Night-time oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

Reactions of the key atmospheric night-time oxidant NO3 with organic monolayers at the air–water interface are used as proxies for the ageing of organic-coated aqueous aerosols. The surfactant molecules chosen for this study are oleic acid (OA), palmitoleic acid (POA), methyl oleate (MO) and stearic acid (SA) to investigate the effects of chain length, head group and degree of unsaturation on the reaction kinetics and products formed. Fully and partially deuterated surfactants were studied using neutron reflectometry (NR) to determine the reaction kinetics of organic monolayers with NO3 at the air–water interface for the first time. Kinetic modelling allowed us to determine the rate coefficients for the oxidation of OA, POA and MO monolayers to be (2.8 ± 0.7) × 10−8 cm2 molecule−1 s−1, (2.4 ± 0.5) × 10−8 cm2 molecule−1 s−1 and (3.3 ± 0.6) × 10−8 cm2 molecule−1 s−1, respectively. The corresponding uptake coefficients were found to be (2.1 ± 0.5) × 10−3, (1.7 ± 0.3) × 10−3 and (2.1 ± 0.4) × 10−3. For the much slower NO3-initiated oxidation of the saturated surfactant SA we found a loss rate of (5 ± 1) × 10−12 cm2 molecule−1 s−1 which we consider to be an upper limit for the reactive loss, and estimated an uptake coefficient of (5 ± 1) × 10−7. Our investigations demonstrate that NO3 will contribute substantially to the processing of unsaturated surfactants at the air–water interface during night-time given its reactivity is ca. two orders of magnitude higher than that of O3. Furthermore, the relative contributions of NO3 and O3 to the oxidative losses vary massively between species that are closely related in structure: NO3 reacts ca. 400 times faster than O3 with the common model surfactant oleic acid, but only ca. 60 times faster with its methyl ester MO. It is therefore necessary to perform a case-by-case assessment of the relative contributions of the different degradation routes for any specific surfactant. The overall impact of NO3 on the fate of saturated surfactants is slightly less clear given the lack of prior kinetic data for comparison, but NO3 is likely to contribute significantly to the loss of saturated species and dominate their loss during night-time. The retention of the organic character at the air–water interface differs fundamentally between the different surfactant species: the fatty acids studied (OA and POA) form products with a yield of ∼ 20% that are stable at the interface while NO3-initiated oxidation of the methyl ester MO rapidly and effectively removes the organic character (≤ 3% surface-active products). The film-forming potential of reaction products in real aerosol is thus likely to depend on the relative proportions of saturated and unsaturated surfactants as well as the head group properties. Atmospheric lifetimes of unsaturated species are much longer than those determined with respect to their reactions at the air–water interface, so that they must be protected from oxidative attack e.g. by incorporation into a complex aerosol matrix or in mixed surface films with yet unexplored kinetic behaviour

Atmospheric Degradation of Ecologically Important Biogenic Volatiles:Investigating the Ozonolysis of (E)-β-Ocimene, Isomers of α and β-Farnesene, α-Terpinene and 6-Methyl-5-Hepten-2-One, and Their Gas-Phase Products

Biogenic volatile organic compounds (bVOCs), synthesised by plants, are important mediators of ecological interactions that can also undergo a series of reactions in the atmosphere. Ground-level ozone is a secondary pollutant generated through sunlight-driven reactions between nitrogen oxides (NOx) and VOCs. Its levels have increased since the industrial revolution and reactions involving ozone drive many chemical processes in the troposphere. While ozone precursors often originate in urban areas, winds may carry these hundreds of kilometres, causing ozone formation to also occur in less populated rural regions. Under elevated ozone conditions, ozonolysis of bVOCs can result in quantitative and qualitative changes in the gas phase, reducing the concentrations of certain bVOCs and resulting in the formation of other compounds. Such changes can result in disruption of bVOC-mediated behavioural or ecological interactions. Through a series of gas-phase experiments using Gas Chromatography Mass Spectrometry (GC-MS) and Proton Transfer Reaction Mass Spectrometry (PTR-MS), we investigated the products and their yields from the ozonolysis of a range of ubiquitous bVOCs, which were selected because of their importance in mediating ecological interactions such as pollinator and natural enemy attraction and plant-to-plant communication, namely: (E)-β-ocimene, isomers of α and β-farnesene, α-terpinene and 6-methyl-5-hepten-2-one. New products from the ozonolysis of these compounds were identified, and the formation of these compounds is consistent with terpene-ozone oxidation mechanisms. We present the degradation mechanism of our model bVOCs and identify their reaction products. We discuss the potential ecological implications of the degradation of each bVOC and of the formation of reaction products

