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1. 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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2. Contributions of biomass-burning, urban, and biogenic emissions to the concentrations and light-absorbing properties of particulate matter in central Amazonia during the dry season

   https://doi.org/10.5194/acp-19-7973-2019  

   de Sá, Suzane S. ; Rizzo, Luciana V. ; Palm, Brett B. ; Campuzano-Jost, Pedro ; Day, Douglas A. ; Yee, Lindsay D. ; Wernis, Rebecca ; Isaacman-VanWertz, Gabriel ; Brito, Joel ; Carbone, Samara ; et al ( January 2019 , Atmospheric Chemistry and Physics)

   Abstract. Urbanization and deforestation have important impacts on atmosphericparticulate matter (PM) over Amazonia. This study presents observations andanalysis of PM₁ concentration, composition, and opticalproperties in central Amazonia during the dry season, focusing on theanthropogenic impacts. The primary study site was located 70 km downwind ofManaus, a city of over 2 million people in Brazil, as part of theGoAmazon2014/5 experiment. A high-resolution time-of-flight aerosol massspectrometer (AMS) provided data on PM₁ composition, and aethalometermeasurements were used to derive the absorption coefficient b_abs,BrC ofbrown carbon (BrC) at 370 nm. Non-refractory PM₁ mass concentrationsaveraged 12.2 µg m⁻³ at the primary study site, dominated byorganics (83 %), followed by sulfate (11 %). A decrease inb_abs,BrC was observed as the mass concentration of nitrogen-containingorganic compounds decreased and the organic PM₁ O:C ratio increased,suggesting atmospheric bleaching of the BrC components. The organic PM₁was separated into six different classes by positive-matrix factorization(PMF), and the mass absorption efficiency E_abs associated with eachfactor was estimated through multivariate linear regression ofb_abs,BrC on the factor loadings. The largest E_abs values wereassociated with urban (2.04±0.14 m² g⁻¹) and biomass-burning(0.82±0.04 to 1.50±0.07 m² g⁻¹) sources. Together, these sources contributed at least 80 % ofb_abs,BrC while accounting for 30 % to 40 % of the organic PM₁ massconcentration. In addition, a comparison of organic PM₁ compositionbetween wet and dry seasons revealed that only part of the 9-foldincrease in mass concentration between the seasons can be attributed tobiomass burning. Biomass-burning factor loadings increased by 30-fold,elevating its relative contribution to organic PM₁ from about 10 % inthe wet season to 30 % in the dry season. However, most of the PM₁mass (>60 %) in both seasons was accounted for by biogenicsecondary organic sources, which in turn showed an 8-fold seasonalincrease in factor loadings. A combination of decreased wet deposition andincreased emissions and oxidant concentrations, as well as a positivefeedback on larger mass concentrations are thought to play a role in theobserved increases. Furthermore, fuzzy c-means clustering identified threeclusters, namely “baseline”, “event”, and “urban” to representdifferent pollution influences during the dry season. The baseline cluster,representing the dry season background, was associated with a mean massconcentration of 9±3 µg m⁻³. This concentration increasedon average by 3 µg m⁻³ for both the urban and the event clusters.The event cluster, representing an increased influence of biomass burningand long-range transport of African volcanic emissions, was characterized byremarkably high sulfate concentrations. The urban cluster, representing theinfluence of Manaus emissions on top of the baseline, was characterized byan organic PM₁ composition that differed from the other two clusters.The differences discussed suggest a shift in oxidation pathways as well asan accelerated oxidation cycle due to urban emissions, in agreement withfindings for the wet season.

    

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3. Arctic Mediterranean exchanges: a consistent volume budget and trends in transports from two decades of observations

   https://doi.org/10.5194/os-15-379-2019  

   Østerhus, Svein ; Woodgate, Rebecca ; Valdimarsson, Héðinn ; Turrell, Bill ; de Steur, Laura ; Quadfasel, Detlef ; Olsen, Steffen M. ; Moritz, Martin ; Lee, Craig M. ; Larsen, Karin Margretha ; et al ( January 2019 , Ocean Science)

