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Transport and chemistry of isoprene and its oxidation products in deep convective clouds

Deep convective clouds can transport trace gases from the planetary boundary layer into the upper troposphere where subsequent chemistry may impact aerosol particle formation and growth. In this modelling study, we investigate processes that affect isoprene and its oxidation products injected into the upper troposphere by an isolated deep convective cloud in the Amazon. We run a photochemical box model with coupled cloud microphysics along hundreds of individual air parcel trajectories sampled from a cloud-resolving model simulation of a convective event. The box model simulates gas-phase chemical reactions, gas scavenging by liquid and ice hydrometeors, and turbulent dilution inside a deep convective cloud. The results illustrate the potential importance of gas uptake to anvil ice in regulating the intensity of the isoprene oxidation and associated low volatility organic vapour concentrations in the outflow. Isoprene transport and fate also depends on the abundance of lightning-generated nitrogen oxide radicals (NO x = NO + NO 2 ). If gas uptake on ice is efficient and lightning activity is low, around 30% of the boundary layer isoprene will survive to the cloud outflow after approximately one hour of transport, while all the low volatile oxidation products will be scavenged by the cloud hydrometeors. If lightning NO x is abundant and gas uptake by ice is inefficient, then all isoprene will be oxidised during transport or in the immediate outflow region, while several low volatility isoprene oxidation products will have elevated concentrations in the cloud outflow. Reducing uncertainties associated with the uptake of vapours on ice hydrometeors, especially HO 2 and oxygenated organics, is essential to improve predictions of isoprene and its oxidation products in deep convective outflows and their potential contribution to new particle formation and growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cosmic ray antiprotons in the closed galaxy model

A calculation is made of the flux of secondary antiprotons expected for the leaky box model and for the closed galaxy model of Peters and Westergaard (1977). The antiproton/proton ratio observed at several GeV is a factor of 4 higher than the prediction for the leaky box model but is consistent with that predicted for the closed galaxy model. It is found that new low-energy data are not consistent with either model. Attention is given to the possibility of a primary antiproton component.

Protheroe, R. J.↗

Modeling and Data Analysis of SONEX Observations

Primary focus of the study is on the sources, photochemistry and transport of reactive nitrogen species, O3, as well as other O3 precursors such as NMHC and CO. Major objectives are: (1) Identify the major sources of NO(x) and quantify the contribution of each source to the NO(x) distribution in the free troposphere, particularly in the upper troposphere. (2) Understand the odd hydrogen photochemistry and the recycling of NO(x) in the free troposphere. (3) Evaluate the photochemical production and destruction of O3. A combination of modeling and data analysis/interpretation approach is used. We use a three-dimensional model and a box model to simulate, analyze, and interpret the observations. Both models are needed because they are complementary and each has its advantages and limitations. Proven analytical techniques, including correlation of NOx with various tracers and with different air masses, are applied to both observations and model results to deduce useful information toward accomplishing the objectives. In addition, the SONEX observations are compared and analyzed in a systematic way against other airborne experiments conducted over remote atmosphere, especially those from NASA GTE experiments, AASE 1 and 2, and SUCCESS.

Liu, Shaw C.↗

Numerical Simulation of Multiphase Magnetohydrodynamic Flow and Deformation of Electrolyte–Metal Interface in Aluminum Electrolysis Cells

A computational fluid dynamics based multiphase magnetohydrodynamic (MHD) flow model for simulating the melt flow and bath–metal interface deformation in realistic aluminum reduction cells is presented. The model accounts for the complex physics of the MHD problem in aluminum reduction cells by coupling two immiscible fluids, electromagnetic field, Lorentz force, flow turbulence, and complex cell geometry with large length scale. Especially, the deformation of bath–metal interface is tracked directly in the simulation, and the condition of constant anode–cathode distance (ACD) is maintained by moving anode bottom dynamically with the deforming bath–metal interface. The metal pad deformation and melt flow predicted by the current model are compared to the predictions using a simplified model where the bath–metal interface is assumed flat. The effects of the induced electric current due to fluid flow and the magnetic field due to the interior cell current on the metal pad deformation and melt flow are investigated. The presented model extends the conventional simplified box model by including detailed cell geometry such as the ledge profile and all channels (side, central, and cross-channels). The simulations show the model sensitivity to different side ledge profiles and the cross-channel width by comparing the predicted melt flow and metal pad heaving. In addition, the model dependencies upon the reduction cell operation conditions such as ACD, current distribution on cathode surface and open/closed channel top, are discussed.

