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- ItemNucleation of jet engine oil vapours is a large source of aviation-related ultrafine particles(London : Springer Nature, 2022) Ungeheuer, Florian; Caudillo, Lucía; Ditas, Florian; Simon, Mario; van Pinxteren, Dominik; Kılıç, Doğuşhan; Rose, Diana; Jacobi, Stefan; Kürten, Andreas; Curtius, Joachim; Vogel, Alexander L.Large airports are a major source of ultrafine particles, which spread across densely populated residential areas, affecting air quality and human health. Jet engine lubrication oils are detectable in aviation-related ultrafine particles, however, their role in particle formation and growth remains unclear. Here we show the volatility and new-particle-formation ability of a common synthetic jet oil, and the quantified oil fraction in ambient ultrafine particles downwind of Frankfurt International Airport, Germany. We find that the oil mass fraction is largest in the smallest particles (10-18 nm) with 21% on average. Combining ambient particle-phase concentration and volatility of the jet oil compounds, we determine a lower-limit saturation ratio larger than 1 × 105 for ultra-low volatility organic compounds. This indicates that the oil is an efficient nucleation agent. Our results demonstrate that jet oil nucleation is an important mechanism that can explain the abundant observations of high number concentrations of non-refractory ultrafine particles near airports.
- ItemMegacity and local contributions to regional air pollution: An aircraft case study over London(Katlenburg-Lindau : EGU, 2020) Ashworth, Kirsti; Bucci, Silvia; Gallimore, Peter J.; Lee, Junghwa; Nelson, Beth S.; Sanchez-Marroquín, Alberto; Schimpf, Marina B.; Smith, Paul D.; Drysdale, Will S.; Hopkins, Jim R.; Lee, James D.; Pitt, Joe R.; Di Carlo, Piero; Krejci, Radovan; McQuaid, James B.In July 2017 three research flights circumnavigating the megacity of London were conducted as a part of the STANCO training school for students and early career researchers organised by EUFAR (European Facility for Airborne Research). Measurements were made from the UK's Facility for Airborne Atmospheric Measurements (FAAM) BAe-146-301 atmospheric research aircraft with the aim to sample, characterise and quantify the impact of megacity outflow pollution on air quality in the surrounding region. Conditions were extremely favourable for airborne measurements, and all three flights were able to observe clear pollution events along the flight path. A small change in wind direction provided sufficiently different air mass origins over the 2 d such that a distinct pollution plume from London, attributable marine emissions and a double-peaked dispersed area of pollution resulting from a combination of local and transported emissions were measured. We were able to analyse the effect of London emissions on air quality in the wider region and the extent to which local sources contribute to pollution events. The background air upwind of London was relatively clean during both days; concentrations of CO were 88-95 ppbv, total (measured) volatile organic compounds (VOCs) were 1.6-1.8 ppbv and NOx was 0.7- 0.8 ppbv. Downwind of London, we encountered elevations in all species with CO>100 ppbv, VOCs 2.8-3.8 ppbv, CH4>2080 ppbv and NOx>4 ppbv, and peak concentrations in individual pollution events were higher still. Levels of O3 were inversely correlated with NOx during the first flight, with O3 concentrations of 37 ppbv upwind falling to 26 ppbv in the well-defined London plume. Total pollutant fluxes from London were estimated through a vertical plane downwind of the city. Our calculated CO2 fluxes are within the combined uncertainty of those estimated previously, but there was a greater disparity in our estimates of CH4 and CO. On the second day, winds were lighter and downwind O3 concentrations were elevated to 39-43 ppbv (from 32 to 35 ppbv upwind), reflecting the contribution of more aged pollution to the regional background. Elevations in pollutant concentrations were dispersed over a wider area than the first day, although we also encountered a number of clear transient enhancements from local sources. This series of flights demonstrated that even in a region of megacity outflow, such as the south-east of the UK, local fresh emissions and more distant UK sources of pollution can all contribute substantially to pollution events. In the highly complex atmosphere around a megacity where a high background level of pollution mixes with a variety of local sources at a range of spatial and temporal scales and atmospheric dynamics are further complicated by the urban heat island, the use of pollutant ratios to track and determine the ageing of air masses may not be valid. The individual sources must therefore all be well-characterised and constrained to understand air quality around megacities such as London. Research aircraft offer that capability through targeted sampling of specific sources and longitudinal studies monitoring trends in emission strength and profiles over time. © 2020 Copernicus GmbH. All rights reserved.
