Dobson Units Research Articles

Updated total ozone climate normals over the territory of Ukraine

The study presents the results of analysis of spatiotemporal distribution of updated total ozone climate normals for the period of 1991–2020. It analyzes the changes since the last total ozone climate normals estimate conducted for the period of 1981–2010. The daily data retrieved using TOMS and OMI satellite instruments over the territory of Ukraine allowed calculation of multiyear average values, climate normals for each day of the year, amplitudes, phases and determination coefficients for total ozone seasonal variations. Use of the NCEP/NCAR reanalysis data allowed establishment of the relation between total ozone and meridional wind changes in the lower stratosphere. The research shows the existence of the regions with higher/lower total ozone content that are not in line with the characteristics of latitudinal distribution. They are formed due to more frequent recurrence of air advection with ozone content that is not typical for the Ukrainian territory, mostly from January to March. The study describes a typical temporal distribution of the total ozone climate normals varying from 285 to 375 Dobson units (D.u.) and analyzes the statistic patterns of deviations distribution and recurrence of extremely high/low total ozone content. The paper emphasizes a small variation of total ozone over the territory of Ukraine. The authors also researched the features of spatial distribution of seasonal variation amplitudes varying within the range of 42–46 D.u. and the specifics of maximum values periods observed from 19 to 30 of March, depending on a region. It was established that, since the previous update of the climate normals, the total ozone decreased for all months with its maximum decrease of about 8 D.u. in winter. However, no increase of recurrence of ultraviolet radiation high levels was observed. Total ozone changes are mainly associated with shifts of meridional wind values to negative ones. This process indicates the increase of recurrence of air advection from the north. The paper also emphasizes the complexness of total ozone changes during the period of research and the lack of consistency of such changes with the circulation factor of summer months.

Numerical Modeling of Ozone Loss in the Exceptional Arctic Stratosphere Winter–Spring of 2020

Dynamical processes and changes in the ozone layer in the Arctic stratosphere during the winter of 2019–2020 were analyzed using numerical experiments with a chemistry-transport model (CTM) and reanalysis data. The results of numerical calculations using CTM with Dynamic parameters specified from the Modern Era Retrospective analysis for Research and Applications, version 2 (MERRA-2) reanalysis data, carried out according to several scenarios of accounting for the chemical destruction of ozone, demonstrated that both Dynamic and chemical processes contribute significantly to ozone changes over the selected World Ozone and Ultraviolet Radiation Data Centre network stations, both in the Eastern and in the Western hemispheres. Based on numerical experiments with the CTM, the specific Dynamic conditions of winter–spring 2019–2020 described a decrease in ozone up to 100 Dobson Units (DU) in the Eastern Hemisphere and over 150 DU in the Western Hemisphere. In this case, the photochemical destruction of ozone in both the Western and Eastern Hemispheres at a maximum was about 50 DU with peaks in April in the Eastern Hemisphere and in March and April in the Western Hemisphere. Heterogeneous activation of halogen gases on the surface of polar stratospheric clouds, on the one hand, led to a sharp increase in the destruction of ozone in chlorine and bromine catalytic cycles, and, on the other hand, decreased its destruction in nitrogen catalytic cycles. Analysis of wave activity using 3D Plumb fluxes showed that the enhancement of upward wave activity propagation in the middle of March over the Gulf of Alaska was observed during the development stage of the minor sudden stratospheric warming (SSW) event that led to displacement of the stratospheric polar vortex to the north of Canada and decrease of polar stratospheric clouds’ volume.

Advanced NO<sub>2</sub> retrieval technique for the Brewer spectrophotometer applied to the 20-year record in Rome, Italy

Abstract. A re-evaluated data set of nitrogen dioxide (NO2) column densities over Rome for the years 1996 to 2017 is here presented. This long-term record is obtained from ground-based direct sun measurements with a MkIV Brewer spectrophotometer (serial number #067) and further reprocessed using a novel algorithm. Compared to the original Brewer algorithm, the new method includes updated NO2 absorption cross sections and Rayleigh scattering coefficients, and it accounts for additional atmospheric compounds and instrumental artefacts, such as the spectral transmittance of the filters, the alignment of the wavelength scale, and internal temperature. Moreover, long-term changes in the Brewer radiometric sensitivity are tracked using statistical methods for in-field calibration. The resulting series presents only a few (about 30) periods with missing data longer than 1 week and features NO2 retrievals for more than 6100 d, covering nearly 80 % of the considered 20-year period. The high quality of the data is demonstrated by two independent comparisons. In the first intensive campaign, Brewer #067 is compared against another Brewer (#066), recently calibrated at the Izaña Atmospheric Observatory through the Langley method and there compared to reference instrumentation from the Network for the Detection of Atmospheric Composition Change (NDACC). Data from this campaign show a highly significant Pearson's correlation coefficient of 0.90 between the two series of slant column densities (SCDs), slope 0.98 and offset 0.05 DU (Dobson units; 1.3×1015 molec.cm-2). The average bias between the vertical column densities is 0.03 DU (8.1×1014 molec.cm-2), well within the combined uncertainty of both instruments. Brewer #067 is also independently compared with new-generation instrumentation, a co-located Pandora spectrometer (#117), over a 1-year-long period (2016–2017) at Sapienza University of Rome, showing linear correlation indices above 0.96 between slant column densities, slope of 0.97, and offset of 0.02 DU (5.4×1014 molec.cm-2). The average bias between vertical column densities is negligible (−0.002 DU or -5.4×1013 molec.cm-2). This, incidentally, represents the first intercomparison of NO2 retrievals between a MkIV Brewer and a Pandora instrument. Owing to its accuracy and length, the Brewer data set collected in Rome can be useful for satellite calibration/validation exercises, comparison with photochemical models, and better aerosol optical depth estimates (NO2 optical depth climatology). In addition, it can be employed to identify long-term trends in NO2 column densities in a metropolitan environment, over two decades witnessing important changes in environmental policies, emission loads and composition, and the effect of a worldwide economic recession, to offer just a few examples. The method can be replicated on the more than 80 MkIV spectrophotometers operating worldwide in the frame of the international Brewer network. The NO2 data set described in this paper can be freely accessed at https://doi.org/10.5281/zenodo.4715219 (Diémoz and Siani, 2021).

