SO2 Mixing Ratios Research Articles

Emissions of Sulphur Dioxide (SO2) from Coal-Fired Power Plants in Serbia and Bosnia-Herzegovina: First Attempts of a Validation of TROPOMI Satellite Products with Airborne In Situ Measurements

The Western Balkan region is known for emitting alarmingly high sulphur dioxide amounts from coal-fired power plants. Though a number of environmental regulations have been introduced in recent years (e.g. desulphurisation installations, construction of modern power plants), the pollution burden is still much higher than recommended by the authorities. A number of different montoring systems are required to observe the growing pollution situation in the Western Balkan region, partly caused by a high energy demand from outside (e.g. Western Europe).Several of the top ten SO2 polluters in Europe are located in Bosnia-Herzegovina and Serbia. Here we present the first in situ measurements of sulphur dioxide in this region conducted with a German research aircraft in cooperation with local scientists in Bosnia-Herzegovina and Serbia. Two of the strongtest emitting coalfired power plants were selected for the measurements in autumn 2020: Tuzla in Bosnia-Herzegovina and Nikola Tesla in Serbia (Nikola Tesla). The measurements were mainly conducted in the boundary layer (below ~1 km altitude in winter). Downwind of the power plants, extremely high SO2 mixing ratios exceeding 100 parts per billion (ppb = nmol mol-1 ) were measured at a distance of ~20-40 km from the sources. The SO2 plumes from the power plants were trapped in well-defined inversion layers between ~500-1000 m altitude. The airborne measurements can be used to validate synchronous spaceborne SO2 measurements from the TROPOspheric Monitoring Instrument (TROPOMI) onboard the Sentinel-5P satellite. A first intercomparison indicates some problems with dense smoke clouds frequently covering these countries in the winter months. However, it turned out that the Nikola Tesla flight is to some extent suited for a TROPOMI-SO2 validation, since it was obtained during cloud-free conditions with a well-defined vertical extension of the probed SO2 plume (needed to estimate the Vertical Column Density, VCD, measured by the satellite). In addition, these airborne measurements accompanied by model simulations can be used to determine the SO2 emission strength of the power plants and to compare it to the source strength reported by the power plant operators. The results indicate a reasonable agreement between the airborne measurements, model results, emission inventories, and satellite measurements for the Nikola Tesla power plants.

HDO and SO2thermal mapping on Venus

Since January 2012, we have been monitoring the behavior of sulfur dioxide and water on Venus using the Texas Echelon Cross-Echelle Spectrograph (TEXES) imaging spectrometer at the NASA InfraRed Telescope Facility (IRTF, Mauna Kea Observatory). We present here new data recorded in 2021 and 2022, after an 18-month interruption due to the Covid pandemic. Most of the observations were recorded in two spectral ranges: the 7.4 µm (1345 cm−1) range, where SO2, CO2, and HDO (used as a proxy for H2O) transitions are observed at the cloud top, at an altitude of about 62 km, and the 19 µm (530 cm−1) range, where SO2and CO2are probed within the clouds at an altitude of about 57 km. We recently added the 8.6 µm (1162 cm−1) range, which probes a few kilometers above the cloud top (z= 67 km). As in our previous studies, the volume mixing ratio of SO2is estimated using the SO2/CO2line depth ratio of weak transitions; the H2O volume mixing ratio is derived from the HDO/CO2line depth ratio, assuming a D/H ratio of 200 times the Vienna Standard Mean Ocean Water (VSMOW). As reported in our previous analyses, the SO2mixing ratio shows strong variations with time and also over the disk, showing evidence of the formation of SO2plumes. These local maxima appear sporadically on the SO2maps and stay visible over a few hours. In contrast, the H2O abundance is remarkably uniform over the disk and shows moderate variations as a function of time. The present dataset shows significant differences with respect to the 2012–2019 dataset: (1) the SO2mixing ratio at the cloud top has decreased by a factor of about 3 with respect to the maximum value observed in July 2018; (2) the long-term anti-correlation between SO2and H2O previously observed between 2014 and 2019 is no longer visible; (3) a very high SO2plume activity was observed in Nov. 2021, in spite of the low SO2mixing ratio at the cloud top. In contrast, the distribution of the SO2plume appearance over the disk is confirmed, with a maximum along the equator and around the morning terminator. Information on the SO2vertical gradient is retrieved from the simultaneous analysis of SO2at 7.4 µm and 19 µm. The gradient is constant in most cases with a few exceptions, especially in November 2021 when the plume activity was high. Finally, the temperature distributions retrieved from the continuum maps in September and November 2021 show an unusual pattern possibly associated with gravity waves, as previously observed by the longwave infrared camera camera aboard the Akatsuki spacecraft.

