The influence of medium-range transport on O3 levels at a rural site in Israel

Simultaneous ozone measurements were made at a rural site, 25 km SSW of the city of Jerusalem, and in the center of the city during a period of 28 months. The ozone data were supplemented by SO₂, NO/NO _x ,and meteorological measurements at both sites. Elevated ozone concentrations were recorded at the rural site, mostly during the spring months (May and June) during which the monthly averages and the monthly averages of the daily 30 min maximum levels equalled those measured in the city. During the summer months, both average and peak levels were lower at the rural site by 20 and 35 ppb. The increased ozone levels at the rural site were accompanied by a parallel increase of SO₂ and NO _x ,suggesting hat the excess ozone at the rural site is a result of a transformation during transport of air pollutants from coastal sources.     

Chemistry–Climate Interactions of Stratospheric and Mesospheric Ozone in EMAC Long-Term Simulations with Different Boundary Conditions for CO2, CH4, N2O,and ODS

Abstract

To evaluate future climate change in the middle atmosphere and the chemistry–climate interaction of stratospheric ozone, we performed a long-term simulation from 1960 to 2050 with boundary conditions from the Intergovernmental Panel on Climate Change A1B greenhouse gas scenario and the World Meteorological Organization Ab halogen scenario using the chemistry–climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC). In addition to this standard simulation we performed five sensitivity simulations from 2000 to 2050 using the rerun files of the simulation mentioned above. For these sensitivity simulations we used the same model setup as in the standard simulation but changed the boundary conditions for carbon dioxide (CO₂), methane (CH₄), nitrous oxide (N₂O), and ozone-depleting substances (ODS). In the first sensitivity simulation we fixed the mixing ratios of CO₂, CH₄, and N₂O in the boundary conditions to the amounts for 2000. In each of the four other sensitivity simulations we fixed the boundary conditions of only one of CO₂, CH₄, N₂O, or ODS to the year 2000.

In our model simulations the future evolution of greenhouse gases leads to significant cooling in the stratosphere and mesosphere. Increasing CO₂ mixing ratios make the largest contributions to this radiative cooling, followed by increasing stratospheric CH₄, which also forms additional H₂O in the upper stratosphere and mesosphere. Increasing N₂O mixing ratios makes the smallest contributions to the cooling. The simulated ozone recovery leads to warming of the middle atmosphere.

In the EMAC model the future development of ozone is influenced by several factors. 1) Cooler temperatures lead to an increase in ozone in the upper stratosphere. The strongest contribution to this ozone production is cooling due to increasing CO₂ mixing ratios, followed by increasing CH₄. 2) Decreasing ODS mixing ratios lead to ozone recovery, but the contribution to the total ozone increase in the upper stratosphere is only slightly higher than the contribution of the cooling by greenhouse gases. In the polar lower stratosphere a decrease in ODS is mainly responsible for ozone recovery. 3) Higher NO_x and HO_x mixing ratios due to increased N₂O and CH₄ lead to intensified ozone destruction, primarily in the middle and upper stratosphere, from additional NO_x; in the mesosphere the intensified ozone destruction is caused by additional HO_x. In comparison to the increase in ozone due to decreasing ODS, ozone destruction caused by increased NO_x is of similar importance in some regions, especially in the middle stratosphere. 4) In the stratosphere the enhancement of the Brewer-Dobson circulation leads to a change in ozone transport. In the polar stratosphere increased downwelling leads to additional ozone in the future, especially at high northern latitudes. The dynamical impact on ozone development is higher at some altitudes in the polar stratosphere than the ozone increase due to cooler temperatures. In the tropical lower stratosphere increased residual vertical upward transport leads to a decrease in ozone.     

Ozone UV spectroscopy. II. Absorption cross-sections and temperature dependence

Absolute absorption cross-sections of ozone have been measured at five temperatures (218–295 K) in the UV wavelength region corresponding to the Hartley and Huggins bands (195–345 nm). The aim is to give to the users, a coherent set of data determined under high resolution. A comparison with previous work has been made.     

