排序方式： 共有99条查询结果，搜索用时 15 毫秒
1.
Experiments were conducted in the field to determine the non-chemical loss rate of methyl iodide in seawater and to examine production rates of methyl halides. The loss rate of added C13 labelled methyl iodide, present at concentrations similar to those found in seawater, corrected for chemical loss due to reaction with Cl− varied from < 1 to 18% day− 1, with a mean value of 7%. This rate of loss is much lower than that which was proposed by Bell et al. [Bell, N., Hsu, L., Jacob, D. J., Schultz, M. G., Blake, D. R., Butler, J. H., King, D. B., Lobert, J. M., Maier-Reimer, E., 2002. Methyl iodide: Atmospheric budget and use as a tracer of marine convection in global models, Journal of Geophysical Research-Atmospheres 107(D17), 4340-4351.] to account for the large discrepancies between observed and predicted mid-latitude concentrations of CH3I based on their global photochemical source model. The suitability of several types of container for seawater incubations was studied and only quartz tubes appeared to be free of experimental artifact. Collapsible polyvinyl fluoride containers showed major production of methyl halides on irradiation with simulated sunlight. Polyethylene containers caused spurious production of methyl iodide at lower rates. 相似文献
2.
Elizabeth B. Kujawinski Rossana Del Vecchio Neil V. Blough Geoffrey C. Klein Alan G. Marshall 《Marine Chemistry》2004,92(1-4):23
Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems. 相似文献
3.
This work presents the temporal evolution and spatial distribution of nitrogen dioxide (NO2) measured with the help of passive diffusion tubes in different environments: rural, sub-urban, urban, at La Réunion Island in December 1997 and November 2000 (austral spring), respectively. NO2 concentration exhibits notable enhancement from 1997 to 2000. For instance, its mean concentration was 16 and 20 μg/m3 in December 1997 and November 2000, respectively, at La Réunion Island, especially in inhabited regions due to increase of local anthropogenic activities, mainly traffic circulation, in the absence of house heating and biomass burning. We also observe a net increase of pollutant levels by a factor two in rural/remote areas within 3 years, which is tied to the extension of inhabited areas and air-flows from enhanced local sources. The increase of atmospheric pollutants is mainly due to enhancement of anthropogenic activities (traffic) since the 1990s at La Réunion Island, which results from a constant increase of population and consequently, from a higher number of vehicles in circulation. Importantly, in cities like Saint-Denis, where traffic network has been subject to notable improvement (e.g. single to double lanes, etc.), pollutant levels exhibit little variability as in temperate continental latitudes. Semi-continuous NO2 concentration measured in parallel with ozone in November 2000 also showed that daytime photochemical ozone production is influenced by pollutant and precursor (NO2) levels at Saint-Denis, while nighttime ozone increase is mainly tied to dynamical processes. The November 2000 ozone diurnal pattern is notably different from that observed in September 1995, during which a daytime ozone loss was observed, pointing out that atmospheric conditions have been subject to notable changes, i.e., clean to moderately polluted, within a few years at La Réunion Island. The results presented here point out that the ‘source enhancement effect’ is superimposed on dynamical and photochemical processes to influence pollutants variability and hence atmospheric chemistry, in a quite ‘pristine’ tropical oceanic region. 相似文献
4.
5.
Robert J. Kieber Joan D. Willey Robert F. Whitehead Seth N. Reid 《Journal of Atmospheric Chemistry》2007,58(3):219-235
Significant photodegradation of chromophoric dissolved organic matter (CDOM) in rainwater was observed after exposure to simulated
sunlight. Fluorescence excitation emission spectra (EEMS) of precipitation revealed the presence of four major peaks all of
which degraded upon photolysis with the greatest loss in the region characteristic of marine CDOM. Photobleaching of absorbance
also occurred in the wavelength region between 250 and 375 nm with the greatest loss of absorbance in the upper end of the
UV-A region near 275 nm. There was a strong positive correlation between absorbance loss and total integrated fluorescence
loss suggesting these optical properties and the degree to which they are photobleached in rainwater are directly related.
