Chemistry Commons^™

Global Stratospheric Measurements Of The Isotopologues Of Methane From The Atmospheric Chemistry Experiment Fourier Transform Spectrometer, Eric M. Buzan, Chris A. Beale, Chris. D. Boone, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

This paper presents an analysis of observations of methane and its two major isotopologues, CH₃D and ¹³CH₄, from the Atmospheric Chemistry Experiment (ACE) satellite between 2004 and 2013. Additionally, atmospheric methane chemistry is modeled using the Whole Atmospheric Community Climate Model (WACCM). ACE retrievals of methane extend from 6 km for all isotopologues to 75 km for ¹²CH₄, 35 km for CH₃D, and 50 km for ¹³CH₄. While total methane concentrations retrieved from ACE agree well with the model, values of δD-CH₄ and δ¹³C-CH …

Detailed Source-Specific Molecular Composition Of Ambient Aerosol Organic Matter Using Ultrahigh Resolution Mass Spectrometry And H Nmr, Amanda S. Willoughby, Andrew S. Wozniak, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Organic aerosols (OA) are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban) using ultrahigh resolution mass spectrometry (UHR-MS) and proton nuclear …

Upper Tropospheric Water Vapour Variability At High Latitudes- Part 1: Influence Of The Annular Modes, Christopher E. Sioris, Jason Zou, David A. Plummer, Chris D. Boone, C. Thomas Mcelroy, Patrick E. Sheese, Omid Moeini, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Seasonal and monthly zonal medians of water vapour in the upper troposphere and lower stratosphere (UTLS) are calculated for both Atmospheric Chemistry Experiment (ACE) instruments for the northern and southern high-latitude regions (60-90° N and 60-90°S). Chosen for the purpose of observing high-latitude processes, the ACE orbit provides sampling of both regions in 8 of 12 months of the year, with coverage in all seasons. The ACE water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS) are currently the only satellite instruments that can probe from …

Mipas Imk/Iaa Cfc-11 (Ccl3f) And Cfc-12 (Ccl2f2) Measurements: Accuracy, Precision And Long-Term Stability, E. Eckert, A. Laeng, S. Lossow, S. Kellmann, G. Stiller, T. Von Clarmann, N. Glatthor, M. Hopfner, M. Kiefer, H. Oelhaf, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Profiles of CFC-11 (CCl₃F) and CFC-12 (CCl₂F₂) of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the European satellite Envisat have been retrieved from versions MIPAS/4.61 to MI-PAS/4.62 and MIPAS/5.02 to MIPAS/5.06 level-1b data using the scientific level-2 processor run by Karlsruhe Institute of Technology (KIT), Institute of Meteorology and Climate Research (IMK) and Consejo Superior de Investigaciones Cientificas (CSIC), Instituto de Astrofisica de Andalucia (IAA). These profiles have been compared to measurements taken by the balloon-borne cryosampler, Mark IV (MkIV) and MIPAS-Balloon (MIPAS-B), the airborne MIPAS-STRatospheric aircraft (MIPAS-STR), the satellite-borne Atmospheric Chemistry …

Study Of No2 Photolysis Rate Coefficients For The Paso Del Norte Region, Pema Wangchuk

Open Access Theses & Dissertations

The photolysis of nitrogen dioxide is one of the most influential chemical processes in the formation of photochemical air pollution. In this study, we compared simulated and measured nitrogen dioxide photolysis rate coefficients (J_(NO_2 )) for the Paso Del Norte (PdN) region. The Tropospheric Ultraviolet-Visible (TUV) radiation transfer model was used to calculate J_(NO_2 ) values. The measurements of hemi-spherically integrated, spectrally resolved solar photon flux between the wavelengths 400 and 700 nm were used to obtain the photolysis rate coefficients for ã??NOã??_2. Results are presented for a selected episode on July, 2015. The work investigated the use of measured …

Validation Of The Global Distribution Of Co2 Volume Mixing Ratio In The Mesosphere And Lower Thermosphere From Saber, L. Rezac, Y. Jian, J. Yue, J. M. Russell Iii, A. Kutepov, R. Garcia, K. Walker, P. Bernath

Chemistry & Biochemistry Faculty Publications

The Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on board the Thermosphere Ionosphere Mesosphere Energetics and Dynamics satellite has been measuring the limb radiance in 10 broadband infrared channels over the altitude range from ~ 400 km to the Earth's surface since 2002. The kinetic temperatures and CO₂ volume mixing ratios (VMRs) in the mesosphere and lower thermosphere have been simultaneously retrieved using SABER limb radiances at 15 and 4.3 μm under nonlocal thermodynamic equilibrium (non-LTE) conditions. This paper presents results of a validation study of the SABER CO₂ VMRs obtained with a two-channel, self-consistent …