42 ENGINEERING↗

Inferring Ozone Production in an Urban Atmosphere using Measurements of Peroxynitric Acid

Observations of peroxynitric acid (HO2NO2) obtained simultaneously with those of NO and NO2 provide a sensitive measure of the ozone photochemical production rate. We illustrate this technique for constraining the ozone production rate with observations obtained from the NCAR C-130 aircraft platform during the Megacity Initiative: Local and Global Research Observations (MILAGRO) intensive in Mexico during the spring of 2006. Sensitive and selective measurements of HO2NO2 were made in situ using chemical ionization mass spectrometry (CIMS). Observations were compared to modeled HO2NO2 concentrations obtained from the NASA Langley highly-constrained photochemical time-dependent box model. The median observed-to-calculated ratio of HO2NO2 is 1.18. At NOx levels greater than 15 ppbv, the photochemical box model underpredicts observations with an observed-to-calculated ratio of HO2NO2 of 1.57. As a result, we find that at high NOx, the ozone production rate calculated using measured HO2NO2 is faster than predicted using accepted photochemistry. Inclusion of an additional HOx source from the reaction of excited state NO2 with H2O or reduction in the rate constant of the reaction of OH with NO2 improves the agreement.

Spencer, K. M.↗

Secondary antiprotons - A valuable cosmic-ray probe

Even in the absence of antiprotons in the primary cosmic rays, a flux of secondary antiprotons will be produced in collisions between cosmic rays and interstellar gas. The predicted antiproton fraction increases with increasing cosmic-ray confinement, so that observations of antiprotons will provide a probe of models of cosmic-ray confinement. It is shown that the expected antiproton fraction (for energies of at least about 10 GeV) ranges between 0.00023 for the 'leaky box' model and 0.0018 for the 'closed box' model. In addition, attention is called to the fact that a detection of cosmic-ray antiprotons at or above a level of 0.0002 will provide a valuable lower limit to the antiproton lifetime.

Steigman, G.↗

Decoupling of Iron and Phosphate in the Global Ocean

Iron is an essential micronutrient for marine phytoplankton, limiting their growth in high nutrient, low chlorophyll regions of the ocean. I use a hierarchy of ocean circulation and biogeochemistry models to understand controls on global iron distribution. I formulate a mechanistic model of iron cycling which includes scavenging onto sinking particles and complexation with an organic ligand. The iron cycle is coupled to a phosphorus cycling model. Iron's aeolian source is prescribed. In the context of a highly idealized multi-box model scheme, the model can be brought into consistency with the relatively sparse ocean observations of iron in the oceans. This biogeochemical scheme is also implemented in a coarse resolution ocean general circulation model. This model also successfully reproduces the broad regional patterns of iron and phosphorus. In particular, the high macronutrient concentrations of the Southern Ocean result from iron limitation in the model. Due to the potential ability of iron to change the efficiency of the carbon pump in the remote Southern Ocean, I study Southern Ocean surface phosphate response to increased aeolian dust flux. My box model and GCM results suggest that a global ten fold increase in dust flux can support a phosphate drawdown of 0.25-0.5 micromolar.

