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1. Airborne and ground-based observations of ammonium-nitrate-dominated aerosols in a shallow boundary layer during intense winter pollution episodes in northern Utah

   https://doi.org/10.5194/acp-18-17259-2018  

   Franchin, Alessandro ; Fibiger, Dorothy L. ; Goldberger, Lexie ; McDuffie, Erin E. ; Moravek, Alexander ; Womack, Caroline C. ; Crosman, Erik T. ; Docherty, Kenneth S. ; Dube, William P. ; Hoch, Sebastian W. ; et al ( January 2018 , Atmospheric Chemistry and Physics)

   Abstract. Airborne and ground-based measurements of aerosol concentrations, chemicalcomposition, and gas-phase precursors were obtained in three valleys innorthern Utah (USA). The measurements were part of the Utah Winter FineParticulate Study (UWFPS) that took place in January–February 2017. Totalaerosol mass concentrations of PM₁ were measured from a Twin Otteraircraft, with an aerosol mass spectrometer (AMS). PM₁ concentrationsranged from less than 2µgm⁻³ during clean periods to over100µgm⁻³ during the most polluted episodes, consistent withPM_2.5 total mass concentrations measured concurrently at groundsites. Across the entire region, increases in total aerosol mass above∼2µgm⁻³ were associated with increases in theammonium nitrate mass fraction, clearly indicating that the highest aerosolmass loadings in the region were predominantly attributable to an increase inammonium nitrate. The chemical composition was regionally homogenous fortotal aerosol mass concentrations above 17.5µgm⁻³, with 74±5% (average±standard deviation) ammonium nitrate, 18±3%organic material, 6±3% ammonium sulfate, and 2±2%ammonium chloride. Vertical profiles of aerosol mass and volume in the regionshowed variable concentrations with height in the polluted boundary layer.Higher average mass concentrations were observed within the first few hundredmeters above ground level in all three valleys during pollution episodes. Gas-phase measurements of nitric acid (HNO₃) and ammonia (NH₃) duringthe pollution episodes revealed that in the Cache and Utah valleys, partitioningof inorganic semi-volatiles to the aerosol phase was usually limited by theamount of gas-phase nitric acid, with NH₃ being in excess. The inorganicspecies were compared with the ISORROPIA thermodynamic model. Total inorganicaerosol mass concentrations were calculated for various decreases in totalnitrate and total ammonium. For pollution episodes, our simulations of a50% decrease in total nitrate lead to a 46±3% decrease in totalPM₁ mass. A simulated 50% decrease in total ammonium leads to a36±17%µgm⁻³ decrease in total PM₁ mass, over the entirearea of the study. Despite some differences among locations, ourresults showed a higher sensitivity to decreasing nitric acid concentrationsand the importance of ammonia at the lowest total nitrate conditions. In theSalt Lake Valley, both HNO₃ and NH₃ concentrations controlledaerosol formation.

    

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2. Physical and optical characteristics of heavily melted “rotten” Arctic sea ice

   https://doi.org/10.5194/tc-13-775-2019  

   Frantz, Carie M. ; Light, Bonnie ; Farley, Samuel M. ; Carpenter, Shelly ; Lieblappen, Ross ; Courville, Zoe ; Orellana, Mónica V. ; Junge, Karen ( January 2019 , The Cryosphere)