Temporal Variation In Optical Properties Of Chromophoric Dissolved Organic Matter (Cdom) In Southern California Coastal Waters With Nearshore Kelp And Seagrass, Catherine D. Clark, Warren J. De Bruyn, Paige Aiona

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Optical properties of chromophoric dissolved organic matter (CDOM) were measured in surf zone waters in diurnal field studies at a Southern California beach with nearshore kelp and seagrass beds and intertidal plant wrack. Absorption coefficients (aCDOM(300 nm)) ranged from 0.35 m21 to 3.7 m21 with short-term variability<1 h, increases at ebb and flood tides and higher values (6 m21) during an offshore storm event. Spectral slopes (S) ranged from 0.0028 nm21 to 0.017 nm21, with higher values after the storm; S was generally inversely correlated with aCDOM(300 nm). 3-D excitation–emission matrix spectra (EEMs) for samples with lower S values had humic-type peaks associated with terrestrial material (A, C), marine microbial material (M) and protein peaks, characteristic of freshly produced organic material. Samples with high S values had no or reduced protein peaks, consistent with aged material. Fluorescent indexes (f450/f500 >2.5, BIX>1.1) were consistent with microbial aquatic sources. Leachates of senescent kelp and seagrass had protein and humic-type EEM peaks. After solar simulator irradiation (4 h), protein peaks rapidly photochemically degraded, humic-type peak C increased in intensity and peak M disappeared. Optical characteristics of kelp leachates were most similar to field samples, …

Ua66 Ogden College Of Science & Engineering Newsletter, Cheryl Stevens, Dean

Ogden College of Science & Engineering Publications

No abstract provided.

Source-Specific Molecular Signatures For Light-Absorbing Organic Aerosols, Amanda Susan Willoughby

Chemistry & Biochemistry Theses & Dissertations

Organic aerosols (OA) are universally regarded as an important component of the atmosphere based on quantitative significance as well as the far-reaching impact they have on global climate forcing and human health. Despite the acknowledged importance, OA amounts and impacts remain the largest uncertainties regarding radiative forcing estimates. Incomplete chemical characterization of aerosol organic matter (OM) and a lack of concrete source apportionment is a major source of this uncertainty. The primary focus of this study is to provide much needed molecular details regarding ambient OA from key emission sources, and establish links between molecular and optical properties.

Complete chemical …

A Mechanism For Biologically Induced Iodine Emissions From Sea Ice, A. Saiz-Lopez, Christopher S. Blaszczak-Boxe, L. J. Carpenter

Publications and Research

Ground- and satellite-based measurements have reported high concentrations of iodine monoxide (IO) in coastal Antarctica. The sources of such a large iodine burden in the coastal Antarctic atmosphere remain unknown.We propose a mechanism for iodine release from sea ice based on the premise that micro-algae are the primary source of iodine emissions in this environment. The emissions are triggered by the biological production of iodide (I�) and hypoiodous acid (HOI) from micro-algae (contained within and underneath sea ice) and their diffusion through sea-ice brine channels, ultimately accumulating in a thin brine layer (BL) on the surface of sea ice. Prior …

Simulation Of Energetic Particle Precipitation Effects During The 2003-2004 Arctic Winter, C. E. Randall, V. L. Harvey, L. A. Holt, D. R. Marsh, D. Kinnison, B. Funke, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Energetic particle precipitation (EPP) during the 2003-2004 Arctic winter led to the production and subsequent transport of reactive odd nitrogen (NO_x=NO+NO₂) from the mesosphere and lower thermosphere (MLT) into the stratosphere. This caused NO_x enhancements in the polar upper stratosphere in April 2004 that were unprecedented in the satellite record. Simulations of the 2003-2004 Arctic winter with the Whole Atmosphere Community Climate Model using Specified Dynamics (SD-WACCM) are compared to satellite measurements to assess our understanding of the observed NO_x enhancements. The comparisons show that SD-WACCM clearly displays the descent of NO_x produced …

Growth In Stratospheric Chlorine From Short-Lived Chemicals Not Controlled By The Montreal Protocol, R. Hossaoni, M. P. Chipperfield, A. Saiz-Lopez, J. J. Harrison, R. Von Glasow, R. Sommariva, E. Atlas, M. Navarro, S. A. Montzka, W. Feng, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS (Cl_y^VSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl₃), dichloromethane (CH₂Cl₂), tetrachloroethene (C₂Cl₄), trichloroethene (C₂HCl₃), and 1,2-dichloroethane (CH₂ClCH₂Cl), we infer a 2013 Cl_y^VSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection …

Ua66 Ogden College Of Science & Engineering Newsletter, Cheryl Stevens, Dean

Ogden College of Science & Engineering Publications

No abstract provided.