GLOBAL OCEAN MODEL↗

Multidecadal Trends in Ozone Chemistry in the Baltimore-Washington Region

Over the past four decades, policy-led reductions in anthropogenic emissions have improved air quality over the Baltimore-Washington region (BWR). Most of the improvements in meeting the ozone air quality metrics (NAAQS) did not occur until the early 2000s despite large reductions in ozone precursors (NOx, CO, and volatile organic compounds (VOCs)) in the prior decades. We use observations of ozone and ozone precursors from satellites, ground-based sites, and the 2011 DISCOVER-AQ aircraft campaign in Maryland to illustrate how ozone chemistry in the BWR evolved between 1972 and 2019. Analysis of weekday vs weekend probability of ozone exceedance indicates the BWR transitioned to the NOx-limited regime by 2000–2003. A data-constrained box model agrees with this transition period and illustrates the key roles of reduced emissions of formaldehyde (HCHO), aromatics, and other VOCs since 1996, which reduced the peak of ozone production at the time of the transition and likely prevented the BWR from experiencing worsening surface air quality as the region transitioned to NOx-limited chemistry. Analysis of satellite observations of tropospheric column HCHO to NO2 analyzed using a new approach for evaluation of chemical regimes derived from DISCOVER-AQ data also provide a consistent depiction of the timing of the transition period that we infer from ground-based observations and the box model. Finally, despite significant improvements in air quality over the past two decades, the BWR still has not met the EPA standard for surface ozone. With predominantly NOx-limited ozone chemistry over the BWR, continued decreases in emission of NOx will slow the rate of ozone production and help improve air quality. We highlight emissions of NO2 from the diesel truck fleet as a worthwhile focus for future policy because emissions from this source appear to influence day-of-week variations in observed NO2, with an accompanying effect on ozone.

Ozone↗

The potential role of organics in new particle formation and initial growth in the remote tropical upper troposphere

Abstract. Global observations and model studies indicate that new particle formation (NPF) in the upper troposphere (UT) and subsequent particles supply 40 %–60 % of cloud condensation nuclei (CCN) in the lower troposphere, thus affecting the Earth's radiative budget. There are several plausible nucleation mechanisms and precursor species in this atmospheric region, which, in the absence of observational constraints, lead to uncertainties in modeled aerosols. In particular, the type of nucleation mechanism and concentrations of nucleation precursors, in part, determine the spatial distribution of new particles and resulting spatial distribution of CCN from this source. Although substantial advances in understanding NPF have been made in recent years, NPF processes in the UT in pristine marine regions are still poorly understood and are inadequately represented in global models. Here, we evaluate commonly used and state-of-the-art NPF schemes in a Lagrangian box model to assess which schemes and precursor concentrations best reproduce detailed in situ observations. Using measurements of aerosol size distributions (0.003 < Dp < 4.8 µm) in the remote marine troposphere between ∼0.18 and 13 km altitude obtained during the NASA Atmospheric Tomography (ATom) mission, we show that high concentrations of newly formed particles in the tropical UT over both the Atlantic and Pacific oceans are associated with outflow regions of deep convective clouds. We focus analysis on observations over the remote Pacific Ocean, which is a region less perturbed by continental emissions than the Atlantic. Comparing aerosol size distribution measurements over the remote Pacific with box model simulations for 32 cases shows that none of the NPF schemes most commonly used in global models, including binary nucleation of sulfuric acid and water (neutral and ion-assisted) and ternary involving sulfuric acid, water, and ammonia, are consistent with observations, regardless of precursor concentrations. Through sensitivity studies, we find that the nucleation scheme among those tested that is able to explain most consistently (21 of 32 cases) the observed size distributions is that of Riccobono et al. (2014), which involves both organic species and sulfuric acid. The method of Dunne et al. (2016), involving charged sulfuric acid–water–ammonia nucleation, when coupled with organic growth of the nucleated particles, was most consistent with the observations for 5 of 32 cases. Similarly, the neutral sulfuric acid–water–ammonia method of Napari (2002), when scaled with a tuning factor and with organic growth added, was most consistent for 6 of 32 cases. We find that to best reproduce both nucleation and growth rates, the mixing ratios of gas-phase organic precursors generally need to be at least twice that of SO2, a proxy for dimethyl sulfide (DMS). Unfortunately, we have no information on the nature of oxidized organic species that participated in NPF in this region. Global models rarely include organic-driven nucleation and growth pathways in UT conditions where globally significant NPF takes place, which may result in poor estimates of NPF and CCN abundance and contribute to uncertainties in aerosol–cloud–radiation effects. Furthermore, our results indicate that the organic aerosol precursor vapors may be important in the tropical UT above marine regions, a finding that should guide future observational efforts.

