The Acidity of Atmospheric Particles and Clouds Pye, Havala O T; Nenes, Athanasios; Alexander, Becky ...
Atmospheric chemistry and physics,
04/2020, Letnik:
20, Številka:
8
Journal Article
Recenzirano
Odprti dostop
Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase ...partitioning of semi-volatile gases such as HNO
, NH
, HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally-constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicates acidity may be relatively constant due to the semi-volatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale.
Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol ...due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron‐sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid‐catalyzed multiphase chemistry of isoprene epoxydiols, particle‐phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process‐related interactions, so that these processes can be accurately represented in atmospheric chemistry‐climate models.
Plain Language Summary
Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, often represents a major fraction of global submicron‐sized atmospheric organic aerosol. Myriad processes affect SOA formation, several of which relate to interactions between natural biogenic emissions and predominantly anthropogenic species such as SO2, NOx, sulfate, nitrate, and ammonium. Many of these key processes are nonlinear and can be synergistic or act to compensate each other in terms of climate forcing. Current atmospheric chemistry‐climate models mostly do not treat these processes. We highlight a number of process‐level mechanisms related to the interactions between anthropogenic and biogenic SOA precursors, for which the corresponding impacts on the radiative effects of SOA need to be investigated in atmospheric chemistry‐climate models. Ultimately, climate models need to capture enough important features of the chemical and dynamic evolution of SOA, in terms of both aerosol number and aerosol mass, as a function of atmospheric variables and anthropogenic perturbations to reasonably predict the spatial and temporal distributions of SOA. A better understanding of SOA formation mechanisms and physical properties is needed to improve estimates of the extent to which anthropogenic emissions and land use changes have modified global aerosol concentrations and size distributions since preindustrial times.
Key Points
We review some important developments in secondary organic aerosol (SOA) that could impact aerosol radiative forcing and response of climate to greenhouse gases
We highlight some of the important processes that involve interactions between natural biogenic emissions and anthropogenic emissions
We discuss fundamental SOA properties volatility and viscosity and their relation to evolution of aerosol mass and number concentrations in the atmosphere
This paper describes and evaluates a new Model for Simulating Aerosol Interactions and Chemistry (MOSAIC), with a special focus on addressing the long‐standing issues in solving the dynamic ...partitioning of semivolatile inorganic gases (HNO3, HCl, and NH3) to size‐distributed atmospheric aerosol particles. The coupled ordinary differential equations (ODE) for dynamic gas‐particle mass transfer are extremely stiff, and the available numerical techniques are either very expensive or produce oscillatory solutions. These limitations are overcome in MOSAIC with a new dynamic gas‐particle partitioning module, which is coupled to an efficient and accurate thermodynamics module. The algorithm includes a new concept of “dynamic pH,” a novel formulation for mass transfer to mixed‐phase and solid particles, and an adaptive time stepping scheme, which together hold the key to smooth, accurate, and efficient solutions of gas‐particle partitioning over the entire relative humidity range. MOSAIC is found to be in excellent agreement with a benchmark version of the model that uses a rigorous solver for integrating the stiff ODEs. The steady‐state MOSAIC results for monodisperse aerosol test cases are also in excellent agreement with those obtained with the benchmark equilibrium model AIM. Moreover, the CPU times required for fully dynamic solutions by MOSAIC per size bin per 5 min intervals (typical 3‐D model time steps) are similar to those for bulk equilibrium solutions by the computationally efficient but relatively less accurate model ISORROPIA. These results show that MOSAIC is extremely efficient without compromising accuracy, and is therefore highly attractive for use in air quality and regional/global aerosol models.
Lability of secondary organic particulate matter Liu, Pengfei; Li, Yong Jie; Wang, Yan ...