An Arctic ozone hole in 2020 if not for the Montreal Protocol

Abstract. Without the Montreal Protocol, the already extreme Arctic ozone losses in the boreal spring of 2020 would be expected to have produced an Antarctic-like ozone hole, based upon simulations performed using the specified dynamics version of the Whole Atmosphere Community Climate Model (SD-WACCM) and using an alternate emission scenario of 3.5 % growth in ozone-depleting substances from 1985 onwards. In particular, we find that the area of total ozone below 220 DU (Dobson units), a standard metric of Antarctic ozone hole size, would have covered about 20 million km2. Record observed local lows of 0.1 ppmv (parts per million by volume) at some altitudes in the lower stratosphere seen by ozonesondes in March 2020 would have reached 0.01, again similar to the Antarctic. Spring ozone depletion would have begun earlier and lasted longer without the Montreal Protocol, and by 2020, the year-round ozone depletion would have begun to dramatically diverge from the observed case. This extreme year also provides an opportunity to test parameterizations of polar stratospheric cloud impacts on denitrification and, thereby, to improve stratospheric models of both the real world and alternate scenarios. In particular, we find that decreasing the parameterized nitric acid trihydrate number density in SD-WACCM, which subsequently increases denitrification, improves the agreement with observations for both nitric acid and ozone. This study reinforces that the historically extreme 2020 Arctic ozone depletion is not cause for concern over the Montreal Protocol's effectiveness but rather demonstrates that the Montreal Protocol indeed merits celebration for avoiding an Arctic ozone hole.

Evaluation of Version 3 Total and Tropospheric Ozone Columns From Earth Polychromatic Imaging Camera on Deep Space Climate Observatory for Studying Regional Scale Ozone Variations

Discrete wavelength radiance measurements from the Deep Space Climate Observatory (DSCOVR) Earth Polychromatic Imaging Camera (EPIC) allows derivation of global synoptic maps of total and tropospheric ozone columns every hour during Northern Hemisphere (NH) Summer or 2 hours during Northern Hemisphere winter. In this study, we present version 3 retrieval of Earth Polychromatic Imaging Camera ozone that covers the period from June 2015 to the present with improved geolocation, calibration, and algorithmic updates. The accuracy of total and tropospheric ozone measurements from EPIC have been evaluated using correlative satellite and ground-based total and tropospheric ozone measurements at time scales from daily averages to monthly means. The comparisons show good agreement with increased differences at high latitudes. The agreement improves if we only accept retrievals derived from the EPIC 317 nm triplet and limit solar zenith and satellite looking angles to 70°. With such filtering in place, the comparisons of EPIC total column ozone retrievals with correlative satellite and ground-based data show mean differences within ±5-7 Dobson Units (or 1.5–2.5%). The biases with other satellite instruments tend to be mostly negative in the Southern Hemisphere while there are no clear latitudinal patterns in ground-based comparisons. Evaluation of the EPIC ozone time series at different ground-based stations with the correlative ground-based and satellite instruments and ozonesondes demonstrated good consistency in capturing ozone variations at daily, weekly and monthly scales with a persistently high correlation (r2 > 0.9) for total and tropospheric columns. We examined EPIC tropospheric ozone columns by comparing with ozonesondes at 12 stations and found that differences in tropospheric column ozone are within ±2.5 DU (or ∼±10%) after removing a constant 3 DU offset at all stations between EPIC and sondes. The analysis of the time series of zonally averaged EPIC tropospheric ozone revealed a statistically significant drop of ∼2–4 DU (∼5–10%) over the entire NH in spring and summer of 2020. This drop in tropospheric ozone is partially related to the unprecedented Arctic stratospheric ozone losses in winter-spring 2019/2020 and reductions in ozone precursor pollutants due to the COVID-19 pandemic.

