scholarly journals Single-particle characterization of biomass burning organic aerosol (BBOA): evidence for non-uniform mixing of high molecular weight organics and potassium

2016 ◽  
Vol 16 (9) ◽  
pp. 5561-5572 ◽  
Author(s):  
Alex K. Y. Lee ◽  
Megan D. Willis ◽  
Robert M. Healy ◽  
Jon M. Wang ◽  
Cheol-Heon Jeong ◽  
...  
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Biomass Burning ◽  
Single Particle ◽  
Radiative Forcing ◽  
Critical Role ◽  
Organic Aerosol ◽  
Mixing State ◽  
Particle Measurements ◽  
Near Ultraviolet

Abstract. Biomass burning organic aerosol (BBOA) can be emitted from natural forest fires and human activities such as agricultural burning and domestic energy generation. BBOA is strongly associated with atmospheric brown carbon (BrC) that absorbs near-ultraviolet and visible light, resulting in significant impacts on regional visibility degradation and radiative forcing. The mixing state of BBOA can play a critical role in the prediction of aerosol optical properties. In this work, single-particle measurements from a Soot-Particle Aerosol Mass Spectrometer coupled with a light scattering module (LS-SP-AMS) were performed to examine the mixing state of BBOA, refractory black carbon (rBC), and potassium (K, a tracer for biomass burning aerosol) in an air mass influenced by wildfire emissions transported from northern Québec to Toronto, representing aged biomass burning plumes. Cluster analysis of single-particle measurements identified five BBOA-related particle types. rBC accounted for 3–14 wt % of these particle types on average. Only one particle type exhibited a strong ion signal for K+, with mass spectra characterized by low molecular weight organic species. The remaining four particle types were classified based on the apparent molecular weight of the BBOA constituents. Two particle types were associated with low potassium content and significant amounts of high molecular weight (HMW) organic compounds. Our observations indicate non-uniform mixing of particles within a biomass burning plume in terms of molecular weight and illustrate that HMW BBOA can be a key contributor to low-volatility BrC observed in BBOA particles. The average mass absorption efficiency of low-volatility BBOA is about 0.8–1.1 m2 g−1 based on a theoretical closure calculation. Our estimates indicate that low-volatility BBOA contributes ∼ 33–44 % of thermo-processed particle absorption at 405 nm; and almost all of the BBOA absorption was associated with low-volatility organics.

scholarly journals Single particle characterization of biomass burning organic aerosol (BBOA): evidence for non-uniform mixing of high molecular weight organics and potassium

2015 ◽  
Vol 15 (22) ◽  
pp. 32157-32183 ◽  
Author(s):  
A. K. Y. Lee ◽  
M. D. Willis ◽  
R. M. Healy ◽  
J. M. Wang ◽  
C.-H. Jeong ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Black Carbon ◽  
High Molecular Weight ◽  
Biomass Burning ◽  
Single Particle ◽  
Critical Role ◽  
Organic Aerosol ◽  
Mixing State ◽  
Particle Measurements ◽  
Near Ultraviolet

Abstract. Biomass burning is a major source of black carbon (BC) and primary organic aerosol globally. In particular, biomass burning organic aerosol (BBOA) is strongly associated with atmospheric brown carbon (BrC) that absorbs near ultraviolet and visible light, resulting in significant impacts on regional visibility degradation and radiative forcing. The mixing state of BBOA can play a critical role in the prediction of aerosol optical properties. In this work, single particle measurements from a soot-particle aerosol mass spectrometer coupled with a light scattering module (LS-SP-AMS) were performed to examine the mixing state of BBOA, refractory black carbon (rBC) and potassium (K+, a tracer for biomass burning aerosol) in an air mass influenced by aged biomass burning. Cluster analysis of single particle measurements identified five BBOA-related particle types. rBC accounted for 3–14 w.t. % of these particle types on average. Only one particle type exhibited a strong ion signal for K+, with mass spectra characterized by low molecular weight organic species. The remaining four particle types were classified based on the apparent molecular weight of the BBOA constituents. Two particle types were associated with low potassium content and significant amounts of high molecular weight (HMW) organic compounds. Our observations indicate non-uniform mixing of particles within a biomass burning plume in terms of molecular weight and illustrate that HMW BBOA can be a key contributor to low-volatility BrC observed in BBOA particles.