54 ENVIRONMENTAL SCIENCES↗

Assessing the Skill of the Improved Treatment of Riverine Freshwater in the Community Earth System Model (CESM) Relative to a New Salinity Climatology

Abstract Recent studies have explored the sensitivity of global ocean model simulations to the treatment of riverine freshwater and the representation of estuarine processes via an estuary box model applied within Community Earth System Model (CESM). This study builds on these efforts by assessing the model skill score relative to a new salinity climatology. The new climatology averages the original observational data of the World Ocean Database directly onto the CESM ocean component tracer grid cells without spatial interpolation, smoothing, or other gap‐filling techniques to mitigate coastal ocean salinity bias present in the World Ocean Atlas. The mean square error for coastal upper ocean salinity relative to climatology is reduced by up to 14%, and the mean square error of near‐surface salinity stratification is reduced by up to 28% near major river mouths in the simulations with improved treatments of river runoff. The improvement in upper ocean bulk salinity is attributed primarily to focusing runoff as point sources thereby avoiding the artificial horizontal spreading of the control run and to applying a locally varying instead of a global constant reference salinity for riverine virtual salt fluxes. The improvements in near‐surface salinity stratification are primarily attributed to adding parameterized estuarine mixing with the estuary box model. Salinity and salinity stratification skill improvements are achieved not just near large rivers but also along the global coast and skill improvements extend far offshore. Despite these improvements, many other sources of model‐climatology mismatch in coastal salinity and stratification remain and merit further attention.

58 GEOSCIENCES↗

Composition of cosmic-ray nuclei from boron to nickel for 1200 to 2400 MeV per nucleon

Balloon-borne measurements of cosmic-ray nuclear abundances for Z = 5-28 and energies 1.2-1.4 GeV/nucleon, obtained using the scintillation/Cerenkov-counter telescope and multiwire proportional counter described by Dwyer et al. (1984) on four flights from Texas and Oklahoma during 1973-1975, are reported. The data are presented in tables and graphs and compared with published observations. Charge separation (sigma = 0.2 units for Fe) and exposure factor (38 sq m sr h) are attained, and the findings are found to be in good agreement with the predictions of a simple leaky-box model of the Galaxy and a pure exponential path-length distribution, although a nested-leaky-box model with some truncation is possible. The delay between e-process nucleosynthesis and cosmic-ray acceleration is estimated on the basis of the Co abundance at greater than 100 d and probably greater than 100,000 yr.

Dwyer, R.↗

Wintertime Formaldehyde: Airborne Observations and Source Apportionment Over the Eastern United States

Formaldehyde (HCHO) is generated from direct urban emission sources and secondary production from the photochemical reactions of urban smog. HCHO is linked to tropospheric ozone formation, and contributes to the photochemical reactions of other components of urban smog. In this study pollution plume intercepts during the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign were used to investigate and characterize the formation of HCHO in relation to several anthropogenic tracers. Analysis of aircraft intercepts combined with detailed chemical box modeling downwind of several cities suggest that the most important contribution to observed HCHO was primary emission. A box model analysis of a single plume suggested that secondary sources contribute 21±10% of observed HCHO. Ratios of HCHO/CO observed in the northeast U.S., from Ohio to New York, ranging from 0.2-0.6%, are consistent with direct emissions combined with at most modest photochemical production. Analysis of the nocturnal boundary layer and residual layer from repeated vertical profiling over urban influenced areas indicate a direct HCHO emission flux of 1.3 x 10 14 molecules cm -2 h -1 . In a case study in Atlanta, GA, nighttime HCHO exhibited a ratio to CO (0.6 – 1.8%) and was anti-correlated with O 3 . Observations were consistent with mixing between direct HCHO emissions in urban air masses with those influenced by more rapid HCHO photochemical production. The HCHO/CO emissions ratios determined from the measured data are 2.3 - 15 times greater than the NEI 2017 emissions database. The largest observed HCHO/CO was 1.7 – 1.8%, located near co-generating power stations.