- ItemEstimation of cloud condensation nuclei number concentrations and comparison to in situ and lidar observations during the HOPE experiments(Katlenburg-Lindau : EGU, 2020) Genz, Christa; Schrödner, Roland; Heinold, Bernd; Henning, Silvia; Baars, Holger; Spindler, Gerald; Tegen, InaAtmospheric aerosol particles are the precondition for the formation of cloud droplets and therefore have large influence on the microphysical and radiative properties of clouds. In this work, four different methods to derive or measure number concentrations of cloud condensation nuclei (CCN) were analyzed and compared for presentday aerosol conditions: (i) a model parameterization based on simulated particle concentrations, (ii) the same parameterization based on gravimetrical particle measurements, (iii) direct CCN measurements with a CCN counter, and (iv) lidarderived and in situ measured vertical CCN profiles. In order to allow for sensitivity studies of the anthropogenic impact, a scenario to estimate the maximum CCN concentration under peak aerosol conditions of the mid-1980s in Europe was developed as well. In general, the simulations are in good agreement with the observations. At ground level, average values between 0.7 and 1:5 × 109 CCNm-3 at a supersaturation of 0.2 % were found with the different methods under present-day conditions. The discrimination of the chemical species revealed an almost equal contribution of ammonium sulfate and ammonium nitrate to the total number of CCN for present-day conditions. This was not the case for the peak aerosol scenario, in which it was assumed that no ammonium nitrate was formed while large amounts of sulfate were present, consuming all available ammonia during ammonium sulfate formation. The CCN number concentration at five different supersaturation values has been compared to the measurements. The discrepancies between model and in situ observations were lowest for the lowest (0.1 %) and highest supersaturations (0.7 %). For supersaturations between 0.3 % and 0.5 %, the model overestimated the potentially activated particle fraction by around 30 %. By comparing the simulation with observed profiles, the vertical distribution of the CCN concentration was found to be overestimated by up to a factor of 2 in the boundary layer. The analysis of the modern (year 2013) and the peak aerosol scenario (expected to be representative of the mid-1980s over Europe) resulted in a scaling factor, which was defined as the quotient of the average vertical profile of the peak aerosol and present-day CCN concentration. This factor was found to be around 2 close to the ground, increasing to around 3.5 between 2 and 5 km and approaching 1 (i.e., no difference between present-day and peak aerosol conditions) with further increasing height. © 2020 Author(s).
- ItemIdentification and source attribution of organic compounds in ultrafine particles near Frankfurt International Airport(Katlenburg-Lindau : European Geosciences Union, 2021) Ungeheuer, Florian; van Pinxteren, Dominik; Vogel, Alexander L.Analysing the composition of ambient ultrafine particles (UFPs) is a challenging task due to the low mass and chemical complexity of small particles, yet it is a prerequisite for the identification of particle sources and the assessment of potential health risks. Here, we show the molecular characterization of UFPs, based on cascade impactor (Nano-MOUDI) samples that were collected at an air quality monitoring station near one of Europe's largest airports, in Frankfurt, Germany. At this station, particle-size-distribution measurements show an enhanced number concentration of particles smaller than 50 nm during airport operating hours. We sampled the lower UFP fraction (0.010-0.018, 0.018-0.032, 0.032-0.056 classCombining double low lineinline-formula/m) when the air masses arrived from the airport. We developed an optimized filter extraction procedure using ultra-high-performance liquid chromatography (UHPLC) for compound separation and a heated electrospray ionization (HESI) source with an Orbitrap high-resolution mass spectrometer (HRMS) as a detector for organic compounds. A non-Target screening detected classCombining double low lineinline-formulag1/4200/ organic compounds in the UFP fraction with sample-To-blank ratios larger than 5. We identified the largest signals as homologous series of pentaerythritol esters (PEEs) and trimethylolpropane esters (TMPEs), which are base stocks of aircraft lubrication oils. We unambiguously attribute the majority of detected compounds to jet engine lubrication oils by matching retention times, high-resolution and accurate mass measurements, and comparing tandem mass spectrometry (MS classCombining double low lineinline-formula2/) fragmentation patterns between both ambient samples and commercially available jet oils. For each UFP stage, we created molecular fingerprints to visualize the complex chemical composition of the organic fraction and their average carbon oxidation state. These graphs underline the presence of the homologous series of PEEs and TMPEs and the appearance of jet oil additives (e.g.Tricresyl phosphate, TCP). Targeted screening of TCP confirmed the absence of the harmful tri-iortho/i isomer, while we identified a thermal transformation product of TMPE-based lubrication oil (trimethylolpropane phosphate, TMP-P). Even though a quantitative determination of the identified compounds is limited, the presented method enables the qualitative detection of molecular markers for jet engine lubricants in UFPs and thus strongly improves the source apportionment of UFPs near airports./p. © 2021 BMJ Publishing Group. All rights reserved.
