Penguin guano: an important source of climate-relevant aerosol in Antarctica | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Penguin guano: an important source of climate-relevant aerosol in Antarctica Matthew Boyer, Lauriane Quéléver, Zoé Brasseur, J McManus, Scott Herndon, and 22 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5372386/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 22 May, 2025 Read the published version in Communications Earth & Environment → Version 1 posted You are reading this latest preprint version Abstract Gaseous ammonia, while influential in atmospheric processes, is critically underrepresented in atmospheric measurements. This limits our understanding of key climate-relevant processes, such as new particle formation, particularly in remote regions. Here, we present highly sensitive, online observations of gaseous ammonia from a coastal site in Antarctica, which allows us to constrain the mechanism of new particle formation in this region in unprecedented detail. Our observations show that penguin colonies are a large source of ammonia in coastal Antarctica, whereas ammonia originating from the Southern Ocean is, in comparison, negligible. In conjunction with sulfur compounds sourced from oceanic microbiology, ammonia initiates new particle formation and is an important source of cloud condensation nuclei. Dimethyl amine, likely originating from penguin guano, also participates in the initial steps of particle formation, effectively boosting particle formation rates up to 10000 times. These findings emphasize the importance of local fauna (penguin/bird colonies and oceanic phytoplankton/bacteria) on climate-relevant aerosol processes in coastal Antarctica. This demonstrates an important connection between ecosystem and atmospheric processes that impact the Antarctic climate, which is crucial given the current rate of environmental changes in the region. Earth and environmental sciences/Climate sciences/Atmospheric science Earth and environmental sciences/Climate sciences/Atmospheric science/Atmospheric chemistry Figures Figure 1 Figure 2 Figure 3 Figure 4 Main Biological processes influence atmospheric composition and climate through a variety of mechanisms. For example, living organisms emit vapors that moderate cloud properties via production of aerosol and cloud condensation nuclei (CCN) or ice nucleating particles (INP), which subsequently impact Earth’s surface radiative balance, precipitation, and weather. Changes in the biology of an ecosystem can therefore impact climate. Vegetation in continental regions emits volatile organic vapors which are subsequently converted to secondary organic aerosol 1 . In pristine marine and polar environments, however, aerosol and CCN production is connected to marine phytoplankton dimethyl sulfide (DMS) and iodine emissions via new particle formation (NPF) 2 . In the remote Southern Ocean and Antarctica, the strength of NPF events has considerable relevance for the climate. These pristine locations typically have low background particle concentrations compared to regions with anthropogenic activities or vegetation. Coincidentally, the chemical mechanism of NPF remains elusive in remote and polar regions, yet NPF is estimated to contribute over 50% of CCN in the atmosphere globally 3 , and potentially more in such environments, including over the Antarctic continent 4 . Interactions of aerosols and clouds, especially the sources and concentrations of CCN in pristine, preindustrial-like environments, are a large source of uncertainty in our understanding of climate change 5 . Climate-relevant cloud properties, such as cloud brightness and lifetime, are very sensitive to the concentration of CCN in such conditions 6 . Therefore, the gases that contribute to NPF events, and their ability to enhance particle formation rates, are critical to understanding the climate response in these locations. Direct observations of DMS-derived sulfuric acid (H 2 SO 4 ) aerosol formation in the polar regions indicate that ammonia (NH 3 ) stabilizes sulfuric acid clusters during NPF events 2 , 7 , 8 . Seabirds are a known source of atmospheric ammonia in remote regions 9 – 12 , and studies have speculated that penguins/seabirds impact aerosol formation and cloud processes 2 , 7 , 8 , 13 , 14 . Even though laboratory experiments have shown that ammonia can enhance sulfuric acid-induced particle formation by several orders of magnitude 15 , there are few measurements of ammonia concentrations in the remote ambient atmosphere with high enough sensitivity and time resolution coupled with comprehensive measurements to resolve the mechanism of NPF. Iodic acid (HIO 3 ) has been shown to contribute to NPF together with iodous acid (HIO 2 ) 16 – 18 in the absence of sulfuric acid and ammonia in sea ice covered regions in the Arctic during spring and autumn. While these particles may contribute to CCN 17 , other observations suggest that they rarely grow to climate-relevant CCN sizes 2 . A recent laboratory study has also proposed that NPF may occur between iodine oxoacids and sulfuric acid without ammonia in remote marine and polar environments, and the presence of approximately 30 to 260 ppt of ammonia can further enhance aerosol nucleation rates 19 . Their conclusions assume that there is at maximum a few hundred ppt of ammonia in the remote polar atmosphere to participate, based on limited ambient data from these environments. Similarly, another study suggested that sulfuric acid and amines, sourced from sea-ice-covered regions, dominate particle formation around the Antarctic Peninsula 20 . Alkylamines, such as dimethyl amine (DMA, (CH 3 ) 2 NH 3 ) are known to nucleate rapidly with sulfuric acid 21 , 22 , yielding formation rates up to 10000 times faster than sulfuric acid-ammonia NPF. These discrepancies show that the chemical mechanism of NPF in this environment remains poorly constrained, where direct measurement of ammonia and amine concentrations comprise a key knowledge gap. In general, ammonia is one of the most under-represented gases in atmospheric measurements, especially online measurements at high sensitivity and in remote regions where ambient ammonia concentrations are estimated to be low (i.e., lower than 100 ppt). However, without ammonia measurements, we are missing critical observations which limits our understanding of climate-relevant aerosol formation processes. The lack of data is particularly pronounced in our ability to constrain new particle formation (NPF) in remote and polar environments. Currently, Antarctic ecosystems are stressed. The region is experiencing accelerated changes due to warming. Sea ice extent is declining 23 , and ice shelfs are shrinking 24 . These changes impact the biology in the Southern Ocean 25 , as well as penguin and seabird colonies, which will result in changes to ecosystem-atmosphere exchanges, and ultimately the climate of the region, with subsequent effects on global climate. Some species of penguins are already threatened due to environmental changes 26 . Therefore, it is imperative to understand the ecosystem-atmosphere interactions that contribute to climate relevant processes – especially now, as environmental conditions in coastal Antarctica and the Southern Ocean are rapidly changing. In this work, we analyze the chemical mechanism of NPF events on the Antarctic Peninsula, featuring highly sensitive online measurements of ambient ammonia concentrations as well as comprehensive measurements of gases and particles to investigate aerosol processes connecting NPF with cloud formation. We show that penguins are a significant source of ammonia that enhances NPF with sulfuric acid sourced from marine phytoplankton in coastal Antarctica, whereas ammonia contributions from the open ocean were negligible. We present evidence that these newly formed particles can grow and contribute to CCN concentrations and cloud/fog formation. This demonstrates that penguins/sea birds play a key role in particle formation and may represent an important climate feedback as their habitat changes. Results Our study combines measurements of aerosol precursor vapors concentrations, ammonia mixing ratios, the chemistry of charged nucleating clusters, aerosol particle number concentrations and size distributions, aerosol chemical composition, CCN concentrations, and in situ cloud droplet distributions from Marambio station on the Antarctic peninsula (Fig. 1 A and B) to investigate the connection between gases, particles, and clouds. In our measurements, we observed ammonia mixing ratios up to 13.5 ppb when winds came from the direction of nearby penguin colonies, as shown in Fig. 1 and Figure S1. In contrast, from other wind directions (including the open ocean), ammonia mixing ratios were low. Excluding the influence of local pollution from Marambio station (19.4% occurrence), 42.8% of the measured ammonia mixing ratios were below the detection limit (10.5 ± 26.8 ppt), 36.2% were between 10.5–40 ppt, 9.8% were between 40–100 ppt, and 11.2% were greater than 100 ppt (Fig. 1 D). Notably, the penguins in the nearby colony left their breeding site in the middle of our measurement campaign as part of their annual migration. For over a month after the penguins left, concentrations of ammonia remained elevated, exceeding 1 ppb (Figure S2) from the favorable wind direction. Therefore, the penguin guano “fertilized” soil, also known as ornithogenic soil 27 , continued to be a strong source of ammonia long after they left the site. Until now, this process has largely only been evaluated in laboratory measurements 28 , models 10 , 12 , 29 , or offline methods 30 . Our data demonstrates that there are local hotspots around the coast of Antarctica that can yield ammonia concentrations similar in magnitude to agricultural plots 31 , 32 during summer. These hotspots correspond to the