The contribution of black carbon to global ice nucleating particle concentrations relevant to mixed-phase clouds.

Black carbon (BC) aerosol plays an important role in the Earth's climate system because it absorbs solar radiation and therefore potentially warms the climate; however, BC can also act as a seed for cloud particles, which may offset much of its warming potential. If BC acts as an ice nucleating particle (INP), BC could affect the lifetime, albedo, and radiative properties of clouds containing both supercooled liquid water droplets and ice particles (mixed-phase clouds). Over 40% of global BC emissions are from biomass burning; however, the ability of biomass burning BC to act as an INP in mixed-phase cloud conditions is almost entirely unconstrained. To provide these observational constraints, we measured the contribution of BC to INP concentrations ([INP]) in real-world prescribed burns and wildfires. We found that BC contributes, at most, 10% to [INP] during these burns. From this, we developed a parameterization for biomass burning BC and combined it with a BC parameterization previously used for fossil fuel emissions. Applying these parameterizations to global model output, we find that the contribution of BC to potential [INP] relevant to mixed-phase clouds is ∼5% on a global average.

Impact of Biofuel Blends on Black Carbon Emissions from a Gas Turbine Engine.

Presented here is an overview of non-volatile particulate matter (nvPM) emissions, i.e. "soot" as assessed by TEM analyses of samples collected after the exhaust of a J-85 turbojet fueled with Jet-A as well as with blends of Jet-A and Camelina biofuel. A unifying explanation is provided to illustrate the combustion dynamics of biofuel and Jet-A fuel. The variation of primary particle size, aggregate size and nanostructure are analyzed as a function of biofuel blend across a range of engine thrust levels. The postulate is based on where fuels start along the soot formation pathway. Increasing biofuel content lowers aromatic concentration while placing increasing dependence upon fuel pyrolysis reactions to form the requisite concentration of aromatics for particle inception and growth. The required "kinetic" time for pyrolysis reactions to produce benzene and multi-ring PAHs allows increased fuel-air mixing by turbulence, diluting the fuel-rich soot-forming regions, effectively lowering their equivalence ratio. With a lower precursor concentration, particle inception is slowed, the resulting concentration of primary particles is lowered and smaller aggregates were measured. The lower equivalence ratio also results in smaller primary particles because of the lower concentration of growth species.

Particle-Phase Diffusion Modulates Partitioning of Semivolatile Organic Compounds to Aged Secondary Organic Aerosol.

The diffusivity of semivolatile organic compounds (SVOCs) in the bulk particle phase of a viscous atmospheric secondary organic aerosol (SOA) can have a profound impact on aerosol growth and size distribution dynamics. Here, we investigate the bulk diffusivity of SVOCs formed from photo-oxidation of isoprene as they partition to a bimodal aerosol consisting of an Aitken (potassium sulfate) and accumulation mode (aged α-pinene SOA) particles as a function of relative humidity (RH). The model analysis of the observed size distribution evolution shows that liquid-like diffusion coefficient values of Db > 10-10 cm2 s-1 fail to explain the growth of the Aitken mode. Instead, much lower values of Db between 2.5 × 10-15 cm2 s-1 at 32% RH and 8 × 10-15 cm2 s-1 at 82% RH were needed to successfully reproduce the growth of both modes. The diffusivity within the aged α-pinene SOA remains appreciably slow even at 80% RH, resulting in hindered partitioning of SVOCs to large viscous particles and allowing smaller and relatively less viscous particles to effectively absorb the available SVOCs and grow much faster than would be possible otherwise. These results have important implications for modeling SOA formation and growth in the ambient atmosphere.

Release of micro- and nanoparticles from biodegradable plastic during in situ composting.

Plastic is ubiquitous in modern life, but most conventional plastic is non-biodegradable and accumulates as waste after use. Biodegradable plastic is a promising alternative to conventional plastic. However, biodegradable plastics must be thoroughly evaluated to ensure that they undergo complete degradation and have no adverse impact on the environment. We evaluated the degradation of biodegradable plastics during 18-week full-scale composting, and determined whether additives from the plastics are released upon degradation. Two biodegradable plastic films-one containing polybutylene co-adipate co-terephthalate (PBAT) and the other containing polylactic acid/poly-hydroxy-alkanoate (PLA/PHA)-were placed into meshbags and buried in the compost. Degradation was assessed by image analysis, scanning electron microscopy, Fourier-transformed infrared spectroscopy, electrophoretic mobility, δ13C isotope analyses, and single particle mass spectrometry of mulch fragments. The results showed >99% macroscopic degradation of PLA/PHA and 97% for PBAT film. Polymers in the biodegradable films degraded; however, micro- and nanoparticles, most likely carbon black, were observed on the meshbags. Overall, biodegradable plastics hold promise, but the release of micro- and nanoparticles from biodegradable plastic upon degradation warrants additional investigation and calls for longer field testing to ensure that either complete biodegradation occurs or that no long-term harm to the environment is caused.

Formation of Polycyclic Aromatic Hydrocarbon Oxidation Products in α-Pinene Secondary Organic Aerosol Particles Formed through Ozonolysis.