- ItemComparison of particle number size distribution trends in ground measurements and climate models(Katlenburg-Lindau : EGU, 2022) Leinonen, Ville; Kokkola, Harri; Yli-Juuti, Taina; Mielonen, Tero; Kühn, Thomas; Nieminen, Tuomo; Heikkinen, Simo; Miinalainen, Tuuli; Bergman, Tommi; Carslaw, Ken; Decesari, Stefano; Fiebig, Markus; Hussein, Tareq; Kivekäs, Niku; Krejci, Radovan; Kulmala, Markku; Leskinen, Ari; Massling, Andreas; Mihalopoulos, Nikos; Mulcahy, Jane P.; Noe, Steffen M.; van Noije, Twan; O'Connor, Fiona M.; O'Dowd, Colin; Olivie, Dirk; Pernov, Jakob B.; Petäjä, Tuukka; Seland, Øyvind; Schulz, Michael; Scott, Catherine E.; Skov, Henrik; Swietlicki, Erik; Tuch, Thomas; Wiedensohler, Alfred; Virtanen, Annele; Mikkonen, SanttuDespite a large number of studies, out of all drivers of radiative forcing, the effect of aerosols has the largest uncertainty in global climate model radiative forcing estimates. There have been studies of aerosol optical properties in climate models, but the effects of particle number size distribution need a more thorough inspection. We investigated the trends and seasonality of particle number concentrations in nucleation, Aitken, and accumulation modes at 21 measurement sites in Europe and the Arctic. For 13 of those sites, with longer measurement time series, we compared the field observations with the results from five climate models, namely EC-Earth3, ECHAM-M7, ECHAM-SALSA, NorESM1.2, and UKESM1. This is the first extensive comparison of detailed aerosol size distribution trends between in situ observations from Europe and five earth system models (ESMs). We found that the trends of particle number concentrations were mostly consistent and decreasing in both measurements and models. However, for many sites, climate models showed weaker decreasing trends than the measurements. Seasonal variability in measured number concentrations, quantified by the ratio between maximum and minimum monthly number concentration, was typically stronger at northern measurement sites compared to other locations. Models had large differences in their seasonal representation, and they can be roughly divided into two categories: for EC-Earth and NorESM, the seasonal cycle was relatively similar for all sites, and for other models the pattern of seasonality varied between northern and southern sites. In addition, the variability in concentrations across sites varied between models, some having relatively similar concentrations for all sites, whereas others showed clear differences in concentrations between remote and urban sites. To conclude, although all of the model simulations had identical input data to describe anthropogenic mass emissions, trends in differently sized particles vary among the models due to assumptions in emission sizes and differences in how models treat size-dependent aerosol processes. The inter-model variability was largest in the accumulation mode, i.e. sizes which have implications for aerosol-cloud interactions. Our analysis also indicates that between models there is a large variation in efficiency of long-range transportation of aerosols to remote locations. The differences in model results are most likely due to the more complex effect of different processes instead of one specific feature (e.g. the representation of aerosol or emission size distributions). Hence, a more detailed characterization of microphysical processes and deposition processes affecting the long-range transport is needed to understand the model variability.