location of penguin/bird breeding settlements/colonies, consistent with previous studies; due to their annual migration patterns, these hotspots may cover a large extent of coastal Antarctica 33 . Our results demonstrate that ammonia is present in the Antarctic environment at sufficient mixing ratios to initiate NPF with sulfuric acid. In fact, we observed NPF almost exclusively when winds were from the direction/wind sector of local penguin colonies, leading to elevated ammonia mixing ratios. Particle formation rates (J 1.7 ) during these NPF events depended primarily on sulfuric acid concentrations. In addition, observations of aerosol precursor vapors, the chemical composition of atmospheric clusters, and online measurement of ammonia show clear participation of ammonia and enhancement of particle formation rates when ammonia mixing ratios exceed ~ 100 ppt (Fig. 2 ). We did not uniformly observe continued enhancement as ammonia mixing ratios increase above ~ 100 ppt, indicating that particle formation with respect to ammonia begins to saturate at this level, similar to laboratory-derived estimates of ammonia saturation in sulfuric acid-ammonia clustering studies 15 , 34 . Additionally, we compared our observations to a formation rate parameterization that considers sulfuric acid and ammonia concentrations 35 . The measured formation rates are consistently between 1–4 orders of magnitude higher than the parameterization (median ratio = 72). It is important to note that there are several possible reasons for discrepancies, particularly with respect to field observations, including errors inherent to the measurements and calculation of formation rates and a factor of two uncertainty in the calibration and quantification of sulfuric acid concentrations. Despite these uncertainties, we can attribute the higher formation rates in our observations to the participation of other gases that can further enhance particle formation rates of the sulfuric acid-ammonia mechanism. While the chemical composition of charged clusters during NPF is dominated by sulfuric acid and ammonia clusters (Fig. 3 A), there are additional clusters present, indicating a multicomponent particle formation mechanism. These include sulfuric acid and DMA clusters, which are known to yield particle formation rates between 100–10000 times faster than sulfuric acid and ammonia 22 . Previously, DMA-containing clusters were observed to dominate at DMA mixing ratios of 4 ppt in the presence of ammonia exceeding 1 ppb 36 . Here, instead, sulfuric acid and ammonia clusters are the dominant growing clusters, suggesting that DMA is present at very low concentrations – enough to stabilize the initial stages of cluster formation and enhance sulfuric acid-ammonia particle formation rates by ~ 2–4 orders of magnitude compared to pure sulfuric acid-ammonia nucleation (Fig. 3 C). These conclusions agree with the findings of Quéléver et al. 8 It is worth noting that we cannot determine the gas phase DMA concentration from cluster measurements, but the detection of DMA in atmospheric clusters in the APi-ToF, which is believed to be the most sensitive detector for the presence of atmospheric amines, does confirm the presence of DMA 22 . We can use the ion counts of clusters containing DMA (in counts per second) to estimate changes in available DMA (Fig. 3 B), but this is qualitative; a direct measure of DMA should be prioritized in future measurements. Despite this limitation on the quantification of DMA, we conclude that DMA does indeed play a role in enhancing formation rates. By comparing with previous chamber measurements 22 , we can estimate that DMA mixing ratios are ~ 1 ppt or lower (Fig. 3 D). Although we cannot offer strong comments on the sources of DMA without direct measurements, wind rose directions with the highest ion counts of DMA in clusters are similar to those associated with high ammonia mixing ratios (Figure S1). Penguin guano has also been identified to produce amines in guano-affected soils 37 . Therefore, it is plausible that penguin colonies are a source of DMA. Recent observations suggest that clustering between sulfuric acid and DMA is the primary mechanism of particle formation around coastal Antarctica, where DMA is sourced from sea-ice-covered regions 20 . Interestingly, Brean et al. 20 did not observe sulfuric acid-ammonia clusters in their measurements. In contrast, our observations show ammonia dominated clustering with sulfuric acid instead of amine-mediated cluster growth. In comparison to Brean et al. 20 , NPF occurred more frequently during our study and produced higher concentrations of new particles. We observed NPF on 34% of our measurement days, resulting in enhanced aerosol concentrations at times exceeding 15,000 #/cm 3 , as shown in Fig. 4 C. Therefore, we propose that while amines may enhance NPF in parts of the Southern Ocean or coastal Antarctica, the multicomponent formation mechanism with sulfuric acid, DMA, and ammonia has a stronger impact on particle concentrations, and subsequently the climate-relevant aerosol formation in these regions. Observations of the atmospheric cluster composition also show participation of iodine oxoacids (HIO 2 and HIO 3 ) in some cases (Figure S3). Although it should be noted that ammonia and amines had a more pronounced role in particle formation in our measurements, as the sulfuric acid-ammonia clusters dominated ionic cluster chemistry, the multicomponent system with ammonia, sulfur, and iodine compounds is a valuable finding. It is important to consider that our measurements only cover the summer period when conditions favor the strongest photochemical production of sulfur compounds from DMS and when penguin breeding colonies are present, whereas the production of iodine oxoacids is expected to be stronger during seasonal transitions in spring and fall 17 , 38 . During seasonal transitions, particle formation may show stronger enhancement from iodine oxoacids; however, in situ observations of the chemical mechanism of NPF during seasonal transitions in Antarctica are lacking, and therefore, it calls for future dedicated studies. NPF in Antarctica has been observed to contribute to background CCN concentrations 39 . Our measurements also demonstrate the connection between NPF, CCN formation, and fog/cloud droplet activation. From a case study on February 1, 2023, we had a very strong NPF and growth event with ammonia from the penguin colonies, resulting in very high concentrations of particles (> 16,000 #·cm − 3 above 10 nm), as shown in Fig. 4 . These particles grew over the next 6 hours up to ~ 30 nm, followed by a period of fog. While sampling in the fog, we measured a reduction in nucleation mode particles from scavenging and an increase in larger particles from cloud droplet residuals, which likely result from rapid growth of particles due to cloud processing 40 . Activated particles are present at all supersaturations in the CCN counter measurements, and the particle composition was dominated by ammonium sulfate. After the 1-hour period in fog, the fog lifted such that sampling occurred below the fog/cloud layer, after which the same mode of newly formed particles was observed again. The persistence in the newly formed particle mode before and after the fog signifies strong regional NPF during which these particles influenced fog microphysics by contributing to the fog/cloud droplet population. The chemical composition of the cloud droplet residuals was composed almost solely of ammonia sulfate, which confirms the participation of ammonia sourced from the penguins. Further details of this case study are discussed in the supplement. Broader climate implications Recent observations suggest that aerosol precursor gases in Antarctica are closely linked to regional ecosystem processes 7 , 8 , 20 . Key sulfur compounds originate from DMS emissions due to marine phytoplankton in the Southern Ocean around coastal Antarctica, which has the one of highest DMS concentrations on the planet during summer 41 , 42 . Iodine compounds are also sourced from processes involving ocean biology and heterogeneous chemistry on ice and snow surfaces 38 . Now, we quantify the contribution of ammonia from penguins/sea birds at mixing ratios high enough to initiate and enhance NPF with sulfuric acid from DMS. Our measurements demonstrate that penguin colonies form strong point sources of particles in a region where cloud formation can be limited by the availability of CCN. Hence, the radiative properties of clouds, a climate relevant process, is affected by penguins/seabirds. Given that penguin colonies span the coast of Antarctica 33 and that they leave guano/nutrient-rich soils that continue to emit ammonia after migration, we estimate that penguins provide a substantial source of ammonia, and particles, across the entire coastal Antarctic region 12 . While the lifetime of gaseous ammonia in the troposphere is estimated to be short, ranging from several hours to ~ 1 day 32 , 43 , the lifetime of the particles that result from NPF events have longer lifetimes up to several days 44 . These newly formed particles could be further transported over parts of the Southern Ocean and continental Antarctica on this timescale, which could subsequently affect aerosol and CCN concentrations over the larger Antarctic region, including further inland 7 where aerosol sources are limited 45 . This suggests that coastal penguin/bird colonies could also comprise an important source of aerosol away from the coast. It is already understood that widespread loss of sea ice extent threatens the habitat, food sources 46 , and breeding behavior 47 of most penguin species that inhabit Antarctica. Consequently, some Antarctic penguin populations are already declining 26 , and some species could be nearly extinct by the end of the 21st century 48 . We provide evidence that declining