218 research outputs found
Ground-based remote sensing of an elevated forest fire aerosol layer at Whistler, BC: implications for interpretation of mountaintop chemistry
On 30 August 2009, intense forest fires in interior British Columbia (BC)
coupled with winds from the east and northeast resulted in transport of a
broad forest fire plume across southwestern BC. The physico-chemical and
optical characteristics of the plume as observed from Saturna Island
(AERONET), CORALNet-UBC and the Whistler Mountain air chemistry facility
were consistent with forest fire plumes that have been observed elsewhere in
continental North America. However, the importance of three-dimensional
transport in relation to the interpretation of mountaintop chemistry
observations is highlighted on the basis of deployment of both a <i>CL31</i> ceilometer
and a single particle mass spectrometer (SPMS) in a mountainous setting. The
SPMS is used to identify the biomass plume based on levoglucosan and
potassium markers. Data from the SPMS are also used to show that the
biomass plume was correlated with nitrate, but not correlated with sulphate
or sodium. This study not only provides baseline measurements of biomass
burning plume physico-chemical characteristics in western Canada, but also
highlights the importance of lidar remote sensing methods in the
interpretation of mountaintop chemistry measurements
Fine particle pH and the partitioning of nitric acid during winter in the northeastern United States
Particle pH is a critical but poorly constrained quantity that affects many aerosol processes and properties, including aerosol composition, concentrations, and toxicity. We assess PM1 pH as a function of geographical location and altitude, focusing on the northeastern U.S., based on aircraft measurements from the Wintertime Investigation of Transport, Emissions, and Reactivity campaign (1 February to 15 March 2015). Particle pH and water were predicted with the ISORROPIA-II thermodynamic model and validated by comparing predicted to observed partitioning of inorganic nitrate between the gas and particle phases. Good agreement was found for relative humidity (RH) above 40%; at lower RH observed particle nitrate was higher than predicted, possibly due to organic-inorganic phase separations or nitrate measurement uncertainties associated with low concentrations (nitrate \u3c 1 µg m−3). Including refractory ions in the pH calculations did not improve model predictions, suggesting they were externally mixed with PM1 sulfate, nitrate, and ammonium. Sample line volatilization artifacts were found to be minimal. Overall, particle pH for altitudes up to 5000 m ranged between −0.51 and 1.9 (10th and 90th percentiles) with a study mean of 0.77 ± 0.96, similar to those reported for the southeastern U.S. and eastern Mediterranean. This expansive aircraft data set is used to investigate causes in variability in pH and pH-dependent aerosol components, such as PM1 nitrate, over a wide range of temperatures (−21 to 19°C), RH (20 to 95%), inorganic gas, and particle concentrations and also provides further evidence that particles with low pH are ubiquitous
Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements
Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O(fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component
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Near-Real-Time Measurement Of Sea-Salt Aerosol During the Seas Campaign: Comparison Of Emission-Based Sodium Detection With an Aerosol Volatility Technique
The first deployment of an emission-based aerosol sodium detector (ASD), designed to chemically characterize marine aerosols on a near-real-time basis, is reported. Deployment occurred as part of the Shoreline Environment Aerosol Study ( SEAS) from 16 April to 1 May 2000 at Bellows Air Force Base on the east side of Oahu, where the University of Hawaii\u27s Department of Oceanography maintains a tower for aerosol measurements. The instrument was operated in size-unsegregated mode and measurements were made that included two extended continuous sampling periods, each of which lasted for 24 h. During this time, the ASD was compared with measurements that used aerosol volatility coupled with optical particle counting to infer sea-salt size distributions. A reasonable agreement was obtained between the instruments when sampling in clean air, suggesting that under these conditions both approaches can provide reliable sea-salt distributions. The combination of these measurements suggested that sea salt was the dominant constituent of aerosol particles with diameters larger than 500 nm and that sulfate was the dominant constituent at smaller diameters during clean air sampling
Size-resolved aerosol composition and its link to hygroscopicity at a forested site in Colorado
Aerosol hygroscopicity describes the ability of a particle to take up water
and form a cloud droplet. Modeling studies have shown sensitivity of
precipitation-producing cloud systems to the availability of aerosol
particles capable of serving as cloud condensation nuclei (CCN), and
hygroscopicity is a key parameter controlling the number of available CCN.
