Seasonal and Diurnal Variation of Surface Ozone and a Preliminary Analysis of Exceedance of its Critical Levels at a Semi-arid Site in India

The mixing ratios of surface O₃ were measured at St. John's College, Agra, an urban and traffic influenced area for the period of 2000–2002. The monthly averaged O₃ mixing ratios ranged between 8 to 40 ppb with an annual average of 21 ppb. Strong diurnal and seasonal variations in O₃ mixing ratios were observed throughout the year except for monsoon season. The mixing ratios of O₃ follow the surface temperature cycle and solar radiation (r = 0.72 and r = 0.65 with temperature and solar radiation, respectively). Concentrations were higher with winds associated with NE and NW direction indicating the impact of pollution sources on surface O₃ concentration. Exceedance of ozone critical level was calculated using the AOT 40 index and found to be 840 ppb.h and 2430 ppb.h for summer and winter seasons, respectively. The present O₃ exposures are lower than the critical level of O₃ and suggest that the present level of O₃ does not have any impact on reduction in crop yields.     

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.     

Measurements of ozone and its precursor nitrogen dioxide and crop yield losses due to cumulative ozone exposures over 40 ppb (AOT40) in rural coastal southern India

Measurements of ground level ozone (O₃), nitrogen dioxide (NO₂) and meteorological parameters (air temperature, relative humidity and wind speed and direction) has been made for 3 years from March 2007 to February 2010 at Nagercoil (8.2°N, 77.5°E, 23 m above sea level), an equatorial rural coastal site of southern India. The monthly average of daytime maximum of O₃ concentrations ranged from 28 to 50 parts per billion (ppb) with an annual average of 19.8 ppb. Similarly, monthly average of NO₂ concentration ranged from 3.4 ppb to 7.7 ppb with an annual average of 5.3 ppb. The monthly variation of meteorological parameters shows the little changes being a coastal site. The estimated summer crops yield losses by 1.1–15.6 % from present O₃ concentration level associated with AOT40 index 3.1–5 ppm h.     

龙凤山大气近地层O3浓度变化及与其它因素的关系

研究首次在龙凤山区域大气本底站测得的地面Ｏ３浓度及其变化的资料表明,中国东北农村地面大气Ｏ３浓度总体水平不很高,但在少数特殊的天气条件下,时均浓度可超过国家二级标准。Ｏ３浓度存在明显的季节和日变化,其月平均浓度１９９５年１月最低（２７．５ｐｐｂ）,１９９４年１１月最高（４３．２ｐｐｂ）。Ｏ３日变化幅度夏季的晴天最大（２８ｐｐｂ）,冬季的阴天最小（８ｐｐｂ）。气象要素（尤其是风速、气温和相对湿度等）和ＮＯｘ与地面Ｏ３浓度有较密切的关系。用多变量分析法探讨了地面Ｏ３各指标随气象因子和ＮＯｘ共同变化的规律,并拟合了寒冷和温暖期里与地面Ｏ３日最高浓度、日最低浓度及日变化幅度有关的方程。     

Impacts of strong El Niño on summertime near-surface ozone over China

The influences of strong El Niño events (1997/98 and 2015/16) on summertime near-surface ozone (O₃) concentrations over China are investigated using the GEOS-Chem model. The results show that near-surface O₃ concentrations increased by a maximum of 6 ppb (parts per billion) during the summer of the developing phase of the 1997/98 El Niño in northeastern China, mainly due to the increased chemical production related to the hot and dry conditions. Besides, the O₃ concentration increased by 3 ppb during the developing summer of both the 1997/98 and 2015/16 El Niño in southern China. It was linked to the weakened prevailing monsoon winds, which led to the accumulation of O₃ in southern China. In contrast, in the summer of the decaying phase of the two El Niño events, O₃ concentrations decreased over many regions of China when the El Niño reversed to the cooling phase. This highlights that El Niño plays an important role in modulating near-surface O₃ concentrations over China.摘要利用全球大气化学三维模式 (GEOS-Chem) 模拟研究两次强厄尔尼诺事件 (1997/98和2015/16) 对中国夏季近地面臭氧 (O₃₎ 浓度的影响. 结果表明1997/98年厄尔尼诺事件发展期夏季中国东北区域O₃浓度升高, 最大值超过6ppb, 这主要归因于高温晴朗低湿等气象因素导致O₃化学生成升高. 此外, 两次厄尔尼诺事件发展期夏季O₃浓度在中国南部均增加了3ppb, 这与盛行季风减弱导致中国南方O₃局地积累有关. 相反, 在两次强厄尔尼诺衰减期夏季, 中国大部分地区O₃浓度下降伴随着海温模态转变为拉尼娜事件. 这表明厄尔尼诺在调节中国近地面O₃浓度中发挥着重要作用.     