- ItemImportance of secondary organic aerosol formation of iα/i-pinene, limonene, and im/i-cresol comparing day- And nighttime radical chemistry(Katlenburg-Lindau : European Geosciences Union, 2021) Mutzel, Anke; Zhang, Yanli; Böge, Olaf; Rodigast, Maria; Kolodziejczyk, Agata; Wang, Xinming; Herrmann, HartmutThe oxidation of biogenic and anthropogenic compounds leads to the formation of secondary organic aerosol mass (SOA). The present study aims to investigate span classCombining double low line"inline-formula"iα/i/span-pinene, limonene, and span classCombining double low line"inline-formula"im/i/span-cresol with regards to their SOA formation potential dependent on relative humidity (RH) under night- (NOspan classCombining double low line"inline-formula"3/span radicals) and daytime conditions (OH radicals) and the resulting chemical composition. It was found that SOA formation potential of limonene with NOspan classCombining double low line"inline-formula"3/span under dry conditions significantly exceeds that of the OH-radical reaction, with SOA yields of 15-30 % and 10-21 %, respectively. Additionally, the nocturnal SOA yield was found to be very sensitive towards RH, yielding more SOA under dry conditions. In contrast, the SOA formation potential of span classCombining double low line"inline-formula"iα/i/span-pinene with NOspan classCombining double low line"inline-formula"3/span slightly exceeds that of the OH-radical reaction, independent from RH. On average, span classCombining double low line"inline-formula"iα/i/span-pinene yielded SOA with about 6-7 % from NOspan classCombining double low line"inline-formula"3/span radicals and 3-4 % from OH-radical reaction. Surprisingly, unexpectedly high SOA yields were found for span classCombining double low line"inline-formula"im/i/span-cresol oxidation with OH radicals (3-9 %), with the highest yield under elevated RH (9 %), which is most likely attributable to a higher fraction of 3-methyl-6-nitro-catechol (MNC). While span classCombining double low line"inline-formula"iα/i/span-pinene and span classCombining double low line"inline-formula"im/i/span-cresol SOA was found to be mainly composed of water-soluble compounds, 50-68 % of nocturnal SOA and 22-39 % of daytime limonene SOA are water-insoluble. The fraction of SOA-bound peroxides which originated from span classCombining double low line"inline-formula"iα/i/span-pinene varied between 2 and 80 % as a function of RH./p pFurthermore, SOA from span classCombining double low line"inline-formula"iα/i/span-pinene revealed pinonic acid as the most important particle-phase constituent under day- and nighttime conditions with a fraction of 1-4 %. Other compounds detected are norpinonic acid (0.05-1.1 % mass fraction), terpenylic acid (0.1-1.1 % mass fraction), pinic acid (0.1-1.8 % mass fraction), and 3-methyl-1,2,3-tricarboxylic acid (0.05-0.5 % mass fraction). All marker compounds showed higher fractions under dry conditions when formed during daytime and showed almost no RH effect when formed during night./p © 2021 Copernicus GmbH. All rights reserved.
- ItemIncreasing the spatial resolution of cloud property retrievals from Meteosat SEVIRI by use of its high-resolution visible channel: Evaluation of candidate approaches with MODIS observations(Katlenburg-Lindau : Copernicus, 2020) Werner, Frank; Deneke, HartwigThis study presents and evaluates several candidate approaches for downscaling observations from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) in order to increase the horizontal resolution of subsequent cloud optical thickness (τ) and effective droplet radius (reff) retrievals from the native ≈ 3km×3km spatial resolution of the narrowband channels to ≈ 1km×1km. These methods make use of SEVIRI's coincident broadband high-resolution visible (HRV) channel. For four example cloud fields, the reliability of each downscaling algorithm is evaluated by means of collocated 1km×1km MODIS radiances, which are reprojected to the horizontal grid of the HRV channel and serve as reference for the evaluation. By using these radiances, smoothed with the modulation transfer function of the native SEVIRI channels, as retrieval input, the accuracy at the SEVIRI standard resolution can be evaluated and an objective comparison of the accuracy of the different downscaling algorithms can be made. For the example scenes considered in this study, it is shown that neglecting high-frequency variations below the SEVIRI standard resolution results in significant random absolute deviations of the retrieved τ and reff of up to ≈ 14 and ≈ 6μm, respectively, as well as biases. By error propagation, this also negatively impacts the reliability of the subsequent calculation of liquid water path (WL) and cloud droplet number concentration (ND), which exhibit deviations of up to ≈ 89gm-2 and ≈ 177cm-3, respectively. For τ , these deviations can be almost completely mitigated by the use of the HRV channel as a physical constraint and by applying most of the presented downscaling schemes. Uncertainties in retrieved reff at the native SEVIRI resolution are smaller, and the improvements from downscaling the observations are less obvious than for τ. Nonetheless, the right choice of downscaling scheme yields noticeable improvements in the retrieved reff. Furthermore, the improved reliability in retrieved cloud products results in significantly reduced uncertainties in derived WL and ND. In particular, one downscaling approach provides clear improvements for all cloud products compared to those obtained from SEVIRI's standard resolution and is recommended for future downscaling endeavors. This work advances efforts to mitigate impacts of scale mismatches among channels of multiresolution instruments on cloud retrievals. © Author(s) 2020.