penguin populations could cause a positive climate warming feedback in the summertime Antarctic atmosphere, as proposed by a modelling study of seabird emissions in the Arctic region 14 . Furthermore, our results demonstrate a multicomponent nucleation mechanism between sulfuric acid and ammonia over broad concentration ranges of both these precursors in ambient conditions and in the absence of anthropogenic influence or vegetation. NPF events rarely occur in the remote marine boundary layer, including over the Southern Ocean, despite the presence of condensable vapors from DMS oxidation 49 . Studies in other environments also suggest that NPF in the ambient atmosphere occurs more readily when ammonia is available 50 – 52 , or that ammonia significantly enhances NPF 53 . We show that ammonia from penguins stabilizes sulfuric acid clusters from DMS oxidation over Antarctica and, together with low level DMA, yields high particle formation rates that can grow to CCN-active particles. We also identify that the Southern Ocean is not a significant source of gaseous ammonia, at least in its current state 54 , which offers a possible explanation to the limited observations of NPF events in the remote marine boundary layer. Therefore, we demonstrate that the ammonia budget is critical to understand the contribution of DMS to NPF in coastal Antarctica, which may also have global atmospheric implications, including in the past, present, and future. The potential contribution of iodine oxoacids may also be important in this context, as they may serve as the “base” to initiate sulfuric acid nucleation at low ammonia concentrations during seasonal transitions. Fundamentally, the prevalence of these gases over Antarctica depends upon the interplay of sea ice, phytoplankton metabolism, and penguin/sea bird populations—all of which are subject to change. The complexity of these processes requires continued, dedicated experimentation and investigation to deconvolve. Methods Measurement site All measurements reported in this work were collected between January 10 – March 20, 2023 in the atmospheric observatory located ~ 300 m southwest of Marambio Station, Antarctica (64°14.68’ S, 56°37.88’ W; Fig. 1 A and B) at an altitude of 198 m above sea level. Marambio station is located on Seymour Island near the northernmost tip of the Antarctic Peninsula and has previously been described in Asmi et al. 55 (2018) and Quéléver et al. (2022). Various features of the measurement site near Marambio station are important for the interpretation of our measurements. Logistical activities at the station contributed a local source of pollution that contaminated the ambient sampling when wind directions originated from between 0–90 degrees and were excluded from our analysis. A large colony of Adelie penguins ( Pygoscelis adeliae ) with approximately 30,000 breeding pairs 56 was located ~ 8 km southwest (~ 200 degrees) of the measurement station. Penguins were present at the colony for the first half of the campaign, until February 21, 2023 (Pablo J. Perchivale, personal observations), when the last birds departed the breeding site for their wintering grounds. A second colony of Adelie penguins was located on Cockburn Island, ~ 10 km northwest (~ 330 degrees) of the measurement site. Although the Cockburn Island colony has fewer breeding pairs, about 15,721 57 , than the colony located to the south, this colony shares the breeding area with a colony of imperial shags ( Phalacrocorax bransfieldensis ) with approximately 800 breeding pairs 58 . Instrumentation Ammonia mixing ratios were measured using a Quantum Cascade Tunable Infrared Laser Differential Absorption Spectrometer 59 , 60 (QC-TILDAS, Aerodyne Research, Inc). Refer to the supplement for further details of the ammonia QC-TILDAS. Aerosol precursor vapors and cluster chemistry were measured using a chemical ionization mass spectrometer 61 (CIMS, Tofwerk) with a multi-scheme chemical ionization inlet 62 (MION, Karsa Ltd.). The MION inlet was used to cycle between two measurements modes: chemical ionization with NO 3 − ion and ambient ions. The NO 3 − mode was used to measure the concentrations of the neutral condensable vapor species, including sulfuric acid, methanesulfonic acid, and iodic acid. The ambient ion mode was used to determine the chemical composition of the growing clusters during NPF events. The number size distribution of atmospheric ions from 0.75–40 nm was measured using a neutral air ion spectrometer 63 , 64 (NAIS, Airel). Particle number size distributions from 10–800 nm were provided by a differential mobility particle spectrometer 65 . The DMPS system used a Hauke-type differential mobility analyzer (DMA) 66 . A merged size distribution product combining the NAIS and DMPS distributions were used in the relevant calculations of aerosol parameters, where the particle concentrations in the NAIS were scaled down by a factor of 3 to account for overcounting in the particle modes in our data 53 . CCN concentrations were measured using a CCN counter 67 (CCN-100, Droplet Measurement Technologies) with scans at five supersaturation setpoints (0.2, 0.4, 0.6, 0.8, 1.0%). The CCN counter sampled downstream of the DMA in the DMPS system to obtain scans of size resolved CCN concentrations. Aerosol chemistry was measured using a Time-of-Flight Aerosol Chemical Speciation Monitor 68 (ToF-ACSM, Aerodyne Research, Inc.). In-situ cloud droplet number concentrations and size distributions between 0.2–40 µm were measured using a cloud droplet analyzer (CDA, Palas GmbH), located on the roof of the measurement container. The optical sensor in the CDA has been previously described in the literature 69 . An automatic weather station, installed on the measurement container, measured global radiation (pyranometer, CMP11, Kipp & Zonen), ambient temperature and relative humidity (HMP155, Vaisala Ltd.), and wind speed and direction (ultrasonic anemometer, Thies 2D, Thies Clima), as described in Quéléver et al. 8 Calculations of aerosol parameters Particle growth rates between 3–7 nm were calculated from the NAIS size distributions using both the maximum-concentration method and log-normal distribution function method presented in Kulmala et al. 70 The median growth rate was used in the formation rate calculation. Formation rates of atmospheric ions at 1.7 nm (J 1.7 ) were calculated using the number size distributions of negative ions from the NAIS according to Eq. 10 in Kulmala et al. 70 using a particle bin of 1.7–3.1 nm. $$\:{J}_{{d}_{p}}^{-}=\frac{d{N}_{{d}_{p}}^{-}}{dt}+{CoagS}_{{d}_{p}}\bullet\:{N}_{{d}_{p}}^{-}+\frac{GR}{\varDelta\:{d}_{p}}\bullet\:{N}_{{d}_{p}}^{-}+\alpha\:\bullet\:{N}_{{d}_{p}}^{-}\bullet\:{N}_{{<d}_{p}}^{-}-\chi\:\bullet\:{N}_{{d}_{p}}\bullet\:{N}_{{<d}_{p}}^{-}$$ The coagulation sink and condensation sink were determined using equations 4 and 5 in Kulmala et al., 70 respectively. Declarations Acknowledgements This work was supported by the Research Council of Finland project funding via ACFA grant #335844, #335845, and #333397; the Atmosphere and Climate Competence Center (ACCC) Flagship support from the Research Council of Finland (337549, 357902, 359340 for the University of Helsinki and 337552, 357904, 359342 for the Finnish Meteorological Institute); by European Europe (FOCI (Non-CO 2 forcers and their climate, weather, air quality and health impacts, agreement no. 101056783); and the European Union’s Horizon 2020 research and innovation programme under CRiCES (Climate Relevant interactions and feedbacks: the key role of sea ice and Snow in the polar and global climate system) grant agreement No 101003826. We thank Aerodyne Research Inc. for loaning an ammonia instrument, and wish to acknowledge Kenji Lizardo, Carolyn Fialkowski, and Ruth Heckbert for logistical support. We thank Palas GmbH for lending instrumentation, and particularly Ann-Kathrin Gossmann for her assistance in the field deployment. We also wish to thank the on-site support from the Argentinian Servicio Meteorológico Nacional team at the Pabellón Científico, including Daniel Sofiev-Rios, Gabriel Arias, and Facundo Penayo. We also thank the Dirección Nacional del Antartico (DNA). Finally, we acknowledge the logistical support from FINNARP, the Fuerza Aérea Argentina, the Comando Conjunto Antártico (COCOANTAR), and all other support personnel at Marambio station. Author contributions M.B., L.Q., Z.B., S.S., G.M. and F.Q., executed the field campaign. M.B., L.Q., Z.B., B.M., analyzed the data. M.B. wrote the manuscript with L.Q., Z.B., V.K., D.W., M.S., and X.H. B.M, S.H., M.A., D.N., R.R., F.W., S.S., H.T., M.A., L.B., C.X., and A.B. provided insight on the operation, analysis, and interpretation of datasets and instrumentation. P.P. gave insights and observations on penguin/seabird populations. L.Q., G.M., F.Q., M.B., Z.B., S.S., A.V., E.A., M.S., and planned and coordinated the field campaign. E.A. oversees the installation, maintenance, and upkeep of the site instrumentation and infrastructure. D.W., M.S., M.K., and T.P. conceived the idea for the manuscript. All authors commented on and approved of the final version of the manuscript. Ethics declaration The authors declare no competing interests. Materials & Correspondence Matthew Boyer ( [email protected] ) and Mikko Sipilä ( [email protected] ) References Ehn M et al (2014) A large source of low-volatility secondary organic aerosol. Nature 506:476–479 Beck LJ et al (2021) Differing Mechanisms of New Particle Formation at Two Arctic Sites. Geophys Res Lett 48 Merikanto J, Spracklen DV, Mann GW, Pickering SJ, Carslaw KS (2009) Atmospheric Chemistry and Physics Impact of Nucleation on Global CCN. Atmos Chem Phys 9:8601–8616. 