Solar eclipse-induced variations in solar flux, j(NO2) and surface ozone at Kannur, India

Surface ozone is mainly produced by the photodissociation of nitrogen dioxide (NO₂) by solar UV radiation. Subsequently, solar eclipses provide one of the unique occasions to explore the variations in the photolysis rate of NO₂ and their significant impact on the production of ozone at a location. This study aims to examine the diurnal variations in the photodissociation rate coefficient of NO₂, (j(NO₂*)), and mixing ratios of surface ozone and NO _X * (NO?+?NO₂*) during the solar eclipse that occurred on 15 January 2010 at Kannur (11.9°N, 75.4°E, 5?m amsl), a tropical coastal site on the Arabian Sea in South India. This investigation was carried out on the basis of the ground level observations of surface ozone and its prominent precursor NO₂*. The j(NO₂*) values were estimated from the observed solar UV-A flux data. A sharp decline in j(NO₂*) and surface ozone was observed during the eclipse phase because of the decreased efficiency of the ozone formation from NO₂. The NO₂* levels were found to increase during this episode, whereas the NO levels remained unchanged. The surface ozone concentration was reduced by 57.5%, whereas, on the other hand, that of NO _X * increased by 62.5% during the solar eclipse. Subsequently a reduction of *% in the magnitude of j(NO₂*) was found here during the maximum obscuration. Reductions in solar insolation, air temperature and wind speed were also observed during the solar eclipse event. The relative humidity showed a 6.4% decrease during the eclipse phase, which was a unique observation at this site.     

The steady‐state structure of the natural stratosphere and ozone distribution in a 2‐D model incorporating radiation and O‐H‐N photochemistry and the effects of stratospheric pollutants

A mean meridional circulation model of the stratosphere, incorporating radiative heating and photochemistry of the oxygen‐hydrogen‐nitrogen atmosphere, is used to simulate the meridional distributions of O₃, HO_X, N₂O,NO_X, temperature and the three components of mean motion for the summer and winter seasons under steady‐state conditions. The results are generally in good agreement with the available observations in the normal stratosphere. The model has been applied to assess the effects of water vapour and nitrogen oxide perturbations resulting from aircraft emissions in the stratosphere. It is found that a fleet of 500 Boeing‐type sst's, flying at 20 km and 45°N in the summer hemisphere and inserting NO_x at a rate of 1.8 megatons per year, has the effect of reducing the global total ozone by 14.7%. Similar calculations for 342 Concorde/TU‐114's, cruising at 17 km and injecting NO_x at a rate of 0.35 megatons per year, show a global‐average total‐ozone reduction of 1.85%. Although water vapour is considered important, because of its ability to convert NO₂ into HNO₃, the direct effect on global‐average total‐ozone reduction resulting from the 100% increase in the stratospheric water content is less than 1%. The changes in the chemical structure (HO^NO^), temperature, and mean motions associated with the ozone reduction are also investigated in the case of the 1.8‐megaton‐per‐year NO_X perturbation. It is shown that the reduced meridional temperature gradient in the middle and upper stratosphere resulting from the NO_x perturbation leads to the weakening of the tropical easterly jet in the summer hemisphere and mid‐latitude westerlies in the winter season.

The sensitivity of the model solutions to an alternate choice of input parameters (diffusion coefficients and solar photodissociation data) is tested and the main deficiency of the model is pointed out.     

Observations of NO2 and O3 during thunderstorm activity using visible spectroscopy

Simultaneous observations for the total column densities of NO2, O3 and H2O were carried on using the porta-ble Spectrometer (438-450 nm and 400-450 nm) and the visible Spectrometer (544.4-628 nm) during premonsoon thunderstorms and embedded hail storm activity at Pune (18o32’N & 73o51’E), India. These observations confirm the fact that there is an increase in O3 and NO2 column densities during thunderstorms. The increase in O3 was observed following onset of thunderstorm, while the increase in NO2 was observed only after the thunder flashes occur. This implies that the production mechanisms for O3 and NO2 in thunderstorm are different. The observed column density of NO2 value (1 to 3 × 1017molecules · cm-2) during thunderstorm activity is 10 to 30 times higher than the value (1 × 1016molecules · cm-2) of a normal day total column density. The spectrometric observations and observations of thunder flashes by electric field meter showed that 6.4 × 1025molecules / flash of NO2 are produced. The increased to-tal column density of ozone during thunderstorm period is 1.2 times higher than normal (clear) day ozone concentra-tion. The multiple scattering in the clouds is estimated from H2O and O2 absorption bands in the visible spectral re-gion. Considering this effect the calculated amount of ozone added in the global atmosphere due to thunderstorm ac-tivity is 0.26 to 0.52 DU, and the annual production of ozone due to thunderstorm activity is of the order of 4.02 × 1037 molecules /year. The annual NO2 production may be of the order of 2.02 × 1035molecules / year.     