Laboratory Studies On The Production Of Alpha-Pinene-Derived Organic Nitrates And Their Atmospheric Fate, Joel David Rindelaub

Open Access Dissertations

Currently, the formation yields of organic nitrates from the oxidation of biogenic volatile organic compounds, such as α-pinene, is highly uncertain, negatively impacting our knowledge on tropospheric ozone production and the fate of atmospheric NO_x. To lower this uncertainty, we quantified the organic nitrate yield from the OH radical oxidation of α-pinene under high NO_x conditions. The α-pinene- derived nitrates created in chamber experiments readily partitioned to the aerosol phase and underwent particle phase hydrolysis, indicating that these processes are likely a sink for atmospheric NO_x. The hydrolysis of organic nitrates was found to be …

Impact Of Biogenic Volatile Organic Compounds On Peroxyacetyl Nitrate Production In The Southeast United States, Christopher John Groff

Open Access Theses

Our atmosphere is arguably the fundamental entity that has made life on Earth possible. Knowledge of the delicate nature of our atmosphere continues to spread as "green" initiatives promote awareness of human influence on the environment. However, many climate scientists fear that unless immediate mitigation occurs, the reversal of human impact on our planet will be impossible, leading to unknown consequence. Perturbations to natural processes are likely to cause drastic change to the planet as we know it and ultimately result in significant health issues. It is important to push the boundaries of our understanding of atmospheric processes with intent …

Studies Of The Interaction Of Biogenic Volatile Organic Compounds And Nox In Forest Environments, Kevin M. Mcavey

Open Access Dissertations

Ozone is a pollutant that causes crop damage, adverse health effects, and is a contributor to global climate change. Ozone concentrations are predicted to rise over the next half-century along with global temperature. Ozone production is controlled by the chemistry between biogenic volatile organic compounds and NO_x (NO + NO₂), and therefore, a greater understanding of NO_x + BVOC chemistry along with their sources and sinks is needed. One large uncertainty in understanding NO_x + BVOC chemistry is the production of organic nitrates (RONO₂), which act as a radical termination step in the …

Spectroscopic Characterization And Photochemistry Of Nitrogen-Containing Molecules Relevant To Titan's Atmosphere, Deepali N. Mehta-Hurt

Open Access Dissertations

Titan's atmospheric chemistry has been the source of intrigue since the planetary body's discovery. Though there is a growing understanding of the atmospheric chemistry of small molecules on Titan, much less is known about larger molecule formation, and particularly about nitrile chemistry. This dissertation characterizes nitrile/isonitrile intermediates that are postulated to be important in Titan's atmosphere, adding to the necessary foundation for understanding Titan's atmospheric chemistry. The vibronic spectroscopy of para-diisocyanobenzene (pDIB, C≡N-Ph-N≡C) has been characterized as a first step towards photochemical studies that can test the transformation of the isonitrile group to other nitrogen-based functionalities.p …

Ua66 Ogden College Of Science & Engineering Newsletter, Cheryl Stevens, Dean

Ogden College of Science & Engineering Publications

No abstract provided.

Comparing Three Methods For Estimating Ozone Depleting Substance Substitute Greenhouse Gases: Case Study Of The New York City Region, Wallace A. Murray Iii

Theses and Dissertations

This thesis evaluates the United States Environmental Protection Agency (EPA) method for estimating emissions from one source, Ozone Depleting Substances Substitutes (ODS substitutes) by comparing results for the New York City Metropolitan Statistical Area (NYC-MSA) with results from two other methodologies. The EPA’s method utilizes population data and GDP data to estimate and geographically allocate emissions, with little regard for the geographies of industrial activity. The two alternative methods use data for industrial employment and activity to provide results for comparison and perhaps a more accurate accounting and allocation of emissions throughout the NYC-MSA.

Ua66 Ogden College Of Science & Engineering Newsletter, Cheryl Stevens, Dean

Ogden College of Science & Engineering Publications

No abstract provided.

