Seasonal connections between meteoric water and streamflow generation along a mountain headwater stream

In snowmelt-driven mountain watersheds, the hydrologic connectivity between meteoric waters and stream flow generation varies strongly with the season, reflecting variable connection to soil and groundwater storage within the watershed. This variable connectivity regulates how streamflow generation mechanisms transform the seasonal and elevational variation in oxygen and hydrogen isotopic composition (δ¹⁸O and δD) of meteoric precipitation. Thus, water isotopes in stream flow can signal immediate connectivity or more prolonged mixing, especially in high-relief mountainous catchments. We characterized δ¹⁸O and δD values in stream water along an elevational gradient in a mountain headwater catchment in southwestern Montana. Stream water isotopic compositions related most strongly to elevation between February and March, exhibiting higher δ¹⁸O and δD values with decreasing elevation. These elevational isotopic lapse rates likely reflect increased connection between stream flow and proximal snow-derived water sources heavily subject to elevational isotopic effects. These patterns disappeared during summer sampling, when consistently lower δ¹⁸O and δD values of stream water reflected contributions from snowmelt or colder rainfall, despite much higher δ¹⁸O and δD values expected in warmer seasonal rainfall. The consistently low isotopic values and absence of a trend with elevation during summer suggest lower connectivity between summer precipitation and stream flow generation as a consequence of drier soils and greater transpiration. As further evidence of intermittent seasonal connectivity between the stream and adjacent groundwaters, we observed a late-winter flush of nitrate into the stream at higher elevations, consistent with increased connection to accumulating mineralized nitrogen in riparian wetlands. This pattern was distinct from mid-summer patterns of nitrate loading at lower elevations that suggested heightened human recreational activity along the stream corridor. These observations provide insights linking stream flow generation and seasonal water storage in high elevation mountainous watersheds. Greater understanding of the connections between surface water, soil water and groundwater in these environments will help predict how the quality and quantity of mountain runoff will respond to changing climate and allow better informed water management decisions.     

The brecciated texture of polymict eucrites: Petrographic investigations of unequilibrated meteorites from the Antarctic Yamato collection

We report on the petrography and mineralogy of five Yamato polymict eucrites to better constrain the formation and alteration of crustal material on differentiated asteroids. Each sample consists of different lithic clasts that altogether form four dominant textures and therefore appear to originate from closely related petrological areas within Vesta′s crust. The textures range from subophitic to brecciated, porphyritic, and quench‐textured, that differ from section to section. Comparison with literature data for these samples is therefore difficult, which stresses that polymict eucrites are extremely complex in their petrography and investigation of only one thick section may not be representative for the host rock. We also show that sample Y‐793548 consists of more than one lithic unit and must therefore be classified as polymict instead of monomict. The variety and nature of lithic textures in the investigated Yamato meteorites indicate shock events, intense post‐magmatic thermal annealing, and secondary alteration. These postmagmatic features occur in different intensities, varying from clast to clast or among coexisting mineral fragments on a small, local scale. Several clasts within the eucrites studied have been modified by late‐stage alteration processes that caused deposition of Fe‐rich olivine and Fe enrichment along cracks crosscutting pyroxene crystals. However, formation of these secondary phases seems to be independent of the degree of thermal metamorphism observed within every type of clast, which would support a late‐stage metasomatism model for their formation.     

40Ar-39Ar dating of the H3 chondrite Sainte Rose

Abstract— A whole rock sample from the H3 chondrite Sainte Rose, which was discovered in 1983, was dated with the ⁴⁰Ar-³⁹Ar technique. From the K/Ca spectrum and from an analysis of the ³⁹Ar recoil effect we conclude that this meteorite has at least two distinguishable K-carriers: a low temperature, high-K/Ca, fine-grained carrier with a typical grain size of about 2 μm and a high temperature, low-K/Ca, more coarse-grained carrier. The K-Ar clocks of both were started 4.40 ± 0.01 Ga ago.     