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Lett. 48, eGL091963 (2021) Asmi E et al (2018) Primary sources control the variability of aerosol optical properties in the Antarctic Peninsula. Tellus B Chem Phys Meteorol 70:1414571 Perchivale PJ et al (2022) Updated estimate of the breeding population of Adélie penguins (Pygoscelis adeliae) at Penguin Point, Marambio / Seymour Island within the proposed Weddell Sea Marine Protected Area. Preprint at https://doi.org/10.21203/rs.3.rs-2117503/v1 Lynch HJ, LaRue MA (2014) First global census of the Adélie Penguin. Auk 131:457–466 Lynch HJ, Naveen R, Casanovas P (2013) Antarctic Site Inventory breeding bird survey data, 1994–2013. Ecology 94:2653–2653 Ellis RA et al (2010) Characterizing a Quantum Cascade Tunable Infrared Laser Differential Absorption Spectrometer (QC-TILDAS) for measurements of atmospheric ammonia. Atmospheric Meas Tech 3:397–406 Moravek A, Singh S, Pattey E, Pelletier L, Murphy JG (2019) Measurements and quality control of ammonia eddy covariance fluxes: a new strategy for high-frequency attenuation correction. Atmospheric Meas Tech 12:6059–6078 Jokinen T et al (2012) Atmospheric sulphuric acid and neutral cluster measurements using CI-APi-TOF. Atmospheric Chem Phys 12:4117–4125 Rissanen MP, Mikkilä J, Iyer S, Hakala J (2019) Multi-scheme chemical ionization inlet (MION) for fast switching of reagent ion chemistry in atmospheric pressure chemical ionization mass spectrometry (CIMS) applications. Atmospheric Meas Tech 12:6635–6646 Mirme S, Mirme A (2013) The mathematical principles and design of the NAIS – a spectrometer for the measurement of cluster ion and nanometer aerosol size distributions. Atmospheric Meas Tech 6:1061–1071 Manninen HE, Mirme S, Mirme A, Petäjä T, Kulmala M (2016) How to reliably detect molecular clusters and nucleation mode particles with Neutral cluster and Air Ion Spectrometer (NAIS). Atmospheric Meas Tech 9:3577–3605 Aalto P et al (2001) Physical characterization of aerosol particles during nucleation events. 53:344–358 Winklmayr W, Reischl GP, Lindner AO, Berner A (1991) A new electromobility spectrometer for the measurement of aerosol size distributions in the size range from 1 to 1000 nm. J Aerosol Sci 22:289–296 Roberts GC, Nenes AA, Continuous-Flow (2005) Streamwise Thermal-Gradient CCN Chamber for Atmospheric Measurements. Aerosol Sci Technol 39:206–221 Fröhlich R et al (2013) The ToF-ACSM: a portable aerosol chemical speciation monitor with TOFMS detection. Atmospheric Meas Tech 6:3225–3241 Möhler O et al (2021) The Portable Ice Nucleation Experiment (PINE): a new online instrument for laboratory studies and automated long-term field observations of ice-nucleating particles. Atmospheric Meas Tech 14:1143–1166 Kulmala M et al (2012) Measurement of the nucleation of atmospheric aerosol particles. Nat Protoc 7:1651–1667 Additional Declarations There is NO Competing Interest. Supplementary Files ammoniamarambioSIv8.docx Supplementary Information Cite Share Download PDF Status: Published Journal Publication published 22 May, 2025 Read the published version in Communications Earth & Environment → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-5372386","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":385051367,"identity":"336c2d75-b3c8-4148-8206-8662c86ce481","order_by":0,"name":"Matthew 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Inc.","correspondingAuthor":false,"prefix":"","firstName":"Douglas","middleName":"","lastName":"Worsnop","suffix":""},{"id":385051393,"identity":"18670312-e98a-4f00-b5f5-0d8a45a86054","order_by":26,"name":"Mikko SIPILA","email":"","orcid":"","institution":"University of Helsinki","correspondingAuthor":false,"prefix":"","firstName":"Mikko","middleName":"","lastName":"SIPILA","suffix":""}],"badges":[],"createdAt":"2024-11-01 09:51:48","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5372386/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5372386/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s43247-025-02312-2","type":"published","date":"2025-05-22T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":70926101,"identity":"3f560a6a-7db4-4914-91ae-8142fbb6ecad","added_by":"auto","created_at":"2024-12-09 09:09:31","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":1682468,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSources of ammonia at Marambio Station, Antarctica. A) \u003c/strong\u003eA map showing the location of the measurement container with respect to Marambio Station. \u003cstrong\u003eB)\u003c/strong\u003e \u0026nbsp;A map showing the relevant points of interest for ammonia on Seymour Island. \u003cstrong\u003eC)\u003c/strong\u003e A wind rose showing the ammonia mixing ratios between 0.01 – 1 ppb according to wind direction and wind speed. Note that mixing ratio axis is zoomed to a maximum of 1 ppb to show further details in the lower range of mixing ratios. \u003cstrong\u003eD) \u003c/strong\u003eThe frequency of observed NH3 mixing ratios.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-5372386/v1/cd0f6915cb1eafe58112f53c.png"},{"id":70926050,"identity":"dcc8ea7c-0cde-48dd-8dfd-245521e529af","added_by":"auto","created_at":"2024-12-09 09:09:24","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":540031,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAmmonia saturation and enhancement in particle formation rates. A)\u003c/strong\u003e Measured negative ion formation rates, J1.7, are presented against sulfuric acid concentration during NPF events.\u0026nbsp; Ammonia mixing ratios above and below 0.1 ppb are shown with red triangles and black crosses, respectively, and the red and black dashed lines are drawn to guide the eyes for these two groups. \u003cstrong\u003eB)\u003c/strong\u003e The frequency of observed particle formation rates during NPF events, where the corresponding ammonia mixing ratios above and below 0.1 ppb are shown by the red (above) and black (below) bars. \u003cstrong\u003eC)\u003c/strong\u003e The frequency distribution of SA concentrations with the range of ammonia mixing ratios show by the red and black bars.\u003cstrong\u003e D) \u003c/strong\u003eA scatter plot of SA and ammonia measurements during the campaign, where the color bar represents the calculated formation rate of negative ions at 1.7 nm (J1.7).\u003c/p\u003e","description":"","filename":"floatimage21.png","url":"https://assets-eu.researchsquare.com/files/rs-5372386/v1/3b2985e8da3b8c8b94ba9644.png"},{"id":70926871,"identity":"2e90203f-834a-4127-acd8-9535b99c20b5","added_by":"auto","created_at":"2024-12-09 09:17:30","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":415418,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eThe multicomponent mechanism of NPF. A)\u003c/strong\u003e A representative mass defect plot showing the chemical composition of the negatively charge clusters during NPF. The colored circles indicate clusters of known composition, where the size corresponds to their relative signal magnitude in counts per second. The data shown are the average signal intensities measured over a NPF event. \u003cstrong\u003eB)\u003c/strong\u003e Ammonia mixing ratios and the signal intensity of DMA. The color bar shows the measured particle formation rates during the campaign. \u003cstrong\u003eC)\u003c/strong\u003e A comparison of the measured particle formation rates, J\u003csub\u003e1.7\u003c/sub\u003e, compared to formation rates predicted using the Dunne et al.\u003csup\u003e35\u003c/sup\u003e parameterization of the sulfuric acid-ammonia nucleation mechanism. The comparison is presented as the ratio of measured/parameterized formation rates against ammonia mixing ratios, where the color bar indicates the signal intensity of DMA in counts per second. The presented data only includes periods identified as NPF events. \u003cstrong\u003eD) \u003c/strong\u003eA comparison between our measurements and CLOUD chamber experiment observations of the nucleation mechanism with DMA, ammonia, and sulfuric acid. The colored lines represent the expected particle formation rates at various concentrations of sulfuric acid, DMA, and ammonia from Almeida et al.\u003csup\u003e22\u003c/sup\u003e, and the points show the measured formation rates compared according to sulfuric acid concentrations. The color bar indicates the corresponding ammonia mixing ratios.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-5372386/v1/5b8c688fe47df30a27d155e9.png"},{"id":70926091,"identity":"a234b00c-87e2-4425-8c51-20fb30e028cf","added_by":"auto","created_at":"2024-12-09 09:09:30","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":478172,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCase study: the connection between NPF, CCN, and clouds in our measurements. \u003c/strong\u003e\u0026nbsp;The timeseries of various atmospheric measurements from a case study on February 01, 2023 during which regional particle formation, growth, and subsequent cloud formation were observed. The dashed gray lines indicate the period while sampling in fog. \u003cstrong\u003eA)\u003c/strong\u003e Relevant meteorological conditions, including ambient temperature (purple line), dew point temperature (orange line), and wind direction (green line), during the case study. \u003cstrong\u003eB)\u003c/strong\u003e the number size distribution of particles/droplets \u0026gt; 0.7 microns and CCN concentrations from 5 different supersaturations (0.2 %: green line, 0.4%: red line, 0.6%: blue line, 0.8%: black line, 1.0%: white line). \u003cstrong\u003eC)\u003c/strong\u003e The particle number size distribution \u0026gt; 3 nm and the particle number concentrations (red line). \u003cstrong\u003eD) \u003c/strong\u003eThe mixing ratio of ammonia (NH\u003csub\u003e3\u003c/sub\u003e; green line), and the concentrations of sulfuric acid (SA; red line), methanesulfonic acid (MSA; blue Line), and iodic acid (IA; black line).