Parameterization of the Absorption of the H2O Continuum, CO2, O2, and Other Trace Gases in the Fu-Liou Solar Radiation Program

The absorption properties of the water vapor continuum and a number of weak bands for H2O, O2, CO2, CO, N2O, CH4, and O3 in the solar spectrum are incorporated into the Fu-Liou radiation parameterization program by using the correlated k-distribution method (CKD) for the sorting of absorption lines. The overlap absorption of the H2O lines and the H2O continuum (2500-14500 cm^-1) are treated by taking the two gases as a single-mixture gas in transmittance calculations. Furthermore, in order to optimize the computation efforts, CO2 and CH4 in the spectral region 2850-5250 cm^-1 are taken as a new singlemixture gas as well. For overlap involving other absorption lines in the Fu-Liou spectral bands, the authors adopt the multiplication rule for transmittance computations under which the absorption spectra for two gases are assumed to be uncorrelated. Compared to the line-by-line (LBL) computation, it is shown that the errors in fluxes introduced by these two approaches within the context of the CKD method are small and less than 0.48% for the H20 line and continuum in the 2500-14500 cm^-1 solar spectral region, -1% for H2O (line) H2O (continuum) CO2 CH4 in the spectral region 2850-5250 cm^-1, and -1.5% for H2O (line) H2O (continuum) O2 in the 7700-14500 cm^-1 spectral region. Analysis also demonstrates that the multiplication rule over a spectral interval as wide as 6800 cm^-1 can produce acceptable errors with a maximum percentage value of about 2% in reference to the LBL calculation. Addition of the preceding gases increases the absorption of solar radiation under all sky conditions. For clear sky, the increase in instantaneous solar absorption is about 9%-13% (-12 W m^-2) among which the H20 continuum produces the largest increase, while the contributions from O2 and CO2 rank second and third, respectively. In cloudy sky, the addition of absorption amounts to about 6-9 W m^-2. The new, improved program with the incorporation of the preceding gases produces a smaller solar absorption in clouds due to the reduced solar flux reaching the cloud top.     

IAP AGCM中短波辐射方案的改进研究I·引入Fu-Liou短波辐射方案

冰云和水云对短波辐射性质(消光系数、单次散射反照率及不对称因子)的影响很不相同,应分别计算。Fu-Liou短波辐射方案(以下称Fu-Liou code)就是对冰云和水云分别采用了不同的参数化方案,云的短波辐射性质直接由云的物理性质来确定。因此,Fu-Liou code在云的处理方面物理意义更清晰且很合理。作者将Fu-Liou code引入IAP AGCM-II中,称为Version 2。对当代气候场的模拟结果表明,Version 2的各个物理过程是协调匹配的,且其对气候场的模拟性能是好的,从而为进一步改进IAP AGCM的短波辐射方案提供了很好的模式基础。     

关于云和云天大气对太阳辐射的吸收异常

本文是关于云和云天大气对太阳辐射吸收异常问题的一个综述，总结了到目前为止的对水云异常吸收的一些解释，指出这些解释的合理性和缺陷。本文的重点在于介绍近年来论争激烈的有云大气的异常吸收问题，对存在和不存在增强吸收的两种截然相反的观点都做了较详细的评述。     

IAP AGCM中短波辐射方案的改进研究II·短波辐射方案的改进

在Version 2的基础上,对短波辐射方案进行进一步的改进:引入了新增非灰体气体吸收效应、冰晶粒子形状效应和尺度效应以及云的不均匀性效应(称为Version 3)。数值模拟试验结果表明:Version 3能更好地模拟出全球冬、夏季的降水场、海平面气压场及地表气温场的主要分布特征,并且能相当准确地反映出这几个场的季节性变化特征。Version 3对这3个场的模拟能力明显优于原版本(Version 1)。此外,它对东亚地区的季风降雨具有很好的模拟能力,能较好地反映东亚区域降水的季节性变化。可见,Version 3为进一步研究云-辐射相互作用提供了很好的模式基础。本工作还清楚地表明,模式的进一步发展必须进行对相关物理过程中各个因子的更精确刻画,只有这样,模式才能得到更好的模拟能力。     

