Nocturnal Atmospheric Oxidative Processes in the Indo-Gangetic Plain and Their Variation During the COVID-19 Lockdowns.

This study investigates selected secondary atmospheric responses to the widely reported emission change attributed to COVID-19 lockdowns in the highly polluted Indo-Gangetic Plain (IGP) using ground-based measurements of trace gases and particulate matter. We used a chemical box-model to show that production of nighttime oxidant, NO3, was affected mainly by emission decrease (average nighttime production rates 1.2, 0.8 and 1.5 ppbv hr-1 before, during and relaxation of lockdown restrictions, respectively), while NO3 sinks were sensitive to both emission reduction and seasonal variations. We have also shown that the maximum potential mixing ratio of nitryl chloride, a photolytic chlorine radical source which has not been previously considered in the IGP, is as high as 5.5 ppbv at this inland site, resulting from strong nitrate radical production and a potentially large particulate chloride mass. This analysis suggests that air quality measurement campaigns and modeling explicitly consider heterogeneous nitrogen oxide and halogen chemistry.

Theoretical and experimental study of peroxy and alkoxy radicals in the NO3-initiated oxidation of isoprene.

The initial stages of the nitrate radical (NO3) initiated oxidation of isoprene, in particular the fate of the peroxy (RO2) and alkoxy (RO) radicals, are examined by an extensive set of quantum chemical and theoretical kinetic calculations. It is shown that the oxidation mechanism is highly complex, and bears similarities to its OH-initiated oxidation mechanism as studied intensively over the last decade. The nascent nitrated RO2 radicals can interconvert by successive O2 addition/elimination reactions, and potentially have access to a wide range of unimolecular reactions with rate coefficients as high as 35 s-1; the contribution of this chemistry could not be ascertained experimentally. The chemistry of the alkoxy radicals derived from these peroxy radicals is affected by the nitrate moiety, and can lead to the formation of nitrated epoxy peroxy radicals in competition with isomerisation and decomposition channels that terminate the organic radical chain by NO2 elimination. The theoretical predictions are implemented in the FZJ-NO3-isoprene mechanism for NO3-initiated atmospheric oxidation of isoprene. The model predictions are compared against peroxy radical (RO2) and methyl vinyl ketone (MVK) measurements in a set of experiments on the isoprene + NO3 reaction system performed in the SAPHIR environmental chamber (IsopNO3 campaign). It is shown that the formation of NO2 from the peroxy radicals can prevent a large fraction of the peroxy radicals from being measured by the laser-induced fluorescence (ROxLIF) technique that relies on a quantitative conversion of peroxy radicals to hydroxyl radicals. Accounting for the relative conversion efficiency of RO2 species in the experiments, the agreement between observations and the theory-based FZJ-NO3-isoprene model predictions improves significantly. In addition, MVK formation in the NO3-initiated oxidation was found to be suppressed by the epoxidation of the unsaturated RO radical intermediates, allowing the model-predicted MVK concentrations to be in good agreement with the measurements. The FZJ-NO3-isoprene mechanism is compared against the MCM v3.3.1 and Wennberg et al. (2018) mechanisms.

Structural MRI at 7T reveals amygdala nuclei and hippocampal subfield volumetric association with Major Depressive Disorder symptom severity.