RESEARCH ON SURFACE O3 WITH METEOROLOGICAL CONDITIONS UNDER ATMOSPHERIC BACKGROUND CONDITIONS IN NORTHEAST CHINA*

Surface O₃ concentration and its precursors have been observed at Longfengshan station,Heilongjiang Province for a period of one year from August 13,1994 to July 30,1995. Relationship between surface O₃ and the meteorological conditions during this period is analyzed in this study.Observation results show that diurnal variation of surface O₃ follows a pattern of double-peaks with amplitude of 27-28 ppb under fine days in summer and autumn.Although the diurnal variation is small(14 ppb),it is still detectable when it is overcast.Diurnal variation of O₃ is irregular under rainy days.Surface O₃ concentration rises when wind speed starts to increase at 0800 BT(Beijing Time)from 0 to 6 m s^-1in autumn,winter and summer.Relative high surface O₃ concentration is noticed frequently when S,SSW,SW and WSW wind are encountered at the station during all seasons.At 0800 BT and 1400 BT the surface O₃ concentration increases with the increase of global radiation accordingly during fine days in winter,spring and autumn.During fine days average peak of O₃ concentration in summer is 20 ppb higher than that in winter while the average peak of global radiation in summer is almost twice as high as that in winter.The average surface O₃ concentration under fine days in autumn at Longfengshan station is 14 ppb lower in comparison to the observation results from Lin'an station where Lin'an is at about the same longitude and lower latitude,with same environment,which is mainly caused by the difference of global radiation due to different latitudes in these two areas(difference of average peak global radiation about 100 W m^-2).     

Simulated Spatial Distribution and Seasonal Variation of Atmospheric Methane over China: Contributions from Key Sources简

We used the global atmospheric chemical transport model,GEOS-Chem,to simulate the spatial distribution and seasonal variation of surface-layer methane （CH4） in 2004,and quantify the impacts of individual domestic sources and foreign transport on CH4 concentrations over China.Simulated surface-layer CH4 concentrations over China exhibit maximum concentrations in summer and minimum concentrations in spring.The annual mean CH4 concentrations range from 1800 ppb over western China to 2300 ppb over the more populated eastern China.Foreign emissions were found to have large impacts on CH4 concentrations over China,contributing to about 85％ of the CH4 concentrations over western China and about 80％ of those over eastern China.The tagged simulation results showed that coal mining,livestock,and waste are the dominant domestic contributors to CH4 concentrations over China,accounting for 36％,18％,and 16％,respectively,of the annual and national mean increase in CH4 concentration from all domestic emissions.Emissions from rice cultivation were found to make the largest contributions to CH4 concentrations over China in the summer,which is the key factor that leads to the maximum seasonal mean CH4 concentrations in summer.     

Application of satellite data in a regional model to improve long-term ozone simulations

To investigate an alternative technique of providing background and transboundary transport inputs for ozone (O₃) simulations on a regional scale, the EPA’s Community Multi-scale Air Quality (CMAQ) model was integrated with high spectral resolution data from the Tropospheric Emission Spectrometer (TES) aboard the NASA’s Aura satellite. This study presents a comprehensive model evaluation of O₃ for the entire year of 2009 over the contiguous United States with a focus on the State of Texas using both ozonesonde and ground measurements. While improving model performance in the upper atmosphere, CMAQ’s initial and boundary conditions (IC/BC) derived from the original TES data do not improve model performance in the troposphere because the satellite data exaggerated concentration of tropospheric O₃. With a 10-ppb deduction of O₃ concentration from TES, the IC/BC derived from the adjusted TES improves model performance from ground level through the upper atmosphere. The mean bias of daily maximum 8-h average concentration of O₃ (MDA8) from the ground monitored in Texas decreased from 7 ppb to 4 ppb. Model results also show small influences of O₃ from the upper troposphere on the concentrations at the ground level. With a complete exclusion of stratospheric layers, changes of annual mean MDA8 of O₃ concentrations at ground-level were smaller than 1.1 % in Dallas and Houston. In addition, limitations of satellite data are discussed and recommendations are provided regarding the future application of satellite data in regional O₃ simulations.     

