Methyl Chavicol: Characterization of its Biogenic Emission Rate, Abundance, and Oxidation Products in the Atmosphere

We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models

In-situ Ambient Quantification of Monoterpenes, Sesquiterpenes and Related Oxygenated Compounds During BEARPEX 2007: Implications for Gas-and Particle-Phase Chemistry

We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS). These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day), but nevertheless these compounds contributed 7.6% to the overall ozone-olefin loss rate above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 6–32% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively), but it contributed 1.1% to the total ozone-olefin loss rate above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models

Photochemical Modeling of Glyoxal at a Rural Site: Observations and Analysis from BEARPEX 2007

We present roughly one month of high time-resolution, direct, in situ measurements of gas-phase glyoxal acquired during the BEARPEX 2007 field campaign. The research site, located on a ponderosa pine plantation in the Sierra Nevada mountains, is strongly influenced by biogenic volatile organic compounds (BVOCs); thus this data adds to the few existing measurements of glyoxal in BVOC-dominated areas. The short lifetime of glyoxal of ~1 h, the fact that glyoxal mixing ratios are much higher during high temperature periods, and the results of a photochemical model demonstrate that glyoxal is strongly influenced by BVOC precursors during high temperature periods. A zero-dimensional box model using near-explicit chemistry from the Leeds Master Chemical Mechanism v3.1 was used to investigate the processes controlling glyoxal chemistry during BEARPEX 2007. The model showed that MBO is the most important glyoxal precursor (~67 %), followed by isoprene (~26 %) and methylchavicol (~6 %), a precursor previously not commonly considered for glyoxal production. The model calculated a noon lifetime for glyoxal of ~0.9 h, making glyoxal well suited as a local tracer of VOC oxidation in a forested rural environment; however, the modeled glyoxal mixing ratios over-predicted measured glyoxal by a factor 2 to 5. Loss of glyoxal to aerosol was not found to be significant, likely as a result of the very dry conditions, and could not explain the over-prediction. Although several parameters, such as an approximation for advection, were found to improve the model measurement discrepancy, reduction in OH was by far the most effective. Reducing model OH concentrations to half the measured values decreased the glyoxal over-prediction from a factor of 2.4 to 1.1, as well as the overprediction of HO2 from a factor of 1.64 to 1.14. Our analysis has shown that glyoxal is particularly sensitive to OH concentration compared to other BVOC oxidation products. This relationship arises from (i) the predominantly secondary- or higher-generation production of glyoxal from (mainly OH-driven, rather than O3-driven) BVOC oxidation at this site and (ii) the relative importance of photolysis in glyoxal loss as compared to reaction with OH. We propose that glyoxal is a useful tracer for OH-driven BVOC oxidation chemistry

Observations of Elevated Formaldehyde Over a Forest Canopy suggest Missing Sources From Rapid Oxidation of Arboreal Hydrocarbons

To better understand the processing of biogenic VOCs (BVOCs) in the pine forests of the US Sierra Nevada, we measured HCHO at Blodgett Research Station using Quantum Cascade Laser Spectroscopy (QCLS) during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) of late summer 2007. Four days of the experiment exhibited particularly copious HCHO, with midday peaks between 15–20 ppbv, while the other days developed delayed maxima between 8–14 ppbv in the early evening. From the expansive photochemical data set, we attempt to explain the observed HCHO concentrations by quantifying the various known photochemical production and loss terms in its chemical budget. Overall, known chemistry predicts a factor of 3–5 times less HCHO than observed. By examining diurnal patterns of the various budget terms we conclude that, during the high HCHO period, local, highly reactive oxidation chemistry produces an abundance of formaldehyde at the site. The results support the hypothesis of previous work at Blodgett Forest suggesting that large quantities of oxidation products, observed directly above the ponderosa pine canopy, are evidence of profuse emissions of very reactive volatile organic compounds (VR-VOCs) from the forest. However, on the majority of days, under generally cooler and more moist conditions, lower levels of HCHO develop primarily influenced by the influx of precursors transported into the region along with the Sacramento plume

Nurturing Student Scientists as People of Faith

The Loyola Marymount University (LMU) campus community fosters the interplay between religious faith and scientific reason. Not only is this evident by honoring scientists in the stained-glass windows of Sacred Heart Chapel, but the culture invigorates a disproportionate number of science students to actively engage with the faith community. This integration might seem counter to society’s norms, but it is well aligned with the teachings of the Catholic Church and Jesuit tradition. Jesuit universities, in particular, have a unique role to play in fostering the mutual enrichment between faith and scientific reason. Education should be used to bridge the misunderstandings between faith and science. Faculty members, particularly at Jesuit universities, have a wonderful opportunity to share their experiences with students through teaching and scholarship

The Chemistry of Atmosphere-Forest Exchange (CAFE) Model-Part 2: Application to BEARPEX-2007 Observations

