An optimized method for airborne peroxyacetyl nitrate (PAN) measurements

In this paper we describe a gas-chromatographic method for PAN measurements in the background atmosphere, which has been adapted to the special requirements of aircraft based campaigns. The instrument is installed in a 1.21 m high, 19 inch rack which has a total weight of 70 kg and a power consumption of 750 VA. The gas chromatograph is equipped with a commercial liquid injector and a valve system for injection of gaseous samples. The gas-inlet system allows automatic injection of samples with defined and constant mass, independent from ambient pressure variations. Two different methods are used for calibration: Liquid PAN calibration samples and a diffusion source for gas-phase calibrations. Both methods have reproducibilities better than 90% and agree with each other to better than 85%. An optimum selectivity of the gas-chromatographic separation is obtained by a combination of two short megabore capillary columns of different polarity. The flow rates are 15 cm³/min, the column temperature is 26°C. For detection an electron-capture detector, operated at 30°C, is used. To allow a reliable control of these relatively low temperatures the instrument is equipped with peltier cooling. To avoid baseline or signal drifts caused by pressure variations in the aircraft cabin an electronic control of the system pressure is integrated into the instrument. The lower limit of detection is better than 15 ppt (3 ), the time needed for one measurement is less than 4 min. Preliminary results from a flight campaign conducted in June 1994 demonstrate the suitability of the instrument for airborne PAN measurements.     

Henry's law constant and hydrolysis of peroxyacetyl nitrate (PAN)

The effect of temperature on the solubility of PAN and on its hydrolysis rate in near-neutral and slightly acidic water were studied in a bubble column apparatus. The results obtained are a Henry's law coefficient H=10^–9.04±0.6 exp[(6513±376)/T] M atm^–1, and a first-order hydrolysis rate constant k=10^6.60±1.0 exp[(–6612±662)/T] s^-1, which was independent of pH in the range 3.2pH6.7. The products formed are nitrite and nitrate in approximately equal proportions under near-neutral conditions. At a pH<4, nitrite is oxidized in a secondary reaction, and nitrate becomes the only product at low pH. Previously measured deposition velocities of PAN on stagnant water surfaces are shown to be hydrolysis rate limited.     

Five years of cloud enhanced surface UV radiation measurements at two sites (in the Northern and Southern Hemispheres)

This is the first paper to report a detailed comparison between ground based measurements of cloud enhanced ultraviolet (UV) radiation at sites located in both hemispheres. The measurements were undertaken at a Northern Hemisphere site (at the campus of the University of Girona in Spain) and a Southern Hemisphere site (campus of the University of Southern Queensland, Toowoomba, Australia). These sites were chosen as they have both simultaneous sky camera and solar radiation (including UV) measurement campaigns operating for at least 5 years over the same time period. Although hemispheric comparisons of UV radiation are not new, this paper focuses on a study of enhancements, including a comparison of the frequency of occurrence and associated cloud types, at the locations with differing climatology. It is found that although there are commonalities between the sites, such as the correlation of the frequency of enhancements with larger solar zenith angle (SZA) both at Girona and Toowoomba, there are differences too, e.g. the frequency of occurrence of the enhancements, and the type of clouds that produce most enhancements (cirrus at Girona, cumulus at Toowoomba). It is suggested that this is due to the differences in latitude coupled with a large amount of Cirriform cloud, especially corresponding to large SZA, at Girona. Possible explanations for this major difference were examined, with the most likely hypothesis relating to multiple scattering due to Cirriform cloud and the subsequent effect on UV radiation on a horizontal surface at large SZA.     