Observation of Filterable Bromine Variabilities During Arctic Tropospheric Ozone Depletion Events in High (1hour) Time Resolution

The halogen ions Br^- and Cl^- together with NO₃ ^-, SO₄ ⁼, MSA^- (methane sulfonate), Na⁺ and NH₄ ⁺ were analysed by ion chromatography in extracts of more than 800 aerosol cellulose filter samples taken at Ny Ålesund, Svalbard (79°N, 12°E) in spring 1996 (March 27 - May 16) within the European Union project ARCTOC (Arctic Tropospheric Ozone Chemistry). Anticorrelated variations between f-Br (filterable bromine, i.e. water soluble bromine species that can be collected by aerosol filters) and ozone within the arctic troposphere were evaluated at a resolution of 1 or 2 hours for periods with depleted ozone and 4 hours at normal ozone. A mean f-Br concentration of 11 ng m^-3 (0.14 nmol m^-3) was observed for the whole campaign, while maximum concentrations of 80 ng m^-3 (1 nmol m^-3) were detected during two total O₃-depletion events (O₃ drop to mixing ratios below the detection limit of < 2 ppb). Anticorrelation between f-Br and O₃ was also seen during minor O₃-depletion episodes (sudden drop in O₃ by at least 10 ppb, but O₃ still exceeding the detection limit) and even for ozone variations near its background level (40-50 ppb). A time lag of about 10 hours between the change of ozone and of f-Br concentrations could only be found during a total ozone depletion event, when f-Br reached its maximum values several hours after ozone was totally destroyed. Bromine oxide (BrO) concentrations, measured by DOAS (Differential Optical Absorption Spectroscopy), and f-Br showed a coincident variability during almost the entire campaign (except in the case of total O₃-loss). Frequently enhanced anthropogenic nitrate and sulphate concentrations were observed during O₃-depletion periods. At O₃ concentrations < 10 ppb sulphate and nitrate exceed their typical mean level by 54% and 77%, respectively. This may indicate a possible connection between acidity and halogen release.     

On the Spatial Distribution and Seasonal Variation of Lower-Troposphere Ozone over Europe

Surface ozone data from 25 Europeanlow-altitude sites and mountain sites located between79°N and 28°N were studied. The analysiscovered the time period March 1989–February 1993.Average summer and winter O₃ concentrations inthe boundary layer over the continent gave rise togradients that were strongest in the north-west tosouth-east direction and west-east direction, respectively. WintertimeO₃ ranged from 19 to 27 ppbover the continent, compared to about 32 ppb at thewestern border, while for summer the continentalO₃ values ranged between 39 and 56 ppb and theoceanic mixing ratios were around 37 ppb. In the lowerfree troposphere average wintertime O₃ mixingratios were around 38 ppb, with only an 8 ppbdifference between 28°N and 79°N. For summerthe average O₃ levels decreased from about 55 ppbover Central Europe to 32 ppb at 79°N. Inaddition, O₃ and O_x(= O₃ + NO₂)in polluted and clean air were compared. Theamplitudes of the seasonal ozone variations increasedin the north-west to south-east direction, while thetime of the annual maximum was shifted from spring (atthe northerly sites) to late summer (at sites inAustria and Hungary), which reflected the contributionof photochemical ozone production in the lower partsof the troposphere.     

Observation of hydrogen peroxide concentrations in a Japanese red pine forest

In order to study the concentrations of hydrogen peroxide (H₂O₂) and the factors controlling its concentrations, we monitored concentrations of H₂O₂ and other gases such as sulfur dioxide, ozone, and NO _x as well as meteorological factors such as air temperature, relative humidity, and wind direction/speed during eight measurement periods from 2000 to 2002 in a Japanese red pine forest in Japan. The H₂O₂ concentrations ranged from below 0.01 to 1.64 ppb, and analysis of the diurnal variation in H₂O₂ concentration showed high concentrations around noon, and low concentrations in the morning and late afternoon. The H₂O₂ concentrations were high in early summer, when O₃ concentration, temperature, and solar radiation were high, and were low in fall, when O₃ concentration, temperature, and solar radiation were low. We propose that O₃ concentration affects the production of H₂O₂ in the monitored region during the period under study, but that high H₂O₂ concentrations were sometimes caused by the transport of polluted air from urban regions. H₂O₂ concentrations decreased remarkably when SO₂ concentrations increased by transported volcanic emission on Miyake Island. In the absence of the effects of SO₂, H₂O₂ concentrations increased with increasing O₃ concentration and temperature.     

