Atmospheric hydroperoxides measured over a rural site in central Japan during spring: helicopter-borne measurements

Measurements of the concentrations of H₂O₂ and methyl hydroperoxide (MHP), O₃, and SO₂ over Imizu City, Toyama Prefecture, Japan were performed in March using a helicopter. H₂O₂ concentrations were higher at an altitude of approximately 2,400 m (8,000 ft). The H₂O₂ concentrations (< 0.8 ppb) in the spring were much lower than those observed during the summer observations. MHP was also higher in the high-altitude atmosphere. Lower concentrations of H₂O₂ were observed when high air pollutants were actively transported from Asian continent. The concentrations of H₂O₂ were mostly lower than those of SO₂; this condition is called oxidant limitation. If H₂O₂ concentration rises in cold months, the acidification of cloud water may be accelerated at high elevations in central Japan where air pollution is actively transported.     

Measurements of atmospheric hydroperoxides at a rural site in central Japan

Measurements of hydroperoxides (H₂O₂ and MHP) at ground level were made from 2012 to 2015 in Imizu City, Toyama Prefecture in central Japan. H₂O₂ and MHP concentrations ranged from 0.01 to 3.5 ppb and from below the level of detection (< 0.01 ppb) to 1.4 ppb, respectively. The concentrations of H₂O₂ and MHP were high in the summer and low in the winter. The H₂O₂ concentration was at its maximum in July and August, whereas the concentration of O₃ in the daytime was highest in May and June. The ratio of [H₂O₂]/[SO₂] presented clear seasonal variations. Many cases showed the condition of [H₂O₂] < [SO₂], called oxidant limitation especially in the cold months. Hydroperoxide concentrations in the rainwater were also high in the summer. The concentrations of MHP were much lower than those of H₂O₂ in the rain water. High concentrations of H₂O₂ (> 2.5 ppb) were detected in the summer during the inflow of air pollution. The concentrations of H₂O₂ were significantly high in July and August of 2013. The H₂O₂ was well correlated with the O₃ in July and August whereas there was no correlation between O₃ and H₂O₂ in May and June. There was a negative correlation between NO_X and H₂O₂.     

The influence of light intensity,SO2, NOx and C3H6 on sulfate aerosol formation

The photochemical oxidation of SO₂ in the presence of NO and C₃H₆ was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO₂ concentration were constant, SO₄ ^2- concentration, derived from the total volume of aerosol produced, peaked when [C₃H₆]/[NO] was approximately 6.0. Another increase im SO₄ ^2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO₂ oxidation mechanisms. At low [C₃H₆]/[NO] ratios, the processes proceed via the HO–SO₂ reaction, while at high ratios the O₃–C₃H₆ adduct is assumed to oxidize SO₂ to produce SO₄ ^2- aerosols.     

Numerical Investigation of Gas Scavenging by Weak Precipitation

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.     

北京秋季一次典型大气污染过程多站点分析

多站点多种大气污染物的同步在线观测对深入剖析大气污染的成因和演变机制有重要意义。以龙潭湖、北京325 m塔、双清路和阳坊4监测站点实时NO_x、SO₂、O₃、PM2.5和PM10浓度观测数据为基础,介绍了北京地区2010年10月3～11日发生的一次典型污染过程。不同污染物在污染过程中变化特征不一致,表现为NO_x、SO₂、O₃浓度有明显日变化,而PM浓度升高后一直维持在高值,日变化幅度很小。通过分析不同站点、相同污染物之间的相关性和变异系数发现,4站点间一次污染物NO和SO₂空间浓度差别大,变异系数分别为77%和70%,相关系数低于0.44;而二次污染物NO₂、PM2.5、O₃空间浓度差别较小,变异系数分别为34%、36%和29%,相关系数均超过0.54。结合中尺度气象模式研究发现,该污染过程中,850 hPa高空持续的西南暖平流造成华北地区显著平流逆温,与近地层辐射逆温共同作用,使北京地区混合层高度维持在1200 m以下。低混合层高度和低风速限制了大气垂直和水平扩散,造成北京地区近地层污染物累积,形成重度污染。     