Vertical ozone distribution characteristics deduced from ∼ 44,000 re-evaluated Umkehr profiles (1957–2000)

Summary Umkehr observations taken during the 1957–2000 period at 15 stations located between 19 and 52° N have been reanalyzed using a significantly improved algorithm-99, developed by DeLuisi and Petropavlovskikh et al. (2000a,b). The alg-99 utilizes new latitudinal and seasonally dependent first guess ozone and temperature profiles, new vector radiative transfer code, complete aerosol corrections, gravimetric corrections, and others. Before reprocessing, all total ozone values as well as the N-values (radiance) readings were thoroughly re-evaluated. For the first time, shifts in the N-values were detected and provisionally corrected. The re-evaluated Umkehr data set was validated against satellite and ground based measurements. The retrievals with alg-99 show much closer agreement with the lidar and SAGE than with the alg-92. Although the latitudinal coverage is limited, this Umkehr data set contains ∼ 44,000 profiles and represent the longest (∼ 40 years) coherent information on the ozone behavior in the stratosphere of the Northern Hemisphere. The 14-months periods following the El-Chichon and the Mt. Pinatubo eruptions were excluded from the analysis. Then the basic climatological characteristics of the vertical ozone distribution in the 44–52° N and more southern locations are described. Some of these characteristics are not well known or impossible to be determined from satellites or single stations. The absolute and relative variability reach their maximum during winter–spring at altitudes below 24 km; the lower stratospheric layers in the middle latitudes contain ∼ 62% of the total ozone and contribute ∼ 57% to its total variability. The layer-5 (between ∼ 24 and 29 km) although containing 20% of the total ozone shows the least fluctuations, no trend and contributes only ∼ 11% to the total ozone variability. Meridional cross-sections from 19 to 52° N of the vertical ozone distribution and its variability illustrate the changes, and show poleward-decreasing altitude of the ozone maximum. The deduced trends above 33 km confirm a strong ozone decline since the mid-1970s of over 5% per decade without significant seasonal differences. In the mid-latitude stations, the decline in the 15–24 km layer is nearly twice as strong in the winter-spring season but much smaller in the summer and fall. The effect of including 1998 and 1999 years with relatively high total ozone data reduces the overall-declining trend. The trends estimated from alg-99 retrievals are statistically not significantly different from those in WMO 1998a; however, they are stronger by about 1% per decade in the lower stratosphere and thus closer to the estimates by sondes. Comparisons of the integrated ozone loss from the Umkehr measurements with the total ozone changes for the same periods at stations with good records show complete concurrence. The altitude and latitude appearances of the long-term geophysical signals like solar (1–2%) and QBO (2–7%) are investigated. Received April 12, 2001 Revised September 19, 2001     

A Eulerian air pollution model for Europe with nonlinear chemistry

A long-range transport model with nonlinear chemical reactions is described. The model contains 35 pollutants and 70 chemical reactions. This is a Eulerian model defined on a space domain containing the whole of Europe. The spherical space domain (corresponding to the Earth's surface covered by the model) is mapped into a square plane domain and discretized by using a 32×32 grid. The grid increments are equidistant (both along the Ox axis and along the Oy axis). The choice of values of the physical parameters involved in the model and the numerical treatment of the model are shortly discussed. The model is tested with meteorological data for 1985 and 1989. The numerical results are compared with measurements at stations located in different European countries. Extensive comparisons of ozone concentrations for July 1985 with measurements taken at 24 European stations are also carried out. Results concerning three episodes in July 1985 as well as results obtained in the study of the sensitivity of the ozone concentrations to variations of NO _x and/or anthropogenic VOC emissions are presented. The advantages and the limitations of such a model are discussed. The model is continuously improved by adding new modules to it. The plans for improvements in the near future are outlined.     

Airborne measurements of turbulent trace gas fluxes and analysis of eddy structure in the convective boundary layer over complex terrain

Using the new high-frequency measurement equipment of the research aircraft DO 128, which is described in detail, turbulent vertical fluxes of ozone and nitric oxide have been calculated from data sampled during the ESCOMPTE program in the south of France. Based on airborne turbulence measurements, radiosonde data and surface energy balance measurements, the convective boundary layer (CBL) is examined under two different aspects. The analysis covers boundary-layer convection with respect to (i) the control of CBL depth by surface heating and synoptic scale influences, and (ii) the structure of convective plumes and their vertical transport of ozone and nitric oxides. The orographic structure of the terrain causes significant differences between planetary boundary layer (PBL) heights, which are found to exceed those of terrain height variations on average. A comparison of boundary-layer flux profiles as well as mean quantities over flat and complex terrain and also under different pollution situations and weather conditions shows relationships between vertical gradients and corresponding turbulent fluxes. Generally, NO_x transports are directed upward independent of the terrain, since primary emission sources are located near the ground. For ozone, negative fluxes are common in the lower CBL in accordance with the deposition of O₃ at the surface.The detailed structure of thermals, which largely carry out vertical transports in the boundary layer, are examined with a conditional sampling technique. Updrafts mostly contain warm, moist and NO_x loaded air, while the ozone transport by thermals alternates with the background ozone gradient. Evidence for handover processes of trace gases to the free atmosphere can be found in the case of existing gradients across the boundary-layer top. An analysis of the size of eddies suggests the possibility of some influence of the heterogeneous terrain in mountainous area on the length scales of eddies.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