The 2019 Raikoke volcanic eruption – Part 1: Dispersion model simulations and satellite retrievals of volcanic sulfur dioxide

Abstract. Volcanic eruptions can cause significant disruption to society, and numerical models are crucial for forecasting the dispersion of erupted material. Here we assess the skill and limitations of the Met Office's Numerical Atmospheric-dispersion Modelling Environment (NAME) in simulating the dispersion of the sulfur dioxide (SO2) cloud from the 21–22 June 2019 eruption of the Raikoke volcano (48.3∘ N, 153.2∘ E). The eruption emitted around 1.5±0.2 Tg of SO2, which represents the largest volcanic emission of SO2 into the stratosphere since the 2011 Nabro eruption. We simulate the temporal evolution of the volcanic SO2 cloud across the Northern Hemisphere (NH) and compare our model simulations to high-resolution SO2 measurements from the TROPOspheric Monitoring Instrument (TROPOMI) and the Infrared Atmospheric Sounding Interferometer (IASI) satellite SO2 products. We show that NAME accurately simulates the observed location and horizontal extent of the SO2 cloud during the first 2–3 weeks after the eruption but is unable, in its standard configuration, to capture the extent and precise location of the highest magnitude vertical column density (VCD) regions within the observed volcanic cloud. Using the structure–amplitude–location (SAL) score and the fractional skill score (FSS) as metrics for model skill, NAME shows skill in simulating the horizontal extent of the cloud for 12–17 d after the eruption where VCDs of SO2 (in Dobson units, DU) are above 1 DU. For SO2 VCDs above 20 DU, which are predominantly observed as small-scale features within the SO2 cloud, the model shows skill on the order of 2–4 d only. The lower skill for these high-SO2-VCD regions is partly explained by the model-simulated SO2 cloud in NAME being too diffuse compared to TROPOMI retrievals. Reducing the standard horizontal diffusion parameters used in NAME by a factor of 4 results in a slightly increased model skill during the first 5 d of the simulation, but on longer timescales the simulated SO2 cloud remains too diffuse when compared to TROPOMI measurements. The skill of NAME to simulate high SO2 VCDs and the temporal evolution of the NH-mean SO2 mass burden is dominated by the fraction of SO2 mass emitted into the lower stratosphere, which is uncertain for the 2019 Raikoke eruption. When emitting 0.9–1.1 Tg of SO2 into the lower stratosphere (11–18 km) and 0.4–0.7 Tg into the upper troposphere (8–11 km), the NAME simulations show a similar peak in SO2 mass burden to that derived from TROPOMI (1.4–1.6 Tg of SO2) with an average SO2 e-folding time of 14–15 d in the NH. Our work illustrates how the synergy between high-resolution satellite retrievals and dispersion models can identify potential limitations of dispersion models like NAME, which will ultimately help to improve dispersion modelling efforts of volcanic SO2 clouds.

Characterizing ozone throughout the atmospheric column over the tropical Andes from in situ and remote sensing observations

In this study, we characterize atmospheric ozone over the tropical Andes in the boundary layer, the free troposphere, and the stratosphere; we quantify each contribution to total column ozone, and we evaluate the performance of the multi-sensor reanalysis (MSR2) in the region. Thus, we present data taken in Ecuador and Peru (2014–2019). The contribution from the surface was determined by integrating ozone concentrations measured in Quito and Cuenca (Ecuador) up to boundary layer height. In addition, tropospheric and stratospheric column ozone were quantified from ozone soundings (38) launched from Quito during the study time period. Profiles were compared against soundings at Natal (SHADOZ network) for being the closest observational reference with sufficient data in 2014–2019. Data were also compared against stratospheric mixing ratios from the Aura Microwave Limb Sounder (Aura MLS). Findings demonstrate that the stratospheric component of total column ozone over the Andes (225.2 ± 8.9 Dobson Units [DU]) is at similar levels as those observed at Natal (223.3 ± 8.6 DU), and observations are comparable to Aura MLS data. In contrast, the tropospheric contribution is lower over the Andes (20.2 ± 4.3 DU) when compared to Natal (35.4 ± 6.4 DU) due to a less deep and cleaner troposphere. From sounding extrapolation of Quito profiles down to sea level, we determined that altitude deducts about 5–7 DU from the total column, which coincides with a 3%–4% overestimation of the MSR2 over Quito and Marcapomacocha (Peru). In addition, when MSR2 data are compared along a transect that crosses from the Amazon over Quito, the Ecuadorian coast side, and into the Pacific, observations are not significantly different among the three first locations. Results point to coarse reanalysis resolution not being suitable to resolve the formidable altitude transition imposed by the Andes mountain chain. This work advances our knowledge of atmospheric ozone over the study region and provides a robust time series of upper air measurements for future evaluations of satellite and reanalysis products.

