Boron isotopic fractionation related to boron sorption on humic acid and the structure of surface complexes formed     

Emmanuel Lemarchand  Jérôme Gaillardet 《Geochimica et cosmochimica acta》2005,69(14):3519-3533

Boron isotopic fractionation during adsorption onto Ca-flocculated Aldrich humic acid (HA) has been investigated experimentally as a function of solution pH at 25°C and I = 0.15 M. Boron aqueous concentration and isotopic composition were determined by Cs₂BO₂⁺ Positive Thermal Ionization Mass Spectrometry analysis, while the structure of B surface complexes on HA was characterized using ¹¹B Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Significant B sorption on HA was observed at 6 < pH < 12 with a maximum value of Kd, the partition coefficient between adsorbed and aqueous boron, equal to 40 at pH = 9.5-10. Combined ¹¹B MAS NMR analysis and FITEQL modeling of B sorption on HA showed that this element forms tetrahedrally coordinated five- or six-membered ring chelates, most likely 1,2-diol and 1,3-diol complexes at alkaline pH (8 < pH < 11) and dicarboxylic complexes at near neutral conditions (6 < pH < 9). Results of this study demonstrate for the first time that boron sorption on HA induces a strong pH-dependent isotope fractionation—with ¹¹B depleted at the surface of HA—that reaches a maximum at 5 < pH < 9 (α = 0.975, Δ = −25‰) and decreases sharply at pH >9. The measured isotope fractionation cannot be modeled assuming that the isotopic composition of the sorbed borate species is identical to that of B(OH)₄^- species in the parent solution. It is shown that the extent of isotopic fractionation depends not only on B aqueous speciation but also on the distribution and structure of the borate surface complexes formed. In agreement with energetic constrains, calculation of the isotope fractionation factors between aqueous boric acid and boron surface complexes suggests that the formation of the strained six-membered ring 1,3-diol complex yields a much higher fractionation (α_BLP1−III = 0.954-0.960, Δ = −41/-47‰) than that of the very stable five-membered ring 1,2-diol (α_BLP2−III = 0.983, Δ = −18‰). The results of this study open new perspectives to understand and model boron biogeochemical cycle. It is predicted that boron sorption onto organic matter can have important consequences for the boron isotopic composition of surface water reservoirs (seawater, groundwater, soil waters) in which either abundant organic surfaces or significant boron concentrations are available. In addition, the large isotope fractionation between aqueous boric acid and surface boron-organic complexes found in the present work makes boron a promising tracer of biologic activity.  相似文献   

Algorithms for time synchronization of wireless structural monitoring sensors     

Ying Lei  Anne S. Kiremidjian  K. Krishnan Nair  Jerome P. Lynch  Kincho H. Law 《地震工程与结构动力学》2005,34(6):555-573

Dense networks of wireless structural health monitoring systems can effectively remove the disadvantages associated with current wire‐based sparse sensing systems. However, recorded data sets may have relative time‐delays due to interference in radio transmission or inherent internal sensor clock errors. For structural system identification and damage detection purposes, sensor data require that they are time synchronized. The need for time synchronization of sensor data is illustrated through a series of tests on asynchronous data sets. Results from the identification of structural modal parameters show that frequencies and damping ratios are not influenced by the asynchronous data; however, the error in identifying structural mode shapes can be significant. The results from these tests are summarized in Appendix A. The objective of this paper is to present algorithms for measurement data synchronization. Two algorithms are proposed for this purpose. The first algorithm is applicable when the input signal to a structure can be measured. The time‐delay between an output measurement and the input is identified based on an ARX (auto‐regressive model with exogenous input) model for the input–output pair recordings. The second algorithm can be used for a structure subject to ambient excitation, where the excitation cannot be measured. An ARMAV (auto‐regressive moving average vector) model is constructed from two output signals and the time‐delay between them is evaluated. The proposed algorithms are verified with simulation data and recorded seismic response data from multi‐story buildings. The influence of noise on the time‐delay estimates is also assessed. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

Ferguson rock slide buries California State Highway near Yosemite National Park     

Edwin L. Harp  Mark E. Reid  Jonathan W. Godt  Jerome V. DeGraff  Alan J. Gallegos 《Landslides》2008,5(3):331-337

During spring 2006, talus from the toe area of a rock-block slide of about 800,000 m³ buried California State Highway 140, one of the main routes into heavily-visited Yosemite National Park, USA. Closure of the highway for 92 days caused business losses of about 4.8 million USD. The rock slide, composed of slate and phyllite, moved slowly downslope from April to June 2006, creating a fresh head scarp with 9–12 m of displacement. Movement of the main rock slide, a re-activation of an older slide, was triggered by an exceptionally wet spring 2006, following a very wet spring 2005. As of autumn 2006, most of the main slide appeared to be at rest, although rocks occasionally continued to fall from steep, fractured rock masses at the toe area of the slide. Future behavior of the slide is difficult to predict, but possible scenarios range from continued scattered rock fall to complete rapid failure of the entire mass. Although unlikely except under very destabilizing circumstances, a worst-case, rapid failure of the entire rock slide could extend across the Merced River, damming the river and creating a reservoir. As a temporary measure, traffic has been rerouted to the opposite side of the Merced River at about the same elevation as the buried section of Highway 140. A state-of-the-art monitoring system has been installed to detect movement in the steep talus slope, movement of the main slide mass, local strong ground motion from regional earthquakes, and sudden changes in stream levels, possibly indicating damming of the river by slide material.  相似文献   

