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.

     

Flow dynamics at the origin of thin clayey sand lacustrine turbidites: Examples from Lake Hazar,Turkey

Turbidity currents and their deposits can be investigated using several methods, i.e. direct monitoring, physical and numerical modelling, sediment cores and outcrops. The present study focused on thin clayey sand turbidites found in Lake Hazar (Turkey) occurring in eleven clusters of closely spaced thin beds. Depositional processes and sources for three of those eleven clusters are studied at three coring sites. Bathymetrical data and seismic reflection profiles are used to understand the specific geomorphology of each site. X‐ray, thin sections and CT scan imagery combined with grain‐size, geochemical and mineralogical measurements on the cores allow characterization of the turbidites. Turbidites included in each cluster were produced by remobilization of surficial slope sediment, a process identified in very few studies worldwide. Three types of turbidites are distinguished and compared with deposits obtained in flume studies published in the literature. Type 1 is made of an ungraded clayey silt layer issued from a cohesive flow. Type 2 is composed of a partially graded clayey sand layer overlain by a mud cap, attributed to a transitional flow. Type 3 corresponds to a graded clayey sand layer overlain by a mud cap issued from a turbulence‐dominated flow. While the published experimental studies show that turbulence is damped by cohesion for low clay content, type 3 deposits of this study show evidence for a turbulence‐dominated mechanism despite their high clay content. This divergence may in part relate to input variables, such as water chemistry and clay mineralogy, that are not routinely considered in experimental studies. Furthermore, the large sedimentological variety observed in the turbidites from one coring site to another is related to the evolution of a sediment flow within a field‐scale basin made of a complex physiography that cannot be tackled by flume experiments.     

Difference in petrophysical properties between foliated and dilatant fault rocks in deeply buried clastics: The case of the Grès d'Annot Formation,SW French Alps

This study describes normal fault zones formed in foreland arkosic turbidites (the Grès d'Annot Formation, SW French Alps) under deep diagenesis conditions (~200 °C) and highlights the occurrence of two markedly different fault‐rock types: (1) the foliated fault rocks of the Moutière‐Restefond area; and (2) the dilatant fault rocks of the Estrop area. The deformation of (1) is dominated by intra‐ and transgranular fracturing, pressure solution of quartz and feldspar grains and syn‐kinematic phyllosilicate precipitation resulting from feldspar alteration. The combination of these mechanisms results in a strongly anisotropic strain with intense shortening normal to the foliation (pressure solution) and extension parallel to the foliation (quartz‐ and calcite‐sealed extension veins). This deformation implies local mass transfer that may be achieved without (or with limited) volume change. The deformation of (2) is expressed as dilatant quartz‐sealed veins and breccia textures in which the main mechanisms are transgranular fracturing and quartz precipitation. Type (2) implies fault volume increase, isotropy of deformation and mass transfer at distances larger than in type (1). This study discusses the origins of (1) and (2) and shows that the permeability of (1) is anisotropic, with higher values than the host rocks parallel to the Y main deformation axis (i.e. perpendicular to the slip vector), whereas the permeability of (2) is isotropic and equivalent to that of the host rocks.     

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.     

Laser ablation coupled with ICP-MS applied to U–Pb zircon geochronology: A review of recent advances

Improvements in the technology of laser ablation and ICP-MS instruments make LA-MC-ICPMS a rapid, precise and accurate method for U–Pb zircon geochronology. In this review we describe the main stages of the evolution of this in situ approach from the early 1990s to the present time. Some key points have been progressively improved. The crater size has been reduced to achieve real in situ measurements. The laser wavelength has been reduced as well as the duration of each pulse in order to lower inter-element fractionation. The blank from the gas has to be lowered as far as possible. Double focusing instruments and magnetic field sectors allow flat-topped peaks required for precise isotope ratio measurement to be obtained. The use of a multi-ion counting system significantly improves the sensitivity of the method and the static mode of integration favours the precision of measurement of the transient signal originating from a noisy laser ablated particle beam.Combining the use of a 213 nm UV laser and a MC-ICPMS equipped with a multi-ion counting system operating in static mode, the common precisions achieved for the key ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U are better than 1% and 3% (2σ) respectively, including error propagation associated with standard normalization. Until now, the use of a zircon standard has remained necessary to ensure the accuracy of the calculated age. A strategy for common-Pb correction is proposed according to the age of the zircon and according to the Th/U ratio of the grains. After recording sixteen to twenty spot analyses the precision usually achieved on the age is about 1% and even significantly better for Proterozoic samples.In order to show the performance achieved by modern LA-MC-ICPMS geochronology, we tested four zircon samples covering a wide age range from 290 to 2440 Ma. These new age determinations can be compared in term of precision and accuracy since they have already been dated by reference methods (ID-TIMS and SHRIMP). Further developments in the technology of ion counters equipping modern MC-ICPMS and in laser systems will certainly be applied to a large field of geochronology studies in the near future as an alternative to SIMS for in situ age determination.     

