The atmospheric impacts of monoterpene ozonolysis on global stabilised Criegee intermediate budgets and SO2 oxidation : experiment, theory and modelling

The gas-phase reaction of alkenes with ozone is known to produce stabilised Criegee intermediates (SCIs). These biradical/zwitterionic species have the potential to act as atmospheric oxidants for trace pollutants such as SO₂, enhancing the formation of sulfate aerosol with impacts on air quality and health, radiative transfer and climate. However, the importance of this chemistry is uncertain as a consequence of limited understanding of the abundance and atmospheric fate of SCIs. In this work we apply experimental, theoretical and numerical modelling methods to quantify the atmospheric impacts, abundance and fate of the structurally diverse SCIs derived from the ozonolysis of monoterpenes, the second most abundant group of unsaturated hydrocarbons in the atmosphere. We have investigated the removal of SO₂ by SCIs formed from the ozonolysis of three atmospherically important monoterpenes (<i>α</i>-pinene, <i>β</i>-pinene and limonene) in the presence of varying amounts of water vapour in large-scale simulation chamber experiments that are representative of boundary layer conditions. The SO₂ removal displays a clear dependence on water vapour concentration, but this dependence is not linear across the range of [H₂O] explored. At low [H₂O] a strong dependence of SO₂ removal on [H₂O] is observed, while at higher [H₂O] this dependence becomes much weaker. This is interpreted as being caused by the production of a variety of structurally (and hence chemically) different SCIs in each of the systems studied, which displayed different rates of reaction with water and of unimolecular rearrangement or decomposition. The determined rate constants, <i>k</i>(SCI+H₂O), for those SCIs that react primarily with H₂O range from 4 to 310  ×  10⁻¹⁵ cm³ s⁻¹. For those SCIs that predominantly react unimolecularly, determined rates range from 130 to 240 s⁻¹. These values are in line with previous results for the (analogous) stereo-specific SCI system of <i>syn</i>-/<i>anti</i>-CH₃CHOO. The experimental results are interpreted through theoretical studies of the SCI unimolecular reactions and bimolecular reactions with H₂O, characterised for <i>α</i>-pinene and <i>β</i>-pinene at the M06-2X/aug-cc-pVTZ level of theory. The theoretically derived rates agree with the experimental results within the uncertainties. A global modelling study, applying the experimental results within the GEOS-Chem chemical transport model, suggests that &gt; 97 % of the total monoterpene-derived global SCI burden is comprised of SCIs with a structure that determines that they react slowly with water and that their atmospheric fate is dominated by unimolecular reactions. Seasonally averaged boundary layer concentrations of monoterpene-derived SCIs reach up to 1.4  ×  10⁴ cm⁻³ in regions of elevated monoterpene emissions in the tropics. Reactions of monoterpene-derived SCIs with SO₂ account for &lt; 1 % globally but may account for up to 60 % of the gas-phase SO₂ removal over areas of tropical forests, with significant localised impacts on the formation of sulfate aerosol and hence the lifetime and distribution of SO₂

Observations of the galactic plane by the zodiacal infrared project

The two rocket flights of the Zodiacal Infrared Project (ZIP), flown 18 August 1980 and 31 July 1981, were intended to provide data on the near-infrared thermal emission of the interplanetary dust cloud over a broad range of ecliptic coordinates (latitudes -60 to +85 degrees, solar elongation angles 22 to 90 degrees and 140 to 180 degrees). In addition, their multiple crossings of the Galactic plane provided low resolution spectral data (delta lambda/lambda ranging from 1. to 0.1, for effective wavelengths from 3 to 30 microns) for most of the first quadrant (longitudes 30 to 100 degrees). Examples are displayed. Having made a thorough reanalysis of the calibration of the ZIP database, researchers present the salient features of the Galactic plane as observed by ZIP. The binned, in-plane data, corrected for zodiacal emission, generally show an exponential decrease with increasing longitude. The fitted exponential scale-length is 0.038/degree, and can be inverted to derive a radial density profile. Channel ratios are converted to temperatures by using model spectra in which thermal emitters with emissivity approx. 1/lambda are convolved with the filter responses. The results for channels 5 (11 microns) and 12 (21 microns) are shown, along with similarly derived temperatures from Infrared Astronomy Satellite (IRAS) 12 microns and 25 microns data. The ZIP data show little variation with longitude, consistent with IRAS results. A narrow spectral feature at 13 microns appears consistently in data for the plane (uncorrected for zodiacal emission). However, this is strongly contaminated by calibration problems for channel 8. Researchers suggest that residual emission at 13 microns arises from the (NeII) line at 12.8 microns

