Seasonal persistence of midlatitude total ozone anomalies

Temporal autocorrelations of monthly mean total ozone anomalies over the 35–60°S and 35–60°N latitude bands reveal that anomalies established in the wintertime midlatitude ozone buildup persist (with photochemical decay) until the end of the following autumn, and then are rapidly erased once the next winter's buildup begins. The photochemical decay rate is found to be identical between the two hemispheres. High predictability of ozone through late summer exists based on the late-spring values. In the northern hemisphere, extending the 1979–2001 springtime ozone trend to other months through regression based on the seasonal persistence of anomalies captures the seasonality of the ozone trends remarkably well. In the southern hemisphere, the springtime trend only accounts for part of the summertime trends. There is a strong correlation between the ozone anomalies in northern hemisphere spring and those in the subsequent southern hemisphere spring, but not the converse.

Arctic ozone depletion in 2002–2003 measured by ASUR and comparison with POAM observations

We present ozone loss estimated from airborne measurements taken during January–February and March in the Arctic winter 2002/2003. The first half of the winter was characterized by unusually cold temperatures and the second half by a major stratospheric sudden warming around 15–18 January 2003. The potential vorticity maps show a vortex split in the lower stratosphere during the major warming (MW) in late January and during the minor warming in mid-February due to wave 1 amplification. However, the warming can be termed as a vortex displacement event as there was no vortex split during the MW period at 10 hPa. Very low temperatures, large areas of polar stratospheric clouds (PSCs), and high chlorine activation triggered significant ozone loss in the early winter, as the vortex moved to the midlatitude regions. The ozone depletion derived from the ASUR measurements sampled inside the vortex, in conjunction with the Mimosa-Chim model tracer, shows a maximum of 1.3 ± 0.2 ppmv at 450–500 K by late March. The partial column loss derived from the ASUR ozone profiles reaches up to 61 ± 4 DU in 400–550 K in the same period. The evolution of ozone and ozone loss assessed from the ASUR measurements is in very good agreement with POAM observations. The reduction in ozone estimated from the POAM measurements shows a similar maximum of 1.3 ± 0.2 ppmv at 400–500 K or 63 ± 4 DU in 400–550 K in late March. Our study reveals that the Arctic winter 2002/2003 was unique as it had three minor warmings and a MW, yet showed large loss in ozone. No such feature was observed in any other Arctic winter in the 1989–2010 period. In addition, an unusually large ozone loss in December, around 0.5 ± 0.2 ppmv at 450–500 K or 12 ± 1 DU in 400–550 K, was estimated for the first time in the Arctic. A careful and detailed diagnosis with all available published results for this winter exhibits an average ozone loss of 1.5 ± 0.3 ppmv at 450–500 K or 65 ± 5 DU in 400–550 K by the end of March, which exactly matches the ozone depletion derived from the ASUR, POAM and model data. The early ozone loss together with considerable loss afterwards put the warm Arctic winter 2002/2003 amongst the moderately cold winters in terms of the significance of the ozone loss.

Comparison of polar ozone loss rates simulated by one-dimensional and three-dimensional models with Match observations in recent Antarctic and Arctic winters

Simulations of ozone loss rates using a three-dimensional chemical transport model and a box model during recent Antarctic and Arctic winters are compared with experimental loss rates. The study focused on the Antarctic winter 2003, during which the first Antarctic Match campaign was organized, and on Arctic winters 1999/2000, 2002/2003. The maximum ozone loss rates retrieved by the Match technique for the winters and levels studied reached 6 ppbv/sunlit hour and both types of simulations could generally reproduce the observations at 2-sigma error bar level. In some cases, for example, for the Arctic winter 2002/2003 at 475 K level, an excellent agreement within 1-sigma standard deviation level was obtained. An overestimation was also found with the box model simulation at some isentropic levels for the Antarctic winter and the Arctic winter 1999/2000, indicating an overestimation of chlorine activation in the model. Loss rates in the Antarctic show signs of saturation in September, which have to be considered in the comparison. Sensitivity tests were performed with the box model in order to assess the impact of kinetic parameters of the ClO-Cl2O2 catalytic cycle and total bromine content on the ozone loss rate. These tests resulted in a maximum change in ozone loss rates of 1.2 ppbv/sunlit hour, generally in high solar zenith angle conditions. In some cases, a better agreement was achieved with fastest photolysis of Cl2O2 and additional source of total inorganic bromine but at the expense of overestimation of smaller ozone loss rates derived later in the winter.