Subcortical volumetric changes in major depressive disorder (MDD) have been purported to underlie depressive symptomology, however, the evidence to date remains inconsistent. Here, we investigated limbic volumes in MDD, utilizing high-resolution structural images to allow segmentation of the hippocampus and amygdala into their constituent substructures. Twenty-four MDD patients and twenty matched controls underwent structural MRI at 7T field strength. All participants completed the Montgomery-Asberg Depression Rating Scale (MADRS) to quantify depressive symptomology. For the MDD group, volumes of the amygdala right lateral nucleus (p = 0.05, r2 = 0.24), left cortical nucleus (p = 0.032, r2 = 0.35), left accessory basal nucleus (p = 0.04, r2 = 0.28) and bilateral corticoamygdaloid transition area (right hemisphere p = 0.032, r2 = 0.38, left hemisphere p = 0.032, r2 = 0.35) each displayed significant negative associations with MDD severity. The bilateral centrocortical (right hemisphere p = 0.032, r2 = 0.31, left hemisphere p = 0.032, r2 = 0.32) and right basolateral complexes (p = 0.05, r2 = 0.24) also displayed significant negative relationships with depressive symptoms. Using high-field strength MRI, we report the novel finding that MDD severity is consistently negatively associated with amygdala nuclei, linking volumetric reductions with worsening depressive symptoms.

Anthropogenic control over wintertime oxidation of atmospheric pollutants.

During winter in the mid-latitudes, photochemical oxidation is significantly slower than in summer and the main radical oxidants driving formation of secondary pollutants, such as fine particulate matter and ozone, remain uncertain, owing to a lack of observations in this season. Using airborne observations, we quantify the contribution of various oxidants on a regional basis during winter, enabling improved chemical descriptions of wintertime air pollution transformations. We show that 25-60% of NOx is converted to N2O5 via multiphase reactions between gas-phase nitrogen oxide reservoirs and aerosol particles, with ~93% reacting in the marine boundary layer to form >2.5 ppbv ClNO2. This results in >70% of the oxidizing capacity of polluted air during winter being controlled, not by typical photochemical reactions, but from these multiphase reactions and emissions of volatile organic compounds, such as HCHO, highlighting the control local anthropogenic emissions have on the oxidizing capacity of the polluted wintertime atmosphere.

Instrumentation and Measurement Strategy for the NOAA SENEX Aircraft Campaign as Part of the Southeast Atmosphere Study 2013.

Natural emissions of ozone-and-aerosol-precursor gases such as isoprene and monoterpenes are high in the southeast of the US. In addition, anthropogenic emissions are significant in the Southeast US and summertime photochemistry is rapid. The NOAA-led SENEX (Southeast Nexus) aircraft campaign was one of the major components of the Southeast Atmosphere Study (SAS) and was focused on studying the interactions between biogenic and anthropogenic emissions to form secondary pollutants. During SENEX, the NOAA WP-3D aircraft conducted 20 research flights between 27 May and 10 July 2013 based out of Smyrna, TN. Here we describe the experimental approach, the science goals and early results of the NOAA SENEX campaign. The aircraft, its capabilities and standard measurements are described. The instrument payload is summarized including detection limits, accuracy, precision and time resolutions for all gas-and-aerosol phase instruments. The inter-comparisons of compounds measured with multiple instruments on the NOAA WP-3D are presented and were all within the stated uncertainties, except two of the three NO2 measurements. The SENEX flights included day- and nighttime flights in the Southeast as well as flights over areas with intense shale gas extraction (Marcellus, Fayetteville and Haynesville shale). We present one example flight on 16 June 2013, which was a daytime flight over the Atlanta region, where several crosswind transects of plumes from the city and nearby point sources, such as power plants, paper mills and landfills, were flown. The area around Atlanta has large biogenic isoprene emissions, which provided an excellent case for studying the interactions between biogenic and anthropogenic emissions. In this example flight, chemistry in and outside the Atlanta plumes was observed for several hours after emission. The analysis of this flight showcases the strategies implemented to answer some of the main SENEX science questions.

Contribution of human-related sources to indoor volatile organic compounds in a university classroom.