   Abstract. The Arctic Mediterranean (AM) is the collective name forthe Arctic Ocean, the Nordic Seas, and their adjacent shelf seas. Water enters into thisregion through the Bering Strait (Pacific inflow) and through the passages across theGreenland–Scotland Ridge (Atlantic inflow) and is modified within the AM. The modifiedwaters leave the AM in several flow branches which are grouped into two differentcategories: (1) overflow of dense water through the deep passages across theGreenland–Scotland Ridge, and (2) outflow of light water – here termed surface outflow– on both sides of Greenland. These exchanges transport heat and salt into and out ofthe AM and are important for conditions in the AM. They are also part of the global oceancirculation and climate system. Attempts to quantify the transports by various methodshave been made for many years, but only recently the observational coverage has becomesufficiently complete to allow an integrated assessment of the AM exchanges based solelyon observations. In this study, we focus on the transport of water and have collecteddata on volume transport for as many AM-exchange branches as possible between 1993 and2015. The total AM import (oceanic inflows plusfreshwater) is found to be 9.1 Sv (sverdrup,1 Sv =10⁶ m³ s⁻¹) with an estimated uncertainty of 0.7 Sv and hasthe amplitude of the seasonal variation close to 1 Sv and maximum import in October.Roughly one-third of the imported water leaves the AM as surface outflow with theremaining two-thirds leaving as overflow. The overflow water is mainly produced frommodified Atlantic inflow and around 70 % of the total Atlantic inflow is convertedinto overflow, indicating a strong coupling between these two exchanges. The surfaceoutflow is fed from the Pacific inflow and freshwater (runoff and precipitation), but isstill approximately two-thirds of modified Atlantic water. For the inflowbranches and the two main overflow branches (Denmark Strait and Faroe Bank Channel),systematic monitoring of volume transport has been established since the mid-1990s, andthis enables us to estimate trends for the AM exchanges as a whole. At the 95 %confidence level, only the inflow of Pacific water through the Bering Strait showed astatistically significant trend, which was positive. Both the total AM inflow and thecombined transport of the two main overflow branches also showed trends consistent withstrengthening, but they were not statistically significant. They do suggest, however,that any significant weakening of these flows during the last two decades is unlikely andthe overall message is that the AM exchanges remained remarkably stable in the periodfrom the mid-1990s to the mid-2010s. The overflows are the densest source water for thedeep limb of the North Atlantic part of the meridional overturning circulation (AMOC),and this conclusion argues that the reported weakening of the AMOC was not due tooverflow weakening or reduced overturning in the AM. Although the combined data set hasmade it possible to establish a consistent budget for the AM exchanges, the observationalcoverage for some of the branches is limited, which introduces considerable uncertainty.This lack of coverage is especially extreme for the surface outflow through the DenmarkStrait, the overflow across the Iceland–Faroe Ridge, and the inflow over the Scottishshelf. We recommend that more effort is put into observing these flows as well asmaintaining the monitoring systems established for the other exchange branches.

    

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4. Photochemistry on the bottom side of the mesospheric Na layer

   https://doi.org/10.5194/acp-19-3769-2019  

   Yuan, Tao ; Feng, Wuhu ; Plane, John M. ; Marsh, Daniel R. ( January 2019 , Atmospheric Chemistry and Physics)

   Abstract. Lidar observations of the mesospheric Na layer have revealed considerablediurnal variations, particularly on the bottom side of the layer, where morethan an order-of-magnitude increase in Na density has been observed below 80 kmafter sunrise. In this paper, multi-year Na lidar observations areutilized over a full diurnal cycle at Utah State University (USU) (41.8^∘ N,111.8^∘ W) and a global atmospheric model of Na with 0.5 kmvertical resolution in the mesosphere and lower thermosphere (WACCM-Na) to explorethe dramatic changes of Na density on the bottom side of the layer. Photolysis of the principal reservoir NaHCO₃ is shown to beprimarily responsible for the increase in Na after sunrise, amplified by theincreased rate of reaction of NaHCO₃ with atomic H, which is mainlyproduced from the photolysis of H₂O and the reaction of OH withO₃. This finding is further supported by Na lidar observation at USUduring the solar eclipse (>96 % totality) event on 21 August 2017, when a decrease and recovery of the Na density on thebottom side of the layer were observed. Lastly, the model simulation showsthat the Fe density below around 80 km increases more strongly and earlierthan observed Na changes during sunrise because of the considerably fasterphotolysis rate of its major reservoir of FeOH.

    

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5. 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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