Surface ozone concentrations in Agra: links with the prevailing meteorological parameters

Measurements of surface ozone (O₃), nitric oxide (NO), nitrogen dioxide (NO₂), oxides of nitrogen (NO_x=NO+NO₂) and meteorological parameters have been made at Agra (North Central India, 27°10??N, 78°05??E) in post monsoon and winter season. The diurnal variation in O₃ concentration shows daytime in situ photochemical production with diurnal maximum in noon hours ranging from 51 to 54 ppb in post monsoon and from 76 to 82 ppb in winter, while minimum (16?C24 ppb) during nighttime and early morning hours. Average 8-h O₃ concentration varied from 12.4 to 83.9 ppb. The relationship between meteorological parameters (solar radiation intensity, temperature, relative humidity, wind speed and wind direction) and surface O₃ variability was studied using principal component analysis (PCA), multiple linear regression (MLR) and correlation analysis (CA). PCA and MLR of daily mean O₃ concentrations on meteorological parameters explain up to 80 % of day to day ozone variability. Correlation with meteorology is strongly emphasized on days having strong solar radiation intensity and longer sunshine time.     

Measurement of the photodissociation coefficient of NO2 in the atmosphere: I. Method and surface measurements

An instrument, specifically designed for measurements from a balloon platform in the stratosphere, has been used to obtain ground-level values of the atmospheric photodissociation coefficient of nitrogen dioxide, J _{NO 2}.A typical clear-sky value is 8.0×10^-3 s^-1 when the solar zenith angle is 40°. Measurements were made as a function of solar zenith angle and correlated with a calibrated Eppley UV radiometer. It is shown that J _{NO 2}may be expressed as a simple function of the radiometer output so that estimates of J _{NO 2}can be made using just an upward looking radiometer to an accuracy of about 20%. The measurements are also found to be in good agreement with calculations of J _{NO 2}using a simplified isotropic multiple scattering computer routine.     

华北地区香河站对流层NO_2的MAX-DOAS光谱仪观测及变化特征分析

利用中国科学院大气物理研究所香河大气探测综合试验站2010年3月至2012年2月(2年)的多轴差分吸收光谱仪(MAX-DOAS)观测数据和32 m高塔常规气象资料,反演了华北地区香河站对流层NO2柱浓度,分析了该区域NO2柱浓度的季节变化特征。研究表明:可见光455~485 nm、紫外330~370 nm都可以作为MAX-DOAS工作波段很好地反演NO2;香河地区NO2柱浓度夏季最低,几乎保持在2×1016 cm–2以下,春、秋季次之,在3×1016 cm–2上下小范围浮动,冬季最高,可达4.5×1016 cm–2;月平均最低值出现在7月,最高值出现在11月。NO2柱浓度与风速、风向密切相关:来自东边唐山方向的风,风速越大时NO2浓度越高,因为唐山是NO2的高值区之一;其它方向风速越大,浓度越低。春、夏两季NO2柱浓度日变化趋势比较平缓,秋、冬两季日变化明显,秋季正午偏高,冬季早晚偏高。     

Aircraft measurements of oxides of nitrogen along the eastern rim of the Asian continent: Winter observations

Aircraft observations of oxides of nitrogen (NO _y ), measured with a ferrous sulfate converter, over the sea surrounding the Japanese islands (30–43° N, 131–141° E) were carried out in the winter of 1983 and 1984 at altitudes mostly between 3 and 8 km. NO _y defined here is the sum of NO, NO₂, and other unstable oxides of nitrogen that are converted to NO by ferrous sulfate. The main observations were:

1. Over the Pacific Ocean between the latitudes of 30–35° N, the observed NO _y mixing ratio between 3 and 8 km was a fairly constant 200 pptv. The NO mixing ratio increased with altitude from 15 pptv at 3 km to 35 pptv at 7 km.
2. Over the Sea of Japan, tropospheric NO _y mesured between 1 and 6 km started increasing with latitude North of 35° N and reached about 1000 pptv at 40° N.
3. NO _y was measured in an air mass transported from the stratosphere near a tropopause fold region. When the ozone mixing ratio was between 80 and 140 ppbv, the NO _y mixing ratio was about 200 pptv.