Three-dimensional modeling of Venus photochemistry and clouds

We present here three-dimensional simulations of the Venus photochemistry and clouds from the ground to the bottom of the thermosphere. For that purpose, we have implemented a state-of-the-art photochemical and equilibrium cloud model in the Venus Planetary Climate Model (Venus PCM). The interactive coupling between dynamics, radiation, chemistry and clouds allows a comprehensive description of the CO2, CO, sulfur, chlorine, oxygen, and hydrogen species, with tracking of the condensed phase. Regarding the clouds, the Venus PCM calculates the composition, number density, and sedimentation rates of the binary H2SO4-H2O liquid aerosols, based on observed altitude-dependent size distributions. The article describes in detail the new components implemented in the Venus PCM. It then presents an overview of the results concerning clouds and atmospheric chemistry, which are compared with a wide range of observations. The modeled cloud characteristics and vertical profiles of minor species are found to be in broad agreement with most of the measurements available between 30 and 100 km. In particular, the Venus PCM reproduces the steep decrease of H2O and SO2 mixing ratio inside the cloud layer, as well as the observed vertical distribution of species well identified above the clouds, such as CO and O3. The model also agrees with the ground-based measurements of HCl, but not with the conflicting HCl vertical profiles derived from Venus Express. On the quasi-horizontal plane, latitudinal contrasts in the modeled trace species mostly result from the Hadley-type mean meridional circulation. Large-scale longitudinal variations are essentially created by the diurnal thermal tide above the clouds, and by photolysis above 80 km.

Enhanced sulfur in the upper troposphere and lower stratosphere in spring 2020

Abstract. Sulfur compounds in the upper troposphere and lower stratosphere (UTLS) impact the atmosphere radiation budget, either directly as particles or indirectly as precursor gas for new particle formation. In situ measurements in the UTLS are rare but are important to better understand the impact of the sulfur budget on climate. The BLUESKY mission in May and June 2020 explored an unprecedented situation. (1) The UTLS experienced extraordinary dry conditions in spring 2020 over Europe, in comparison to previous years, and (2) the first lockdown of the COVID-19 pandemic caused major emission reductions from industry, ground, and airborne transportation. With the two research aircraft HALO and Falcon, 20 flights were conducted over central Europe and the North Atlantic to investigate the atmospheric composition with respect to trace gases, aerosol, and clouds. Here, we focus on measurements of sulfur dioxide (SO2) and particulate sulfate (SO42-) in the altitude range of 8 to 14.5 km which show unexpectedly enhanced mixing ratios of SO2 in the upper troposphere and of SO42- in the lowermost stratosphere. In the UT, we find SO2 mixing ratios of (0.07±0.01) ppb, caused by the remaining air traffic, and reduced SO2 sinks due to low OH and low cloud fractions and to a minor extent by uplift from boundary layer sources. Particulate sulfate showed elevated mixing ratios of up to 0.33 ppb in the LS. We suggest that the eruption of the volcano Raikoke in June 2019, which emitted about 1 Tg SO2 into the stratosphere in northern midlatitudes, caused these enhancements, in addition to Siberian and Canadian wildfires and other minor volcanic eruptions. Our measurements can help to test models and lead to new insights in the distribution of sulfur compounds in the UTLS, their sources, and sinks. Moreover, these results can contribute to improving simulations of the radiation budget in the UTLS with respect to sulfur effects.

Measurement report: Variations in surface SO<sub>2</sub> and NO<sub><i>x</i></sub> mixing ratios from 2004 to 2016 at a background site in the North China Plain