\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-5372386/v1/1ec910636e4adaa0b3b6846c.png"},{"id":83328819,"identity":"bdaa2065-fd1e-47a6-9ee0-cef480d325c1","added_by":"auto","created_at":"2025-05-23 07:09:53","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3597963,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5372386/v1/8272f914-2bb6-47f2-82b5-36846950ac55.pdf"},{"id":70926110,"identity":"d937d882-5a0c-4c7a-b3d7-d7208658e6fa","added_by":"auto","created_at":"2024-12-09 09:09:34","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1958445,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"ammoniamarambioSIv8.docx","url":"https://assets-eu.researchsquare.com/files/rs-5372386/v1/184543b5eb33e048e600b3cd.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Penguin guano: an important source of climate-relevant aerosol in Antarctica","fulltext":[{"header":"Main","content":"\u003cp\u003eBiological processes influence atmospheric composition and climate through a variety of mechanisms. For example, living organisms emit vapors that moderate cloud properties via production of aerosol and cloud condensation nuclei (CCN) or ice nucleating particles (INP), which subsequently impact Earth\u0026rsquo;s surface radiative balance, precipitation, and weather. Changes in the biology of an ecosystem can therefore impact climate.\u003c/p\u003e \u003cp\u003eVegetation in continental regions emits volatile organic vapors which are subsequently converted to secondary organic aerosol\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. In pristine marine and polar environments, however, aerosol and CCN production is connected to marine phytoplankton dimethyl sulfide (DMS) and iodine emissions via new particle formation (NPF)\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIn the remote Southern Ocean and Antarctica, the strength of NPF events has considerable relevance for the climate. These pristine locations typically have low background particle concentrations compared to regions with anthropogenic activities or vegetation. Coincidentally, the chemical mechanism of NPF remains elusive in remote and polar regions, yet NPF is estimated to contribute over 50% of CCN in the atmosphere globally\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e, and potentially more in such environments, including over the Antarctic continent\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e. Interactions of aerosols and clouds, especially the sources and concentrations of CCN in pristine, preindustrial-like environments, are a large source of uncertainty in our understanding of climate change\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. Climate-relevant cloud properties, such as cloud brightness and lifetime, are very sensitive to the concentration of CCN in such conditions\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e. Therefore, the gases that contribute to NPF events, and their ability to enhance particle formation rates, are critical to understanding the climate response in these locations.\u003c/p\u003e \u003cp\u003eDirect observations of DMS-derived sulfuric acid (H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e) aerosol formation in the polar regions indicate that ammonia (NH\u003csub\u003e3\u003c/sub\u003e) stabilizes sulfuric acid clusters during NPF events\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e,\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e. Seabirds are a known source of atmospheric ammonia in remote regions\u003csup\u003e\u003cspan additionalcitationids=\"CR10 CR11\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e, and studies have speculated that penguins/seabirds impact aerosol formation and cloud processes\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e,\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e,\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e,\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e. Even though laboratory experiments have shown that ammonia can enhance sulfuric acid-induced particle formation by several orders of magnitude\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e, there are few measurements of ammonia concentrations in the remote ambient atmosphere with high enough sensitivity and time resolution coupled with comprehensive measurements to resolve the mechanism of NPF.\u003c/p\u003e \u003cp\u003eIodic acid (HIO\u003csub\u003e3\u003c/sub\u003e) has been shown to contribute to NPF together with iodous acid (HIO\u003csub\u003e2\u003c/sub\u003e)\u003csup\u003e\u003cspan additionalcitationids=\"CR17\" citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e in the absence of sulfuric acid and ammonia in sea ice covered regions in the Arctic during spring and autumn. While these particles may contribute to CCN\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e, other observations suggest that they rarely grow to climate-relevant CCN sizes\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. A recent laboratory study has also proposed that NPF may occur between iodine oxoacids and sulfuric acid without ammonia in remote marine and polar environments, and the presence of approximately 30 to 260 ppt of ammonia can further enhance aerosol nucleation rates\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e. Their conclusions assume that there is at maximum a few hundred ppt of ammonia in the remote polar atmosphere to participate, based on limited ambient data from these environments. Similarly, another study suggested that sulfuric acid and amines, sourced from sea-ice-covered regions, dominate particle formation around the Antarctic Peninsula\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e. Alkylamines, such as dimethyl amine (DMA, (CH\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eNH\u003csub\u003e3\u003c/sub\u003e) are known to nucleate rapidly with sulfuric acid\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e,\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e, yielding formation rates up to 10000 times faster than sulfuric acid-ammonia NPF. These discrepancies show that the chemical mechanism of NPF in this environment remains poorly constrained, where direct measurement of ammonia and amine concentrations comprise a key knowledge gap.\u003c/p\u003e \u003cp\u003eIn general, ammonia is one of the most under-represented gases in atmospheric measurements, especially online measurements at high sensitivity and in remote regions where ambient ammonia concentrations are estimated to be low (i.e., lower than 100 ppt). However, without ammonia measurements, we are missing critical observations which limits our understanding of climate-relevant aerosol formation processes. The lack of data is particularly pronounced in our ability to constrain new particle formation (NPF) in remote and polar environments.\u003c/p\u003e \u003cp\u003eCurrently, Antarctic ecosystems are stressed. The region is experiencing accelerated changes due to warming. Sea ice extent is declining\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e, and ice shelfs are shrinking\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e. These changes impact the biology in the Southern Ocean\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e, as well as penguin and seabird colonies, which will result in changes to ecosystem-atmosphere exchanges, and ultimately the climate of the region, with subsequent effects on global climate. Some species of penguins are already threatened due to environmental changes\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e. Therefore, it is imperative to understand the ecosystem-atmosphere interactions that contribute to climate relevant processes \u0026ndash; especially now, as environmental conditions in coastal Antarctica and the Southern Ocean are rapidly changing.\u003c/p\u003e \u003cp\u003eIn this work, we analyze the chemical mechanism of NPF events on the Antarctic Peninsula, featuring highly sensitive online measurements of ambient ammonia concentrations as well as comprehensive measurements of gases and particles to investigate aerosol processes connecting NPF with cloud formation. We show that penguins are a significant source of ammonia that enhances NPF with sulfuric acid sourced from marine phytoplankton in coastal Antarctica, whereas ammonia contributions from the open ocean were negligible. We present evidence that these newly formed particles can grow and contribute to CCN concentrations and cloud/fog formation. This demonstrates that penguins/sea birds play a key role in particle formation and may represent an important climate feedback as their habitat changes.\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003eOur study combines measurements of aerosol precursor vapors concentrations, ammonia mixing ratios, the chemistry of charged nucleating clusters, aerosol particle number concentrations and size distributions, aerosol chemical composition, CCN concentrations, and in situ cloud droplet distributions from Marambio station on the Antarctic peninsula (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA and B) to investigate the connection between gases, particles, and clouds. In our measurements, we observed ammonia mixing ratios up to 13.5 ppb when winds came from the direction of nearby penguin colonies, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Figure S1. In contrast, from other wind directions (including the open ocean), ammonia mixing ratios were low. Excluding the influence of local pollution from Marambio station (19.4% occurrence), 42.8% of the measured ammonia mixing ratios were below the detection limit (10.5\u0026thinsp;\u0026plusmn;\u0026thinsp;26.8 ppt), 36.2% were between 10.5\u0026ndash;40 ppt, 9.8% were between 40\u0026ndash;100 ppt, and 11.2% were greater than 100 ppt (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eD).