Applications of Lagrangian Dispersion Modeling to the Analysis of Changes in the Specific Absorption of Elemental Carbon

We use a Lagrangian dispersion model driven by a mesoscale model with four-dimensional data assimilation to simulate the dispersion of elemental carbon (EC) over a region encompassing Mexico City and its surroundings, the study domain for the 2006 MAX-MEX experiment, which was a component of the MILAGRO campaign. The results are used to identify periods when biomass burning was likely to have had a significant impact on the concentrations of elemental carbon at two sites, T1 and T2, downwind of the city, and when emissions from the Mexico City Metropolitan Area (MCMA) were likely to have been more important. They are also used to estimate the median ages of EC affecting the specific absorption of light, aABS, at 870 nm as well as to identify periods when the urban plume from the MCMA was likely to have been advected over T1 and T2. Values of aABS at T1, the nearer of the two sites to Mexico City, were smaller at night and increased rapidly after mid-morning, peaking in the mid-afternoon. The behavior is attributed to the coating of aerosols with substances such as sulfate or organic carbon during daylight hours, but such coating appears to be limited or absent at night. Evidence for this is provided by scanning electron microscope images of aerosols collected at three sampling sites. During daylight hours the values of aABS did not increase with aerosol age for median ages in the range of 1-4 hours. There is some evidence for absorption increasing as aerosols were advected from T1 to T2 but the statistical significance of that result is not strong

Correlations between Optical, Chemical and Physical Properties of Biomass Burn Aerosols

Aerosols generated from burning different plant fuels were characterized to determine relationships between chemical, optical and physical properties. Single scattering albedo ({omega}) and Angstrom absorption coefficients ({alpha}{sub ap}) were measured using a photoacoustic technique combined with a reciprocal nephelometer. Carbon-to-oxygen atomic ratios, sp{sup 2} hybridization, elemental composition and morphology of individual particles were measured using scanning transmission X-ray microscopy coupled with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) and scanning electron microscopy with energy dispersion of X-rays (SEM/EDX). Particles were grouped into three categories based on sp2 hybridization and chemical composition. Measured {omega} (0.4-1.0 at 405 nm) and {alpha}{sub ap} (1.0-3.5) values displayed a fuel dependence. The category with sp{sup 2} hybridization >80% had values of {omega} (<0.5) and {alpha}{sub ap} ({approx}1.25) characteristic of light absorbing soot. Other categories with lower sp2 hybridization (20 to 60%) exhibited higher {omega} (>0.8) and {alpha}{sub ap} (1.0 to 3.5) values, indicating increased absorption spectral selectivity

Chemical Speciation of Sulfur in Marine Cloud Droplets and Particles: Analysis of Individual Particles from Marine Boundary Layer over the California Current

Detailed chemical speciation of the dry residue particles from individual cloud droplets and interstitial aerosol collected during the Marine Stratus Experiment (MASE) was performed using a combination of complementary microanalysis techniques. Techniques include computer controlled scanning electron microscopy with energy dispersed analysis of X-rays (CCSEM/EDX), time-of-flight secondary ionization mass spectrometry (TOF-SIMS), and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Samples were collected at the ground site located in Point Reyes National Seashore, approximately 1 km from the coast. This manuscript focuses on the analysis of individual particles sampled from air masses that originated over the open ocean and then passed through the area of the California current located along the northern California coast. Based on composition, morphology, and chemical bonding information, two externally mixed, distinct classes of sulfur containing particles were identified: chemically modified (aged) sea salt particles and secondary formed sulfate particles. The results indicate substantial heterogeneous replacement of chloride by methanesulfonate (CH3SO3-) and non-sea salt sulfate (nss-SO42-) in sea-salt particles with characteristic ratios of nss-S/Na>0.10 and CH3SO3-/nss-SO42->0.6

Transport, biomass burning, and in-situ formation contribute to fine particle concentrations at a remote site near Grand Teton National Park

Ecosystem health and visibility degradation due to fine-mode atmospheric particles have been documented in remote areas and motivate particle characterization that can inform mitigation strategies. This study explores submicron (PM1) particle size, composition, and source apportionment at Grand Teton National Park using High-Resolution Time-of-Flight Aerosol Mass Spectrometer data with Positive Matrix Factorization and MODIS fire information. Particulate mass averages 2.08 mu g/m(3) (max = 21.91 mu g/m(3)) of which 75.0% is organic; PMF-derived Low-Volatility Oxygenated Organic Aerosol (LV-OOA) averages 61.1% of PM1 (or 1.05 mu g/m(3)), with sporadic but higher-concentration biomass burning (BBOA) events contributing another 13.9%. Sulfate (12.5%), ammonium (8.7%), and nitrate (3.8%) are generally low in mass. Ammonium and sulfate have correlated time-series and association with transport from northern Utah and the Snake River Valley. A regionally disperse and/or in situ photochemical LV-OOA source is suggested by 1) afternoon concentration enhancement not correlated with upslope winds, anthropogenic NOx, or ammonium sulfate, 2) smaller particle size, higher polydispersity, and lower levels of oxidation during the day and in comparison to a biomass burning plume inferred to have traveled similar to 480 km, and 3) lower degree of oxidation than is usually observed in transported urban plumes and alpine sites with transported anthropogenic OA. CHN fragment spectra suggest organic nitrogen in the form of nitriles and/or pyridines during the day, with the addition of amine fragments at night. Fires near Boise, ID may be the source of a high-concentration biomass-burning event on August 15-16, 2011 associated with SW winds (upslope from the Snake River Valley) and increased sulfate, ammonium, nitrate, and CHN and CHON fragments (nominally, amines and organonitrates). Comparison to limited historical data suggests that the amounts and sources of organics and inorganics presented here typify summer conditions in this area. (C) 2015 Elsevier Ltd. All rights reserved

