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  • 1
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 23, No. 17 ( 2023-09-08), p. 10035-10056
    Abstract: Abstract. Carbonyl sulfide (OCS) has emerged as a valuable proxy for photosynthetic uptake of carbon dioxide (CO2) and is known to be important in the formation of aerosols in the stratosphere. However, uncertainties in the global OCS budget remain large. This is mainly due to the following three flux terms: vegetation uptake, soil uptake and oceanic emissions. Bottom-up estimates do not yield a closed budget, which is thought to be due to tropical emissions of OCS that are not accounted for. Here we present a simulation of atmospheric OCS over the period 2004–2018 using the TOMCAT 3-D chemical transport model that is aimed at better constraining some terms in the OCS budget. Vegetative uptake of OCS is estimated by scaling gross primary productivity (GPP) output from the Joint UK Land Environment Simulator (JULES) using the leaf relative uptake (LRU) approach. The remaining surface budget terms are taken from available literature flux inventories and adequately scaled to bring the budget into balance. The model is compared with limb-sounding satellite observations made by the Atmospheric Chemistry Experiment – Fourier Transform Spectrometer (ACE-FTS) and surface flask measurements from 14 National Oceanic and Atmospheric Administration – Earth System Research Laboratory (NOAA-ESRL) sites worldwide. We find that calculating vegetative uptake using the LRU underestimates the surface seasonal cycle amplitude (SCA) in the Northern Hemisphere (NH) mid-latitudes and high latitudes by approximately 37 ppt (35 %). The inclusion of a large tropical source is able to balance the global budget, but further improvement to the SCA and phasing would likely require a flux inversion scheme. Compared to co-located ACE-FTS OCS profiles between 5 and 30 km, TOMCAT remains within 25 ppt (approximately 5 % of mean tropospheric concentration) of the measurements throughout the majority of this region and lies within the standard deviation of these measurements. This provides confidence in the representation of atmospheric loss and surface fluxes of OCS in the model. Atmospheric sinks account for 154 Gg S of the annual budget, which is 10 %–50 % larger than previous studies. Comparing the surface monthly anomalies from the NOAA-ESRL flask data to the model simulations shows a root-mean-square error range of 3.3–25.8 ppt. We estimate the total biosphere uptake to be 951 Gg S, which is in the range of recent inversion studies (893–1053 Gg S), but our terrestrial vegetation flux accounts for 629 Gg S of the annual budget, which is lower than other recent studies (657–756 Gg S). However, to close the budget, we compensate for this with a large annual oceanic emission term of 689 Gg S focused over the tropics, which is much larger than bottom-up estimates (285 Gg S). Hence, we agree with recent findings that missing OCS sources likely originate from the tropical region. This work shows that satellite OCS profiles offer a good constraint on atmospheric sinks of OCS through the troposphere and stratosphere and are therefore useful for helping to improve surface budget terms. This work also shows that the LRU approach is an adequate representation of the OCS vegetative uptake, but this method could be improved by various means, such as using a higher-resolution GPP product or plant-functional-type-dependent LRU. Future work will utilise TOMCAT in a formal inversion scheme to better quantify the OCS budget.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2023
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  • 2
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 18, No. 16 ( 2018-08-17), p. 11753-11777
    Abstract: Abstract. We describe the motivation, design, and execution of the Greenhouse gAs Uk and Global Emissions (GAUGE) project. The overarching scientific objective of GAUGE was to use atmospheric data to estimate the magnitude, distribution, and uncertainty of the UK greenhouse gas (GHG, defined here as CO2, CH4, and N2O) budget, 2013–2015. To address this objective, we established a multi-year and interlinked measurement and data analysis programme, building on an established tall-tower GHG measurement network. The calibrated measurement network comprises ground-based, airborne, ship-borne, balloon-borne, and space-borne GHG sensors. Our choice of measurement technologies and measurement locations reflects the heterogeneity of UK GHG sources, which range from small point sources such as landfills to large, diffuse sources such as agriculture. Atmospheric mole fraction data collected at the tall towers