Simulation of Record Arctic Stratospheric Ozone Depletion in 2020

AbstractIn the Arctic winter/spring of 2019/2020, stratospheric temperatures were exceptionally low until early April and the polar vortex was very stable. As a consequence, significant chemical ozone depletion occurred in the Arctic polar vortex in spring 2020. Here, we present simulations using the Chemical Lagrangian Model of the Stratosphere that address the development of chlorine compounds and ozone in the Arctic stratosphere in 2020. The simulation reproduces relevant observations of ozone and chlorine compounds, as shown by comparisons with data from the Microwave Limb Sounder, Atmospheric Chemistry Experiment‐Fourier Transform Spectrometer, balloon‐borne ozone sondes, and the Ozone Monitoring Instrument. Although the concentration of chlorine and bromine compounds in the polar stratosphere has decreased by more than 10% compared to peak values around the year 2000, the meteorological conditions in winter/spring 2019/2020 caused unprecedented ozone depletion. The lowest simulated ozone mixing ratio was about 40 ppbv. Because extremely low ozone mixing ratios were reached in the lower polar stratosphere, chlorine deactivation into HCl occurred as is normally observed in the Antarctic polar vortex. The depletion in partial column ozone in the lower stratosphere (potential temperature from 350 to 600 K, corresponding to about 12–24 km) in the vortex core was calculated to reach 143 Dobson Units, which is more than the ozone loss in 2011 and 2016, the years which —until 2020— had seen the largest Arctic ozone depletion on record.

Three-Year Observations of Ozone Columns over Polar Vortex Edge Area above West Antarctica

Ozone vertical column densities (VCDs) were retrieved by Zenith Scattered Light-Differential Optical Absorption Spectroscopy (ZSL-DOAS) from January 2017 to February 2020 over Fildes Peninsula, West Antarctica (62.22°S, 58.96°W). Each year, ozone VCDs started to decline around July with a comparable gradient around 1.4 Dobson Units (DU) per day, then dropped to their lowest levels in September and October, when ozone holes appeared (less than 220 DU). Daily mean values of retrieved ozone VCDs were compared with Ozone Monitoring Instrument (OMI) and Global Ozone Monitoring Experiment 2 (GOME-2) satellite observations and the Modern-Era Retrospective analysis for Research and Applications Version 2 (MERRA-2) reanalysis dataset, with correlation coefficients (R2) of 0.86, 0.94, and 0.90, respectively. To better understand the causes of ozone depletion, the retrieved ozone VCDs, temperature, and potential vorticity (PV) at certain altitudes were analyzed. The profiles of ozone and PV were positively correlated during their fluctuations, which indicates that the polar vortex has a strong influence on stratospheric ozone depletion during Antarctic spring. Located at the edge of polar vortex, the observed data will provide a basis for further analysis and prediction of the inter-annual variations of stratospheric ozone in the future.

Persistent Stratospheric Warming Due to 2019–2020 Australian Wildfire Smoke

AbstractAustralian wildfires burning from December 2019 to January 2020 injected approximately 0.9 Tg of smoke into the stratosphere; this is the largest amount observed in the satellite era. A comparison of numerical simulations to satellite observations of the plume rise suggests that the smoke mass contained 2.5% black carbon. Model calculations project a 1 K warming in the stratosphere of the Southern Hemisphere midlatitudes for more than 6 months following the injection of black‐carbon containing smoke. The 2020 average global mean clear sky effective radiative forcing at top of atmosphere is estimated to be −0.03 W m−2 with a surface value of −0.32 W m−2. Assuming that smoke particles coat with sulfuric acid in the stratosphere and have similar heterogeneous reaction rates as sulfate aerosol, we estimate a smoke‐induced chemical decrease in total column ozone of 10–20 Dobson units from August to December in mid‐high southern latitudes.

Biases of Global Tropopause Altitude Products in Reanalyses and Implications for Estimates of Tropospheric Column Ozone

Accuracy of global tropopause altitude products from reanalyses is important to applications of the products, including the derivation of tropospheric column ozone (TCO). Here, monthly biases in lapse-rate tropopause pressure (PLRT) in two reanalyses, NCEP/NCAR and MERRA-2, and associated implications for estimating TCO are examined, based on global radiosonde observations over 1980–2017 at 689 stations. Our analysis suggests that the global mean PLRT is underestimated by −2.3 hPa in NCEP/NCAR and by −0.9 hPa in MERRA-2, mainly attributable to large negative biases around the subtropics (~20°–50°) in both hemispheres, with generally positive biases at other latitudes. Overall, NCEP/NCAR outperforms MERRA-2 in the Northern Hemisphere but underperforms MERRA-2 in the Southern Hemisphere. PLRT biases in the two reanalyses vary more evidently with latitude than with longitude. From winter to summer, the peaks of negative PLRT biases around the subtropics shift poleward by ~10°. Approximately, 70% of the reanalysis PLRT biases are within −10–10 hPa. Consequently, a negative (positive) PLRT bias induces a positive (negative) TCO bias. In absolute magnitude, the mean ozonesonde TCO bias attributable to PLRT biases is ~0.2, ~0.8 and ~1.2 Dobson Units (DU) if a PLRT bias is within 0–5, 10–15, and 10–15 hPa. Using a global ozone climatology, we estimate that the global mean bias in TCO induced by the PLRT biases in both reanalyses is positive, being 0.64 DU (or 2.2%) for NCEP/NCAR and 0.28 DU (or 1.1%) for MERRA-2.

