Aging Effects on Biomass Burning Aerosol Mass and Composition: A Critical Review of Field and Laboratory Studies.

Biomass burning is a major source of atmospheric particulate matter (PM) with impacts on health, climate, and air quality. The particles and vapors within biomass burning plumes undergo chemical and physical aging as they are transported downwind. Field measurements of the evolution of PM with plume age range from net decreases to net increases, with most showing little to no change. In contrast, laboratory studies tend to show significant mass increases on average. On the other hand, similar effects of aging on the average PM composition (e.g., oxygen-to-carbon ratio) are reported for lab and field studies. Currently, there is no consensus on the mechanisms that lead to these observed similarities and differences. This review summarizes available observations of aging-related biomass burning aerosol mass concentrations and composition markers, and discusses four broad hypotheses to explain variability within and between field and laboratory campaigns: (1) variability in emissions and chemistry, (2) differences in dilution/entrainment, (3) losses in chambers and lines, and (4) differences in the timing of the initial measurement, the baseline from which changes are estimated. We conclude with a concise set of research needs for advancing our understanding of the aging of biomass burning aerosol.

Ambient observations of sub-1.0 hygroscopic growth factor and f(RH) values: Case studies from surface and airborne measurements.

This study reports on the first set of ambient observations of sub-1.0 hygroscopicity values (i.e., growth factor, ratio of humidified-to-dry diameter, GF=D p,wet /D p,dry and f(RH), ratio of humidified-to-dry scattering coefficients, less than 1) with consistency across different instruments, regions, and platforms. We utilized data from (i) a shipboard humidified tandem differential mobility analyzer (HTDMA) during Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) in 2011, (ii) multiple instruments on the DC-8 aircraft during Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) in 2013, as well as (iii) the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe (DASH-SP) during measurement intensives during Summer 2014 and Winter 2015 in Tucson, Arizona. Sub-1.0 GFs were observed across the range of relative humidity (RH) investigated (75-95%), and did not show a RH-dependent trend in value below 1.0 or frequency of occurrence. A commonality between suppressed hygroscopicity in these experiments, including sub-1.0 GF, was the presence of smoke. Evidence of externally mixed aerosol, and thus multiple GFs, was observed during smoke periods resulting in at least one mode with GF < 1. Time periods during which the DASH-SP detected externally mixed aerosol coincide with sub-1.0 f(RH) observations. Mechanisms responsible for sub-1.0 hygroscopicity are discussed and include refractive index (RI) modifications due to aqueous processing, particle restructuring, and volatilization effects. To further investigate ambient observations of sub-1.0 GFs, f(RH), and particle restructuring, modifying hygroscopicity instruments with pre-humidification modules is recommended.

Surface and Airborne Measurements of Organosulfur and Methanesulfonate Over the Western United States and Coastal Areas.

This study reports on ambient measurements of organosulfur (OS) and methanesulfonate (MSA) over the western United States and coastal areas. Particulate OS levels are highest in summertime, and generally increase as a function of sulfate (a precursor) and sodium (a marine tracer) with peak levels at coastal sites. The ratio of OS to total sulfur (TS) is also highest at coastal sites, with increasing values as a function of Normalized Difference Vegetation Index (NDVI) and the ratio of organic carbon to elemental carbon. Correlative analysis points to significant relationships between OS and biogenic emissions from marine and continental sources, factors that coincide with secondary production, and vanadium due to a suspected catalytic role. A major OS species, methanesulfonate (MSA), was examined with intensive field measurements and the resulting data support the case for vanadium's catalytic influence. Mass size distributions reveal a dominant MSA peak between aerodynamic diameters of 0.32-0.56 µm at a desert and coastal site with nearly all MSA mass (≥ 84%) in sub-micrometer sizes; MSA:non-sea salt sulfate ratios vary widely as a function of particle size and proximity to the ocean. Airborne data indicate that relative to the marine boundary layer, particulate MSA levels are enhanced in urban and agricultural areas, and also the free troposphere when impacted by biomass burning. Some combination of fires and marine-derived emissions leads to higher MSA levels than either source alone. Finally, MSA differences in cloud water and out-of-cloud aerosol are discussed.

Modeling the radical chemistry in an oxidation flow reactor: radical formation and recycling, sensitivities, and the OH exposure estimation equation.

Oxidation flow reactors (OFRs) containing low-pressure mercury (Hg) lamps that emit UV light at both 185 and 254 nm ("OFR185") to generate OH radicals and O3 are used in many areas of atmospheric science and in pollution control devices. The widely used potential aerosol mass (PAM) OFR was designed for studies on the formation and oxidation of secondary organic aerosols (SOA), allowing for a wide range of oxidant exposures and short experiment duration with reduced wall loss effects. Although fundamental photochemical and kinetic data applicable to these reactors are available, the radical chemistry and its sensitivities have not been modeled in detail before; thus, experimental verification of our understanding of this chemistry has been very limited. To better understand the chemistry in the OFR185, a model has been developed to simulate the formation, recycling, and destruction of radicals and to allow the quantification of OH exposure (OHexp) in the reactor and its sensitivities. The model outputs of OHexp were evaluated against laboratory calibration experiments by estimating OHexp from trace gas removal and were shown to agree within a factor of 2. A sensitivity study was performed to characterize the dependence of the OHexp, HO2/OH ratio, and O3 and H2O2 output concentrations on reactor parameters. OHexp is strongly affected by the UV photon flux, absolute humidity, reactor residence time, and the OH reactivity (OHR) of the sampled air, and more weakly by pressure and temperature. OHexp can be strongly suppressed by high OHR, especially under low UV light conditions. A OHexp estimation equation as a function of easily measurable quantities was shown to reproduce model results within 10% (average absolute value of the relative errors) over the whole operating range of the reactor. OHexp from the estimation equation was compared with measurements in several field campaigns and shows agreement within a factor of 3. The improved understanding of the OFR185 and quantification of OHexp resulting from this work further establish the usefulness of such reactors for research studies, especially where quantifying the oxidation exposure is important.

Three-component synthesis and anticancer evaluation of polycyclic indenopyridines lead to the discovery of a novel indenoheterocycle with potent apoptosis inducing properties.

A multicomponent reaction of indane-1,3-dione, an aldehyde and an amine-containing aromatic compound leading to the formation of indenopyridine-based heterocyclic medicinal scaffolds has been investigated. It was found that the yields significantly improve when oxygen gas is bubbled through the reaction mixture, facilitating the oxidation of the intermediate dihydropyridine-containing compounds to their aromatic counterparts. Investigation of the reaction scope revealed that formaldehyde, as well as various aliphatic, aromatic and heteroaromatic aldehydes, works well as the aldehyde component. In addition, substituted anilines and diverse aminoheterocycles can be utilized in this process as the amine-containing component. Preliminary biological evaluation of the synthesized library identified a pyrimidine-based polycycle, which rivals the anticancer drug etoposide in its toxicity and apoptosis inducing properties toward a human T-cell leukemia cell line.