Seasonal dependence of peroxy radical concentrations at a Northern hemisphere marine boundary layer site during summer and winter: evidence for radical activity in winter

Peroxy radicals (HO2+Σ RO2) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer was higher than winter (1.51±0.5 ppbv h−1 and 1.11±0.47 ppbv h−1, respectively). The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5 min in summer and 21 minutes in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and that significant oxidant levels are sustained in winter. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state

H3+ in Diffuse Interstellar Clouds: a Tracer for the Cosmic-Ray Ionization Rate

Using high resolution infrared spectroscopy we have surveyed twenty sightlines for H3+ absorption. H3+ is detected in eight diffuse cloud sightlines with column densities varying from 0.6x10^14 cm^-2 to 3.9x10^14 cm^-2. This brings to fourteen the total number of diffuse cloud sightlines where H3+ has been detected. These detections are mostly along sightlines concentrated in the Galactic plane, but well dispersed in Galactic longitude. The results imply that abundant H3+ is common in the diffuse interstellar medium. Because of the simple chemistry associated with H3+ production and destruction, these column density measurements can be used in concert with various other data to infer the primary cosmic-ray ionization rate, zeta_p. Values range from 0.5x10^-16 s^-1 to 3x10^-16 s^-1 with an average of 2x10^-16 s^-1. Where H3+ is not detected the upper limits on the ionization rate are consistent with this range. The average value of zeta_p is about an order of magnitude larger than both the canonical rate and rates previously reported by other groups using measurements of OH and HD. The discrepancy is most likely due to inaccurate measurements of rate constants and the omission of effects which were unknown when those studies were performed. We believe that the observed column density of H3+ is the most direct tracer for the cosmic-ray ionization rate due to its simple chemistry. Recent models of diffuse cloud chemistry require cosmic-ray ionization rates on the order of 10^-16 s^-1 to reproduce observed abundances of various atomic and molecular species, in rough accord with our observational findings.Comment: Accepted to ApJ, 35 pages, 5 figures, 5 table

Ozonolysis of a-phellandrene - Part 2 : Compositional analysis of secondary organic aerosol highlights the role of stabilized Criegee intermediates

The molecular composition of secondary organic aerosol (SOA) generated from the ozonolysis of α-phellandrene is investigated for the first time using high pressure liquid chromatography coupled to high-resolution Quadrupole-Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017a). Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid, and indirect evidence from double bond equivalency factors, suggests the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs) with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments, hence dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around Eucalypt forests regions where α-phellandrene is primarily emitted

On Morita and derived equivalences for cohomological Mackey algebras

By results of the second author, a source algebra equivalence between two p-blocks of finite groups induces an equivalence between the categories of cohomological Mackey functors associated with these blocks, and a splendid derived equivalence between two blocks induces a derived equivalence between the corresponding categories ofcohomological Mackey functors. The main result of this paper proves a partial converse: an equivalence (resp. Rickard equivalence) between the categories of cohomological Mackey functors of two blocks of finite groups induces a permeable Morita (resp. derived) equivalence between the two block algebras

The LWA1 Radio Telescope

LWA1 is a new radio telescope operating in the frequency range 10-88 MHz, located in central New Mexico. The telescope consists of 258 pairs of dipole-type antennas whose outputs are individually digitized and formed into beams. Simultaneously, signals from all dipoles can be recorded using one of the instrument's "all dipoles" modes, facilitating all-sky imaging. Notable features of the instrument include high intrinsic sensitivity (about 6 kJy zenith system equivalent flux density), large instantaneous bandwidth (up to 78 MHz), and 4 independently-steerable beams utilizing digital "true time delay" beamforming. This paper summarizes the design of LWA1 and its performance as determined in commissioning experiments. We describe the method currently in use for array calibration, and report on measurements of sensitivity and beamwidth.Comment: 9 pages, 14 figures, accepted by IEEE Trans. Antennas & Propagation. Various minor changes from previous versio