The Combined Effect of Ozone and Aerosols on Erythemal Irradiance in an Extremely Low Ozone Event during May 2020

In this study we focus on measurements and modeled UV index in the region of Athens, Greece, during a low ozone event. During the period of 12–19 May 2020, total ozone column (TOC) showed extremely low values, 35–55 Dobson Units (up to 15%) decrease from the climatic mean (being lower than the −2σ). This condition favors the increase of UV erythemal irradiance, since stratospheric ozone is the most important attenuator at the UVB spectral region. Simultaneously, an intrusion of Saharan dust aerosols in the region has masked a large part of the low ozone effect on UV irradiance. In order to investigate the event, we have used spectral solar irradiance measurements from the Precision Solar Radiometer (PSR), TOC from the Brewer spectrophotometer, and Radiative Transfer Model (RTM) calculations. Model calculations of the UV Index (UVI) showed an increase of ~30% compared to the long-term normal UVI due to the low TOC while at the same time and for particular days, aerosols masked this effect by ~20%. The RTM has been used to investigate the response in the UV spectral region of these variations at different solar zenith angles (SZAs). Spectra simulated with the RTM have been compared to measured ones and an average difference of ~2% was found. The study points out the importance of accurate measurements or forecasts of both ozone and aerosols when deriving UVI under unusual low ozone–high aerosol conditions.

Record low ozone values over the Arctic in boreal spring 2020

Abstract. Ozone data derived from the Tropospheric Monitoring Instrument (TROPOMI) sensor on board the Sentinel-5 Precursor satellite show exceptionally low total ozone columns in the polar region of the Northern Hemisphere (Arctic) in spring 2020. Minimum total ozone column values around or below 220 Dobson units (DU) were seen over the Arctic for 5 weeks in March and early April 2020. Usually the persistence of such low total ozone column values in spring is only observed in the polar Southern Hemisphere (Antarctic) and not over the Arctic. These record low total ozone columns were caused by a particularly strong polar vortex in the stratosphere with a persistent cold stratosphere at higher latitudes, a prerequisite for ozone depletion through heterogeneous chemistry. Based on the ERA5, which is the fifth generation of the European Centre for Medium-Range Weather Forecasts (ECMWF) atmospheric reanalysis, the Northern Hemisphere winter 2019/2020 (from December to March) showed minimum polar cap temperatures consistently below 195 K around 20 km altitude, which enabled enhanced formation of polar stratospheric clouds. The special situation in spring 2020 is compared and discussed in context with two other Northern Hemisphere spring seasons, namely those in 1997 and 2011, which also displayed relatively low total ozone column values. However, during these years, total ozone columns below 220 DU over several consecutive days were not observed in spring. The similarities and differences of the atmospheric conditions of these three events and possible explanations for the observed features are presented and discussed. It becomes apparent that the monthly mean of the minimum total ozone column value for March 2020 (221 DU) was clearly below the respective values found in March 1997 (267 DU) and 2011 (252 DU), which highlights the special evolution of the polar stratospheric ozone layer in the Northern Hemisphere in spring 2020. A comparison with a typical ozone hole over the Antarctic (e.g., in 2016) indicates that although the Arctic spring 2020 situation is remarkable, with total ozone column values around or below 220 DU observed over a considerable area (up to 0.9 million km2), the Antarctic ozone hole shows total ozone columns typically below 150 DU over a much larger area (of the order of 20 million km2). Furthermore, total ozone columns below 220 DU are typically observed over the Antarctic for about 4 months.

Vertical ozone profiles in the atmosphere over the Antarctic Peninsula and Kyiv by Umkehr observations

The Umkehr observations over Kyiv (Ukraine) and Antarctic Peninsula areas were processed for the first time to retrieve and analyse the vertical distribution of ozone. The Umkehr observations have been pre-processed using the UMK92 software package proposed by the World Ozone and UV-radiation Data Centre (WOUDC). The set of the calculated vertical ozone profiles for Kyiv–Goloseyev station (2011–2020) and Akademik Vernadsky station (2005–2009) has been obtained. Analysis of ozone profiles observed with Dobson spectrophotometer D040 indicates that the maximum ozone concentration is located in the altitude range of 15–25 km with an average height of 19.8 ± 1.4 km. It corresponds to the layer of maximum ozone concentration in the mid-latitude stratosphere. The maximum ozone partial content in Dobson Units per the layers (DU/layer) with thickness of 5 km altitude for most of the years are of 60–80 DU/layer. There are also days with the maximum ozone content significantly larger than an average. A characteristic feature of the profiles is that the lower ozone content occur in summer and autumn months in the range of 60–75 DU/layer. The winter and spring profiles demonstrate higher ozone values at the maximum. To analyse the vertical profiles of ozone in Antarctic Peninsula area, we use Umkehr data from observations at the Akademik Vernadsky station with the Dobson D123 spectrophotometers in 2005–2009. The data processing and the calculation of the vertical ozone profiles was provided according to the methodology developed at the Kyiv–Goloseyev station. It is shown that the ozone profiles at the Akademik Vernadsky station vary in a wide range of values of the maximum ozone concentration from 40 to 110 DU/layer. Ozone content at maximum of vertical distribution was changing dramatically from day to day in the Antarctic region during the ozone hole period.