Forecast, measurement, and modeling of an unprecedented polar ozone filament event over Mauna Loa Observatory, Hawaii

In mid-March 2005 the northern lower stratospheric polar vortex experienced a severe stretching episode, bringing a large polar filament far south of Alaska toward Hawaii. This meridional intrusion of rare extent, coinciding with the polar vortex final warming and breakdown, was followed by a zonal stretching in the wake of the easterly propagating subtropical main flow. This caused polar air to remain over Hawaii for several days before diluting into the subtropics. After being successfully forecasted to pass over Hawaii by the high-resolution potential vorticity advection model Modèle Isentrope du transport Méso-échelle de l'Ozone Stratosphérique par Advection (MIMOSA), the filament was observed on isentropic surfaces between 415 K and 455 K (17–20 km) by the Jet Propulsion Laboratory stratospheric ozone lidar measurements at Mauna Loa Observatory, Hawaii, between 16 and 19 March 2005. It was materialized as a thin layer of enhanced ozone peaking at 1.6 ppmv in a region where the climatological values usually average 1.0 ppmv. These values were compared to those obtained by the three-dimensional Chemistry-Transport Model MIMOSA-CHIM. Agreement between lidar and model was excellent, particularly in the similar appearance of the ozone peak near 435 K (18.5 km) on 16 March, and the persistence of this layer at higher isentropic levels for the following three days. Passive ozone, also modeled by MIMOSA-CHIM, was at about 3–4 ppmv inside the filament while above Hawaii. A detailed history of the modeled chemistry inside the filament suggests that the air mass was still polar ozone–depleted when passing over Hawaii. The filament quickly separated from the main vortex after its Hawaiian overpass. It never reconnected and, in less than 10 days, dispersed entirely in the subtropics

Statistical analysis of eight surface ozone measurement series for various sites in Ireland

Data from various stations having different measurement record periods between 1988 and 2007 are analyzed to investigate the surface ozone concentration, long-term trends, and seasonal changes in and around Ireland. Time series statistical analysis is performed on the monthly mean data using seasonal and trend decomposition procedures and the Box-Jenkins approach (autoregressive integrated moving average). In general, ozone concentrations in the Irish region are found to have a negative trend at all sites except at the coastal sites of Mace Head and Valentia. Data from the most polluted Dublin city site have shown a very strong negative trend of −0.33 ppb/yr with a 95% confidence limit of 0.17 ppb/yr (i.e., −0.33 ± 0.17) for the period 2002−2007, and for the site near the city of Cork, the trend is found to be −0.20 ± 0.11 ppb/yr over the same period. The negative trend for other sites is more pronounced when the data span is considered from around the year 2000 to 2007. Rural sites of Wexford and Monaghan have also shown a very strong negative trend of −0.99 ± 0.13 and −0.58 ± 0.12, respectively, for the period 2000−2007. Mace Head, a site that is representative of ozone changes in the air advected from the Atlantic to Europe in the marine planetary boundary layer, has shown a positive trend of about +0.16 ± 0.04 ppb per annum over the entire period 1988−2007, but this positive trend has reduced during recent years (e.g., in the period 2001−2007). Cluster analysis for back trajectories are performed for the stations having a long record of data, Mace Head and Lough Navar. For Mace Head, the northern and western clean air sectors have shown a similar positive trend (+0.17 ± 0.02 ppb/yr for the northern sector and +0.18 ± 0.02 ppb/yr for the western sector) for the whole period, but partial analysis for the clean western sector at Mace Head shows different trends during different time periods with a decrease in the positive trend since 1988 indicating a deceleration in the ozone trend for Atlantic air masses entering Europe.

