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1. 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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2. 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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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 ( $k_{\mathrm{ALK}+3{\mathrm{BP}}^{\ast }}$) 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 $k_{\mathrm{ALK}+3{\mathrm{BP}}^{\ast }}$ 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. Carbon Flux Explorer optical assessment of C, N and P fluxes

   https://doi.org/10.5194/bg-16-1249-2019  

   Bourne, Hannah L.; Bishop, James K.; Wood, Todd J.; Loew, Timothy J.; Liu, Yizhuang (January 2019, Biogeosciences)

   Abstract. The magnitude and controls of particulate carbon exported from surface watersand its remineralization at depth are poorly constrained. The Carbon FluxExplorer (CFE), a Lagrangian float-deployed imaging sediment trap, has beendesigned to optically measure the hourly variations of particle flux tokilometer depths for months to seasons while relaying data in near-real timeto shore via satellite without attending ships. The main optical proxy forparticle load recorded by the CFE, volume attenuance (VA; units ofmATN cm²), while rigorously defined and highly precise, has not beenrobustly calibrated in terms of particulate organic carbon (POC), nitrogen(PN) and phosphorus (PP). In this study, a novel 3-D-printed particle samplerusing cutting edge additive manufacturing was developed and integrated withthe CFE. Two such modified floats (CFE-Cals) were deployed a total of15 times for 18–24 h periods to gain calibration imagery and samples atdepths near 150 m in four contrasting productivity environments during theJune 2017 California Current Ecosystem Long-Term Ecological Research (LTER)process study. Regression slopes for VA : POC and VA : PN (unitsmATN cm²: mmol; R², n, p value in parentheses) were1.01×10⁴ (0.86, 12, < 0.001) and 1.01×10⁵(0.86, 15, < 0.001), respectively, and were not sensitive toparticle size classes or the contrasting environments encountered. PP was notwell correlated with VA, reflecting the high lability of P relative to C andN. The volume attenuance flux (VAF) to POC flux calibration is compared toprevious estimates. 

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5. Supercooled liquid fogs over the central Greenland Ice Sheet

   https://doi.org/10.5194/acp-19-7467-2019  

   Cox, Christopher J.; Noone, David C.; Berkelhammer, Max; Shupe, Matthew D.; Neff, William D.; Miller, Nathaniel B.; Walden, Von P.; Steffen, Konrad (January 2019, Atmospheric Chemistry and Physics)

   Abstract. Radiation fogs at Summit Station, Greenland (72.58^∘ N,38.48^∘ W; 3210 m a.s.l.), are frequently reported by observers. Thefogs are often accompanied by fogbows, indicating the particles are composedof liquid; and because of the low temperatures at Summit, this liquid issupercooled. Here we analyze the formation of these fogs as well as theirphysical and radiative properties. In situ observations of particle size anddroplet number concentration were made using scattering spectrometers near 2 and 10 m height from 2012 to 2014. These data are complemented bycolocated observations of meteorology, turbulent and radiative fluxes, andremote sensing. We find that liquid fogs occur in all seasons with thehighest frequency in September and a minimum in April. Due to thecharacteristics of the boundary-layer meteorology, the fogs are elevated,forming between 2 and 10 m, and the particles then fall toward the surface.The diameter of mature particles is typically 20–25 µm in summer.Number concentrations are higher at warmer temperatures and, thus, higher insummer compared to winter. The fogs form at temperatures as warm as −5 ^∘C, while the coldest form at temperatures approaching −40 ^∘C. Facilitated by the elevated condensation, in winter two-thirds offogs occurred within a relatively warm layer above the surface when thenear-surface air was below −40 ^∘C, as cold as −57 ^∘C,which is too cold to support liquid water. This implies that fog particlessettling through this layer of cold air freeze in the air column beforecontacting the surface, thereby accumulating at the surface as ice withoutriming. Liquid fogs observed under otherwise clear skies annually imparted1.5 W m⁻² of cloud radiative forcing (CRF). While this is a smallcontribution to the surface radiation climatology, individual events areinfluential. The mean CRF during liquid fog events was 26 W m⁻², andwas sometimes much higher. An extreme case study was observed toradiatively force 5 ^∘C of surface warming during the coldest partof the day, effectively damping the diurnal cycle. At lower elevations ofthe ice sheet where melting is more common, such damping could signal a rolefor fogs in preconditioning the surface for melting later in the day. 

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