- ItemMultiphase MCM-CAPRAM modeling of the formation and processing of secondary aerosol constituents observed during the Mt. Tai summer campaign in 2014(Katlenburg-Lindau : EGU, 2020) Zhu, Yanhong; Tilgner, Andreas; Hoffmann, Erik Hans; Herrmann, Hartmut; Kawamura, Kimitaka; Yang, Lingxiao; Xue, Likun; Wang, WenxingDespite the high abundance of secondary aerosols in the atmosphere, their formation mechanisms remain poorly understood. In this study, the Master Chemical Mechanism (MCM) and the Chemical Aqueous-Phase Radical Mechanism (CAPRAM) are used to investigate the multiphase formation and processing of secondary aerosol constituents during the advection of air masses towards the measurement site of Mt. Tai in northern China. Trajectories with and without chemical–cloud interaction are modeled. Modeled radical and non-radical concentrations demonstrate that the summit of Mt. Tai, with an altitude of ∼1.5 km a.m.s.l., is characterized by a suburban oxidants budget. The modeled maximum gas-phase concentrations of the OH radical are 3.2×106 and 3.5×106 molec. cm−3 in simulations with and without cloud passages in the air parcel, respectively. In contrast with previous studies at Mt. Tai, this study has modeled chemical formation processes of secondary aerosol constituents under day vs. night and cloud vs. non-cloud cases along the trajectories towards Mt. Tai in detail. The model studies show that sulfate is mainly produced in simulations where the air parcel is influenced by cloud chemistry. Under the simulated conditions, the aqueous reaction of HSO−3 with H2O2 is the major contributor to sulfate formation, contributing 67 % and 60 % in the simulations with cloud and non-cloud passages, respectively. The modeled nitrate formation is higher at nighttime than during daytime. The major pathway is aqueous-phase N2O5 hydrolysis, with a contribution of 72 % when cloud passages are considered and 70 % when they are not. Secondary organic aerosol (SOA) compounds, e.g., glyoxylic, oxalic, pyruvic and malonic acid, are found to be mostly produced from the aqueous oxidations of hydrated glyoxal, hydrated glyoxylic acid, nitro-2-oxopropanoate and hydrated 3-oxopropanoic acid, respectively. Sensitivity studies reveal that gaseous volatile organic compound (VOC) emissions have a huge impact on the concentrations of modeled secondary aerosol compounds. Increasing the VOC emissions by a factor of 2 leads to linearly increased concentrations of the corresponding SOA compounds. Studies using the relative incremental reactivity (RIR) method have identified isoprene, 1,3-butadiene and toluene as the key precursors for glyoxylic and oxalic acid, but only isoprene is found to be a key precursor for pyruvic acid. Additionally, the model investigations demonstrate that an increased aerosol partitioning of glyoxal can play an important role in the aqueous-phase formation of glyoxylic and oxalic acid. Overall, the present study is the first that provides more detailed insights in the formation pathways of secondary aerosol constituents at Mt. Tai and clearly emphasizes the importance of aqueous-phase chemical processes on the production of multifunctional carboxylic acids.