Abstract. Strict air pollution control strategies have been implemented in recent decades in the North China Plain (NCP), previously one of the most polluted regions in the world, and have resulted in considerable changes in emissions of air pollutants. However, little is so far known about the long-term trends of the regional background level of NOx and SO2, along with the increase and decrease processes of regional emissions. In this study, the seasonal and diurnal variations of NOx and SO2 as well as their long-term trends at a regional background station in the NCP were characterized from 2004 to 2016. On average, SO2 and NOx mixing ratios were 5.7 ± 8.4 and 14.2 ± 12.4 ppb, respectively. The seasonal variations in SO2 and NOx mixing ratios showed a similar pattern, with a peak in winter and a valley in summer. However, the diurnal variations in SO2 and NOx mixing ratios greatly differed for all seasons, indicating different sources for SO2 and NOx and meteorological effects on their concentrations. Overall, the annual mean SO2 exhibited a significant decreasing trend of −6.1 % yr−1 (R = −0.84, P < 0.01) from 2004 to 2016, which is very close to −6.3 % yr−1 of the annual SO2 emission in Beijing, and a greater decreasing trend of −7.4 % yr−1 (R = −0.95, P < 0.01) from 2008 to 2016. The annual mean of NOx showed a fluctuating rise of +3.4 % yr−1 (R = 0.38, P = 0.40) from 2005 to 2010, reaching the peak value (16.9 ppb) in 2010, and then exhibited an extremely significant fluctuating downward trend of −4.5 % yr−1 (R = 0.95, P < 0.01) from 2010 to 2016. After 2010, the annual mean NOx mixing ratios correlated significantly (R = 0.94, P < 0.01) with the annual NOx emission in North China. The decreasing rate (−4.8 % yr−1, R = −0.92, P < 0.01) of the annual mean NOx mixing ratios from 2011 to 2016 at the Shangdianzi (SDZ) regional atmospheric background station is lower than the one (−8.8 % yr−1, R = −0.94, P < 0.01) for the annual NOx emission in the NCP and in Beijing (−9.0 % yr−1, R = −0.96, P < 0.01). This indicated that surface NOx mixing ratios at SDZ had a weaker influence than SO2 on the emission reduction in Beijing and its surrounding areas in the NCP. The increase in the number of motor vehicles led to an increase in traffic emissions for NOx. This study supported conclusions from previous studies that the measures taken for controlling NOx and SO2 in the NCP in the past decades were generally successful. However, NOx emission control should be strengthened in the future.

Measurement report: Long-term variations in surface NO<sub><i>x</i></sub> and SO<sub>2</sub> mixing ratios from 2006 to 2016 at a background site in the Yangtze River Delta region, China

Abstract. China has been experiencing rapid changes in emissions of air pollutants in recent decades. Increased emissions of primary particulates and reactive gases caused severe haze in several polluted regions including the Yangtze River Delta (YRD). Measures implemented in recent years for improving air quality have reduced the emissions of NOx, SO2, etc. The emission changes in these gases are reflected by tropospheric columns from satellite observations and surface measurements of surface concentrations from urban sites. However, little is known about the long-term variations in regional background NOx and SO2. In this study, we present NOx and SO2 measurements from the Lin'an station (LAN; 30∘18' N, 119∘44′ E; 138.6 m a.s.l.), one of the Global Atmosphere Watch (GAW) stations in China. We characterize the seasonal and diurnal variations and study the long-term trends of NOx and SO2 mixing ratios observed at LAN from 2006 to 2016. We also interpret the observed variations and trends in terms of changes in meteorological conditions as well as emission of these gases. The overall average mixing ratios of NOx (NO2) and SO2 during 2006–2016 were 13.6 ± 1.2 ppb (12.5 ± 4.6) and 7.0 ± 4.2 ppb, respectively. The averaged seasonal variations showed maximum values of NOx and SO2 in December (23.5 ± 4.4 ppb) and January (11.9 ± 6.2 ppb), respectively, and minimum values of 7.1 ± 0.8 and 2.8 ± 2.3 ppb (both in July), respectively. The average diurnal variation characteristics of NOx and SO2 differed considerably from each other, though the daily average mixing ratios of both gases were significantly correlated (R2=0.29, P<0.001). The annual average mixing ratio of NOx increased during 2006–2011 and then decreased significantly at 0.78 ppb/yr (−5.16 %/yr, P<0.01). The annual 95th and 5th percentiles of hourly NOx mixing ratios showed upward trends until 2012 and 2014, respectively, before a clear decline. The annual average mixing ratio of SO2 decreased significantly at 0.99 ppb/yr (−8.27 %/yr, P<0.01) from 2006–2016. The annual 95th and 5th percentiles of hourly SO2 mixing ratios all exhibited significant (P<0.001) downward trends at 3.18 and 0.19 ppb/yr, respectively. Changes in the total NOx and SO2 emissions as well as the industrial emissions in the YRD region were significantly correlated with the changes in annual NOx and SO2 mixing ratios. The significant decreases in NOx from 2011 to 2016 and SO2 from 2006 to 2016 highlight the effectiveness of relevant control measures on the reduction in NOx and SO2 emissions in the YRD region. A decrease in annual SO2 / NOx ratio was found, suggesting a better efficacy in the emission reduction in SO2 than NOx. We found gradual changes in average diurnal patterns of NOx and SO2, which could be attributed to increasing contributions of vehicle emissions to NOx and weakening impacts of large sources on the SO2 concentration. This study reaffirms China's success in controlling both NOx and SO2 in the YRD but indicates at the same time a necessity to strengthen the NOx emission control.

