Ab initio calculation of H, O, Al and Si NMR parameters, vibrational frequencies and bonding energetics in hydrous silica and Na-aluminosilicate glasses     

J.D. Kubicki  D.G. Sykes 《Geochimica et cosmochimica acta》2004,68(19):3909-3918

Ab initio, molecular orbital (MO) calculations were performed on model systems of SiO₂, NaAlSi₃O₈ (albite), H₂O-SiO₂ and H₂O-NaAlSi₃O₈ glasses. Model nuclear magnetic resonance (NMR) isotropic chemical shifts (δ_iso) for ¹H, ¹⁷O, ²⁷Al and ²⁹Si are consistent with experimental data for the SiO₂, NaAlSi₃O₈, H₂O-SiO₂ systems where structural interpretations of the NMR peak assignments are accepted. For H₂O-NaSi₃AlO₈ glass, controversy has surrounded the interpretation of NMR and infrared (IR) spectra. Calculated δ_iso¹H, δ_iso¹⁷O, δ_iso²⁷Al and δ_iso²⁹Si are consistent with the interpretation of Kohn et al. (1992) that Si-(OH)-Al linkages are responsible for the observed peaks in hydrous Na-aluminosilicate glasses. In addition, a theoretical vibrational frequency associated with the Kohn et al. (1992) model agrees well with the observed shoulder near 900 cm⁻¹ in the IR and Raman spectra of hydrous albite glasses. MO calculations suggest that breaking this Si-(OH)-Al linkage requires ∼+56 to +82 kJ/mol which is comparable to the activation energies for viscous flow in hydrous aluminosilicate melts.  相似文献   

Recharge estimation for transient ground water modeling   总被引：11，自引：0，他引：11  

Jyrkama MI  Sykes JF  Normani SD 《Ground water》2002,40(6):638-648

Reliable ground water models require both an accurate physical representation of the system and appropriate boundary conditions. While physical attributes are generally considered static, boundary conditions, such as ground water recharge rates, can be highly variable in both space and time. A practical methodology incorporating the hydrologic model HELP3 in conjunction with a geographic information system was developed to generate a physically based and highly detailed recharge boundary condition for ground water modeling. The approach uses daily precipitation and temperature records in addition to land use/land cover and soils data. The importance of the method in transient ground water modeling is demonstrated by applying it to a MODFLOW modeling study in New Jersey. In addition to improved model calibration, the results from the study clearly indicate the importance of using a physically based and highly detailed recharge boundary condition in ground water quality modeling, where the detailed knowledge of the evolution of the ground water flowpaths is imperative. The simulated water table is within 0.5 m of the observed values using the method, while the water levels can differ by as much as 2 m using uniform recharge conditions. The results also show that the combination of temperature and precipitation plays an important role in the amount and timing of recharge in cooler climates. A sensitivity analysis further reveals that increasing the leaf area index, the evaporative zone depth, or the curve number in the model will result in decreased recharge rates over time, with the curve number having the greatest impact.  相似文献   

Guidelines for assessing the petroleum potential of coaly source rocks using Rock-Eval pyrolysis     

R Sykes  L.R Snowdon 《Organic Geochemistry》2002,33(12):2

Coaly source rocks are sufficiently different from marine and lacustrine source rocks in their organic matter characteristics to warrant separate guidelines for their assessment using Rock-Eval pyrolysis. The rank threshold for oil generation is indicated by the increase in BI (S1/TOC) at Rank(S_r)9–10 (T_max 420–430 °C, R_o 0.55–0.6%), and the threshold for oil expulsion is indicated by the peak in QI ([S1+S2]/TOC) at Rank(S_r)11–12.5 (T_max 430–440 °C, R_o 0.65–0.85%). The pronounced rank-related increase in HI (S2/TOC) prior to oil expulsion renders the use of immature samples inappropriate for source rock characterisation. A more realistic indication of the petroleum generative potential and oil expulsion efficiency of coaly source rocks can be gained from samples near the onset of expulsion. Alternatively, effective HI′ values (i.e. HIs near the onset of expulsion) can be estimated by translating the measured HIs of immature samples along the maturation pathway defined by the New Zealand (or other defined) Coal Band. Coaly source rocks comprise a continuum of coaly lithologies, including coals, shaly coals and coaly mudstones. Determination of the total genetic potential of coaly source rock sequences is best made using lithology-based samples near the onset of expulsion.  相似文献   

