scholarly journals Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere

2020 ◽  
Vol 117 (52) ◽  
pp. 33011-33016
Author(s):  
Krystal T. Vasquez ◽  
John D. Crounse ◽  
Benjamin C. Schulze ◽  
Kelvin H. Bates ◽  
Alexander P. Teng ◽  
...  
Keyword(s):  
Transport Model ◽  
Deuterium Oxide ◽  
Ambient Air ◽  
Water Volume ◽  
Isomer Ratio ◽  
Atmospheric Measurements ◽  
Laboratory Findings ◽  
Loss Process ◽  
Isomer Distribution ◽  
Hydrolysis Of

The formation of a suite of isoprene-derived hydroxy nitrate (IHN) isomers during the OH-initiated oxidation of isoprene affects both the concentration and distribution of nitrogen oxide free radicals (NOx). Experiments performed in an atmospheric simulation chamber suggest that the lifetime of the most abundant isomer, 1,2-IHN, is shortened significantly by a water-mediated process (leading to nitric acid formation), while the lifetime of a similar isomer, 4,3-IHN, is not. Consistent with these chamber studies, NMR kinetic experiments constrain the 1,2-IHN hydrolysis lifetime to less than 10 s in deuterium oxide (D2O) at 298 K, whereas the 4,3-IHN isomer has been observed to hydrolyze much less efficiently. These laboratory findings are used to interpret observations of the IHN isomer distribution in ambient air. The IHN isomer ratio (1,2-IHN to 4,3-IHN) in a high NOx environment decreases rapidly in the afternoon, which is not explained using known gas-phase chemistry. When simulated with an observationally constrained model, we find that an additional loss process for the 1,2-IHN isomer with a time constant of about 6 h best explains our atmospheric measurements. Using estimates for 1,2-IHN Henry’s law constant and atmospheric liquid water volume, we show that condensed-phase hydrolysis of 1,2-IHN can account for this loss process. Simulations from a global chemistry transport model show that the hydrolysis of 1,2-IHN accounts for a substantial fraction of NOx lost (and HNO3 produced), resulting in large impacts on oxidant formation, especially over forested regions.

scholarly journals Abundances, emissions, and loss processes of the long-lived and potent greenhouse gas octafluorooxolane (octafluorotetrahydrofuran, <i>c</i>-C<sub>4</sub>F<sub>8</sub>O) in the atmosphere

2019 ◽  
Vol 19 (6) ◽  
pp. 3481-3492 ◽  
Author(s):  
Martin K. Vollmer ◽  
François Bernard ◽  
Blagoj Mitrevski ◽  
L. Paul Steele ◽  
Cathy M. Trudinger ◽  
...  
Keyword(s):  
Greenhouse Gas ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Semiconductor Industry ◽  
Infrared Absorption Spectrum ◽  
Full Range ◽  
Ambient Air ◽  
Atmospheric Measurements ◽  
Air Samples ◽  
Atmospheric Observations

Abstract. The first atmospheric observations of octafluorooxolane (octafluorotetrahydrofuran, c-C4F8O), a persistent greenhouse gas, are reported. In addition, a complementary laboratory study of its most likely atmospheric loss processes, its infrared absorption spectrum, and global warming potential (GWP) are reported. First atmospheric measurements of c-C4F8O are provided from the Cape Grim Air Archive (41∘ S, Tasmania, Australia, 1978–present), supplemented by two firn air samples from Antarctica, in situ measurements of ambient air at Aspendale, Victoria (38∘ S), and a few archived air samples from the Northern Hemisphere. The atmospheric abundance in the Southern Hemisphere has monotonically grown over the past decades and leveled at 74 ppq (parts per quadrillion, femtomole per mole in dry air) by 2015–2018. The growth rate of c-C4F8O has decreased from a maximum in 2004 of 4.0 to <0.25 ppq yr−1 in 2017 and 2018. Using a 12-box atmospheric transport model, globally averaged yearly emissions and abundances of c-C4F8O are calculated for 1951–2018. Emissions, which we speculate to derive predominantly from usage of c-C4F8O as a solvent in the semiconductor industry, peaked at 0.15 (±0.04, 2σ) kt yr−1 in 2004 and have since declined to <0.015 kt yr−1 in 2017 and 2018. Cumulative emissions over the full range of our record amount to 2.8 (2.4–3.3) kt, which correspond to 34 Mt of CO2-equivalent emissions. Infrared and ultraviolet absorption spectra for c-C4F8O as well as the reactive channel rate coefficient for the O(1D) + c-C4F8O reaction were determined from laboratory studies. On the basis of these experiments, a radiative efficiency of 0.430 W m−2 ppb−1 (parts per billion, nanomol mol−1) was determined, which is one of the largest found for synthetic greenhouse gases. The global annually averaged atmospheric lifetime, including mesospheric loss, is estimated to be >3000 years. GWPs of 8975, 12 000, and 16 000 are estimated for the 20-, 100-, and 500-year time horizons, respectively.

