3.1. Global Distribution of TOC Variations and Trends in the TOC
In the present study, which aims to determine macroscale changes in the Ozone layer, mean monthly and zonal mean values of TOC are used, which eliminates short-period variations in O
3 concentration and longitudinal inhomogeneities.
Figure 1 shows the average seasonal cycle of the TOC for the latitude range of 60° S to 60° N.
The presented 16-year climatological seasonal course of the average monthly zonal averages of TOC shows the regularities of the geographical distribution of O
3 in the atmosphere during the different seasons.
Figure 1 shows the well-defined seasonal cycle, which increases in latitude and has the highest values in the northern hemisphere at high latitudes, which in this article reach 60°, where TOC has values around 400 DU. At mid-latitudes (between 30° and 60° in both hemispheres), the concentration of O
3 reaches maximum values in spring and minimum in autumn. In the equatorial region, the seasonal maximum is in September–October, and the minimum is in December–January. The mean diabatic circulation allows the transport of stratospheric O
3, which is the explanation for the seasonal variation in TOC. Seasonal variations in TOC are significant, reaching about 100 DU in the northern hemisphere. The obtained average seasonal rate coincides well with that published in [
3]. In their work, the authors illustrate a similar figure for the global distribution of TOC, and the results show that the O
3 is low in the tropics and increases with latitude.
Figure 2 presents the course of the average monthly values of TOC for the period 2005–2020, which illustrates the repeatability of the seasonal cycle of all latitudes for the studied period of time. The trends of the zonal mean values of TOC are represented by the angular coefficient of the linear approximation of their time dependence, obtained by the method of least squares. The trends thus obtained actually determine the trend of the annual TOC values for the relevant latitude. The values presented are given in units of DU/decade, i.e., the amendment of the TOC for ten years.
Figure 3 presents the course of the monthly mean zonal values of TOC for selected latitudes of the northern and southern hemispheres and for the equator and the corresponding linear trends. For these trends, their standard error is calculated by the following formula:
where
σ2 is the dispersion of the differences between the data and the regression, and
Sxx is the sum of the squares of the differences between the values of the independent time variable and its mean value.
The presented examples show that the obtained trends are insignificant compared to the seasonal variations of TOC, which are the main variability of the Ozone layer. The quasi-biennial oscillation is also visible at the equator, which is due to the quasi-biennial oscillation of the stratospheric zonal wind [
20]. The values of the linear trend of TOC show clear latitude dependence. At 60° S, the value is positive 8 DU per decade, at the equator, it decreases to 2.88 DU per decade, and in the northern hemisphere, it becomes negative at 30° N, it is −0.69 DU per decade, and at 60° N, it is −0.73 DU per decade.
Figure 4 shows the latitude dependence of the linear trend, calculated in steps of 1°. The change in the sign of the linear trend occurs at 25° N. The largest negative value is observed at 55° N and is about −2 DU per decade. The obtained values of the linear trend can be compared with the results of [
22], which were received by ground-based measurements for the time interval 1979–2016. Trends are summarized for latitude intervals from 35° S to 60° S and from 35° N to 60° N. The authors receive two sub-periods with a boundary around 1997. In the first period in both hemispheres, there is a negative trend, which is replaced by a small positive trend in the second period. The authors think that the period after 1997 is a period of recovery of the Ozone layer after its depletion in the previous period. The results received in the present study for the period 2005–2020 do not contradict this conclusion. The results show that the O
3 recovery process has a latitude dependence. The presented latitude dependence is more significant in the southern hemisphere, while in the northern hemisphere, at mid-latitudes, there is a slight decrease in O
3 concentration. The resulting latitude dependence is related to purely intra-atmospheric asymmetry of both hemispheres, which is clearly evident in the climatology of the seasonal cycle of TOC. The range of probable, with 50% probability values of the linear trend (trend ± SEtrend) at the latitudes between 60° S and 10° N, shown in
Figure 4, is located in the area of positive values. The increase in standard error at high latitudes in both hemispheres is due to the increase in seasonal variation of TOC.
