Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

Source and movement of helium in the eastern Morongo groundwater Basin: The influence of regional tectonics on crustal and mantle helium fluxes

We assess the role of fracturing and seismicity on fluid-driven mass transport of helium using groundwaters from the eastern Morongo Basin (EMB), California, USA. The EMB, located ∼200 km east of Los Angeles, lies within a tectonically active region known as the Eastern California Shear Zone that exhibits both strike-slip and extensional deformation. Helium concentrations from 27 groundwaters range from 0.97 to 253.7 × 10⁻⁷ cm³ STP g⁻¹H₂O, with corresponding ³He/⁴He ratios falling between 1.0 and 0.26 R_A (where R_A is the ³He/⁴He ratio of air). All groundwaters had helium isotope ratios significantly higher than the crustal production value of ∼0.02 R_A. Dissolved helium concentrations were resolved into components associated with solubility equilibration, air entrainment, in situ production within the aquifer, and extraneous fluxes (both crustal and mantle derived). All samples contained a mantle helium-3 (³He_m) flux in the range of 4.5 to 1351 × 10⁻¹⁴ cm³ STP ³He cm⁻² yr⁻¹ and a crustal flux (J₀) between 0.03 and 300 × 10⁻⁷ cm³ STP ⁴He cm⁻² yr⁻¹. Groundwaters from the eastern part of the basin contained significantly higher ³He_m and deep crustal helium-4 (⁴He_dc) concentrations than other areas, suggesting a localized source for these components. ⁴He_dc and ³He_m are strongly correlated, and are associated with faults in the basin. A shallow thermal anomaly in a >3,000 m deep graben in the eastern basin suggests upflow of fluids through active faults associated with extensional tectonics. Regional tectonics appears to drive large scale crustal fluid transport, whereas episodic hydrofracturing provides an effective mechanism for mantle-crust volatile transport identified by variability in the magnitude of degassing fluxes (³He_m and J₀) across the basin.     

Isotopic variability in the aragonite shells of freshwater gastropods living in springs with nearly constant temperature and isotopic composition

We conducted a year-long, intensive monitoring program of live aquatic gastropods (Helisoma duryi, Melanoides tuberculata, Physa virgata, Pyrgulopsis sp., and Tyronia sp.) and their host springs in the Ash Meadows National Wildlife Refuge of southern Nevada. Our purpose was to constrain the degree of natural variation in the isotopic values of shell aragonite for gastropods living in near-constant conditions. Inter- and intraspecies variations, as well as within-shell variations, of δ¹⁸O and δ¹³C values for all taxa were larger than predicted based on variations in environmental conditions alone. This result suggests that different organisms growing in identical or nearly identical environmental conditions may not produce shells with equilibrium isotopic compositions and that these offsets from equilibrium may differ by small, but statistically significant amounts. For the gill-breathing, fully aquatic gastropods M. tuberculata, Pyrgulopsis sp., and Tyronia sp., the deviation of measured isotopic values compared to predicted values based on average environmental conditions were consistent with differences between taxa in the seasonal timing of shell growth. Measured values for the lung-breathing gastropods H. duryi and P. virgata were higher for δ¹⁸O and lower for δ¹³C than predicted at isotopic equilibrium, even when accounting for seasonality effects. We suggest that explaining the differences between the shell isotopic composition of lung- and gill-breathing snails requires a combination of both behavioral and physiologic factors. Our results illustrate the potential complexities of interpreting stable isotopic data from fossil gastropod shells even when environmental conditions are nearly constant, and place limitations on the paleoenvironmental deductions that can be made from the isotopic measurements on fossil gastropods.     

Development of a soil moisture‐based distributed hydrologic model for determining hydrologically based critical source areas

A simple grid cell‐based distributed hydrologic model was developed to provide spatial information on hydrologic components for determining hydrologically based critical source areas. The model represents the critical process (soil moisture variation) to run‐off generation accounting for both local and global water balance. In this way, it simulates both infiltration excess run‐off and saturation excess run‐off. The model was tested by multisite and multivariable evaluation on the 50‐km² Little River Experimental Watershed I in Georgia, U.S. and 2 smaller nested subwatersheds. Water balance, hydrograph, and soil moisture were simulated and compared to observed data. For streamflow calibration, the daily Nash‐Sutcliffe coefficient was 0.78 at the watershed outlet and 0.56 and 0.75 at the 2 nested subwatersheds. For the validation period, the Nash‐Sutcliffe coefficients were 0.79 at the watershed outlet and 0.85 and 0.83 at the 2 subwatersheds. The per cent bias was less than 15% for all sites. For soil moisture, the model also predicted the rising and declining trends at 4 of the 5 measurement sites. The spatial distribution of surface run‐off simulated by the model was mainly controlled by local characteristics (precipitation, soil properties, and land cover) on dry days and by global watershed characteristics (relative position within the watershed and hydrologic connectivity) on wet days when saturation excess run‐off was simulated. The spatial details of run‐off generation and travel time along flow paths provided by the model are helpful for watershed managers to further identify critical source areas of non‐point source pollution and develop best management practices.     

Spatiotemporal estimation of snow depth using point data from snow stakes,digital terrain models,and satellite data

Snow availability in Alpine catchments plays an important role in water resources management. In this paper, we propose a method for an optimal estimation of snow depth (areal extension and thickness) in Alpine systems from point data and satellite observations by using significant explanatory variables deduced from a digital terrain model. It is intended to be a parsimonious approach that may complement physical‐based methodologies. Different techniques (multiple regression, multicriteria analysis, and kriging) are integrated to address the following issues: We identify the explanatory variables that could be helpful on the basis of a critical review of the scientific literature. We study the relationship between ground observations and explanatory variables using a systematic procedure for a complete multiple regression analysis. Multiple regression models are calibrated combining all suggested model structures and explanatory variables. We also propose an evaluation of the models (using indices to analyze the goodness of fit) and select the best approaches (models and variables) on the basis of multicriteria analysis. Estimation of the snow depth is performed with the selected regression models. The residual estimation is improved by applying kriging in cases with spatial correlation. The final estimate is obtained by combining regression and kriging results, and constraining the snow domain in accordance with satellite data. The method is illustrated using the case study of the Sierra Nevada mountain range (Southern Spain). A cross‐validation experiment has confirmed the efficiency of the proposed procedure. Finally, although it is not the scope of this work, the snow depth is used to asses a first estimation of snow water equivalent resources.     

Does stress transmission in forelands depend on structural style? Distinctive stress magnitudes during Sevier thin‐skinned and Laramide thick‐skinned layer‐parallel shortening in the Bighorn Basin (USA) revealed by stylolite and calcite twinning paleopiezometry

The Sheep Mountain‐Little Sheep Mountain Anticlines, Bighorn Basin (USA) formed as basement‐cored Laramide structures in the formerly undeformed foreland of the thin‐skinned Sevier orogen. We take advantage of the well‐constrained microstructural network there to reconstruct differential stress magnitudes that prevailed during both Sevier and Laramide layer‐parallel shortening (LPS), before the onset of large‐scale folding. Differential stress magnitudes determined from tectonic stylolites are compared and combined to previous stress estimates from calcite twinning paleopiezometry in the same formations. During stress loading related to LPS, differential stress magnitudes transmitted from the distant Sevier thin‐skinned orogen into the sedimentary cover of the Bighorn basin (11–43 MPa) are higher than the differential stress magnitudes accompanying the early stage of LPS related to the thick‐skinned Laramide deformation (2–19 MPa). This study illustrates that the tectonic style of an orogen affects the transmission of early orogenic stress into the stable continental interior.