Uncertainties in projected impacts of climate change on European agriculture and terrestrial ecosystems based on scenarios from regional climate models     

J. E. Olesen  T. R. Carter  C. H. Díaz-Ambrona  S. Fronzek  T. Heidmann  T. Hickler  T. Holt  M. I. Minguez  P. Morales  J. P. Palutikof  M. Quemada  M. Ruiz-Ramos  G. H. Rubæk  F. Sau  B. Smith  M. T. Sykes 《Climatic change》2007,81(1):123-143

The uncertainties and sources of variation in projected impacts of climate change on agriculture and terrestrial ecosystems depend not only on the emission scenarios and climate models used for projecting future climates, but also on the impact models used, and the local soil and climatic conditions of the managed or unmanaged ecosystems under study. We addressed these uncertainties by applying different impact models at site, regional and continental scales, and by separating the variation in simulated relative changes in ecosystem performance into the different sources of uncertainty and variation using analyses of variance. The crop and ecosystem models used output from a range of global and regional climate models (GCMs and RCMs) projecting climate change over Europe between 1961–1990 and 2071–2100 under the IPCC SRES scenarios. The projected impacts on productivity of crops and ecosystems included the direct effects of increased CO₂ concentration on photosynthesis. The variation in simulated results attributed to differences between the climate models were, in all cases, smaller than the variation attributed to either emission scenarios or local conditions. The methods used for applying the climate model outputs played a larger role than the choice of the GCM or RCM. The thermal suitability for grain maize cultivation in Europe was estimated to expand by 30–50% across all SRES emissions scenarios. Strong increases in net primary productivity (NPP) (35–54%) were projected in northern European ecosystems as a result of a longer growing season and higher CO₂ concentrations. Changing water balance dominated the projected responses of southern European ecosystems, with NPP declining or increasing only slightly relative to present-day conditions. Both site and continental scale models showed large increases in yield of rain-fed winter wheat for northern Europe, with smaller increases or even decreases in southern Europe. Site-based, regional and continental scale models showed large spatial variations in the response of nitrate leaching from winter wheat cultivation to projected climate change due to strong interactions with soils and climate. The variation in simulated impacts was smaller between scenarios based on RCMs nested within the same GCM than between scenarios based on different GCMs or between emission scenarios.  相似文献   

The complex gravitational lens system B1933+503     

C. M. Sykes  I. W. A. Browne  N. J. Jackson  D. R. Marlow  S. Nair  P. N. Wilkinson  R. D. Blandford  J. Cohen  C. D. Fassnacht  D. Hogg  T. J. Pearson  A. C. S. Readhead  D. S. Womble  S. T. Myers  A. G. de Bruyn  M. Bremer  G. K. Miley  & R. T. Schilizzi 《Monthly notices of the Royal Astronomical Society》1998,301(2):310-314

We report the discovery of the most complex arcsec-scale radio gravitational lens system yet known. B1933+503 was found during the course of the CLASS survey and MERLIN and VLA radio maps reveal up to 10 components. Four of these are compact and have flat spectra; the rest are more extended and have steep spectra. The background lensed object appears to consist of a flat-spectrum core (quadruply imaged) and two compact 'lobes' symmetrically disposed relative to the core. One of the lobes is quadruply imaged while the other is doubly imaged. An HST observation of the system with the WFPC2 shows a galaxy with an axial ratio of 0.5, but none of the images of the background object is detected. A redshift of 0.755 has been measured for the lens galaxy.  相似文献   

Seismic gaps and plate tectonics: Seismic potential for major boundaries   总被引：5，自引：0，他引：5  