Simulation of the Effect of an Increase in Methane on Air Temperature

The infrared radiative effect of methane was analyzed using the 2D, interactive chemical dynamical radiative SOCRATES model of the National Center for Atmospheric Research. Then, a sensitivity experi ment, with the methane volume mixing ratio increased by 10%, was carried out to study the influence of an increase of methane on air temperature. The results showed that methane has a heating effect through the infrared radiative process in the troposphere and a cooling effect in the stratosphere. However, the cooling effect of the methane is much smaller than that of water vapor in the stratosphere and is negligible in the mesosphere. The simulation results also showed that when methane concentration is increased by 10%, the air temperature lowers in the stratosphere and mesosphere and increases in the troposphere. The cooling can reach 0.2 K at the stratopause and can vary from 0.2-0.4 K in the mesosphere, and the temperature rise varies by around 0.001-0.002 K in the troposphere. The cooling results from the increase of the infrared radiative cooling rate caused by increased water vapor and O3 concentration, which are stimulated by the increase in methane in most of the stratosphere. The infrared radiation cooling of methane itself is minor. The depletion of O3 stimulated by the methane increase results indirectly in a decrease in the rate of so- lar radiation heating, producing cooling in the stratopause and mesosphere. The tropospheric warming is mainly caused by the increase of methane, which produces infrared radiative heating. The increase in H2O and O3 caused by the methane increase also contributes to a rise in temperature in the troposphere.     

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.     

SO2 Oxidation in a rainband: Effects of in‐cloud H2O2 Production

Abstract

Aqueous‐phase H₂O₂ production in a rainband and its possible effect on sulphate production are studied by means of a two‐dimensional numerical model. In‐cloud peroxide production is incorporated into this chemistry model and its simulation results are compared with those in which aqueous‐phase H₂O₂ came only from the dissolution of gaseous H₂O₂ from the cloud interstitial air.

Results are presented for two different polluted situations ‐ Case 1 having initial SO₂ and sulphate aerosol profiles representative of a moderately polluted air mass, and Case 2 having chemical profiles expected to increase the relative importance of oxidation to nucleation as a means of contributing sulphate to cloud and rain. Sulphate production increased in both cases, although in Case 1 the effect of this increase on the concentration of sulphate in rain is negligible because nucleation and scavenging of aerosol are the major processes by which sulphate enters cloud and rain. In Case 2, sulphate concentrations in rain increase by 5–10%. Under environmental conditions of low sulphate aerosol, where oxidation reactions are the dominant means for sulphate to enter cloud and rain, the neglect of sulphate produced by the additional H₂O₂ may lead to error. The usual uncertainties in the initial SO₂ and sulphate aerosol vertical profiles, however, could be a more significant source of error in simulations of the chemistry of cloud and precipitation than the neglect of aqueous‐phase peroxide production during the lifetime of even a long‐lived system.     

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.     

Photochemical Effects in the Heterogeneous Reaction of Soot with Ozone at Low Concentrations

The soot-ozone reaction at low concentrations (ppm O₃) hasbeen examined todetermine any influence of solar radiation on its products and kinetics. Theeffect of simulatedsolar radiation is to change the product distribution towardsCO₂(g), CO (g) and H₂O(g) at theexpense of soot surface functional groups formation. Little effect on theextent or rate ofdiminution of O₃ through this rapid reaction is observed. Theinitial rate laws for formation ofall products remain the same under simulated solar radiation, with changes inthe rate constants(and thus in the relative importance of mechanistic pathways) responsible forthe differingproduct distributions. Decarboxylation of soot surface functionalities hasbeen shown to be onepossible mechanism underlying these effects. Atmospheric soot, particularlythat emitted nearthe tropopause by increasing numbers of subsonic and supersonic aircraft, mayplay a role inozone depletion; the rapid diminution of ozone in soot's presence isunaffected by solarradiation.     

