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11.
G2 theory calculations were performed on [H3SiO4]?, H4SiO4, [H3AlO4]2?, [H4AlO4]?, and [H5AlO4]. Molecular structures, atomic charges, and infrared spectra at the HF/6-31G* and MP2/6-31G* levels are compared. The influence of polarization and diffuse functions on the structure of [H3SiO4]? is also examined. Basis set and electron correlation effects on potential energies are assessed by comparing various levels of theory. Proton affinities of these gas-phase molecules and related mineral surface species are predicted based on corrections for cluster-size effects.  相似文献   
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We present a 16-month record of ozone (O3), carbon monoxide (CO), total reactive nitrogen (NOy), sulphur dioxide (SO2), methane (CH4), C2 – C8 non-methane hydrocarbons (NMHCs), C1 – C2 halocarbons, and dimethyl sulfide (DMS) measured at a southern China coastal site. The study aimed to establish/update seasonal profiles of chemically active trace gases and pollution tracers in subtropical Asia and to characterize the composition of the `background' atmosphere over the South China Sea (SCS) and of pollution outflow from the industrialized Pearl River Delta (PRD) region and southern China. Most of the measured trace gases of anthropogenic origin exhibited a winter maximum and a summer minimum, while O3 showed a maximum in autumn which is in contrast to the seasonal behavior of O3 in rural eastern China and in many mid-latitude remote locations in the western Pacific. The data were segregated into two groups representing the SCS background air and the outflow of regional continental pollution (PRD plus southern China), based on CO mixing ratios and meteorological conditions. NMHCs and halocarbon data were further analyzed to examine the relationships between their variability and atmospheric lifetime and to elucidate the extent of atmospheric processing in the sampled air parcels. The trace gas variability (S) versus lifetime (τ) relationship, defined by the power law, Slnx = Aτb, (where X is the trace gas mixing ratio) gives a fit parameter A of 1.39 and exponent b of 0.42 for SCS air, and A of 2.86 and b of 0.31 for the regional continental air masses. An examination of ln[n-butane]/ln[ethane] versus ln[propane]/ln[ethane] indicates that their relative abundance was dominated by mixing as opposed to photochemistry in both SCS and regional outflow air masses. The very low ratios of ethyne/CO, propane/ethane and toluene/benzene suggest that the SCS air mass has undergone intense atmospheric processing since these gases were released into the atmosphere. Compared to the results from other polluted rural sites and from urban areas, the large values of these species in the outflow of PRD/southern China suggest source(s) emitting higher levels of ethyne, benzene, and toluene, relative to light alkanes. These chemical characteristics could be unique indicators of anthropogenic emissions from southern China.  相似文献   
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Short‐term (contemporary) and long‐term denudation rates were determined for the Blue Mountains Plateau in the western Sydney Basin, Australia, to explore the role of extreme events (wildfires and catastrophic floods) in landscape denudation along a passive plate margin. Contemporary denudation rates were reconstructed using 40 years of river sediment load data from the Nattai catchment in the south‐west of the basin, combined with an analysis of hillslope erosion following recent wildfires. Long‐term denudation rates (10 kyr–10 Myr) were determined from terrestrial cosmogenic nuclides, apatite fission track thermochronology and post‐basalt flow valley incision. Contemporary denudation rates average several times lower than the long‐term average (5·5 ± 4 mm kyr?1 versus 21·5 ± 7 mm kyr?1). Erosion of sediment following wildfires accounts for only a small proportion (5%) of the contemporary rate. Most post‐fire sediment is stored on the lower slopes and valley floor, with the amount transported to the river network dependent on rainfall–run‐off conditions within the first few years following the fire. Historical catastrophic floods account for a much larger proportion (35%) of the contemporary erosion rate, and highlight the importance of these events in reworking stored material. Evidence for palaeofloods much larger than those experienced over the past 200 years suggests even greater sediment export potential. Mass movement on hillslopes along valleys incised into softer lithology appears to be a dominant erosion process that supplies substantial volumes of material to the valley floor. It is possible that a combination of infrequent mass movement events and high fluvial discharge could account for a significant proportion of the discrepancy between the contemporary and long‐term denudation rates. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   
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Quantification of levels of cytochrome P4501A (CYP1A) gene expression in sentinel species of fishes has been proposed as a management tool to evaluate contamination of aquatic systems. Based on preliminary studies, we hypothesized that differences in CYP1A mRNA inducibility among individuals, populations, or species might lead to spurious conclusions when using this approach in environmental monitoring programs. To address this possibility, we quantitated and compared CYP1A mRNA induction levels in four species of common Atlantic Coast estuarine fish: smooth flounder, hogchoker, striped bass, and Atlantic tomcod, which were treated with model chemicals (beta naphthoflavone (β-NF), or benzo[a]pyrene at 10 ppm) known to induce CYP1A mRNA, or were exposed to contaminated environments. Species-specific CYP1A DNA probes were generated from PCR (polymerase chain reaction) amplification of genomic DNA using conserved oligonucleotide primers, and, along with cloned rainbow trout and Atlantic tomcod CYP1A cDNA probes were used to quantify CYP1A mRNA levels in northern blot analyses. Successful PCR amplification of CYP1A hybridizable DNA fragments was observed for all four species. Results from northern blot analyses showed large differences in CYP1A mRNA induction among species; only Atlantic tomcod exhibited significant induction of CYP1A mRNA for both chemically treated (97-fold) and environmentally exposed fish (34-fold). Significant, although lower, levels of induction were observed in β-NF treated (14-fold) smooth flounder, but not in environmentally exposed smooth flounder. Only low levels (not significant) of CYP1A gene induction were detected in hogchokers and striped bass. We conclude that CYP1A mRNA inducibility differed significantly among fish taxa perhaps due to differences in regulation of gene expression, suggesting that careful selection of sentinel species should be exercised prior to the use of CYP1A mRNA induction in environmental monitoring programs. However, the significance of differences in CYP1A mRNA inducibility in relation to higher level biological endpoints has yet to be determined.  相似文献   
