system where volatiles exist/have existed in the upper part of the target.