and on the ships provide information on sub-continental fluxes, representing the backbone to the GAUGE network. Additional spatial and temporal details of GHG fluxes over East Anglia were inferred from data collected by a regional network. Data collected during aircraft flights were used to study the transport of GHGs on local and regional scales. We purposely integrated new sensor and platform technologies into the GAUGE network, allowing us to lay the foundations of a strengthened UK capability to verify national GHG emissions beyond the project lifetime. For example, current satellites provide sparse and seasonally uneven sampling over the UK mainly because of its geographical size and cloud cover. This situation will improve with new and future satellite instruments, e.g. measurements of CH4 from the TROPOspheric Monitoring Instrument (TROPOMI) aboard Sentinel-5P. We use global, nested, and regional atmospheric transport models and inverse methods to infer geographically resolved CO2 and CH4 fluxes. This multi-model approach allows us to study model spread in a posteriori flux estimates. These models are used to determine the relative importance of different measurements to infer the UK GHG budget. Attributing observed GHG variations to specific sources is a major challenge. Within a UK-wide spatial context we used two approaches: (1) Δ14CO2 and other relevant isotopologues (e.g. δ13CCH4) from collected air samples to quantify the contribution from fossil fuel combustion and other sources, and (2) geographical separation of individual sources, e.g. agriculture, using a high-density measurement network. Neither of these represents a definitive approach, but they will provide invaluable information about GHG source attribution when they are adopted as part of a more comprehensive, long-term national GHG measurement programme. We also conducted a number of case studies, including an instrumented landfill experiment that provided a test bed for new technologies and flux estimation methods. We anticipate that results from the GAUGE project will help inform other countries on how to use atmospheric data to quantify their nationally determined contributions to the Paris Agreement.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2018
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  • 3
    In: Atmospheric Measurement Techniques, Copernicus GmbH, Vol. 15, No. 6 ( 2022-03-28), p. 1871-1901
    Abstract: Abstract. High quality long-term data sets of altitude-resolved measurements of the atmospheric composition are important because they can be used both to study the evolution of the atmosphere and as a benchmark for future missions. For the final ESA reprocessing of MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) on ENVISAT (ENViromental SATellite) data, numerous improvements were implemented in the Level 2 (L2) processor Optimised Retrieval Model (ORM) version 8.22 (V8) and its auxiliary data. The implemented changes involve all aspects of the processing chain, from the modelling of the measurements with the handling of the horizontal inhomogeneities along the line of sight to the use of the optimal estimation technique to retrieve the minor species, from a more sensitive approach to detecting the spectra affected by clouds to a refined method for identifying low quality products. Improvements in the modelling of the measurements were also obtained with an update of the used spectroscopic data and of the databases providing the a priori knowledge of the atmosphere. The HITRAN_mipas_pf4.45 spectroscopic database was finalised with new spectroscopic data verified with MIPAS measurements themselves, while recently measured cross-sections were used for the heavy molecules. The Level 2 Initial Guess (IG2) data set, containing the climatology used by the MIPAS L2 processor to generate the initial guess and interfering species profiles when the retrieved profiles from previous scans are not available, was improved taking into account the diurnal variation of the profiles defined using climatologies from both measurements and models. Horizontal gradients were generated using the ECMWF ERA-Interim data closest in time and space to the MIPAS data. Further improvements in the L2 V8 products derived from the use of the L1b V8 products, which were upgraded to reduce the instrumental temporal drift and to handle the abrupt changes in the calibration gain. The improvements introduced into the ORM V8 L2 processor and its upgraded auxiliary data, together with the use of the L1b V8 products, lead to the generation of the MIPAS L2 V8 products, which are characterised by an increased accuracy, better temporal stability and a greater number of retrieved species.