- ItemInflux of African biomass burning aerosol during the Amazonian dry season through layered transatlantic transport of black carbon-rich smoke(Katlenburg-Lindau : EGU, 2020) Holanda, Bruna A.; Pöhlker, Mira L.; Walter, David; Saturno, Jorge; Sörgel, Matthias; Ditas, Jeannine; Ditas, Florian; Schulz, Christiane; Aurélio Franco, Marco; Wang, Qiaoqiao; Donth, Tobias; Artaxo, Paulo; Barbosa, Henrique M.J.; Borrmann, Stephan; Braga, Ramon; Brito, Joel; Cheng, Yafang; Dollner, Maximilian; Kaiser, JohannesW.; Klimach, Thomas; Knote, Christoph; Krüger, Ovid O.; Fütterer, Daniel; Lavrič, Jošt V.; Ma, Nan; Machado, Luiz A.T.; Ming, Jing; Morais, Fernando G.; Paulsen, Hauke; Sauer, Daniel; Schlager, Hans; Schneider, Johannes; Su, Hang; Weinzierl, Bernadett; Walser, Adrian; Wendisch, Manfred; Ziereis, Helmut; Zöger, Martin; Pöschl, Ulrich; Andreae, Meinrat O.; Pöhlker, ChristopherBlack carbon (BC) aerosols influence the Earth's atmosphere and climate, but their microphysical properties, spatiotemporal distribution, and long-range transport are not well constrained. This study presents airborne observations of the transatlantic transport of BC-rich African biomass burning (BB) smoke into the Amazon Basin using a Single Particle Soot Photometer (SP2) as well as several complementary techniques. We base our results on observations of aerosols and trace gases off the Brazilian coast onboard the HALO (High Altitude and LOng range) research aircraft during the ACRIDICON-CHUVA campaign in September 2014. During flight AC19 over land and ocean at the northeastern coastline of the Amazon Basin, we observed a BCrich layer at ∼ 3:5 km altitude with a vertical extension of ∼ 0:3 km. Backward trajectories suggest that fires in African grasslands, savannas, and shrublands were the main source of this pollution layer and that the observed BB smoke had undergone more than 10 d of atmospheric transport and aging over the South Atlantic before reaching the Amazon Basin. The aged smoke is characterized by a dominant accumulation mode, centered at about 130 nm, with a particle concentration of Nacc D 850±330 cm-3. The rBC particles account for ∼ 15 % of the submicrometer aerosol mass and ∼ 40 % of the total aerosol number concentration. This corresponds to a mass concentration range from 0.5 to 2 μ g m-3 (1st to 99th percentiles) and a number concentration range from 90 to 530 cm-3. Along with rBC, high cCO (150 ± 30 ppb) and cO3 (56 ± 9 ppb) mixing ratios support the biomass burning origin and pronounced photochemical aging of this layer. Upon reaching the Amazon Basin, it started to broaden and to subside, due to convective mixing and entrainment of the BB aerosol into the boundary layer. Satellite observations show that the transatlantic transport of pollution layers is a frequently occurring process, seasonally peaking in August/September. By analyzing the aircraft observations together with the long-term data from the Amazon Tall Tower Observatory (ATTO), we found that the transatlantic transport of African BB smoke layers has a strong impact on the northern and central Amazonian aerosol population during the BBinfluenced season (July to December). In fact, the early BB season (July to September) in this part of the Amazon appears to be dominated by African smoke, whereas the later BB season (October to December) appears to be dominated by South American fires. This dichotomy is reflected in pronounced changes in aerosol optical properties such as the single scattering albedo (increasing from 0.85 in August to 0.90 in November) and the BC-to-CO enhancement ratio (decreasing from 11 to 6 ng m-3 ppb-1). Our results suggest that, despite the high fraction of BC particles, the African BB aerosol acts as efficient cloud condensation nuclei (CCN), with potentially important implications for aerosol-cloud interactions and the hydrological cycle in the Amazon. © 2020 Author(s).
- ItemTracing the Snowball bifurcation of aquaplanets through time reveals a fundamental shift in critical-state dynamics(Göttingen : Copernicus, 2023) Feulner, Georg; Bukenberger, Mona; Petri, StefanThe instability with respect to global glaciation is a fundamental property of the climate system caused by the positive ice-albedo feedback. The atmospheric concentration of carbon dioxide (CO2) at which this Snowball bifurcation occurs changes through Earth's history, most notably because of the slowly increasing solar luminosity. Quantifying this critical CO2 concentration is not only interesting from a climate dynamics perspective but also constitutes an important prerequisite for understanding past Snowball Earth episodes, as well as the conditions for habitability on Earth and other planets. Earlier studies are limited to investigations with very simple climate models for Earth's entire history or studies of individual time slices carried out with a variety of more complex models and for different boundary conditions, making comparisons and the identification of secular changes difficult. Here, we use a coupled climate model of intermediate complexity to trace the Snowball bifurcation of an aquaplanet through Earth's history in one consistent model framework. We find that the critical CO2 concentration decreased more or less logarithmically with increasing solar luminosity until about 1 billion years ago but dropped faster in more recent times. Furthermore, there was a fundamental shift in the dynamics of the critical state about 1.2 billion years ago (unrelated to the downturn in critical CO2 values), driven by the interplay of wind-driven sea-ice dynamics and the surface energy balance: for critical states at low solar luminosities, the ice line lies in the Ferrel cell, stabilised by the poleward winds despite moderate meridional temperature gradients under strong greenhouse warming. For critical states at high solar luminosities, on the other hand, the ice line rests at the Hadley cell boundary, stabilised against the equatorward winds by steep meridional temperature gradients resulting from the increased solar energy input at lower latitudes and stronger Ekman transport in the ocean.