The H2/CO ratio of emissions from combustion sources: comparison of top-down with bottom-up measurements in southwest Germany

The hydrogen-to-carbon monoxide (H₂/CO) emission ratio of anthropogenic combustion sources was determined from more than two years of quasi-continuous atmospheric observations in Heidelberg (49°24' N, 8°42' E), located in the polluted Rhein-Neckar region. Evaluating concurrent mixing ratio changes of H₂ and CO during morning rush hours yielded mean molar H₂/CO ratios of 0.40 ± 0.06, while respective results inferred from synoptic pollution events gave a mean value of 0.31 ± 0.05 mole H₂/mole CO. After correction for the influence of the H₂ soil sink on the measured ratios, mean values of 0.46 ± 0.07 resp. 0.48 ± 0.07 mole H₂/mole CO were obtained, which are in excellent agreement with direct source studies of traffic emissions in the Heidelberg/Mannheim region (0.448 ± 0.003 mole H₂/mole CO). Including results from other European studies, our best estimate of the mean H₂/CO emission ratio from anthropogenic combustion sources (mainly traffic) ranges from 0.45 to 0.48 mole H₂/mole CO, which is about 20% smaller than the value of 0.59 mole H₂/mole CO which is frequently used as the basis to calculate global H₂ emissions from anthropogenic combustion sources.     

Long-term high-frequency measurements of dibromomethane in the atmosphere at algae-rich and algae-poor coastal sites

Dibromomethane (CH₂Br₂), a natural stratospheric ozone depleting substance, is mostly emitted from the ocean, but the relative importance of coastal (or macroalgae) and open ocean emissions is unknown. We made long-term high-frequency measurements of CH₂Br₂ concentrations at two remote coastal sites in Japan, on the subtropical Hateruma Island (poor in macroalgae) and at Cape Ochiishi (rich in macroalgae). CH₂Br₂ concentrations at Hateruma showed prominent seasonal variation, being lower in summer (around 0.94 ppt) than in winter (around 1.23 ppt). In contrast, CH₂Br₂ concentrations at Ochiishi were highly variable, often exceeding 2 ppt in the summer but with minimum baseline concentrations close to those from Hateruma; in the winter the concentrations were almost constant at about 1.3 ppt. Analysis of the data suggested that (1) emissions from macroalgae were not likely to extend offshore, but instead were localized near the shore, (2) strong macroalgal emissions of CH₂Br₂ were almost limited to the summer, but it was not reflected in the seasonality of the baseline concentrations of CH₂Br₂ in the atmosphere, and therefore (3) macroalgal or coastal emissions of CH₂Br₂ in the temperate zone might have a rather limited contribution to the global CH₂Br₂ sources. These findings are especially important for the understanding of the tropospheric and stratospheric bromine budget.     

Simultaneous measurements of ozone and its precursors on a diurnal scale at a semi urban site in India

Simultaneous observations of surface ozone (O₃) with its precursors namely, carbon monoxide (CO) and oxides of nitrogen (NO_x) have been taken on diurnal scale from a tropical semi-urban site, Pune (18.54°N, 73.81°E) in India. We present the data for one year (2003–2004) period to study the salient features of these trace gases. The peak in amplitude of ozone is found during the noontime whereas in CO and NO_X it is observed in the morning hours between 0800 and 0900 H. The concentration of these pollutants drop down considerably during southwest monsoon months and the diurnal pattern also become very weak. The diurnal trends of these gases are found to be different for different seasons, which are specific to the receptor site. Model simulations using 3-D chemical-transport model with regional emission inventories and observed winds have also been carried out. The comparison of model results with observations, on seasonal basis yielded a reasonable qualitative agreement. The relative role of local emissions and long range transport in the diurnal pattern for different seasons has been outlined, which reveals that the ozone is highly influenced by regional/long range transport in this region. The effect of precursor amounts in the morning on afternoon ozone peak levels has been investigated using the lag correlation study, which reveals that a time lag of 5–7 h is required for most of these precursor gases to photo-chemically produce ozone to its maximum potential. Results are discussed in the light of available topographic and meteorological conditions.     

Groundbased Doas UV/visible measurements at Kiruna (Sweden) during the sesame winters 1993/94 and 1994/95.