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eNotably, the penguins in the nearby colony left their breeding site in the middle of our measurement campaign as part of their annual migration. For over a month after the penguins left, concentrations of ammonia remained elevated, exceeding 1 ppb (Figure S2) from the favorable wind direction. Therefore, the penguin guano \u0026ldquo;fertilized\u0026rdquo; soil, also known as ornithogenic soil\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e, continued to be a strong source of ammonia long after they left the site. Until now, this process has largely only been evaluated in laboratory measurements\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e, models\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e,\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e,\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e, or offline methods\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e. Our data demonstrates that there are local hotspots around the coast of Antarctica that can yield ammonia concentrations similar in magnitude to agricultural plots\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e,\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e during summer. These hotspots correspond to the location of penguin/bird breeding settlements/colonies, consistent with previous studies; due to their annual migration patterns, these hotspots may cover a large extent of coastal Antarctica\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eOur results demonstrate that ammonia is present in the Antarctic environment at sufficient mixing ratios to initiate NPF with sulfuric acid. In fact, we observed NPF almost exclusively when winds were from the direction/wind sector of local penguin colonies, leading to elevated ammonia mixing ratios. Particle formation rates (J\u003csub\u003e1.7\u003c/sub\u003e) during these NPF events depended primarily on sulfuric acid concentrations. In addition, observations of aerosol precursor vapors, the chemical composition of atmospheric clusters, and online measurement of ammonia show clear participation of ammonia and enhancement of particle formation rates when ammonia mixing ratios exceed\u0026thinsp;~\u0026thinsp;100 ppt (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). We did not uniformly observe continued enhancement as ammonia mixing ratios increase above ~\u0026thinsp;100 ppt, indicating that particle formation with respect to ammonia begins to saturate at this level, similar to laboratory-derived estimates of ammonia saturation in sulfuric acid-ammonia clustering studies\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e,\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAdditionally, we compared our observations to a formation rate parameterization that considers sulfuric acid and ammonia concentrations\u003csup\u003e\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. The measured formation rates are consistently between 1\u0026ndash;4 orders of magnitude higher than the parameterization (median ratio\u0026thinsp;=\u0026thinsp;72). It is important to note that there are several possible reasons for discrepancies, particularly with respect to field observations, including errors inherent to the measurements and calculation of formation rates and a factor of two uncertainty in the calibration and quantification of sulfuric acid concentrations. Despite these uncertainties, we can attribute the higher formation rates in our observations to the participation of other gases that can further enhance particle formation rates of the sulfuric acid-ammonia mechanism.\u003c/p\u003e \u003cp\u003eWhile the chemical composition of charged clusters during NPF is dominated by sulfuric acid and ammonia clusters (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eA), there are additional clusters present, indicating a multicomponent particle formation mechanism. These include sulfuric acid and DMA clusters, which are known to yield particle formation rates between 100\u0026ndash;10000 times faster than sulfuric acid and ammonia\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. Previously, DMA-containing clusters were observed to dominate at DMA mixing ratios of 4 ppt in the presence of ammonia exceeding 1 ppb\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e. Here, instead, sulfuric acid and ammonia clusters are the dominant growing clusters, suggesting that DMA is present at very low concentrations \u0026ndash; enough to stabilize the initial stages of cluster formation and enhance sulfuric acid-ammonia particle formation rates by ~\u0026thinsp;2\u0026ndash;4 orders of magnitude compared to pure sulfuric acid-ammonia nucleation (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eC). These conclusions agree with the findings of Qu\u0026eacute;l\u0026eacute;ver et al.\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIt is worth noting that we cannot determine the gas phase DMA concentration from cluster measurements, but the detection of DMA in atmospheric clusters in the APi-ToF, which is believed to be the most sensitive detector for the presence of atmospheric amines, does confirm the presence of DMA\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. We can use the ion counts of clusters containing DMA (in counts per second) to estimate changes in available DMA (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eB), but this is qualitative; a direct measure of DMA should be prioritized in future measurements. Despite this limitation on the quantification of DMA, we conclude that DMA does indeed play a role in enhancing formation rates. By comparing with previous chamber measurements\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e, we can estimate that DMA mixing ratios are ~\u0026thinsp;1 ppt or lower (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eD). Although we cannot offer strong comments on the sources of DMA without direct measurements, wind rose directions with the highest ion counts of DMA in clusters are similar to those associated with high ammonia mixing ratios (Figure S1). Penguin guano has also been identified to produce amines in guano-affected soils\u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e. Therefore, it is plausible that penguin colonies are a source of DMA.\u003c/p\u003e \u003cp\u003eRecent observations suggest that clustering between sulfuric acid and DMA is the primary mechanism of particle formation around coastal Antarctica, where DMA is sourced from sea-ice-covered regions\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e. Interestingly, Brean et al.\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e did not observe sulfuric acid-ammonia clusters in their measurements. In contrast, our observations show ammonia dominated clustering with sulfuric acid instead of amine-mediated cluster growth. In comparison to Brean et al.\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e, NPF occurred more frequently during our study and produced higher concentrations of new particles. We observed NPF on 34% of our measurement days, resulting in enhanced aerosol concentrations at times exceeding 15,000 #/cm\u003csup\u003e3\u003c/sup\u003e, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eC. Therefore, we propose that while amines may enhance NPF in parts of the Southern Ocean or coastal Antarctica, the multicomponent formation mechanism with sulfuric acid, DMA, and ammonia has a stronger impact on particle concentrations, and subsequently the climate-relevant aerosol formation in these regions.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eObservations of the atmospheric cluster composition also show participation of iodine oxoacids (HIO\u003csub\u003e2\u003c/sub\u003e and HIO\u003csub\u003e3\u003c/sub\u003e) in some cases (Figure S3). Although it should be noted that ammonia and amines had a more pronounced role in particle formation in our measurements, as the sulfuric acid-ammonia clusters dominated ionic cluster chemistry, the multicomponent system with ammonia, sulfur, and iodine compounds is a valuable finding. It is important to consider that our measurements only cover the summer period when conditions favor the strongest photochemical production of sulfur compounds from DMS and when penguin breeding colonies are present, whereas the production of iodine oxoacids is expected to be stronger during seasonal transitions in spring and fall\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. During seasonal transitions, particle formation may show stronger enhancement from iodine oxoacids; however, in situ observations of the chemical mechanism of NPF during seasonal transitions in Antarctica are lacking, and therefore, it calls for future dedicated studies.\u003c/p\u003e \u003cp\u003eNPF in Antarctica has been observed to contribute to background CCN concentrations\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e. Our measurements also demonstrate the connection between NPF, CCN formation, and fog/cloud droplet activation. From a case study on February 1, 2023, we had a very strong NPF and growth event with ammonia from the penguin colonies, resulting in very high concentrations of particles (\u0026gt;\u0026thinsp;16,000 #\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e above 10 nm), as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. These particles grew over the next 6 hours up to ~\u0026thinsp;30 nm, followed by a period of fog. While sampling in the fog, we measured a reduction in nucleation mode particles from scavenging and an increase in larger particles from cloud droplet residuals, which likely result from rapid growth of particles due to cloud processing\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e. Activated particles are present at all supersaturations in the CCN counter measurements, and the particle composition was dominated by ammonium sulfate. After the 1-hour period in fog, the fog lifted such that sampling occurred below the fog/cloud layer, after which the same mode of newly formed particles was observed again. The persistence in the newly formed particle mode before and after the fog signifies strong regional NPF during which these particles influenced fog microphysics by contributing to the fog/cloud droplet population. The chemical composition of the cloud droplet residuals was composed almost solely of ammonia sulfate, which confirms the participation of ammonia sourced from the penguins. Further details of this case study are discussed in the supplement.