scholarly journals Inverse modelling of CF<sub>4</sub> and NF<sub>3</sub> emissions in East Asia

2018 ◽  
Vol 18 (18) ◽  
pp. 13305-13320 ◽  
Author(s):  
Tim Arnold ◽  
Alistair J. Manning ◽  
Jooil Kim ◽  
Shanlan Li ◽  
Helen Webster ◽  
...  
Keyword(s):  
South Korea ◽  
East Asia ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Atmospheric Gases ◽  
Atmospheric Measurements ◽  
Small Uncertainty ◽  
Measurement Location ◽  
Atmospheric Transport Model ◽  
Good Agreement

Abstract. Decadal trends in the atmospheric abundances of carbon tetrafluoride (CF4) and nitrogen trifluoride (NF3) have been well characterised and have provided a time series of global total emissions. Information on locations of emissions contributing to the global total, however, is currently poor. We use a unique set of measurements between 2008 and 2015 from the Gosan station, Jeju Island, South Korea (part of the Advanced Global Atmospheric Gases Experiment network), together with an atmospheric transport model, to make spatially disaggregated emission estimates of these gases in East Asia. Due to the poor availability of good prior information for this study, our emission estimates are largely influenced by the atmospheric measurements. Notably, we are able to highlight emission hotspots of NF3 and CF4 in South Korea due to the measurement location. We calculate emissions of CF4 to be quite constant between the years 2008 and 2015 for both China and South Korea, with 2015 emissions calculated at 4.3±2.7 and 0.36±0.11 Gg yr−1, respectively. Emission estimates of NF3 from South Korea could be made with relatively small uncertainty at 0.6±0.07 Gg yr−1 in 2015, which equates to ∼1.6 % of the country's CO2 emissions. We also apply our method to calculate emissions of CHF3 (HFC-23) between 2008 and 2012, for which our results find good agreement with other studies and which helps support our choice in methodology for CF4 and NF3.

scholarly journals Underway seawater and atmospheric measurements of volatile organic compounds in the Southern Ocean

2020 ◽  
Vol 17 (9) ◽  
pp. 2593-2619 ◽  
Author(s):  
Charel Wohl ◽  
Ian Brown ◽  
Vassilis Kitidis ◽  
Anna E. Jones ◽  
William T. Sturges ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Southern Ocean ◽  
Organic Compounds ◽  
Dimethyl Sulfide ◽  
Ambient Air ◽  
Atmospheric Measurements ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Air Mixing ◽  
Net Flux

Abstract. Dimethyl sulfide and volatile organic compounds (VOCs) are important for atmospheric chemistry. The emissions of biogenically derived organic gases, including dimethyl sulfide and especially isoprene, are not well constrained in the Southern Ocean. Due to a paucity of measurements, the role of the ocean in the atmospheric budgets of atmospheric methanol, acetone, and acetaldehyde is even more poorly known. In order to quantify the air–sea fluxes of these gases, we measured their seawater concentrations and air mixing ratios in the Atlantic sector of the Southern Ocean, along a ∼ 11 000 km long transect at approximately 60∘ S in February–April 2019. Concentrations, oceanic saturations, and estimated fluxes of five simultaneously sampled gases (dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde) are presented here. Campaign mean (±1σ) surface water concentrations of dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde were 2.60 (±3.94), 0.0133 (±0.0063), 67 (±35), 5.5 (±2.5), and 2.6 (±2.7) nmol dm−3 respectively. In this dataset, seawater isoprene and methanol concentrations correlated positively. Furthermore, seawater acetone, methanol, and isoprene concentrations were found to correlate negatively with the fugacity of carbon dioxide, possibly due to a common biological origin. Campaign mean (±1σ) air mixing ratios of dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde were 0.17 (±0.09), 0.053 (±0.034), 0.17 (±0.08), 0.081 (±0.031), and 0.049 (±0.040) ppbv. We observed diel changes in averaged acetaldehyde concentrations in seawater and ambient air (and to a lesser degree also for acetone and isoprene), which suggest light-driven production. Campaign mean (±1σ) fluxes of 4.3 (±7.4) µmol m−2 d−1 DMS and 0.028 (±0.021) µmol m−2 d−1 isoprene are determined where a positive flux indicates from the ocean to the atmosphere. Methanol was largely undersaturated in the surface ocean with a mean (±1σ) net flux of −2.4 (±4.7) µmol m−2 d−1, but it also had a few occasional episodes of outgassing. This section of the Southern Ocean was found to be a source and a sink for acetone and acetaldehyde this time of the year, depending on location, resulting in a mean net flux of −0.55 (±1.14) µmol m−2 d−1 for acetone and −0.28 (±1.22) µmol m−2 d−1 for acetaldehyde. The data collected here will be important for constraining the air–sea exchange, cycling, and atmospheric impact of these gases, especially over the Southern Ocean.

