This study examines the uncertainties in simulating mass balance and radiative forcing of mineral dust due to biases in the dust size parameterization. Simulations are conducted quasi-globally (180° ...W–180° E and 60° S–70° N) using the WRF-Chem model with three different approaches to represent dust size distribution (8-bin, 4-bin, and 3-mode). The biases in the 3-mode or 4-bin approaches against a relatively more accurate 8-bin approach in simulating dust mass balance and radiative forcing are identified. Compared to the 8-bin approach, the 4-bin approach simulates similar but coarser size distributions of dust particles in the atmosphere, while the 3-mode approach retains more fine dust particles but fewer coarse dust particles due to its prescribed σg of each mode. Although the 3-mode approach yields up to 10 days of longer dust mass lifetime over the remote oceanic regions than the 8-bin approach, the three size approaches produce a similar dust mass lifetime (3.2 days to 3.5 days) on quasi-global average, reflecting that the global dust mass lifetime is mainly determined by the dust mass lifetime near the dust source regions. With the same global dust emission (~4600 Tg yr−1), the 8-bin approach produces a dust mass loading of 39 Tg, while the 4-bin and 3-mode approaches produce 3% (40.2 Tg) and 25% (49.1 Tg) higher dust mass loading, respectively. The difference in dust mass loading between the 8-bin approach and the 4-bin or 3-mode approaches has large spatial variations, with generally smaller relative difference (<10%) near the surface over the dust source regions. The three size approaches also result in significantly different dry and wet deposition fluxes and number concentrations of dust. The difference in dust aerosol optical depth (AOD) (a factor of 3) among the three size approaches is much larger than their difference (25%) in dust mass loading. Compared to the 8-bin approach, the 4-bin approach yields stronger dust absorptivity, while the 3-mode approach yields weaker dust absorptivity. Overall, on quasi-global average, the three size parameterizations result in a significant difference of a factor of 2~3 in dust surface cooling (−1.02~−2.87 W m−2) and atmospheric warming (0.39~0.96 W m−2) and in a tremendous difference of a factor of ~10 in dust TOA (top of atmosphere) cooling (−0.24~−2.20 W m−2). The impact of different size representations on dust radiative forcing efficiency is smaller. An uncertainty of a factor of 2 is quantified in dust emission estimation due to the different size parameterizations. This study also highlights the uncertainties in modeling dust mass and number loading, deposition fluxes, and radiative forcing resulting from different size parameterizations, and motivates further investigation of the impact of size parameterizations on modeling dust impacts on air quality, climate, and ecosystems.
The mixing state of soot particles in the atmosphere is of crucial importance for assessing their climatic impact, since it governs their chemical reactivity, cloud condensation nuclei activity, and ...radiative properties. To improve the mixing state representation in models, we present a new approach, the stochastic particle‐resolved model PartMC‐MOSAIC, which explicitly resolves the composition of individual particles in a given population of different types of aerosol particles. This approach tracks the evolution of the mixing state of particles due to emission, dilution, condensation, and coagulation. To make this direct stochastic particle‐based method practical, we implemented a new multiscale stochastic coagulation method. With this method we achieved high computational efficiency for situations when the coagulation kernel is highly nonuniform, as is the case for many realistic applications. PartMC‐MOSAIC was applied to an idealized urban plume case representative of a large urban area to simulate the evolution of carbonaceous aerosols of different types due to coagulation and condensation. For this urban plume scenario we quantified the individual processes that contributed to the aging of the aerosol distribution, illustrating the capabilities of our modeling approach. The results showed for the first time the multidimensional structure of particle composition, which is usually lost in sectional or modal aerosol models.
This paper describes and evaluates a new framework for modeling kinetic gas-particle partitioning of secondary organic aerosol (SOA) that takes into account diffusion and chemical reaction within the ...particle phase. The framework uses a combination of (a) an analytical quasi-steady-state treatment for the diffusion–reaction process within the particle phase for fast-reacting organic solutes, and (b) a two-film theory approach for slow- and nonreacting solutes. The framework is amenable for use in regional and global atmospheric models, although it currently awaits specification of the various gas- and particle-phase chemistries and the related physicochemical properties that are important for SOA formation. Here, the new framework is implemented in the computationally efficient Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) to investigate the competitive growth dynamics of the Aitken and accumulation mode particles. Results show that the timescale of SOA partitioning and the associated size distribution dynamics depend on the complex interplay between organic solute volatility, particle-phase bulk diffusivity, and particle-phase reactivity (as exemplified by a pseudo-first-order reaction rate constant), each of which can vary over several orders of magnitude. In general, the timescale of SOA partitioning increases with increase in volatility and decrease in bulk diffusivity and rate constant. At the same time, the shape of the aerosol size distribution displays appreciable narrowing with decrease in volatility and bulk diffusivity and increase in rate constant. A proper representation of these physicochemical processes and parameters is needed in the next generation models to reliably predict not only the total SOA mass, but also its composition- and number-diameter distributions, all of which together determine the overall optical and cloud-nucleating properties.