    Type of Medium: Online Resource
    ISSN: 1867-8548
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2022
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  • 4
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 16, No. 21 ( 2016-11-01), p. 13541-13559
    Abstract: Abstract. Peroxyacetyl nitrate (PAN) is an important chemical species in the troposphere as it aids the long-range transport of NOx and subsequent formation of O3 in relatively clean remote regions. Over the past few decades observations from aircraft campaigns and surface sites have been used to better understand the regional distribution of PAN. However, recent measurements made by satellites allow for a global assessment of PAN in the upper troposphere–lower stratosphere (UTLS). In this study, we investigate global PAN distributions from two independent retrieval methodologies, based on measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, on board Envisat from the Institute of Meteorology and Climate Research (IMK), Karlsruhe Institute of Technology, and the Department of Physics and Astronomy, University of Leicester (UoL). Retrieving PAN from MIPAS is challenging due to the weak signal in the measurements and contamination from other species. Therefore, we compare the two MIPAS datasets with observations from the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), in situ aircraft data and the 3-D chemical transport model TOMCAT. MIPAS shows peak UTLS PAN concentrations over the biomass burning regions (e.g. ranging from 150 to  〉  200 pptv at 150 hPa) and during the summertime Asian monsoon as enhanced convection aids the vertical transport of PAN from the lower atmosphere. At 150 hPa, we find significant differences between the two MIPAS datasets in the tropics, where IMK PAN concentrations are larger by 50–100 pptv. Comparisons between MIPAS and ACE-FTS show better agreement with the UoL MIPAS PAN concentrations at 200 hPa, but with mixed results above this altitude. TOMCAT generally captures the magnitude and structure of climatological aircraft PAN profiles within the observational variability allowing it to be used to investigate the MIPAS PAN differences. TOMCAT–MIPAS comparisons show that the model is both positively (UoL) and negatively (IMK) biased against the satellite products. These results indicate that satellite PAN observations are able to detect realistic spatial variations in PAN in the UTLS, but further work is needed to resolve differences in existing retrievals to allow quantitative use of the products.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2016
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  • 5
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 21, No. 6 ( 2021-04-01), p. 5235-5251
    Abstract: Abstract. We have estimated the spatial changes in NO2 levels over different regions of India during the COVID-19 lockdown (25 March–3 May 2020) using the satellite-based tropospheric column NO2 observed by the Ozone Monitoring Instrument (OMI) and the Tropospheric Monitoring Instrument (TROPOMI), as well as surface NO2 concentrations obtained from the Central Pollution Control Board (CPCB) monitoring network. A substantial reduction in NO2 levels was observed across India during the lockdown compared to the same period during previous business-as-usual years, except for some regions that were influenced by anomalous fires in 2020. The reduction (negative change) over the urban agglomerations was substantial (∼ 20 %–40 %) and directly proportional to the urban size and population density. Rural regions across India also experienced lower NO2 values by ∼ 15 %–25 %. Localised enhancements in NO2 associated with isolated emission increase scattered across India were also detected. Observed percentage changes in satellite and surface observations were consistent across most regions and cities, but the surface observations were subject to larger variability depending on their proximity to the local emission sources. Observations also indicate NO2 enhancements of up to ∼ 25 % during the lockdown associated with fire emissions over the north-east of India and some parts of the central regions. In addition, the cities located near the large fire emission sources show much smaller NO2 reduction than other urban areas as the decrease at the surface was masked by enhancement in NO2 due to the transport of the fire emissions.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2021
    detail.hit.zdb_id: 2092549-9
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  • 6
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 17, No. 2 ( 2017-01-20), p. 883-898