Influence of atmospheric in-cloud aqueous-phase chemistry on the global simulation of SO<sub>2</sub> in CESM2

Abstract. Sulfur dioxide (SO2) is a major atmospheric pollutant and precursor of sulfate aerosols, which influences air quality, cloud microphysics, and climate. Therefore, better understanding the conversion of SO2 to sulfate is essential to simulate and predict sulfur compounds more accurately. This study evaluates the effects of in-cloud aqueous-phase chemistry on SO2 oxidation in the Community Earth System Model version 2 (CESM2). We replaced the default parameterized SO2 aqueous-phase reactions with detailed HOx, Fe, N, and carbonate chemistry in cloud droplets and performed a global simulation for 2014–2015. Compared with the observations, the results incorporating detailed cloud aqueous-phase chemistry greatly reduced SO2 overestimation. This overestimation was reduced by 0.1–10 ppbv (parts per billion by volume) in most of Europe, North America, and Asia and more than 10 ppbv in parts of China. The biases in annual simulated SO2 mixing ratios decreased by 46 %, 41 %, and 22 % in Europe, the USA, and China, respectively. Fe chemistry and HOx chemistry contributed more to SO2 oxidation than N chemistry. Higher concentrations of soluble Fe and higher pH values could further enhance the oxidation capacity. This study emphasizes the importance of detailed in-cloud aqueous-phase chemistry for the oxidation of SO2. These mechanisms can improve SO2 simulation in CESM2 and deepen understanding of SO2 oxidation and sulfate formation.

Potential Source Regions and Transportation Pathways of Reactive Gases at a Regional Background Site in Northwestern China

Reactive gases (O3, CO, NO2, and SO2) were collected hourly at the Akedala regional background station in northwestern China during September 2017 to August 2018. Wind rose, cluster analysis, potential source contribution function (PSCF), and concentration-weighted trajectory (CWT) methods were adopted for identifying the transport pathways and potential source regions of these atmosphere components at Akedala. The average O3, CO, NO2, and SO2 mixing ratios detected were 29.65 ± 11.44 ppb, 123.78 ± 73.35 ppb, 3.79 ± 0.98 ppb, and 4.59 ± 0.88 ppb during the observation period, and the statistical results of the monthly mean values revealed that there were differences during the highest pollution period, with O3 and CO mainly peaking in February, with mixing ratios of 38.03 ± 7.10 ppb and 208.50 ± 106.50 ppb, respectively. Meanwhile, NO2 peaked in March (4.51 ± 0.54 ppb) and SO2 in January (5.70 ± 1.92 ppb). The most obvious diurnal variation of CO and SO2 was observed in the winter, with maximum levels reaching between 13 : 00 and 14 : 00. The diurnal variations of O3 exhibited low values during the night and maximum values in the afternoon (16 : 00–18 : 00). Diurnal variation was not significant in the case of NO2. Cluster analysis showed that six main paths affected the Akedala atmosphere. In turn, the PSCF and CWT analysis results indicated that the Akedala reactive gas was affected by both local and foreign sources. The high PSCF value of the reactive gas potential source areas appeared in eastern Kazakhstan, northern Xinjiang, Western Mongolia, and Southern Russia. The WCWT (weighted concentration-weight trajectory) values of CO and SO2 in winter were the highest, totaling 180–240 ppb and 5–6.5 ppb, respectively. The WCWT value of O3 in the spring and summer was higher than that in the autumn and winter. The main source area of O3 was about 32–36 ppb in the spring and summer, and the main source area of NO2 in the summer had a low WCWT value of 3–3.5 ppb, whereas the NO2 WCWT value was concentrated at 4–4.5 ppb in the other seasons.

