Determining the sequence and structure of peptides is crucial for understanding their structure-property relationships. Among many techniques, structures are typically elucidated using nuclear magnetic resonance spectroscopy and single crystal X-ray diffraction measurements. In this study, we present terahertz time-domain spectroscopy (THz-TDS) as a complementary, nondestructive technique that is sensitive to both the primary and secondary structures of tetrapeptides. Using only a few milligrams of peptide, THz-TDS spectra have been measured, some of which have been supported by density functional theory (DFT) calculations, to distinguish six tetrameric peptides with similar primary and secondary structures.

Macrophage death in advanced atherosclerosis promotes necrosis and plaque destabilization. A likely cause of macrophage death is accumulation of free cholesterol (FC) in the ER, leading to activation of the unfolded protein response (UPR) and C/EBP homologous protein (CHOP)-induced apoptosis. Here we show that p38 MAPK signaling is necessary for CHOP induction and apoptosis. Additionally, two other signaling pathways must cooperate with p38-CHOP to effect apoptosis. One involves the type A scavenger receptor (SRA). As evidence, FC loading by non-SRA mechanisms activates p38 and CHOP, but not apoptosis unless the SRA is engaged. The other pathway involves c-Jun NH2-terminal kinase (JNK)2, which is activated by cholesterol trafficking to the ER, but is independent of CHOP. Thus, FC-induced apoptosis requires cholesterol trafficking to the ER, which triggers p38-CHOP and JNK2, and engagement of the SRA. These findings have important implications for understanding how the UPR, MAPKs, and the SRA might conspire to cause macrophage death, lesional necrosis, and plaque destabilization in advanced atherosclerotic lesions.

Aromatic organosulfates are identified and quantified in fine particulate matter (PM_2.5) from Lahore, Pakistan, Godavari, Nepal, and Pasadena, California. To support detection and quantification, authentic standards of phenyl sulfate, benzyl sulfate, 3-and 4-methylphenyl sulfate and 2-, 3-, and 4-methylbenzyl sulfate were synthesized. Authentic standards and aerosol samples were analyzed by ultra-performance liquid chromatography (UPLC) coupled to negative electrospray ionization (ESI) quadrupole time-of-flight (ToF) mass spectrometry. Benzyl sulfate was present in all three locations at concentrations ranging from 4 - 90 pg m^-3. Phenyl sulfate, methylphenyl sulfates and methylbenzyl sulfates were observed intermittently with abundances of 4 pg m^-3, 2-31 pg m^-3, 109 pg m^-3, respectively. Characteristic fragment ions of aromatic organosulfates include the sulfite radical (^•SO₃^-, m/z 80) and the sulfate radical (^•SO₄^-,m/z 96). Instrumental response factors of phenyl and benzyl sulfates varied by a factor of 4.3, indicating that structurally-similar organosulfates may have significantly different instrumental responses and highlighting the need to develop authentic standards for absolute quantitation organosulfates. In an effort to better understand the sources of aromatic organosulfates to the atmosphere, chamber experiments with the precursor toluene were conducted under conditions that form biogenic organosulfates. Aromatic organosulfates were not detected in the chamber samples, suggesting that they form through different pathways, have different precursors (e.g. naphthalene or methylnaphthalene), or are emitted from primary sources.