Version 2 Ozone Monitoring Instrument SO<sub>2</sub> product (OMSO2 V2): new anthropogenic SO<sub>2</sub> vertical column density dataset

Abstract. The Ozone Monitoring Instrument (OMI) has been providing global observations of SO2 pollution since 2004. Here we introduce the new anthropogenic SO2 vertical column density (VCD) dataset in the version 2 OMI SO2 product (OMSO2 V2). As with the previous version (OMSO2 V1.3), the new dataset is generated with an algorithm based on principal component analysis of OMI radiances but features several updates. The most important among those is the use of expanded lookup tables and model a priori profiles to estimate SO2 Jacobians for individual OMI pixels, in order to better characterize pixel-to-pixel variations in SO2 sensitivity including over snow and ice. Additionally, new data screening and spectral fitting schemes have been implemented to improve the quality of the spectral fit. As compared with the planetary boundary layer SO2 dataset in OMSO2 V1.3, the new dataset has substantially better data quality, especially over areas that are relatively clean or affected by the South Atlantic Anomaly. The updated retrievals over snow/ice yield more realistic seasonal changes in SO2 at high latitudes and offer enhanced sensitivity to sources during wintertime. An error analysis has been conducted to assess uncertainties in SO2 VCDs from both the spectral fit and Jacobian calculations. The uncertainties from spectral fitting are reflected in SO2 slant column densities (SCDs) and largely depend on the signal-to-noise ratio of the measured radiances, as implied by the generally smaller SCD uncertainties over clouds or for smaller solar zenith angles. The SCD uncertainties for individual pixels are estimated to be ∼ 0.15–0.3 DU (Dobson units) between ∼ 40∘ S and ∼ 40∘ N and to be ∼ 0.2–0.5 DU at higher latitudes. The uncertainties from the Jacobians are approximately ∼ 50 %–100 % over polluted areas and are primarily attributed to errors in SO2 a priori profiles and cloud pressures, as well as the lack of explicit treatment for aerosols. Finally, the daily mean and median SCDs over the presumably SO2-free equatorial east Pacific have increased by only ∼ 0.0035 DU and ∼ 0.003 DU respectively over the entire 15-year OMI record, while the standard deviation of SCDs has grown by only ∼ 0.02 DU or ∼ 10%. Such remarkable long-term stability makes the new dataset particularly suitable for detecting regional changes in SO2 pollution.

Stratospheric Ozone in the Last Glacial Maximum

AbstractUsing the Whole Atmosphere Community Climate Model version 6, stratospheric ozone in the Last Glacial Maximum (LGM) is investigated. It is shown that, compared with preindustrial (PI) times, LGM modeled stratospheric temperatures are increased by up to 8 K, leading to faster ozone destruction rates for gas phase reactions, especially via the Chapman mechanism. On the other hand, stratospheric hydroxyl radical (OH) and nitrogen oxides (NOx) concentrations are decreased by 10–20%, which decreases catalytic ozone destruction, thereby decreasing ozone loss rates. The net effect of these two compensating mechanisms in the upper stratosphere (above 15 hPa) is a vertically integrated 1–3 Dobson unit (DU) decrease during the LGM. In the lower stratosphere (tropopause to 15 hPa), changes in the stratospheric overturning circulation and resulting transport dominate changes in ozone. Consistent with a weakening of the residual circulation in the LGM, lower stratospheric ozone is increased by 2–5 DU in the tropics and decreased by 5–10 DU in the extratropics, but the latter is partly compensated by ozone increases due to a lower tropopause. It is found that tropospheric ozone is decreased by about 5 DU in the LGM versus PI. Combined changes in stratospheric and tropospheric ozone lead to a decrease in total ozone column everywhere except over the northeast North America, equatorial Indian and West Pacific Oceans. Surface ultraviolet radiation in the LGM versus PI is increased over the Northern Hemisphere middle and high latitudes, especially over the ice caps, and over the Southern Hemisphere near 60°S.