Formaldehyde↗

An Observationally Constrained Evaluation of the Oxidative Capacity in the Tropical Western Pacific Troposphere

Hydroxyl radical (OH) is the main daytime oxidant in the troposphere and determines the atmospheric lifetimes of many compounds. We use aircraft measurements of O3, H2O, NO, and other species from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, which occurred in the tropical western Pacific (TWP) during January-February 2014, to constrain a photochemical box model and estimate concentrations of OH throughout the troposphere. We find that tropospheric column OH (OHCOL) inferred from CONTRAST observations is 12 to 40% higher than found in chemical transport models (CTMs), including CAM-chem-SD run with 2014 meteorology as well as eight models that participated in POLMIP (2008 meteorology). Part of this discrepancy is due to a clear-sky sampling bias that affects CONTRAST observations; accounting for this bias and also for a small difference in chemical mechanism results in our empirically based value of OHCOL being 0 to 20% larger than found within global models. While these global models simulate observed O3 reasonably well, they underestimate NOx (NO +NO2) by a factor of 2, resulting in OHCOL approx.30% lower than box model simulations constrained by observed NO. Underestimations by CTMs of observed CH3CHO throughout the troposphere and of HCHO in the upper troposphere further contribute to differences between our constrained estimates of OH and those calculated by CTMs. Finally, our calculations do not support the prior suggestion of the existence of a tropospheric OH minimum in the TWP, because during January-February 2014 observed levels of O3 and NO were considerably larger than previously reported values in the TWP.

Hydroxyl radical↗

Interpretation of lidar and satellite data sets using a global photochemical model

The status in the beginning of the report period was that the existing General Circulation Model (GCM) was running with a chemistry module compiled for stratospheric simulation studies. The chemistry simulation was not working sufficiently in the troposphere and any tropospheric trace gas sources or dry deposition sinks were not yet incorporated. The current status concerning the chemistry module is that the chemistry simulation has been modified to also simulate the chemistry in the troposphere with resulting mixing ratios close to other model simulations as described in Olson et al. (1996). The mechanism to incorporate trace gas source and dry deposition sinks, testing for H202, CH300H, 03, HCHO, HN03, and N02, are incorporated and is currently being tested. Existing model and development versions include: the full GCM model, currently still running with the original stratospheric chemistry module; an off-line version of the GCM, i.e. wind and photolysis rates are pre-calculated and prescribed in read-in arrays; a box model version of the modified chemistry module for developments and first tests of new modifications; and a box model with the same chemistry simulated but flexible partitioning and integration methods for test purposes of those. The grantee's work focused mainly on three areas: trace gas sources and dry deposition; method to introduce a NO source instead of a NO(x) source; and investigating integration methods.

Chyba, Thomas↗

Exploration of oxidative chemistry and secondary organic aerosol formation in the Amazon during the wet season: explicit modeling of the Manaus urban plume with GECKO-A

The GoAmazon 2014/5 field campaign took place in Manaus, Brazil, and allowed the investigation of the interaction between background-level biogenic air masses and anthropogenic plumes. We present in this work a box model built to simulate the impact of urban chemistry on biogenic secondary organic aerosol (SOA) formation and composition. An organic chemistry mechanism is generated with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate the explicit oxidation of biogenic and anthropogenic compounds. A parameterization is also included to account for the reactive uptake of isoprene oxidation products on aqueous particles. The biogenic emissions estimated from existing emission inventories had to be reduced to match measurements. The model is able to reproduce ozone and NO x for clean and polluted situations. The explicit model is able to reproduce background case SOA mass concentrations but does not capture the enhancement observed in the urban plume. The oxidation of biogenic compounds is the major contributor to SOA mass. A volatility basis set (VBS) parameterization applied to the same cases obtains better results than GECKO-A for predicting SOA mass in the box model. The explicit mechanism may be missing SOA-formation processes related to the oxidation of monoterpenes that could be implicitly accounted for in the VBS parameterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integration of a grey-box refrigerated case model in EnergyPlus via Python plugin

