A large landslide on the urban fringe of metropolitan Phoenix, Arizona

A granitic rock avalanche, one of the largest Quaternary landslides in Arizona outside the Grand Canyon with a volume of approximately 5.25 M m³ and a width a little under 0.5 km, ran 1 km from the eastern McDowell Mountains. With lateral levees and pressure ridges, the rock avalanche deposit displays many features found on classic sturzstroms. Failure occurred along a major joint plane paralleling the slope with a dip of 44°, when a major base level lowering event in the Salt River system would have undermined the base of the failed slope, and probably during a period of more moisture than normally available in the present-day arid climate. Failure at the subsurface weathering front highlights the importance of the dramatic permeability change between grussified regolith and relatively fresh bedrock. Rock varnish microlaminations (VMLs) dating, in concert with other geomorphic evidence, suggests that the rock avalanche deposit is slightly older than 500 ka. The rock vanish results also have important implications for sampling strategies designed to use cosmogenic nuclide to date Quaternary landslide deposits. Discovery of a large landslide in close proximity to the extending urban fringe of metropolitan Phoenix argues for a more careful analysis of landslide hazards in the region, especially where rapid development excavates bedrock at the base of steep mountain slopes and where the subsurface weathering front is near the surface.     

Denitrification rates measured along a salinity gradient in the eutrophic Neuse River estuary, North Carolina, USA

Denitrification rates along a salinity gradient in the eutrophic Neuse River Estuary, North Carolina, were quantified using membrane inlet mass spectrometry (MIMS) within short-term batch incubations. Denitrification rates within the system were highly variable, ranging from 0 to 275 μmol N m⁻² h⁻¹. Intrasite variability increased with salinity, but no significant differences were observed across the salinity gradient. Denitrification rates were positively correlated with sediment oxygen demand at the upstream sampling site where sediment organic carbon levels were lowest. This relationship was not observed in the more saline sampling sites. Denitrification rates were highest during winter. On an annual basis, denitrification accounted for 26% of the dissolved inorganic nitrogen and 12% of the total nitrogen supplied to the system.     

Phase equilibria in the system CO2-H2O I: New equilibrium relations at low temperatures

Graphical analysis of free-energy relationships involving binary quadruple points and their associated univariant equilibria in the system CO₂-H₂O suggests the presence of at least 2 previously unrecognized quadruple points and a degenerate binary invariant point involving an azeotrope between CO₂-rich gas and liquid. Thermodynamic data extracted from the equilibrium involving clathrate (hydrate), gas, and ice (H = G+I) are employed along with published data to calculate the P-T range of the 3-ice equilibrium curve, S+I = H, where S is solid CO₂. This equilibrium curve intersects the H = G+I curve approximately where the latter curve intersects the S+H = G curve, thus confirming the existence of one of the inferred quadruple points involving the phases S, G, H, and I. Recognition of some binary equilibria probably have been hampered by extremely low mutual solubilities of CO₂ and H₂O in the fluids phases which, for example, render the S+H = G virtually indistinguishable from the CO₂-sublimation curve.To make the published portion of the L(liquid CO₂)-G-H equilibrium “connect” with the other new quadruple point involving S, L, G, and H, it is necessary to change the sense of the equilibrium from L = G+H at higher pressures to L+H = G at lower pressures by positing a L = G azeotrope at very low concentrations of H₂O. At the low-pressure origin of the azeotrope, which is only a few bars above the CO₂-triple point, the azeotrope curve intersects the 3-phase curve tangentially, creating a degenerate invariant point at which the 3-phase equilibrium changes from L+H = G at lower pressures to L = G+H at higher pressures. The azeotrope curve is offset at slightly lower temperature from the L = G+H curve until the 3-phase equilibrium terminates at the quadruple point involving G, L, H, and W (water). With further increase in pressure the azeotrope curve tracks the L = G+W equilibrium and apparently terminates at a critical end point in close proximity to critical endpoints for the CO₂-saturation curve and the L = G+W curve.Thermodynamic data for clathrate extracted from the slope of the H = G+I curve are consistent with a solid-state phase transformation in CO₂-clathrate between 235 and 255 K. Published work shows that the type-I clathrate phase, whose atomic structure is a framework of water molecules with CO₂ molecules situated in large “guest” sites within the framework, is variable in composition with ∼1 guest site vacancy per unit cell at the high-temperature limit of its stability; the number of water molecules, however, remains constant. The formula (CO₂)_8-y·46H₂O, where y is the number of vacancies per unit cell, is in keeping with the atomic structure, whereas the traditional formula, CO₂·nH₂O, where n (hydration number) = 5.75, is misleading.Ambient P-T conditions in the Antarctic and Greenland ice sheets are compatible with sequestering large amounts of carbon as liquid CO₂ and/or clathrate.     

