Physical constraints in engineering seismic hazard analysis

In engineering seismic hazard probabilistic analysis, physical constraints are generally overlooked. We formulate such constraints for the general case of a site within an annular seismogenic zone. This configuration provides a first approximation of seismic hazard analysis within a broad zone undergoing crustal deformation; such zones are a common expression of continental tectonics. Applications are restricted to medium size earthquakes (M_s < 7). The formulation is applied to two cases reflecting the mid-plate (case I) and plate boundary (case II) seismotectonic environments. It is found that, for a given strain rate and for an upper bound magnitude of 6 3/4, the extreme hazard in both the environments is the same but of different character. In the plate boundary example, it is associated with widespread ground deformation while in the mid-plate example, it involves more intense ground motion. On the other hand, if the upper bound magnitude is 5 3/4, the extreme hazard is likely to be an order of magnitude less in case I than in case II. Moreover, when the extreme hazard is associated with singular conditions generated by a single fault, the assumption of a Poissonian process may not be safe for earthquake resistant design decisions.     

Speciation and natural attenuation of arsenic and iron in a tidally influenced shallow aquifer

The mobility of subsurface arsenic is controlled by sorption, precipitation, and dissolution processes that are tied directly to coupled redox reactions with more abundant, but spatially and temporally variable, iron and sulfur species. Adjacent to the site of a former pesticide manufacturing facility near San Francisco Bay (California, USA), soil and groundwater arsenic concentrations are elevated in sediments near the prior source, but decrease to background levels downgradient where shallow groundwater mixes with infiltrating tidal waters at the plume periphery, which has not migrated appreciably in over two decades of monitoring. We used synchrotron X-ray absorption spectroscopy, together with supporting characterizations and sequential chemical extractions, to directly determine the oxidation state of arsenic and iron as a function of depth in sediments from cores recovered from the unsaturated and saturated zones of a shallow aquifer (to 3.5 m below the surface). Arsenic oxidation state and local bonding in sediments, as As-sulfide, As(III)-oxide, or As(V)-oxide, were related to lithologic redox horizons and depth to groundwater. Based on arsenic and iron speciation, three subsurface zones were identified: (i) a shallow reduced zone in which sulfide phases were found in either the arsenic spectra (realgar-like or orpiment-like local structure), the iron spectra (presence of pyrite), or both, with and without As(III) or As(V) coordinated by oxygen; (ii) a middle transitional zone with mixed arsenic oxidation states (As(III)–O and As(V)–O) but no evidence for sulfide phases in either the arsenic or iron spectra; and (iii) a lower oxidized zone in the saturated freshwater aquifer in which sediments contained only oxidized As(V) and Fe(III) in labile (non-detrital) phases. The zone of transition between the presence and absence of sulfide phases corresponded to the approximate seasonal fluctuation in water level associated with shallow groundwater in the sand-dominated, lower oxic zone. Total sediment arsenic concentrations showed a minimum in the transition zone and an increase in the oxic zone, particularly in core samples nearest the former source. Equilibrium and reaction progress modeling of aqueous-sediment reactions in response to decreasing oxidation potential were used to illustrate the dynamics of arsenic uptake and release in the shallow subsurface. Arsenic attenuation was controlled by two mechanisms, precipitation as sulfide phases under sulfate-reducing conditions in the unsaturated zone, and adsorption of oxidized arsenic to iron hydroxide phases under oxidizing conditions in saturated groundwaters. This study demonstrates that both realgar-type and orpiment-type phases can form in sulfate-reducing sediments at ambient temperatures, with realgar predicted as the thermodynamically stable phase in the presence of pyrite and As(III) under more reduced conditions than orpiment. Field and modeling results indicate that the potential for release of arsenite to solution is maximized in the transition between sulfate-reduced and iron-oxidized conditions when concentrations of labile iron are low relative to arsenic, pH-controlled arsenic sorption is the primary attenuation mechanism, and mixed Fe(II,III)-oxide phases do not form and generate new sorption sites.     