    Abstract: Abstract. We have used the Whole Atmosphere Community Climate Model (WACCM), with an updated treatment of loss processes, to determine the atmospheric lifetime of sulfur hexafluoride (SF6). The model includes the following SF6 removal processes: photolysis, electron attachment and reaction with mesospheric metal atoms. The Sodankylä Ion Chemistry (SIC) model is incorporated into the standard version of WACCM to produce a new version with a detailed D region ion chemistry with cluster ions and negative ions. This is used to determine a latitude- and altitude-dependent scaling factor for the electron density in the standard WACCM in order to carry out multi-year SF6 simulations. The model gives a mean SF6 lifetime over an 11-year solar cycle (τ) of 1278 years (with a range from 1120 to 1475 years), which is much shorter than the currently widely used value of 3200 years, due to the larger contribution (97.4 %) of the modelled electron density to the total atmospheric loss. The loss of SF6 by reaction with mesospheric metal atoms (Na and K) is far too slow to affect the lifetime. We investigate how this shorter atmospheric lifetime impacts the use of SF6 to derive stratospheric age of air. The age of air derived from this shorter lifetime SF6 tracer is longer by 9 % in polar latitudes at 20 km compared to a passive SF6 tracer. We also present laboratory measurements of the infrared spectrum of SF6 and find good agreement with previous studies. We calculate the resulting radiative forcings and efficiencies to be, on average, very similar to those reported previously. Our values for the 20-, 100- and 500-year global warming potentials are 18 000, 23 800 and 31 300, respectively.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2017
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  • 7
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 19, No. 2 ( 2019-01-22), p. 767-783
    Abstract: Abstract. Despite the recently reported beginning of a recovery in global stratospheric ozone (O3), an unexpected O3 decline in the tropical mid-stratosphere (around 30–35 km altitude) was observed in satellite measurements during the first decade of the 21st century. We use SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) measurements for the period 2004–2012 to confirm the significant O3 decline. The SCIAMACHY observations show that the decrease in O3 is accompanied by an increase in NO2. To reveal the causes of these observed O3 and NO2 changes, we performed simulations with the TOMCAT 3-D chemistry-transport model (CTM) using different chemical and dynamical forcings. For the 2004–2012 time period, the TOMCAT simulations reproduce the SCIAMACHY-observed O3 decrease and NO2 increase in the tropical mid-stratosphere. The simulations suggest that the positive changes in NO2 (around 7 % decade−1) are due to similar positive changes in reactive odd nitrogen (NOy), which are a result of a longer residence time of the source gas N2O and increased production via N2O + O(1D). The model simulations show a negative change of 10 % decade−1 in N2O that is most likely due to variations in the deep branch of the Brewer–Dobson Circulation (BDC). Interestingly, modelled annual mean “age of air” (AoA) does not show any significant changes in transport in the tropical mid-stratosphere during 2004–2012. However, further analysis of model results demonstrates significant seasonal variations. During the autumn months (September–October) there are positive AoA changes that imply transport slowdown and a longer residence time of N2O allowing for more conversion to NOy, which enhances O3 loss. During winter months (January–February) there are negative AoA changes, indicating faster N2O transport and less NOy production. Although the variations in AoA over a year result in a statistically insignificant linear change, non-linearities in the chemistry–transport interactions lead to a statistically significant negative N2O change.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2019
    detail.hit.zdb_id: 2092549-9
    detail.hit.zdb_id: 2069847-1
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  • 8
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 23, No. 8 ( 2023-04-24), p. 4849-4861
    Abstract: Abstract. Hydrogen cyanide (HCN) is an important tracer of biomass burning, but there are significant uncertainties in its atmospheric budget, especially its photochemical and ocean sinks. Here we use a tracer version of the TOMCAT global 3-D chemical transport model to investigate the physical and chemical processes driving the abundance of HCN in the troposphere and stratosphere over the period 2004–2016. The modelled HCN distribution is compared with version 4.1 of the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) HCN satellite data, which provide profiles up to around 42 km, and with ground-based column measurements from the Network for the Detection of Atmospheric Composition Change (NDACC). The long-term ACE-FTS measurements reveal the strong enhancements in upper-tropospheric HCN due to large wildfire events in Indonesia in 2006 and 2015. Our 3-D model simulations confirm previous lower-altitude balloon comparisons that the currently recommended NASA Jet Propulsion Laboratory (JPL) reaction rate coefficient