Contribution of source emissions in the air pollution modeling - a WRF/Chem case study

We investigate the capability of the WRF/Chem model in the simulation of some criteria air pollutants, during a major air pollution episode between 16 and 21 December 2017. In this study, by employing the EDGAR-HTAP_v2 global emissions data in the WRF/Chem model, we evaluate the simulations of the surface mixing ratios of NO2, SO2, and CO. The RADM2 chemical mechanism with MADE-SORGAM aerosol scheme has been used as the chemical option of the WRF/Chem model, to simulate the meteorology-chemistry interactions. The variations of the time series of the pollutants and the comparisons of the results in Tehran with the measurement data showed that although the WRF/Chem simulations in Tehran presented considerable over-estimations, but the model’s performance with regard to the time variations of the concentrations of the gaseous agents over the polluted episode is acceptable, and therefore, could be considered in the operational air quality systems. Since emission data are not available for many metropolitan areas over Iran, the HTAP_v2 global dataset could be used as the emissions data with reliable accuracy for the numerical air quality models.

Increased new particle yields with largely decreased probability of survival to CCN size at the summit of Mt. Tai under reduced SO<sub>2</sub> emissions

Abstract. Because anthropogenic sulfur dioxide (SO2) emissions have decreased considerably in the last decade, PM2.5 pollution in China has been alleviated to some extent. However, the effects of reduced SO2 on the particle number concentrations and subsequent contributions of grown new particles to cloud condensation nuclei (CCN) populations, particularly at high altitudes with low aerosol number loadings, are poorly understood. In contrast, the increase in provincial forest areas in China with rapid afforestation over the last few decades expectedly increases the biogenic emissions of volatile organic compounds and their oxidized products as nucleating precursors therein. In this study, we evaluated the campaign-based measurements made at the summit of Mt. Tai (1534 m a.s.l.) from 2007 to 2018. With the decrease in SO2 mixing ratios from 15 ± 13 ppb in 2007 to 1.6 ± 1.6 ppb in 2018, the apparent formation rate (FR) of new particles and the net maximum increase in the nucleation-mode particle number concentration (NMINP) in the spring campaign of 2018 was 2- to 3-fold higher than those in the spring campaign of 2007 with almost the same occurrence frequency of new particle formation (NPF) events. In contrast, the campaign-based comparison showed that the occurrence frequency, in which the maximum geometric median diameter of the grown new particles (Dpgmax) was > 50 nm, decreased considerably from 43 %–78 % of the NPF events before 2015 to < 12 % in 2017–2018. Assuming > 50 nm as a CCN threshold size at high supersaturations, the observed net CCN production decreased from 3.7 × 103 cm−3 (on average) in the five campaigns before 2015 to 1.0 × 103 cm−3 (on average) in the two campaigns in 2017–2018. We argue that the increases in the apparent FR and NMINP are mainly determined by the availability of organic precursors that participate in nucleation and initial growth, whereas the decrease in the growth probability is caused by the reduced emissions of anthropogenic precursors. However, large uncertainties still exist because of a lack of data on the chemical composition of these smaller particles.

Variations in <i>N</i><sub>cn</sub> and <i>N</i><sub>ccn</sub> over marginal seas in China related to marine traffic emissions, new particle formation and aerosol aging

Abstract. In this study, a cruise campaign was conducted over marginal seas in China to measure the concentrations of condensation nuclei (Ncn), cloud condensation nuclei (Nccn) and other pollutants from day of year (DOY) 110 to DOY 135 of 2018. The ship self-emission signals were exhaustively excluded, and the mean values of Nccn during the cruise campaign were found to slightly increase from 3.2±1.1×103 cm−3 (mean ± standard deviation) at supersaturation (SS) of 0.2 % to 3.9±1.4×103 cm−3 at SS of 1.0 %, and the mean value for Ncn was 8.1±4.4×103 cm−3. Data analysis showed that marine traffic emissions apparently largely contributed to the increase in Ncn in the daytime, especially in the marine atmospheres over heavily traveled sea zones; however, the fresh sources made no clear contribution to the increase in Nccn. This finding was supported by the quantitative relations between Ncn and Nccn at SS = 0.2 %–1.0 % against the mixing ratios of SO2 in the ship self-emission plumes – i.e., a 1 ppb increase in SO2 corresponded to a 1.4×104 cm−3 increase in Ncn but only a 30–170 cm−3 increase in Nccn, possibly because of abundant organics in the aerosols. Smooth growth can be observed in the marine-traffic-derived particles, reflecting aerosol aging. The estimated hygroscopicity parameter (κ) values were generally as high as 0.46–0.55 under the dominant onshore winds, suggesting that inorganic ammonium aerosols likely acted as the major contributor to Nccn largely through aerosol aging processes of decomposing organics. Moreover, the influences of the new transported particles from the continent on the Ncn and Nccn in the marine atmosphere were investigated.

