Using chemical ionization mass spectrometry to probe indoor and outdoor atmospheric chemistry

2021 Spring.Includes bibliographical references.People spend the majority of their time in indoor environments. Knowledge of the sources, sinks, and chemistry of indoor pollutants is therefore imperative to indoor air quality and human health. We studied the indoor chemistry of cooking and cleaning at the House Observations of Microbial and Environmental Chemistry (HOMEChem) field campaign during summer 2018 at the University of Texas test house (UTest house) in Austin, TX. We performed measurements of several gas-phase cooking- and cleaning-related analytes using a fast (1 Hz), online chemical ionization mass spectrometry (CIMS) measurement technique utilizing iodide reagent ions. Combining these and other measurements of gas-phase analytes and particulate matter present in indoor air during HOMEChem enables us to piece together a holistic story of the indoor chemistry of cooking and cleaning. We observed enhanced levels of several chlorinated and nitrogenated compounds when cleaning indoors with a commercial bleach solution during HOMEChem. We observed production of several inorganic chlorinated and nitrogenated pollutants from bleaching, including hypochlorous acid, chlorine gas, and chloramines. Levels of hypochlorous acid and nitrogen trichloride observed during cleaning are likely detrimental to human health. Bleach cleaning indoors also lead to the production of secondary organic aerosol—a common outdoor atmospheric pollutant associated with respiratory and cardiovascular issues—as well as potentially harmful organic isocyanates, cyanogen chloride, and chlorocarbons. These results collectively demonstrate bleach cleaning as a source of indoor pollution which impacts indoor air quality and occupant health. We characterized indoor reactive organic carbon (ROC) emissions from cooking and cleaning during HOMEChem, and directly compared resultant chemical complexity of indoor air to outdoors. Cooking indoors greatly impacts ROC concentrations and physiochemical properties, and thus carbon reactivities and lifetimes. Cleaning indoors yielded relatively insubstantial changes. Consistently higher indoor ROC concentrations compared to outdoors demonstrated that indoor emissions were a net source of reactive carbon to the outdoor atmosphere, following their removal by ventilation. ROC dominated indoor and outdoor oxidant reactivity compared to other atmospheric carbon species, thereby greatly influencing secondary pollutant formation, including carbon dioxide, ozone, and secondary particulate matter. Most oxidation chemistry to produce these secondary pollutants likely took place outdoors following the ventilation of ROC species, given the low oxidant levels typical of indoor environments. Moving outdoors, we demonstrated the efficacy of a CIMS instrument utilizing acetate ionization toward quantifying various gas-phase acids in the troposphere. Here, we performed measurements during the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) field campaign in summer 2014. Diurnal increases in mixing ratios were consistent with photochemical sources of nitric, isocyanic, formic, propionic, butyric, valeric, and pyruvic acid. Vertical profiles taken on the 300 m Boulder Atmospheric Observatory tower demonstrated net surface-level emissions of alkanoic acids, but net surface deposition of nitric and pyruvic acid. Nearby traffic emissions and agricultural activity were a primary source of propionic, butyric, and valeric acids, and likely contributed photochemical precursors to nitric and isocyanic acids. The combined diel and vertical profiles of the alkanoic acids and isocyanic acid were inconsistent with dry deposition and photochemical losses being the only sinks, suggesting additional loss mechanisms

On the multiple supernova population of Arp 299: constraints on progenitor properties and host galaxy star formation characteristics

Throughout the last 20 years 7 supernovae (SNe) have been discovered within Arp 299. One of these is unclassified, leaving 6 core-collapse events; 2 type II, 2 type Ib, a type IIb and one object of indistinct type; Ib/IIb. We analyse the relative numbers of these types, together with their positions with respect to host galaxy properties, to investigate implications for both progenitor characteristics and star formation (SF) properties. Our findings are: 1) the ratio of 'stripped envelope' (SE) events to other type II is higher than that found in the local Universe. 2) All SE SNe are more centrally concentrated within the system than the other type II. 3) All SN environments have similar metallicities and there are no significant metallicity gradients across the system. 4) The SE SNe all fall on bright SF regions while the other type II are found to occur away from bright HII regions. We draw two different -but non-mutually exclusive- interpretations on the system and its supernovae: 1) The distribution of SNe, and the relatively high fraction of types Ib and IIb events over other type II can be explained by the young age of the most recent SF in the system, where insufficient time has expired for the observed to match the 'true' relative SN rates. This explanation provides additional independent evidence that both types Ib and IIb SNe arise from progenitors of shorter stellar lifetime and hence higher mass than other type II. 2) Given the assumption that types Ib and IIb trace higher mass progenitor stars, the relatively high frequency of types Ib and IIb to other type II, and also the centralisation of the former over the latter with respect to host galaxy light implies that in the centrally peaked and enhanced SF within this system, the initial mass function is biased towards the production of high mass stars.Comment: 13 pages, 4 figures. Accepted for publication in MNRAS. The abstract has been edited to fit within arXiv.org submission requirement