地基曙暮光光谱观测反演平流层O3和NO2柱含量

用差分光学吸收光谱(DOAS)方法,从曙暮光天顶散射可见光光谱资料反演了北京上空的O3和NO2柱含量,并对反演结果进行了验证和误差分析.斜柱含量的反演采用了线性和非线性最小二乘拟合方法,拟合时考虑了O3、NO2和H2O的吸收、Ring效应和散射的影响;斜柱含量除以空气质量因子转换成垂直柱含量.空气质量因子的计算使用伪球面DISORT辐射传输模式.O3和NO2总量的检验分别用北京的Dobson O3资料和卫星SAGE Ⅱ的NO2廓线资料.反演的O3总量与Dobson O3总量相比偏差小于10%;NO2总量与SAGE Ⅱ的偏差约20%.     

Measurements of Trace Gases in the Inflow of South China Sea Background Air and Outflow of Regional Pollution at Tai O, Southern China

We present a 16-month record of ozone (O₃), carbon monoxide (CO), total reactive nitrogen (NO_y), 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, S_lnx = Aτ^{− b}, (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.     

On the scavenging of SO2 by cloud and rain drops: IV. A wind tunnel and theoretical study of the absorption of SO2 in the ppb(v) range by water drops in the presence of H2O2

An experimental study involving the Mainz vertical wind tunnel is described where the rate of SO₂ removed from the air by freely suspended water drops was measured for SO₂ concentrations in the gas phase ranging between 50 and 500 ppb, and for various H₂O₂ concentrations in the liquid phase. In a first set of experiments, the pH inside the SO₂ absorbing drops was monitored by means of colour pH indicators added to the drops. In a second set of experiments, the amount of SO₂ scavenged by the drops was determined as sulfate by an ionchromatograph after the drops had been removed from the vertical air stream of the wind tunnel after various times of exposure to SO₂. The results of our experimental study were compared with the theoretical gas diffusion model of Walcek and Pruppacher which was reformulated for the case of SO₂ concentrations in the ppbv(v) range for which the main resistance to diffusion lies in the gas phase surrounding the drop. Excellent agreement between experiment and theory was obtained. Encouraged by this agreement, the theory was used to investigate the rate of sulfate production inside a drop as a function of pH. The sulfate production rate, which includes transport and oxidation, was compared with the production rate based on bulk equilibrium, as cited in the literature.     

On the scavenging of SO2 by cloud and raindrops: II. An experimental study of SO2 absorption and desorption for water drops in air

For the purpose of testing our previously described theory of SO₂ scavenging a laboratory investigation was carried out in the UCLA 33 m long rainshaft. Drops with radii between 250 and 2500 m were allowed to come to terminal velocity, after which they passed through a chamber of variable length filled with various SO₂ concentrations in air. After falling through a gas separating chamber consisting of a fluorocarbon gas the drops were collected and analyzed for their total S content in order to determine the rate of SO ₂ absorption.The SO₂ concentration in air studied ranged between 1 and 60% (v). Such relatively large concentrations were necessary due to the short times the drops were exposed to SO₂ in the present setup. The present experimental results were therefore not used to simulate atmospheric conditions but rather to test our previously derived theory which is applicable to any laboratory or atmospheric condition. Comparison of our studies with the results from our theory applied to our laboratory conditions led to predicted values for the S concentration in the drops which agreed well with those observed if the drops had radii smaller than 500 m. In order to obtain agreement between predicted and observed S concentrations in larger drops, an empirically derived eddy diffusivity for SO₂ in water had to be included in the theory to take into account the effect of turbulent mixing inside such large drops.In a subsequent set of experiments, drops initially saturated with S (IV) were allowed to fall through S-free air to determine the rate of SO ₂ desorption. The results of these studies also agreed well with the results of our theoretical model, thus justifying the reversibility assumption made in our theoretical models.In a final set of experiments, the effects of oxidation on SO₂ absorption was studied by means of drops containing various amounts of H₂O₂. For comparable exposure times to SO₂, the S concentration in drops with H₂O₂ was found to be up to 10 times higher than the concentration in drops in which no oxidation occurred.     

