Global modeling of the nitrate radical (NO3) for present and pre-industrial scenarios

AbstractIncreasing the complexity of the chemistry scheme in the global chemistry transport model STOCHEM to STOCHEM-CRI (Utembe et al., 2010) leads to an increase in NOx as well as ozone resulting in higher NO3 production over forested regions and regions impacted by anthropogenic emission. Peak NO3 is located over the continents near NOx emission sources. NO3 is formed in the main by the reaction of NO2 with O3, and the significant losses of NO3 are due to the photolysis and the reactions with NO and VOCs. Isoprene is an important biogenic VOC, and the possibility of HOx recycling via isoprene chemistry and other mechanisms such as the reaction of RO2 with HO2 has been investigated previously (Archibald et al., 2010a). The importance of including HOx recycling processes on the global budget of NO3 for present and pre-industrial scenarios has been studied using STOCHEM-CRI, and the results are compared. The large increase (up to 60% for present and up to 80% for pre-industrial) in NO3 is driven by the reduced lifetime of emitted VOCs because of the increase in the HOx concentration. The maximum concentration changes (up to 15ppt) for NO3 from pre-industrial to present day are found at the surface between 30oN and 60oN because of the increase in NOx concentrations in the present day integrations

Quasi-simultaneous Radio/X-Ray Observations of the Candidate Transitional Millisecond Pulsar 3FGL J1544.6-1125 during its Low-luminosity Accretion-disk State

3FGL J1544.6-1125 is a candidate transitional millisecond pulsar (tMSP). Similar to the well-established tMSPs - PSR J1023+0038, IGR J18245-2452, and XSS J12270-4859 -- 3FGL J1544.6-1125 shows $\gamma$-ray emission and discrete X-ray "low" and "high" modes during its low-luminosity accretion-disk state. Coordinated radio/X-ray observations of PSR J1023+0038 in its current low-luminosity accretion-disk state showed rapidly variable radio continuum emission-possibly originating from a compact, self-absorbed jet, the "propellering" of accretion material, and/or pulsar moding. 3FGL J1544.6-1125 is currently the only other (candidate) tMSP system in this state, and can be studied to see whether tMSPs are typically radio-loud compared to other neutron star binaries. In this work, we present a quasi-simultaneous Very Large Array and Swift radio/X-ray campaign on 3FGL J1544.6-1125. We detect 10 GHz radio emission varying in flux density from $47.7 \pm 6.0$ $\mu$Jy down to $\sim$15 $\mu$Jy (3$\sigma$ upper limit) at four epochs spanning three weeks. At the brightest epoch, the radio luminosity is $L_{5 GHz}$ $= (2.17 \pm 0.17) \times 10^{27}$ erg s$^{-1}$ for a quasi-simultaneous X-ray luminosity $L_{2-10 keV}$ $= (4.32 \pm 0.23) \times 10^{33}$ erg s$^{-1}$ (for an assumed distance of 3.8 kpc). These luminosities are close to those of PSR J1023+0038, and the results strengthen the case that 3FGL J1544.6-1125 is a tMSP showing similar phenomenology to PSR J1023+0038.Comment: Accepted for publication in the Astrophysical Journa

Lightning NOx, a key chemistry–climate interaction: impacts of future climate change and consequences for tropospheric oxidising capacity

Lightning is one of the major natural sources of NOx in the atmosphere. A suite of time slice experiments using a stratosphere-resolving configuration of the Unified Model (UM), containing the United Kingdom Chemistry and Aerosols sub-model (UKCA), has been performed to investigate the impact of climate change on emissions of NOx from lightning (LNOx) and to highlight its critical impacts on photochemical ozone production and the oxidising capacity of the troposphere. Two Representative Concentration Pathway (RCP) scenarios (RCP4.5 and RCP8.5) are explored. LNOx is simulated to increase in a year-2100 climate by 33% (RCP4.5) and 78% (RCP8.5), primarily as a result of increases in the depth of convection. The total tropospheric chemical odd oxygen production (P(Ox)) increases linearly with increases in total LNOx and consequently, tropospheric ozone burdens of 29±4 Tg(O3) (RCP4.5) and 46±4 Tg(O3) (RCP8.5) are calculated here. By prescribing a uniform surface boundary concentration for methane in these simulations, methane-driven feedbacks are essentially neglected. A simple estimate of the contribution of the feedback reduces the increase in ozone burden to 24 and 33 Tg(O3), respectively. We thus show that, through changes in LNOx, the effects of climate change counteract the simulated mitigation of the ozone burden, which results from reductions in ozone precursor emissions as part of air quality controls projected in the RCP scenarios. Without the driver of increased LNOx, our simulations suggest that the net effect of climate change would be to lower free tropospheric ozone. In addition, we identify large climate-change-induced enhancements in the concentration of the hydroxyl radical (OH) in the tropical upper troposphere (UT), particularly over the Maritime Continent, primarily as a consequence of greater LNOx. The OH enhancement in the tropics increases oxidation of both methane (with feedbacks onto chemistry and climate) and very short-lived substances (VSLS) (with implications for stratospheric ozone depletion). We emphasise that it is important to improve our understanding of LNOx in order to gain confidence in model projections of composition change under future climate