Derivation of the material models for ultra-high molecular-weight polyethylene fiber-reinforced armor-grade composites with different architectures

2016 ◽  
Vol 33 (3) ◽  
Author(s):  
Mica Grujicic ◽  
Jennifer Snipes ◽  
S. Ramaswami ◽  
Vasudeva Avuthu ◽  
Chian-Fong Yen ◽  
...  
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Design Methodology ◽  
Critical Role ◽  
Fiber Reinforcement ◽  
Mechanical Tests ◽  
Transverse Impact ◽  
Material Models ◽  
Polyethylene Fiber ◽  
Ultra High Molecular Weight

Purpose To overcome the problem of inferior through-the-thickness mechanical properties displayed by armor-grade composites based on 2-D reinforcement architectures, armor-grade composites based on 3D fiber-reinforcement architectures have recently been investigated experimentally. Design/methodology/approach The subject of the present work is armor-grade composite materials reinforced using ultra-high-molecular-weight polyethylene fibers and having four (two 2D and two 3D) prototypical architectures, as well as the derivation of the corresponding material models. The effect of the reinforcement architecture is accounted for by constructing the appropriate unit cells (within which the constituent materials and their morphologies are represented explicitly) and subjecting them to a series of virtual mechanical tests. The results obtained are used within a post-processing analysis to derive and parameterize the corresponding homogenized-material models. One of these models (specifically, the one for 0°/90° cross-collimated fiber architecture) was directly validated by comparing its predictions with the experimental counterparts. The other models are validated by examining their physical soundness and details of their predictions. Lastly, the models are integrated as user-material subroutines, and linked with a commercial finite-element package, in order to carry out a transient non-linear dynamics analysis of ballistic transverse impact of armor-grade composite-material panels with different reinforcement architectures. Findings It is found that the reinforcement architecture plays a critical role in the overall ballistic limit of the armor panel, as well as in its structural and damage/failure response. Originality/value To the authors’ knowledge, the present work is the first reported attempt to assess, computationally, the utility and effectiveness of 3D fiber-reinforcement architectures for ballistic impact applications.

High-Molecular-Weight, High-Unsaturation Copolymers of Isobutylene and Conjugated Dienes. I. Synthesis

1976 ◽  
Vol 49 (4) ◽  
pp. 960-966 ◽  
Author(s):  
W. A. Thaler ◽  
D. J. Buckley
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Cationic Polymerization ◽  
Critical Role ◽  
Conjugated Dienes ◽  
Solution Properties ◽  
Insight Into

Abstract This investigation has provided insight into the critical role of solution properties on the course of cationic polymerization and has led to a technique for reconciling the opposing demands for synthesis of isoolefin-diene copolymers both free from gel and high in molecular weight. By this technique, the synthesis of a broad range of intermediate-unsaturation elastomers of quality has been realized.

scholarly journals Measurement Report: Optical properties and sources of water-soluble brown carbon in Tianjin, North China: insights from organic molecular compositions

2022 ◽  
Author(s):  
Junjun Deng ◽  
Hao Ma ◽  
Xinfeng Wang ◽  
Shujun Zhong ◽  
Zhimin Zhang ◽  
...  
Keyword(s):  
Optical Properties ◽  
Biomass Burning ◽  
Light Absorption ◽  
Radiative Forcing ◽  
North China ◽  
Water Soluble ◽  
Formation Mechanisms ◽  
Chemical Compositions ◽  
Brown Carbon ◽  
Near Ultraviolet