Although significant progress has been made in understanding the sources and chemistry of indoor volatile organic compounds (VOCs) during the past decades, much is unknown about the role of humans in indoor air chemistry. In the spring of 2014, we conducted continuous measurements of VOCs using a proton transfer reaction mass spectrometer (PTR-MS) in a university classroom. Positive matrix factorization (PMF) of the measured VOCs revealed a 'human influence' component, which likely represented VOCs produced from human breath and ozonolysis of human skin lipids. The concentration of the human influence component increased with the number of occupants and decreased with ventilation rate in a similar way to CO2 , with an average contribution of 40% to the measured daytime VOC concentration. In addition, the human skin lipid ozonolysis products were observed to correlate with CO2 and anticorrelate with O3 , suggesting that reactions on human surfaces may be important sources of indoor VOCs and sinks for indoor O3 . Our study suggests that humans can substantially affect VOC composition and oxidative capacity in indoor environments.

Complex refractive indices in the near-ultraviolet spectral region of biogenic secondary organic aerosol aged with ammonia.

Atmospheric absorption by brown carbon aerosol may play an important role in global radiative forcing. Brown carbon arises from both primary and secondary sources, but the mechanisms and reactions of the latter are highly uncertain. One proposed mechanism is the reaction of ammonia or amino acids with carbonyl products in secondary organic aerosol (SOA). We generated SOA in situ by reacting biogenic alkenes (α-pinene, limonene, and α-humulene) with excess ozone, humidifying the resulting aerosol, and reacting the humidified aerosol with gaseous ammonia. We determined the complex refractive indices (RI) in the 360-420 nm range for these aerosols using broadband cavity enhanced spectroscopy (BBCES). The average real part (n) of the measured spectral range of the NH3-aged α-pinene SOA increased from n = 1.50 (±0.01) for the unreacted SOA to n = 1.57 (±0.01) after 1.5 h of exposure to 1.9 ppm NH3, whereas the imaginary component (k) remained below k < 0.001((+0.002)(-0.001)). For the limonene and α-humulene SOA the real part did not change significantly, and we observed a small change in the imaginary component of the RI. The imaginary component increased from k = 0.000 to an average k = 0.029 (±0.021) for α-humulene SOA, and from k < 0.001((+0.002)(-0.001)) to an average k = 0.032 (±0.019) for limonene SOA after 1.5 h of exposure to 1.3 and 1.9 ppm of NH3, respectively. Collected filter samples of the aged and unreacted α-pinene SOA and limonene SOA were analyzed off-line by nanospray desorption electrospray ionization high resolution mass spectrometry (nano-DESI/HR-MS), and in situ using a Time-of-Flight Aerosol Mass Spectrometer (ToF-AMS), confirming that the SOA reacted and that various nitrogen-containing reaction products formed. If we assume that NH3 aging reactions scale linearly with time and concentration, which will not necessarily be the case in the atmosphere, then a 1.5 h reaction with 1 ppm NH3 in the laboratory is equivalent to 24 h reaction with 63 ppbv NH3, indicating that the observed aerosol absorption will be limited to atmospheric regions with high NH3 concentrations.

Measurement of atmospheric ozone by cavity ring-down spectroscopy.

Ozone plays a key role in both the Earth's radiative budget and photochemistry. Accurate, robust analytical techniques for measuring its atmospheric abundance are of critical importance. Cavity ring-down spectroscopy has been successfully used for sensitive and accurate measurements of many atmospheric species. However, this technique has not been used for atmospheric measurements of ozone, because the strongest ozone absorption bands occur in the ultraviolet spectral region, where Rayleigh and Mie scattering cause significant cavity losses and dielectric mirror reflectivities are limited. Here, we describe a compact instrument that measures O3 by chemical conversion to NO2 in excess NO, with subsequent detection by cavity ring-down spectroscopy. This method provides a simple, accurate, and high-precision measurement of atmospheric ozone. The instrument consists of two channels. The sum of NO2 and converted O3 (defined as Ox) is measured in the first channel, while NO2 alone is measured in the second channel. NO2 is directly detected in each channel by cavity ring-down spectroscopy with a laser diode light source at 404 nm. The limit of detection for O3 is 26 pptv (2 sigma precision) at 1 s time resolution. The accuracy of the measurement is ±2.2%, with the largest uncertainty being the effective NO2 absorption cross-section. The linear dynamic range of the instrument has been verified from the detection limit to above 200 ppbv (r2>99.99%). The observed precision on signal (2 sigma) with 41 ppbv O3 is 130 pptv in 1 s. Comparison of this instrument to UV absorbance instruments for ambient O3 concentrations shows linear agreement (r2=99.1%) with slope of 1.012±0.002.