Proceedings of the National Academy of Sciences - PNAS,
11/2016, Letnik:
113, Številka:
45
Journal Article
Recenzirano
Odprti dostop
The energy flows in Earth’s natural and modified climate systems are strongly influenced by the concentrations of atmospheric particulate matter (PM). For predictions of concentration, equilibrium ...partitioning of semivolatile organic compounds (SVOCs) between organic PM and the surrounding vapor has widely been assumed, yet recent observations show that organic PM can be semisolid or solid for some atmospheric conditions, possibly suggesting that SVOC uptake and release can be slow enough that equilibrium does not prevail on timescales relevant to atmospheric processes. Herein, in a series of laboratory experiments, the mass labilities of films of secondary organic material representative of similar atmospheric organic PM were directly determined by quartz crystal microbalance measurements of evaporation rates and vapor mass concentrations. There were strong differences between films representative of anthropogenic comparedwith biogenic sources. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH) between 20% and 30%, indicating rapid partitioning above a transition RH but not below. Below the threshold, the characteristic time for equilibration is estimated as up to 1 wk for a typically sized particle. In contrast, for films representing biogenic PM, no RH threshold was observed, suggesting equilibrium partitioning is rapidly obtained for all RHs. The effective diffusion rate D
org for the biogenic case is at least 10³ times greater than that of the anthropogenic case. These differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PMin Earth’s atmosphere.
The large concentrations of ultrafine particles consistently observed at high altitudes over the tropics represent one of the world’s largest aerosol reservoirs, which may be providing a globally ...important source of cloud condensation nuclei. However, the sources and chemical processes contributing to the formation of these particles remain unclear. Here we investigate new particle formation (NPF) mechanisms in the Amazon free troposphere by integrating insights from laboratory measurements, chemical transport modeling, and field measurements. To account for organic NPF, we develop a comprehensive model representation of the temperature-dependent formation chemistry and thermodynamics of extremely low volatility organic compounds as well as their roles in NPF processes. We find that pure-organic NPF driven by natural biogenic emissions dominates in the uppermost troposphere above 13 km and accounts for 65 to 83% of the column total NPF rate under relatively pristine conditions, while ternary NPF involving organics and sulfuric acid dominates between 8 and 13 km. The large organic NPF rates at high altitudes mainly result from decreased volatility of organics and increased NPF efficiency at low temperatures, somewhat counterbalanced by a reduced chemical formation rate of extremely low volatility organic compounds. These findings imply a key role of naturally occurring organic NPF in high-altitude preindustrial environments and will help better quantify anthropogenic aerosol forcing from preindustrial times to the present day.
Measurements of the optical properties (absorption, scattering and extinction) of PM1, PM2.5 and PM10 made at two sites around Sacramento, CA, during the June 2010 Carbonaceous Aerosols and Radiative ...Effects Study (CARES) are reported. These observations are used to establish relationships between various intensive optical properties and to derive information about the dependence of the optical properties on photochemical aging and sources. Supermicron particles contributed substantially to the total light scattering at both sites, about 50 % on average. A strong, linear relationship is observed between the scattering Ångström exponent for PM10 and the fraction of the scattering that is contributed by submicron particles (fsca, PM1) at both sites and with similar slopes and intercepts (for a given pair of wavelengths), suggesting that the derived relationship may be generally applicable for understanding variations in particle size distributions from remote sensing measurements. At the more urban T0 site, the fsca, PM1 increased with photochemical age, whereas at the downwind, more rural T1 site the fsca, PM1 decreased slightly with photochemical age. This difference in behavior reflects differences in transport, local production and local emission of supermicron particles between the sites. Light absorption is dominated by submicron particles, but there is some absorption by supermicron particles ( ∼ 15 % of the total). The supermicron absorption derives from a combination of black carbon that has penetrated into the supermicron mode and from dust, and there is a clear increase in the mass absorption coefficient of just the supermicron particles with increasing average particle size. The mass scattering coefficient (MSC) for the supermicron particles was directly observed to vary inversely with the average particle size, demonstrating that MSC cannot always be treated as a constant in estimating mass concentrations from scattering measurements, or vice versa. The total particle backscatter fraction exhibited some dependence upon the relative abundance of sub- versus supermicron particles; however this was modulated by variations in the median size of particles within a given size range; variations in the submicron size distribution had a particularly large influence on the observed backscatter efficiency and an approximate method to account for this variability is introduced. The relationship between the absorption and scattering Ångström exponents is examined and used to update a previously suggested particle classification scheme. Differences in composition led to differences in the sensitivity of PM2.5 to heating in a thermodenuder to the average particle size, with more extensive evaporation (observed as a larger decrease in the PM2.5 extinction coefficient) corresponding to smaller particles; i.e., submicron particles were generally more susceptible to heating than the supermicron particles. The influence of heating on the particle hygroscopicity varied with the effective particle size, with larger changes observed when the PM2.5 distribution was dominated by smaller particles.