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.     

臭氧对水稻叶片伤害、光合作用及产量的影响

OTC- 1型农田开顶式气室 ,对水稻进行不同臭氧浓度处理的长期接触试验 ,结果表明 :当试验浓度超过 1 0 0× 1 0 - 9时将对水稻叶片造成直接伤害 ,从而使水稻的光合能力和产量降低。     

Impacts of Future NOx and CO Emissions on Regional Chemistry and Climate over Eastern China

A coupled chemical/dynamical model (SOCOL-SOlar Climate Ozone Links) is applied to study the impacts of future enhanced CO and NOx emissions over eastern China on regional chemistry and climate. The result shows that the increase of CO and NOx emissions has significant effects on regional chemistry, including NOx, CO, O₃, and OH concentrations. During winter, the CO concentration is uniformly increased in the northern hemisphere by about 10 ppbv. During summer, the increase of CO has a regional distribution. The change in O₃, concentrations near eastern China has both strong seasonal and spatial variations. During winter, the surface O₃, concentrations decrease by about 2 ppbv, while during summer they increase by about 2 ppbv in eastern China. The changes of CO, NOx, and O₃, induce important impacts on OH concentrations. The changes in chemistry, especially O₃, induce important effects on regional climate. The analysis suggests that during winter, the surface temperature decreases and air pressure increases in central-eastern China. The changes of temperature and pressure produce decreases in vertical velocity. We should mention that the model resolution is coarse, and the calculated concentrations are generally underestimated when they are compared to measured results. However, because this model is a coupled dynamical/chemical model, it can provide some useful insights regarding the climate impacts due to changes in air pollutant emissions.     

Surface ozone measurements in the Venezuelan tropical savannah

A one-year set of surface ozone measurements in a four-station network located in the Venezuelan savannah is reported. The diurnal ozone variation is typical of continental stations with a maximum in the afternoon, when vertical turbulent mixing is strongest. The annual O₃ average concentration, based on the monthly averages of daily maxima, was 17±2 ppb, which is in good agreement with values reported for similar latitudes. The boundary-layer ozone levels did not fall below 8 ppb, in contrast with previous sporadic measurements made in tropical latitudes. No evidence was found that mesoscale O₃ downdrafts in the ITCZ in the South American continent are an important source of surface ozone. Finally, it is suggested that the relatively high ozone levels observed at the end of the dry season are probably of photochemical origin.     

Growth of monodisperse,submicron aerosol particles exposed to SO2, H2O2, and NH3

The growth of monodisperse particles (0.07 to 0.5 µm) exposed to SO₂ (0–860 ppb), H₂O₂ (0–150 ppb) and sometimes NH₃ (0–550 ppb) in purified air at 22 °C at relative humidities ranging from 25 to 75% were measured using the Tandem Differential Mobility Analyzer technique. The experiments were performed in a flow reactor with aqueous (NH₄)₂SO₄ and Na₂SO₄ droplets. For (NH₄)₂SO₄ droplets the fractional diameter growth was independent of size above 0.3 µm but decreased with decreasing size below that. When NH₃ was added the fractional growth increased with decreasing size. Measurements were compared with predictions of a model that accounts for solubility of the reactive gases, the liquid phase oxidation of SO₂ by H₂O₂, and ionic equilibria. Agreement between measured and predicted droplet growth is reasonable when the ionic strength effects are included. Theory and experiments suggest that NH₃ evaporation is responsible for the decrease in relative growth rates for small aqueous ammonium sulfate particles. The observed droplet growth rates are too slow to explain observed growth rates of secondary atmospheric sulfate particles.     

Spatial and temporal changes in vapor pressure deficit and their impacts on crop yields in China during 1980–2008