Modal decomposition method for stationary response of non-classically damped systems     

Takeru Igusa  Armen Der Kiureghian  Jerome L. Sackman 《地震工程与结构动力学》1984,12(1):121-136

The stationary response of multi-degree-of-freedom non-classically damped linear systems subjected to stationary input excitation is studied. A modal decomposition procedure based on the complex eigenvectors and eigenvalues of the system is used to derive general expressions for the spectral moments of response. These expressions are in terms of cross-modal spectral moments and explicitly account for the correlation between modal responses; thus, they are applicable to structures characterized with significant non-classical damping as well as structures with closely spaced frequencies. Closed form solutions are presented for the important case of response to white-noise input. Various quantities of response of general engineering interest can be obtained in terms of these spectral moments. These include mean zero-crossing rate and mean, variance and distribution of peak response over a specified duration. Examples point out several instances where non-classical damping effects become significant and illustrate the marked improvement of the results of this study over conventional analysis based on classical damping approximations.  相似文献   

The Flatness of U.S. States     

Jerome E. Dobson  Joshua S. Campbell 《Geographical review》2014,104(1):1-9

Does perception match reality when people judge the flatness of large areas, such as U.S. states? The authors conducted a geomorphometric analysis of the contiguous United States, employing publicly available geographic software, Shuttle Radar Topography Mission (SRTM) elevation data, and a new algorithm for measuring flatness. Each 90‐meter cell was categorized as not flat, flat, flatter, or flattest, and each state was measured in terms of percentage flat, flatter, and flattest as well as absolute area in each category. Ultimately, forty‐eight states plus the District of Columbia were mapped and ranked according to these values. Keywords: flatness, U.S. states, slope, Kansas, Florida.  相似文献   

Forced oscillation measurements of seismic wave attenuation and stiffness moduli dispersion in glycerine-saturated Berea sandstone     

Samuel Chapman  Jan V. M. Borgomano  Hanjun Yin  Jerome Fortin  Beatriz Quintal 《Geophysical Prospecting》2019,67(4):956-968

Fluid pressure diffusion occurring on the microscopic scale is believed to be a significant source of intrinsic attenuation of mechanical waves propagating through fully saturated porous rocks. The so-called squirt flow arises from compressibility heterogeneities in the microstructure of the rocks. To study squirt flow experimentally at seismic frequencies the forced oscillation method is the most adequate, but such studies are still scarce. Here we present the results of forced hydrostatic and axial oscillation experiments on dry and glycerine-saturated Berea sandstone, from which we determine the dynamic stiffness moduli and attenuation at micro-seismic and seismic frequencies (0.004–30 Hz). We observe frequency-dependent attenuation and the associated moduli dispersion in response to the drained–undrained transition (∼0.1 Hz) and squirt flow (>3 Hz), which are in fairly good agreement with the results of the corresponding analytical solutions. The comparison with very similar experiments performed also on Berea sandstone in addition shows that squirt flow can potentially be a source of wave attenuation across a wide range of frequencies because of its sensitivity to small variations in the rock microstructure, especially in the aspect ratio of micro-cracks or grain contacts.  相似文献   

A single vs. double spike approach to improve the accuracy of Th measurements in small-volume seawater samples     

Alessia M. Rodriguez y Baena  Juan Carlos Miquel  Pere Masqu  Pavel P. Povinec  Jerome La Rosa 《Marine Chemistry》2006,100(3-4):269

²³⁴Th is a particle-reactive radionuclide widely used to trace biogeochemical oceanic processes occurring over short timescales. During the last few years, small-volume techniques based on the co-precipitation of ²³⁴Th with MnO₂ coupled with beta-counting have been developed as an alternative to large volume gamma-spectrometric techniques. Here a procedure has been developed to enhance quantitative measurement of ²³⁴Th in MnO₂ precipitates. The main objectives were to obtain a purified Th fraction for beta-counting and to determine the chemical recovery of ²³⁴Th using Th spikes and alpha-spectrometry as an alternative to ICP-MS based methods. Two variations of the procedure are presented. In the first “1 spike” method a ²³⁰Th tracer is added to the sample prior to precipitation of MnO₂, and UTEVA® extraction chromatography is used to obtain a NdF₃(Th) purified source that can be used for both beta-counting of ²³⁴Th and alpha-spectrometry of ²³⁰Th. In the “2 spike” method a ²³⁰Th spike is added and the MnO₂(Th) precipitate is directly beta-counted for ²³⁴Th and subsequently spiked with ²²⁸Th or ²²⁹Th prior to UTEVA® purification and alpha-spectrometry. The results confirm the need to process small-volume seawater samples for ²³⁴Th measurement in presence of a yield tracer, and show that both the 1 spike and 2 spike methods allow an accurate and precise determination of ²³⁴Th (relative percent difference, RPD, between expected and mean measured value < 1%; CV between replicate samples < 3%). Our work also suggests that, although the combined analytical uncertainty on total ²³⁴Th measurements accomplished with both versions of the NdF₃ procedure is promising (6% for 2-L samples), the precision of the ²³⁴Th flux estimation will ultimately depend on the degree of disequilibrium between ²³⁴Th and ²³⁸U.  相似文献