The surface properties of small asteroids: Peculiar Betulia—A case study

We present the results of extensive thermal-infrared observations of the C-type near-Earth Asteroid (1580) Betulia obtained in June 2002 with the 3-m NASA Infrared Telescope Facility (IRTF) on Mauna Kea, Hawaii. Betulia is a highly unusual object for which earlier radiometric observations, interpreted on the basis of simple thermal models, indicated a surface of high thermal inertia. A high thermal inertia implies a lack of thermally insulating regolith. Radiometric observations of other asteroids of comparable size indicate that regolith is present in nearly all cases. Knowledge of the surface thermal properties of small near-Earth asteroids is crucial for meaningful calculations of the Yarkovsky effect, which is invoked to explain the delivery of collisional fragments from the main belt into near-Earth orbits, and apparently has a significant influence on the orbital evolution of potentially hazardous near-Earth asteroids. Furthermore, apart from being an indicator of the presence of thermally insulating regolith on the surface of an asteroid, the thermal inertia determines the magnitude of the diurnal temperature variation and is therefore of great importance in the design of instrumentation for lander missions to small asteroids. In the case of Betulia our database is sufficiently broad to allow the use of more sophisticated thermal models than were available for earlier radiometric observations. The measured fluxes have been fitted with thermal-model emission continua to determine the asteroid's size and geometric albedo, pv. Fits obtained with a new thermophysical model imply an effective diameter of 4.57±0.46 km and an albedo of 0.077±0.015 and indicate a moderate surface thermal inertia of around 180 J m⁻² s^−0.5 K⁻¹. It is difficult to reconcile our results with earlier work, which indicate a larger diameter for Betulia and a high-thermal-inertia surface of bare rock.     

Archean high-Mg monzodiorite–syenite,epidote skarn,and biotite–sericite gold lodes in the Granny Smith–Wallaby district,Australia: U–Pb and Re–Os chronometry of two intrusion-related hydrothermal systems

The Granny Smith (37 t Au production) and Wallaby deposits (38 t out of a 180 t Au resource) are located northeast of Kalgoorlie, in 2.7 Ga greenstones of the Eastern Goldfields Province, the youngest orogenic belt of the Yilgarn craton, Western Australia. At Granny Smith, a zoned monzodiorite–granodiorite stock, dated by a concordant titanite–zircon U–Pb age of 2,665 ± 3 Ma, cuts across east-dipping thrust faults. The stock is fractured but not displaced and sets a minimum age for large-scale (1 km) thrust faulting (D2), regional folding (D1), and dynamothermal metamorphism in the mining district. The local gold–pyrite mineralization, controlled by fractured fault zones, is younger than 2,665 ± 3 Ma. In augite–hornblende monzodiorite, alteration progressed from a hematite-stained alkali feldspar–quartz–calcite assemblage and quartz–molybdenite–pyrite veins to a late reduced sericite–dolomite–albite assemblage. Gold-related monazite and xenotime define a U–Pb age of 2,660 ± 5 Ma, and molybdenite from veins a Re–Os isochron age of 2,661 ± 6 Ma, indicating that mineralization took place shortly after the emplacement of the main stock, perhaps coincident with the intrusion of late alkali granite dikes. At Wallaby, a NE-trending swarm of porphyry dikes comprising augite monzonite, monzodiorite, and minor kersantite intrudes folded and thrust-faulted molasse. The conglomerate and the dikes are overprinted by barren (<0.01 g/t Au) anhydrite-bearing epidote–actinolite–calcite skarn, forming a 600-m-wide and >1,600-m-long replacement pipe, which is intruded by a younger ring dike of syenite porphyry pervasively altered to muscovite + calcite + pyrite. Skarn and syenite are cut by pink biotite–calcite veins, containing magnetite + pyrite and subeconomic gold–silver mineralization (Au/Ag = 0.2). The veins are associated with red biotite–sericite–calcite–albite alteration in adjacent monzonite dikes. Structural relations and the concordant titanite U–Pb age of the skarn constrain intrusion-related mineralization to 2,662 ± 3 Ma. The main-stage gold–pyrite ore (Au/Ag >10) forms hematite-stained sericite–dolomite–albite lodes in stacked D2 reverse faults, which offset skarn, syenite, and the biotite–calcite veins by up to 25 m. The molybdenite Re–Os age (2,661 ± 10 Ma) of the ore suggests a genetic link to intrusive activity but is in apparent conflict with a monazite–xenotime U–Pb age (2,651 ± 6 Ma), which differs from that of the skarn at the 95% confidence level. The time relationships at both gold deposits are inconsistent with orogenic models invoking a principal role for metamorphic fluids released during the main phase of compression in the fold belt. Instead, mineralization is related in space and time to late-orogenic, magnetite-series, high-Mg monzodiorite–syenite intrusions of mantle origin, characterized by Mg/(Mg + Fe_TOTAL) = 0.31–0.57, high Cr (34–96 ppm), Ni (22–63 ppm), Ba (1,056–2,321 ppm), Sr (1,268–2,457 ppm), Th (15–36 ppm), and rare earth elements (total REE: 343–523 ppm). At Wallaby, shared Ca–K–CO₂ metasomatism and Th-REE enrichment (in allanite) link Au–Ag mineralization in biotite–calcite veins to the formation of the giant epidote skarn, implicating a Th + REE-rich syenite pluton at depth as the source of the oxidized hydrothermal fluid. At Granny Smith, lead isotope data and the Rb–Th–U signature of early hematite-bearing wall-rock alteration point to fluid released by the source pluton of the differentiated alkali granite dikes.     