Accurate long-range atmospheric transport (LRAT) modeling of polycyclic aromatic hydrocarbons (PAHs) and PAH oxidation products (PAH-OPs) in secondary organic aerosol (SOA) particles relies on the known chemical composition of the particles. Four PAHs, phenanthrene (PHE), dibenzothiophene (DBT), pyrene (PYR), and benz(a)anthracene (BaA), were studied individually to identify and quantify PAH-OPs produced and incorporated into SOA particles formed by ozonolysis of α-pinene in the presence of PAH vapor. SOA particles were characterized using real-time in situ instrumentation, and collected on quartz fiber filters for offline analysis of PAHs and PAH-OPs. PAH-OPs were measured in all PAH experiments at equal or greater concentrations than the individual PAHs they were produced from. The total mass of PAH and PAH-OPs, relative to the total SOA mass, varied for different experiments on individual parent PAHs: PHE and 6 quantified PHE-OPs (3.0%), DBT and dibenzothiophene sulfone (4.9%), PYR and 3 quantified PYR-OPs (3.1%), and BaA and benz(a)anthracene-7,12-dione (0.26%). Further exposure of PAH-SOA to ozone generally increased the concentration ratio of PAH-OPs to PAH, suggesting longer atmospheric lifetimes for PAH-OPs, relative to PAHs. These data indicate that PAH-OPs are formed during SOA particle formation and growth.

The effect of gas-phase polycyclic aromatic hydrocarbons on the formation and properties of biogenic secondary organic aerosol particles.

When secondary organic aerosol (SOA) particles are formed by ozonolysis in the presence of gas-phase polycyclic aromatic hydrocarbons (PAHs), their formation and properties are significantly different from SOA particles formed without PAHs. For all SOA precursors and all PAHs, discussed in this study, the presence of the gas-phase PAHs during SOA formation significantly affects particle mass loadings, composition, growth, evaporation kinetics, and viscosity. SOA particles formed in the presence of PAHs have, as part of their compositions, trapped unreacted PAHs and products of heterogeneous reactions between PAHs and ozone. Compared to 'pure' SOA particles, these particles exhibit slower evaporation kinetics, have higher fractions of non-volatile components, like oligomers, and higher viscosities, assuring their longer atmospheric lifetimes. In turn, the increased viscosity and decreased volatility provide a shield that protects PAHs from chemical degradation and evaporation, allowing for the long-range transport of these toxic pollutants. The magnitude of the effect of PAHs on SOA formation is surprisingly large. The presence of PAHs during SOA formation increases mass loadings by factors of two to five, and particle number concentrations, in some cases, by more than a factor of 100. Increases in SOA mass, particle number concentrations, and lifetime have important implications to many atmospheric processes related to climate, weather, visibility, and human health, all of which relate to the interactions between biogenic SOA and anthropogenic PAHs. The synergistic relationship between SOA and PAHs presented here are clearly complex and call for future research to elucidate further the underlying processes and their exact atmospheric implications.

Laboratory Studies of the Cloud Droplet Activation Properties and Corresponding Chemistry of Saline Playa Dust.

Playas emit large quantities of dust that can facilitate the activation of cloud droplets. Despite the potential importance of playa dusts for cloud formation, most climate models assume that all dust is nonhygroscopic; however, measurements are needed to clarify the role of dusts in aerosol-cloud interactions. Here, we report measurements of CCN activation from playa dusts and parameterize these results in terms of both κ-Köhler theory and adsorption activation theory for inclusion in atmospheric models. κ ranged from 0.002 ± 0.001 to 0.818 ± 0.094, whereas Frankel-Halsey-Hill (FHH) adsorption parameters of AFHH = 2.20 ± 0.60 and BFHH = 1.24 ± 0.14 described the water uptake properties of the dusts. Measurements made using aerosol time-of-flight mass spectrometry (ATOFMS) revealed the presence of halite, sodium sulfates, and sodium carbonates that were strongly correlated with κ underscoring the role that mineralogy, including salts, plays in water uptake by dust. Predictions of κ made using bulk chemical techniques generally showed good agreement with measured values. However, several samples were poorly predicted suggesting that chemical heterogeneities as a function of size or chemically distinct particle surfaces can determine the hygroscopicity of playa dusts. Our results further demonstrate the importance of dust in aerosol-cloud interactions.

Dust and biological aerosols from the Sahara and Asia influence precipitation in the western U.S.

Winter storms in California's Sierra Nevada increase seasonal snowpack and provide critical water resources and hydropower for the state. Thus, the mechanisms influencing precipitation in this region have been the subject of research for decades. Previous studies suggest Asian dust enhances cloud ice and precipitation, whereas few studies consider biological aerosols as an important global source of ice nuclei (IN). Here, we show that dust and biological aerosols transported from as far as the Sahara were present in glaciated high-altitude clouds coincident with elevated IN concentrations and ice-induced precipitation. This study presents the first direct cloud and precipitation measurements showing that Saharan and Asian dust and biological aerosols probably serve as IN and play an important role in orographic precipitation processes over the western United States.