Revisiting the Sulfur‐Water Chemical System in the Middle Atmosphere of Venus

AbstractSulfur‐water chemistry plays an important role in the middle atmosphere of Venus. Ground‐based observations have found that simultaneously observed SO2 and H2O at ~64 km vary with time and are temporally anticorrelated. To understand these observations, we explore the sulfur‐water chemical system using a one‐dimensional chemistry‐diffusion model. We find that SO2 and H2O mixing ratios above the clouds are highly dependent on mixing ratios of the two species at the middle cloud top (58 km). The behavior of sulfur‐water chemical system can be classified into three regimes, but there is no abrupt transition among these regimes. In particular, there is no bifurcation behavior as previously claimed. We also find that the SO2 self‐shielding effect causes H2O above the clouds to respond to the middle cloud top in a nonmonotonic fashion. Through comparison with observations, we find that mixing ratio variations at the middle cloud top can explain the observed variability of SO2 and H2O. The sulfur‐water chemistry in the middle atmosphere is responsible for the H2O‐SO2 anticorrelation at 64 km. Eddy transport change alone cannot explain the variations of both species. These results imply that variations of species abundance in the middle atmosphere are significantly influenced by the lower atmospheric processes. Continued ground‐based measurements of the coevolution of SO2 and H2O above the clouds and new spacecraft missions will be crucial for uncovering the complicated processes underlying the interaction among the lower atmosphere, the clouds, and the middle atmosphere of Venus.

HDO and SO2thermal mapping on Venus

Since January 2012, we have been monitoring the behavior of sulfur dioxide and water on Venus, using the Texas Echelon Cross-Echelle Spectrograph imaging spectrometer at the NASA InfraRed Telescope Facility (IRTF, Mauna Kea Observatory). Here, we present new data recorded in February and April 2019 in the 1345 cm−1(7.4μm) spectral range, where SO2, CO2, and HDO (used as a proxy for H2O) transitions were observed. The cloud top of Venus was probed at an altitude of about 64 km. As in our previous studies, the volume mixing ratio (vmr) of SO2was estimated using the SO2/CO2line depth ratio of weak transitions; the H2O volume mixing ratio was derived from the HDO/CO2line depth ratio, assuming a D/H ratio of 200 times the Vienna standard mean ocean water. As reported in our previous analyses, the SO2mixing ratio shows strong variations with time and also over the disk, showing evidence for the formation of SO2plumes with a lifetime of a few hours; in contrast, the H2O abundance is remarkably uniform over the disk and shows moderate variations as a function of time. We have used the 2019 data in addition to our previous dataset to study the long-term variations of SO2and H2O. The data reveal a long-term anti-correlation with a correlation coefficient of −0.80; this coefficient becomes −0.90 if the analysis is restricted to the 2014–2019 time period. The statistical analysis of the SO2plumes as a function of local time confirms our previous result with a minimum around 10:00 and two maxima near the terminators. The dependence of the SO2vmr with respect to local time shows a higher abundance at the evening terminator with respect to the morning. The dependence of the SO2vmr with respect to longitude exhibits a broad maximum at 120–200° east longitudes, near the region of Aphrodite Terra. However, this trend has not been observed by other measurements and has yet to be confirmed.

MAX-DOAS measurements of NO<sub>2</sub>, SO<sub>2</sub>, HCHO, and BrO at the Mt. Waliguan WMO GAW global baseline station in the Tibetan Plateau

Abstract. Mt. Waliguan Observatory (WLG) is a World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) global baseline station in China. WLG is located at the northeastern part of the Tibetan Plateau (36∘17′ N, 100∘54′ E, 3816 m a.s.l.) and is representative of the pristine atmosphere over the Eurasian continent. We made long-term ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements at WLG during the period 2012–2015. In this study, we retrieve the differential slant column densities (dSCDs) and estimate the tropospheric background mixing ratios of different trace gases, including NO2, SO2, HCHO, and BrO, using the measured spectra at WLG. Averaging of 10 original spectra is found to be an “optimum option” for reducing both the statistical error of the spectral retrieval and systematic errors in the analysis. The dSCDs of NO2, SO2, HCHO, and BrO under clear-sky and low-aerosol-load conditions are extracted from measured spectra at different elevation angles at WLG. By performing radiative transfer simulations with the model TRACY-2, we establish approximate relationships between the trace gas dSCDs at 1∘ elevation angle and the corresponding average tropospheric background volume mixing ratios. Mixing ratios of these trace gases in the lower troposphere over WLG are estimated to be in a range of about 7 ppt (January) to 100 ppt (May) for NO2, below 0.5 ppb for SO2, between 0.4 and 0.9 ppb for HCHO, and lower than 0.3 ppt for BrO. The chemical box model simulations constrained by the NO2 concentration from our MAX-DOAS measurements show that there is a little net ozone loss (−0.8 ppb d−1) for the free-tropospheric conditions and a little net ozone production (0.3 ppb d−1) for the boundary layer conditions over WLG during summertime. Our study provides valuable information and data sets for further investigating tropospheric chemistry in the background atmosphere and its links to anthropogenic activities.