     

Calculations of the temperature dependence of the NO2 photodissociation coefficient in the atmosphere

The photodissociation coefficient, J _NO2 of NO₂ in the atmosphere was calculated at 235 and 298 K using the measured temperature dependences of the absorption cross-sections and quantum yields. These calculations gave a ratio J _NO2(298 K)/J _NO2(235 K)=1.155±0.010 which is only weakly dependent on altitude, surface albedo and solar zenith angle.     

Evaluation of a catalytic reduction technique for the measurement of total reactive odd-nitrogen NO y in the atmosphere

A catalytic reduction technique for the measurement of total reactive odd-nitrogen NO _y in the atmosphere was evaluated in laboratory and field tests. NO _y component species include NO, NO₂, NO₃, HNO₃, N₂O₅, CH₃COO₂NO₂(PAN), and particulate nitrate. The technique utilizes the reduction of the higher oxides to NO in reaction with CO on a metal catalyst and the subsequent detection of NO by chemiluminescence produced in reaction with O₃. The efficiency and linearity of the conversion of the principal NO _y species were examined for mixing ratios in the range of 0.1 to 100 parts per billion by volume (ppbv). Results of tests with Au, Ni, and stainless steel as the catalyst in the temperature range of 25–500°C showed Au to be the preferred catalyst. NH₃, HCN, N₂O, CH₄, and various chlorine and sulfur compounds were checked as possible sources of NO _y interference with the Au catalyst. The effects of pressure, O₃, and H₂O on NO _y conversion were also examined. The results of the checks and tests in the laboratory showed the technique to be suitable for initial NO _y measurements in the atmosphere. The technique was subsequently tested in ambient air at a remote ground-based field site located near Niwot Ridge, Colorado. The results of conversion and inlet tests made in the field and a summary of the NO _y data are included in the discussion.     

Atmospheric and Oceanic Variability Associated with Growing Season Droughts and Pluvials on the Canadian Prairies

Abstract

The importance of measurements of the vertical distribution of odd nitrogen in studies of ozone chemistry and climate change has long being recognized. In this paper, we use the optimal estimation method developed by Rodgers (1976, 1990) to retrieve NO₂ vertical profiles from slant column observations made with a portable ultraviolet (UV)‐visible zenith‐sky spectrometer operated on the ground during the Middle Atmosphere Nitrogen TRend Assessment (MANTRA) balloon campaign carried out at Vanscoy, Saskatchewan, Canada (52°N, 107°W), from 18 to 25 August 1998. Late summer was chosen for the campaign because the stratospheric zonal wind velocity changes sign at that time. Under such conditions the stratospheric winds are at a minimum, leaving the stratosphere in a dynamically quiescent state and closer to photochemical control (Fahey et al., 2001; Fioletov and Shepherd, 2003). The NO₂ profile retrieved from the ground‐based observations is compared with the co‐located and simultaneous NO₂ profile measured by a balloon‐borne UV‐visible spectrometer during sunrise on 24 August. Good agreement is observed, giving us confidence in the retrieval technique adopted. The retrieved NO₂ profiles are also compared with the output of the Model for Evaluating oZONe trends (MEZON) 3D stratospheric chemical transport model. It is observed that, for altitudes below the peak concentration, the model underestimates the NO₂ amount, and at the altitude of peak concentration, the model values lie between the values measured from the balloon and those retrieved from the ground‐based measurements. Nevertheless, the model reproduces the general shape of the retrieved profiles, including the altitude of the NO₂ maximum, for both sunrise and sunset 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.     

Emission of nitrogen oxides (NO x ) from a flooded soil fertilized with urea: Relation to other nitrogen loss processes

Emissions of nitric oxide and other odd nitrogen oxides (NO _x ) from a flooded rice field were studied after urea had been broadcast into the floodwater.The NO _x flux from the fertilized area was very low (0.2×10^-9 g N m^-2 s^-1) for the first few days after application of urea and was high (0.95×10^-9 g N m^-2 s^-1) in the subsequent period when significant nitrite and nitrate were present in the floodwater. At night, little if any NO _x was exhaled but ambient NO₂ was absorbed by the floodwater. An uptake velocity for NO₂ of 3×10^-4 m s^-1 was measured during one night. Maximum NO _x losses were observed near 1300 h when temperature and solar ultraviolet light were maximum.While the amounts of nitrogen oxides emitted are of little agronomic importance (2×10^-3 per cent of the fertilizer nitrogen was lost as NO _x during the 10-day study period), they may well be of significance as a source for some gas reactions in the atmosphere and for the global nitrogen cycle.Of the fertilizer nitrogen applied (as urea) approximately 30% was lost to the atmosphere by NH₃ volatilization, 15% by denitrification, presumably as N₂, and the remainder, less minor losses of NO and N₂O, remained in the plant/soil/water system.Now at Forestry Department, Australian National University, G.P.O. Box 4, ACT 2601, Australia.     