Zenith sky observations of O3, NO2, OClO and BrO are reported, which were performed at Kiruna (67.9°N, 21.1°E) within the SESAME winters 1993/1994 and 1994/95. For both winters large total amounts of OClO were observed inside the polar vortex at twilight, indicating the degree and the temporal variation of the halogen activation of the polar stratosphere. Occasionally OClO could also be observed outside the polar vortex, most likely due to export of halogen activated vortex air masses into the ambient stratosphere. BrO could also be detected in winter 1994/95, with the largest slant column amounts (5·1014/cm2) occuring in the polar vortex in mid-winter. Similar abundances of stratospheric BrO were observed at dusk and dawn, for both, air masses inside and outside the vortex. This observation is in reasonable agreement with previous studies on stratospheric BrO (observations and models) of Wahner et al. (1992), Arpag et al. (1994), Krug et al. (1996), and Lary et al. (1996a,b), but partly in disagreement with those of Solomon et al. (1989), Fish et al. (1995), and Sessler et al. (1996).     

Temporal analysis of thermal bioclimate conditions between Kolkata (India) and its three neighbouring suburban sites

Theoretical and Applied Climatology - The study of human biometeorological conditions is becoming increasingly important in climate perception for the improvement of public health system. The...     

Concentrations of metallic elements in long-range-transported aerosols measured simultaneously at three coastal sites in China and Japan

To determine the effects of long-range transport of aerosols from an upwind area in East Asia to a downwind area in Japan, we chemically analyzed aerosols collected simultaneously on Tuoji Island (Shandong Province, China), Fukue Island (Nagasaki Prefecture, Japan), and Cape Hedo (Okinawa Prefecture, Japan). We focused on changes in the metallic composition of PM_2.5 aerosols during long-range transport. The average mass concentrations of PM_2.5 at the three sites decreased in the order Tuoji Island > Fukue Island ≈ Cape Hedo (48.3 ± 4.5, 13.9 ± 1.5, and 13.2 ± 0.9 μg/m³, respectively). The fraction of coarse particles in total suspended particles estimated by (1–PM_2.5/TSP) was highest on Cape Hedo, indicating that the contribution of sea salts was increased by long-range transport of the aerosols over the ocean. Enrichment factor analysis revealed that at all three sites, Al, K, Ca, Mn, Fe, Co, Sr, and Ba originated from soil; whereas Cr, Ni, Cu, Zn, As, Mo, Ag, Cd, Sn, Sb, Tl, and P appeared to be of anthropogenic origin. Na was the most abundant element on Cape Hedo, indicating the addition of sea salts during aerosol transport. The V concentration was highest at Fukue Island, which was ascribed to V emission from ships. Sixty-one percent of the V on Fukue Island and 62% of the V on Cape Hedo were determined to have originated from ships, implicating of data obtained on dates during which backward trajectory analysis indicated that the same air mass passed over Tuoji Island, Fukue Island, and Cape Hedo in that order.     

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.     

Analyses of Orissa Super Cyclone using TRMM (TMI), DMSP (SSM/I) and OceanSat-I (MSMR) Derived Data

The super cyclone in October 1999 was the most intense tropical cyclone in the last century in Orissa, a coastal state in India. This state was battered for more than two days by strong winds and intense rain killing thousands of people. The main objective of this study is to examine the impact of total precipitable water content (TPWC) and surface wind speed data from sensors on board the Tropical Rainfall Measuring Mission (TRMM), Defense Meteorological Satellite Project (DMSP), and Indian Remote Sensing Satellite (OceanSat-I) satellites on the data assimilation system at NCMRWF, New Delhi during the Orissa cyclone period. Comparison of various assimilation experiments suggests that the utilization of TRMM Microwave Imager (TMI) data in the assimilation produced the best analyses. However, in all the forecasts, the storm was predicted to weaken and did not have a reasonably good track. Assimilation experiments with the other two satellite data showed the cyclone track much to the south of the observed track and also it was a weak storm. Biases in the data, when compared with each other, are evident in the analyses also. Better analyses are obtained when the satellite data are used in the originally obtained resolution than when reduced by averaging. A forecast experiment with assimilated data, utilizing the Cloud Motion Vectors (CMVs) from METEOSAT along with TMI data, produced the best forecast among all the experiments. However, the forecast quality was poor. A high-resolution data assimilation experiment was carried out to see the impact of model resolution on the analyses of the cyclone. The strength of the cyclone further increased when higher resolution TMI data were included. The study highlights the need for more satellite data over the Indian Ocean, where conventional data coverage is too poor to define the vertical structure of the atmosphere.     