A 10-year study of background surface ozone concentrations on the island of Gozo in the Central Mediterranean

A 10-year study of surface ozone mixing ratios in the Central Mediterranean was conducted based on continuous ozone measurements from 1997 to 2006 by a background regional Global Atmospheric Watch (GAW) station on the island of Gozo. The mean annual maximum mixing ratio is of the order of 66 ppbv in April–May with a broad secondary maximum of 64 ppbv in July–September. No long-term increase or decrease in the background level of surface ozone could be observed over the last 10 years. This is contrary to observations made in the Eastern Mediterranean, where a slow decrease in the background ozone mixing ratio was observed over the past 7 years. Despite the very high average annual ozone mixing ratio exceeding 50 ppbv—in fact, the highest average background ozone mixing ratio ever measured in Europe—, the diurnal O _{3 max}/O _{3 min} index of <1.40 indicates that the island of Gozo is a good site for measuring background surface ozone. However, frequent photosmog events from June to September during the past 10 years with ozone mixing ratios exceeding 90 ppbv indicate that the Central Mediterranean is prone to long-range transport of air pollutants from Europe by northerly winds. This was particularly evident during the so-called “August heatwave” of the year 2003 when the overall ozone mixing ratio was 4.6 ppbv higher than the average of all other 9 months of August since 1997. Air mass back-trajectory analysis of the August 2003 photosmog episodes on Gozo confirmed that ozone pollution originated from the European continent. Regression analysis was used to analyse the 10-year data set in order to model the behaviour of the ozone mixing ratio in terms of the meteorological parameters of wind speed, relative humidity, global radiation, temperature, month of year, wind sector, atmospheric pressure, and time of day (predictors). Most of these predictors were found to significantly affect the ozone mixing ratios. From March to November, the monthly average of the AOT40 threshold value for the protection of crops and vegetation against ozone was constantly exceeded on Gozo during the past 10 years.     

Homogenisation and trend detection analysis of broken series of solar UV-B data

Summary Statistical techniques have been developed to homogenise a broken series of clear-sky solar UV-B radiation, measured by a Robertson Berger (RB) meter over the period 1981–90 at Invercargill, New Zealand, and to analyse the series for long term trend. Statistical modelling of the quasi-linear UV-B/ozone relationship evident in the departures of daily clear-sky UV-B data and coincident satellite ozone data from their respective mean references has been used to provide a self-consistent de-seasonalised data set of UV-B and ozone departures, and to bridge a major gap in calibration that separates the data set into two periods, 1981–86 and 1988–90. The choice of UV-B reference is important to the quality of the results and particular attention was given to the methodology for defining it. Four alternative objective adjustment procedures for calibrating the 1988–90 period against the 1981–86 period were examined. Because our interest lies primarily in the higher values of summer, a UV-B-weighted procedure was chosen. The modelling and homogenisation techniques developed may have application in related analysis problems. Analysis of the data for the independent 1981–86 period showed large trends in ozone and UV-B, but this was mostly due to a period of very low ozone values during 1985. Over the whole period, 1981–90, the ozone trend was –4.7%/decade. The corresponding UV-B trend was +5.8%/decade, but this result is not independent of the corresponding ozone trend because the homogenisation procedure imposes the assumption of the derived UV-B/ozone relationship on the 1988–90 UV-B data. However, the evidence suggests there is little reason to doubt that solar UV-B radiation has increased at the site by about +6% per decade.With 10 Figures     

The Influence of Selected Meteorological Parameters on the Concentration of Surface Ozone in the Central Region of Poland