Seasonal, interannual and decadal variability of tropospheric ozone in the North Atlantic: comparison of UM-UKCA and remote sensing observations for 2005–2018

Tropospheric ozone is an important component of the Earth system as it can affect both climate and air quality. In this work, we use observed tropospheric column ozone derived from the Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) OMI-MLS, in addition to OMI ozone retrieved in discrete vertical layers, and compare it to tropospheric ozone from UM-UKCA simulations (which utilize the Unified Model, UM, coupled to UK Chemistry and Aerosol, UKCA). Our aim is to investigate recent changes (2005–2018) in tropospheric ozone in the North Atlantic region, specifically its seasonal, interannual and decadal variability, and to understand what factors are driving such changes. The model exhibits a large positive bias (greater than 5 DU or ∼ 50 %) in the tropical upper troposphere: through sensitivity experiments, time series correlation, and comparison with the Lightning Imaging Sensor and Optical Transient Detector lightning flash dataset, the model positive bias in the tropics is attributed to shortcomings in the convection and lightning parameterizations, which overestimate lightning flashes in the tropics relative to mid-latitudes. Use of OMI data, for which vertical averaging kernels and a priori information are available, suggests that the model negative bias (6–10 DU or ∼ 20 %) at mid-latitudes, relative to OMI-MLS tropospheric column, could be the result of vertical sampling. Ozone in the North Atlantic peaks in spring and early summer, with generally good agreement between the modelled and observed seasonal cycle. Recent trends in tropospheric ozone were investigated: whilst both observational datasets indicate positive trends of ∼ 5 % and ∼ 10 % in North Atlantic ozone, the modelled ozone trends are much closer to zero and have large uncertainties. North Atlantic ozone interannual variability (IAV) in the model was found to be correlated to the IAV of ozone transported to the North Atlantic from the stratosphere (R=0.77) and emission of NOx from lightning in the tropics (R=0.72). The discrepancy between modelled and observed trends for 2005–2018 could be linked to the model underestimating lower stratospheric ozone trends and associated stratosphere to troposphere transport. Modelled tropospheric ozone IAV is driven by IAV of tropical emissions of NOx from lightning and IAV of ozone transport from the stratosphere; however, the modelled and observed IAV differ. To understand the IAV discrepancy we investigated how modelled ozone and its drivers respond to large-scale modes of variability. Using OMI height-resolved data and model idealized tracers, we were able to identify stratospheric transport of ozone into the troposphere as the main driver of the dynamical response of North Atlantic ozone to the Arctic Oscillation (AO) and the North Atlantic Oscillation (NAO). Finally, we found that the modelled ozone IAV is too strongly correlated to the El Niño–Southern Oscillation (ENSO) compared to observed ozone IAV. This is again linked to shortcomings in the lightning flashes parameterization, which underestimates (overestimates) lightning flash production in the tropics during positive (negative) ENSO events

Development, intercomparison, and evaluation of an improved mechanism for the oxidation of dimethyl sulfide in the UKCA model