Effects of natural attenuation processes on groundwater contamination caused by abandoned waste sites in Berlin

The aim of this research project is to identify, characterize and quantify natural attenuation (NA) processes in groundwater affected by emissions of abandoned waste disposal sites in Berlin-Kladow/Gatow, Germany. It is part of the funding priority called KORA established by the Federal Ministry for Education and Research (BMBF) to explore the extent to which NA can be used for remedial purposes for varied forms of soil and groundwater contamination. Information on the emission behaviour of individual parameters is generated on the basis of hydrogeochemical comparison of 20 years old and new data. Using groundwater-modelling and CFC-analysis, information on the transport and retention of pollutants in groundwater is compiled. The microbial colonization of contaminated aquifers is characterized by molecular biological methods [polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE)] to differentiate between contaminated and not contaminated zones.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Defect properties of albite

Knowledge of the defect properties of Lunar and Mercurian minerals has recently become important, with the advent of models which attempt to explain the formation of the thin exosphere of these celestial bodies. Here, we have calculated the formation energies of sodium and oxygen vacancies in the mineral albite (NaAlSi₃O₈), as well as the Schottky defect energy for the removal of a Na₂O unit. We have employed both the supercell and Mott–Littleton approaches, using Kohn–Sham density functional theory and classical interatomic potential methods. As well as reporting the defect energies and structures, we comment upon the relative merits of the methods used.     

Modelling phytoplankton succession on the Bering Sea shelf: role of climate influences and trophic interactions in generating Emiliania huxleyi blooms 1997–2000

Several years of continuous physical and biological anomalies have been affecting the Bering Sea shelf ecosystem starting from 1997. Such anomalies reached their peak in a striking visual phenomenon: the first appearance in the area of bright waters caused by massive blooms of the coccolithophore Emiliania huxleyi (E. huxleyi). This study is intended to provide an insight into the mechanisms of phytoplankton succession in the south-eastern part of the shelf during such years and addresses the causes of E. huxleyi success by means of a 2-layer ecosystem model, field data and satellite-derived information. A number of potential hypotheses are delineated based on observations conducted in the area and on previous knowledge of E. huxleyi general ecology. Some of these hypotheses are then considered as causative factors and explored with the model. The unusual climatic conditions of 1997 resulted most notably in a particularly shallow mixed layer depth and high sea surface temperature (about 4 °C above climatological mean). Despite the fact that the model could not reproduce for E. huxleyi a clear non-bloom to bloom transition (pre- vs. post-1997), several tests suggest that this species was favoured by the shallow mixed layer depth in conjunction with a lack of photoinhibition. A top-down control by microzooplankton selectively grazing phytoplankton other than E. huxleyi appears to be responsible for the long persistence of the blooms. Interestingly, observations reveal that the high N:P ratio hypothesis, regarded as crucial in the formation of blooms of this species in previous studies, does not hold on the Bering Sea shelf.