Long-Term Measurements of SO2 Over Delhi, India

Long-term measurements (2011–2018) of ambient sulphur dioxide (SO2) and meteorology were carried out at an urban site of Delhi, India, to study the seasonal and inter-annual variations of SO2 over Delhi. The average mixing ratio of SO2 was estimated as 2.26 ± 0.48 ppb for the entire study period. Mixing ratio of ambient SO2 was estimated as 2.19 ± 0.64 ppb, 2.07 ± 0.89 ppb, 2.49 ± 1.05 ppb and 2.27 ± 0.71 ppb during winter, pre-monsoon, monsoon and post-monsoon seasons, respectively. SO2 mixing ratio was recorded maxima during monsoon (2.49 ± 1.05 ppb) season, whereas minima during pre-monsoon season (2.07 ± 0.89 ppb). The mixing ratio of SO2 showed slightly increase in the trend during observational period. Surface wind speed and wind directions analysis indicates the influence of local sources on the mixing ratio of SO2 at the study site. Backward trajectories and potential source contributing factor (PSCF) analysis also showed the local as well as the regional sources (industrial activities, coal burning and thermal power plants etc.,) influencing the mixing ratio of SO2 over Delhi.

HDO and SO2 thermal mapping on Venus

Since January 2012 we have been monitoring the behavior of sulfur dioxide and water on Venus, using the Texas Echelon Cross-Echelle Spectrograph (TEXES) imaging spectrometer at the NASA InfraRed Telescope Facility (IRTF, Mauna Kea Observatory). We present here the observations obtained between January 2016 and September 2018. As in the case of our previous runs, data were recorded around 1345 cm−1 (7.4 μm). The molecules SO2, CO2, and HDO (used as a proxy for H2O) were observed, and the cloudtop of Venus was probed at an altitude of about 64 km. The volume mixing ratio of SO2 was estimated using the SO2/CO2 line depth ratios of weak transitions; the H2O volume mixing ratio was derived from the HDO/CO2 line depth ratio, assuming a D/H ratio of 200 times the Vienna Standard Mean Ocean Water (VSMOW). As reported in our previous analyses, the SO2 mixing ratio shows strong variations with time and also over the disk, showing evidence of the formation of SO2 plumes with a lifetime of a few hours; in contrast, the H2O abundance is remarkably uniform over the disk and shows moderate variations as a function of time. We performed a statistical analysis of the behavior of the SO2 plumes, using all TEXES data between 2012 and 2018. They appear mostly located around the equator. Their distribution as a function of local time seems to show a depletion around noon; we do not have enough data to confirm this feature definitely. The distribution of SO2 plumes as a function of longitude shows no clear feature, apart from a possible depletion around 100E–150E and around 300E–360E. There seems to be a tendency for the H2O volume mixing ratio to decrease after 2016, and for the SO2 mixing ratio to increase after 2014. However, we see no clear anti-correlation between the SO2 and H2O abundances at the cloudtop, neither on the individual maps nor over the long term. Finally, there is a good agreement between the TEXES results and those obtained in the UV range (SPICAV/Venus Express and UVI/Akatsuki) at a slightly higher altitude. This agreement shows that SO2 observations obtained in the thermal infrared can be used to extend the local time coverage of the SO2 measurements obtained in the UV range.

Calibration and assessment of electrochemical air quality sensors by co-location with regulatory-grade instruments