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO₂, H₂O and dimethyl sulfide

Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting sulfate aerosol) and NO2 processing (affecting NOx levels) depends critically upon the fate of the SCIs with respect to reaction with water and decomposition. Here, we have investigated the removal of SO2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene-derived SCIs with H2O. Under excess SO2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (+/-0.03). The observed SO2 removal kinetics are consistent with a relative rate constant, k (SCI + H2O) = k (SCI + SO2), of 3.1 (+/-0.5) x 10(-5) for isoprene-derived SCIs. The relative rate constant for k (SCI decomposition) = k (SCI + SO2) is 3.0 (+/-3.2) x 10(11) cm(-3). Uncertainties are +/-2 sigma and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprenederived SCIs are unlikely to make a substantial contribution to gas-phase SO2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO2 removal in the isopreneozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCIs and dimethyl sulfide (DMS); the observed SO2 removal kinetics are consistent with a relative rate constant, k (SCI + DMS) = k (SCI + SO2), of 3.5 (+/-1.8). This result suggests that SCIs may contribute to the oxidation of DMS in the atmosphere and that this process could therefore influence new particle formation in regions impacted by emissions of unsaturated hydrocarbons and DMS

Support varieties for selfinjective algebras

Support varieties for any finite dimensional algebra over a field were introduced by Snashall-Solberg using graded subalgebras of the Hochschild cohomology. We mainly study these varieties for selfinjective algebras under appropriate finite generation hypotheses. Then many of the standard results from the theory of support varieties for finite groups generalize to this situation. In particular, the complexity of the module equals the dimension of its corresponding variety, all closed homogeneous varieties occur as the variety of some module, the variety of an indecomposable module is connected, periodic modules are lines and for symmetric algebras a generalization of Webb's theorem is true

The effects of long-term fertilizations on soil hydraulic properties vary with scales

Soil structural alterations instigated by cropping system conversion and fertilization change have been well documented, but how such alterations vary with scale remains elusive. We investigated this based on the Rothamsted long-term wheat experiment (since 1843) in the UK. Triplicate cores 7cm high and 10cm in diameter were taken from plots that have been under different fertilizations and returned to natural woodland for more than one century for imaging with X-ray computed tomography at resolution of 40µm. We then broke each core and sampled three aggregates from it to scan them at resolution of 1.5µm. For each core or aggregate sample, we calculated its pore size distribution, as well as permeability and tortuosity from pore-scale simulations. The results showed that the fertilization change more than 170 years ago reshaped the soil structure but differently between the core scale and aggregate scale. Macro-porosity of the pores (>40µm) in the cores unfertilized or fertilized with inorganic fertilizers were low and poorly connected in the top 10cm of soil, compared to the cores given farmyard manure or in the woodland. In all treatments, the large macropores in the cores were hydraulically anisotropic with their permeability being higher in the horizontal direction than in the vertical direction, whereas the aggregates were comparatively isotropic. The fertilization affected porosity and permeability of macropores at core scale more significantly than those at aggregate scale, and the aggregates fertilized with farmyard manure and in the woodland were more permeable than aggregates in other treatments. It is also found that, compared to no-fertilization or fertilization with complete fertilizers, fertilizing without phosphorus over the past 20 years increased the porosity and permeability of the aggregates but not of the cores. Fertilization with inorganic fertilizers increased tortuosity of the macropores in the cores but not of the intra-aggregates micropores, compared to no-fertilization. Porosity-permeability relationship for aggregates unfertilized or fertilized with inorganic fertilisers follows a power law with R2 > 0.8. In contrast, the permeability of aggregates in farmyard manure and in the woodland trended differently with the porosity. Aggregates and cores responded differently to carbon in that, with soil carbon increasing, the permeability of the aggregates increased asymptotically while the permeability of the cores increased approximately exponentially. Since soil structure is indicators of soil quality and evolves slowly, our results have important implications for understanding how agronomical practice changes reshape soil structure at different scales as well as the long-term consequence for hydrological and biochemical processes