of HCN with OH greatly overestimates the HCN loss. The use of the rate coefficient proposed by Kleinböhl et al. (2006) in combination with the HCN oxidation by O(1D) gives good agreement between ACE-FTS observations and the model. Furthermore, the model photochemical loss terms show that the reduction in the HCN mixing ratio with height in the middle stratosphere is mainly driven by the O(1D) sink with only a small contribution from a reaction with OH. From comparisons of the model tracers with ground-based HCN observations we test the magnitude of the ocean sink in two different published schemes (Li et al., 2000, 2003). We find that in our 3-D model the two schemes produce HCN abundances which are very different to the NDACC observations but in different directions. A model HCN tracer using the Li et al. (2000) scheme overestimates the HCN concentration by almost a factor of 2, while a HCN tracer using the Li et al. (2003) scheme underestimates the observations by about one-third. To obtain good agreement between the model and observations, we need to scale the magnitudes of the global ocean sinks by factors of 0.25 and 2 for the schemes of Li et al. (2000) and Li et al. (2003), respectively. This work shows that the atmospheric photochemical sinks of HCN now appear well constrained but improvements are needed in parameterizing the major ocean uptake sink.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2023
    detail.hit.zdb_id: 2092549-9
    detail.hit.zdb_id: 2069847-1
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  • 9
    In: Geoscientific Model Development, Copernicus GmbH, Vol. 13, No. 3 ( 2020-03-17), p. 1223-1266
    Abstract: Abstract. Here we present a description of the UKCA StratTrop chemical mechanism, which is used in the UKESM1 Earth system model for CMIP6. The StratTrop chemical mechanism is a merger of previously well-evaluated tropospheric and stratospheric mechanisms, and we provide results from a series of bespoke integrations to assess the overall performance of the model. We find that the StratTrop scheme performs well when compared to a wide array of observations. The analysis we present here focuses on key components of atmospheric composition, namely the performance of the model to simulate ozone in the stratosphere and troposphere and constituents that are important for ozone in these regions. We find that the results obtained for tropospheric ozone and its budget terms from the use of the StratTrop mechanism are sensitive to the host model; simulations with the same chemical mechanism run in an earlier version of the MetUM host model show a range of sensitivity to emissions that the current model does not fall within. Whilst the general model performance is suitable for use in the UKESM1 CMIP6 integrations, we note some shortcomings in the scheme that future targeted studies will address.
    Type of Medium: Online Resource
    ISSN: 1991-9603
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
    detail.hit.zdb_id: 2456725-5
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  • 10
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 18, No. 11 ( 2018-06-15), p. 8389-8408
    Abstract: Abstract. We have used satellite observations and a simulation from the TOMCAT chemistry transport model (CTM) to investigate the influence of the well-known wintertime North Atlantic Oscillation (NAO) on European tropospheric composition. Under the positive phase of the NAO (NAO-high), strong westerlies tend to enhance transport of European pollution (e.g. nitrogen oxides, NOx; carbon monoxide, CO) away from anthropogenic source regions. In contrast, during the negative phase of the NAO (NAO-low), more stable meteorological conditions lead to a build-up of pollutants over these regions relative to the wintertime average pollution levels. However, the secondary pollutant ozone shows the opposite signal of larger values during NAO-high. NAO-high introduces Atlantic ozone-enriched air into Europe, while under NAO-low westerly transport of ozone is reduced, yielding lower values over Europe. Furthermore, ozone concentrations are also decreased by chemical loss through the reaction with accumulated primary pollutants such as nitric oxide (NO) in NAO-low. Peroxyacetyl nitrate (PAN) in the upper troposphere–lower stratosphere (UTLS) peaks over Iceland and southern Greenland in NAO-low, between 200 and 100 hPa, consistent with the trapping by an anticyclone at this altitude. Model simulations show that enhanced PAN over Iceland and southern Greenland in NAO-low is associated with vertical transport of polluted air from the mid-troposphere into the UTLS. Overall, this work shows that NAO circulation patterns are an important governing factor for European wintertime composition and air pollution.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2018
    detail.hit.zdb_id: 2092549-9
    detail.hit.zdb_id: 2069847-1
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