Commercial buildings, in particular grocery stores (due mainly to their large refrigeration load), provide opportunities for energy cost reductions. Grocery stores could offer substantial load flexibility to the power grid through participation in demand response programs because of their usage patterns and relatively high energy intensity. This load flexibility could come from modifying the control of heating, ventilation, and air conditioning (HVAC) systems, refrigeration systems, or both. Although estimation of the HVAC system’s load flexibility potential is relatively targeted in the literature, estimating load flexibility of refrigeration systems is nascent and has been a challenge, in part because of the lack of proper simulation tools that capture the dynamics in the refrigeration cases. The existing refrigerated case model within EnergyPlus, a whole building energy simulation program, assumes a constant case temperature throughout the simulation period and does not explicitly model the cycling of the compressor serving the refrigerated case. In addition, it does not encompass modeling of temperatures of the product inside the refrigerated case. This difference between modeled and actual operation can be a barrier to the development of demand control algorithm and accurate analysis of load flexibility potential. In this paper, we present a grey-box model for modeling refrigerated cases in grocery stores, which include medium temperature and low temperature. Four cases are modeled; two are low-temperature closed cases and two are medium-temperature cases with one closed and one open. Data from an experimental facility are used to train and test the models. Results demonstrate the efficacy of the grey-box models in predicting the temperatures. This model is integrated into EnergyPlus to capture the dynamic effects of case temperature on the environment and enhance the calculation of sensible and latent heat exchange with the environment (case credits). These enhancements can be leveraged more broadly to model advanced refrigeration controls such as defrost, develop and test unique algorithms that could affect refrigeration interactions with HVAC, and refine store design for any commercial building with refrigeration.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Modeling pN2 Through Geological Time: Implications for Planetary Climates and Atmospheric Biosignatures

Nitrogen is a major nutrient for all life on Earth and could plausibly play a similar role in extraterrestrial biospheres. The major reservoir of nitrogen at Earth’s surface is atmospheric N2, but recent studies have proposed that the size of this reservoir may have fluctuated significantly over the course of Earth’s history with particularly low levels in the Neoarchean—presumably as a result of biological activity. We used a biogeochemical box model to test which conditions are necessary to cause large swings in atmospheric N2 pressure. Parameters for our model are constrained by observations of modern Earth and reconstructions of biomass burial and oxidative weathering in deep time. A 1-D climate model was used to model potential effects on atmospheric climate. In a second set of tests, we perturbed our box model to investigate which parameters have the greatest impact on the evolution of atmospheric pN2 and consider possible implications for nitrogen cycling on other planets. Our results suggest that (a) a high rate of biomass burial would have been needed in the Archean to draw down atmospheric pN2 to less than half modern levels, (b) the resulting effect on temperature could probably have been compensated by increasing solar luminosity and a mild increase in pCO2, and (c) atmospheric oxygenation could have initiated a stepwise pN2 rebound through oxidative weathering. In general, life appears to be necessary for significant atmospheric pN2 swings on Earth-like planets. Our results further support the idea that an exoplanetary atmosphere rich in both N2 and O2 is a signature of an oxygen-producing biosphere.

Biosignatures↗

Midlatitude Ozone Depletion and Air Quality Impacts from Industrial Halogen Emissions in the Great Salt Lake Basin

We report aircraft observations of extreme levels of HCl and the dihalogens Cl 2 , Br 2 , and BrCl in an industrial plume near the Great Salt Lake, Utah. Complete depletion of O 3 was observed concurrently with halogen enhancements as a direct result of photochemically produced halogen radicals. Observed fluxes for Cl 2 , HCl, and NO x agreed with facility-reported emissions inventories. Bromine emissions are not required to be reported in the inventory, but are estimated as 173 Mg year –1 Br 2 and 949 Mg year –1 BrCl, representing a major uncounted oxidant source. A zero-dimensional photochemical box model reproduced the observed O 3 depletions and demonstrated that bromine radical cycling was principally responsible for the rapid O 3 depletion. Inclusion of observed halogen emissions in both the box model and a 3D chemical model showed significant increases in oxidants and particulate matter (PM 2.5 ) in the populated regions of the Great Salt Lake Basin, where winter PM 2.5 is among the most severe air quality issues in the U.S. The model shows regional PM 2.5 increases of 10%–25% attributable to this single industrial halogen source, demonstrating the impact of underreported industrial bromine emissions on oxidation sources and air quality within a major urban area of the western U.S.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