Recent research in atmospheric chemistry suggested that gaseous amines may rapidly react with the acidic components in the aerosol to be incorporated in the particle phase. However, laboratory experiments suggested that these heterogeneous processes may be sensitive to the reaction conditions, such as relative humidity (RH), the initial aerosol acidity and the initial concentration of gaseous ammonia which is ubiquitous in the atmosphere. We studied the heterogenous reactions between several amines and ammonium sulfate using a series of thermodynamic simulations under varying initial conditions, including RH, particle-phase acidity and gaseous amine and ammonia concentrations. Several distinctively different trends in the particle-phase ammonium, amines and water content were observed, depending significantly on the particle-phase acidity and the initial amine to ammonia mole ratio. One notable observation was that alkylamines may facilitate the water uptake of ammonium sulfate even in the presence of 1000 times more ammonia gas. Such change in aerosol water content may alter the surface tension, uptake coefficient and could formation properties of aerosol and influence the radiative forcing of the particles.
more »
« less
Modelling the effects of atmospheric alkylamines on the properties of sea salt aerosols using the extended aerosols and inorganics model (E-AIM)
Sea salt aerosols contribute significantly to the mass loading of ambient aerosol, which may serve as cloud condensation nuclei and can contribute to light scattering in the atmosphere. Two major chemical components commonly found in sea salts are ammonium sulfate (AS) and sodium chloride (NaCl). It has been shown that alkylamines, derivatives of ammonia, can react with ammonium salts in the particle-phase to displace ammonia and likely change the particle properties. This study investigated the effects of atmospheric alkylamines on the composition and properties of sea salt aerosols using a chemical system of methylamine (MA, as a proxy of alkylamines), AS and NaCl (as a proxy of sea salt aerosol). The concentrations of ammonia and MA in aqueous/gas phases at the thermodynamic equilibrium were determined using the Extended Aerosols and Inorganics Model (E-AIM) under varying initial inputs, along with the deliquescence relative humidity (DRH) and the corresponding particle water content. Our findings indicated a notable negative relationship between MA concentration and the DRH for both AS and NaCl while the effect of MA on NaCl is smaller than that on AS. The salt of MA in the particle phase may absorb water vapor and may lead to the displacement reaction between AS and NaCl due to the low solubility of sodium sulfate. The acidity in the particle phase also played a significant role in affecting the DRH of sea salt aerosols. Since both sea salt aerosol and alkylamines are emitted into the atmosphere from the ocean in large quantities, our study suggested the potential impact of alkylamines on the environment and the climate via the modification of sea salt aerosol properties.
more »
« less
- Award ID(s):
- 1847019
- NSF-PAR ID:
- 10330184
- Date Published:
- Journal Name:
- The 262nd American Chemical Society National Meeting & Exposition
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract. Even though the Arctic is remote, aerosol properties observed there arestrongly influenced by anthropogenic emissions from outside the Arctic. Thisis particularly true for the so-called Arctic haze season (January throughApril). In summer (June through September), when atmospheric transportpatterns change, and precipitation is more frequent, local Arctic sources,i.e., natural sources of aerosols and precursors, play an important role.Over the last few decades, significant reductions in anthropogenic emissionshave taken place. At the same time a large body of literature shows evidencethat the Arctic is undergoing fundamental environmental changes due toclimate forcing, leading to enhanced emissions by natural processes that mayimpact aerosol properties. In this study, we analyze 9 aerosol chemical species and 4 particleoptical properties from 10 Arctic observatories (Alert, Kevo, Pallas,Summit, Thule, Tiksi, Barrow/Utqiaġvik, Villum, and Gruvebadet and ZeppelinObservatory – both at Ny-Ålesund Research Station) to understand changesin anthropogenic and natural aerosol contributions. Variables includeequivalent black carbon, particulate sulfate, nitrate, ammonium,methanesulfonic acid, sodium, iron, calcium and potassium, as well asscattering and absorption coefficients, single scattering albedo andscattering Ångström exponent. First, annual cycles are investigated, which despite anthropogenic emissionreductions still