Search

We introduce the new Global Ozone Monitoring Experiment-2 (GOME-2) daily and monthly level-3 product of total column ozone (O3), total and tropospheric column nitrogen dioxide (NO2), total column water vapour, total column bromine oxide (BrO), total column formaldehyde (HCHO), and total column sulfur dioxide (SO2) (daily products https://doi.org/10.15770/EUM_SAF_AC_0048, AC SAF, 2023a; monthly products https://doi.org/10.15770/EUM_SAF_AC_0049, AC SAF, 2023b). The GOME-2 level-3 products aim to provide easily translatable and user-friendly data sets to the scientific community for scientific progress as well as to satisfy public interest. The purpose of this paper is to present the theoretical basis as well as the verification and validation of the GOME-2 daily and monthly level-3 products. The GOME-2 level-3 products are produced using the overlapping area-weighting method. Details of the gridding algorithm are presented. The spatial resolution of the GOME-2 level-3 products is selected based on the sensitivity study. The consistency of the resulting level-3 products among three GOME-2 sensors is investigated through time series of global averages, zonal averages, and bias. The accuracy of the products is validated by comparison to ground-based observations. The verification and validation results show that the GOME-2 level-3 products are consistent with the level-2 data. Small discrepancies are found among three GOME-2 sensors, which are mainly caused by the differences in the instrument characteristic and level-2 processor. The comparison of GOME-2 level-3 products to ground-based observations in general shows very good agreement, indicating that the products are consistent and fulfil the requirements to serve the scientific community and general public.

We introduce the new GOME-2 daily and monthly level 3 product of total column ozone (O3), total and tropospheric column nitrogen dioxide (NO2), total column water vapour, total column bromine oxide (BrO), total column formaldehyde (HCHO) and total column sulphur dioxide (SO2). The GOME-2 level 3 products are aimed to provide easily translatable and user-friendly data sets to the scientific community for scientific progress as well as satisfying public interest. The purpose of this paper is to present the theoretical basis as well as the verification and validation of the GOME-2 daily and monthly level 3 products. The GOME-2 level 3 products are produced using the overlapping area weighting method. Details of the gridding algorithm are presented. The spatial resolution of the GOME-2 level 3 products is selected based on sensitivity study. The consistency of the resulting level 3 products among three GOME-2 sensors is investigated through time series of global averages, zonal averages, and bias. The accuracy of the products is validated by comparing to ground-based observations. The verification and validation results show that the GOME-2 level 3 products are consistent with the level 2 data. Small discrepancies are found among three GOME-2 sensors, which are mainly caused by the differences in instrument characteristic and level 2 processor. The comparison of GOME-2 level 3 products to ground-based observations in general shows very good agreement, indicating the products are consistent and fulfil the requirements to serve the scientific community and general public.

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) and direct sun NO2 vertical column network data are used to investigate the accuracy of tropospheric NO2 column measurements of the GOME-2 instrument on the MetOp-A satellite platform and the OMI instrument on Aura. The study is based on 23 MAX-DOAS and 16 direct sun instruments at stations distributed worldwide. A method to quantify and correct for horizontal dilution effects in heterogeneous NO2 field conditions is proposed. After systematic application of this correction to urban sites, satellite measurements are found to present smaller biases compared to ground-based reference data in almost all cases. We investigate the seasonal dependence of the validation results as well as the impact of using different approaches to select satellite ground pixels in coincidence with ground-based data. In optimal comparison conditions (satellite pixels containing the station) the median bias between satellite tropospheric NO2 column measurements and the ensemble of MAX-DOAS and direct sun measurements is found to be significant and equal to −34 % for GOME-2A and −24 % for OMI. These biases are further reduced to −24 % and −18 % respectively, after application of the dilution correction. Comparisons with the QA4ECV satellite product for both GOME-2A and OMI are also performed, showing less scatter but also a slightly larger median tropospheric NO2 column bias with respect to the ensemble of MAX-DOAS and direct sun measurements.