Simultaneous lidar and EOS MLS measurements, and modeling, of a rare polar ozone filament event over Mauna Loa Observatory, Hawaii

In mid-March 2005, a rare lower stratospheric polar vortex filamentation event was observed simultaneously by the JPL lidar at Mauna Loa Observatory, Hawaii, and by the EOS MLS instrument onboard the Aura satellite. The event coincided with the beginning of the spring 2005 final warming. On 16 March, the filament was observed by lidar around 0600 UT between 415 K and 455 K, and by MLS six hours earlier. It was seen on both the lidar and MLS profiles as a layer of enhanced ozone, peaking at 1.7 ppmv in a region where the climatological values are usually around or below 1 ppmv. Ozone profiles measured by lidar and MLS were compared to profiles from the Chemical Transport Model MIMOSA-CHIM. The agreement between lidar, MLS, and the model is excellent considering the difference in the sampling techniques. MLS was also able to identify the filament at another location north of Hawaii.

High resolution simulation of recent Arctic and Antarctic stratospheric chemical ozone loss compared to observations

Simulations of polar ozone losses were performed using the three-dimensional high-resolution (1∘ × 1∘) chemical transport model MIMOSA-CHIM. Three Arctic winters 1999–2000, 2001–2002, 2002–2003 and three Antarctic winters 2001, 2002, and 2003 were considered for the study. The cumulative ozone loss in the Arctic winter 2002–2003 reached around 35% at 475 K inside the vortex, as compared to more than 60% in 1999–2000. During 1999–2000, denitrification induces a maximum of about 23% extra ozone loss at 475 K as compared to 17% in 2002–2003. Unlike these two colder Arctic winters, the 2001–2002 Arctic was warmer and did not experience much ozone loss. Sensitivity tests showed that the chosen resolution of 1∘ × 1∘ provides a better evaluation of ozone loss at the edge of the polar vortex in high solar zenith angle conditions. The simulation results for ozone, ClO, HNO3, N2O, and NO y for winters 1999–2000 and 2002–2003 were compared with measurements on board ER-2 and Geophysica aircraft respectively. Sensitivity tests showed that increasing heating rates calculated by the model by 50% and doubling the PSC (Polar Stratospheric Clouds) particle density (from 5 × 10−3 to 10−2 cm−3) refines the agreement with in situ ozone, N2O and NO y levels. In this configuration, simulated ClO levels are increased and are in better agreement with observations in January but are overestimated by about 20% in March. The use of the Burkholder et al. (1990) Cl2O2 absorption cross-sections slightly increases further ClO levels especially in high solar zenith angle conditions. Comparisons of the modelled ozone values with ozonesonde measurement in the Antarctic winter 2003 and with Polar Ozone and Aerosol Measurement III (POAM III) measurements in the Antarctic winters 2001 and 2002, shows that the simulations underestimate the ozone loss rate at the end of the ozone destruction period. A slightly better agreement is obtained with the use of Burkholder et al. (1990) Cl2O2 absorption cross-sections.

An assessment of the surface ozone trend in Ireland relevant to air pollution and environmental protection

Hourly data (1994–2009) of surface ozone concentrations at eight monitoring sites have been investigated to assess target level and long–term objective exceedances and their trends. The European Union (EU) ozone target value for human health (60 ppb–maximum daily 8–hour running mean) has been exceeded for a number of years for almost all sites but never exceeded the set limit of 25 exceedances in one year. Second highest annual hourly and 4th highest annual 8–hourly mean ozone concentrations have shown a statistically significant negative trend for in–land sites of Cork–Glashaboy, Monaghan and Lough Navar and no significant trend for the Mace Head site. Peak afternoon ozone concentrations averaged over a three year period from 2007 to 2009 have been found to be lower than corresponding values over a three–year period from 1996 to 1998 for two sites: Cork–Glashaboy and Lough Navar sites. The EU long–term objective value of AOT40 (Accumulated Ozone Exposure over a threshold of 40 ppb) for protection of vegetation (3 ppm–hour, calculated from May to July) has been exceeded, on an individual year basis, for two sites: Mace Head and Valentia. The critical level for the protection of forest (10 ppm–hour from April to September) has not been exceeded for any site except at Valentia in the year 2003. AOT40–Vegetation shows a significant negative trend for a 3–year running average at Cork–Glashaboy (–0.13±0.02 ppm–hour per year), at Lough Navar (–0.05±0.02 ppm–hour per year) and at Monaghan (–0.03±0.03 ppm–hour per year–not statistically significant) sites. No statistically significant trend was observed for the coastal site of Mace head. Overall, with the exception of the Mace Head and Monaghan sites, ozone measurement records at Irish sites show a downward negative trend in peak values that affect human health and vegetation.