Secondary Analysis of a Randomized Controlled Trial on Weight Loss Maintenance

Funding Information: This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement 643309. The material presented and views expressed here are the responsibility of the author(s) only. The European Commission takes no responsibility for any use made of the information set out.Background: The use of digital interventions can be accurately monitored via log files. However, monitoring engagement with intervention goals or enactment of the actual behaviors targeted by the intervention is more difficult and is usually evaluated based on pre-post measurements in a controlled trial. Objective: The objective of this paper is to evaluate if engaging with 2 digital intervention modules focusing on (1) physical activity goals and action plans and (2) coping with barriers has immediate effects on the actual physical activity behavior. Methods: The NoHoW Toolkit (TK), a digital intervention developed to support long-term weight loss maintenance, was evaluated in a 2 x 2 factorial randomized controlled trial. The TK contained various modules based on behavioral self-regulation and motivation theories, as well as contextual emotion regulation approaches, and involved continuous tracking of weight and physical activity through connected commercial devices (Fitbit Aria and Charge 2). Of the 4 trial arms, 2 had access to 2 modules directly targeting physical activity: a module for goal setting and action planning (Goal) and a module for identifying barriers and coping planning (Barriers). Module visits and completion were determined based on TK log files and time spent in the module web page. Seven physical activity metrics (steps; activity; energy expenditure; fairly active, very active and total active minutes; and distance) were compared before and after visiting and completing the modules to examine whether the modules had immediate or sustained effects on physical activity. Immediate effect was determined based on 7-day windows before and after the visit, and sustained effects were evaluated for 1 to 8 weeks after module completion. Results: Out of the 811 participants, 498 (61.4%) visited the Goal module and 406 (50.1%) visited the Barriers module. The Barriers module had an immediate effect on very active and total active minutes (very active minutes: before median 24.2, IQR 10.4-43.0 vs after median 24.9, IQR 10.0-46.3; P=.047; total active minutes: before median 45.1, IQR 22.9-74.9 vs after median 46.9, IQR 22.4-78.4; P=.03). The differences were larger when only completed Barriers modules were considered. The Barriers module completion was also associated with sustained effects in fairly active and total active minutes for most of the 8 weeks following module completion and for 3 weeks in very active minutes. Conclusions: The Barriers module had small, significant, immediate, and sustained effects on active minutes measured by a wrist-worn activity tracker. Future interventions should pay attention to assessing barriers and planning coping mechanisms to overcome them. Trial Registration: ISRCTN Registry ISRCTN88405328; https://www.isrctn.com/ISRCTN88405328publishersversionpublishe

New Measurements of the Motion of the Zodiacal Dust

Using the Wisconsin H-Alpha Mapper (WHAM), we have measured at high spectral resolution and high signal-to-noise the profile of the scattered solar Mg I 5184 absorption line in the zodiacal light. The observations were carried out toward 49 directions that sampled the ecliptic equator from solar elongations of 48\dg (evening sky) to 334\dg (morning sky) plus observations near +47\dg and +90\dg ecliptic latitude. The spectra show a clear prograde kinematic signature that is inconsistent with dust confined to the ecliptic plane and in circular orbits influenced only by the sun's gravity. In particular, the broadened widths of the profiles, together with large amplitude variations in the centroid velocity with elongation angle, indicate that a significant population of dust is on eccentric orbits. In addition, the wide, flat-bottomed line profile toward the ecliptic pole indicates a broad distribution of orbital inclinations extending up to about 30\dg - 40\dg with respect to the ecliptic plane. The absence of pronounced asymmetries in the shape of the profiles limits the retrograde population to less than 10% of the prograde population and also places constraints on the scattering phase function of the particles. These results do not show the radial outflow or evening--morning velocity amplitude asymmetry reported in some earlier investigations. The reduction of the spectra included the discovery and removal of extremely faint, unidentified terrestrial emission lines that contaminate and distort the underlying Mg I profile. This atmospheric emission is too weak to have been seen in earlier, lower signal-to-noise observations, but it probably affected the line centroid measurements of previous investigations.Comment: 24 pages, 8 figures, 1 table, to appear in ApJ v612; figures appear low-res only on scree