Upper mantle structure of the South American continent and neighboring oceans from surface wave tomography

We present a new three-dimensional SV-wave velocity model for the upper mantle beneath South America and the surrounding oceans, built from the waveform inversion of 5850 Rayleigh wave seismograms. The dense path coverage and the use of higher modes to supplement the fundamental mode of surface waves allow us to constrain seismic heterogeneities with horizontal wavelengths of a few hundred kilometres in the uppermost 400 km of the mantle.The large scale features of our tomographic model confirm previous results from global and regional tomographic studies (e.g. the depth extent of the high velocity cratonic roots down to about 200–250 km).Several new features are highlighted in our model. Down to 100 km depth, the high velocity lid beneath the Amazonian craton is separated in two parts associated with the Guyana and Guapore shields, suggesting that the rifting episode responsible for the formation of the Amazon basin has involved a significant part of the lithosphere. Along the Andean subduction belt, the structure of the high velocity anomaly associated with the sudbduction of the Nazca plate beneath the South American plate reflects the along-strike variation in dip of the subducting plate. Slow velocities are observed down to about 100 km and 150 km at the intersection of the Carnegie and Chile ridges with the continent and are likely to represent the thermal anomalies associated with the subducted ridges. These lowered velocities might correspond to zones of weakness in the subducted plate and may have led to the formation of “slab windows” developed through unzipping of the subducted ridges; these windows might accommodate a transfer of asthenospheric mantle from the Pacific to the Atlantic ocean. From 150 to 250 km depth, the subducting Nazca plate is associated with high seismic velocities between 5°S and 37°S. We find high seismic velocities beneath the Paraná basin down to about 200 km depth, underlain by a low velocity anomaly in the depth range 200–400 km located beneath the Ponta Grossa arc at the southern tip of the basin. This high velocity anomaly is located southward of a narrow S-wave low velocity structure observed between 200 and 500–600 km depth in body wave studies, but irresolvable with our long period datasets. Both anomalies point to a model in which several, possibly diachronous, plumes have risen to the surface to generate the Paraná large igneous province (LIP).     

Late Cenozoic transpressional ductile deformation north of the Nazca–South America–Antarctica triple junction

The southern Andes plate boundary zone records a protracted history of bulk transpressional deformation during the Cenozoic, which has been causally related to either oblique subduction or ridge collision. However, few structural and chronological studies of regional deformation are available to support one hypothesis or the other. We address along- and across-strike variations in the nature and timing of plate boundary deformation to better understand the Cenozoic tectonics of the southern Andes.Two east–west structural transects were mapped at Puyuhuapi and Aysén, immediately north of the Nazca–South America–Antarctica triple junction. At Puyuhuapi (44°S), north–south striking, high-angle contractional and strike-slip ductile shear zones developed from plutons coexist with moderately dipping dextral-oblique shear zones in the wallrocks. In Aysén (45–46°), top to the southwest, oblique thrusting predominates to the west of the Cenozoic magmatic arc, whereas dextral strike-slip shear zones develop within it.New ⁴⁰Ar–³⁹Ar data from mylonites and undeformed rocks from the two transects suggest that dextral strike-slip, oblique-slip and contractional deformation occurred at nearly the same time but within different structural domains along and across the orogen. Similar ages were obtained on both high strain pelitic schists with dextral strike-slip kinematics (4.4±0.3 Ma, laser on muscovite–biotite aggregates, Aysén transect, 45°S) and on mylonitic plutonic rocks with contractional deformation (3.8±0.2 to 4.2±0.2 Ma, fine-grained, recrystallized biotite, Puyuhuapi transect). Oblique-slip, dextral reverse kinematics of uncertain age is documented at the Canal Costa shear zone (45°S) and at the Queulat shear zone at 44°S. Published dates for the undeformed protholiths suggest both shear zones are likely Late Miocene or Pliocene, coeval with contractional and strike-slip shear zones farther north. Coeval strike-slip, oblique-slip and contractional deformation on ductile shear zones of the southern Andes suggest different degrees of along- and across-strike deformation partitioning of bulk transpressional deformation.The long-term dextral transpressional regime appears to be driven by oblique subduction. The short-term deformation is in turn controlled by ridge collision from 6 Ma to present day. This is indicated by most deformation ages and by a southward increase in the contractional component of deformation. Oblique-slip to contractional shear zones at both western and eastern margins of the Miocene belt of the Patagonian batholith define a large-scale pop-up structure by which deeper levels of the crust have been differentially exhumed since the Pliocene at a rate in excess of 1.7 mm/year.