show the Arctic haze phenomenon. Second, long-term trendsare studied using the Mann–Kendall Theil–Sen slope method. We find in total41 significant trends over full station records, i.e., spanning more than adecade, compared to 26 significant decadal trends. The majority ofsignificantly declining trends is from anthropogenic tracers and occurredduring the haze period, driven by emission changes between 1990 and 2000.For the summer period, no uniform picture of trends has emerged. Twenty-sixpercent of trends, i.e., 19 out of 73, are significant, and of those 5 arepositive and 14 are negative. Negative trends include not only anthropogenictracers such as equivalent black carbon at Kevo, but also natural indicatorssuch as methanesulfonic acid and non-sea-salt calcium at Alert. Positivetrends are observed for sulfate at Gruvebadet. No clear evidence of a significant change in the natural aerosolcontribution can be observed yet. However, testing the sensitivity of theMann–Kendall Theil–Sen method, we find that monotonic changes of around 5 % yr−1 in an aerosol property are needed to detect a significanttrend within one decade. This highlights that long-term efforts well beyonda decade are needed to capture smaller changes. It is particularly importantto understand the ongoing natural changes in the Arctic, where interannualvariability can be high, such as with forest fire emissions and theirinfluence on the aerosol population. To investigate the climate-change-induced influence on the aerosolpopulation and the resulting climate feedback, long-term observations oftracers more specific to natural sources are needed, as well as of particlemicrophysical properties such as size distributions, which can be used toidentify changes in particle populations which are not well captured bymass-oriented methods such as bulk chemical composition.more » « less
-
more » « less
Abstract Here we report the ice nucleating temperatures of marine aerosols sampled in the subarctic Atlantic Ocean during a phytoplankton bloom. Ice nucleation measurements were conducted on primary aerosol samples and phytoplankton isolated from seawater samples. Primary marine aerosol samples produced by a specialized aerosol generator (the Sea Sweep) catalyzed droplet freezing at temperatures between −33.4 °C and − 24.5 °C, with a mean freezing temperature of −28.5 °C, which was significantly warmer than the homogeneous freezing temperature of pure water in the atmosphere (−36 °C). Following a storm‐induced deep mixing event, ice nucleation activity was enhanced by two metrics: (1) the fraction of aerosols acting as ice nucleating particles (INPs) and (2) the nucleating temperatures, which were the warmest observed throughout the project. Seawater samples were collected from the ocean's surface and phytoplankton groups, including
Synechococcus , picoeukaryotes, and nanoeukaryotes, were isolated into sodium chloride sheath fluid solution using a cell‐sorting flow cytometer. Marine aerosol containingSynechococcus , picoeukaryotes, and nanoeukaryotes serves as INP at temperatures significantly warmer than the homogeneous freezing temperature of pure water in the atmosphere. Samples containing whole organisms in 30 g L−1NaCl had freezing temperatures between −33.8 and − 31.1 °C. Dilution of samples to representative atmospheric aerosol salt concentrations (as low as 3.75 g L−1NaCl) raised freezing temperatures to as high as −22.1 °C. It follows that marine aerosols containing phytoplankton may have widespread influence on marine ice nucleation events by facilitating ice nucleation. -
Anthropogenic and natural emissions contribute to enhanced concentrations of aerosols in the Arctic winter and early spring, with most attention being paid to anthropogenic aerosols that contribute to so-called Arctic haze. Less-well-studied wintertime sea-spray aerosols (SSAs) under Arctic haze conditions are the focus of this study, since they can make an important contribution to wintertime Arctic aerosol abundances. Analysis of field campaign data shows evidence for enhanced local sources of SSAs, including marine organics at Utqiaġvik (formerly known as Barrow) in northern Alaska, United States, during winter 2014. Models tend to underestimate sub-micron SSAs and overestimate super-micron SSAs in the Arctic during winter, including the base version of the Weather Research Forecast coupled with Chemistry (WRF-Chem) model used here, which includes a widely used SSA source function based on Gong et al. (1997). Quasi-hemispheric simulations for winter 2014 including updated wind speed and sea-surface temperature (SST) SSA emission dependencies and sources of marine sea-salt organics and sea-salt sulfate lead to significantly improved model