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1.
Generally, it is assumed that UV-light, high temperature or reactive molecules like O3 and OH are needed to activate gas reactions in air. In consequence, the catalytic activity on natural materials such as sand and soil on the earth's surface is assumed to be insignificant. We have measured O2-dissociation rates on natural quartz sand at 40˚C and compared these with O2-dissociation rates near 500˚C on materials with well-known catalytic activity. In terms of probabilities for dissociation of impinging O2-molecules the measured rates are in the 10−12–10−4 range. We have also measured dissociation rates of H2 and N2, water-formation from H2 and O2 mixtures, exchange of N between N2, NO x and a breakdown of HNO3, NO2 and CH4 on natural quartz sand at 40˚C. The measured rates together with an effective global land area have been used to estimate the impact of thermodynamically driven reactions on the earth's surface on the global atmospheric budgets of H2, NO2 and CH4. The experimental data on natural quartz sand together with data from equilibrium calculations of air suggest that an expected increase in anthropogenic supply of air pollutants, such as NO x or other “reactive” nitrogen compounds, hydrogen and methane, will be counter-acted by catalysis on the earth's surface. On the other hand, at Polar Regions and boreal forests where the “reactive” nitrogen concentration is below equilibrium, the same catalytic effect activates formation of bio-available nitrogen compounds from N2, O2 and H2O.  相似文献   

2.
In order to investigate the upper troposphere/lower stratosphere (UTLS) region of the earth's atmosphere, ESA/ESTEC (European space agency) is considering the opportunity to develop the spaceborne limb sounding millimeter sensor “MASTER” (millimeter wave acquisitions for stratosphere/troposphere exchange research). This instrument is part of the “atmospheric composition explorer for chemistry and climate interactions” (ACECHEM) project. In addition, ESA/ESTEC is developing the “MARSCHALS” (millimeter-wave airborne receiver for spectroscopic characterization of atmospheric limb sounding) airborne instrument which will demonstrate the feasibility of MASTER. The present paper describes the line-by-line database which was generated in order to meet at best the needs of the MASTER (or MARSCHALS) instrument. The linelist involves line positions, line intensities, line broadening and line shift parameters in the 294–305, 316–325, 342–348, 497–506 and 624–626 GHz spectral microwindows. This database was first generated for the target molecules for MASTER (H2O, O3, N2O, CO, O2, HNO3, HCl, ClO, CH3Cl, BrO). In addition, ten additional molecules (SO2, NO2, OCS, H2CO, HOCl, HCN, H2O2, COF2, HO2 and HOBr) had also to be considered in the database as “possible interfering species” for the retrieval of the target molecules of MASTER. The line parameters were derived, depending on their estimated accuracy, (i) from a combination of spectral parameters included in the JPL and HITRAN catalogs (ii) from data taken into the literature or (iii) using data obtained through experimental measurements (and/or) calculations performed during the present study.  相似文献   

3.
We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO4) on the concentrations and budgets of NOx, SOx, O3 and H2O2. Laboratory studies have shown that the aqueous reaction of HNO4aq withHSO 3aq, and the uni-molecular decomposition of the NO4 anion to form NO2 (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO 3aq with HNO4aq to the overall in-cloud conversion of SO2 to SO4 2–, a simultaneous decrease of other oxidants (most notably H2O2) more than compensated the increase in SO4 2– production. The strongest influence of heterogeneous HNO4 chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H2O2 between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO2 was increased by 10% to 20% and SO4 2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO4 reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO4 in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.  相似文献   

4.
5.
大气过氧化氢(H2O2)是一种重要的光化学产物,也是硫酸盐气溶胶生成及降水酸化过程的关键氧化剂。然而,我国对H2O2的观测研究较少,尤其对雾霾期间H2O2浓度变化特征认识不足。该文介绍了冬春时段(2016年12月-2017年4月)在北京城区中国气象局的H2O2观测结果,并结合同期O3,PAN,NOX,PM2.5等污染物和气象要素观测数据,分析H2O2浓度变化特征与影响因素。观测结果表明:观测期间H2O2体积混合比(简称为浓度)为(0.65±0.59)×10-9,其中,春季浓度(0.83±0.67)×10-9高于冬季浓度(0.51±0.47)×10-9;H2O2平均日变化基本呈现单峰特征,峰值出现在18:00-21:00,比其他地区峰值出现稍晚,并滞后于O3峰值时间4~7 h;相对湿度对H2O2日峰值时间和浓度水平有影响,小于55%时日峰值出现于18:00-24:00,平均峰值浓度1.52×10-9;大于65%时日峰值出现于11:00-16:00,日峰值浓度均小于1×10-9。H2O2,O3和PAN虽然同属光化学产物,但在不同污染状况下浓度水平和变化趋势差异明显;H2O2清洁日峰值浓度高于污染日,但11:00-15:00污染日浓度略高于清洁日。  相似文献   

6.
A one-dimensional cloud model with size-resolved microphysics and size-resolved aqueous-phase chemistry, driven by prescribed dynamics, has been used to study gas scavenging by weak precipitation developed from low-level, warm stratiform clouds. The dependence of the gas removal rate on the physical and chemical properties of precipitation has been explored under controlled initial conditions. It is found that the removal of four gaseous species (SO2, NH3, H2O2 and HNO3) strongly depends on the total droplet surface area, regardless the mean size of droplets. The removal rates also correlate positively with the precipitation rate, especially for precipitation having a mean radius larger than 20 μm. The dependence of the scavenging coefficients on the total droplet surface area is stronger than on the precipitation rate. The removal rates of SO2, NH3 and H2O2 by precipitation strongly depend on the others' initial concentrations. When NH3 (or H2O2) concentration is much lower than that of SO2, the removal rate of SO2 is then controlled by the concentration of H2O2 (or NH3). The removal of NH3 (or H2O2) also directly depends on the concentration of SO2. NH3 and H2O2 can also indirectly affect each other's removal rate through interaction with SO2. The scavenging coefficient of SO2 increases with the concentration ratio of NH3 to SO2 if the ratio is larger than 0.5, while the scavenging coefficient of NH3 increases with the concentration ratio of SO2 to NH3 when the ratio is smaller than 1. The scavenging coefficient of H2O2 generally increases with the concentration ratio of SO2 to H2O2. Although the Henry's law equilibrium approach seems to be able to simulate gas scavenging by cloud droplets, it causes large errors when used for simulating the scavenging of soluble gas species by droplets of precipitating sizes.  相似文献   