The trends received for the period 1979–1991 are −3.7 DU per decade for the tropics and −7.2 DU per decade for mid-latitudes, respectively [
23]. The values obtained in the present investigation for the next time period confirm that the Ozone layer has been recovering for the last 16 years. In order to eliminate the influence of the seasonal cycle of TOC, the relative deviation of the average monthly TOC from the climatological average value is marked as
TOCmean (
month) by the following formula:
In the time series of the calculated relative TOC by Formula (2), there is no stationary seasonal cycle, but all long-period trends are preserved.
Figure 5 shows examples of the course of the relative monthly mean and their trends of the same latitudes as in
Figure 3, namely: (i) the equator, (ii) the northern and southern hemispheres of mid-latitudes (30° N and 30° S, respectively), and (iii) the distribution and trend of high latitudes in both hemispheres (northern hemisphere 60° N and southern hemisphere 60° S).
Figure 6 illustrates the latitude dependence of the linear trends of the relative TOC values, analogous to
Figure 4. Compared to
Figure 3 and
Figure 4, the relative TOC has a positive trend at all latitudes, with maximum values of around 2% per decade in the area between 60° S and 40° S. In the area between 30° S and 30° N, the trend is between 0.5° and 1° per decade. The lowest value is indicated at 30° N of about 0.2% per decade. The range of probable values of the relative trend shown in the figure with a 50% probability with small exceptions around 30° N is in the range of positive values. Eliminating the seasonal cycle in determining the relative TOC values significantly reduces the dispersion of data around the regression line and, therefore, reduces the standard error of the trend. The values of the relative trend can be compared with those obtained by Weber et al., 2018, for the period 1979–2016. The obtained values for the latitude range from 60° S to 35° S are about 0.7% per decade and about 0.5% per decade for 35° N–60° N; these are close enough to those received in the present work.
It is of interest to study the influence of the season on TOC trends. The meridional transport of O
3 from tropical latitudes to mid-latitudes and high latitudes under the action of Brewer–Dobson circulation [
3] is strongest during the winter period, and different values of trends can be expected depending on the season. For this purpose, the TOC trends for each calendar month in the studied time period were calculated. The results are shown in
Figure 7. It turns out that in the northern hemisphere, the trends show an increase in the months of November–March. In the southern hemisphere, an increase is observed in the months of April–July. These months coincide with the winter periods in the respective hemispheres.
3.1.1. Trends in Seasonal Components of TOC
In the present work, an attempt is made to determine whether there are long-term trends in the characteristics of the seasonal cycle of TOC. The results of the climatology of the seasonal cycle of TOC for the period 2005–2020 (see
Figure 1) show that at all latitudes, the seasonal cycle has a distinct periodicity with a period of one year. For this reason, the seasonal cycle of the zonal mean TOC was decomposed for each latitude and year by the following formula:
The quantity
TOC0 introduces the average annual value of TOC. The quantity
TOC1 represents the amplitude of the seasonal cycle. The quantity
Phase presents the month of the year in which the TOC has a maximum value. The three characteristics of the seasonal cycle for each latitude and year are determined unambiguously by the condition for the best approximation to the data by the method of least squares. The next few figures, namely
Figure 8,
Figure 9 and
Figure 10, show the course of these three quantities in years and in latitude.
The results show that the average annual value of O
3 in latitudes has a maximum of about 60° N for the northern hemisphere and about 50° S for the southern hemisphere. A similar result is obtained for the hemispheric asymmetry visible in
Figure 1 and
Figure 2. In the southern hemisphere, the maximum observed influence of quasi-biennial oscillation is based on the equatorial zonal stratospheric wind QBO, while in the northern hemisphere. there is a periodicity of about 4 years, probably also associated with QBO [
3]. At the same latitudes where the average annual TOC value is maximized, the amplitude of the seasonal cycle is maximized, and in the southern hemisphere, the influence of QBO is very clear.