   Abstract. Field investigations of the properties of heavily melted “rotten” Arcticsea ice were carried out on shorefast and drifting ice off the coast ofUtqiaġvik (formerly Barrow), Alaska, during the melt season. While noformal criteria exist to qualify when ice becomes rotten, the objectiveof this study was to sample melting ice at the point at which its structural andoptical properties are sufficiently advanced beyond the peak of the summerseason. Baseline data on the physical (temperature, salinity, density,microstructure) and optical (light scattering) properties of shorefast icewere recorded in May and June 2015. In July of both 2015 and 2017, smallboats were used to access drifting rotten ice within ∼32 km of Utqiaġvik. Measurements showed that pore space increased as icetemperature increased (−8 to 0 ^∘C), ice salinitydecreased (10 to 0 ppt), and bulk density decreased (0.9 to0.6 g cm⁻³). Changes in pore space were characterized with thin-sectionmicrophotography and X-ray micro-computed tomography in the laboratory. Theseanalyses yielded changes in average brine inclusion number density (whichdecreased from 32 to 0.01 mm⁻³), mean pore size (whichincreased from 80 µm to 3 mm), and total porosity (increased from0 % to > 45 %) and structural anisotropy (variable, withvalues of generally less than 0.7). Additionally, light-scattering coefficientsof the ice increased from approximately 0.06 to > 0.35 cm⁻¹ as the ice melt progressed. Together, these findings indicate thatthe properties of Arctic sea ice at the end of melt season are significantlydistinct from those of often-studied summertime ice. If such rotten ice wereto become more prevalent in a warmer Arctic with longer melt seasons, thiscould have implications for the exchange of fluid and heat at the oceansurface.

    

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3. Aqueous reactions of organic triplet excited states with atmospheric alkenes

   https://doi.org/10.5194/acp-19-5021-2019  

   Kaur, Richie ; Hudson, Brandi M. ; Draper, Joseph ; Tantillo, Dean J. ; Anastasio, Cort ( January 2019 , Atmospheric Chemistry and Physics)

   Abstract. Triplet excited states of organic matter are formed when colored organicmatter (i.e., brown carbon) absorbs light. While these “triplets” can beimportant photooxidants in atmospheric drops and particles (e.g., theyrapidly oxidize phenols), very little is known about their reactivity towardmany classes of organic compounds in the atmosphere. Here we measure thebimolecular rate constants of the triplet excited state of benzophenone(³BP^∗), a model species, with 17 water-solubleC₃–C₆ alkenes that have either been found in theatmosphere or are reasonable surrogates for identified species. Measured rateconstants ($k_{\mathrm{ALK}+\mathrm{3}{\mathrm{BP}}^{\ast }}$) vary by a factor of 30 and are in therange of (0.24–7.5) ×10⁹ M⁻¹ s⁻¹. Biogenic alkenesfound in the atmosphere – e.g., cis-3-hexen-1-ol, cis-3-hexenyl acetate, andmethyl jasmonate – react rapidly, with rate constants above 1×10⁹ M⁻¹ s⁻¹. Rate constants depend on alkene characteristicssuch as the location of the double bond, stereochemistry, and alkylsubstitution on the double bond. There is a reasonable correlation between$k_{\mathrm{ALK}+\mathrm{3}{\mathrm{BP}}^{\ast }}$ and the calculated one-electron oxidation potential(OP) of the alkenes (R²=0.58); in contrast, rate constants are notcorrelated with bond dissociation enthalpies, bond dissociation freeenergies, or computed energy barriers for hydrogen abstraction. Using the OPrelationship, we estimate aqueous rate constants for a number of unsaturatedisoprene and limonene oxidation products with ³BP^∗: values are inthe range of (0.080–1.7) ×10⁹ M⁻¹ s⁻¹, withgenerally faster values for limonene products. Rate constants with lessreactive triplets, which are probably more environmentally relevant, arelikely roughly 25 times slower. Using our predicted rate constants, alongwith values for other reactions from the literature, we conclude thattriplets are probably minor oxidants for isoprene- and limonene-relatedcompounds in cloudy or foggy atmospheres, except in cases in which the tripletsare very reactive.

