Characterization of diurnal cycles in ZTD from a decade of global GPS observations

The diurnal cycle of the tropospheric zenith total delay (ZTD) is one of the most obvious signals for the various physical processes relating to climate change on a short time scale. However, the observation of such ZTD oscillations on a global scale with traditional techniques (e.g. radiosondes) is restricted due to limitations in spatial and temporal resolution. Nowadays, the International GNSS Service (IGS) provides an important data source for investigating the diurnal and semidiurnal cycles of ZTD and related climatic signals. In this paper, 10 years of ZTD data from 1997 to 2007 with a 2-hour temporal resolution are derived from global positioning system (GPS) observations taken at 151 globally distributed IGS reference stations. These time series are used to investigate diurnal and semidiurnal oscillations. Significant diurnal and semidiurnal oscillations of ZTD are found for all GPS stations used in this study. The diurnal cycles (24 hours period) have amplitudes between 0.2 and 10.9 mm with an uncertainty of about 0.5 mm and the semidiurnal cycles (12 h period) have amplitudes between 0.1 and 4.3 mm with an uncertainty of about 0.2 mm. The larger amplitudes of the diurnal and semidiurnal ZTD cycles are observed in the low-latitude equatorial areas. The peak times of the diurnal cycles spread over the whole day, while the peak value of the semidiurnal cycles occurs typically about local noon. These GPS-derived diurnal and semidiurnal ZTD signals are similar with the surface pressure tides derived from surface synoptic pressure observations, indicating that atmospheric tides are the main driver of the diurnal and semidiurnal ZTD variations.     

反应HO2+O→OH+O2对OH夜气辉辐射的贡献

本文探讨了OH Meinel夜气辉辐射的光化学模式,给出OH(ν≤9)分子数密度分布的计算通式,重点研究了化学反应HO2 O→OH(ν≤6) O2对ν≤6各振动能级上OH分子数密度分布以及(ν′—ν″)(ν′≤6)振动带气辉辐射的影响.结果表明,该反应对数密度的贡献随振动能级的减小而增大,对(ν′—ν″)振动带辐射的贡献随着较高振动能级ν′的减小而增大,以春分时为例,它可使第1振动能级上的OH分子最大数密度和(1—0)带的最大辐射率增加约33%,第6振动能级上的最大数密度和(6—ν″)带的最大辐射率增加约7%,(1—0)带的辐射强度增加约30%,(6—ν″)带的强度增加约11%.该反应使各振动能级上分子数密度的高度分布剖面以及各振动带体辐射率的高度分布剖面变宽,最大数密度、最大发射率所处的高度下降1km左右.此外,该反应的影响程度随着原子氧密度的降低而增大,随着温度的升高而增大,并且在夏至时最大,在冬至时最小.     

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10^-12 cm³ s^-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10^-12 cm³ s^-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.     

Responses of the tropospheric ozone and odd hydrogen radicals to column ozone change

The response of tropospheric ozone to a change in solar UV penetration due to perturbation on column ozone depends critically on the tropospheric NO _x (NO+NO₂) concentration. At high NO _x or a polluted area where there is net ozone production, a decrease in column ozone will increase the solar UV penetration to the troposphere and thus increase the tropospheric ozone concentration. However, the opposite will occur, for example, at a remote oceanic area where NO _x is so low that there is net ozone destruction. This finding may have important implication on the interpretation of the long term trend of tropospheric ozone. A change in column ozone will also induce change in tropospheric OH, HO₂, and H₂O₂ concentrations which are major oxidants in the troposphere. Thus, the oxidation capacity and, in turn, the abundances of many reduced gases will be perturbed. Our model calculations show that the change in OH, HO₂, and H₂O₂ concentrations are essentially independent of the NO _x concentration.     

Prediction of the abiotic degradability of organic compounds in the troposphere

A statistically relevant correlation between the reaction rate coefficient, k _OH, for the OH radical reaction with 161 organic compounds in the gas phase at 300 K, and the corresponding vertical ionisation energies E _i,v, reveals two classes of compounds: aromatics where –log(k _OH/cm³s^-1)3/2E _i,v(eV)–2 and aliphatics where –log(k _OH/cm³s^-1)4/5E _i,v(eV)+3. The prediction of the rate coefficient, k _OH, for the reaction of OH with organic molecules from the above equations has a probability of about 90%. Assuming a global diurnal mean of the OH radical concentration of 5×10⁵ cm³, the upper limit of the tropospheric half-life of organic compounds and their persistence can be estimated.     

