Inferring Glacier Mass Balance Using Radarsat: Results From Peyto Glacier, Canada

The capability of RADARSAT synthetic aperture radar (SAR) for the purpose of snow-line/accumulation area mapping for a temperate alpine glacier is examined. In agreement with other orbital C-band SAR studies, RADARSAT can discriminate between firn and bare ice facies. Limited observations are reported with respect to the electromagnetic variability of the ice facies in the ablation area, but they are inconclusive. Operational considerations are discussed with respect to reconciling the uncertainties of late-summer weather and their possible impact on the dielectric and scattering properties of the glacier surface. Vagaries associated with other glacier settings, mass balance states and their associated facies configurations are discussed including the difficulty of using the transient snow-line to define the equilibrium line and the lower extent of the accumulation area for glaciers where superimposed ice may form.
The radar remote-sensing reconnaissance of equilibrium line altitude (ELA) and accumulation area ratio (AAR) for estimating glacier mass balance requires serious consideration in those instances where traditional ground measurements used in the direct glaciological method are absent. However, with respect to the ELA, such estimates can vary depending on the accuracy of the reference digital elevation information. Moreover, for many glacier configurations, where mass balance variations due to altitude are influenced or in some cases completely masked by local balance variations, defining the ELA may be an irreconcilable problem. Using the AAR may be more robust in this regard. It is further determined that the total error inherent in the reconnaissance method would have serious implications for the confident estimation of mass balance normals and climate-related trends if the method were to be utilized over the longer term.     

Conflicting structural and geochronological data from the Ibituruna quartz-syenite (SE Brazil): Effect of protracted “hot” orogeny and slow cooling rate?

The Ibituruna quartz-syenite was emplaced as a sill in the Ribeira-Araçuaí Neoproterozoic belt (Southeastern Brazil) during the last stages of the Gondwana supercontinent amalgamation. We have measured the Anisotropy of Magnetic Susceptibility (AMS) in samples from the Ibituruna sill to unravel its magnetic fabric that is regarded as a proxy for its magmatic fabric. A large magnetic anisotropy, dominantly due to magnetite, and a consistent magnetic fabric have been determined over the entire Ibituruna massif. The magmatic foliation and lineation are strikingly parallel to the solid-state mylonitic foliation and lineation measured in the country-rock. Altogether, these observations suggest that the Ibituruna sill was emplaced during the high temperature (~ 750 °C) regional deformation and was deformed before full solidification coherently with its country-rock. Unexpectedly, geochronological data suggest a rather different conclusion. LA-ICP-MS and SHRIMP ages of zircons from the Ibituruna quartz-syenite are in the range 530–535 Ma and LA-ICP-MS ages of zircons and monazites from synkinematic leucocratic veins in the country-rocks suggest a crystallization at ~ 570–580 Ma, i.e., an HT deformation > 35My older than the emplacement of the Ibituruna quartz-syenite. Conclusions from the structural and the geochronological studies are therefore conflicting. A possible explanation arises from ⁴⁰Ar–³⁹Ar thermochronology. We have dated amphiboles from the quartz-syenite, and amphiboles and biotites from the country-rock. Together with the ages of monazites and zircons in the country-rock, ⁴⁰Ar–³⁹Ar mineral ages suggest a very low cooling rate: < 3 °C/My between 570 and ~ 500 Ma and ~ 5 °C/My between 500 and 460 Ma. Assuming a protracted regional deformation consistent over tens of My, under such stable thermal conditions the fabric and microstructure of deformed rocks may remain almost unchanged even if they underwent and recorded strain pulses separated by long periods of time. This may be a characteristic of slow cooling “hot orogens” that rocks deformed at significantly different periods during the orogeny, but under roughly unchanged temperature conditions, may display almost indiscernible microstructure and fabric.     