The latitude distribution of the seasonal phase shows that at high northern latitudes, the maximum TOC occurs in the middle of northern winter (January and February). At high southern latitudes, the maximum of TOC is observed in May and June, also in the middle of the southern winter. Towards low latitudes in both hemispheres, the phase increases, which can be explained by the way in which O3 is transported by Brewer–Dobson circulation. Once transported meridionally at altitudes of about 30 km to latitudes of about 50–60°, the O3 is transported to lower altitudes, causing an increase in TOC at these latitudes. The process is associated with delays, which increase at lower latitudes.
Figure 11,
Figure 12 and
Figure 13 show the latitude distribution of trends in the three quantities, which characterize the seasonal cycle of TOC. The trends of the average annual values (see
Figure 11) match with those obtained on the basis of the monthly values (see
Figure 4). However, the latitude dependence of the trends on the annual averages (
Figure 11) is more similar to that shown in
Figure 6; latitude dependence of the trend of relative TOC, which is explained by the elimination of seasonal variations in both cases. In particular, trends in high mid-latitudes are positive.
Figure 12 does not show a significant trend in the amplitudes of the seasonal cycle. The trends in the phases are also insignificant, with only the southern hemisphere having any latitude dependence observed, which is difficult to explain on the basis of the available data. The obvious effect of QBO on TOC, which can be seen in
Figure 8,
Figure 9 and
Figure 10; the influence of which has been the subject of a significant number of studies [
20,
24,
25].
The latitude dependence of the seasonal phase shown in
Figure 13 illustrates the change in the months in which the TOC acquires its maximum and minimum. In particular, in the interval between 10° N and 50° N, the trend of the phase is negative, which means that the seasonal maximum moves to earlier months. The sharp change in the trend in the phase around 10° S coincides with the sharp change in the phase itself (see
Figure 10).
Figure 14 shows the course of average monthly values of the equatorial zonal wind at an altitude of 30 hPa (about 24 km). A positive trend of 7.44 (m/s)/decade was observed for the studied time period.
The latitude distribution of the correlation coefficient (zero time-lag) between the equatorial wind speeds and the relative TOC is shown in
Figure 15. The dependence is very close to that received for the period 1989–1997 [
25]. The latitude distribution of the correlation shows that it is positive in the tropics. In the southern hemisphere, the correlation is negative south of 10° S, and in the southern mid-latitudes, it reaches −0.4 (see
Figure 15). In the northern hemisphere, in mid-latitudes, it varies in small limits around zero. It can be hypothesized that the positive trend in the equatorial zonal wind speed is the reason for the positive trend in the equatorial TOC due to the strong positive correlation between the two quantities. Another assumption that can be made is that the asymmetry between the correlations in the mid-latitudes in the two hemispheres is related to the resulting asymmetry between the TOC trends. Contrary to this assumption is the discrepancy between the signs of correlation and trends.
3.1.2. Trends in Mass of O3
In the present work, the course of the mass of O
3 in the atmosphere has been calculated as an additional study of the trends in the recovery of the Earth’s Ozone layer. The results of a study of O
3 variations over Europe at around 50° N between 1964 and 2004 show the presence of O
3 recovery, and the proposed explanation is that this is due to overlapping ‘natural’ processes. All this gives grounds to study the trend in O
3 based on its mass [
26]. The calculation of the O
3 mass was performed on the basis of TOC data. The altitude of the Ozone layer (1 DU = 0.01 mm) adjusted to normal pressure and temperature is assumed to be evenly distributed for each cell in the data network (1 × 1 deg).
Taking into account the different length of the section of 1° longitude of the different latitudes, the area of each cell in the network and the volume of O
3 adjusted to normal conditions were determined. Based on the results, the mass of O
3 in MT was calculated for each latitude zone, for the individual hemispheres between 60° and the equator, and for the latitude range 60° S–60° N. The climatological seasonal cycle of the mean zonal mass of O
3 shown in
Figure 16, which shows that the main part of the O
3 mass is in low and mid-latitudes.