Behaviour,of stratospheric NO2 during stratospheric warming of January‐February 1979

Abstract

Ground‐based measurements of stratospheric NO₂, using absorption spectroscopy of twilight sky in the spectral region 437–451 nm, have been made at Calgary (51.08°N, 114.13°W), Alberta, Canada, during the period December 1978‐March 10, 1979. The NO₂ showed a rather steady behaviour in the month of December when there was no stratospheric warming in progress; the monthly average of the afternoon vertical column abundance for December was 1.7 × 10¹⁵ cm². In the rest of the observation period the NO₂ showed a complex behaviour, but this behaviour appears to be explicable in terms of the stratospheric circulation changes taking place in that period due to the occurrence of a stratospheric warming event.     

香河地区冬季NO2光解速率的变化特征及其估算方法的建立

NO₂的光解速率j(NO₂)是对流层化学研究中的一个重要的参数，它是对流层臭氧（O₃）和OH自由基的形成关键影响因子之一。本文利用香河站2017年11月至2018年1月的观测资料对NO₂的光解速率j(NO₂)、太阳辐射的变化特征，及光解速率与分波段辐射相关性进行分析，在此基础上建立了一套适合于构建香河地区j(NO₂)的参数化方案。结果表明，香河地区的j(NO₂)与太阳辐射的变化趋势基本一致，日变化均呈正午高、早晚低的单峰型。香河地区冬季j(NO₂)的变化范围是0.00046～0.0044 s-1，平均值为0.0029 s-1。j(NO₂)与晴空指数（K_S）和定义的紫外辐射晴空指数（K_UV）存在很好的相关性，因此，利用j(NO₂)与大气质量数和晴空指数的相互依赖关系，基于K_UV构建了适合于香河地区j(NO₂) 的估算方程。由于总辐射是气象站的常规观测要素，晴空指数K_S更容易获取，继而建立了通过K_S参数化计算j(NO₂)的估算方程。利用K_UV和K_S建立的j(NO₂)估算方程的瞬时估算值与观测值的平均相对误差分别为6.5%和13.9%，均方根误差分别为0.00029和0.00051。     

A fractal climate response function can simulate global average temperature trends of the modern era and the past millennium

A climate response function is introduced that consists of six exponential (low-pass) filters with weights depending as a power law on their e-folding times. The response of this two-parameter function to the combined forcings of solar irradiance, greenhouse gases, and SO₂-related aerosols is fitted simultaneously to reconstructed temperatures of the past millennium, the response to solar cycles, the response to the 1991 Pinatubo volcanic eruption, and the modern 1850–2010 temperature trend. Assuming strong long-term modulation of solar irradiance, the quite adequate fit produces a climate response function with a millennium-scale response to doubled CO₂ concentration of 2.0 ± 0.3 °C (mean ± standard error), of which about 50 % is realized with e-folding times of 0.5 and 2 years, about 30 % with e-folding times of 8 and 32 years, and about 20 % with e-folding times of 128 and 512 years. The transient climate response (response after 70 years of 1 % yearly rise of CO₂ concentration) is 1.5 ± 0.2 °C. The temperature rise from 1820 to 1950 can be attributed for about 70 % to increased solar irradiance, while the temperature changes after 1950 are almost completely produced by the interplay of anthropogenic greenhouse gases and aerosols. The SO₂-related forcing produces a small temperature drop in the years 1950–1970 and an inflection of the temperature curve around the year 2000. Fitting with a tenfold smaller modulation of solar irradiance produces a less adequate fit with millennium-scale and transient climate responses of 2.5 ± 0.4 and 1.9 ± 0.3 °C, respectively.     