\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eBroader climate implications\u003c/h2\u003e \u003cp\u003eRecent observations suggest that aerosol precursor gases in Antarctica are closely linked to regional ecosystem processes\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e,\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e. Key sulfur compounds originate from DMS emissions due to marine phytoplankton in the Southern Ocean around coastal Antarctica, which has the one of highest DMS concentrations on the planet during summer\u003csup\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e,\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e. Iodine compounds are also sourced from processes involving ocean biology and heterogeneous chemistry on ice and snow surfaces\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. Now, we quantify the contribution of ammonia from penguins/sea birds at mixing ratios high enough to initiate and enhance NPF with sulfuric acid from DMS. Our measurements demonstrate that penguin colonies form strong point sources of particles in a region where cloud formation can be limited by the availability of CCN. Hence, the radiative properties of clouds, a climate relevant process, is affected by penguins/seabirds. Given that penguin colonies span the coast of Antarctica\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e and that they leave guano/nutrient-rich soils that continue to emit ammonia after migration, we estimate that penguins provide a substantial source of ammonia, and particles, across the entire coastal Antarctic region\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eWhile the lifetime of gaseous ammonia in the troposphere is estimated to be short, ranging from several hours to ~\u0026thinsp;1 day\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e,\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e, the lifetime of the particles that result from NPF events have longer lifetimes up to several days\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e. These newly formed particles could be further transported over parts of the Southern Ocean and continental Antarctica on this timescale, which could subsequently affect aerosol and CCN concentrations over the larger Antarctic region, including further inland\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e where aerosol sources are limited\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e. This suggests that coastal penguin/bird colonies could also comprise an important source of aerosol away from the coast.\u003c/p\u003e \u003cp\u003eIt is already understood that widespread loss of sea ice extent threatens the habitat, food sources\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e, and breeding behavior\u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e of most penguin species that inhabit Antarctica. Consequently, some Antarctic penguin populations are already declining\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e, and some species could be nearly extinct by the end of the 21st century\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e. We provide evidence that declining penguin populations could cause a positive climate warming feedback in the summertime Antarctic atmosphere, as proposed by a modelling study of seabird emissions in the Arctic region\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eFurthermore, our results demonstrate a multicomponent nucleation mechanism between sulfuric acid and ammonia over broad concentration ranges of both these precursors in ambient conditions and in the absence of anthropogenic influence or vegetation. NPF events rarely occur in the remote marine boundary layer, including over the Southern Ocean, despite the presence of condensable vapors from DMS oxidation\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e. Studies in other environments also suggest that NPF in the ambient atmosphere occurs more readily when ammonia is available\u003csup\u003e\u003cspan additionalcitationids=\"CR51\" citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e, or that ammonia significantly enhances NPF\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e. We show that ammonia from penguins stabilizes sulfuric acid clusters from DMS oxidation over Antarctica and, together with low level DMA, yields high particle formation rates that can grow to CCN-active particles. We also identify that the Southern Ocean is not a significant source of gaseous ammonia, at least in its current state\u003csup\u003e\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e, which offers a possible explanation to the limited observations of NPF events in the remote marine boundary layer. Therefore, we demonstrate that the ammonia budget is critical to understand the contribution of DMS to NPF in coastal Antarctica, which may also have global atmospheric implications, including in the past, present, and future. The potential contribution of iodine oxoacids may also be important in this context, as they may serve as the \u0026ldquo;base\u0026rdquo; to initiate sulfuric acid nucleation at low ammonia concentrations during seasonal transitions. Fundamentally, the prevalence of these gases over Antarctica depends upon the interplay of sea ice, phytoplankton metabolism, and penguin/sea bird populations\u0026mdash;all of which are subject to change. The complexity of these processes requires continued, dedicated experimentation and investigation to deconvolve.\u003c/p\u003e \u003c/div\u003e"},{"header":"Methods","content":"\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eMeasurement site\u003c/h2\u003e \u003cp\u003eAll measurements reported in this work were collected between January 10 \u0026ndash; March 20, 2023 in the atmospheric observatory located\u0026thinsp;~\u0026thinsp;300 m southwest of Marambio Station, Antarctica (64\u0026deg;14.68\u0026rsquo; S, 56\u0026deg;37.88\u0026rsquo; W; Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA and B) at an altitude of 198 m above sea level. Marambio station is located on Seymour Island near the northernmost tip of the Antarctic Peninsula and has previously been described in Asmi et al.\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e (2018) and Qu\u0026eacute;l\u0026eacute;ver et al. (2022).\u003c/p\u003e \u003cp\u003eVarious features of the measurement site near Marambio station are important for the interpretation of our measurements. Logistical activities at the station contributed a local source of pollution that contaminated the ambient sampling when wind directions originated from between 0\u0026ndash;90 degrees and were excluded from our analysis. A large colony of Adelie penguins (\u003cem\u003ePygoscelis adeliae\u003c/em\u003e) with approximately 30,000 breeding pairs\u003csup\u003e\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e was located\u0026thinsp;~\u0026thinsp;8 km southwest (~\u0026thinsp;200 degrees) of the measurement station. Penguins were present at the colony for the first half of the campaign, until February 21, 2023 (Pablo J. Perchivale, personal observations), when the last birds departed the breeding site for their wintering grounds. A second colony of Adelie penguins was located on Cockburn Island, ~\u0026thinsp;10 km northwest (~\u0026thinsp;330 degrees) of the measurement site. Although the Cockburn Island colony has fewer breeding pairs, about 15,721\u003csup\u003e57\u003c/sup\u003e, than the colony located to the south, this colony shares the breeding area with a colony of imperial shags (\u003cem\u003ePhalacrocorax bransfieldensis\u003c/em\u003e) with approximately 800 breeding pairs\u003csup\u003e\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eInstrumentation\u003c/h3\u003e\n\u003cp\u003eAmmonia mixing ratios were measured using a Quantum Cascade Tunable Infrared Laser Differential Absorption Spectrometer\u003csup\u003e\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e,\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e\u003c/sup\u003e (QC-TILDAS, Aerodyne Research, Inc). Refer to the supplement for further details of the ammonia QC-TILDAS.\u003c/p\u003e \u003cp\u003eAerosol precursor vapors and cluster chemistry were measured using a chemical ionization mass spectrometer\u003csup\u003e\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e\u003c/sup\u003e (CIMS, Tofwerk) with a multi-scheme chemical ionization inlet\u003csup\u003e\u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e62\u003c/span\u003e\u003c/sup\u003e (MION, Karsa Ltd.). The MION inlet was used to cycle between two measurements modes: chemical ionization with NO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e ion and ambient ions. The NO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e mode was used to measure the concentrations of the neutral condensable vapor species, including sulfuric acid, methanesulfonic acid, and iodic acid. The ambient ion mode was used to determine the chemical composition of the growing clusters during NPF events.