Continental aerosol is typically assumed to have a representative
hygroscopicity parameter, κ, of 0.3; however, in remote locations
this value can be lower due to relatively large mass fractions of organic
components. To further our understanding of aerosol properties in remote
areas, we measured size-resolved aerosol chemical composition and
hygroscopicity in a forested, mountainous site in Colorado during the
six-week BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols,
Carbon, H<sub>2</sub>O, Organics and Nitrogen–Rocky Mountain Biogenic
Aerosol Study) campaign. This campaign followed a year-long
measurement period at this site, and results from the intensive campaign
shed light on the previously reported seasonal cycle in aerosol
hygroscopicity. New particle formation events were observed routinely at
this site and nucleation mode composition measurements indicated that the
newly formed particles were predominantly organic. These events likely
contribute to the dominance of organic species at smaller sizes, where
aerosol organic mass fractions were between 70 and 90%. Corresponding
aerosol hygroscopicity was observed to be in the range κ = 0.15–0.22,
with hygroscopicity increasing with particle size. Aerosol chemical
composition measured by an aerosol mass spectrometer and calculated from
hygroscopicity measurements agreed very well during the intensive study, with
an assumed value of κ<sub>org</sub> = 0.13 resulting in the best
agreement
Evolution of brown carbon in wildfire plumes
Particulate brown carbon (BrC) in the atmosphere absorbs light at subvisible wavelengths and has poorly constrained but potentially large climate forcing impacts. BrC from biomass burning has virtually unknown lifecycle and atmospheric stability. Here, BrC emitted from intense wildfires was measured in plumes transported over 2 days from two main fires, during the 2013 NASA SEAC4RS mission. Concurrent measurements of organic aerosol (OA) and black carbon (BC) mass concentration, BC coating thickness, absorption Ångström exponent, and OA oxidation state reveal that the initial BrC emitted from the fires was largely unstable. Using back trajectories to estimate the transport time indicates that BrC aerosol light absorption decayed in the plumes with a half-life of 9 to 15 h, measured over day and night. Although most BrC was lost within a day, possibly through chemical loss and/or evaporation, the remaining persistent fraction likely determines the background BrC levels most relevant for climate forcing
The potential role of methanesulfonic acid (MSA) in aerosol formation and growth and the associated radiative forcings
Atmospheric
marine aerosol particles impact Earth's albedo and climate. These particles
can be primary or secondary and come from a variety of sources, including sea
salt, dissolved organic matter, volatile organic compounds, and
sulfur-containing compounds. Dimethylsulfide (DMS) marine emissions
contribute greatly to the global biogenic sulfur budget, and its oxidation
products can contribute to aerosol mass, specifically as sulfuric acid and
methanesulfonic acid (MSA). Further, sulfuric acid is a known nucleating
compound, and MSA may be able to participate in nucleation when bases are
available. As DMS emissions, and thus MSA and sulfuric acid from DMS
oxidation, may have changed since pre-industrial times and may change in a
warming climate, it is important to characterize and constrain the climate
impacts of both species. Currently, global models that simulate aerosol size
distributions include contributions of sulfate and sulfuric acid from DMS
oxidation, but to our knowledge, global models typically neglect the impact
of MSA on size distributions.
In this study, we use the GEOS-Chem-TOMAS (GC-TOMAS) global aerosol
microphysics model to determine the impact on aerosol size distributions and
subsequent aerosol radiative effects from including MSA in the size-resolved
portion of the model. The effective equilibrium vapor pressure of MSA is
currently uncertain, and we use the Extended Aerosol Inorganics Model (E-AIM)
to build a parameterization for GC-TOMAS of MSA's effective volatility as a
function of temperature, relative humidity, and available gas-phase bases,
allowing MSA to condense as an ideally nonvolatile or semivolatile species or
too volatile to condense. We also present two limiting cases for MSA's
volatility, assuming that MSA is always ideally nonvolatile (irreversible
condensation) or that MSA is always ideally semivolatile (quasi-equilibrium
condensation but still irreversible condensation). We further present
simulations in which MSA participates in binary and ternary nucleation with
the same efficacy as sulfuric acid whenever MSA is treated as ideally
nonvolatile. When using the volatility parameterization described above (both
with and without nucleation), including MSA in the model changes the global
annual averages at 900 hPa of submicron aerosol mass by 1.2 %, N3
(number concentration of particles greater than 3 nm in diameter) by
−3.9 % (non-nucleating) or 112.5 % (nucleating), N80 by 0.8 %
(non-nucleating) or 2.1 % (nucleating), the cloud-albedo aerosol indirect
effect (AIE) by −8.6 mW m−2 (non-nucleating) or −26 mW m−2
(nucleating), and the direct radiative effect (DRE) by −15 mW m−2
(non-nucleating) or −14 mW m−2 (nucleating). The sulfate and
sulfuric acid from DMS oxidation produces 4–6 times more submicron mass than
MSA does, leading to an ∼10 times stronger cooling effect in the DRE.
But the changes in N80 are comparable between the contributions from MSA and
from DMS-derived sulfate/sulfuric acid, leading to comparable changes in the
cloud-albedo AIE.
Model–measurement comparisons with the Heintzenberg et al. (2000) dataset
over the Southern Ocean indicate that the default model has a missing source
or sources of ultrafine particles: the cases in which MSA participates in
nucleation (thus increasing ultrafine number) most closely match the
Heintzenberg distributions, but we cannot conclude nucleation from MSA is the
correct reason for improvement. Model–measurement comparisons with
particle-phase MSA observed with a customized Aerodyne high-resolution
time-of-flight aerosol mass spectrometer (AMS) from the ATom campaign show
that cases with the MSA volatility parameterizations (both with and without
nucleation) tend to fit the measurements the best (as this is the first use
of MSA measurements from ATom, we provide a detailed description of these
measurements and their calibration). However, no one model sensitivity case
shows the best model–measurement agreement for both Heintzenberg and the
ATom campaigns. As there are uncertainties in both MSA's behavior (nucleation
and condensation) and the DMS emissions inventory, further studies on both
fronts are needed to better constrain MSA's past, current, and future impacts
upon the global aerosol size distribution and radiative forcing.</p
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