High-resolution historical records from Pettaquamscutt River basin sediments: 1. Pb and varve chronologies validate record of Cs released by the Chernobyl accident

Cesium-137 derived from the explosion of the Chernobyl reactor in 1986 was preserved in anoxic sediments from a coastal environment in southern Rhode Island. Although the radioactive plume was detected in surface air samples at several locations in the United States, this is the first known record of a Chernobyl ¹³⁷Cs peak in sediments from North America. The inventory of Chernobyl ¹³⁷Cs that was preserved in the Pettaquamscutt River is small compared to European counterparts and should only be detectable for the next 15-20 yr. However, the presence of two ¹³⁷Cs peaks (1963 and 1987) identifies a well-dated segment of the sediment column that could be exploited in understanding the decomposition and preservation of terrestrial and aquatic organic matter. Different methods for calculating the ²¹⁰Pb chronology were also evaluated in this study and checked against independent varve counting. The end result is a detailed chronology of a site well suited for reconstruction of historical records of environmental change.     

Ab initio molecular orbital calculations for boron isotope fractionations on boric acids and borates

Ab initio quantum chemistry calculations have been performed on the isotopic exchange reaction between B(OH)₃ and B(OH)₄⁻. Several calculation methods have been carefully compared and evaluated. The “water-droplet” method is chosen to investigate this isotope exchange reaction using cluster models with up to 34 water molecules surrounding the solute. HF/6-31G* level calculations coupled with a 0.920 scaling factor are used for the frequency calculations. A larger K value (1.027) is obtained from this study compared to the commonly used 1.0194 (Kakihana et al., 1977).The fractionations for several boric acid polymers and boron minerals are also studied. Our results suggest that assuming the BO₄ bonding in B(OH)₄⁻ is identical to that in borosilicates is wrong. Tetrahedral boron in silicates has a significantly smaller reduced isotopic partition function ratio (RPFR) and hence will be much isotopically lighter than in B(OH)₄⁻.The new theoretical curve of pH vs. δ¹¹B composition of B(OH)₄⁻ using our calculated 1.027 can be used to predict pH values for equilibrium cases such as incorporation into inorganic calcite. We also find that the shape of this curve is very sensitive to both K and pK_a value, giving the possibility of also predicting salinity from the different shapes of the curve.     

Including spatial distribution in a data‐driven rainfall‐runoff model to improve reservoir inflow forecasting in Taiwan

Multi‐step ahead inflow forecasting has a critical role to play in reservoir operation and management in Taiwan during typhoons as statutory legislation requires a minimum of 3‐h warning to be issued before any reservoir releases are made. However, the complex spatial and temporal heterogeneity of typhoon rainfall, coupled with a remote and mountainous physiographic context, makes the development of real‐time rainfall‐runoff models that can accurately predict reservoir inflow several hours ahead of time challenging. Consequently, there is an urgent, operational requirement for models that can enhance reservoir inflow prediction at forecast horizons of more than 3 h. In this paper, we develop a novel semi‐distributed, data‐driven, rainfall‐runoff model for the Shihmen catchment, north Taiwan. A suite of Adaptive Network‐based Fuzzy Inference System solutions is created using various combinations of autoregressive, spatially lumped radar and point‐based rain gauge predictors. Different levels of spatially aggregated radar‐derived rainfall data are used to generate 4, 8 and 12 sub‐catchment input drivers. In general, the semi‐distributed radar rainfall models outperform their less complex counterparts in predictions of reservoir inflow at lead times greater than 3 h. Performance is found to be optimal when spatial aggregation is restricted to four sub‐catchments, with up to 30% improvements in the performance over lumped and point‐based models being evident at 5‐h lead times. The potential benefits of applying semi‐distributed, data‐driven models in reservoir inflow modelling specifically, and hydrological modelling more generally, are thus demonstrated. Copyright © 2012 John Wiley & Sons, Ltd.     

Mid‐Miocene initiation of E‐W extension and recoupling of the Himalaya

The Tibetan plateau is host to numerous ~N‐S striking graben that have accommodated E‐W directed extension. The development of these structures has been interpreted to reflect a variety of different geological processes including plateau collapse, oroclinal bending or mid‐to‐lower crustal flow. New ⁴⁰Ar/³⁹Ar thermochronology and quartz c‐axis data from the Thakkhola graben of west‐central Nepal show that E‐W extension was ongoing at least locally by the early Miocene (ca. 17 Ma). Our new, and previously published chronologic information on the initiation of graben across the orogen shows that they typically developed immediately after cessation of the South Tibetan detachment system, a structural network that facilitated differential southward movement of the upper and middle crust. We interpret this fundamental switch in orogen kinematics to reflect recoupling of the middle and upper Himalayan crust such that the subsequent widespread flow of the mid‐to‐lower crust out of the system to the east forced brittle accommodation in the upper crust.