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni–NiO–H₂O (ΔFMQ = ??0.21 to ??1.01), employing a double-capsule setting. Fluids, binary H₂O–CO₂ mixtures at the P, T, and fO₂ conditions investigated, were generated from graphite, oxalic acid anhydrous (H₂C₂O₄) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO₂-bearing fluids. The experimental data show that forsterite?+?enstatite solubility in H₂O–CO₂ fluids is higher compared to pure water, both in terms of dissolved silica (mSiO₂?=?1.24 mol/kg_H2O versus mSiO₂?=?0.22 mol/kg_H2O at P?=?1 GPa, T?=?800 °C) and magnesia (mMgO?=?1.08 mol/kg_H2O versus mMgO?=?0.28 mol/kg_H2O) probably due to the formation of organic C–Mg–Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H₂O–CO₂ fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO₂ ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO₂ ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P–T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.     

Strengthening the Ties Between Tourism and Economic Geography: A Theoretical Agenda*

This paper stresses the importance of bridging the conceptual gap between tourism research and economic geography. It explains why the tourism production system has been unable to avoid its peripheral position in economic geography. The paper then focuses on the structure and organization of the principal agents comprising the tourism production system and identifies the state's pivotal role as coordinator of these agents. Lastly, it highlights two under-researched issues relating to entreprcneurship and labor pools and makes recommendations for further research.     

Prediction of Gibbs free energies of calcite-type carbonates and the equilibrium distribution of trace elements between carbonates and aqueous solutions

A linear correlation exists between the standard Gibbs free energies of formation of calcite-type carbonates (MCO3) and the corresponding conventional standard Gibbs free energies of formation of the aqueous divalent cations (M2+) at 25 °C and 1 bar ΔGMCO30 = m(ΔGf,M2+0) ? 141,200 cal · mole?1 where m is equal to 0.9715. This relationship enables prediction of the standard free energies of formation of numerous hypothetical carbonates with the calcite structure. Associated uncertainties typically range from about ± 250 to 600 cal · mole?1. An important consequence of the above correlation is that the thermodynamic equilibrium constant for the distribution of two trace elements M and N between carbonate mineral and aqueous solution at 25 °C and 1 bar is proportional to the free energy difference between the corresponding two aqueous ions: In Combination of predicted standard free energies, entropies and volumes of carbonate minerals at 25°C and 1 bar with standard free energies of aqueous ions and the equation of state in Helgesonet al. (1981) enables prediction of the thermodynamic equilibrium constant for trace element distribution between carbonates and aqueous solutions at elevated temperatures and pressures. Interpretation of the thermodynamic equilibrium constant in terms of concentration ratios in the aqueous phase is considerably simplified if pairs of divalent trace elements are considered that have very similar ionic radii (e.g., $\text{Sr}{}^{\mathrm{2+}}\text{Pb}{}^{\mathrm{2+}}$, $\text{Mg}{}^{\mathrm{2+}}\text{Zn}{}^{\mathrm{2+}}$). In combination with data for the stabilities of complex ions in aqueous solutions, the above calculations enable useful limits to be placed on the concentrations of trace elements in hydrothermal solutions.     

Macrobenthic community response to copper in Shelter Island Yacht Basin, San Diego Bay, California

We examined Cu contamination effects on macrobenthic communities and Cu concentration in invertebrates within Shelter Island Yacht Basin, San Diego Bay, California. Results indicate that at some sites, Cu in sediment has exceeded a threshold for “self defense” mechanisms and highlight the potential negative impacts on benthic faunal communities where Cu accumulates and persists in sediments. At sites with elevated Cu levels in sediment, macrobenthic communities were not only less diverse but also their total biomass and body size (individual biomass) were reduced compared to sites with lower Cu. Cu concentration in tissue varied between species and within the same species, reflecting differing abilities to “regulate” their body load. The spatial complexity of Cu effects in a small marina such as SIYB emphasizes that sediment-quality criteria based solely on laboratory experiments should be used with caution, as they do not necessarily reflect the condition at the community and ecosystem levels.     