Abstract. The use of low-cost air quality sensors for air pollution research has outpaced our understanding of their capabilities and limitations under real-world conditions, and there is thus a critical need for understanding and optimizing the performance of such sensors in the field. Here we describe the deployment, calibration, and evaluation of electrochemical sensors on the island of Hawai`i, which is an ideal test bed for characterizing such sensors due to its large and variable sulfur dioxide (SO2) levels and lack of other co-pollutants. Nine custom-built SO2 sensors were co-located with two Hawaii Department of Health Air Quality stations over the course of 5 months, enabling comparison of sensor output with regulatory-grade instruments under a range of realistic environmental conditions. Calibration using a nonparametric algorithm (k nearest neighbors) was found to have excellent performance (RMSE < 7 ppb, MAE < 4 ppb, r2 > 0.997) across a wide dynamic range in SO2 (< 1 ppb, > 2 ppm). However, since nonparametric algorithms generally cannot extrapolate to conditions beyond those outside the training set, we introduce a new hybrid linear–nonparametric algorithm, enabling accurate measurements even when pollutant levels are higher than encountered during calibration. We find no significant change in instrument sensitivity toward SO2 after 18 weeks and demonstrate that calibration accuracy remains high when a sensor is calibrated at one location and then moved to another. The performance of electrochemical SO2 sensors is also strong at lower SO2 mixing ratios (< 25 ppb), for which they exhibit an error of less than 2.5 ppb. While some specific results of this study (calibration accuracy, performance of the various algorithms, etc.) may differ for measurements of other pollutant species in other areas (e.g., polluted urban regions), the calibration and validation approaches described here should be widely applicable to a range of pollutants, sensors, and environments.

On the use of different spectral windows in DOAS evaluations: Effects on the estimation of SO2 emission rate and mixing ratios during strong emission of Popocatépetl volcano

Reported SO2 emission values at strongly degassing volcanoes might be underestimated. Scanning spectroscopic instruments are widely used at volcanoes to quantify SO2 emission rates and, occasionally, molar ratios between SO2 and other gases such as BrO. Frequently, Differential Optical Absorption Spectroscopy is applied to evaluate spectra in the ultraviolet range. If radiative transfer effects are not considered in the evaluations, the retrieved column densities may vary depending on which spectral window is used. We compare the use of different windows for data collected at Popocatépetl volcano during strong degassing periods, when high column densities lead to especially high dependence on the applied evaluation window. We propose the use of three different windows (310–322nm, 314.7–326.7nm and 322–334nm) and a simple algorithm to choose the most accurate column density from them. The SO2 evaluation using proper spectral windows would allow a more realistic estimation of the SO2 emission rates.

The Role of Sulfur Dioxide in Stratospheric Aerosol Formation Evaluated Using In-Situ Measurements in the Tropical Lower Stratosphere.

Stratospheric aerosols (SAs) are a variable component of the Earth's albedo that may be intentionally enhanced in the future to offset greenhouse gases (geoengineering). The role of tropospheric-sourced sulfur dioxide (SO2) in maintaining background SAs has been debated for decades without in-situ measurements of SO2 at the tropical tropopause to inform this issue. Here we clarify the role of SO2 in maintaining SAs by using new in-situ SO2 measurements to evaluate climate models and satellite retrievals. We then use the observed tropical tropopause SO2 mixing ratios to estimate the global flux of SO2 across the tropical tropopause. These analyses show that the tropopause background SO2 is about 5 times smaller than reported by the average satellite observations that have been used recently to test atmospheric models. This shifts the view of SO2 as a dominant source of SAs to a near-negligible one, possibly revealing a significant gap in the SA budget.

First results of the Piton de la Fournaise STRAP 2015 experiment: multidisciplinary tracking of a volcanic gas and aerosol plume

Abstract. The STRAP (Synergie Transdisciplinaire pour Répondre aux Aléas liés aux Panaches volcaniques) campaign was conducted over the entire year of 2015 to investigate the volcanic plumes of Piton de La Fournaise (La Réunion, France). For the first time, measurements at the local (near the vent) and at the regional scales were conducted around the island. The STRAP 2015 campaign has become possible thanks to strong cross-disciplinary collaboration between volcanologists and meteorologists. The main observations during four eruptive periods (85 days) are summarised. They include the estimates of SO2, CO2 and H2O emissions, the altitude of the plume at the vent and over different areas of La Réunion Island, the evolution of the SO2 concentration, the aerosol size distribution and the aerosol extinction profile. A climatology of the volcanic plume dispersion is also reported. Simulations and measurements show that the plumes formed by weak eruptions have a stronger interaction with the surface of the island. Strong SO2 mixing ratio and particle concentrations above 1000 ppb and 50 000 cm−3 respectively are frequently measured over a distance of 20 km from Piton de la Fournaise. The measured aerosol size distribution shows the predominance of small particles in the volcanic plume. Several cases of strong nucleation of sulfuric acid have been observed within the plume and at the distal site of the Maïdo observatory. The STRAP 2015 campaign provides a unique set of multi-disciplinary data that can now be used by modellers to improve the numerical parameterisations of the physical and chemical evolution of the volcanic plumes.