Diurnal Variations of Atmospheric Hydrogen Peroxide Concentrations in Saxony (Germany)

During a 3-year study, gaseous hydrogenperoxide (H₂O₂) concentrations were measuredas part of the SANA project at the Melpitz FieldResearch Station and in the city of Leipzig. Typicaldaily mean H₂O₂ mixing ratios on sunny dayswere 0.15 to 0.25 ppbv with maximum values of 0.3 to0.5 ppbv at Melpitz, and 0.3 to 0.6 ppbv with maximumvalues of 0.4 to 1.0 ppbv in Leipzig. Over the entireperiod of the project the maximum hourly mean valueswere 2.1 ppbv and 5.3 ppbv in Melpitz and Leipzig,respectively. The data were not complete enough to show a trend.Linear regression analysis shows, that ozone(O₃), temperature and solar radiation arepositively correlated with H₂O₂, whereasnitrogen oxides (NO_x), carbon monoxide (CO) andrelative humidity are negatively correlated. Negativecorrelation between H₂O₂ and CO is caused byjoint occurrence of CO with NO_x in exhaust gases.Negative correlation between H₂O₂ andrelative humidity is not necessarily in contradictionto the accelerating effect of water vapour onH₂O₂ formation. The strong positivecorrelation of H₂O₂ with the dew pointdifference however seems to better reflect theinfluence of water vapour. Multiple linear regression analysis (MLRA) of thecomponents measured, indicates the great influence of CO on the formation of H₂O₂ in the gasphase.     

OH in the tropical upper troposphere and its relationships to solar radiation and reactive nitrogen

In situ measurements of [OH], [HO₂] (square brackets denote species concentrations), and other chemical species were made in the tropical upper troposphere (TUT). [OH] showed a robust correlation with solar zenith angle. Beyond this dependence, however, [OH] did not correlate to its primary source, the product of [O₃] and [H₂O] ([O₃]?[H₂O]), or its sink [NO_y]. This suggests that [OH] is heavily buffered in the TUT. One important exception to this result is found in regions with very low [O₃], [NO], and [NO_y]. Under these conditions, [OH] is highly suppressed, pointing to the critical role of NO in sustaining OH in the TUT and the possibility of low [OH] over the western Pacific warm pool due to strong marine convections bringing NO-poor air to the TUT. In contrast to [OH], [HO_x] ([OH] + [HO₂]) correlated reasonably well with [O₃]?[H₂O]/[NO_y], suggesting that [O₃]?[H₂O] and [NO_y] are the significant source and sink, respectively, of [HO_x].     

基于京津冀高密度地面观测网络的大气污染物浓度地面观测代表性误差估计

地面观测提供空间点的浓度信息,三维化学模式提供网格面的浓度信息,两者在进行对比验证或同化融合时会因为空间尺度不匹配引入误差,即观测代表性误差。本研究将大气污染地面国控监测站与区县监测站结合起来,获得了京津冀地区高密度地面观测数据,利用该数据首次对京津冀地区6项常规大气污染物（PM_2.5、PM₁₀、SO₂、NO₂、CO和O₃）的地面观测代表性误差进行了客观估计,并与Elbern et al.（2007）方法估计的代表性误差进行了对比。结果发现:两种方法对京津冀地区NO₂地面观测代表性误差估计非常接近,但Elbern et al.（2007）方法显著低估了SO₂、CO和O₃地面观测的代表性误差。在此基础上,我们对Elbern et al.（2007）方法及其误差特征参数进行了本地化修正,并增加了PM_2.5和PM₁₀的代表性误差特征参数,建立了京津冀大气污染地面观测代表性误差的客观估计方法。     

Tropospheric ozone chemistry. The impact of cloud chemistry

The effect of clouds and cloud chemistry on tropospheric ozone chemistry is tested out in a two-dimensional channel model covering a latitudinal band from 30 to 60° N. Three different methods describing how clouds affect gaseous species are applied, and the results are compared. The three methods are:

?A first order parameterization scheme for the removal of sulphur and other soluble gases by liquid droplets.