Characterization of Aerosols Containing Zn, Pb, and Cl from an Industrial Region of Mexico City

Recent ice core measurements show lead concentrations increasing since 1970, suggesting new non automobile-related sources of Pb are becoming important worldwide (1). Developing a full understanding of the major sources of Pb and other metals is critical to controlling these emissions. During the March, 2006 MILAGRO campaign, single particle measurements in Mexico City revealed the frequent appearance of particles internally mixed with Zn, Pb, Cl, and P. Pb concentrations were as high as 1.14 μg/m3 in PM10 and 0.76 μg/m3 in PM2.5. Real time measurements were used to select time periods of interest to perform offline analysis to obtain detailed aerosol speciation. Many Zn-rich particles had needle-like structures and were found to be composed of ZnO and/or Zn(NO3)2·6H2O. The internally mixed Pb-Zn-Cl particles represented as much as 73% of the fine mode particles (by number) in the morning hours between 2-5 am. The Pb-Zn-Cl particles were primarily in the submicrometer size range and typically mixed with elemental carbon suggesting a combustion source. The unique single particle chemical associations measured in this study closely match signatures indicative of waste incineration. Our findings also show these industrial emissions play an important role in heterogeneous processing of NOy species. Primary emissions of metal and sodium chloride particles emitted by the same source underwent heterogeneous transformations into nitrate particles as soon as photochemical production of nitric acid began each day at ~7 am

Ice nucleation by particles containing long-chain fatty acids of relevance to freezing by sea spray aerosols.

Heterogeneous ice nucleation in the atmosphere regulates cloud properties, such as phase (ice versus liquid) and lifetime. Aerosol particles of marine origin are relevant ice nucleating particle sources when marine aerosol layers are lifted over mountainous terrain and in higher latitude ocean boundary layers, distant from terrestrial aerosol sources. Among many particle compositions associated with ice nucleation by sea spray aerosols are highly saturated fatty acids. Previous studies have not demonstrated their ability to freeze dilute water droplets. This study investigates ice nucleation by monolayers at the surface of supercooled droplets and as crystalline particles at temperatures exceeding the threshold for homogeneous freezing. Results show the poor efficiency of long chain fatty acid (C16, C18) monolayers in templating freezing of pure water droplets and seawater subphase to temperatures of at least -30 °C, consistent with theory. This contrasts with freezing of fatty alcohols (C22 used here) at nearly 20 °C warmer. Evaporation of μL-sized droplets to promote structural compression of a C19 acid monolayer did not favor warmer ice formation of drops. Heterogeneous ice nucleation occurred for nL-sized droplets condensed on 5 to 100 μm crystalline particles of fatty acid (C12 to C20) at a range of temperatures below -28 °C. These experiments suggest that fatty acids nucleate ice at warmer than -36 °C only when the crystalline phase is present. Rough estimates of ice active site densities are consistent with those of marine aerosols, but require knowledge of the proportion of surface area comprised of fatty acids for application

Ice nucleation by particles containing long-chain fatty acids of relevance to freezing by sea spray aerosols.

Heterogeneous ice nucleation in the atmosphere regulates cloud properties, such as phase (ice versus liquid) and lifetime. Aerosol particles of marine origin are relevant ice nucleating particle sources when marine aerosol layers are lifted over mountainous terrain and in higher latitude ocean boundary layers, distant from terrestrial aerosol sources. Among many particle compositions associated with ice nucleation by sea spray aerosols are highly saturated fatty acids. Previous studies have not demonstrated their ability to freeze dilute water droplets. This study investigates ice nucleation by monolayers at the surface of supercooled droplets and as crystalline particles at temperatures exceeding the threshold for homogeneous freezing. Results show the poor efficiency of long chain fatty acid (C16, C18) monolayers in templating freezing of pure water droplets and seawater subphase to temperatures of at least -30 °C, consistent with theory. This contrasts with freezing of fatty alcohols (C22 used here) at nearly 20 °C warmer. Evaporation of μL-sized droplets to promote structural compression of a C19 acid monolayer did not favor warmer ice formation of drops. Heterogeneous ice nucleation occurred for nL-sized droplets condensed on 5 to 100 μm crystalline particles of fatty acid (C12 to C20) at a range of temperatures below -28 °C. These experiments suggest that fatty acids nucleate ice at warmer than -36 °C only when the crystalline phase is present. Rough estimates of ice active site densities are consistent with those of marine aerosols, but require knowledge of the proportion of surface area comprised of fatty acids for application

Residential Coal Combustion as a Source of Levoglucosan in China

Levoglucosan (LG) has been widely identified as a specific marker for biomass burning (BB) sources and frequently utilized in estimating the BB contribution to atmospheric fine particles all over the world. However, this study provides direct evidence to show that coal combustion (CC) is also a source of LG, especially in the wintertime in Northern China, based on both source testing and ambient measurement. Our results show that low-temperature residential CC could emit LG with emission factors (EF) ranging from 0.3 to 15.9 mg kg^–1. Ratios of LG to its isomers, mannosan and galactosan, differ between CC and BB emissions, and the wintertime ratios in Beijing ambient PM_2.5 and source-specific tracers including carbon isotopic signatures all indicated a significant contribution from CC to ambient levoglucosan in winter in Beijing. The results suggest that LG cannot be used as a distinct source marker for biomass burning in special cases such as some cities in the northern China, where coal is still widely used in the residential and industrial sectors. Biomass burning sources could be overestimated, although such an over-estimation could vary spatially and temporally