Interpretation Of Complexometric Titration Data: An Intercomparison Of Methods For Estimating Models Of Trace Metal Complexation By Natural Organic Ligands, I. Pižeta, S. G. Sander, R. J. M. Hudson, D. Omanović, O. Baars, K. A. Barbeau, K. N. Buck, R. M. Bundy, G. Carrasco, P. L. Croot

OES Faculty Publications

With the common goal of more accurately and consistently quantifying ambient concentrations of free metal ions and natural organic ligands in aquatic ecosystems, researchers from 15 laboratories that routinely analyze trace metal speciation participated in an intercomparison of statistical methods used to model their most common type of experimental dataset, the complexometric titration. All were asked to apply statistical techniques that they were familiar with to model synthetic titration data that are typical of those obtained by applying state-of-the-art electrochemical methods – anodic stripping voltammetry (ASV) and competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE-ACSV) – to the analysis of natural …

Spectroscopic Characterization Of Oceanic Dissolved Organic Matter Isolated By Reverse Osmosis Coupled With Electrodialysis, John R. Helms, Jingdong Mao, Hongmei Chen, E. Michael Perdue, Nelson W. Green, Patrick G. Hatcher, Kenneth Mopper, Aron Stubbins

Chemistry & Biochemistry Faculty Publications

Oceanic dissolved organic matter (DOM) is one of the largest pools of reduced carbon on Earth, yet DOM remains poorly chemically characterized. Studies to determine the chemical nature of oceanic DOM have been impeded by the lack of efficient and non-fractioning methods to recover oceanic DOM. Here, a DOM fraction (~40 to 86% recovery) was isolated using reverse osmosis/electrodialysis (RO/ED) and analyzed by solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Samples were obtained from biogeochemically distinct environments: photobleached surface gyre, productive coastal upwelling zone, oxygen minimum, North Atlantic Deep Water, and North Pacific Deep Water. A ubiquitous ‘background’ refractory …

Characterization And Photodegradation Of Dissolved Organic Matter (Dom) From A Tropical Lake And Its Dominant Primary Producer, The Cyanobacteria Microcystis Aeruginosa, Thais B. Bittar, Aron Stubbins, Armando A. H. Vieira, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

This study investigates optical and high-resolution molecular signatures and photochemical degradation of DOM from the Barra Bonita Reservoir (BB-DOM), a tropical eutrophic lake, as well as from its dominant phytoplankton species, the cyanobacteria Microcystis aeruginosa (Microcystis-DOM). Consistent with a predominantly autotrophic source, BB-DOM and Microcystis-DOM exhibited high protein-like fluorescence and contained a large number of aliphatics. Microcystis-DOM was enriched in peptide-like formulae, while BB-DOM had higher chromophoric and fluorescent DOM(CDOM and FDOM) and was enriched in moderately unsaturated formulae, indicating additions of terrigenous DOM and/or in situ processing of autochthonous material in the lake. Consistent with …

Relative Drifts And Biases Between Six Ozone Limb Satellite Measurements From The Last Decade, N. Rahpoe, M. Weber, A. V. Rozanov, K. Weigel, H. Bovensmann, J. P. Burrows, A. Laeng, G. Stiller, T. Von Clarmann, E. Kyrölä, V. F. Sofieva, J. Tamminen, K. Walker, D. Degenstein, A. E. Bourassa, R. Hargreaves, P. Bernath, J. Urban, D. P. Murtagh

Chemistry & Biochemistry Faculty Publications

As part of European Space Agency's (ESA) climate change initiative, high vertical resolution ozone profiles from three instruments all aboard ESA's Envisat (GOMOS, MIPAS, SCIAMACHY) and ESA's third party missions (OSIRIS, SMR, ACE-FTS) are to be combined in order to create an essential climate variable data record for the last decade. A prerequisite before combining data is the examination of differences and drifts between the data sets. In this paper, we present a detailed analysis of ozone profile differences based on pairwise collocated measurements, including the evolution of the differences with time. Such a diagnosis is helpful to identify strengths …

Retrieval And Validation Of Carbon Dioxide, Methane, And Water Vapor For The Canary Islands Ir-Laser Occultation Experiment, V. Proschek, G. Kirchengast, S. Schweitzer, J.S. A. Brooke, P. F. Bernath, C. B. Thomas, J. G. Wang, K. A. Tereszchuk, G. González Abad, R. J. Hargreaves, C. A. Beale, J. J. Harrison, P. A. Martin, V. L. Kasyutich, C. Gerbig, O. Kolle, A. Loescher