\u003c/p\u003e \u003cp\u003eThe number size distribution of atmospheric ions from 0.75\u0026ndash;40 nm was measured using a neutral air ion spectrometer\u003csup\u003e\u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e63\u003c/span\u003e,\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e\u003c/sup\u003e (NAIS, Airel). Particle number size distributions from 10\u0026ndash;800 nm were provided by a differential mobility particle spectrometer\u003csup\u003e\u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e65\u003c/span\u003e\u003c/sup\u003e. The DMPS system used a Hauke-type differential mobility analyzer (DMA)\u003csup\u003e\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e\u003c/sup\u003e. A merged size distribution product combining the NAIS and DMPS distributions were used in the relevant calculations of aerosol parameters, where the particle concentrations in the NAIS were scaled down by a factor of 3 to account for overcounting in the particle modes in our data\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eCCN concentrations were measured using a CCN counter\u003csup\u003e\u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e67\u003c/span\u003e\u003c/sup\u003e (CCN-100, Droplet Measurement Technologies) with scans at five supersaturation setpoints (0.2, 0.4, 0.6, 0.8, 1.0%). The CCN counter sampled downstream of the DMA in the DMPS system to obtain scans of size resolved CCN concentrations.\u003c/p\u003e \u003cp\u003eAerosol chemistry was measured using a Time-of-Flight Aerosol Chemical Speciation Monitor\u003csup\u003e\u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e68\u003c/span\u003e\u003c/sup\u003e (ToF-ACSM, Aerodyne Research, Inc.).\u003c/p\u003e \u003cp\u003eIn-situ cloud droplet number concentrations and size distributions between 0.2\u0026ndash;40 \u0026micro;m were measured using a cloud droplet analyzer (CDA, Palas GmbH), located on the roof of the measurement container. The optical sensor in the CDA has been previously described in the literature\u003csup\u003e\u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e69\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eAn automatic weather station, installed on the measurement container, measured global radiation (pyranometer, CMP11, Kipp \u0026amp; Zonen), ambient temperature and relative humidity (HMP155, Vaisala Ltd.), and wind speed and direction (ultrasonic anemometer, Thies 2D, Thies Clima), as described in Qu\u0026eacute;l\u0026eacute;ver et al.\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n\u003ch3\u003eCalculations of aerosol parameters\u003c/h3\u003e\n\u003cp\u003eParticle growth rates between 3\u0026ndash;7 nm were calculated from the NAIS size distributions using both the maximum-concentration method and log-normal distribution function method presented in Kulmala et al.\u003csup\u003e\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e\u003c/sup\u003e The median growth rate was used in the formation rate calculation.\u003c/p\u003e \u003cp\u003eFormation rates of atmospheric ions at 1.7 nm (J\u003csub\u003e1.7\u003c/sub\u003e) were calculated using the number size distributions of negative ions from the NAIS according to Eq.\u0026nbsp;10 in Kulmala et al.\u003csup\u003e\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e\u003c/sup\u003e using a particle bin of 1.7\u0026ndash;3.1 nm.\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:{J}_{{d}_{p}}^{-}=\\frac{d{N}_{{d}_{p}}^{-}}{dt}+{CoagS}_{{d}_{p}}\\bullet\\:{N}_{{d}_{p}}^{-}+\\frac{GR}{\\varDelta\\:{d}_{p}}\\bullet\\:{N}_{{d}_{p}}^{-}+\\alpha\\:\\bullet\\:{N}_{{d}_{p}}^{-}\\bullet\\:{N}_{{\u0026lt;d}_{p}}^{-}-\\chi\\:\\bullet\\:{N}_{{d}_{p}}\\bullet\\:{N}_{{\u0026lt;d}_{p}}^{-}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eThe coagulation sink and condensation sink were determined using equations 4 and 5 in Kulmala et al.,\u003csup\u003e\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e\u003c/sup\u003e respectively.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the Research Council of Finland project funding via ACFA grant #335844, \u0026nbsp;#335845, and #333397; the Atmosphere and Climate Competence Center (ACCC) Flagship support from the Research Council of Finland (337549, 357902, 359340 for the University of Helsinki and 337552, 357904, 359342 for the Finnish Meteorological Institute); by European Europe (FOCI (Non-CO\u003csub\u003e2\u003c/sub\u003e forcers and their climate, weather, air quality and health impacts, agreement no. 101056783); and the European Union\u0026rsquo;s Horizon 2020 research and innovation programme under CRiCES (Climate Relevant interactions and feedbacks: the key role of sea ice and Snow in the polar and global climate system) grant agreement No 101003826. We thank Aerodyne Research Inc. for loaning an ammonia instrument, and wish to acknowledge Kenji Lizardo, Carolyn Fialkowski, and Ruth Heckbert for logistical support. We thank Palas GmbH for lending instrumentation, and particularly Ann-Kathrin Gossmann for her assistance in the field deployment. We also wish to thank the on-site support from the Argentinian Servicio Meteorol\u0026oacute;gico Nacional team at the Pabell\u0026oacute;n Cient\u0026iacute;fico, including Daniel Sofiev-Rios, Gabriel Arias, and Facundo Penayo. We also thank the Direcci\u0026oacute;n Nacional del Antartico (DNA). Finally, we acknowledge the logistical support from FINNARP, the Fuerza A\u0026eacute;rea Argentina, the Comando Conjunto Ant\u0026aacute;rtico (COCOANTAR), and all other support personnel at Marambio station.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eM.B., L.Q., Z.B., S.S., G.M. and F.Q., executed the field campaign.\u003c/p\u003e\n\u003cp\u003eM.B., L.Q., Z.B., B.M., analyzed the data.\u003c/p\u003e\n\u003cp\u003eM.B. wrote the manuscript with L.Q., Z.B., V.K., D.W., M.S., and X.H.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eB.M, S.H., M.A., D.N., R.R., F.W., S.S., H.T., M.A., L.B., C.X., and A.B. provided insight on the operation, analysis, and interpretation of datasets and instrumentation.\u003c/p\u003e\n\u003cp\u003eP.P. gave insights and observations on penguin/seabird populations.\u003c/p\u003e\n\u003cp\u003eL.Q., G.M., F.Q., M.B., Z.B., S.S., A.V., E.A., M.S., and planned and coordinated the field campaign.\u003c/p\u003e\n\u003cp\u003eE.A. oversees the installation, maintenance, and upkeep of the site instrumentation and infrastructure.\u003c/p\u003e\n\u003cp\u003eD.W., M.S., M.K., and T.P. conceived the idea for the manuscript.\u003c/p\u003e\n\u003cp\u003eAll authors commented on and approved of the final version of the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics declaration\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMaterials \u0026amp; Correspondence\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eMatthew Boyer (
[email protected]) and Mikko Sipil\u0026auml; (
[email protected])\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eEhn M et al (2014) A large source of low-volatility secondary organic aerosol. Nature 506:476\u0026ndash;479\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBeck LJ et al (2021) Differing Mechanisms of New Particle Formation at Two Arctic Sites. Geophys Res Lett 48\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMerikanto J, Spracklen DV, Mann GW, Pickering SJ, Carslaw KS (2009) Atmospheric Chemistry and Physics Impact of Nucleation on Global CCN. 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Earth Syst Sci Data 14:2963\u0026ndash;2987\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAdams PJ, Seinfeld JH, Koch DM (1999) Global concentrations of tropospheric sulfate, nitrate, and ammonium aerosol simulated in a general circulation model. J Geophys Res Atmos 104:13791\u0026ndash;13823\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePye HOT et al (2009) Effect of changes in climate and emissions on future sulfate-nitrate-ammonium aerosol levels in the United States. J Geophys Res Atmos 114\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKyr\u0026ouml; E-M et al (2013) Antarctic new particle formation from continental biogenic precursors. Atmospheric Chem Phys 13:3527\u0026ndash;3546\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTrathan PN et al (2020) The emperor penguin - Vulnerable to projected rates of warming and sea ice loss. 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Nat Protoc 7:1651\u0026ndash;1667\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"
[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-5372386/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5372386/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eGaseous ammonia, while influential in atmospheric processes, is critically underrepresented in atmospheric measurements. This limits our understanding of key climate-relevant processes, such as new particle formation, particularly in remote regions. Here, we present highly sensitive, online observations of gaseous ammonia from a coastal site in Antarctica, which allows us to constrain the mechanism of new particle formation in this region in unprecedented detail. Our observations show that penguin colonies are a large source of ammonia in coastal Antarctica, whereas ammonia originating from the Southern Ocean is, in comparison, negligible. In conjunction with sulfur compounds sourced from oceanic microbiology, ammonia initiates new particle formation and is an important source of cloud condensation nuclei. Dimethyl amine, likely originating from penguin guano, also participates in the initial steps of particle formation, effectively boosting particle formation rates up to 10000 times. These findings emphasize the importance of local fauna (penguin/bird colonies and oceanic phytoplankton/bacteria) on climate-relevant aerosol processes in coastal Antarctica. This demonstrates an important connection between ecosystem and atmospheric processes that impact the Antarctic climate, which is crucial given the current rate of environmental changes in the region.\u003c/p\u003e","manuscriptTitle":"Penguin guano: an important source of climate-relevant aerosol in Antarctica","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-12-09 09:08:48","doi":"10.21203/rs.3.rs-5372386/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"
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