MAX-DOAS and direct sun NO2 vertical column network data are used to investigate the accuracy of tropospheric NO2 column measurements of the GOME-2 instrument on the MetOP-A satellite platform and the OMI instrument on Aura. The study is based on 23 MAX-DOAS and 16 direct sun instruments at stations distributed worldwide. A method to quantify and correct for horizontal dilution effects in heterogeneous NO2 field conditions is proposed. After systematic application of this correction to urban sites, satellite measurements are found to present smaller biases compared to ground-based reference data in almost all cases. We investigate the seasonal dependence of the validation results, as well as the impact of using different approaches to select satellite ground pixels in coincidence with ground-based data. In optimal comparison conditions (satellite pixels containing the station) the median bias between satellite tropospheric NO2 column measurements and the ensemble of MAX-DOAS and direct sun measurements is found to be significant and equal to −36 % for GOME-2A and −20 % for OMI. These biases are further reduced to −24 % and −8 % respectively, after application of the dilution correction. Comparisons with the QA4ECV satellite product for both GOME-2A and OMI is also performed, showing less scatter but also a slightly larger median tropospheric NO2 column bias with respect to the ensemble of MAX-DOAS and direct sun measurements.

As a toxic and reactive gas, nitrogen dioxide (NO2) influences air quality and health, the self-cleaning power of the atmosphere and photochemical smog formation. Reliable scientific data with high quality and comparability are required for national and international decision-makers. The quality of the NO2 measurements is crucially dependent on the quality of the calibration standards. In order to achieve the quality goals required, the MetNO2 project within the EMPIR (European Metrology Program for Innovation and Research) program aims to provide accurate and stable NO2 calibration standards for operational use at air quality stations.To characterise the impurities of the newly developed standards a Thermal Dissociation - Cavity Attenuated Phase Shift (TD - CAPS) system has been set up, based on the design from Sadanaga et al. (2016). The device includes four heated channels for the differentiation of NO2, peroxy and alkyl nitrates and HNO3. In parallel, a gold converter coupled with a chemiluminescence detector was deployed for detection of the total sum of NOy. First results of the performance of the TD-CAPS used for impurity analysis of NO2 standards will be presented. Reference: Sadanaga et al. Review of Scientific Instruments 87.7 (2016), 074102

We present direct measurements of the summertime total reactivity of NO3 towards organic trace gases, k OTG NO 3 , at a rural mountain site (988 m a.s.l.) in southern Germany in 2017. The diel cycle of k OTG NO 3 was strongly influenced by local meteorology with high reactivity observed during the day (values of up to 0.3 s −1 ) and values close to the detection limit (0.005 s −1 ) at night when the measurement site was in the residual layer and free troposphere. Daytime values of k OTG NO 3 were sufficiently large that the loss of NO3 due to reaction with organic trace gases competed with its photolysis and reaction with NO. Within experimental uncertainty, monoterpenes and isoprene accounted for all of the measured NO3 reactivity. Averaged over the daylight hours, more than 25 % of NO3 was removed via reaction with biogenic volatile organic compounds (BVOCs), implying a significant daytime loss of NOx and the formation of organic nitrates due to NO3 chemistry. Ambient NO3 concentrations were measured on one night and were comparable to those derived from a stationary-state calculation using measured values of k OTG NO 3 . We present and compare the first simultaneous, direct reactivity measurements for the NO3 and OH radicals. The decoupling of the measurement site from ground-level emissions resulted in lower reactivity at night for both radicals, though the correlation between OH and NO3 reactivity was weak as would be anticipated given their divergent trends in rate constants with many organic trace gases.

An operational chemical ionization mass spectrometer (CIMS) for hydroxyl radical (OH) and sulfuric acid (H2SO4) concentration measurements was adapted to include observations of OH reactivity, which is the inverse of OH lifetime, for long-term monitoring at the Global Atmosphere Watch (GAW) site Hohenpeissenberg (MOHp), Germany. OH measurement using CIMS is achieved by reacting OH with SO2, leading to the production of H2SO4, which is then detected. The adaptation for OH reactivity consists of the implementation of a second SO2 injection, at a fixed point further down flow in the sample tube to detect the OH decay caused by reactions with OH reactants present in the sample. The method can measure OH reactivity from less than 1 to 40 s−1 with the upper limit due to the fixed positioning of the second SO2 injection. To determine OH reactivity from OH concentration measurements, the reaction time between the two titration zones and OH wall losses in the sample tube need to be determined accurately through OH reactivity calibration. Potential measurement artefacts as a result of HOx recycling in the presence of NO have to be considered. Therefore, NO contamination from gases used in instrument operation must be minimized and ambient NO must be measured concurrently to determine the measurement error. This CIMS system is shown here to perform very well for OH reactivity below 15 s−1 and NO concentrations below 4 ppb, both values that are rarely exceeded at the MOHp site. Thus when deployed in suitable chemical environments, this method can provide valuable continuous long-term measurements of OH reactivity. The characterization utilizes results from chamber, laboratory and modelling studies and includes the discussion and quantification of sources of uncertainties.