Chemistry & Biochemistry Faculty Publications

The first ground-based experiment to prove the concept of a novel space-based observation technique for microwave and infrared-laser occultation between low-Earthorbit satellites was performed in the Canary Islands between La Palma and Tenerife. For two nights from 21 to 22 July 2011 the experiment delivered the infrared-laser differential transmission principle for the measurement of greenhouse gases (GHGs) in the free atmosphere. Such global and long-term stable measurements of GHGs, accompanied also by measurements of thermodynamic parameters and line-of-sight wind in a self-calibrating way, have become very important for climate change monitoring. The experiment delivered promising initial data for demonstrating the …

Decrease Of Carbon Tetrachloride (Ccl⁴) Over 2004-2013 As Inferred From Global Occultation Measurements With Ace-Fts, E. Mahieu, Peter F. Bernath, Christopher D. Boone, Kaley A. Walker

Chemistry & Biochemistry Faculty Publications

In this contribution, we use infrared solar occultation measurements performed by the ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) instrument onboard the SCISAT-1 Canadian satellite (Bernath et al., 2005). Since its launch in August 2003, this spectrometer has been in continuous operation with no significant degradation of its performance, and global measurements are available from late February 2004 onwards, spanning now more than a decade.

Global Ozone Chemistry And Related Trace Gas Data Records For The Stratosphere (Gozcards): Methodology And Sample Results With A Focus On Hcl, H20, And 03, L. Froidevaux, J. Anderson, H. J. Wang, R. A. Fuller, M. J. Schwartz, M. L. Santee, N. J. Livesey, H. C. Pumphrey, P. F. Bernath, J. M. Russell Iii, M. P. Mccormick

Chemistry & Biochemistry Faculty Publications

We describe the publicly available data from the Global OZone Chemistry And Related trace gas Data records for the Stratosphere (GOZCARDS) project and provide some results, with a focus on hydrogen chloride (HCl), water vapor (H₂O), and ozone (O₃). This data set is a global long-term stratospheric Earth system data record, consisting of monthly zonal mean time series starting as early as 1979. The data records are based on high-quality measurements from several NASA satellite instruments and the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on SCISAT. We examine consistency aspects between the various data sets. …

Recent Increase Of Ethane Detected In The Remote Atmosphere Of The Northern Hemisphere, Bruno Franco, Whitney Bader, Benoît Bovy, Emmanuel Mahieu, Emily V. Fischer, Kimberly Strong, Stephanie Conway, James W. Hannigan, Eric Nussbaumer, Peter F. Bernath, Chris D. Boone, Kaley A. Walker

Chemistry & Biochemistry Faculty Publications

Ethane (C₂H₆) has a large impact on tropospheric composition and air quality because of its involvement in the global VOC (volatile organic compound) – HO_x – NO_x chemistry responsible for generating and destroying tropospheric ozone. By acting as a major sink for tropospheric OH radicals, the abundance of C₂H₆ influences the atmospheric content of carbon monoxide and impacts the lifetime of methane. Moreover, it is an important source of PAN, a thermally unstable reservoir for NOx radicals.

On a global scale, the main sources of C₂H₆ are leakage from the production, transport of natural gas loss, biofuel consumption …

Assessment Of Water Vapor Isotopologue Measurements By Ace-Fts And Odin-Smr, Ralf Bauer, Patrick Sheese, Kaley Walker, Joachim Urban, Donal Murtagh, Chris Boone, Peter Bernath, Gloria Manney

Chemistry & Biochemistry Faculty Publications

[Introduction] Knowing the isotopic composition of trace gases can improve our understanding of processes in the Earth's atmosphere causing isotopic fractionation. In many studies, isotopologue (molecules of identical chemical but different isotopic composition) amounts are primarily discussed as δ values, which are defined relative to a standard, e.g.:

Ace-Fts And Haloe Observations Of Hydrogen Fluoride (Hf) And Their Comparison With Slimcat Chemical Transport Model Calculations, Jeremy Harrison, Martyn Chipperfield, Chris Boone, Peter Bernath, Lucien Froidevaux, John Anderson, James Russell Iii

Chemistry & Biochemistry Faculty Publications

The majority of fluorine in the atmosphere has resulted from the anthropogenic emission of chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Most tropospheric fluorine is present in its emitted 'organic' form due to the molecules having long lifetimes (up to a decade or longer). Thus they are able to reach the stratosphere where they are broken down, liberating fluorine. The principal degradation products are carbonyl fluoride (COF2), carbonyl chloride fluoride (COClF), and hydrogen fluoride (HF); of these HF is the most abundant. In fact at the top of the stratosphere most of the fluorine is present as HF, which, due …