Enhanced identification of a hydrologic model using streamflow and satellite water storage data: A multicriteria sensitivity analysis and optimization approach

Hydrologic model development and calibration have continued in most cases to focus only on accurately reproducing streamflows. However, complex models, for example, the so‐called physically based models, possess large degrees of freedom that, if not constrained properly, may lead to poor model performance when used for prediction. We argue that constraining a model to represent streamflow, which is an integrated resultant of many factors across the watershed, is necessary but by no means sufficient to develop a high‐fidelity model. To address this problem, we develop a framework to utilize the Gravity Recovery and Climate Experiment's (GRACE) total water storage anomaly data as a supplement to streamflows for model calibration, in a multiobjective setting. The VARS method (Variogram Analysis of Response Surfaces) for global sensitivity analysis is used to understand the model behaviour with respect to streamflow and GRACE data, and the BORG multiobjective optimization method is applied for model calibration. Two subbasins of the Saskatchewan River Basin in Western Canada are used as a case study. Results show that the developed framework is superior to the conventional approach of calibration only to streamflows, even when multiple streamflow‐based error functions are simultaneously minimized. It is shown that a range of (possibly false) system trajectories in state variable space can lead to similar (acceptable) model responses. This observation has significant implications for land‐surface and hydrologic model development and, if not addressed properly, may undermine the credibility of the model in prediction. The framework effectively constrains the model behaviour (by constraining posterior parameter space) and results in more credible representation of hydrology across the watershed.     

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.

     

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.     

Seasonal DOC accumulation in the Black Sea: a regional explanation for a general mechanism

During three cruises in the Black Sea, organised in July 1995 and April–May 1997, biological and chemical parameters that can influence the carbon budget were measured in the water column on the NW shelf, particularly in the mixing zone with Danube River waters. We observed in early spring (end of April–May) conditions an important input of freshwater organisms that enhanced the microbial activity in the low salinity range. High bacterial activity regenerates nitrogen in the form of nitrates, but is also responsible for an important consumption of ammonium and phosphate, leading to a high N/P ratio and a strong deficit in phosphorus. The consequence is a limitation of phytoplankton development but also a production of carbohydrates that accumulate all along the salinity gradient. These mechanisms are responsible for a seasonal accumulation of dissolved organic carbon (DOC) that increases from 210 μM in winter to about 280 μM in summer. All this excess DOC disappears during winter, probably degraded by bacterial activity. The degradation of carbon-rich organic matter increases the phosphorus demand by bacteria bringing limitation to phytoplankton primary production.     

Structure cristalline d'une ménéghinite naturelle pauvre en cuivre,Cu0,58Pb12,72(Sb7,04Bi0,24)S24Crystal structure of a Cu-poor natural meneghinite,Cu0.58Pb12.72(Sb7.04Bi0.24)S24

Cu-poor meneghinite from La Lauzière Massif (Savoy, France) has the composition (electron microprobe) (in wt%): Pb 59.50, Sb 20.33, Bi 1.19, Cu 0.87, Ag 0.05, Fe 0.03, S 17.62, Se 0.05, Total 99.64. Its crystal structure (X-ray on a single crystal) was solved with R1=0.0506, wR2=0.1026, with an orthorhombic symmetry, space group Pnma, and a=24.080(5) Å, b=4.1276(8) Å, c=11.369(2) Å, V=1130.0(4) Å³, Z=4. Relatively to the model of Euler and Hellner (1960), this structure shows a significantly lower site occupancy factor for the tetrahedral Cu site (0.146 against 0.25). Among the five other metallic sites, Bi appears in the one with predominant Sb. Developed structural formula: Cu_0.15Pb₂(Pb_0.53Sb_0.47)(Pb_0.46Sb_0.54)(Sb_0.75Pb_0.19Bi_0.06)S₆; the reduced one: Cu_0.58Pb_12.72(Sb_7.04Bi_0.24)S₂₄. The formation of such a Cu-poor variety seems to be related to specific paragenetic conditions (absence of coexisting galena), or to crystallochemical constraints (minor Bi). To cite this article: Y. Moëlo et al., C. R. Geoscience 334 (2002) 529–536.