Evidence for proton acceleration up to TeV energies based on VERITAS and Fermi-LAT observations of the Cas A SNR

We present a study of $\gamma$-ray emission from the core-collapse supernova remnant Cas~A in the energy range from 0.1GeV to 10TeV. We used 65 hours of VERITAS data to cover 200 GeV - 10 TeV, and 10.8 years of \textit{Fermi}-LAT data to cover 0.1-500 GeV. The spectral analysis of \textit{Fermi}-LAT data shows a significant spectral curvature around $1.3 \pm 0.4_{stat}$ GeV that is consistent with the expected spectrum from pion decay. Above this energy, the joint spectrum from \textit{Fermi}-LAT and VERITAS deviates significantly from a simple power-law, and is best described by a power-law with spectral index of $2.17\pm 0.02_{stat}$ with a cut-off energy of $2.3 \pm 0.5_{stat}$ TeV. These results, along with radio, X-ray and $\gamma$-ray data, are interpreted in the context of leptonic and hadronic models. Assuming a one-zone model, we exclude a purely leptonic scenario and conclude that proton acceleration up to at least 6 TeV is required to explain the observed $\gamma$-ray spectrum. From modeling of the entire multi-wavelength spectrum, a minimum magnetic field inside the remnant of $B_{\mathrm{min}}\approx150\,\mathrm{\mu G}$ is deduced.Comment: 33 pages, 9 Figures, 6 Table

Search for Ultraheavy Dark Matter from Observations of Dwarf Spheroidal Galaxies with VERITAS

Dark matter is a key piece of the current cosmological scenario, with weakly interacting massive particles (WIMPs) a leading dark matter candidate. WIMPs have not been detected in their conventional parameter space (100 GeV $\lesssim M_{\chi} \lesssim$ 100 TeV), a mass range accessible with current Imaging Atmospheric Cherenkov Telescopes. As ultraheavy dark matter (UHDM; $M_{\chi} \gtrsim$ 100 TeV) has been suggested as an under-explored alternative to the WIMP paradigm, we search for an indirect dark matter annihilation signal in a higher mass range (up to 30 PeV) with the VERITAS gamma-ray observatory. With 216 hours of observations of four dwarf spheroidal galaxies, we perform an unbinned likelihood analysis. We find no evidence of a $\gamma$-ray signal from UHDM annihilation above the background fluctuation for any individual dwarf galaxy nor for a joint-fit analysis, and consequently constrain the velocity-weighted annihilation cross section of UHDM for dark matter particle masses between 1 TeV and 30 PeV. We additionally set constraints on the allowed radius of a composite UHDM particle.Comment: 10 pages, 7 figure

VERITAS Discovery of VHE Emission from the Radio Galaxy 3C 264: A Multi-Wavelength Study

The radio source 3C 264, hosted by the giant elliptical galaxy NGC 3862, was observed with VERITAS between February 2017 and May 2019. These deep observations resulted in the discovery of very-high-energy (VHE; E $>100$ GeV) $\gamma$-ray emission from this active galaxy. An analysis of $\sim$57 hours of quality-selected live time yields a detection at the position of the source, corresponding to a statistical significance of 7.8 standard deviations above background. The observed VHE flux is variable on monthly time scales, with an elevated flux seen in 2018 observations. The VHE emission during this elevated state is well-characterized by a power-law spectrum with a photon index $\Gamma = 2.20 \pm 0.27$ and flux F($>315$ GeV) = ($7.6\pm 1.2_{\mathrm stat} \pm 2.3_{\mathrm syst})\times 10^{-13}$ cm$^{-2}$ s$^{-1}$, or approximately 0.7% of the Crab Nebula flux above the same threshold. 3C 264 ($z = 0.0217$) is the most distant radio galaxy detected at VHE, and the elevated state is thought to be similar to that of the famously outbursting jet in M 87. Consequently, extensive contemporaneous multi-wavelength data were acquired in 2018 at the time of the VHE high state. An analysis of these data, including VLBA, VLA, HST, Chandra and Swift observations in addition to the VERITAS data, is presented, along with a discussion of the resulting spectral energy distribution.Comment: 19 pages, 11 figures, Accepted for publication in Astrophysical Journa

Measurement of the extragalactic background light spectral energy distribution with VERITAS

The extragalactic background light (EBL), a diffuse photon field in the optical and infrared range, is a record of radiative processes over the Universe's history. Spectral measurements of blazars at very high energies ($>$100 GeV) enable the reconstruction of the spectral energy distribution (SED) of the EBL, as the blazar spectra are modified by redshift- and energy-dependent interactions of the gamma-ray photons with the EBL. The spectra of 14 VERITAS-detected blazars are included in a new measurement of the EBL SED that is independent of EBL SED models. The resulting SED covers an EBL wavelength range of 0.56--56 $\mu$m, and is in good agreement with lower limits obtained by assuming that the EBL is entirely due to radiation from cataloged galaxies.Comment: Accepted for publication in The Astrophysical Journa