?A parameterization scheme for SO₂, O₃, and H₂O₂ removal is constructed. The scheme is based on the solubility of gases in liquid droplets, cycling times of air masses between clouds and cloud free areas and on the chemical interaction of SO₂ with H₂O₂ and O₃ in the liquid phase.

?Gas-aqueous-phase interactions and aqueous-phase chemical reactions are included in the reaction scheme for a number of components in areas where clouds are present.

In all three methods, a full gas-phase chemistry scheme is used. Particular emphasis is given to the study of how the ozone and hydrogen peroxide levels are affected. Significant changes in the distributions are found when aqueous-phase chemical reactions are included. The result is loss of ozone in the aqueous phase, with pronounced reductions in ozone levels in the middle and lower troposphere. Ozone levels are reduced by 10 to 30% with the largest reductions in the remote middle troposphere, bringing the values in better agreement with observations. Changes in H₂O₂ are harder to predict. Although, in one case study, hydrogen peroxide is produced within the aqueous phase, concentrations are mostly comparable or even lower than in the other cases. Hydrogen peroxide levels are, however, shown to be very pH sensitive. pH values around 5 seem to favour high H₂O₂ levels. High H₂O₂ concentrations may be found particularly in the upper part of the clouds under favourable conditions.     

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.     

Air pollutant emission rates and concentrations in medieval churches

A series of indoor air quality parameters were determined in two medieval churches, in Cyprus (temperature, relative humidity, total and UV solar radiation, CO₂ indoors and O₃, NO, NO₂ ^*, HNO₃ ^*, HCl, HCOOH, CH₃COOH indoors and outdoors). These data were used as input in a validated indoor air quality model to predict indoor air pollutant source strengths and species concentrations that resulted from dark or photochemical reactions. The NO and NO₂ emission rates due to the burning of incense or candles were estimated. Model results revealed that heterogeneous NO formation takes place simultaneously with the heterogeneous HONO formation. Also, model application has shown that indoor NO_x emissions resulted in decreased free radical concentrations, in contrast to the organic compound emissions, which increased free radical concentrations. This effect of indoor emissions on indoor radicals can partly explain the indoor enhancement/depression of indoor gaseous acid formation.     

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.     

Development and performance evaluation of statistical models correlating air pollutants and meteorological variables at Pantnagar,India

Ambient air quality in respect of SO₂, NO₂ and total suspended particulate matter (TSPM) was monitored at Pantnagar, India from May, 2008 to April, 2009 and statistically analyzed with meteorological variables such as relative humidity (RH), wind speed (WS), precipitation (P) and mean air temperature (T). TSPM was found to be the major air pollutant causing significant deterioration of air quality with annual mean concentrations of 280 μg/m³. Further, weekly mean air pollutant concentrations were statistically analyzed through stepwise multiple linear regression analysis in respect of independent meteorological variables to develop suitable statistical models. Both NO₂ and TSPM concentrations were found to have been influenced by meteorological variables with coefficient of determination (R²) of 82.21 and 92.84%, respectively. However, atmospheric SO₂ revealed only 22.87% of dependencies on meteorological variables. Partial correlation coefficients revealed that wind speed has the maximum influence (77.80 and 31.50%) on proposed equations for NO₂ and SO₂, closely followed by weekly mean temperature (73.60 and 24.30%). However, in case of TSPM, individual contribution of ambient temperature (94.40%) was found maximum, followed by relative humidity (86.50%). Model performances were evaluated through both quantitative data analysis techniques and statistical methods. Nearly 98 and 95% of potential error has been explained by the model developed for TSPM and NO₂, while in case of SO₂, it is found as only 61%. Therefore, performances of models (for TSPM and NO₂) to predict ambient weekly mean concentrations based on forecasted weather parameters were found to be excellent, however, performance of model developed for SO₂ was found only satisfactory.