The quantum yield of CDOM photodegradation in rainwater decreased dramatically with increasing wavelength and decreasing energy
of incoming radiation with the average quantum yield at 325 nm approximately an order of magnitude greater than at 460 nm.
The similarity of photolytic response between rainwater and Cape Fear estuarine CDOM indicates that some fraction of the compounds
that make up rainwater CDOM may be derived from surface sources and/or that the processes that produce or modify humic-like
substances in the atmosphere result in similar types of compounds as non-atmospheric processes. 相似文献
6.
R. Krishna Rao Vupputuri 《Pure and Applied Geophysics》1978,117(3):448-485
two-dimensional time dependent model of the stratosphere incorporating the major interactions between radiative-photochemical and dynamical processes is described. The main prognostic equations considered are the thermodynamic equation and the general conservation equation for the minor chemical constituents representing the odd oxygen (O
x
=O+('D)+O3), odd hydrogen (HO
x
=HO+HO2), N2O, odd nitrogen (NO
x
=NO+NO2+HNO3), CF2Cl2, CFCl3 and odd chlorine (Cl
x
=Cl+ClO+HCl). The zonal wind and mean meridional circulations are determined diagnostically by the integration of the thermal wind equation and the stream function equation in the meridional plane espectively. The large scale eddy processes are parameterized in terms of zonal mean quantities using the generalized diffusion formulation on a sloping surface. The radiative heating and cooling and the hotochemical sources and sinks are incorporated in a form which allows for the major interactions among the minor trace constituents, temperature and mean circulation.Two integrations consisting of natural stratosphere and a stratosphere contaminated by the chlorofluoromethanes through lower boundary fluxes are carried out for 23 model years by changing the declination of the sun every day and using 6-hour time step. The model simulations of temperature, mean circulation, ozone, HO
x
, N2O and NO
x
in the meridional plane for the normal stratosphere, show satisfactory agreement with the available observations. Based on the results of second integration it is found that the injection of chlorofluoromethanes in the atmosphere at the estimated current production rates can lead to significant changes in the meridional distribution of ozone, temperature and NO
x
in the middle and upper stratosphere. The results also indicate that the percentage total ozone depletion increases from tropics to high latitudes and from summer to winter high latitudes. Also discussed are the results of additional experiments incorporating the reaction of HO2 with NO and the reactions involving ClNO3. 相似文献
7.
A one-dimensional photochemical-transport model for the martian lower atmosphere has been developed to study the diurnal cycles of wave-photochemistry coupling. The model self-consistently calculates water vapor mixing ratio profiles, which exhibit strong vertical and diurnal variations mainly due to the high sensitivity of the saturation vapor pressure to temperature variation. The dynamical coupling of water vapor caused by the temperature variation induced by tidal waves, vertical transport parameterized by eddy diffusion, and linear relaxation introduced in condensation-sublimation processes all have similar timescales of diurnal variation. This leads to a significant asymmetric distribution of water vapor concentration as a function of local time. As a result, the net effect of the temperature variation by tidal waves depletes the water vapor concentration in its diurnal mean. The coupling processes also deplete the diurnally averaged HOx concentration, which in turn leads to significant enhancements of both ozone concentration and the associated airglow emissions in the martian atmosphere. The model also shows explicitly the importance of photochemical-transport coupling to the airglow emissions and its implications in species retrievals when the photochemical times of the excited states are comparable to the timescale of diurnal variation. 相似文献
8.
The neutral gas environment of a comet is largely influenced by dissociation of parent molecules created at the surface of the comet and collisions of all the involved species. We compare the results from a kinetic model of the neutral cometary environment with measurements from the Neutral Mass Spectrometer and the Dust Impact Detection System onboard the Giotto spacecraft taken during the fly-by at Comet 1P/Halley in 1986. We also show that our model is in good agreement with contemporaneous measurements obtained by the International Ultraviolet Explorer, sounding rocket experiments, and various ground based observations.The model solves the Boltzmann equation with a Direct Simulation Monte Carlo technique (Tenishev, V., Combi, M., Davidsson, B. [2008]. Astrophys. J. 685, 659-677) by tracking trajectories of gas molecules and dust grains under the influence of the comet’s weak gravity field with momentum exchange among particles modeled in a probabilistic manner. The cometary nucleus is considered to be the source of dust and the parent species (in our model: H2O, CO, H2CO, CO2, CH3OH, C2H6, C2H4, C2H2, HCN, NH3, and CH4) in the coma. Subsequently our model also tracks the corresponding dissociation products (H, H2, O, OH, C, CH, CH2, CH3, N, NH, NH2, C2, C2H, C2H5, CN, and HCO) from the comet’s surface all the way out to 106 km.As a result we are able to further constrain cometary the gas production rates of CO (13%), CO2 (2.5%), and H2CO (1.5%) relative to water without invoking unknown extended sources. 相似文献
9.