Abstract. Brown carbon (BrC) aerosols exert vital impacts on climate change and atmospheric photochemistry due to their light absorption in the wavelength range from near-ultraviolet (UV) to visible light. However, the optical properties and formation mechanisms of ambient BrC remain poorly understood, limiting the estimation of their radiative forcing. In the present study, fine aerosols (PM2.5) were collected during 2016–2017 on a day/night basis over urban Tianjin, a megacity in North China, to obtain seasonal and diurnal patterns of atmospheric water-soluble BrC. There were obvious seasonal but no evident diurnal variations in light absorption properties of BrC. In winter, BrC showed much stronger light absorbing ability since mass absorption efficiency at 365 nm (MAE365) (1.54 ± 0.33 m2 g−1), which was 1.8 times larger than that (0.84 ± 0.22 m2 g−1) in summer. Direct radiative effects by BrC absorption relative to black carbon in the UV range were 54.3 ± 16.9 % and 44.6 ± 13.9 %, respectively. In addition, five fluorescent components in BrC, including three humic-like fluorophores and two protein-like fluorophores were identified with excitation-emission matrix fluorescence spectrometry and parallel factor (PARAFAC) analysis. The lowly-oxygenated components contributed more to winter and nighttime samples, while more-oxygenated components increased in summer and daytime samples. The higher humification index (HIX) together with lower biological index (BIX) and fluorescence index (FI) suggest that the chemical compositions of BrC were associated with a high aromaticity degree in summer and daytime due to photobleaching. Fluorescent properties indicate that wintertime BrC were predominantly affected by primary emissions and fresh secondary organic aerosol (SOA), while summer ones were more influenced by aging processes. Results of source apportionments using organic molecular compositions of the same set of aerosols reveal that fossil fuel combustion and aging processes, primary bioaerosol emission, biomass burning, and biogenic and anthropogenic SOA formation were the main sources of BrC. Biomass burning contributed much larger to BrC in winter and at nighttime, while biogenic SOA contributed more in summer and at daytime. Especially, our study highlights that primary bioaerosol emission is an important source of BrC in urban Tianjin in summer.

scholarly journals Single particle diversity and mixing state measurements

2014 ◽  
Vol 14 (12) ◽  
pp. 6289-6299 ◽  
Author(s):  
R. M. Healy ◽  
N. Riemer ◽  
J. C. Wenger ◽  
M. Murphy ◽  
M. West ◽  
...  
Keyword(s):  
Species Diversity ◽  
Ammonium Nitrate ◽  
Black Carbon ◽  
Mass Spectrometer ◽  
Single Particle ◽  
Organic Aerosol ◽  
Particle Mass ◽  
Mixing State ◽  
Mass Fractions ◽  
State Index

Abstract. A newly developed framework for quantifying aerosol particle diversity and mixing state based on information-theoretic entropy is applied for the first time to single particle mass spectrometry field data. Single particle mass fraction estimates for black carbon, organic aerosol, ammonium, nitrate and sulfate, derived using single particle mass spectrometer, aerosol mass spectrometer and multi-angle absorption photometer measurements are used to calculate single particle species diversity (Di). The average single particle species diversity (Dα) is then related to the species diversity of the bulk population (Dγ) to derive a mixing state index value (χ) at hourly resolution. The mixing state index is a single parameter representation of how internally/externally mixed a particle population is at a given time. The index describes a continuum, with values of 0 and 100% representing fully external and internal mixing, respectively. This framework was applied to data collected as part of the MEGAPOLI winter campaign in Paris, France, 2010. Di values are low (~ 2) for fresh traffic and wood-burning particles that contain high mass fractions of black carbon and organic aerosol but low mass fractions of inorganic ions. Conversely, Di values are higher (~ 4) for aged carbonaceous particles containing similar mass fractions of black carbon, organic aerosol, ammonium, nitrate and sulfate. Aerosol in Paris is estimated to be 59% internally mixed in the size range 150–1067 nm, and mixing state is dependent both upon time of day and air mass origin. Daytime primary emissions associated with vehicular traffic and wood-burning result in low χ values, while enhanced condensation of ammonium nitrate on existing particles at night leads to higher χ values. Advection of particles from continental Europe containing ammonium, nitrate and sulfate leads to increases in Dα, Dγ and χ. The mixing state index represents a useful metric by which to compare and contrast ambient particle mixing state at other locations globally.

scholarly journals Mixing state of carbonaceous aerosol in an urban environment: single particle characterization using the soot particle aerosol mass spectrometer (SP-AMS)

