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1. PTR-TOF-MS eddy covariance measurements of isoprene and monoterpene fluxes from an eastern Amazonian rainforest

   https://doi.org/10.5194/acp-20-7179-2020  

   Sarkar, Chinmoy ; Guenther, Alex B. ; Park, Jeong-Hoo ; Seco, Roger ; Alves, Eliane ; Batalha, Sarah ; Santana, Raoni ; Kim, Saewung ; Smith, James ; Tóta, Julio ; et al ( January 2020 , Atmospheric Chemistry and Physics)

   Abstract. Biogenic volatile organic compounds (BVOCs) are important components of the atmosphere due to their contribution to atmospheric chemistry and biogeochemical cycles. Tropical forests are the largest source of the dominant BVOC emissions (e.g. isoprene and monoterpenes). In this study, we report isoprene and total monoterpene flux measurements with a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) using the eddy covariance (EC) method at the Tapajós National Forest (2.857∘ S, 54.959∘ W), a primary rainforest in eastern Amazonia. Measurements were carried out from 1 to 16 June 2014, during the wet-to-dry transition season. During the measurement period, the measured daytime (06:00–18:00 LT) average isoprene mixing ratios and fluxes were 1.15±0.60 ppb and 0.55±0.71 mg C m−2 h−1, respectively, whereas the measured daytime average total monoterpene mixing ratios and fluxes were 0.14±0.10 ppb and 0.20±0.25 mg C m−2 h−1, respectively. Midday (10:00–14:00 LT) average isoprene and total monoterpene mixing ratios were 1.70±0.49 and 0.24±0.05 ppb, respectively, whereas midday average isoprene and monoterpene fluxes were 1.24±0.68 and 0.46±0.22 mg C m−2 h−1, respectively. Isoprene and total monoterpene emissions in Tapajós were correlated with ambient temperature and solar radiation. Significant correlation with sensible heat flux, SHF (r2=0.77), was also observed. Measured isoprene and monoterpene fluxes were strongly correlated with each other (r2=0.93). The MEGAN2.1 (Model of Emissions of Gases and Aerosols from Nature versionmore »2.1) model could simulate most of the observed diurnal variations (r2=0.7 to 0.8) but declined a little later in the evening for both isoprene and total monoterpene fluxes. The results also demonstrate the importance of site-specific vegetation emission factors (EFs) for accurately simulating BVOC fluxes in regional and global BVOC emission models.« less
2. OH and HO₂ radical chemistry in a midlatitude forest: measurements and model comparisons

   https://doi.org/10.5194/acp-20-9209-2020  

   Lew, Michelle M. ; Rickly, Pamela S. ; Bottorff, Brandon P. ; Reidy, Emily ; Sklaveniti, Sofia ; Léonardis, Thierry ; Locoge, Nadine ; Dusanter, Sebastien ; Kundu, Shuvashish ; Wood, Ezra ; et al ( January 2020 , Atmospheric Chemistry and Physics)

   Abstract. Reactions of the hydroxyl (OH) and peroxy (HO2 and RO2) radicals playa central role in the chemistry of the atmosphere. In addition to controlling the lifetimes ofmany trace gases important to issues of global climate change, OH radical reactionsinitiate the oxidation of volatile organic compounds (VOCs) which can lead to the production ofozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicalsin forest environments characterized by high mixing ratios of isoprene and low mixing ratios ofnitrogen oxides (NOx) (typically less than 1–2 ppb) have shown seriousdiscrepancies with modeled concentrations. These results bring into question our understanding ofthe atmospheric chemistry of isoprene and other biogenic VOCs under low NOxconditions. During the summer of 2015, OH and HO2 radical concentrations, as well as totalOH reactivity, were measured using laser-induced fluorescence–fluorescence assay by gasexpansion (LIF-FAGE) techniques as part of the Indiana Radical Reactivity and Ozone productioN InterComparison (IRRONIC). This campaign took place in a forested area near Indiana University's Bloomington campus which is characterized by high mixing ratios of isoprene (average daily maximum ofapproximately 4 ppb at 28 ∘C) and low mixing ratios of NO (diurnal averageof approximately 170 ppt). Supporting measurements of photolysis rates, VOCs,NOx, and other species were used to constrain a zero-dimensional boxmore »model basedon the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM 3.2),including versions of the Leuven isoprene mechanism (LIM1) for HOx regeneration(RACM2-LIM1 and MCM 3.3.1). Using an OH chemical scavenger technique, the study revealed thepresence of an interference with the LIF-FAGE measurements of OH that increased with bothambient concentrations of ozone and temperature with an average daytime maximum equivalentOH concentration of approximately 5×106 cm−3. Subtraction of theinterference resulted in measured OH concentrations of approximately4×106 cm−3 (average daytime maximum) that were in better agreement with modelpredictions although the models underestimated the measurements in the evening. The addition ofversions of the LIM1 mechanism increased the base RACM2 and MCM 3.2 modeled OH concentrationsby approximately 20 % and 13 %, respectively, with the RACM2-LIM1 mechanism providing thebest agreement with the measured concentrations, predicting maximum daily OH concentrationsto within 30 % of the measured concentrations. Measurements of HO2 concentrationsduring the campaign (approximately a 1×109 cm−3 average daytime maximum)included a fraction of isoprene-based peroxy radicals(HO2*=HO2+αRO2) and were found to agree with modelpredictions to within 10 %–30 %. On average, the measured reactivity was consistent with thatcalculated from measured OH sinks to within 20 %, with modeled oxidation productsaccounting for the missing reactivity, however significant missing reactivity (approximately40 % of the total measured reactivity) was observed on some days.« less
3. Emerging investigator series: primary emissions, ozone reactivity, and byproduct emissions from building insulation materials