On the scavenging of SO2 by cloud and raindrops: I. A theoretical study of SO2 absorption and desorption for water drops in air

An extention of our previous theory for trace gas absorption into freely-falling cloud and raindrops is presented. This theory describes the convective diffusion of a trace gas through air and into a water drop with internal circulation, the drop falling at its terminal velocity. Using flow fields for the circulating water inside and for the moving air outside the drop, obtained by numerical solutions to the Navier—Stokes equation of motion, we numerically solved the convective diffusion equation to determine the uptake of SO₂ by water drops of various sizes, time exposure to the gas phase, and concentration of SO₂ in the gas phase. It was found that for drops of radius larger than 1 mm and relatively low gas concentrations (10 ppb (v)), resistance to gas diffusion lies mainly in the gas phase; while for drops of radius less than 500 m and gas concentrations larger than those found in the atmosphere (1% (v)), the resistance to diffusion lies primarily in the liquid phase. With drop sizes and gas concentrations between these limits, the rate of SO₂ uptake is controlled by a coupled resistance to diffusion inside and outside the drop. In addition to our general model, a simplified version was formulated which allows considerable savings in computer time for evaluation and improved ease of handling without significant loss of accuracy. A comparison between our simplified model and that of Barrie (1978) shows that the boundary-layer approach of Barrie may be a useful alternate approach to estimating trace gas absorption by water drops, provided appropriate values are chosen for the thickness of the boundary layers involved.     

Gas phase measurements of hydrogen peroxide in Greenland and their meaning for the interpretation of H2O2 records in ice cores

The gas phase concentration of hydrogen peroxide at Summit, Central Greenland, has been measured continuously during June/July 1990 using a coil scrubber technique combined with liquid phase fluorometry. The concentrations ranged between 0.3 ppbv and 3.5 ppbv, which is considerably higher than expected from model calculations and can be explained by low deposition rates. The record shows pronounced diurnal variations with minimum concentrations during night and maximum concentrations in the afternoon. The nocturnal minima can be explained by scavenging of H₂O₂ by hoarfrost. The scavenging mechanisms of H₂O₂ by snow and the redistribution of H₂O₂ during firnification are discussed. There is indirect evidence, that H₂O₂ is uniformly distributed in the ice lattice and that the fractionation between H₂O₂ and H₂O is small during diffusional crystal growth from the vapor phase (co-condensation).     

On the scavenging of gaseous nitrogen compounds by large and small rain drops: II. Wind tunnel and theoretical studies of the simultaneous uptake of NH3, SO2 and CO2 by water drops

An experimental investigation of the simultaneous absorption of NH₃ and SO₂ from the ambient atmosphere by freely falling water drops has been carried out in the Mainz vertical wind tunnel. The experimental results were found to be in good agreement with the results derived from computations with the Kronig-Brink convective diffusion model and also with a model which assumes a drop to be well mixed at all times. Encouraged by this agreement, these computation schemes for the uptake of gas by single drops where incorporated in a pollution washout model with realistic SO₂, NH₃ and CO₂ gas profiles. This model allows an entire raindrop size distribution to fall through a gas layer. The results of this plume-model show that the SO₂ uptake is strongly dependent on the NH₃ concentration in the atmosphere and on the rainrate. We also find that the small drops contribute more towards the washout of these gases. In the case of simultaneous presence of NH₃ and SO₂, desorption of these gases is negligible.     