Dimethyl sulfide (DMS) is an important trace gas emitted from the ocean. The oxidation of DMS has long been recognised as being important for global climate through the role DMS plays in setting the sulfate aerosol background in the troposphere. However, the mechanisms in which DMS is oxidised are very complex and have proved elusive to accurately determine in spite of decades of research. As a result the representation of DMS oxidation in global chemistry–climate models is often greatly simplified. Recent field observations and laboratory and ab initio studies have prompted renewed efforts in understanding the DMS oxidation mechanism, with implications for constraining the uncertainty in the oxidation mechanism of DMS as incorporated in global chemistry–climate models. Here we build on recent evidence and develop a new DMS mechanism for inclusion in the UK Chemistry Aerosol (UKCA) chemistry–climate model. We compare our new mechanism (CS2-HPMTF) to a number of existing mechanisms used in UKCA (including the highly simplified three-reactions–two-species mechanism used in CMIP6 studies with the model) and to a range of recently developed mechanisms reported in the literature through a series of global and box model experiments. Global model runs with the new mechanism enable us to simulate the global distribution of hydroperoxylmethyl thioformate (HPMTF), which we calculate to have a burden of 2.6–26 Gg S (in good agreement with the literature range of 0.7–18 Gg S). We show that the sinks of HPMTF dominate uncertainty in the budget, not the rate of the isomerisation reaction forming it and that, based on the observed DMS / HPMTF ratio from the global surveys during the NASA Atmospheric Tomography mission (ATom), rapid cloud uptake of HPMTF worsens the model–observation comparison. Our box model experiments highlight that there is significant variance in simulated secondary oxidation products from DMS across mechanisms used in the literature, with significant divergence in the sensitivity of the rates of formation of these products to temperature exhibited; especially for methane sulfonic acid (MSA). Our global model studies show that our updated DMS scheme performs better than the current scheme used in UKCA when compared against a suite of surface and aircraft observations. However, sensitivity studies underscore the need for further laboratory and observational constraints. In particular our results suggest that as a priority long-term DMS observations be made to better constrain the highly uncertain inputs into the system and that laboratory studies be performed that address (1) the uptake of HPMTF onto aerosol surfaces and the products of this reaction and (2) the kinetics and products of the following reactions: CH3SO3 decomposition, CH3S + O2, CH3SOO decomposition, and CH3SO + O3

Airborne observations of trace gases over boreal Canada during BORTAS: campaign climatology, air mass analysis and enhancement ratios

In situ airborne measurements were made over eastern Canada in summer 2011 as part of the BORTAS experiment (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites). In this paper we present observations of greenhouse gases (CO2 and CH4) and other biomass burning tracers (CO, HCN and CH3CN), both climatologically and through case studies, as recorded on board the FAAM BAe-146 research aircraft.Vertical profiles of CO2 were generally characterised by depleted boundary layer concentrations relative to the free troposphere, consistent with terrestrial biospheric uptake. In contrast, CH4 concentrations were found to rise with decreasing altitude due to strong local and regional surface sources. BORTAS observations were found to be broadly comparable with both previous measurements in the region during the regional burning season and with reanalysed composition fields from the EU Monitoring Atmospheric Composition and Change (MACC) project. We use coincident tracer–tracer correlations and a Lagrangian trajectory model to characterise and differentiate air mass history of intercepted plumes. In particular, CO, HCN and CH3CN were used to identify air masses that have been recently influenced by biomass burning.Examining individual cases we were able to quantify emissions from biomass burning. Using both near-field ( 1 day) sampling, boreal forest fire plumes were identified throughout the troposphere. Fresh plumes from fires in northwestern Ontario yield emission factors for CH4 and CO2 of 8.5 ± 0.9 g (kg dry matter)−1 and 1512 ± 185 g (kg dry matter)−1, respectively. We have also investigated the efficacy of calculating emission factors from far-field sampling, in which there might be expected to be limited mixing with background and other characteristic air masses, and we provide guidance on best practice and limitations in such analysis. We have found that for measurements within plumes that originated from fires in northwestern Ontario 2–4 days upwind, emission factors can be calculated that range between 1618 ± 216 and 1702 ± 173 g (kg dry matter)−1 for CO2 and 1.8 ± 0.2 and 6.1 ± 1 g (kg dry matter)−1 for CH4

Gravitational Radiation from Compact Binary Pulsars

An outstanding question in modern Physics is whether general relativity (GR) is a complete description of gravity among bodies at macroscopic scales. Currently, the best experiments supporting this hypothesis are based on high-precision timing of radio pulsars. This chapter reviews recent advances in the field with a focus on compact binary millisecond pulsars with white-dwarf (WD) companions. These systems - if modeled properly - provide an unparalleled test ground for physically motivated alternatives to GR that deviate significantly in the strong-field regime. Recent improvements in observational techniques and advances in our understanding of WD interiors have enabled a series of precise mass measurements in such systems. These masses, combined with high-precision radio timing of the pulsars, result to stringent constraints on the radiative properties of gravity, qualitatively very different from what was available in the past.Comment: Short review chapter to appear in "Gravitational Wave Astrophysics" by Springer-Verlag, edited by Carlos F. Sopuerta; v3: a few major corrections and updated references. Comments are welcome

An Isoprene Mechanism Intercomparison

Annual; Electronic coverage as of Dec. 15, 2005: 2000-; Description based on: 2000; title from cover of PDF document (viewed Dec. 15, 2005).; Report year runs from Jan. 1-Dec. 31.; Harvested from the web on 6/16/06Annual program and geographic summaries of contractual agreements for loans and grants managed by the Dept. of Development.Annual program and geographic summaries of contractual agreements for loans and grants managed by the Dept. of Development