    

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4. A simplified parameterization of isoprene-epoxydiol-derived secondary organic aerosol (IEPOX-SOA) for global chemistry and climate models: a case study with GEOS-Chem v11-02-rc

   https://doi.org/10.5194/gmd-12-2983-2019  

   Jo, Duseong S. ; Hodzic, Alma ; Emmons, Louisa K. ; Marais, Eloise A. ; Peng, Zhe ; Nault, Benjamin A. ; Hu, Weiwei ; Campuzano-Jost, Pedro ; Jimenez, Jose L. ( January 2019 , Geoscientific Model Development)

   Abstract. Secondary organic aerosol derived from isopreneepoxydiols (IEPOX-SOA) is thought to contribute the dominant fraction oftotal isoprene SOA, but the current volatility-based lumped SOAparameterizations are not appropriate to represent the reactive uptake ofIEPOX onto acidified aerosols. A full explicit modeling of this chemistryis however computationally expensive owing to the many species and reactionstracked, which makes it difficult to include it in chemistry–climate modelsfor long-term studies. Here we present three simplified parameterizations(version 1.0) for IEPOX-SOA simulation, based on an approximateanalytical/fitting solution of the IEPOX-SOA yield and formation timescale.The yield and timescale can then be directly calculated using the globalmodel fields of oxidants, NO, aerosol pH and other key properties, and drydeposition rates. The advantage of the proposed parameterizations is thatthey do not require the simulation of the intermediates while retaining thekey physicochemical dependencies. We have implemented the newparameterizations into the GEOS-Chem v11-02-rc chemical transport model,which has two empirical treatments for isoprene SOA (the volatility-basis-set, VBS, approach and a fixed 3 % yield parameterization), and comparedall of them to the case with detailed fully explicit chemistry. The bestparameterization (PAR3) captures the global tropospheric burden of IEPOX-SOAand its spatiotemporal distribution (R²=0.94) vs. thosesimulated by the full chemistry, while being more computationally efficient(∼5 times faster), and accurately captures the response tochanges in NO_x and SO₂ emissions. On the other hand, the constant3 % yield that is now the default in GEOS-Chem deviates strongly (R²=0.66), as does the VBS (R²=0.47, 49 % underestimation), withneither parameterization capturing the response to emission changes. Withthe advent of new mass spectrometry instrumentation, many detailed SOAmechanisms are being developed, which will challenge global and especiallyclimate models with their computational cost. The methods developed in thisstudy can be applied to other SOA pathways, which can allow includingaccurate SOA simulations in climate and global modeling studies in thefuture.

    

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5. Using collision-induced dissociation to constrain sensitivity of ammonia chemical ionization mass spectrometry (NH₄⁺ CIMS) to oxygenated volatile organic compounds

   https://doi.org/10.5194/amt-12-1861-2019  

   Zaytsev, Alexander ; Breitenlechner, Martin ; Koss, Abigail R. ; Lim, Christopher Y. ; Rowe, James C. ; Kroll, Jesse H. ; Keutsch, Frank N. ( January 2019 , Atmospheric Measurement Techniques)

   Abstract. Chemical ionization massspectrometry (CIMS) instruments routinely detect hundreds of oxidized organic compoundsin the atmosphere. A major limitation of these instruments is the uncertaintyin their sensitivity to many of the detected ions. We describe thedevelopment of a new high-resolution time-of-flight chemical ionization massspectrometer that operates in one of two ionization modes: using eitherammonium ion ligand-switching reactions such as for ${\mathrm{NH}}_{\mathrm{4}}^{+}$ CIMS orproton transfer reactions such as for proton-transfer-reaction massspectrometer (PTR-MS). Switching between the modes can be done within 2 min.The ${\mathrm{NH}}_{\mathrm{4}}^{+}$ CIMS mode of the new instrument has sensitivities of upto 67 000 dcps ppbv⁻¹ (duty-cycle-corrected ion counts per second perpart per billion by volume) and detection limits between 1 and 60 pptv at2σ for a 1 s integration time for numerous oxygenated volatileorganic compounds. We present a mass spectrometric voltage scanning procedurebased on collision-induced dissociation that allows us to determine thestability of ammonium-organic ions detected by the ${\mathrm{NH}}_{\mathrm{4}}^{+}$ CIMS instrument.Using this procedure, we can effectively constrain the sensitivity of theammonia chemical ionization mass spectrometer to a wide range of detectedoxidized volatile organic compounds for which no calibration standards exist.We demonstrate the application of this procedure by quantifying thecomposition of secondary organic aerosols in a series of laboratoryexperiments.

    

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