2015 ◽  
Vol 15 (4) ◽  
pp. 1823-1841 ◽  
Author(s):  
A. K. Y. Lee ◽  
M. D. Willis ◽  
R. M. Healy ◽  
T. B. Onasch ◽  
J. P. D. Abbatt
Keyword(s):  
Cluster Analysis ◽  
Urban Environment ◽  
Mass Spectrometer ◽  
Single Particle ◽  
Soot Particle ◽  
Organic Aerosol ◽  
Mixing State ◽  
Aerosol Mass Spectrometer ◽  
Mass Spectral ◽  
Aerosol Mass

Abstract. Understanding the impact of atmospheric black carbon (BC)-containing particles on human health and radiative forcing requires knowledge of the mixing state of BC, including the characteristics of the materials with which it is internally mixed. In this study, we examine the mixing state of refractory BC (rBC) and other aerosol components in an urban environment (downtown Toronto) utilizing the Aerodyne soot particle aerosol mass spectrometer equipped with a light scattering module (LS-SP-AMS). k-means cluster analysis was used to classify single particle mass spectra into chemically distinct groups. One resultant particle class is dominated by rBC mass spectral signals (C1+ to C5+) while the organic signals fall into a few major particle classes identified as hydrocarbon-like organic aerosol (HOA), oxygenated organic aerosol (OOA), and cooking emission organic aerosol (COA). A gradual mixing is observed with small rBC particles only thinly coated by HOA (~ 28% by mass on average), while over 90% of the HOA-rich particles did not contain detectable amounts of rBC. Most of the particles classified into other inorganic and organic particle classes were not significantly associated with rBC. The single particle results also suggest that HOA and COA emitted from anthropogenic sources were likely major contributors to organic-rich particles with vacuum aerodynamic diameter (dva) ranging from ~ 200 to 400 nm. The similar temporal profiles and mass spectral features of the organic classes identified by cluster analysis and the factors from a positive matrix factorization (PMF) analysis of the ensemble aerosol data set validate the interpretation of the PMF results.

scholarly journals Effect of secondary organic aerosol coating thickness on the real-time detection and characterization of biomass-burning soot by two particle mass spectrometers

2016 ◽  
Vol 9 (12) ◽  
pp. 6117-6137 ◽  
Author(s):  
Adam T. Ahern ◽  
Ramachandran Subramanian ◽  
Georges Saliba ◽  
Eric M. Lipsky ◽  
Neil M. Donahue ◽  
...  
Keyword(s):  
Black Carbon ◽  
Biomass Burning ◽  
Radiative Forcing ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Particle Mass ◽  
Laser Vaporization ◽  
Mass Spectrometers ◽  
Ir Laser ◽  
Biomass Burning Particles

Abstract. Biomass burning is a large source of light-absorbing refractory black carbon (rBC) particles with a wide range of morphologies and sizes. The net radiative forcing from these particles is strongly dependent on the amount and composition of non-light-absorbing material internally mixed with the rBC and on the morphology of the mixed particles. Understanding how the mixing state and morphology of biomass-burning aerosol evolves in the atmosphere is critical for constraining the influence of these particles on radiative forcing and climate. We investigated the response of two commercial laser-based particle mass spectrometers, the vacuum ultraviolet (VUV) ablation LAAPTOF and the IR vaporization SP-AMS, to monodisperse biomass-burning particles as we sequentially coated the particles with secondary organic aerosol (SOA) from α-pinene ozonolysis. We studied three mobility-selected soot core sizes, each with a number of successively thicker coatings of SOA applied. Using IR laser vaporization, the SP-AMS had different changes in sensitivity to rBC compared to potassium as a function of applied SOA coatings. We show that this is due to different effective beam widths for the IR laser vaporization region of potassium versus black carbon. The SP-AMS's sensitivity to black carbon (BC) mass was not observed to plateau following successive SOA coatings, despite achieving high OA : BC mass ratios greater than 9. We also measured the ion fragmentation pattern of biomass-burning rBC and found it changed only slightly with increasing SOA mass. The average organic matter ion signal measured by the LAAPTOF demonstrated a positive correlation with the condensed SOA mass on individual particles, despite the inhomogeneity of the particle core compositions. This demonstrates that the LAAPTOF can obtain quantitative mass measurements of aged soot-particle composition from realistic biomass-burning particles with complex morphologies and composition.