Role of the ocean in controlling atmospheric CO2 concentration in the course of global glaciations

Responses of ocean circulation and ocean carbon cycle in the course of a global glaciation from the present Earth conditions are investigated by using a coupled climate-biogeochemical model. We investigate steady states of the climate system under colder conditions induced by a reduction of solar constant from the present condition. A globally ice-covered solution is obtained under the solar constant of 92.2% of the present value. We found that because almost all of sea water reaches the frozen point, the ocean stratification is maintained not by temperature but by salinity just before the global glaciation (at the solar constant of 92.3%). It is demonstrated that the ocean circulation is driven not by the surface cooling but by the surface freshwater forcing associated with formation and melting of sea ice. As a result, the deep ocean is ventilated exclusively by deep water formation in southern high latitudes where sea ice production takes place much more massively than northern high latitudes. We also found that atmospheric CO₂ concentration decreases through the ocean carbon cycle. This reduction is explained primarily by an increase of solubility of CO₂ due to a decrease of sea surface temperature, whereas the export production weakens by 30% just before the global glaciation. In order to investigate the conditions for the atmospheric CO₂ reduction to cause global glaciations, we also conduct a series of simulations in which the total amount of carbon in the atmosphere?Cocean system is reduced from the present condition. Under the present solar constant, the results show that the global glaciation takes place when the total carbon decreases to be 70% of the present-day value. Just before the glaciation, weathering rate becomes very small (almost 10% of the present value) and the organic carbon burial declines due to weakened biological productivity. Therefore, outgoing carbon flux from the atmosphere?Cocean system significantly decreases. This suggests the atmosphere?Cocean system has strong negative feedback loops against decline of the total carbon content. The results obtained here imply that some processes outside the atmosphere?Cocean feedback loops may be required to cause global glaciations.     

Modelling of the vertical fluxes of nitric acid,ammonia, and ammonium nitrate

Results from numerical investigations regarding the exchange of HNO₃, NH₃, and NH₄NO₃ between the atmosphere and the biosphere are presented. The investigations were performed with a modified inferential method which is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these nitrogen compounds. This modified inferential method calculates the micrometeorological quantities (such as the friction velocity and the fluxes of sensible and latent heat), the height-invariant fluxes of the composed chemically conservative trace species with group concentrationsc ₁=[HNO₃]+[NH₄NO₃] (total nitrate),c ₂=[NH₃]+[NH₄NO₃] (total ammonia), andc ₃=[HNO₃]-[NH₃] as well as the fluxes of the individual nitrogen compounds. The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The modified inferential method requires only the data of wind velocity, temperature, humidity and concentrations (HNO₃, NH₃, and NH₄NO₃) measured at a reference height by stations of a monitoring network.     

Total column densities of tropospheric and stratospheric trace gases in the undisturbed Arctic summer atmosphere

Ground-based FTIR measurements have been performed in the Arctic summer in July 1993 and June 1994 at 79° N to study the zenith column densities of several trace gases in the undisturbed Arctic summer atmosphere. Zenith column densities of H₂O, N₂O, HNO₃, NO₂, NO, ClONO₂, ClO, HCl, HF, COF₂, OCS, SF₆, HCN, CH₄, C₂H₆, C₂H₂, CO, O₃, CFC-12, CFC-22, and CO₂ were retrieved by line-by-line calculations. The results are compared with winter and springtime observations measured at the same site, with column densities obtained in the Antarctic summer atmosphere, and with measurements at midlatitudes. For HCl the spectra give lower total zenith columns than expected, but the ratio HF/HCl agrees well with midlatitude literature data. Measurements of ClONO₂ give low total columns in agreement with observations at midlatitudes. In the undisturbed atmosphere HCl was found to be in excess of ClONO₂. The total columns of HNO₃, N₂O and the sum of NO and NO₂ agree with summer observations in Antarctica. Results for the tropospheric trace gas C₂H₆ are higher by 250% when compared with Antarctic observations. Contrary to N₂O and CH₄ the seasonal cycle of C₂H₆ and C₂H₂ give much higher total columns in winter/spring compared to the summer observations. This is assigned to transport of polluted airmasses from mid-latitudes into the Arctic.     

Measurements of stratospheric NO2 profiles using a gas correlation radiometer in the solar occultation mode

Compact two-channel IR radiometers for solar occultation experiments have been constructed in order to measure concentration profiles of stratospheric trace gases. The instruments can be used as filter-or gas correlation-type radiometers depending on the trace gas under investigation. Within the LIMS correlative measurement program, balloon flights were performed with a payload of up to four of these two-channel radiometers. From the gas correlation-type measurements, profiles of the trace gas NO₂ are inferred for the altitude region between about 20 km and the balloon float level. The data evaluation also includes a comprehensive analysis of the error sources and their effect on the accuracy of the NO₂ profiles. The derived profiles are compared among themselves and are assessed against the observations of other authors by accounting for the diurnal, latitudinal and seasonal changes of NO₂. As a by-product of our measurements, the mean absorption of the O₂ collision-induced band at 6.4 m was determined within the range of the interference filter used and compared with calculations based on known absorption coefficients.