The CARES campaign was conducted during June, 2010 in the vicinity of Sacramento, California to study aerosol formation and aging in a region where anthropogenic and biogenic emissions regularly mix. ...Here, we describe measurements from an Aerodyne High Resolution Aerosol Mass Spectrometer (AMS), an Ionicon Proton Transfer Reaction Mass Spectrometer (PTR-MS), and trace gas detectors (CO, NO, NO sub(x)) deployed on the G-1 research aircraft to investigate ambient gas- and particle-phase chemical composition. AMS measurements showed that the particle phase is dominated by organic aerosol (OA) (85% on average) with smaller concentrations of sulfate (5%), nitrate (6%) and ammonium (3%) observed. PTR-MS data showed that isoprene dominated the biogenic volatile organic compound concentrations (BVOCs), with monoterpene concentrations generally below the detection limit. Using two different metrics, median OA concentrations and the slope of plots of OA vs. CO concentrations (i.e., Delta OA/ Delta CO), we contrast organic aerosol evolution on flight days with different prevailing meteorological conditions to elucidate the role of anthropogenic and biogenic emissions on OA formation. Airmasses influenced predominantly by biogenic emissions had median OA concentrations of 2.2 mu g m super(-3) and near zero Delta OA/ Delta CO. Those influenced predominantly by anthropogenic emissions had median OA concentrations of 4.7 mu g m super(-3) and Delta OA/ Delta CO ratios of 35-44 mu g m super(-3) ppmv. But, when biogenic and anthropogenic emissions mixed, OA levels were enhanced, with median OA concentrations of 11.4 mu g m super(-3) and Delta OA/ Delta CO ratios of 77-157 mu g m super(-3) ppmv. Taken together, our observations show that production of OA was enhanced when anthropogenic emissions from Sacramento mixed with isoprene-rich air from the foothills. After considering several anthropogenic/biogenic interaction mechanisms, we conclude that NO sub(x) concentrations play a strong role in enhancing SOA formation from isoprene, though the chemical mechanism for the enhancement remains unclear. If these observations are found to be robust in other seasons and in areas outside of Sacramento, regional and global aerosol modules will need to incorporate more complex representations of NO sub(x)-dependent SOA mechanisms and yields into their algorithms. Ultimately, accurately predicting OA mass concentrations and their effect on radiation balance will require a mechanistically-based treatment of the interactions of biogenic and anthropogenic emissions.
An Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed during the Carbonaceous Aerosols and Radiative Effects Study (CARES) that took place in northern ...California in June 2010. We present results obtained at Cool (denoted as the T1 site of the project) in the foothills of the Sierra Nevada Mountains, where intense biogenic emissions are periodically mixed with urban outflow transported by daytime southwesterly winds from the Sacramento metropolitan area. During this study, the average mass loading of submicrometer particles (PM1) was 3.0 μg m−3, dominated by organics (80%) and sulfate (9.9%). The organic aerosol (OA) had a nominal formula of C1H1.38N0.004OM0.44, thus an average organic mass-to-carbon (OM/OC) ratio of 1.70. Two distinct oxygenated OA factors were identified via Positive matrix factorization (PMF) of the high-resolution mass spectra of organics. The more oxidized MO-OOA (O/C = 0.54) was interpreted as a surrogate for secondary OA (SOA) influenced by biogenic emissions whereas the less oxidized LO-OOA (O/C = 0.42) was found to represent SOA formed in photochemically processed urban emissions. LO-OOA correlated strongly with ozone and MO-OOA correlated well with two 1st generation isoprene oxidation products (methacrolein and methyl vinyl ketone), indicating that both SOAs were relatively fresh. A hydrocarbon like OA (HOA) factor was also identified, representing primary emissions mainly due to local traffic. On average, SOA (= MO-OOA + LO-OOA) accounted for 91% of the total OA mass and 72% of the PM1 mass observed at Cool. Twenty three periods of urban plumes from T0 (Sacramento) to T1 (Cool) were identified using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The average PM1 mass loading was considerably higher in urban plumes than in air masses dominated by biogenic SOA. The change in OA mass relative to CO (ΔOA/ΔCO) varied in the range of 5-196 μg m−3 ppm−1, reflecting large variability in SOA production. The highest ΔOA/ΔCO was reached when air masses were dominated by anthropogenic emissions in the presence of a high concentration of biogenic volatile organic compounds (BVOCs). This ratio, which was 97 μg m−3 ppm−1 on average, was much higher than when urban plumes arrived in a low BVOC environment (~36 μg m−3 ppm−1) or during other periods dominated by biogenic SOA (35 μg m−3 ppm−1). These results demonstrate that SOA formation is enhanced when anthropogenic emissions interact with biogenic precursors.