Quantification of chemical and physical processes influencing ozone during long-range transport using a trajectory ensemble

During long-range transport, many distinct processes – including photochemistry, deposition, emissions and mixing – contribute to the transformation of air mass composition. Partitioning the effects of different processes can be useful when considering the sensitivity of chemical transformation to, for example, a changing environment or anthropogenic influence. However, transformation is not observed directly, since mixing ratios are measured, and models must be used to relate changes to processes. Here, four cases from the ITCT-Lagrangian 2004 experiment are studied. In each case, aircraft intercepted a distinct air mass several times during transport over the North Atlantic, providing a unique dataset and quantifying the net changes in composition from all processes. A new framework is presented to deconstruct the change in O3 mixing ratio (Δ O3) into its component processes, which were not measured directly, taking into account the uncertainty in measurements, initial air mass variability and its time evolution. The results show that the net chemical processing (Δ O3chem) over the whole simulation is greater than net physical processing (Δ O3phys) in all cases. This is in part explained by cancellation effects associated with mixing. In contrast, each case is in a regime of either net photochemical destruction (lower tropospheric transport) or production (an upper tropospheric biomass burning case). However, physical processes influence O3 indirectly through addition or removal of precursor gases, so that changes to physical parameters in a model can have a larger effect on Δ O3chem than Δ O3phys. Despite its smaller magnitude, the physical processing distinguishes the lower tropospheric export cases, since the net photochemical O3 change is −5 ppbv per day in all three cases. Processing is quantified using a Lagrangian photochemical model with a novel method for simulating mixing through an ensemble of trajectories and a background profile that evolves with them. The model is able to simulate the magnitude and variability of the observations (of O3, CO, NOy and some hydrocarbons) and is consistent with the time-average OH following air-masses inferred from hydrocarbon measurements alone (by Arnold et al., 2007). Therefore, it is a useful new method to simulate air mass evolution and variability, and its sensitivity to process parameters.

Ozone climatology using interactive chemistry: results from the Canadian Middle Atmosphere Model

The climatology of ozone produced by the Canadian Middle Atmosphere Model (CMAM) is presented. This three-dimensional global model incorporates the radiative feedbacks of ozone and water vapor calculated on-line with a photochemical module. This module includes a comprehensive gas-phase reaction set and a limited set of heterogeneous reactions to account for processes occurring on background sulphate aerosols. While transport is global, photochemistry is solved from about 400 hPa to the top of the model at ∼95 km. This approach provides a complete and comprehensive representation of transport, emission, and photochemistry of various constituents from the surface to the mesopause region. A comparison of model results with observations indicates that the ozone distribution and variability are in agreement with observations throughout most of the model domain. Column ozone annual variation is represented to within 5–10% of the observations except in the Southern Hemisphere for springtime high latitudes. The vertical ozone distribution is generally well represented by the model up to the mesopause region. Nevertheless, in the upper stratosphere, the model generally underestimates the amount of ozone as well as the latitudinal tilting of ozone isopleths at high latitude. Ozone variability is analyzed and compared with measurements. The comparison shows that the phase and amplitude of the seasonal variation as well as shorter timescale variations are well represented by the model at various latitudes and heights. Finally, the impact of incorporating ozone radiative feedback on the model climatology is isolated. It is found that the incorporation of ozone radiative feedback results in a cooling of ∼8 K in the summer stratopause region, which corrects a warm bias that results when climatological ozone is used.