The latitudinal distribution of carbon monoxide across the pacific from California to Antarctica

The results of a research study of the carbon monoxide concentration from California to 90° S, Antarctica are presented. The data both extend and support other research studies of the latitudinal distribution of carbon monoxide in that higher concentrations are evident over the Northern Hemisphere than over the Southern Hemisphere. Carbon monoxide concentrations range between 50 to 60 ppb with a few peaks into the 60s in the latitudinal area south of the ITCZ and values of 80 ppb or higher at latitudes north of Hawaii. A comparison is also made of carbon monoxide and ozone concentrations along the flight tract between California and Antarctica, over the Ellsworth Mountains of Antarctica, and between 78° S and the South Pole. These ozone-carbon monoxide data show statistically significant negative correlations in the upper troposphere and lower stratosphere over Antarctica. It is believed that this is a good indication of mixing across the tropopause.     

大气中一氧化碳浓度变化的模拟研究

应用全球二维大气化学模式,模拟了CO、CH4和OH自由基等成分自工业革命到2020年的长期变化.模拟的全球CO平均体积分数在1840年、1991年和2020年分别为27×10-6、76×10-6和105×10-6.从1840到1991年,OH自由基数浓度从7.17×105个分子/cm3下降到5.79×105个分子/cm3,降低了19%.模拟的CH4长期变化与冰芯资料相符.模拟的20世纪80年代CO体积分数年增长率为1.03%～1.06%.大气中CO在20世纪90年代前是增长的,而到90年代初观测到CO体积分数突然下降.应用二维大气化学模式对此原因进行了模拟研究,结果表明,CO排放源的减少是CO体积分数下降的主要因子,平流层臭氧减少是另一个重要因子.尽管CO排放源的减少对大气CH4增长率的变化有较大影响,而CH4排放源减少对CO体积分数变化却几乎没有影响.     

NUMERICAL SIMULATION OF ATMOSPHERIC METHANE TRENDS OVER THE LAST 150 YEARS*

A global two-dimensional chemistry model is developed to study long-term trends of CH₄ since industrial revolution.The sources of CH₄,CO and NO_x are parameterized as functions of latitude and time.With two long-term emission scenarios,long-term trends of CH₄ are simulated.The results have a good agreement with observation from ice cores.The modeled CH₄ increased from 760 ppbv in 1840 to 1611.9 ppbv in 1991, while the modeled number concentration of tropospheric OH decreased from 7.17×10⁵ cm^-3 in 1840 to 5.79×10⁵ cm^-3 in 1991.The increase of atmospheric CH₄ can be explained by the increase of emission of CH₄ and build-up because of decrease of OH radicals that remove CH₄ from the atmosphere.The model is also used to simulate the distribution of CH₄.Comparisons between the model results and observations show that the model can simulate both latitudinal distribution and seasonal variation of CH₄ well.     

Location and quantitative analysis of OH in coesite

 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm⁻¹ (ν₁ to ν₃, respectively) and two very weak bands at 3296 and 3210 cm⁻¹ (ν₄ and ν₅, respectively). The band at 3516 cm⁻¹ is strongly asymmetric and can be resolved into two bands, 3528 (ν_2a) and 3508 (ν_2b) cm⁻¹, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ _{i ,tot}=190 000 ± 30 000 l mol⁻¹ _H2O cm⁻²). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν₁, ν₂, and ν₃ bands decrease linearly with pressure. The mode Grüneisen parameters for ν₁, ν₂, and ν₃ are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν₁, ν₂, and ν₃ bands increase from 35, 21, and 28 cm⁻¹ in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si^4+(Si2)+4O²⁻= ^[4]□^(Si2) + 4OH⁻, which gives rise to four vibrations, ν₁, ν_2a, ν_2b, and ν₃. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν₄ and ν₅ may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001     

MEASUREMENTS AND MODEL SIMULATIONS OF SURFACE OZONE VARIATIONS AT DIFFERENT BACKGROUND CONCENTRATIONS OF THE PRECURSORS

Ozone photochemical production and loss in very different environments at Waliguan baselinestation and Lin'an background station were simulated by using the measurement data and photo-chemical box model.The results show that net ozone photochemical production rate is negative,about 0.5 ppb/d,at Waliguan baseline sation,because of very low precursor concentrations.Butat Lin'an background station,the net photochemical ozone production is positive,about 2—3 ppb/h.which is very closed with the measurement at Lin'an.That means ozone production was con-trolled by photochemical reactions at Lin'an background station,because of the higher precursorconcentrations.The net destruction rate,at Waliguan Mt.,is not large,so that future increase inanthropogenic emission of reactive nitrogen will lead to larger production rates of steady-state O_3concentration.