HCO quantum yields in the photolysis of HC(O)C(O)H (glyoxal) between 290 and 420 nm.

Quantum yields, Phi, for the production of the formyl radical, HCO, in the photolysis of glyoxal were determined at 85 wavelengths, lambda, in the range of 290-420 nm at pressures between 50 and 550 Torr (N(2)) at 298 K using pulsed-laser photolysis combined with cavity ring-down spectroscopy detection of HCO. HCO quantum yields were parametrized using a Stern-Volmer analysis to obtain extrapolated zero-pressure HCO quantum yields, Phi(0)(lambda), and values for the ratio of the rate coefficients for quenching and dissociation, k(q)/k(d)(lambda), at each wavelength. Phi(0)(lambda) varied smoothly with wavelength with a maximum value of approximately 1.8 in the range 300-385 nm with values decreasing to near 0 at 420 nm and 0.4 at 290 nm. k(q)/k(d)(lambda) was measurable at nearly all photolysis wavelengths and is well-represented by the relationship k(q)/k(d)(lambda) = (2.3 x 10(-20)) + (1.5 x 10(-19)) exp(-0.4DeltaE) (cm(3) molecule (-1)) where DeltaE = ((28,571/lambda) - 72.5) (kcal mol(-1)), lambda is the photolysis wavelength (nm), and 72.5 kcal mol(-1) is the threshold for glyoxal photodissociation. Differences in our HCO quantum yield wavelength- and pressure-dependence with previous studies are discussed. The present HCO quantum yield data are appropriate for use in atmospheric model calculations, and revised wavelength-dependent photolysis branching ratios for the production of 2HCO, H(2)CO + O(2), and H(2) + 2CO at atmospheric pressure are presented.

Variability in nocturnal nitrogen oxide processing and its role in regional air quality.

Nitrogen oxides in the lower troposphere catalyze the photochemical production of ozone (O3) pollution during the day but react to form nitric acid, oxidize hydrocarbons, and remove O3 at night. A key nocturnal reaction is the heterogeneous hydrolysis of dinitrogen pentoxide, N2O5. We report aircraft measurements of NO3 and N2O5, which show that the N2O5 uptake coefficient, g(N2O5), on aerosol particles is highly variable and depends strongly on aerosol composition, particularly sulfate content. The results have implications for the quantification of regional-scale O3 production and suggest a stronger interaction between anthropogenic sulfur and nitrogen oxide emissions than previously recognized.

Anxiety and depression in the workplace: effects on the individual and organisation (a focus group investigation).

BACKGROUND: While the prevalence of anxiety and depression has increased, little is known of the impact on working life. The aim of this study was to explore the effects of anxiety and depression and the treatment for these conditions on performance and safety in the workplace. METHOD: Nine focus groups were conducted with employees who had suffered anxiety and depression. A further 3 groups comprised staff from human resources and occupational health. The sample comprised 74 individuals aged 18-60 years, from a range of occupations. Results were presented to a panel of experts to consider the clinical implications. RESULTS: Workers reported that the symptoms and medication impaired work performance, describing accidents which they attributed to their condition/medication. Respondents were largely unprepared for the fact that the medication might make them feel worse initially. Employees were reluctant to disclose their condition to colleagues due to the stigma attached to mental illness. LIMITATIONS: People who had experienced problems with managing their symptoms and medication at work are more likely to volunteer to participate in such a study than those who had a satisfactory experience. Also, the researchers had no background information on severity of mental health problems of participants. CONCLUSIONS: Anxiety and depression were associated with impaired work performance and safety. The authors consider the implications for health care and the management of mental health problems at work.