Measurements of stratospheric ozone at a mid-latitude observing station Valentia, Ireland (51.94° N, 10.25° W), using ground-based and ozonesonde observations from 1994 to 2009

Sixteen years (1994 – 2009) of ozone profiling by ozonesondes at Valentia Meteorological and Geophysical Observatory, Ireland (51.94° N, 10.23° W) along with a co-located MkIV Brewer spectrophotometer for the period 1993–2009 are analyzed. Simple and multiple linear regression methods are used to infer the recent trend, if any, in stratospheric column ozone over the station. The decadal trend from 1994 to 2010 is also calculated from the monthly mean data of Brewer and column ozone data derived from satellite observations. Both of these show a 1.5 % increase per decade during this period with an uncertainty of about ±0.25 %. Monthly mean data for March show a much stronger trend of ~ 4.8 % increase per decade for both ozonesonde and Brewer data. The ozone profile is divided between three vertical slots of 0–15 km, 15–26 km, and 26 km to the top of the atmosphere and a 11-year running average is calculated. Ozone values for the month of March only are observed to increase at each level with a maximum change of +9.2 ± 3.2 % per decade (between years 1994 and 2009) being observed in the vertical region from 15 to 26 km. In the tropospheric region from 0 to 15 km, the trend is positive but with a poor statistical significance. However, for the top level of above 26 km the trend is significantly positive at about 4 % per decade. The March integrated ozonesonde column ozone during this period is found to increase at a rate of ~6.6 % per decade compared with the Brewer and satellite positive trends of ~5 % per decade.

Contributions to twentieth century total column ozone change from halocarbons, tropospheric ozone precursors, and climate change

We investigate ozone changes from preindustrial times to the present using a chemistry-climate model. The influence of changes in physical climate, ozone-depleting substances, N2O, and tropospheric ozone precursors is estimated using equilibrium simulations with these different factors set at either preindustrial or present-day values. When these effects are combined, the entire decrease in total column ozone from preindustrial to present day is very small (–1.8 DU) in the global annual average, though with significant decreases in total column ozone over large parts of the Southern Hemisphere during austral spring and widespread increases in column ozone over the Northern Hemisphere during boreal summer. A significant contribution to the total ozone column change is the increase in lower stratospheric ozone associated with the increase in ozone precursors (5.9 DU). Also noteworthy is the near cancellation of the global average climate change effect on ozone (3.5 DU) by the increase in N2O (–3.9 DU).

SPARC Data Initiative: A comparison of ozone climatologies from international satellite limb sounders

A comprehensive quality assessment of the ozone products from 18 limb-viewing satellite instruments is provided by means of a detailed intercomparison. The ozone climatologies in form of monthly zonal mean time series covering the upper troposphere to lower mesosphere are obtained from LIMS, SAGE I/II/III, UARS-MLS, HALOE, POAM II/III, SMR, OSIRIS, MIPAS, GOMOS, SCIAMACHY, ACE-FTS, ACE-MAESTRO, Aura-MLS, HIRDLS, and SMILES within 1978–2010. The intercomparisons focus on mean biases of annual zonal mean fields, interannual variability, and seasonal cycles. Additionally, the physical consistency of the data is tested through diagnostics of the quasi-biennial oscillation and Antarctic ozone hole. The comprehensive evaluations reveal that the uncertainty in our knowledge of the atmospheric ozone mean state is smallest in the tropical and midlatitude middle stratosphere with a 1σ multi-instrument spread of less than ±5%. While the overall agreement among the climatological data sets is very good for large parts of the stratosphere, individual discrepancies have been identified, including unrealistic month-to-month fluctuations, large biases in particular atmospheric regions, or inconsistencies in the seasonal cycle. Notable differences between the data sets exist in the tropical lower stratosphere (with a spread of ±30%) and at high latitudes (±15%). In particular, large relative differences are identified in the Antarctic during the time of the ozone hole, with a spread between the monthly zonal mean fields of ±50%. The evaluations provide guidance on what data sets are the most reliable for applications such as studies of ozone variability, model-measurement comparisons, detection of long-term trends, and data-merging activities.