An Archival Search for Neutron-Star Mergers in Gravitational Waves and Very-High-Energy Gamma Rays

The recent discovery of electromagnetic signals in coincidence with neutron-star mergers has solidified the importance of multimessenger campaigns in studying the most energetic astrophysical events. Pioneering multimessenger observatories, such as LIGO/Virgo and IceCube, record many candidate signals below the detection significance threshold. These sub-threshold event candidates are promising targets for multimessenger studies, as the information provided by them may, when combined with contemporaneous gamma-ray observations, lead to significant detections. Here we describe a new method that uses such candidates to search for transient events using archival very-high-energy gamma-ray data from imaging atmospheric Cherenkov telescopes (IACTs). We demonstrate the application of this method to sub-threshold binary neutron star (BNS) merger candidates identified in Advanced LIGO's first observing run. We identify eight hours of archival VERITAS observations coincident with seven BNS merger candidates and search them for TeV emission. No gamma-ray emission is detected; we calculate upper limits on the integral flux and compare them to a short gamma-ray burst model. We anticipate this search method to serve as a starting point for IACT searches with future LIGO/Virgo data releases as well as in other sub-threshold studies for multimessenger transients, such as IceCube neutrinos. Furthermore, it can be deployed immediately with other current-generation IACTs, and has the potential for real-time use that places minimal burden on experimental operations. Lastly, this method may serve as a pilot for studies with the Cherenkov Telescope Array, which has the potential to observe even larger fields of view in its divergent pointing mode

VERITAS Observations of the Galactic Center Region at Multi-TeV Gamma-Ray Energies

The Galactic Center (GC) region hosts a variety of powerful astronomical sources and rare astrophysical processes that emit a large flux of non-thermal radiation. The inner 375 pc x 600 pc region, called the Central Molecular Zone, is home to the supermassive black hole Sagittarius A*, massive cloud complexes, and particle accelerators such as supernova remnants. We present the results of our improved analysis of the very-high-energy (VHE) gamma-ray emission above 2 TeV from the GC using 125 hours of data taken with the VERITAS imaging-atmospheric Cherenkov telescope between 2010 and 2018. The central source VER J1745-290, consistent with the position of Sagittarius A*, is detected at a significance of 38 standard deviations above the background level $(38\sigma)$, and we report its spectrum and light curve. Its differential spectrum is consistent with a power law with exponential cutoff, with a spectral index of $2.12^{+0.22}_{-0.17}$, a flux normalization at 5.3 TeV of $1.27^{+0.22}_{-0.23}\times 10^{-13}$ TeV-1 cm-2 s-1, and cutoff energy of $10.0^{+4.0}_{-2.0}$ TeV. We also present results on the diffuse emission near the GC, obtained by combining data from multiple regions along the GC ridge which yield a cumulative significance of $9.5\sigma$. The diffuse GC ridge spectrum is best fit by a power law with a hard index of 2.19 $\pm$ 0.20, showing no evidence of a cutoff up to 40 TeV. This strengthens the evidence for a potential accelerator of PeV cosmic rays being present in the GC. We also provide spectra of the other sources in our field of view with significant detections, composite supernova remnant G0.9+0.1 and HESS J1746-285.Comment: 19 pages, 8 figures, Accepted for publication in Astrophysical Journa

VERITAS and Fermi-LAT constraints on the Gamma-ray Emission from Superluminous Supernovae SN2015bn and SN2017egm

Superluminous supernovae (SLSNe) are a rare class of stellar explosions with luminosities ~10-100 times greater than ordinary core-collapse supernovae. One popular model to explain the enhanced optical output of hydrogen-poor (Type I) SLSNe invokes energy injection from a rapidly spinning magnetar. A prediction in this case is that high-energy gamma rays, generated in the wind nebula of the magnetar, could escape through the expanding supernova ejecta at late times (months or more after optical peak). This paper presents a search for gamma-ray emission in the broad energy band from 100 MeV to 30 TeV from two Type I SLSNe, SN2015bn, and SN2017egm, using observations from Fermi-LAT and VERITAS. Although no gamma-ray emission was detected from either source, the derived upper limits approach the putative magnetar's spin-down luminosity. Prospects are explored for detecting very-high-energy (VHE; 100 GeV - 100 TeV) emission from SLSNe-I with existing and planned facilities such as VERITAS and CTA.Comment: 20 pages, 7 figures, 2 table