Organonitrate (ON) groups are thought to be important substituents in secondary organic aerosols (SOAs). Model simulations and laboratory studies indicate a large fraction of ON groups in aerosol ...particles, but much lower quantities are observed in the atmosphere. Hydrolysis of ON groups in aerosol particles has been proposed recently to account for this discrepancy. To test this hypothesis, we simulated formation of ON molecules in a reaction chamber under a wide range of relative humidity (RH) (0 to 90%). The mass fraction of ON groups (5 to 20% for high-NO
x
experiments) consistently decreased with increasing RH, which was best explained by hydrolysis of ON groups at a rate of 4 day
−1
(lifetime of 6 h) for reactions under RH greater than 20%. In addition, we found that secondary nitrogen-containing molecules absorb light, with greater absorption under dry and high-NO
x
conditions. This work provides the first evidence for particle-phase hydrolysis of ON groups, a process that could substantially reduce ON group concentration in atmospheric SOAs.
Copyright 2012 American Association for Aerosol Research
Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution ...dynamics are poorly understood. Here, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.
The influence of relative humidity (RH) on the condensational growth of organic aerosol particles remains incompletely understood. Herein, the RH dependence was investigated via a series of ...experiments for α-pinene ozonolysis in a continuously mixed flow chamber in which recurring cycles of particle growth occurred every 7 to 8 h at a given RH. In 5 h, the mean increase in the particle mode diameter was 15 nm at 0% RH and 110 nm at 75% RH. The corresponding particle growth coefficients, representing a combination of the thermodynamic driving force and the kinetic resistance to mass transfer, increased from 0.35 to 2.3 nm2 s–1. The chemical composition, characterized by O:C and H:C atomic ratios of 0.52 and 1.48, respectively, and determined by mass spectrometry, did not depend on RH. The Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) was applied to reproduce the observed size- and RH-dependent particle growth by optimizing the diffusivities D b within the particles of the condensing molecules. The D b values increased from 5 α–1 × 10–16 at 0% RH to 2 α–1 × 10–12 cm–2 s–1 at 75% RH for mass accommodation coefficients α of 0.1 to 1.0, highlighting the importance of particle-phase properties in modeling the growth of atmospheric aerosol particles.
Quantitative assessment of gas-particle partitioning of individual components within complex atmospheric organic aerosol (OA) mixtures is critical for predicting and comprehending the formation and ...evolution of OA particles in the atmosphere. This investigation leverages previously documented data obtained through a temperature-programmed desorption–direct analysis in real-time, high-resolution mass spectrometry (TPD-DART-HRMS) platform. This methodology facilitates the bottom-up construction of volatility basis set (VBS) distributions for constituents found in three biogenic secondary organic aerosol (SOA) mixtures produced through the ozonolysis of α-pinene, limonene, and ocimene. The apparent enthalpies (ΔH*, kJ mol–1) and saturation mass concentrations (C T *, μg·m–3) of individual SOA components, determined as a function of temperature (T, K), facilitated an assessment of changes in VBS distributions and gas-particle partitioning with respect to T and atmospheric total organic mass loadings (tOM, μg·m–3). The VBS distributions reveal distinct differences in volatilities among monomers, dimers, and trimers, categorized into separate volatility bins. At the ambient temperature of T = 298 K, only monomers efficiently partition between gas and particle phases across a broad range of atmospherically relevant tOM values of 1–100 μg·m–3. Partitioning of dimers and trimers becomes notable only at T > 360 K and T > 420 K, respectively. The viscosity of SOA mixtures is assessed using a bottom-up calculation approach, incorporating the input of elemental formulas, ΔH*, C T *, and particle-phase mass fractions of the SOA components. Through this approach, we are able to accurately estimate the variations in SOA viscosity that result from the evaporation of its components. These variations are, in turn, influenced by atmospherically relevant changes in tOM and T. Comparison of the calculated SOA viscosity and diffusivity values with literature reported experimental results shows close agreement, thereby validating the employed calculation approach. These findings underscore the significant potential for TPD-DART-HRMS measurements in enabling the untargeted analysis of organic molecules within OA mixtures. This approach facilitates quantitative assessment of their gas-particle partitioning and allows for the estimation of their viscosity and condensed-phase diffusion, thereby contributing valuable insights to atmospheric models.
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