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.
This work investigates the development of ultra‐lightweight, hybrid fireproof composite material. The composite panels are made of 2,5‐polybenizimidazole (ABPBI) a thermally stable high‐performance ...fiber and poly ether ketone (PEK) a high‐performance film. The surface of ABPBI fiber and PEK film were treated by nitrogen plasma to increase the adhesion characteristics. The composite was fabricated through the stacking method. The hybrid composite was developed by sandwiching silicone rubber foam between surface‐treated ABPBI/PEK composite. The entire sample was covered with surface‐treated ABPBI fiber using silicone adhesive. The hybrid composite was tested in exposure to dry ice, fire and compression tests. After exposure to fire for 10 min, negligible loss of material was noticed. The Scanning Electron Microscopy (SEM) analysis at the interface indicated strong interfacial adhesion between the PEK matrix and the ABPBI fiber. Limiting oxygen index (LOI) of ABPBI fiber and PEK film appear to be promising in terms of fire resistivity and hence the hybrid composite of PEK/ABPBI sandwiched by silicone foam results one of the best fireproof composite. This composite also shows significant improvement of impact and compressive strength. Analysis under Ansys Fluent software also shows similar results.
Development of thermally insulated ultra‐lightweight fireproof composite.
Carbonaceous aerosols impact climate directly by scattering and absorbing radiation, and hence play a major, although highly uncertain, role in global radiative forcing. Commonly, ambient ...carbonaceous aerosols are internally mixed with secondary species such as nitrate, sulfate, and ammonium, which influences their optical properties, hygroscopicity, and atmospheric lifetime, thus impacting climate forcing. Aircraft-aerosol time-of-flight mass spectrometry (A-ATOFMS), which measures single-particle mixing state, was used to determine the fraction of organic and soot aerosols that are internally mixed and the variability of their mixing state in California during the Carbonaceous Aerosols and Radiative Effects Study (CARES) and the Research at the Nexus of Air Quality and Climate Change (CalNex) field campaigns in the late spring and early summer of 2010. Nearly 88% of all A-ATOFMS measured particles (100-1000 nm in diameter) were internally mixed with secondary species, with 96% and 75% of particles internally mixed with nitrate and/or sulfate in southern and northern California, respectively. Even though atmospheric particle composition in both regions was primarily influenced by urban sources, the mixing state was found to vary greatly, with nitrate and soot being the dominant species in southern California, and sulfate and organic carbon in northern California. Furthermore, mixing state varied temporally in northern California, with soot becoming the prevalent particle type towards the end of the study as regional pollution levels increased. The results from these studies demonstrate that the majority of ambient carbonaceous particles in California are internally mixed and are heavily influenced by secondary species that are most prevalent in the particular region. Based on these findings, considerations of regionally dominant sources and secondary species, as well as temporal variations of aerosol physical and optical properties, will be required to obtain more accurate predictions of the climate impacts of aerosol in California.
We present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry ...neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO2 and low-NO conditions, highly oxygenated (O:C ≥ 1) C5 compounds were major components (∼ 50%) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2h) for some individual components, significant errors in group-contribution methods are revealed. In addition, >30% of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.
The lumped‐structure approach for condensing organic chemical mechanisms is attractive, since it yields fewer species and reactions and reduces computational costs. This paper leads through the ...development of a new lumped‐structure mechanism, largely based on the widely used Carbon Bond Mechanism (CBM‐IV) developed by Gery et al. 1989. The new mechanism called CBM‐Z extends the original framework to function properly at larger spatial and longer timescales. The major modifications in the mechanism include revised inorganic chemistry; explicit treatment of the lesser reactive paraffins, methane and ethane; revised parameterizations of the reactive paraffin, olefin, and aromatic reactions; inclusion of alkyl and acyl peroxy radical interactions and their reactions with NO3; inclusion of organic nitrates and hydroperoxides; and refined isoprene chemistry based on the condensed one‐product mechanism of Carter 1996. CBM‐Z was successfully evaluated along with the CBM‐IV, a partially revised CBM‐IV, and a revised Regional Acid Deposition Model (RADM2) mechanism Stockwell et al., 1990; Kirchner and Stockwell, 1996 using the low NOx and volatile organic compound concentration smog chamber experiments of Simonaitis et al. 1997. Box model versions of the four mechanisms were also evaluated under a variety of hypothetical urban and rural scenarios for a period of 30 days. Results from CBM‐Z and revised RADM2 were found to be within ±20% of each other, while CBM‐IV and revised CBM‐IV results deviated significantly by up to 50–95%. Sensitivity tests were performed to elucidate the effects of some of the new features added in CBM‐Z. Relative computational memory and time requirements of these mechanisms are also discussed.
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