南京北郊 O3、NO2和 SO2变化特征分析

利用 2008年1-12月南京北郊O₃、NO₂及SO₂质量浓度连续观测资料,分析了南京北郊气体污染物(O₃、NO₂、SO₂) 的质量浓度变化规律。结果表明：南京北郊O₃浓度夏季较高,日变化曲线呈单峰型,NO₂和SO₂浓度夏季较低,日变化曲线呈双峰型,NO₂与O₃的日变化呈现负相关关系,该地区SO₂浓度整体较高,夏季周末效应NO₂和SO₂较O₃更明显。     

Production of N2O,CH4, and CO2 from soils in the tropical savanna during the dry season

Emissions of N₂O, CH₄, and CO₂ from soils at two sites in the tropical savanna of central Venezuela were determined during the dry season in February 1987. Measured arithmetic mean fluxes of N₂O, CH₄, and CO₂ from undisturbed soil plots to the atmosphere were 2.5×10⁹, 4.3×10¹⁰, and 3.0×10¹³ molecules cm^-2 s^-1, respectively. These fluxes were not significantly affected by burning the grass layer. Emissions of N₂O increased fourfold after simulated rainfall, suggesting that production of N₂O in savanna soils during the rainy season may be an important source for atmospheric N₂O. The CH₄ flux measurements indicate that these savanna soils were not a sink, but a small source, for atmospheric methane. Fluxes of CO₂ from savanna soils increased ninefold two hours after simulated rainfall, and remained three times higher than normal after 16 hours. More research is needed to clarify the significance of savannas in the global cycles of N₂O, CH₄, CO₂, and other trace gases, especially during the rainy season.     

A comparison between natural and anthropogenic emissions of the reduced sulfur compounds H2S, COS, and CS2 in a tropical industrialized region

Extensive ambient concentration and flux measurements have been performed in the heavily polluted region of Cubatão/Brazil. Substantial contribution of anthropogenic sources to the local reduced sulfur burden has been observed. As a result of this atmospheric sulfur burden average gas exchange between vegetated soils and the atmosphere shows net deposition. Based mainly on own field measurements a local budget for H₂S, COS, and CS₂ has been made up in order to calculate anthropogenic emissions. All major sources and sinks in the chosen atmospheric reservoir (24×20×1 km) have been taken into account. Due to the small reservoir size fluxes across its boundaries are dominant sources and sinks. The differences between outflux and influx therefore account for the unknown anthropogenic emissions which have been determined to be 80±10 (H₂S), 66±15 (COS), and 29±6 Mmol year^-1 (CS₂). Other sources and sinks like natural emissions, chemical conversion, and dry deposition turned out to be of minor importance on a local scale. In fact, inside the investigated reservoir natural emissions were below 0.5% of anthropogenic emissions. Anthropogenic emissions of H₂S, COS, and CS₂ quantified in this work have been compared with global emission estimates for these compounds made by other authors. We conclude that global anthropogenic emissions of reduced sulfur compounds especially of COS and CS₂ are currently under-estimated.     

In situ Measurement of H2O and CH4 with Telecommunication Laser Diodes in the Lower Stratosphere: Dehydration and Indication of a Tropical Air Intrusion at Mid-Latitudes

Telecommunication laser diodes emitting near 1.39 m and 1.65 m in combination with direct-differential absorption spectroscopy are efficient tools to monitor in situ stratospheric H₂O andCH₄ with a good precision error (a few percents), a high temporal resolution (ranging from 10 ms to 1 s), a large dynamic range in the concentration measurements (four orders of magnitude) and a high selectivity in the analyte species. To illustrate the capability of laser probing technique, we report balloonborne H₂Oand CH₄ simultaneous measurements obtained on October 2001 atmidlatitudes (43° N). The H₂O vertical profile achieved with the lasersensor in the lower stratosphere is compared with the H₂O data yielded by a balloonborne frost-point hygrometer. The total hydrogen mixing ratio in the lower stratosphere, 2[CH₄] + [H₂O], appears to beconstant at 7.5 ± 0.1 ppmv. Nevertheless, an unexpected largedehydration of 0.5 ppmv was detected by both the laser sensor and thehygrometer between 16 km and 23 km. We suspect the occurrence of a tropicalair intrusion into mid-latitudes. We support this interpretation using a high-resolution advection model for potential vorticity.