   https://doi.org/10.1039/c9em00024k  

   Chin, Kyle ; Laguerre, Aurelie ; Ramasubramanian, Pradeep ; Pleshakov, David ; Stephens, Brent ; Gall, Elliott T. ( August 2019 , Environmental Science: Processes & Impacts)

   Building insulation materials can affect indoor air by (i) releasing primary volatile organic compounds (VOCs) from building enclosure cavities to the interior space, (ii) mitigating exposure to outdoor pollutants through reactive deposition (of oxidants, e.g. , ozone) or filtration (of particles) in infiltration air, and (iii) generating secondary VOCs and other gas-phase byproducts resulting from oxidant reactions. This study reports primary VOC emission fluxes, ozone (O 3 ) reaction probabilities ( γ ), and O 3 reaction byproduct yields for eight common, commercially available insulation materials. Fluxes of primary VOCs from the materials, measured in a continuous flow reactor using proton transfer reaction-time of flight-mass spectrometry, ranged from 3 (polystyrene with thermal backing) to 61 (cellulose) μmol m −2 h −1 (with total VOC mass emission rates estimated to be between ∼0.3 and ∼3.3 mg m −2 h −1 ). Major primary VOC fluxes from cellulose were tentatively identified as compounds likely associated with cellulose chemical and thermal decomposition products. Ozone-material γ ranged from ∼1 × 10 −6 to ∼30 × 10 −6 . Polystyrene with thermal backing and polyisocyanurate had the lowest γ , while cellulose and fiberglass had the highest. In the presence of O 3 , totalmore »observed volatile byproduct yields ranged from 0.25 (polystyrene) to 0.85 (recycled denim) moles of VOCs produced per mole of O 3 consumed, or equivalent to secondary fluxes that range from 0.71 (polystyrene) to 10 (recycled denim) μmol m −2 h −1 . Major emitted products in the presence of O 3 were generally different from primary emissions and were characterized by yields of aldehydes and acetone. This work provides new data that can be used to evaluate and eventually model the impact of “hidden” materials ( i.e. , those present inside wall cavities) on indoor air quality. The data may also guide building enclosure material selection, especially for buildings in areas of high outdoor O 3 .« less
4. Seasonal Contribution of Isoprene‐Derived Organosulfates to Total Water‐Soluble Fine Particulate Organic Sulfur in the United States.

   Chen, Yuzhi ; Dombek, Tracy ; Hand, Jenny ; Zhang, Zhenfa ; Gold, Avram ; Ault, Andrew ; Levine, Levine ; Surratt, Jason ( October 2021 , 2021 AAAR 39th Annual Conference)