W. R. McCann  S. P. Nishenko  L. R. Sykes  J. Krause 《Pure and Applied Geophysics》1979,117(6):1082-1147

The theory of plate tectonics provides a basic framework for evaluating the potential for future great earthquakes to occur along major plate boundaries. Along most of the transform and convergent plate boundaries considered in this paper, the majority of seismic slip occurs during large earthquakes, i.e., those of magnitude 7 or greater. The concepts that rupture zones, as delineated by aftershocks, tend to abut rather than overlap, and large events occur in regions with histories of both long- and short-term seismic quiescence are used in this paper to delineate major seismic gaps.In detail, however, the distribution of large shallow earthquakes along convergent plate margins is not always consistent with a simple model derived from plate tectonics. Certain plate boundaries, for example, appear in the long term to be nearly aseismic with respect to large earthquakes. The identification of specific tectonic regimes, as defined by dip of the inclined seismic zone, the presence or absence of aseismic ridges and seamounts on the downgoing lithospheric plate, the age contrast between the overthrust and underthrust plates, and the presence or absence of back-arc spreading, have led to a refinement in the application of plate tectonic theory to the evaluation of seismic potential.The term seismic gap is taken to refer to any region along an active plate boundary that has not experienced a large thrust or strike-slip earthquake for more than 30 years. A region of high seismic potential is a seismic gap that, for historic or tectonic reasons, is considered likely to produce a large shock during the next few decades. The seismic gap technique provides estimates of the location, size of future events and origin time to within a few tens of years at best.The accompanying map summarizes six categories of seismic potential for major plate boundaries in and around the margins of the Pacific Ocean and the Caribbean, South Sandwich and Sunda (Indonesia) regions for the next few decades. These categories range from what we consider high to low potential for being the site of large earthquakes during that period of time. Categories 1, 2 and 6 define a time-dependent potential based on the amount of time elapsed since the last large earthquake. The remaining categories, 3, 4, and 5, are used for areas that have ambiguous histories for large earthquakes; their seismic potential is inferred from various tectonic criteria. These six categories are meant to be interpreted as forecasts of the location and size of future large shocks and should not be considered to be predictions in which a precise estimate of the time of occurrence is specified.Several of the segments of major plate boundaries that are assigned the highest potential, i.e., category 1, are located along continental margins, adjacent to centers of population. Some of them are hundreds of kilometers long. High priority should be given to instrumenting and studying several of these major seismic gaps since many are now poorly instrumented. The categories of potential assigned here provide a rationale for assigning prorities for instrumentation, for future studies aimed at predicting large earthquakes and for making estimates of tsunami potential.Lamont-Doherty Geological Observatory Contribution No. 2906.  相似文献   

Nondestructive determination of the physical properties of Antarctic meteorites: Importance for the meteorite—parent body connection     

T. A. Harvey  J. L. MacArthur  K. H. Joy  D. Sykes  N. V. Almeida  R. H. Jones 《Meteoritics & planetary science》2023,58(12):1707-1746

Photogrammetry is a low-cost, nondestructive approach for producing 3-D models of meteorites for the purpose of determining sample bulk density. Coupled with the use of a nondestructive magnetic susceptibility/electrical conductivity field probe, we present measurements for the interrogation of several physical properties, on a set of Antarctic meteorites. Photogrammetry is an effective technique over a range of sample sizes, with meteorite bulk density results that are closely comparable with literature values, determined using Archimedean glass bead or laser scanning techniques. The technique is completely noncontaminating and suitable for the analysis of rare or fragile samples, although there are limitations for analyzing reflective samples. It is also flexible, and, with variations in equipment setup, may be appropriate for samples of a wide range of sizes. X-ray computed tomography analyses of the same meteorite samples yielded slightly different bulk density results, predominantly for samples below 10 g, although the reason for this is unclear. Such analyses are expensive and potentially damaging to certain features of the sample (e.g., organic compounds), but may be useful in expanding the measurements to accommodate an understanding of internal voids within the sample, lending itself to measurement of grain density. Measurements of bulk density are valuable for comparisons with estimates of the bulk densities of asteroids that are suggested as meteorite parent bodies.  相似文献   