7.
Hoarfrost and rime analysis was based on the collection of samples between 2003 and 2006 from 8 sites, which represent both lowland (northern) and mountainous (southern) parts of Poland. On the other hand 4 of these sites belong to “urban” and 4 to “rural” category. pH, conductivity, SO42−, NO3, Cl, H+, NH4+, Ca2+, Mg2+, Na+, K+ have been determined in order to study the chemistry of hoarfrost and rime. Higher total inorganic ionic content (TIC) in hoarfrost and rime (2.46 meq·l−1 and 1.23 meq·l−1 respectively) was observed when compared with precipitation (0.37 meq·l−1). Large variability of TIC and chemical composition of individual samples were typical at each of the measurement sites depending on emission patterns, atmospheric conditions and local terrain topography. Higher concentrations of both hoarfrost and rime occurred in southern (mountainous) rather than in northern (lowland) part of Poland which can be explained by worse pollutant dispersion conditions in the south. The surprisingly low hoarfrost concentrations in urban coastal stations in the area of the Bay of Gdansk were attributed to the cleaning effect of nocturnal breeze-type circulation, best pronounced in cool part of the year. Due to relatively high pollutant concentration and long duration, hoarfrost and rime are at least significant factors in environmental processes in different ecosystems in Poland.  相似文献   

8.
A new version of an atmospheric pressure chemical ionisation mass spectrometer has been developed for ground based in situ atmospheric measurements of OH and total peroxy (HO2 + organic peroxy) radicals. Based on the previously developed principle of chemical conversion of OH radicals to H2SO4 in reaction with SO2 and detection of H2SO4 using an ion molecule reaction with NO3, the new instrument is equipped with a turbulent chemical conversion reactor allowing for measurements in moderately polluted atmosphere at NO concentrations up to several ppb. Unlike other similar devices, where the primary NO3 ions are produced using radioactive ion sources, the new instrument is equipped with a specially developed corona discharge ion source. According to laboratory measurements, the overall accuracy and detection limits are estimated to be, respectively, 25% and 2 × 105 molecule cm-3 for OH and 30% and 1 × 105 molecule cm-3 for HO2 at 10 min integration times. The detection limit for measurements of OH radicals under polluted conditions is 5 × 105 molecules cm-3 at 10 min integration times. Examples of ambient air measurements during a field campaign near Paris in July 2007 are presented demonstrating the capability of the new instrument, although with reduced performance due to the employment of non isotopic SO2.  相似文献   

9.
Photochemical indicators for determination of O3–NOx–ROG sensitivity and their sensitivity to model parameters are studied for a variety of polluted conditions using a comprehensive mixed-phase chemistry box model and the novel automatic differentiation ADIFOR tool. The main chemical reaction pathways in all phases, interfacial mass transfer processes, and ambient physical parameters that affect the indicators are identified and analyzed. Condensed mixed-phase chemical mechanisms are derived from the sensitivity analysis.Our results show that cloud chemistry has a significant impact on the indicators and their sensitivities, particularly on those involving H2O2, HNO3, HCHO, and NOz. Caution should be taken when applying the established threshold values of indicators in regions with large cloud coverage. Among the commonly used indicators, NOy and O3/NOy are relatively insensitive to most model parameters, whereas indicators involving H2O2, HNO3, HCHO, and NOz are highly sensitive to changes in initial species concentrations, reaction rate constants, equilibrium constants, temperature, relative humidity, cloud droplet size, and cloud water content.  相似文献   

10.
In view of the uncertainty of the origin of the secular increase of N2O, we studied heterogeneous processes that contribute to formation of N2O in an environment that comes as close as possible to exhaust conditions containing NO and SO2, among other constituents. The N2O formation was followed using electron capture gas chromatography (ECD-GC). The other reactants and intermediates (SO2, NO, NO2 and HONO) were monitored using gas phase UV-VIS absorption spectroscopy. Experiments were conducted at 298 and 368 K as well as at dry and high humidity (approaching 100% rh) conditions. There is a significant heterogeneous rate of N 2 O formation at conditions that mimic an exhaust plume from combustion processes.The simultaneous presence of NO, SO2, O2 in the gas phase and condensed phase water, either in the bulk liquid or adsorbed state has been confirmed to be necessary for the production of significant levels of N2O. The stoichiometry of the overall reaction is: 2 NO+SO2+H2O N2O+H2SO4. The maximum rate of N2O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. A significant rate of N2O formation at 368 K at 100% rh was also observed in the absence of a bulk substrate. The diffusion of both gas and liquid phase reactants is not rate limiting as the reaction kenetics is dominated by the rate ofN2O formation under the experimental conditions used in this work. The simultaneous presence of high humidity (90–100% rh at 368 K) and bulk condensed phase results in the maximum rate and final yield of N2O approaching 60% and 100% conversion after one hour in the presence of amorphous carbon and fly-ash, respectively.Work performed in partial fulfillment of the requirements of Dr ès Sciences at EPFL.  相似文献   

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