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Precise orbit determination for the GRACE mission using only GPS data   总被引:1,自引:1,他引:1  
The GRACE (gravity recovery and climate experiment) satellites, launched in March 2002, are each equipped with a BlackJack GPS onboard receiver for precise orbit determination and gravity field recovery. Since launch, there have been significant improvements in the background force models used for satellite orbit determination, most notably the model for the geopotential. This has resulted in significant improvements to orbit accuracy for very low altitude satellites. The purpose of this paper is to investigate how well the orbits of the GRACE satellites (about 470 km in altitude) can currently be determined using only GPS data and based on the current models and methods. The orbit accuracy is assessed using a number of tests, which include analysis of orbit fits, orbit overlaps, orbit connecting points, satellite Laser ranging residuals and K-band ranging (KBR) residuals. We show that 1-cm radial orbit accuracy for the GRACE satellites has probably been achieved. These precise GRACE orbits can be used for such purposes as improving gravity recovery from the GRACE KBR data and for atmospheric profiling, and they demonstrate the quality of the background force models being used.  相似文献   
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 The rates of passive degassing from volcanoes are investigated by modelling the convective overturn of dense degassed and less dense gas-rich magmas in a vertical conduit linking a shallow degassing zone with a deep magma chamber. Laboratory experiments are used to constrain our theoretical model of the overturn rate and to elaborate on the model of this process presented by Kazahaya et al. (1994). We also introduce the effects of a CO2–saturated deep chamber and adiabatic cooling of ascending magma. We find that overturn occurs by concentric flow of the magmas along the conduit, although the details of the flow depend on the magmas' viscosity ratio. Where convective overturn limits the supply of gas-rich magma, then the gas emission rate is proportional to the flow rate of the overturning magmas (proportional to the density difference driving convection, the conduit radius to the fourth power, and inversely proportional to the degassed magma viscosity) and the mass fraction of water that is degassed. Efficient degassing enhances the density difference but increases the magma viscosity, and this dampens convection. Two degassing volcanoes were modelled. At Stromboli, assuming a 2 km deep, 30% crystalline basaltic chamber, containing 0.5 wt.% dissolved water, the ∼700 kg s–1 magmatic water flux can be modelled with a 4–10 m radius conduit, degassing 20–100% of the available water and all of the 1 to 4 vol.% CO2 chamber gas. At Mount St. Helens in June 1980, assuming a 7 km deep, 39% crystalline dacitic chamber, containing 4.6 wt.% dissolved water, the ∼500 kg s–1 magmatic water flux can be modelled with a 22–60 m radius conduit, degassing ∼2–90% of the available water and all of the 0.1 to 3 vol.% CO2 chamber gas. The range of these results is consistent with previous models and observations. Convection driven by degassing provides a plausible mechanism for transferring volatiles from deep magma chambers to the atmosphere, and it can explain the gas fluxes measured at many persistently active volcanoes. Received: 26 September 1997 / Accepted: 11 July 1998  相似文献   
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We investigate the environments and clustering properties of starburst galaxies selected from the 2dF Galaxy Redshift Survey (2dFGRS) in order to determine which, if any, environmental factors play a role in triggering a starburst. We quantify the local environments, clustering properties and luminosity functions of our starburst galaxies and compare to random control samples. The starburst galaxies are also classified morphologically in terms of their broad Hubble type and evidence of tidal merger/interaction signatures. We find the starburst galaxies to be much less clustered on large (5–15 Mpc) scales compared to the overall 2dFGRS galaxy population. In terms of their environments, we find just over half of the starburst galaxies to reside in low to intermediate luminosity groups, and a further ∼30 per cent residing in the outskirts and infall regions of rich clusters. Their luminosity functions also differ significantly from that of the overall 2dFGRS galaxy population, with the sense of the difference being critically dependent on the way their star formation rates are measured. In terms of pin-pointing what might trigger the starburst, it would appear that factors relating to their local environment are most germane. Specifically, we find clear evidence that the presence of a near neighbour of comparable luminosity/mass within 20 kpc is likely to be important in triggering a starburst. We also find that a significant fraction (20–30 per cent) of the galaxies in our starburst samples have morphologies indicative of either an ongoing or a recent tidal interaction and/or merger. These findings notwithstanding, there remain a significant portion of starburst galaxies where such local environmental influences are not in any obvious way playing a triggering role, leading us to conclude that starbursts can also be internally driven.  相似文献   
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