We present a new aerosol profile retrieval algorithm for Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements at high altitude sites. The study is based on the long-term measurement (February 2012 to February 2016) at the Environmental Research Station Schneefernerhaus (UFS), Germany, which is located near the summit of Zugspitze, at an altitude of 2,650 m. Due to the low signal to noise ratio, commonly used MAX-DOAS retrieval algorithms based on the optimal estimation method are not suitable for the retrieval of high altitude measurements. We developed a new retrieval algorithm using an O4 differential slant column density (DSCD) look-up table. The look-up table consists of simulated O4 DSCDs corresponding to numerous possible aerosol profiles. The sensitivities of O4 absorption to several parameters were investigated for the design and parameterization of the look-up table. In the retrieval, the simulated O4 DSCDs for each possible profile are derived by interpolating the look-up table to the observation geometries. The cost functions are calculated for each aerosol profile in the look-up table based on the simulated O4 DSCDs, the O4 DSCD observations as well as the measurement uncertainties. Valid profiles are selected from all the possible profiles according to the cost function, and the optimal solution is defined as the weighted mean of all valid profiles. A comprehensive error analysis is performed to better estimate the total uncertainty. Based on the assumption that the look-up table covers all the possible profiles under clear sky conditions, we determined a set of O4 DSCD scaling factors for different elevation angles and wavelengths. The dependence of the scaling factors on elevation angle might be partly related to the specific properties of the high altitude station, e.g. the highly structured topography, horizontal gradients of the aerosol extinction and the systematic dependence of the surface albedo on altitude. The retrieved aerosol optical depths (AODs) are compared to coincident and co-located sun photometer observations. High correlation coefficients of 0.733 and 0.798 are found for measurements at 360 and 477 nm, respectively. However, especially in summer the sun photometer AODs are systematically higher than the MAX-DOAS retrievals by a factor of 2. The discrepancy might be related to the limited measurement range of the MAX-DOAS, and is probably also related to the decreased sensitivity of the MAX-DOAS measurements at higher altitudes. Our results also show maximum AOD and maximum Ångström exponent in summer which is consistent with observations from an AERONET station located ~ 43 km of the MAX-DOAS.

An operational chemical ionisation mass spectrometer (CIMS) for hydroxyl radical (OH) and sulfuric acid (H2SO4) concentration measurements was adapted to include observations of OH reactivity, which is the inverse of OH lifetime, for long-term monitoring at the Global Atmosphere Watch (GAW) site Hohenpeissenberg (MOHp), Germany. OH measurement using CIMS is achieved by reacting OH with SO2, leading to the production of H2SO4 which is then detected. The adaptation for OH reactivity consists of the implementation of a second SO2 injection, at a fixed point further down flow in the sample tube to detect the OH decay caused by reactions with OH reactants present in the sample. The method can measure OH reactivity between below 1 and 40 s−1 with the upper limit due to the fixed positioning of the second SO2 injection. To determine OH reactivity from OH concentration measurements, the reaction time between the two titration zones and OH wall losses in the sample tube need to be determined accurately through OH reactivity calibration. Potential measurement artefacts as a result of HOx recycling in the presence of NO have to be considered. Therefore NO contamination from gases used in instrument operation must be minimised and ambient NO must be measured concurrently to determine the measurement error. This CIMS system is shown here to perform very well for OH reactivity below 15 s−1 and NO concentrations below 4 ppb, both values that are rarely exceeded at the MOHp site. Thus when deployed in suitable chemical environments, this method can provide valuable continuous long-term measurements of OH reactivity. The characterisation utilises results from chamber, laboratory and modelling studies and includes the discussion and quantification of sources of uncertainties.

We present direct measurements of the summertime, total reactivity of NO3 towards organic trace gases, kOTGNO3, at a rural mountain site (988 m a.s.l.) in southern Germany in 2017. The diel cycle of kOTGNO3 was strongly influenced by local meteorology with reactivity high during the day (values of up to 0.3 s-1) but usually close to the detection limit (0.005 s-1) at night when the measurement site was in the residual layer/free troposphere. Daytime values of kOTGNO3 were sufficiently large that the loss of NO3 due to reaction with organic trace gases competed with its photolysis and reaction with NO. Within experimental uncertainty, monoterpenes and isoprene accounted for all of the measured NO3-reactivity. Averaged over the daylight hours, more than 25 % of NO3 was removed via reaction with biogenic volatile organic compounds (BVOCs), implying a significant daytime loss of NOx and formation of organic nitrates due to NO3 chemistry. Ambient NO3 concentrations were measured on one night and were comparable to those derived from a stationary state calculation using measured values of kOTGNO3. We present and compare the first simultaneous, direct-reactivity measurements for the NO3 and OH radicals. The decoupling of the measurement site from ground level emissions resulted in lower reactivity at night for both radicals, though the correlation between OH- and NO3-reactivity was weak as would be anticipated given their divergent trends in rate constants with many organic trace gases.