scholarly journals Overview of and first observations from the TILDAE High-Altitude Balloon Mission

2017 ◽  
Vol 10 (4) ◽  
pp. 1595-1607 ◽  
Author(s):  
Bennett A. Maruca ◽  
Raffaele Marino ◽  
David Sundkvist ◽  
Niharika H. Godbole ◽  
Stephane Constantin ◽  
...  
Keyword(s):  
Sonic Anemometer ◽  
Ambient Air ◽  
Small Scale ◽  
New Paradigm ◽  
Intermittent Turbulence ◽  
Atmospheric Measurements ◽  
Long Duration ◽  
In Situ Observations ◽  
Robust Separation

Abstract. Though the presence of intermittent turbulence in the stratosphere has been well established, much remains unknown about it. In situ observations of this phenomenon, which have provided the greatest details of it, have mostly been achieved via sounding balloons (i.e., small balloons which burst at peak altitude) carrying constant-temperature hot-wire anemometers (CTAs). The Turbulence and Intermittency Long-Duration Atmospheric Experiment (TILDAE) was developed to test a new paradigm for stratospheric observations. Rather than flying on a sounding balloon, TILDAE was incorporated as an add-on experiment to the payload of a NASA long-duration balloon mission that launched in January 2016 from McMurdo Station, Antarctica. Furthermore, TILDAE's key instrument was a sonic anemometer, which (relative to a CTA) provides better-calibrated measurements of wind velocity and a more robust separation of velocity components. During the balloon's ascent, TILDAE's sonic anemometer provided atmospheric measurements up to an altitude of about 18 km, beyond which the ambient air pressure was too low for the instrument to function properly. Efforts are currently underway to scientifically analyze these observations of small-scale fluctuations in the troposphere, tropopause, and stratosphere and to develop strategies for increasing the maximum operating altitude of the sonic anemometer.

scholarly journals Detectability of Arctic methane sources at six sites performing continuous atmospheric measurements

2017 ◽  
Author(s):  
Thibaud Thonat ◽  
Marielle Saunois ◽  
Philippe Bousquet ◽  
Isabelle Pison ◽  
Zeli Tan ◽  
...  
Keyword(s):  
Land Surface ◽  
Transport Model ◽  
Land Surface Model ◽  
Arctic Region ◽  
The Arctic ◽  
Surface Model ◽  
Multiple Sources ◽  
Atmospheric Measurements ◽  
Methane Cycle ◽  
Methane Budget

Abstract. Understanding the recent evolution of methane emissions in the Arctic is necessary to interpret the global methane cycle. Emissions are affected by significant uncertainties and are sensitive to climate change, leading to potential feedbacks. A polar version of the CHIMERE chemistry-transport model is used to simulate the evolution of tropospheric methane in the Arctic during 2012, including all known regional anthropogenic and natural sources. CHIMERE simulations are compared to atmospheric continuous observations at six measurement sites in the Arctic region. In winter, the Arctic is dominated by anthropogenic emissions; emissions from continental seepages and oceans, including from the East Siberian Arctic Shelf, can contribute significantly in more limited areas. In summer, emissions from wetland and freshwater sources dominate across the whole region. The model is able to reproduce the seasonality and synoptic variations of methane measured at the different sites. We find that all methane sources significantly affect the measurements at all stations at least at the synoptic scale, except for biomass burning; this indicates the relevance of continuous observations to gain a mechanistic understanding of Arctic methane sources. Sensitivity tests reveal that the choice of the land surface model used to prescribe wetland emissions can be critical in correctly representing methane concentrations. Also testing different freshwater emission inventories leads to large differences in modelled methane. Attempts to include methane sinks (OH oxidation and soil uptake) reduced the model bias relative to observed atmospheric CH4. The study illustrates how multiple sources, having different spatiotemporal dynamics and magnitudes, jointly influence the overall Arctic methane budget, and highlights ways towards further improved assessments.