Discerning alumina ball wear from confounding metal transfer artifact.

On dismounting a ceramic femoral ball from its metal trunnion, there is usually a range of gray metallic bands transferred to the trunnion bore inside the ball. This creates an artifact that may compromise detection by weight of the exceedingly low wear rates of ceramic balls. The objective of this study was to compare the weight trending of the metal trunnions and their ceramic balls during conditioning studies. Our hypothesis was that a pretest conditioning protocol would eliminate or greatly reduce the metal transfer artifact. The balls and tapers were placed on a hip simulator under 300-600 load cycles but with no articulation. The balls were then dismounted from the trunnions, and both were cleaned and weighed. This was repeated 6-23 times. We developed a novel hydraulic method for dismounting balls from trunnions that proved to be safe and efficient. There was significant weight loss in the trunnions after the ball removal, but there was no corresponding weight gain in the alumina balls. The weight effect of the metal transfer appeared to have been removed from the balls with our standard cleaning procedures. Therefore, wear rates for alumina balls may be gravimetrically determined without compensating for the metal transfer from trunnion to ball.

Quantitative analysis of the principle soy isoflavones genistein, daidzein and glycitein, and their primary conjugated metabolites in human plasma and urine using reversed-phase high-performance liquid chromatography with ultraviolet detection.

Soy isoflavones are becoming of increasing interest as nutritional agents which can be used to combat osteoporosis and hyperlipidemia, and are also being considered as potential cancer chemopreventive compounds. However, prior to their formulation and distribution as therapeutic agents, thorough pharmacokinetic and toxicological assessment needs to be completed in men and women in a variety of health conditions in order to ensure their therapeutic efficacy and safety. At this time, studies of purified soy isoflavones are possible, and are being designed to fully evaluate the pharmacological utility of these preparations. In support of these studies, quantitative analysis of soy isoflavones in biological fluids can be accomplished with a wide variety of methods and analytical instrumentation. However, the relatively ubiquitous presence of high-performance liquid chromatography with ultraviolet detection (HPLC-UV) in most analytical laboratories, the relative ease of its operation, and the lesser expense of this instrumentation as compared to more sophisticated techniques such as liquid chromatography-mass spectrometry, offers some distinct advantages for its use in pharmacokinetic studies. In this manuscript, the development and validation of an HPLC-UV method for the quantitation of the principal soy isoflavones, genistein, daidzein, and glycitein, and their primary metabolites, in human plasma and urine is described. This analytical approach allows for pharmacologically relevant concentrations of the analytes and their principle metabolites to be detected, and has been validated in close agreement with the US Food and Drug Administration's guidelines for the validation of methods to be used in support of pharmacokinetic studies.

Factors affecting the efficiency of embryo cryopreservation and rederivation of rat and mouse models.

The efficiency of embryo banking for rat and mouse models of human disease and normal biological processes depends on the ease of obtaining embryos. Authors report on the effect of genotype on embryo production and rederivation. In an effort to establish banks of cryopreserved embryos, they provide two databases for comparing banking efficiency: one that contains the embryo collection results from approximately 11,000 rat embryo donors (111 models) and another that contains the embryo collection results from 4,023 mouse embryo donors (57 induced mutant models). The genotype of donor females affected the efficiency of embryo collection in two ways. First, the proportion of females yielding embryos varied markedly among genotypes (rats: 16-100 %, mean =71 %; mice: 24-95 %, mean =65 %). Second, the mean number of embryos recovered from females yielding embryos varied considerably (rats: 4-10.6, mean =7.8; mice 5.3-32.2, mean =13.7). Genotype also affected the efficiency of rederivation of banked rat and mouse embryos models by embryo transfer. For rats, thawed embryos (n =684) from 33 genotypes were transferred into 66 recipient females (pregnancy rate, 78 %). The average rate of developing live newborns for individual rat genotypes was 30 % with a range of 10 to 58 %. For mice, thawed embryos (n =2,064) from 59 genotypes were transferred into 119 pseudopregnant females (pregnancy rate: 76 %). The average rate of development of individual mouse genotypes was 33 % with a range of 11 to 53 %. This analysis demonstrates that genotype is an important consideration when planning embryo banking programs.