Soil–structure interaction effects on seismic inelastic analysis of 3-D tunnels

This paper investigates the importance of seismic soil–structure interaction in three-dimensional lined tunnels, assuming inelastic material behaviour for both the concrete liner and the soft rock type of soil. The seismic response of the soil–structure system is determined by the finite element method (FEM) in the time domain. Viscous absorbing boundaries are used in conjunction with the discretization of the rock medium. Both the rock medium and the concrete liner are assumed to behave inelastically on the basis of the continuum damage mechanics theory. The seismic waves are assumed to have any arbitrary time variation and direction of propagation. The system is analysed with and without soil–structure interaction in order to assess its importance on the response of the system. Through parametric studies, the influence of the most critical parameters affecting the structural response is determined and critically discussed.     

Distribution of erosion across bedrock channels

Lateral erosion in bedrock rivers is an important control on the shape of channel cross‐sections, and the coupling of channels and hillslopes. Recent observations link lateral erosion to the variability of flow. We propose two mechanisms to explain this. One is based on changing shear stress distributions within the channel with varying flood level, the other on the competition between cover and tool effects in fluvial bedrock erosion. We assess these processes for the Liwu River, Taiwan, and conclude that cover and tool effects dominate the partitioning of lateral and vertical erosion in this case. Copyright © 2007 John Wiley & Sons, Ltd.     

Instance‐based learning compared to other data‐driven methods in hydrological forecasting

Data‐driven techniques based on machine learning algorithms are becoming popular in hydrological modelling, in particular for forecasting. Artificial neural networks (ANNs) are often the first choice. The so‐called instance‐based learning (IBL) has received relatively little attention, and the present paper explores the applicability of these methods in the field of hydrological forecasting. Their performance is compared with that of ANNs, M5 model trees and conceptual hydrological models. Four short‐term flow forecasting problems were solved for two catchments. Results showed that the IBL methods often produce better results than ANNs and M5 model trees, especially if used with the Gaussian kernel function. The study showed that IBL is an effective data‐driven method that can be successfully used in hydrological forecasting. Copyright © 2007 John Wiley & Sons, Ltd.     

In search of the Earth‐forming reservoir: Mineralogical,chemical, and isotopic characterizations of the ungrouped achondrite NWA 5363/NWA 5400 and selected chondrites

High‐precision isotope data of meteorites show that the long‐standing notion of a “chondritic uniform reservoir” is not always applicable for describing the isotopic composition of the bulk Earth and other planetary bodies. To mitigate the effects of this “isotopic crisis” and to better understand the genetic relations of meteorites and the Earth‐forming reservoir, we performed a comprehensive petrographic, elemental, and multi‐isotopic (O, Ca, Ti, Cr, Ni, Mo, Ru, and W) study of the ungrouped achondrites NWA 5363 and NWA 5400, for both of which terrestrial O isotope signatures were previously reported. Also, we obtained isotope data for the chondrites Pillistfer (EL6), Allegan (H6), and Allende (CV3), and compiled available anomaly data for undifferentiated and differentiated meteorites. The chemical compositions of NWA 5363 and NWA 5400 are strikingly similar, except for fluid mobile elements tracing desert weathering. We show that NWA 5363 and NWA 5400 are paired samples from a primitive achondrite parent‐body and interpret these rocks as restite assemblages after silicate melt extraction and siderophile element addition. Hafnium‐tungsten chronology yields a model age of 2.2 ± 0.8 Myr after CAI, which probably dates both of these events within uncertainty. We confirm the terrestrial O isotope signature of NWA 5363/NWA 5400; however, the discovery of nucleosynthetic anomalies in Ca, Ti, Cr, Mo, and Ru reveals that the NWA5363/NWA 5400 parent‐body is not the “missing link” that could explain the composition of the Earth by the mixing of known meteorites. Until this “missing link” or a direct sample of the terrestrial reservoir is identified, guidelines are provided of how to use chondrites for estimating the isotopic composition of the bulk Earth.