Peat fires in Southeast Asia have become a major annual source of trace gases and particles to the regional-global atmosphere. The assessment of their influence on atmospheric chemistry, climate, air quality, and health has been uncertain partly due to a lack of field measurements of the smoke characteristics. During the strong 2015 El Niño event we deployed a mobile smoke sampling team in the Indonesian province of Central Kalimantan on the island of Borneo and made the first, or rare, field measurements of trace gases, aerosol optical properties, and aerosol mass emissions for authentic peat fires burning at various depths in different peat types. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared spectroscopy, whole air sampling, photoacoustic extinctiometers (405 and 870 nm), and a small subset of the data from analyses of particulate filters. The trace gas measurements provide emission factors (EFs; grams of a compound per kilogram biomass burned) for up to ∼ 90 gases, including CO2, CO, CH4, non-methane hydrocarbons up to C10, 15 oxygenated organic compounds, NH3, HCN, NOx, OCS, HCl, etc. The modified combustion efficiency (MCE) of the smoke sources ranged from 0.693 to 0.835 with an average of 0.772 ± 0.053 (n = 35), indicating essentially pure smoldering combustion, and the emissions were not initially strongly lofted. The major trace gas emissions by mass (EF as g kg-1) were carbon dioxide (1564 ± 77), carbon monoxide (291 ± 49), methane (9.51 ± 4.74), hydrogen cyanide (5.75 ± 1.60), acetic acid (3.89 ± 1.65), ammonia (2.86 ± 1.00), methanol (2.14 ± 1.22), ethane (1.52 ± 0.66), dihydrogen (1.22 ± 1.01), propylene (1.07 ± 0.53), propane (0.989 ± 0.644), ethylene (0.961 ± 0.528), benzene (0.954 ± 0.394), formaldehyde (0.867 ± 0.479), hydroxyacetone (0.860 ± 0.433), furan (0.772 ± 0.035), acetaldehyde (0.697 ± 0.460), and acetone (0.691 ± 0.356). These field data support significant revision of the EFs for CO2 (g-8 %), CH4 (g-55 %), NH3 (g-86 %), CO (+39 %), and other gases compared with widely used recommendations for tropical peat fires based on a lab study of a single sample published in 2003. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) are important air toxics and aerosol precursors and were emitted in total at 1.5 ± 0.6 g kg-1. Formaldehyde is probably the air toxic gas most likely to cause local exposures that exceed recommended levels. The field results from Kalimantan were in reasonable agreement with recent lab measurements of smoldering Kalimantan peat for "overlap species," lending importance to the lab finding that burning peat produces large emissions of acetamide, acrolein, methylglyoxal, etc., which were not measurable in the field with the deployed equipment and implying value in continued similar efforts. The aerosol optical data measured include EFs for the scattering and absorption coefficients (EF Bscat and EF Babs, m2 kg-1 fuel burned) and the single scattering albedo (SSA) at 870 and 405 nm, as well as the absorption Ångström exponents (AAE). By coupling the absorption and co-located trace gas and filter data we estimated black carbon (BC) EFs (g kg-1) and the mass absorption coefficient (MAC, m2 g-1) for the bulk organic carbon (OC) due to brown carbon (BrC). Consistent with the minimal flaming, the emissions of BC were negligible (0.0055 ± 0.0016 g kg-1). Aerosol absorption at 405 nm was ∼ 52 times larger than at 870 nm and BrC contributed ∼ 96 % of the absorption at 405 nm. Average AAE was 4.97 ± 0.65 (range, 4.29-6.23). The average SSA at 405 nm (0.974 ± 0.016) was marginally lower than the average SSA at 870 nm (0.998 ± 0.001). These data facilitate modeling climate-relevant aerosol optical properties across much of the UV/visible spectrum and the high AAE and lower SSA at 405 nm demonstrate the dominance of absorption by the organic aerosol. Comparing the Babs at 405 nm to the simultaneously measured OC mass on filters suggests a low MAC (∼ 0.1) for the bulk OC, as expected for the low BC/OC ratio in the aerosol. The importance of pyrolysis (at lower MCE), as opposed to glowing (at higher MCE), in producing BrC is seen in the increase of AAE with lower MCE (r2 = 0.65).

The Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) campaign took place in and around the Kathmandu Valley and in the Indo-Gangetic Plain (IGP) of southern Nepal during April 2015. The source characterization phase targeted numerous important but undersampled (and often inefficient) combustion sources that are widespread in the developing world such as cooking with a variety of stoves and solid fuels, brick kilns, open burning of municipal solid waste (a.k.a. trash or garbage burning), crop residue burning, generators, irrigation pumps, and motorcycles. NAMaSTE produced the first, or rare, measurements of aerosol optical properties, aerosol mass, and detailed trace gas chemistry for the emissions from many of the sources. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared (FTIR) spectroscopy, whole-air sampling (WAS), and photoacoustic extinctiometers (PAX; 405 and 870nm) based on field work with a moveable lab sampling authentic sources. The primary aerosol optical properties reported include emission factors (EFs) for scattering and absorption coefficients (EF Bscat, EF Babs, inm2kg-1 fuel burned), single scattering albedos (SSAs), and absorption Ångström exponents (AAEs). From these data we estimate black and brown carbon (BC, BrC) emission factors (gkg-1 fuel burned). The trace gas measurements provide EFs (gkg-1) for CO2, CO, CH4, selected non-methane hydrocarbons up to C10, a large suite of oxygenated organic compounds, NH3, HCN, NOx, SO2, HCl, HF, etc. (up to ∼ 80 gases in all). The emissions varied significantly by source, and light absorption by both BrC and BC was important for many sources. The AAE for dung-fuel cooking fires (4.63±0.68) was significantly higher than for wood-fuel cooking fires (3.01±0.10). Dung-fuel cooking fires also emitted high levels of NH3 (3.00±1.33gkg-1), organic acids (7.66±6.90gkg-1), and HCN (2.01±1.25gkg-1), where the latter could contribute to satellite observations of high levels of HCN in the lower stratosphere above the Asian monsoon. HCN was also emitted in significant quantities by several non-biomass burning sources. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) were major emissions from both dung- (∼4.5gkg-1) and wood-fuel (∼1.5gkg-1) cooking fires, and a simple method to estimate indoor exposure to the many measured important air toxics is described. Biogas emerged as the cleanest cooking technology of approximately a dozen stove-fuel combinations measured. Crop residue burning produced relatively high emissions of oxygenated organic compounds (∼12gkg-1) and SO2 (2.54±1.09gkg-1). Two brick kilns co-firing different amounts of biomass with coal as the primary fuel produced contrasting results. A zigzag kiln burning mostly coal at high efficiency produced larger amounts of BC, HF, HCl, and NOx, with the halogenated emissions likely coming from the clay. The clamp kiln (with relatively more biomass fuel) produced much greater quantities of most individual organic gases, about twice as much BrC, and significantly more known and likely organic aerosol precursors. Both kilns were significant SO2 sources with their emission factors averaging 12.8±0.2gkg-1. Mixed-garbage burning produced significantly more BC (3.3±3.88gkg-1) and BTEX (∼4.5gkg-1) emissions than in previous measurements. For all fossil fuel sources, diesel burned more efficiently than gasoline but produced larger NOx and aerosol emission factors. Among the least efficient sources sampled were gasoline-fueled motorcycles during start-up and idling for which the CO EF was on the order of ∼700gkg-1 - or about 10 times that of a typical biomass fire. Minor motorcycle servicing led to minimal if any reduction in gaseous pollutants but reduced particulate emissions, as detailed in a companion paper (Jayarathne et al., 2016). A small gasoline-powered generator and an "insect repellent fire" were also among the sources with the highest emission factors for pollutants. These measurements begin to address the critical data gap for these important, undersampled sources, but due to their diversity and abundance, more work is needed.

In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA) that contributes to fine particulate matter (PM_2.5). Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO₂), oxides of nitrogen (NO _x ), and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH)-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM_2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM_2.5 filter samples were collected at the Birmingham, Alabama (BHM), ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS). Sample extracts were analyzed by gas chromatography-electron ionization-mass spectrometry (GC/EI-MS) with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH) network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM) (~ 7 to ~ 20 %). Isoprene-derived SOA tracers correlated with sulfate ( SO42- ) (r² = 0.34, n = 117) but not with NO _x . Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML)-derived SOA tracers with nitrate radical production (P[NO₃]) (r² = 0.57, n = 40) were observed during nighttime, suggesting a potential role of the NO₃ radical in forming this SOA type. However, the nighttime correlation of these tracers with nitrogen dioxide (NO₂) (r² = 0.26, n = 40) was weaker. Ozone (O₃) correlated strongly with MAE/HMML-derived tracers (r² = 0.72, n = 30) and moderately with 2-methyltetrols (r² = 0.34, n = 15) during daytime only, suggesting that a fraction of SOA formation could occur from isoprene ozonolysis in urban areas. No correlation was observed between aerosol pH and isoprene-derived SOA. Lack of correlation between aerosol acidity and isoprene-derived SOA is consistent with the observation that acidity is not a limiting factor for isoprene SOA formation at the BHM site as aerosols were acidic enough to promote multiphase chemistry of isoprene-derived epoxides throughout the duration of the study. All in all, these results confirm previous studies suggesting that anthropogenic pollutants enhance isoprene-derived SOA formation.