First measurements of SO2 and SO in the Venus mesosphere (70-100 km) are reported. This altitude range is distinctly above the ∼60-70 km range to which nadir-sounding IR and UV investigations are sensitive. Since July 2004, use of ground-based sub-mm spectroscopy has yielded multiple discoveries. Abundance of each molecule varies strongly on many timescales over the entire sub-Earth Venus hemisphere. Diurnal behavior is evident, with more SO2, and less SO, at night than during the day. Non-diurnal variability is also present, with measured SO2 and SO abundances each changing by up to 2× or more between observations conducted on different dates, but at fixed phase, hence identical sub-Earth Venus local times. Change as large and rapid as a 5σ doubling of SO on a one-week timescale is seen. The sum of SO2 and SO abundances varies by an order of magnitude or more, indicating at least one additional sulfur reservoir must be present, and that it must function as both a sink and source for these molecules. The ratio SO2/SO varies by nearly two orders of magnitude, with both diurnal and non-diurnal components. In contrast to the strong time dependence of molecular abundances, their altitude distributions are temporally invariant, with far more SO2 and SO at 85-100 km than at 70-85 km. The observed increase of SO2 mixing ratio with altitude requires that the primary SO2 source be upper mesospheric photochemistry, contrary to atmospheric models which assert upward transport as the only source of above-cloud SO2. Abundance of upper mesospheric aerosol, with assumption that it is composed primarily of sulfuric acid, is at least sufficient to provide the maximum gas phase (SO + SO2) sulfur reported in this study. Sulfate aerosol is thus a plausible source of upper mesospheric SO2. 相似文献
10.
The atmosphere of Mars does little to attenuate incoming ultraviolet (UV) radiation. Large amounts of UV radiation sterilize the hardiest of terrestrial organisms within minutes, and chemically alter the soil such that organic molecules at or near the surface are rapidly destroyed. Thus the survival of any putative martian life near the surface depends to a large extent on how much UV radiation it receives. Variations in small-scale geometry of the surface such as pits, trenches, flat faces and overhangs can have a significant effect on the incident UV flux and may create “safe havens” for organisms and organic molecules. In order to examine this effect, a 1-D radiative transfer sky model with 836 meshed points (plus the Sun) was developed which includes both diffuse and direct components of the surface irradiance. This model derives the variation of UV flux with latitude and an object's Geometric Shielding Ratio (a ratio which describes the geometry of each situation). The best protection is offered by overhangs with flux reduced to a factor of 1.8±0.2×10−5 of the unprotected value, a reduction which does not vary significantly by latitude. Pits and cracks are less effective with a reduction in UV flux of only up to 4.5±0.5×10−3 for the modeled scenarios; however, they are more effective for the same geometric shielding ratio than overhangs at high latitudes due to the low height of the Sun in the sky. Lastly, polar faces of rocks have the least effective shielding geometry with at most a 1.1±0.1×10−1 reduction in UV flux. Polar faces of rocks are most effective at mid latitudes where the Sun is never directly overhead, as at tropical latitudes, and never exposes the back of the rock, as at polar latitudes. In the most favorable cases, UV flux is sufficiently reduced such that organic in-fall could accumulate beneath overhanging surfaces and in pits and cracks. As well, hardy terrestrial microorganisms such as Bacillus pumilus could persist for up to 100 sols on the outer surfaces of typical spacecraft or several tens of martian years in the most shielded surface niches. 相似文献