Type Ibc supernovae in disturbed galaxies: evidence for a top-heavy IMF

We compare the radial locations of 178 core-collapse supernovae to the R-band and H alpha light distributions of their host galaxies. When the galaxies are split into `disturbed' and `undisturbed' categories, a striking difference emerges. The disturbed galaxies have a central excess of core-collapse supernovae, and this excess is almost completely dominated by supernovae of types Ib, Ic and Ib/c, whereas type II supernovae dominate in all other environments. The difference cannot easily be explained by metallicity or extinction effects, and thus we propose that this is direct evidence for a stellar initial mass function that is strongly weighted towards high mass stars, specifically in the central regions of disturbed galaxies.Comment: 22 pages, 5 figures, accepted for publication in Ap

Core-collapse supernova progenitor constraints using the spatial distributions of massive stars in local galaxies

We study the spatial correlations between the H$\alpha$ emission and different types of massive stars in two local galaxies, the Large Magellanic Cloud (LMC) and Messier 33. We compare these to correlations derived for core-collapse supernovae (CCSNe) in the literature to connect CCSNe of different types with the initial masses of their progenitors and to test the validity of progenitor mass estimates which use the pixel statistics method. We obtain samples of evolved massive stars in both galaxies from catalogues with good spatial coverage and/or completeness, and combine them with coordinates of main-sequence stars in the LMC from the SIMBAD database. We calculate the spatial correlation of stars of different classes and spectral types with H$\alpha$ emission. We also investigate the effects of distance, noise and positional errors on the pixel statistics method. A higher correlation with H$\alpha$ emission is found to correspond to a shorter stellar lifespan, and we conclude that the method can be used as an indicator of the ages, and therefore initial masses, of SN progenitors. We find that the spatial distributions of type II-P SNe and red supergiants of appropriate initial mass ($\gtrsim$9 $M_{\odot}$) are consistent with each other. We also find the distributions of type Ic SNe and WN stars with initial masses $\gtrsim$20 $M_{\odot}$ consistent, while supergiants with initial masses around 15 $M_{\odot}$ are a better match for type IIb and II-L SNe. The type Ib distribution corresponds to the same stellar types as type II-P, which suggests an origin in interacting binaries. On the other hand, we find that luminous blue variable stars show a much stronger correlation with H$\alpha$ emission than do type IIn SNe.ERC, STF

Adaptive optics imaging and optical spectroscopy of a multiple merger in a luminous infrared galaxy

(abridged) We present near-infrared (NIR) adaptive optics imaging obtained with VLT/NACO and optical spectroscopy from the Southern African Large Telescope (SALT) of a luminous infrared galaxy (LIRG) IRAS 19115-2124. These data are combined with archival HST imaging and Spitzer imaging and spectroscopy, allowing us to study this disturbed interacting/merging galaxy, dubbed the Bird, in extraordinary detail. In particular, the data reveal a triple system where the LIRG phenomenon is dominated by the smallest of the components. One nucleus is a regular barred spiral with significant rotation, while another is highly disturbed with a surface brightness distribution intermediate to that of disk and bulge systems, and hints of remaining arm/bar structure. We derive dynamical masses in the range 3-7x10^10 M_solar for both. The third component appears to be a 1-2x10^10 M_solar mass irregular galaxy. The total system exhibits HII galaxy-like optical line ratios and strengths, and no evidence for AGN activity is found from optical or mid-infrared data. The star formation rate is estimated to be 190 M_solar/yr. We search for SNe, super star clusters, and detect 100-300 km/s outflowing gas from the Bird. Overall, the Bird shows kinematic, dynamical, and emission line properties typical for cool ultra luminous IR galaxies. However, the interesting features setting it apart for future studies are its triple merger nature, and the location of its star formation peak - the strongest star formation does not come from the two major K-band nuclei, but from the third irregular component. Aided by simulations, we discuss scenarios where the irregular component is on its first high-speed encounter with the more massive components.Comment: 24 pages, 16 figures. Accepted MNRAS version, minor corrections only, references added. Higher resolution version (1.3MB) is available from http://www.saao.ac.za/~petri/bird/ulirg_bird_highres_vaisanen_v2.pd