scholarly journals Synergistic effects of engineered nanoparticles and organics released from laser printers using nano-enabled toners: potential health implications from exposures to the emitted organic aerosol

2017 ◽  
Vol 4 (11) ◽  
pp. 2144-2156 ◽  
Author(s):  
Marie-Cecile G. Chalbot ◽  
Sandra V. Pirela ◽  
Laura Schifman ◽  
Varun Kasaraneni ◽  
Vinka Oyanedel-Craver ◽  
...  
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Synergistic Effects ◽  
Organic Aerosol ◽  
Engineered Nanoparticles ◽  
Engineered Nanomaterials ◽  
Potential Health ◽  
Health Implications ◽  
Laser Printers ◽  
High Molecular Weight Pahs

Engineered nanomaterials released from nano-enabled toners result in formation of high molecular weight PAHs.

scholarly journals In-cloud processes of methacrolein under simulated conditions – Part 2: Formation of secondary organic aerosol

2009 ◽  
Vol 9 (14) ◽  
pp. 5107-5117 ◽  
Author(s):  
I. El Haddad ◽  
L. Nieto-Gligorovski ◽  
V. Michaud ◽  
B. Temime-Roussel ◽  
E. Quivet ◽  
...  
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Aqueous Phase ◽  
Mass Concentration ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oh Radicals ◽  
Aerosol Formation ◽  
Esi Ms ◽  
Aerosol Mass Concentration

Abstract. The fate of methacrolein in cloud evapo-condensation cycles was experimentally investigated. To this end, aqueous-phase reactions of methacrolein with OH radicals were performed (as described in Liu et al., 2009), and the obtained solutions were then nebulized and dried into a mixing chamber. ESI-MS and ESI-MS/MS analyses of the aqueous phase composition denoted the formation of high molecular weight multifunctional products containing hydroxyl, carbonyl and carboxylic acid moieties. The time profiles of these products suggest that their formation can imply radical pathways. These high molecular weight organic products are certainly responsible for the formation of secondary organic aerosol (SOA) observed during the nebulization experiments. The size, number and mass concentration of these particles increased significantly with the reaction time: after 22 h of reaction, the aerosol mass concentration was about three orders of magnitude higher than the initial aerosol quantity. The evaluated SOA yield ranged from 2 to 12%. These yields were confirmed by another estimation method based on the hygroscopic and volatility properties of the obtained SOA measured and reported by Michaud et al. (2009). These results provide, for the first time to our knowledge, strong experimental evidence that cloud processes can act, through photooxidation reactions, as important contributors to secondary organic aerosol formation in the troposphere.

scholarly journals Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

2014 ◽  
Vol 14 (8) ◽  
pp. 4201-4218 ◽  
Author(s):  
K. Kristensen ◽  
T. Cui ◽  
H. Zhang ◽  
A. Gold ◽  
M. Glasius ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Gas Phase ◽  
High Molecular Weight ◽  
Carboxylic Acids ◽  
Particle Number ◽  
Organic Aerosol ◽  
Number Concentration ◽  
Particle Number Concentration ◽  
Aerosol Acidity ◽  
Homogenous Nucleation

Abstract. The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a factor of two at higher RH (50–90%) relative to lower RH (30–50%). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to carboxylic acids and dimers. The results support the formation of the high-molecular weight dimers through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of α-pinene. The high molecular weight and polar nature of dimers formed in the gas phase may explain increased particle number concentration as a result of homogenous nucleation. Since three of these dimers (i.e. pinyl-diaterpenyl dimer (MW 358), pinyl-diaterebyl dimer (MW 344) and pinonyl-pinyl dimer (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimers observed in this study can be used as tracers for the O3-initiated oxidation of α-pinene, and are therefore indicative of enhanced anthropogenic activities, and that the high molecular weight and low volatility dimers result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.

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