   Organosulfates (OSs) are the most abundant class of organosulfur compounds (OrgS) in atmospheric fine particulate matter (PM2.5). Globally, isoprene‐derived OSs (iOSs) are the most abundantly reported OSs. The methyltetrol sulfates (MTSs), formed from multiphase chemical reactions of isoprene‐derived epoxidiols (IEPOX) with acidic sulfate aerosols, are the predominant iOSs. A recent study revealed that the heterogeneous hydroxyl radical (•OH) oxidation of fine particulate MTSs yields several highly oxygenated and functionalized OSs previously attributed to non‐IEPOX pathways. By using hydrophilic interaction liquid chromatography interfaced to electrospray ionization high‐resolution quadrupole time‐of‐flight mass spectrometry (HILIC/ESI‐HRQTOFMS), iOSs were quantitatively characterized in PM2.5 collected from 20 ground sites within the Interagency Monitoring of Protected Visual Environments (IMPROVE) network during the 2016 summer and winter seasons. Total water‐soluble sulfur (TWS‐S) and sulfur in the form of inorganic sulfate (Sinorg) were determined by inductively coupled plasmaoptical emission spectroscopy (ICP‐OES) and ion chromatography (IC), respectively. The difference between TWS‐S and Sinorg was used as an upper bound estimate of water‐soluble OrgS concentration. Significantly higher OrgS concentrations, coincident with elevated iOS concentrations, were observed only in summer. On average, iOSs (130 ± 60, up to 240 ng m‐3) explained 29% (± 7%) of OrgS and 5% (± 2%) of organicmore »matter (OM = 1.8*OC) in summertime PM2.5 collected from the eastern U.S. For the western U.S., iOSs (11 ± 6 ng m‐3) account for 6% (± 5%) of OrgS and 0.7% (± 0.4%) of OM. This study provides critical insights into the abundance, prevalence, spatial variability of iOSs across the U.S.« less
5. Measurement report: Molecular composition and volatility of gaseous organic compounds in a boreal forest – from volatile organic compounds to highly oxygenated organic molecules

   https://doi.org/10.5194/acp-21-8961-2021  

   Huang, Wei ; Li, Haiyan ; Sarnela, Nina ; Heikkinen, Liine ; Tham, Yee Jun ; Mikkilä, Jyri ; Thomas, Steven J. ; Donahue, Neil M. ; Kulmala, Markku ; Bianchi, Federico ( January 2021 , Atmospheric Chemistry and Physics)

   Abstract. The molecular composition and volatility of gaseous organiccompounds were investigated during April–July 2019 at the Station forMeasuring Ecosystem – Atmosphere Relations (SMEAR) II situated in a borealforest in Hyytiälä, southern Finland. In order to obtain a morecomplete picture and full understanding of the molecular composition andvolatility of ambient gaseous organic compounds (from volatile organiccompounds, VOCs, to highly oxygenated organic molecules, HOMs), twodifferent instruments were used. A Vocus proton-transfer-reactiontime-of-flight mass spectrometer (Vocus PTR-ToF; hereafter Vocus) wasdeployed to measure VOCs and less oxygenated VOCs (i.e., OVOCs). Inaddition, a multi-scheme chemical ionization inlet coupled to an atmosphericpressure interface time-of-flight mass spectrometer (MION API-ToF) was usedto detect less oxygenated VOCs (using Br− as the reagent ion; hereafterMION-Br) and more oxygenated VOCs (including HOMs; using NO3- asthe reagent ion; hereafter MION-NO3). The comparison among differentmeasurement techniques revealed that the highest elemental oxygen-to-carbonratios (O : C) of organic compounds were observed by the MION-NO3 (0.9 ± 0.1, average ± 1 standard deviation), followed by the MION-Br(0.8 ± 0.1); lowest O : C ratios were observed by Vocus (0.2 ± 0.1). Diurnal patternsof the measured organic compounds were found to vary among differentmeasurement techniques, even for compounds with the same molecular formula,suggesting contributions of different isomers detected by the differenttechniques and/or fragmentation from different parent compounds inside theinstruments.more »Based on the complementary molecular information obtained fromVocus, MION-Br, and MION-NO3, a more complete picture of the bulkvolatility of all measured organic compounds in this boreal forest wasobtained. As expected, the VOC class was the most abundant (about 53.2 %), followed by intermediate-volatility organic compounds (IVOCs, about45.9 %). Although condensable organic compounds (low-volatility organiccompounds, LVOCs; extremely low volatility organic compounds, ELVOCs; andultralow-volatility organic compounds, ULVOCs) only comprised about 0.2 %of the total gaseous organic compounds, they play an important role in newparticle formation as shown in previous studies in this boreal forest. Ourstudy shows the full characterization of the gaseous organic compounds inthe boreal forest and the advantages of combining Vocus and MION API-ToF formeasuring ambient organic compounds with different oxidation extents (fromVOCs to HOMs). The results therefore provide a more comprehensiveunderstanding of the molecular composition and volatility of atmosphericorganic compounds as well as new insights into interpreting ambientmeasurements or testing/improving parameterizations in transport and climatemodels.« less