Rotationally-resolved spectroscopy of Vesta I: 2-4 μm region     

A.S. Rivkin  L.A. McFadden  M. Sykes 《Icarus》2006,180(2):464-472

We present new infrared (2-4 μm) spectroscopic observations of Vesta obtained in 2001, 2003, and 2004. Together with previously published work, these present a picture of how Vesta's spectrum changes with sub-Earth latitude and longitude. Vesta's albedo and 2-μm band vary regularly with its rotational phase. While establishing the continuum level for Vesta in the 3-μm region is not straightforward, Vesta appears to have a spectrum consistent with the HED meteorites and not requiring a 3-μm water of hydration band. We cannot formally rule out a shallow (∼1%) band, however. We place limits on the extent to which solar-wind implantation and contamination by CM-like impactors has changed the surface spectrum of Vesta.  相似文献   

Changes in bulk properties and molecular compositions within New Zealand Coal Band solvent extracts from early diagenetic to catagenetic maturity levels     

T.T.A. Vu  K.-G. Zink  K. Mangelsdorf  R. Sykes  H. Wilkes  B. Horsfield 《Organic Geochemistry》2009,40(9):963-977

The bulk properties and bitumen molecular compositions of a rank-series of 38 humic coals from the New Zealand Coal Band (Cretaceous–Cenozoic) have been analysed to investigate early maturation processes affecting coaly organic matter through diagenesis to moderate catagenesis (Rank(S_r) 0.0–11.8, R_o 0.23–0.81%). The samples comprise a relatively restricted range of vitrinite rich coal types formed largely from higher land plant material under relatively oxic conditions, but with a significant contribution from microbial biomass. With increasing rank, total organic carbon contents show a general increase, whereas moisture and asphaltene contents decrease. Bitumen yields also decrease through the stages of diagenesis and early catagenesis (Rank(S_r) < 9, R_o < 0.55%), indicating partial loss of initial bitumen during early maturation. Thermal generation of hydrocarbons begins slowly at Rank(S_r)  5–6 (R_o  0.40%) as indicated by the constant occurrence and gradual increase of isoprenoids (e.g., pristane and phytane) and hopanoids in their more mature αβ configuration. This early phase of catagenesis, not previously recognised in New Zealand coals, is followed at Rank(S_r)  9 (R_o  0.55%) by the main catagenesis phase characterised by a more rapid increase in the generation of hydrocarbons, including total n-alkanes, isoprenoids and αβ-hopanes. Changes in the maturity of New Zealand coals can be traced by the Carbon Preference Index and several hopane maturity parameters, including 22S/(22S + 22R), αβ/(αβ + βα) and ββ/(αβ + βα + ββ).  相似文献   

Mid-infrared lightcurve of Vesta     

M.A. Chamberlain  M.V. Sykes  E.F. Tedesco 《Icarus》2011,215(1):57-61

We present a thermal mid-infrared lightcurve of Asteroid 4 Vesta and use this to infer variations in thermophysical properties over the surface. Vesta was observed over three nights during the May 2007 opposition with the Infrared Telescope Facility on Mauna Kea. Mid-infrared observations are compared to a model based on the Standard Thermal Model which is draped over a Vesta shape model derived from Hubble Space Telescope observations.A visible lightcurve with similar aspect was used to estimate the albedo as Vesta rotates. Shape and albedo can explain some of the features observed in the mid-infrared lightcurve. However, variations in the thermophysical properties, such as the “beaming parameter,” over Vesta’s surface are required to completely explain the observations.In order to match the mid-infrared magnitudes observed of Vesta, a beaming parameter of ∼0.862 is required which is higher than other Main Belt Asteroids such as Ceres and Pallas (0.756), indicating a smoother and/or rockier surface on Vesta. Variations in the beaming parameter with longitude are invoked to reproduce the observed thermal variations. Surface materials with relatively high beaming values, indicating a smoother and/or rockier surface, in the eastern hemisphere of Vesta coincide with locations where impact excavations may have produced surfaces that are younger and brighter relative to the western hemisphere.  相似文献