performance compared to observations at remote Arctic sites, notably for coarse-mode sodium and chloride, which are reduced. The improved model also simulates more realistic contributions of SSAs to inorganic aerosols at different sites, ranging from 20 %–93 % in the observations. Two-thirds of the improved model performance is from the inclusion of the dependence on SSTs. The simulation of nitrate aerosols is also improved due to less heterogeneous uptake of nitric acid on SSAs in the coarse mode and related increases in fine-mode nitrate. This highlights the importance of interactions between natural SSAs and inorganic anthropogenic aerosols that contribute to Arctic haze. Simulation of organic aerosols and the fraction of sea-salt sulfate are also improved compared to observations. However, the model underestimates episodes with elevated observed concentrations of SSA components and sub-micron non-sea-salt sulfate at some Arctic sites, notably at Utqiaġvik. Possible reasons are explored in higher-resolution runs over northern Alaska for periods corresponding to the Utqiaġvik field campaign in January and February 2014. The addition of a local source of sea-salt marine organics, based on the campaign data, increases modelled organic aerosols over northern Alaska. However, comparison with previous available data suggests that local natural sources from open leads, as well as local anthropogenic sources, are underestimated in the model. Missing local anthropogenic sources may also explain the low modelled (sub-micron) non-sea-salt sulfate at Utqiaġvik. The introduction of a higher wind speed dependence for sub-micron SSA emissions, also based on Arctic data, reduces biases in modelled sub-micron SSAs, while sea-ice fractions, including open leads, are shown to be an important factor controlling modelled super-micron, rather than sub-micron, SSAs over the north coast of Alaska. The regional results presented here show that modelled SSAs are more sensitive to wind speed dependence but that realistic modelling of sea-ice distributions is needed for the simulation of local SSAs, including marine organics. This study supports findings from the Utqiaġvik field campaign that open leads are the primary source of fresh and aged SSAs, including marine organic aerosols, during wintertime at Utqiaġvik; these findings do not suggest an influence from blowing snow and frost flowers. To improve model simulations of Arctic wintertime aerosols, new field data on processes that influence wintertime SSA production, in particular for fine-mode aerosols, are needed as is improved understanding about possible local anthropogenic sources.more » « less
-
Internally-mixed aerosol particles containing organic molecules and inorganic salts are prevalent in the atmosphere, arising from direct emission ( e.g., from the ocean) or indirect production by condensation of organic vapors onto existing inorganic particle seeds. Aerosol particles co-exist with water vapor and, under humid conditions, will exist as dilute aqueous solution particles that can be well described by thermodynamic models. Under low humidity conditions, the increase in solute concentrations leads to molecular interactions and significant non-ideality effects that drive changes in important physical properties, such as viscosity and phase state, that are not predicted using simple models. Here, we explore a model system containing ammonium sulfate (AS) and citric acid (CA). We measure the hygroscopicity, viscosity, and rate of water diffusion in particles across a range of RH conditions and organic fractions to better understand the influence of organic–inorganic mixtures on particle properties. We report the RH dependence of these properties and explore the applicability of commonly used methods that connect them together, such as the Stokes–Einstein relationship and thermodynamic modelling methods. We show that at low RH, the addition of AS to CA leads to a reduction in the amount of water as indicated by the radial growth factor at a fixed RH, while observing an increase in the viscosity over several orders of magnitude. Contrary to the viscosity, only minor changes in water diffusion were measured, and analysis with the fractional Stokes–Einstein relationship indicates that changes in the molecular matrix due to the presence of AS could explain the observed phenomena. This work reveals that small additions of electrolytes can drive large changes in particle properties, with implications for chemical reactivity, lifetime, and particle phase that will influence the environmental impacts and chemistry of aerosol particles.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Conference Paper:
- The DOI is not currently available.