The yeast kinesin-related protein Smy1p exerts its effects on the class V myosin Myo2p via a physical interaction.

We have discovered evidence for a physical interaction between a class V myosin, Myo2p, and a kinesin-related protein, Smy1p, in budding yeast. These proteins had previously been linked by genetic and colocalization studies, but we had been unable to determine the nature of their association. We now show by two-hybrid analysis that a 69-amino acid region of the Smy1p tail interacts with the globular portion of the Myo2p tail. Deletion of this myosin-binding region of Smy1p eliminates its ability to colocalize with Myo2p and to overcome the myo2-66 mutant defects, suggesting that the interaction is necessary for these functions. Further insights about the Smy1p-Myo2p interaction have come from studies of a new mutant allele, myo2-2, which causes a loss of Myo2p localization. We report that Smy1p localization is also lost in the myo2-2 mutant, demonstrating that Smy1p localization is dependent on Myo2p. We also found that overexpression of Smy1p partially restores myo2-2p localization in a myosin-binding region-dependent manner. Thus, overexpression of Smy1p can overcome defects in both the head and tail domains of Myo2p (caused by the myo2-66 and myo2-2 alleles, respectively). We propose that Smy1p enhances some aspect of Myo2p function, perhaps delivery or docking of vesicles at the bud tip.

Cooperation between microtubule- and actin-based motor proteins.

Organelle transport has been proposed to proceed in two steps: long-range transport along microtubules and local delivery via actin filaments. This model is supported by recent studies of pigment transport in several cell types and transport in neurons, and in several cases, class V myosin has been implicated as the actin-based motor. Mutations in mice (dilute) and yeast (myo2) have also implicated this class of myosin in organelle transport, and genetic interactions in yeast have indicated that a kinesin-related protein (Smy1p) plays a supporting role. This link between members of two different motor superfamilies has now taken a surprising turn: There is evidence for a physical interaction between class V myosins and kinesin or Smy1p in both mice and yeast.

Smy1p, a kinesin-related protein that does not require microtubules.

We have previously reported that a defect in Myo2p, a myosin in budding yeast (Saccharomyces cerevisiae), can be partially corrected by overexpression of Smy1p, which is by sequence a kinesin-related protein (Lillie, S.H., and S.S. Brown. 1992. Nature. 356:358- 361). Such a functional link between putative actin- and microtubule-based motors is surprising, so here we have tested the prediction that Smy1p indeed acts as a microtubule-based motor. Unexpectedly, we found that abolition of microtubules by nocodazole does not interfere with the ability of Smy1p to correct the mutant Myo2p defect, nor does it interfere with the ability of Smy1p to localize properly. In addition, other perturbations of microtubules, such as treatment with benomyl or introduction of tubulin mutations, do not exacerbate the Myo2p defect. Furthermore, a mutation in SMY1 strongly predicted to destroy motor activity does not destroy Smy1p function. We have also observed a genetic interaction between SMY1 and two of the late SEC mutations, sec2 and sec4. This indicates that Smy1p can play a role even when Myo2p is wild type, and that Smy1p acts at a specific step of the late secretory pathway. We conclude that Smy1p does not act as a microtubule-based motor to localize properly or to compensate for defective Myo2p, but that it must instead act in some novel way.

Myosins in yeast.

It has been a banner year for the study of yeast myosins. Thanks to the completion of the Saccharomyces cerevisiae genome project, it is now known that budding yeast contains a total of five myosins. Furthermore, functions have been newly ascribed to several of them: two have been implicated in endocytosis, and another has been implicated in generating asymmetry between mother and daughter cells.