In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE) model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. Here, we apply CAFE to noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007). In this work we evaluate the CAFE modeling approach, demonstrate the significance of in-canopy chemistry for forest-atmosphere exchange and identify key shortcomings in the current understanding of intra-canopy processes. CAFE generally reproduces BEARPEX-2007 observations but requires an enhanced radical recycling mechanism to overcome a factor of 6 underestimate of hydroxyl (OH) concentrations observed during a warm (~29 °C) period. Modeled fluxes of acyl peroxy nitrates (APN) are quite sensitive to gradients in chemical production and loss, demonstrating that chemistry may perturb forest-atmosphere exchange even when the chemical timescale is long relative to the canopy mixing timescale. The model underestimates peroxy acetyl nitrate (PAN) fluxes by 50% and the exchange velocity by nearly a factor of three under warmer conditions, suggesting that near-surface APN sinks are underestimated relative to the sources. Nitric acid typically dominates gross dry N deposition at this site, though other reactive nitrogen (NOy) species can comprise up to 28% of the N deposition budget under cooler conditions. Upward NO2 fluxes cause the net above-canopy NOy flux to be ~30% lower than the gross depositional flux. CAFE under-predicts ozone fluxes and exchange velocities by ~20%. Large uncertainty in the parameterization of cuticular and ground deposition precludes conclusive attribution of non-stomatal fluxes to chemistry or surface uptake. Model-measurement comparisons of vertical concentration gradients for several emitted species suggests that the lower canopy airspace may be only weakly coupled with the upper canopy. Future efforts to model forest-atmosphere exchange will require a more mechanistic understanding of non-stomatal deposition and a more thorough characterization of in-canopy mixing processes

Textbook-Bundled Metacognitive Tools: A Study of LearnSmart’s Efficacy in General Chemistry

College textbook publishers increasingly bundle sophisticated technology-based study tools with their texts. These tools appear promising, but empirical work on their efficacy is needed. We examined whether LearnSmart, a study tool bundled with McGraw-Hill’s textbook Chemistry (Chang & Goldsby, 2013), improved learning in an undergraduate general chemistry course. Content-knowledge gains of those students who used LearnSmart, those who did not use it, and those who used it with scaffolding questions that supported use of the tool’s metacognitive features were compared. The metacognitive scaffolding questions appeared to help students use LearnSmart more effectively than did using LearnSmart by itself, which did not confer learning benefits. Implications for adopting LearnSmart and similar tools are discussed

The mass ratio distribution of B-type visual binaries in the Sco OB2 association

The sample of 115 B-type stars in Sco OB2 association is examined for existence of visual companions with ADONIS near-infrared adaptive optics system and coronograph in J and K bands. Practically all components in the separation range 0.3"-6" (45-900 A.U.) were detected, with magnitudes down to K=16. The K and J-K photometry of primaries and differential photometry and astrometry of 96 secondaries are presented. Ten secondaries are new physical components, as inferred from photometric and statistical criteria, while remaining are faint background stars. After small correction for detection incompleteness and conversion of fluxes into masses, an unbiased distribution of the components mass ratio q is derived. The power law f(q)\propto q^{-0.5} fits well the observations, whereas a q^{-1.8} distribution which corresponds to random pairing of stars is rejected. The companion star fraction is 0.20 +- 0.04 per decade of separation, comparable to the highest measured binary fraction among low-mass PMS stars and ~1.6 times higher than the binary fraction of low-mass dwarfs in solar neighborhood and open clusters in the same separation range.Comment: 12 pages, submitted to Astronomy & Astrophysic

Magnetic fields and accretion flows on the classical T Tauri star V2129 Oph

From observations collected with the ESPaDOnS spectropolarimeter, we report the discovery of magnetic fields at the surface of the mildly accreting classical T Tauri star V2129 Oph. Zeeman signatures are detected, both in photospheric lines and in the emission lines formed at the base of the accretion funnels linking the disc to the protostar, and monitored over the whole rotation cycle of V2129 Oph. We observe that rotational modulation dominates the temporal variations of both unpolarized and circularly polarized line profiles. We reconstruct the large-scale magnetic topology at the surface of V2129 Oph from both sets of Zeeman signatures simultaneously. We find it to be rather complex, with a dominant octupolar component and a weak dipole of strengths 1.2 and 0.35 kG, respectively, both slightly tilted with respect to the rotation axis. The large-scale field is anchored in a pair of 2-kG unipolar radial field spots located at high latitudes and coinciding with cool dark polar spots at photospheric level. This large-scale field geometry is unusually complex compared to those of non-accreting cool active subgiants with moderate rotation rates. As an illustration, we provide a first attempt at modelling the magnetospheric topology and accretion funnels of V2129 Oph using field extrapolation. We find that the magnetosphere of V2129 Oph must extend to about 7R* to ensure that the footpoints of accretion funnels coincide with the high-latitude accretion spots on the stellar surface. It suggests that the stellar magnetic field succeeds in coupling to the accretion disc as far out as the corotation radius, and could possibly explain the slow rotation of V2129 Oph. The magnetospheric geometry we derive produces X-ray coronal fluxes typical of those observed in cTTSs.Comment: MNRAS, in press (18 pages, 17 figures

College Student Depression Throughout COVID-19: Fall 2019-Spring 2022

The current study examined the trends in depression and emotion regulation for students (n = 899) at one university in the Midwest United States from prior to the COVID-19 pandemic (Fall 2019) through the Spring 2022 semester. An analysis of covariance (ANCOVA) was conducted, controlling for difficulties in emotion regulation and gender identity. The ANCOVA indicated that depression was significantly lower in Fall 2019 than in the remaining five semesters under investigation. Results of these analyses appear to indicate that depression rose significantly in students after the onset of the pandemic and implementation of social restrictions. This negative effect appears to have had a lasting impact and the pandemic appears to have had deleterious effects on mental health regardless of emotion regulation abilities and/or gender identity. Limitations and implications for researchers, clinicians, and professionals in higher education will be discussed