Abstract?This paper presents the results of measurements of the concentration of surface ozone and concurrent standard meteorological parameters: total solar radiation, temperature, relative humidity, pressure, wind speed, and vertical and horizontal components of the wind. The data were collected from 2005 to 2010 at stations located in central Poland (Mazowieckie voivodeship): Warszawa (urban), Legionowo (suburban), Granica and Belsk (rural). Furthermore, Granica is situated in the forested area of Kampinoski National Park. Continuously measured surface ozone concentrations demonstrated the well-known diurnal cycle of surface ozone concentration with a maximum in the afternoon and a minimum in the early morning hours. The averaged diurnal variations over six years reveal that the highest concentrations appear at rural stations (Belsk: 55?µg?m^?3 and Granica: 50?µg?m^?3) and the lowest at the urban station (Warszawa: 41?µg?m^?3). The threshold for high levels of surface ozone (120?µg?m^?3 per 8?h) was exceeded most often at Granica and Belsk. The occurrence of the ozone “weekend effect,” especially at urban stations, has been identified. The difference between weekend and weekday surface ozone concentrations at urban and rural stations was as high as 6.5?µg?m^?3 and approximately 2?µg?m^?3, respectively. Using appropriate statistical tools, it has been shown that meteorological conditions have a significant influence on ozone concentration. High correlation coefficients were found between ozone concentration and solar radiation, temperature, relative humidity, and wind speed. The forward stepwise regression model explains up to 75% of the variations in daily surface ozone concentration in terms of meteorological variability in summer and up to 70% in winter. At the same time, a multilayer perceptron neural network model was used to reconstruct the concentration of surface ozone. High correlation coefficients (up to 0.89) indicate that, on the basis of standard meteorological parameters and NO₂ concentration, we can determine ozone concentration with high accuracy.     

Observational study of surface ozone at an urban site in East China

In this study, we present the observational data of near surface ozone and some meteorological parameters during 2004, at an urban site (36°42′ N, 117°08′ E, 34.5 m a.s.l.) of Jinan, China. Hourly ozone concentrations exceeding the standard value of China, 100 ppbv, were observed for 65 h (in 23 days) from April to October, and values exceeding US NAAQS (National Ambient Air Quality Standard) for 1 h ozone, 120 ppbv, were observed for 15 h (in 7 days) from late May to early July. Ozone formation presented the phenomenon of “weekend effect”, especially in summer. Monthly variation of ozone coincided with temperature except for July and August. The low ozone levels in July and August may be due to the short sunshine duration and much rainfall during this period. Among these meteorological parameters, daily averaged ozone shows a significant correlation with temperature (r = 0.66) in the year and with relative humidity (r = − 0.75) in summer. Throughout the year, high ozone concentrations were mainly associated with the wind from 180 to 247.5°, while high ozone concentration seemed to have no obvious correlation with a given wind direction in summer. An anomalous nocturnal high ozone episode during 23–25 May 2004 was investigated. Growth fractions of ozone during the nighttime episode were 62.2% and 71.1% for 23 and 24 May, respectively. Synoptic analysis shows that favorable synoptic condition had presumably elevated the background ozone level in this region. Backward trajectory analysis shows that the increase of ozone concentration and the relatively constant high ozone concentrations during the night of May 23 might originate from the transport of ozone rich air mass above boundary layer. Transport of ozone from Yangtze Delta and East Central China might be a significant process for the high ozone level during night May 24 at Jinan.     

Subsonic aircraft and ozone trends

Growth in subsonic air traffic over the past 20 years has been dramatic, with an annual increase of }6.1% over the decade between 1978 and 1988. Furthermore, aircraft activities in the year 2000 are predicted to be double those of 1990, with a shift towards more high-flying, longhaul subsonics. Aircraft exhaust gases increase the amount of nitrogen oxides (NO _x ) in the upper troposphere/lower stratosphere through injection at cruise altitudes. Given that NO _x is instrumental in tropospheric ozone production and stratospheric ozone destruction, it is important to determine the influence of subsonic aircraft NO _x emissions on levels of atmospheric ozone. This paper describes calculations designed to investigate the impact that subsonic aircraft may already have had on the atmosphere during the 1980s, run in a 2-D chemical-radiative-transport model. The results indicate a significant increase in upper tropospheric ozone over the decade arising from aircraft emissions. However, when comparing model results with observational data, certain discrepancies appear. Lower stratospheric ozone loss over the 1980s does not appear to be greatly altered by the inclusion of aircraft emissions in the model. However, given the trend in greater numbers of long-haul subsonic aircraft, this factor must be considered in any further calculations.     

双差分吸收激光雷达:-种能有效减小气溶胶对臭氧测量影响的方法

文中提出了一种新的激光雷达测量臭氧的方法：双差分吸收方法。理论分析和数值模拟表明这种方法可以有效减小气溶胶消光和后向散射对臭氧测量的影响，从而使激光雷达在气溶胶影响严重地区测量的臭氧精度比传统差分吸收激光雷达大大提高。利用（２８９，３１３；２７７．１，２９９．１ｎｍ）或（２６８．４，２８９；２７７．１，２９９．１ｎｍ）４波长进行双差分吸收可以用于对流层大气气溶胶含量丰富或分布不均匀地区臭氧的测量。利用（２９９．１，３４１．５；３０８，３５３ｎｍ）４波长进行双差分吸收可以对火山爆发后平流层臭氧进行较精确的测量。     

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.     