Observations of the tropical atmosphere are fundamental to the understanding of global changes in air quality, atmospheric oxidation capacity and climate, yet the tropics are under-populated with long-term measurements. The first three years (October 2006–September 2009) of meteorological, trace gas and particulate data from the global WMO/Global Atmospheric Watch (GAW) Cape Verde Atmospheric Observatory Humberto Duarte Fonseca (CVAO; 16° 51′ N, 24° 52′ W) are presented, along with a characterisation of the origin and pathways of air masses arriving at the station using the NAME dispersion model and simulations of dust deposition using the COSMO-MUSCAT dust model. The observations show a strong influence from Saharan dust in winter with a maximum in super-micron aerosol and particulate iron and aluminium. The dust model results match the magnitude and daily variations of dust events, but in the region of the CVAO underestimate the measured aerosol optical thickness (AOT) because of contributions from other aerosol. The NAME model also captured the dust events, giving confidence in its ability to correctly identify air mass origins and pathways in this region. Dissolution experiments on collected dust samples showed a strong correlation between soluble Fe and Al and measured solubilities were lower at high atmospheric dust concentrations. Fine mode aerosol at the CVAO contains a significant fraction of non-sea salt components including dicarboxylic acids, methanesulfonic acid and aliphatic amines, all believed to be of oceanic origin. A marine influence is also apparent in the year-round presence of iodine and bromine monoxide (IO and BrO), with IO suggested to be confined mainly to the surface few hundred metres but BrO well mixed in the boundary layer. Enhanced CO2 and CH4 and depleted oxygen concentrations are markers for air-sea exchange over the nearby northwest African coastal upwelling area. Long-range transport results in generally higher levels of O3 and anthropogenic non-methane hydrocarbons (NMHC) in air originating from North America. Ozone/CO ratios were highest (up to 0.42) in relatively fresh European air masses. In air heavily influenced by Saharan dust the O3/CO ratio was as low as 0.13, possibly indicating O3 uptake to dust. Nitrogen oxides (NOx and NOy) show generally higher concentrations in winter when air mass origins are predominantly from Africa. High photochemical activity at the site is shown by maximum spring/summer concentrations of OH and HO2 of 9 × 106 molecule cm−3 and 6 × 108 molecule cm−3, respectively. After the primary photolysis source, the most important controls on the HOx budget in this region are IO and BrO chemistry, the abundance of HCHO, and uptake of HOx to aerosol.

Environmental context Reactive halogen species affect chemical processes in the troposphere in many ways. The reactive bromine species bromine monoxide (BrO) is found in high concentrations at the Dead Sea, but processes for its formation and its spatial distribution are largely unknown. Information on the vertical distribution of BrO at the Dead Sea obtained in this work may give insight into the processes leading to BrO release and its consequences. Abstract We present results of multi-axis differential optical absorption spectroscopy (MAX‐DOAS) and long‐path DOAS (LP‐DOAS) measurements from two measurement campaigns at the Dead Sea in 2002 and 2012. The special patterns of its dynamics and topography in combination with the high salt and especially bromide content of its water lead to the particular large atmospheric abundances of more than 100 ppt BrO close to the ground and in several hundred meters above ground level. We conclude that vertical transport barriers induced by the special dynamics in the Dead Sea Valley lead to an accumulation of aerosol and reactive bromine species. This occurs in situations of weak synoptic winds and of mountain induced thermal circulations. Thus BrO release strongly depends on the topography and local and meso-scale meteorology. In case of strong zonal winds, the Dead Sea valley is flushed and high BrO levels cannot accumulate. NO2 levels below 1–2 ppb seem to be a prerequisite for a high BrO production. We assume that at least a part of the missing NO2 might be converted to BrONO2 leading to a deposition of nitrate within the aerosol and acting as a reservoir for reactive bromine. From these measurements, it was possible for the first time to simultaneously retrieve vertical profiles of aerosols, BrO and NO2 and gain also information on the distribution at the Dead Sea, allowing for a thorough characterization of the chemical processes leading to halogen release in the context of the special atmospheric dynamics in the Dead Sea Valley.