An analysis of ozone measurements at Cerro Tololo (30°S, 70°W, 2200 m.a.s.l.) in Chile

Increases in tropospheric ozone (O₃) abundance are likely to take place in the near future in the populous and rapidly developing countries in the tropics and subtropics. An accurate evaluation of the future impact of increasing industrial activities in tropical and subtropical areas requires knowledge of the background levels of ozone. New ozone monitoring stations have been installed at several sites by the World Meteorological Organization (WMO) since the mid‐90s. We analyze ozone data collected during two years since April 1996 at Cerro Tololo (30°S, 70°W, 2200 m.a.s.l.) some 50 km east from the city of La Serena. In this paper, we describe some of the atmospheric chemistry and meteorology that characterizes the Tololo site. The data show a seasonal variation with maximum mixing ratios in late winter and spring and minimum mixing ratios in late summer and early fall. These variations are most likely associated with the large‐scale subsidence of the Hadley circulation and the location of the subtropical jet stream (STJ). Also, there is a diurnal variation that is probably partly associated with a mountain wind flow which is strongest in late spring and summer months. No significant mixing with marine boundary layer air perturbed by anthropogenic activities is apparent from the data. We find the Cerro Tololo site to be generally representative for background conditions of free‐tropospheric air in the subtropics of the Southern Hemisphere. This work is done within the framework of a larger effort recently started by several Chilean institutions in cooperation with research centers abroad.     

Daily and monthly averaged aerosol optical properties and diurnal variability deduced from AERONET sun-photometric measurements at Thala site (Tunisia)

Summary Spectral aerosol optical thickness have been measured at Thala site (central West of Tunisia) from March to October 2001. The measurement site is located in a continental and non industrialized region, approximately 150 km from the North coast of the Mediterranean Sea and nearby the Algerian border. Thala site could be then influenced by the dust content of the continental air masses carried by western and southern winds. A second pollution source is constituted by industrial and/or maritime particles carried by northern and eastern winds. AOT measurements acquired through the ground-based AERONET are analyzed. The diurnal cycle over Thala and two other areas within the network showed various trends and a prevailing pattern of the optical thickness increase by 10–40% during the day. Daily AOT and monthly averaged aerosol optical thickness, ?ngstr?m coefficient and precipitable water vapor are computed and compared with those of other sites. Measured meteorological parameters represent a valuable supplement to the data sets with the sunphotometer measurements. The analysis of the results shows that there is a high correlation between aerosol optical properties (AOT and ?ngstr?m coefficient) and the local weather conditions, essentially wind speed and direction and air specific humidity.     

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.     

延安市能见度与相对湿度和PM_(2.5)及PM_(10)的关系

为分析延安市能见度与相对湿度、气溶胶质量浓度的关系,利用2016年延安大气成分站PM_(2.5)、PM_(10)和国家基本气象站相对湿度、能见度观测资料,对能见度与相对湿度、PM_(2.5)和PM_(10)的关系进行分析。结果表明:全年能见度与相对湿度的线性相关系数最高,与PM_(10)次之;随相对湿度的增大,能见度明显降低。相对湿度<50%时,能见度与PM_(2.5)的非线性相关性高于与PM_(10)的相关性;相对湿度>50%时,能见度与PM_(10)的非线性相关性则较PM_(2.5)好。相较于线性拟合方法,能见度与相对湿度的非线性拟合公式能更好地表现二者的关系。利用相对湿度、PM_(2.5)和PM_(10)观测数据对能见度做多元非线性拟合,检验结果表明,计算得出的拟合公式能较好地模拟延安市能见度的变化规律。