Daytime variations of ozone eddy fluxes to maize

The vertical fluxes of ozone, momentum and heat in the atmospheric surface layer have been measured by eddy correlation above both mature and senescent maize canopies. Aerodynamic formulae are applied to find that the bulk canopy surface resistancer _c to ozone uptake and destruction varies between 4.0 and 0.5 s cm⁻¹ during the daytime. Apparently, surface properties tend to control the removal of ozone at the surface of the earth. For a lush canopy, the stomatal diffusion resistance is the most important property, while changes in surface temperature have little effect. Destruction at the soil and exterior plant surfaces appears to account for 20–50% of the total loss if leaf mesophyll resistances are assumed to be very small. Free water at leaf surfaces may at times inhibit ozone removal by both senescent and healthy plants.     

Ozone Concentrations in Rural Regions of the Yangtze Delta in China

Elevated concentrations of ozone have been observed at six non-urban, surface monitoring sites in the Yangtze Delta of China during a 16-month field experiment carried out in 1999 and 2000 as part of the joint Chinese-American China-MAP Project (the Yangtze Delta of china as an Evolving Metro-Agro-Plex). The average daytime (0900–1600 h) ozone levels for the monitoring period at sites ranged from 35 to 47 ppbv (parts per billion by volume) and the mean ozone levels from 26 to 35 ppbv. Observed data show seasonal variation obviously, with highest mixing ratios of ozone in May. Average daytime ozone levels in May at sites were between 60 and 79 ppbv. High ozone concentrations were most prevalent during the late spring. Frequency counts of hourly mean ozone concentration over 60 ppbv and 40 ppbv appeared peak values of 22–39% and 42–74% in May at sites. Even higher daytime ozone levels were observed during two regional episodes, in which average daytime (0900–1600 h) ozone concentrations during 10 May and 23 May 2000 were 68 to 81 ppbv, during Oct. 18 and Oct. 28, 1999 were 59 to 67 ppbv at sites. Peak value of ozone mixing ratio appearing in late spring, instead of in summer, was attributed to summer monsoon. Backward trajectories showed that ozone episodes associated with meteorological conditions. Also many high ozone levels associated with high CO levels and high CO to NO _x ratios, which suggests a contribution from sources of emission involving incomplete combustion.     

Calculation of cloud modification factors for the horizontal plane eye damaging ultraviolet radiation

This research examines the influence of cloud on the cataract effective UV (UV_Cat) irradiances on a horizontal plane over an extended period of 12months that included the range of cloud conditions, solar zenith angle (SZA) and ozone conditions experienced over that time. The data were collected at five minute intervals. Cloud modification factors were determined from the influence of clouds on the global broadband solar radiation and these were applied to the cloud free cataract effective UV to evaluate the UV_Cat irradiances on a horizontal plane for all cloud conditions. A comparison of the measured and calculated UV_Cat irradiances for the 2004 data set in the range of SZA of 70° or less provided an R² value of 0.85. The data in the first 6months of 2005 for an SZA of 70° or less that were at a different time to that when the technique was developed provided an R² value of 0.83 for the comparison of the measured and calculated UV_Cat irradiances.     

A model investigation of the impact of increases in anthropogenic NO x emissions between 1967 and 1980 on tropospheric ozone

Recent observations suggest that the abundance of ozone between 2 and 8 km in the Northern Hemisphere mid-latitudes has increased by about 12% during the period from 1970 to 1981. Earlier estimates were somewhat more conservative suggesting increases at the rate of 7% per decade since the start of regular observations in 1967. Previous photochemical model studies have indicated that tropospheric ozone concentrations would increase with increases in emissions of CO, CH₄ and NO _x . This paper presents an analysis of tropospheric ozone which suggests that a significant portion of its increase may be attributed to the increase in global anthropogenic NO _x emissions during this period while the contribution of CH₄ to the increase is quite small. Two statistical models are presented for estimating annual global anthropogenic emissions of NO _x and are used to derive the trend in the emissions for the years 1966–1980. These show steady increase in the emissions during this interval except for brief periods of leveling off after 1973 and 1978. The impact of this increase in emissions on ozone is estimated by calculations with a onedimensional (latitudinal) model which includes coupled tropospheric photochemistry and diffusive meridional transport. Steady-state photochemical calculations with prescribed NO _x emissions appropriate for 1966 and 1980 indicate an ozone increase of 8–11% in the Northern Hemisphere, a result which is compatible with the rise in ozone suggested by the observations.