Vapor pressure deficit (VPD) is a widely used measure of atmospheric water demand. It is closely related to crop evapotranspiration and consequently has major impacts on crop growth and yields. Most previous studies have focused on the impacts of temperature, precipitation, and solar radiation on crop yields, but the impact of VPD is poorly understood. Here, we investigated the spatial and temporal changes in VPD and their impacts on yields of major crops in China from 1980 to 2008. The results showed that VPD during the growing period of rice, maize, and soybean increased by more than 0.10 kPa (10 yr)^–1 in northeastern and southeastern China, although it increased the least during the wheat growing period. Increases in VPD had different impacts on yields for different crops and in different regions. Crop yields generally decreased due to increased VPD, except for wheat in southeastern China. Maize yield was sensitive to VPD in more counties than other crops. Soybean was the most sensitive and rice was the least sensitive to VPD among the major crops. In the past three decades, due to the rising trend in VPD, wheat, maize, and soybean yields declined by more than 10.0% in parts of northeastern China and the North China Plain, while rice yields were little affected. For China as a whole, the trend in VPD during 1980–2008 increased rice yields by 1.32%, but reduced wheat, maize, and soybean yields by 6.02%, 3.19%, and 7.07%, respectively. Maize and soybean in the arid and semi-arid regions in northern China were more sensitive to the increase in VPD. These findings highlight that climate change can affect crop growth and yield through increasing VPD, and water-saving technologies and agronomic management need to be strongly encouraged to adapt to ongoing climate change.     

中美大气化学联合考察实验结果的初步分析与比较

根据临安区域本底站观测资料分析结果得出,中国中纬度地区秋、冬季O₃及其前体物NO_x等浓度偏高,可以对农作物和地表生态系统产生影响.观测结果表明:近地层大气O₃浓度主要决定于地面总辐射量控制下的光化学反应过程;O₃的生成受到前体物NO_x的控制,但O₃与NO_x存在着明显的非线性关系.从PEM-WESTA和B的实验及1995年的观测资料表明,O₃的生成效率随着NO_x浓度的增大而减小.尽管O₃的生成速率秋季比冬季的大,但由于秋季较高的NO_x抑制了过氧基的生成,因此冬季O₃的累积量几乎可以和秋季相比拟.在临安观测的NMHC和NO_x的比值比国外同纬度地区测值要大.这说明在临安本底站O₃的光化学生成中,NMHC不是控制物种.从而提示我们,在这些季节临安O₃光化学产物能够被NO_x浓度所控制.中美大气化学联合考察(PEM-WEST-B)实验期间,台湾省的卡盯站SO₂的平均浓度为0.29ppb,O₃的平均浓度为42.2ppb,可以认为此值为低纬度海岛的本底值.1994年PEM-WEST-B实验期间临安站的观测资料和台湾省的卡盯站资料相比,临安站SO₂的浓度约为卡盯站SO₂浓度的50倍左右,从而可以看出人类活动对大气本底的显着影响.     

The Influence of O3, Relative Humidity, NO and NO2 on the Oxidation of α-Pinene and Δ3-Carene

Upto 13% of -pinene and ³-carene had reacted after 213 s in this dark experimental set-up, where O₃, NO and NO₂ were mixed with terpenes at different relative humidities (RHs). The different experiments were planned according to an experimental design, where O₃, NO₂, NO, RH and reaction time were varied between high and low settings (25 and 75 ppb, 15 and 42%, 44 and 213 s). An increased amount of -pinene and ³-carene reacted in the chamber was observed, when the level of O₃, NO and reaction time was increased and RH was decreased. In the study, it was found that different interactions affected the amount of terpene reacted as well. These interactions were between O₃ and NO, O₃ and reaction time, NO and RH, and between NO and reaction time.     

Temperature variations and rice yields in China: historical contributions and future trends

Temperature is the principal factor that determines rice growth, development and ultimately grain yield. In this study, normal growing-degree-days (NGDD) and killing growing-degree-days (KGDD) were used to capture the different effects of normal and extreme temperatures on rice yields, respectively. Based on these indexes, we assessed the contributions of temperature variations to county-level rice yields across China during the historical period (1980–2008), and estimated the potential exposure of rice to extreme temperature stress in the near future (2021–2050). The results showed that historical temperature variations had measurable impacts on rice yields with a distinct spatial pattern: for different regions, such variations had contributed much to the increased rice yields in Northeast China (Region I) (0.59 % yield year^?1) and some portions of the Yunnan-Guizhou Plateau (Region II) (0.34 % yield year^?1), but seriously hindered the improvements of rice yields in the Sichuan Basin (SB) (?0.29 % yield year^?1) and the southern cultivation areas (Region IV) (?0.17 % yield year^?1); for the entire country, half of the contributions were positive and the other half were negative, resulting in a balance pattern with an average of 0.01 % yield year^?1. Under the RCP8.5 scenario, climate warming during 2021–2050 would substantially reduce cold stress but increase heat stress in the rice planting areas across China. For the future period, Region I, II and eastern China would be continually exposed to more severe cold stress than the other regions; Region III (including SB and the mid-lower reaches of Yangtze River (MLRYR)) would be the hot spot of heat stress.