Surface reservoirs dominate dynamic gas-surface partitioning of many indoor air constituents

Human health is affected by indoor air quality. One distinctive aspect of the indoor environment is its very large surface area that acts as a poorly characterized sink and source of gas-phase chemicals. In this work, air-surface interactions of 19 common indoor air contaminants with diverse properties and sources were monitored in a house using fast-response, on-line mass spectrometric and spectroscopic methods. Enhanced-ventilation experiments demonstrate that most of the contaminants reside in the surface reservoirs and not, as expected, in the gas phase. They participate in rapid air-surface partitioning that is much faster than air exchange. Phase distribution calculations are consistent with the observations when assuming simultaneous equilibria between air and large weakly polar and polar absorptive surface reservoirs, with acid-base dissociation in the polar reservoir. Chemical exposure assessments must account for the finding that contaminants that are fully volatile under outdoor air conditions instead behave as semivolatile compounds indoors

The Type Ib SN 1999dn: One Year of Photometric and Spectroscopic Monitoring

Extensive optical and near-infrared (NIR) observations of the type Ib supernova 1999dn are presented, covering the first year after explosion. These new data turn this object, already considered a prototypical SNIb, into one of the best observed objects of its class. The light curve of SN 1999dn is mostly similar in shape to that of other SNeIb but with a moderately faint peak M_V=-17.2 mag). From the bolometric light curve and ejecta expansion velocities, we estimate that about 0.11 Msun of 56Ni were produced during the explosion and that the total ejecta mass was 4-6 Msun with a kinetic energy of at least 5x10^{51} erg. The spectra of SN 1999dn at various epochs are similar to those of other Stripped Envelope (SE) SNe showing clear presence of H at early epochs. The high explosion energy and ejected mass, along with the small flux ratio [CaII]/[OI] measured in the nebular spectrum, together with the lack of signatures of dust formation and the relatively high-metallicity environment point toward a single massive progenitor (M_ZAMS>=23-25 Msun) for SN 1999dn.Comment: 15 pages, 11 figures. MNRAS accepted; This version matches the published on

Core-collapse supernova progenitor constraints using the spatial distributions of massive stars in local galaxies

We study the spatial correlations between the H$alpha$ emission and different types of massive stars in two local galaxies, the Large Magellanic Cloud (LMC) and Messier 33. We compare these to correlations derived for core-collapse supernovae (CCSNe) in the literature to connect CCSNe of different types with the initial masses of their progenitors and to test the validity of progenitor mass estimates which use the pixel statistics method. We obtain samples of evolved massive stars in both galaxies from catalogues with good spatial coverage and/or completeness, and combine them with coordinates of main-sequence stars in the LMC from the SIMBAD database. We calculate the spatial correlation of stars of different classes and spectral types with H$alpha$ emission. We also investigate the effects of distance, noise and positional errors on the pixel statistics method. A higher correlation with H$alpha$ emission is found to correspond to a shorter stellar lifespan, and we conclude that the method can be used as an indicator of the ages, and therefore initial masses, of SN progenitors. We find that the spatial distributions of type II-P SNe and red supergiants of appropriate initial mass ($gtrsim$9 $M_{odot}$) are consistent with each other. We also find the distributions of type Ic SNe and WN stars with initial masses $gtrsim$20 $M_{odot}$ consistent, while supergiants with initial masses around 15 $M_{odot}$ are a better match for type IIb and II-L SNe. The type Ib distribution corresponds to the same stellar types as type II-P, which suggests an origin in interacting binaries. On the other hand, we find that luminous blue variable stars show a much stronger correlation with H$alpha$ emission than do type IIn SNe.</p