The effects of atmospheric aging on single-particle nascent sea spray aerosol (nSSA) physicochemical properties, such as morphology, composition, phase state, and water uptake, are important to understanding their impacts on the Earth's climate. The present study investigates these properties by focusing on the aged SSA (size range of 0.1-0.6 μm) and comparing with a similar size range nSSA, both generated at a peak of a phytoplankton bloom during a mesocosm study. The aged SSAs were generated by exposing nSSA to OH radicals with exposures equivalent to 4-5 days of atmospheric aging. Complementary filter-based thermal optical analysis, atomic force microscopy (AFM), and AFM photothermal infrared spectroscopy were utilized. Both nSSA and aged SSA showed an increase in the organic mass fraction with decreasing particle sizes. In addition, aging results in a further increase of the organic mass fraction, which can be attributed to new particle formation and oxidation of volatile organic compounds followed by condensation on pre-existing particles. The results are consistent with single-particle measurements that showed a relative increase in the abundance of aged SSA core-shells with significantly higher organic coating thickness, relative to nSSA. Increased hygroscopicity was observed for aged SSA core-shells, which had more oxygenated organic species. Rounded nSSA and aged SSA had similar hygroscopicity and no apparent changes in the composition. The observed changes in aged SSA physicochemical properties showed a significant size-dependence and particle-to-particle variability. Overall, results showed that the atmospheric aging can significantly influence the nSSA physicochemical properties, thus altering the SSA effects on the climate.

The impact of sea spray aerosols (SSAs) on Earth’s climate remains uncertain in part due to size-dependent particle-to-particle variability in SSA physicochemical properties such as morphology, composition, phase state, and water uptake that can be further modulated by the environment relative humidity (RH). The current study investigates these properties as a function of particle size and RH, while focusing on submicrometer nascent SSA (0.1–0.6 μm) collected throughout a phytoplankton bloom. Filter-based thermal optical analysis, atomic force microscopy (AFM), and AFM photothermal infrared spectroscopy (AFM–PTIR) were utilized in this regard. AFM imaging at 20% RH identified five main SSA morphologies: prism-like, core–shell, rounded, rod, and aggregate. The majority of smaller SSAs throughout a bloom were rounded, while larger SSAs were core–shell. Filter-based measurements revealed an increasing organic mass fraction with decreasing SSA size. The organic matter is shown to primarily reside in a rounded and core–shell SSA, while the prism-like and rod SSA are predominantly inorganic salts (i.e., sodium chloride, nitrates, and sulfates) with relatively low organic content, as determined by AFM–PTIR spectroscopy. AFM phase state measurements at 20% RH revealed an increasing abundance of core–shell SSA with semisolid shells and rounded SSA with a solid phase state, as the particle size decreases. At 60% RH, shells of core–shell and rounded SSA uptake water, become less viscous, and their phase states change into either semisolid or liquid. Collectively, findings reveal the dynamic and size-dependent nature of SSA’s morphology, composition, phase states, and water uptake, which should be considered to accurately predict their climate-related effects.

The impact of sea spray aerosol (SSA) on climate depends on the size and chemical composition of individual particles that make up the total SSA ensemble. There remains a lack of understanding as to the composition of individual particles within the SSA ensemble and how it changes in response to dynamic ocean biology. Here, we characterize the classes of organic compounds as well as specific molecules within individual SSA particles. The diversity of molecules within the organic fraction was observed to vary between submicrometer- and supermicrometer-sized particles and included contributions from fatty acids, monosaccharides, polysaccharides, and siliceous material. Significant changes in this molecular diversity were observed to coincide with the rise and fall of phytoplankton and heterotrophic bacteria populations within the seawater. Furthermore, the water uptake of individual particles was affected, as learned from studying the hygroscopicity of model systems composed of representative mixtures of salts and organic compounds.