scholarly journals Do contemporary (1980–2015) emissions determine the elemental carbon deposition trend at Holtedahlfonna glacier, Svalbard?

2017 ◽  
Vol 17 (20) ◽  
pp. 12779-12795 ◽  
Author(s):  
Meri M. Ruppel ◽  
Joana Soares ◽  
Jean-Charles Gallet ◽  
Elisabeth Isaksson ◽  
Tõnu Martma ◽  
...  
Keyword(s):  
Elemental Carbon ◽  
Transport Model ◽  
Ice Core ◽  
Climate Impact ◽  
The Arctic ◽  
Chemical Transport Model ◽  
Atmospheric Measurements ◽  
Atmospheric Concentration ◽  
Scavenging Efficiency ◽  
Firn Core

Abstract. The climate impact of black carbon (BC) is notably amplified in the Arctic by its deposition, which causes albedo decrease and subsequent earlier snow and ice spring melt. To comprehensively assess the climate impact of BC in the Arctic, information on both atmospheric BC concentrations and deposition is essential. Currently, Arctic BC deposition data are very scarce, while atmospheric BC concentrations have been shown to generally decrease since the 1990s. However, a 300-year Svalbard ice core showed a distinct increase in EC (elemental carbon, proxy for BC) deposition from 1970 to 2004 contradicting atmospheric measurements and modelling studies. Here, our objective was to decipher whether this increase has continued in the 21st century and to investigate the drivers of the observed EC deposition trends. For this, a shallow firn core was collected from the same Svalbard glacier, and a regional-to-meso-scale chemical transport model (SILAM) was run from 1980 to 2015. The ice and firn core data indicate peaking EC deposition values at the end of the 1990s and lower values thereafter. The modelled BC deposition results generally support the observed glacier EC variations. However, the ice and firn core results clearly deviate from both measured and modelled atmospheric BC concentration trends, and the modelled BC deposition trend shows variations seemingly independent from BC emission or atmospheric BC concentration trends. Furthermore, according to the model ca. 99 % BC mass is wet-deposited at this Svalbard glacier, indicating that meteorological processes such as precipitation and scavenging efficiency have most likely a stronger influence on the BC deposition trend than BC emission or atmospheric concentration trends. BC emission source sectors contribute differently to the modelled atmospheric BC concentrations and BC deposition, which further supports our conclusion that different processes affect atmospheric BC concentration and deposition trends. Consequently, Arctic BC deposition trends should not directly be inferred based on atmospheric BC measurements, and more observational BC deposition data are required to assess the climate impact of BC in Arctic snow.

The Hydrolysis of Disubstituted Alkyl Phosphorochloridates and N,N,N′,N′-Tetra-stibstituted Phosphorodiamidic Chlorides in Water and Deuterium Oxide: Heat Capacity of Activation and Kinetic Solvent Isotope Effects

1973 ◽  
Vol 51 (4) ◽  
pp. 597-603 ◽  
Author(s):  
E. C. F. Ko ◽  
R. E. Robertson
Keyword(s):  
Heat Capacity ◽  
Thermodynamic Parameters ◽  
Alkyl Group ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
Potential Relationship ◽  
Mechanism Of Reaction ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

The pseudo-thermodynamic parameters, ΔH≠, ΔS≠, and ΔCp≠ and the kinetic solvent isotope effects have been determined for the three alkyl-phosphorochloridates, where the alkyl group is ethylisopropyl and n-propyl; for tetra-methyl and tetra-ethyl phosphorodiamidic chlorides; the di-n-propyl and di-isopropyl analog, the di(isopropylmethylcarbinyl)phosphorochloridate and the tetra-ethylthiophosphorodiamidic chloride. These compounds have a potential relationship to compounds used as insecticides and as polymers. The mechanism of reaction is discussed on the basis of these data.

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