Comparison of SCIPUFF predictions to SO2 measurements from instruments on the MetOp-A, MetOp-B, Aura and Suomi satellites from the 2016 fire at Al-Mishraq

On October 20th, 2016, Daesh (Islamic State) set fire to the sulfur production and storage site at Al-Mishraq, Iraq. The fire burned continuously for seven days resulting in the release of a buoyant dynamic sulfur dioxide (SO2) toxic plume extending geographically for over 300 km. This Al-Mishraq event provides an opportunity for scientists to address probabilistic atmospheric transport and dispersion (PATD) hazard model performance across multiple downwind scales over a large area. In using any PATD model, a fair evaluation of the model depends on the quality of the source term – especially for a very dynamic source term such as a burning sulfur stockpile. An innovative approach to derive such a source for Al-Mishraq was explored by the Swedish Defence Research Agency (in Swedish Totalförsvarets forskningsinstitut, or FOI). The experts from FOI characterized the SO2 source term based on satellite observations, which reflect vertically-integrated concentrations and are expressed in Dobson units (DU). The work throughout this paper is a novel approach and leverages the FOI analysis to evaluate a PATD, the Second Order Closure Integrated Puff (SCIPUFF) transport and dispersion code as adapted within the Hazard Prediction and Assessment Capability (HPAC). SCIPUFF predictions are compared to the satellite-based vertically-integrated SO2 measurements from the Moderate Resolution Imaging Spectro-radiometer (MODIS) instruments. Satellite measurements were available at 07Z and 11Z daily from 21 to 26 Oct 2016. A 1-DU background was assumed. SCIPUFF over predicts (factor of 2) column density (DU) peaks in the near field (40, 80, and 120 km) and under predicts in the far field (200, 280 and 320 km); best agreement is at the 160 km arc. Plume direction errors of 25–80° are found when comparing the azimuths of peak observed and predicted column densities. Performance metrics traditionally used for model evaluation included fractional bias (FB), normalized mean-square error (NMSE), and figure of merit in space (FMS). The FB at 07Z was −0.2 to +0.09 across the eight arcs, 40–320 km downwind. Upon analyses, SCIPUFF showed approximate equal over and under prediction for the 07Z; and the FB at 11Z under predicted seven of eight arcs, with values that ranged from −0.07 to +0.36. The NMSE was 3.11–5.06 with no identifiable trends on arc distance. The FMS, averaged over each arc, by day, was between 0.31 and 0.56. Higher values were found in the early and later stages of the fire 21–22 and 25–26 October. Lower averaged FMS values were calculated for 23–24 October which corresponds to a period where the fire burned hotter and SO2 mass was injected to higher altitudes of 1–4 km.

An overview of and issues with sky radiometer technology and SKYNET

Abstract. This paper is an overview of the progress in sky radiometer technology and the development of the network called SKYNET. It is found that the technology has produced useful on-site calibration methods, retrieval algorithms, and data analyses from sky radiometer observations of aerosol, cloud, water vapor, and ozone. A formula was proposed for estimating the accuracy of the sky radiometer calibration constant F0 using the improved Langley (IL) method, which was found to be a good approximation to observed monthly mean uncertainty in F0, around 0.5 % to 2.4 % at the Tokyo and Rome sites and smaller values of around 0.3 % to 0.5 % at the mountain sites at Mt. Saraswati and Davos. A new cross IL (XIL) method was also developed to correct an underestimation by the IL method in cases with large aerosol retrieval errors. The root-mean-square difference (RMSD) in aerosol optical thickness (AOT) comparisons with other networks took values of less than 0.02 for λ≥500 nm and a larger value of about 0.03 for shorter wavelengths in city areas and smaller values of less than 0.01 in mountain comparisons. Accuracies of single-scattering albedo (SSA) and size distribution retrievals are affected by the propagation of errors in measurement, calibrations for direct solar and diffuse sky radiation, ground albedo, cloud screening, and the version of the analysis software called the Skyrad pack. SSA values from SKYNET were up to 0.07 larger than those from AERONET, and the major error sources were identified as an underestimation of solid viewing angle (SVA) and cloud contamination. Correction of these known error factors reduced the SSA difference to less than 0.03. Retrievals of other atmospheric constituents by the sky radiometer were also reviewed. Retrieval accuracies were found to be about 0.2 cm for precipitable water vapor amount and 13 DU (Dobson Unit) for column ozone amount. Retrieved cloud optical properties still showed large deviations from validation data, suggesting a need to study the causes of the differences. It is important that these recent studies on improvements presented in the present paper are introduced into the existing operational systems and future systems of the International SKYNET Data Center.