The total mass of O3 in the latitude range 60° S–60° N has a seasonal cycle with a minimum in the northern winter and a maximum in the northern summer. Seasonal variations in the total mass of O3 are not significant. For the whole study period, the mass of O3 varied between 2417 and 2640 MT, which means a variation of ±4.4% at an average of 2547 MT. The determined most probable trend in the total O3 mass—21.89 MT per decade, means that for the whole studied period (16 years), the O3 mass has increased by an average of 35 MT. This represents 1.37%. The results show that the total O3 mass in low and mid-latitudes remains constant. This conclusion confirms the received results obtained based on a TOC study.
Figure 17 shows the course and trend of O
3 mass in the northern and southern hemispheres. The seasonal variation is significant but is in antiphase for the northern and southern hemispheres. The obtained result for a weak seasonal cycle of the total O
3 mass for both hemispheres and the insignificant positive trend over time means that seasonal changes in O
3 mass in both hemispheres, and, therefore, O
3 concentrations, are due to redistribution of O
3 in latitudes under the action of the dynamics of the middle atmosphere. Due to the missing data from high latitudes, no conclusions can be drawn about the processes in the polar latitudes, in particular for the area of the Antarctic Ozone hole.
Figure 18 shows the course of the O
3 mass in three latitudinal bands—southern mid-latitudes (between 60° S and 30° S), tropical region (between 30° S and 30° N), and the northern mid-latitudes (between 30° N and 60° N) and trends in these bands. In northern mid-latitudes, the trend is negligibly small. In the other bands, the trend is practically the same and is half the trend of the total O
3 mass.
3.2. Investigation of TOC for the Territory of Bulgaria in the Period 1996–2020
One of the tasks of the National Institute of Geophysics, Geodesy and Geography is to study the state of the Ozone layer over Bulgaria. Due to the impossibility of obtaining a continuous series of data (measurements with ground-based devices are only possible in clear weather), O3 data with ground-based devices are supplemented by measurements from satellite equipment.
Based on data from ground-based measurements and satellite data, an analysis of the seasonal distribution of TOC in Bulgaria was performed. To obtain a long and continuous database, a regression analysis was used to determine the relationship between the values of the total O
3 obtained from the measurements in Sofia and the respective satellite data of OMI and TOMS. The results of the analysis of the studied period (1997–2012) show that the state of stratospheric O
3 is stable, and there are no tendencies toward its destruction. It was found that the seasonal cycle of TOC over Bulgaria is described by the average annual value and the amplitudes and phases of the 12 and 6-month components. The annual component shows clear trends in amplitude and phase, with the best coincidence being observed with variations in the average annual zonal wind values of 68 hPa [
18,
19,
20]. The results of spectral analysis of the short-term variations in TOC over Bulgaria show that they are not of a completely random character and are quasi periodical variations [
19]. Recent research of the seasonal cycle of the Total Ozone Content over Bulgaria during the period 1997–2018 shows no trends towards its destruction. On the contrary, the results show that (i) the TOC tends to increase slightly and (ii) the resulting seasonal variations are relatively constant [
21].
All the results described above give reason to conduct a study to show whether there is a positive trend of TOC over Bulgaria at the moment.
Figure 19 shows the trend in the TOC values obtained by supplementing the measurements and satellite data for the territory of Bulgaria in the period from 1996 to 2020. The results show a positive linear trend of almost 1 DU/decade, which is less than 1% of the average TOC value for the period considered. The standard error of the linear trend is 4.28.
Figure 20 is analogous to
Figure 19 and shows the trend in relative TOC values. The results illustrate a positive linear trend of 0.29 per cent/decade, which confirms the positive values obtained in the relative TOC trends for the northern hemisphere, shown in
Figure 5. The standard error of the linear trend is 1.18.