Deposition, recycling, and archival of nitrate stable isotopes between the air–snow interface: comparison between Dronning Maud Land and Dome C, Antarctica

Abstract. The nitrogen stable isotopic composition in nitrate (δ15N-NO3-) measured in ice cores from low-snow-accumulation regions in East Antarctica has the potential to provide constraints on past ultraviolet (UV) radiation and thereby total column ozone (TCO) due to the sensitivity of nitrate (NO3-) photolysis to UV radiation. However, understanding the transfer of reactive nitrogen at the air–snow interface in polar regions is paramount for the interpretation of ice core records of δ15N-NO3- and NO3- mass concentrations. As NO3- undergoes a number of post-depositional processes before it is archived in ice cores, site-specific observations of δ15N-NO3- and air–snow transfer modelling are necessary to understand and quantify the complex photochemical processes at play. As part of the Isotopic Constraints on Past Ozone Layer Thickness in Polar Ice (ISOL-ICE) project, we report new measurements of NO3- mass concentration and δ15N-NO3- in the atmosphere, skin layer (operationally defined as the top 5 mm of the snowpack), and snow pit depth profiles at Kohnen Station, Dronning Maud Land (DML), Antarctica. We compare the results to previous studies and new data, presented here, from Dome C on the East Antarctic Plateau. Additionally, we apply the conceptual 1D model of TRansfer of Atmospheric Nitrate Stable Isotopes To the Snow (TRANSITS) to assess the impact of NO3- recycling on δ15N-NO3- and NO3- mass concentrations archived in snow and firn. We find clear evidence of NO3- photolysis at DML and confirmation of previous theoretical, field, and laboratory studies that UV photolysis is driving NO3- recycling and redistribution at DML. Firstly, strong denitrification of the snowpack is observed through the δ15N-NO3- signature, which evolves from the enriched snowpack (−3 ‰ to 100 ‰), to the skin layer (−20 ‰ to 3 ‰), to the depleted atmosphere (−50 ‰ to −20 ‰), corresponding to mass loss of NO3- from the snowpack. Based on the TRANSITS model, we find that NO3- is recycled two times, on average, before it is archived in the snowpack below 15 cm and within 0.75 years (i.e. below the photic zone). Mean annual archived δ15N-NO3- and NO3- mass concentration values are 50 ‰ and 60 ng g−1, respectively, at the DML site. We report an e-folding depth (light attenuation) of 2–5 cm for the DML site, which is considerably lower than Dome C. A reduced photolytic loss of NO3- at DML results in less enrichment of δ15N-NO3- than at Dome C mainly due to the shallower e-folding depth but also due to the higher snow accumulation rate based on TRANSITS-modelled sensitivities. Even at a relatively low snow accumulation rate of 6 cm yr−1 (water equivalent; w.e.), the snow accumulation rate at DML is great enough to preserve the seasonal cycle of NO3- mass concentration and δ15N-NO3-, in contrast to Dome C where the depth profiles are smoothed due to longer exposure of surface snow layers to incoming UV radiation before burial. TRANSITS sensitivity analysis of δ15N-NO3- at DML highlights that the dominant factors controlling the archived δ15N-NO3- signature are the e-folding depth and snow accumulation rate, with a smaller role from changes in the snowfall timing and TCO. Mean TRANSITS model sensitivities of archived δ15N-NO3- at the DML site are 100 ‰ for an e-folding depth change of 8 cm, 110 ‰ for an annual snow accumulation rate change of 8.5 cm yr−1 w.e., 10 ‰ for a change in the dominant snow deposition season between winter and summer, and 10 ‰ for a TCO change of 100 DU (Dobson units). Here we set the framework for the interpretation of a 1000-year ice core record of δ15N-NO3- from DML. Ice core δ15N-NO3- records at DML will be less sensitive to changes in UV than at Dome C; however the higher snow accumulation rate and more accurate dating at DML allows for higher-resolution δ15N-NO3- records.

Anthropogenic and volcanic point source SO<sub>2</sub> emissions derived from TROPOMI on board Sentinel-5 Precursor: first results

Abstract. The paper introduces the first TROPOMI-based sulfur dioxide (SO2) emissions estimates for point sources. A total of about 500 continuously emitting point sources releasing about 10 kt yr−1 to more than 2000 kt yr−1 of SO2, previously identified from Ozone Monitoring Instrument (OMI) observations, were analyzed using TROPOMI (TROPOspheric Monitoring Instrument) measurements for 1 full year from April 2018 to March 2019. The annual emissions from these sources were estimated and compared to similar estimates from OMI and Ozone Mapping Profiling Suite (OMPS) measurements. Note that emissions from many of these 500 sources have declined significantly since 2005, making their quantification more challenging. We were able to identify 274 sources where annual emissions are significant and can be reliably estimated from TROPOMI. The standard deviations of TROPOMI vertical column density data, about 1 Dobson unit (DU, where 1 DU =2.69×1016 molecules cm−2) over the tropics and 1.5 DU over high latitudes, are larger than those of OMI (0.6–1 DU) and OMPS (0.3–0.4 DU). Due to its very high spatial resolution, TROPOMI produces 12–20 times more observations over a certain area than OMI and 96 times more than OMPS. Despite higher uncertainties of individual TROPOMI observations, TROPOMI data averaged over a large area have roughly 2–3 times lower uncertainties compared to OMI and OMPS data. Similarly, TROPOMI annual emissions can be estimated with uncertainties that are 1.5–2 times lower than the uncertainties of annual emissions estimates from OMI. While there are area biases in TROPOMI data over some regions that have to be removed from emission calculations, the absolute magnitude of these are modest, typically within ±0.25 DU, which can be comparable with SO2 values over large sources.