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68 records · Page 4

Chemical Loss of Polar Ozone: Present Understanding and Remaining Uncertainties

Not long after the discovery of the Antarctic ozone hole, it was established that halogen compounds, supplied to the atmosphere mainly by anthropogenic activities, are the primary driver of polar ozone loss. We will briefly review the chemical mechanisms that cause polar ozone loss and the early evidence showing the key role played by anthropogenic halogens. Recently, stratospheric halogen loading has leveled off, due to adherence to the Montreal Protocol and its amendments that has essentially banned CFCs (chlorofluorocarbons) and other halocarbons. We will describe recent reports of the first stage of recovery of the Antarctic ozone hole (e.g., a statistically significant slowing of the downward trend), associated with the leveling off of stratospheric halogens. Despite this degree of understanding, we will discuss the tendency of photochemical models to underestimate the observed rate of polar ozone loss and a hypothesis that has recently been put forth that might resolve this discrepancy. Finally, we will briefly discuss chemical loss of Arctic ozone, which

climate change↗

Permanent Sequestration of Emitted Gases in the Form of Clathrate Hydrates

Underground sequestration has been proposed as a novel method of permanent disposal of harmful gases emitted into the atmosphere as a result of human activity. The method was conceived primarily for disposal of carbon dioxide (CO2, greenhouse gas causing global warming), but could also be applied to CO, H2S, NOx, and chorofluorocarbons (CFCs, which are super greenhouse gases). The method is based on the fact that clathrate hydrates (e.g., CO2 6H2O) form naturally from the substances in question (e.g., CO2) and liquid water in the pores of sub-permafrost rocks at stabilizing pressures and temperatures. The proposed method would be volumetrically efficient: In the case of CO2, each volume of hydrate can contain as much as 184 volumes of gas. Temperature and pressure conditions that favor the formation of stable clathrate hydrates exist in depleted oil reservoirs that lie under permafrost. For example, CO2-6H2O forms naturally at a temperature of 0 C and pressure of 1.22 MPa. Using this measurement, it has been calculated that the minimum thickness of continuous permafrost needed to stabilize CO2 clathrate hydrate is only about 100 m, and the base of the permafrost is known to be considerably deeper at certain locations (e.g., about 600 m at Prudhoe Bay in Alaska). In this disposal method, the permafrost layers over the reservoirs would act as impermeable lids that would prevent dissociation of the clathrates and diffusion of the evolved gases up through pores.

Duxbury, N.↗

Identifying the Molecular Origin of Global Warming

We have investigated the physical characteristics of greenhouse gases (GHGs) to assess which properties are most important in determining the efficiency of a GHG. Chlorofluorcarbons (CFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), nitrogen fluorides, and various other known atmospheric trace molecules have been included in this study. Compounds containing the halogens F or Cl have in common very polar X-F or X-Cl bonds, particularly the X-F bonds. It is shown that as more F atoms bond to the same central atom, the bond dipoles become larger as a result of the central atom becoming more positive. This leads to a linear increase in the total or integrated XF bond dipole derivatives for the molecule, which leads to a non-linear (quadratic) increase in infrared (IR) intensity. Moreover, virtually all of the X-F bond stretches occur in the atmospheric IR window as opposed to X-H stretches, which do not occur in the atmospheric window. It is concluded that molecules possessing several F atoms will always have a large radiative forcing parameter in the calculation of their global warming potential. Some of the implications for global warming and climate change are discussed.

Bera, Partha P.↗

Overview of the Airborne Tropical TRopopause EXperiment (ATTREX)

The NASA Airborne Tropical TRopopause EXperiment (ATTREX) is a series of airborne campaigns focused on understanding physical processes in the Tropical Tropopause Layer (TTL) and their role in atmospheric chemistry and climate. ATTREX is using the high-altitude, long-duration NASA Global Hawk Unmanned Air System to make in situ and remote-sensing measurements spanning the Pacific. A particular ATTREX emphasis is to better understand the dehydration of air as it passes through the cold tropical tropopause region. The ATTREX payload contains 12 in situ and remote sensing instruments that measure water vapor, clouds, multiple gaseous tracers (CO, CO2, CH4, NMHC, SF6, CFCs, N2O), reactive chemical compounds (O3, BrO, NO2), meteorological parameters, and radiative fluxes. ATTREX flight series have been conducted in the fall of 2011 from Armstrong Flight Research Center (AFRC) in California, in the winter of 2013 from AFRC, and in the winter/spring of 2014 from Guam. The first two flight series provided extensive sampling of the central and eastern Pacific, whereas the last flight series permitted sampling in the western Pacific. The sampling strategy has primarily involved repeated ascents and descents through the depth of the TTL (about 13-19 km). Over 100 TTL profiles were obtained on each flight series. The ATTREX dataset includes TTL water vapor measurements with unprecedented accuracy, ice crystal size distributions and habits. The cloud and water measurements provide unique information about TTL cloud formation, the persistence of super-saturation with respect to ice, and dehydration. The plethora of tracers measured on the Global Hawk flights are providing unique information about TTL transport pathways and time scales. The meteorological measurements are revealing dynamical phenomena controlling the TTL thermal structure, and the radiation measurements are providing information about heating rates associated with TTL clouds and water vapor. This presentation will provide an overview of the ATTREX flights, examples of measurements from the flights, and plans for modeling/analysis of the ATTREX dataset.

ATTREX↗

Overview of the Airborne Tropical TRopopause EX

The NASA Airborne Tropical TRopopause EXperiment (ATTREX) is a series of airborne campaigns focused on understanding physical processes in the Tropical Tropopause Layer (TTL) and their role in atmospheric chemistry and climate. ATTREX is using the high-altitude, long-duration NASA Global Hawk Unmanned Air System to make in situ and remote-sensing measurements spanning the Pacific. A particular ATIREX emphasis is to better understand the dehydration of air as it passes through the cold tropical tropopause region. The ATTREX payload contains 12 in situ and remote sensing instruments that measure water vapor, clouds, multiple gaseous tracers (CO, CO2, CH4, NMHC, SF6, CFCs, N2O), reactive chemical compounds (O3, BrO, NO2), meteorological parameters, and radiative fluxes. ATTREX flight series have been conducted in the fall of 2011 from Armstrong Flight Research Center (AFRC) in California, in the winter of 2013 from AFRC, and in the winter/spring of 2014 from Guam. The first two f light series provided extensive sampling of the central and eastern Pacific, whereas the last flight series permitted sampling in the western Pacific. The sampling strategy has primarily involved repeated ascents and descents through the depth of the TTL (about 13-19 km). Over 100 TTL profiles were obtained on each flight series. The ATTREX dataset includes TTL water vapor measurements with unprecedented accuracy, ice crystal size distributions and habits. The cloud and water measurements provide unique information about TTL cloud formation, the persistence of supersaturation with respect to ice, and dehydration. The plethora of tracers measured on the Global Hawk flights are providing unique information about TTL transport pathways and time scales. The meteorological measurements are revealing dynamical phenomena controlling the TTL thermal structure, and the radiation measurements are providing information about heating rates associated with TTL clouds and water vapor. This presentation will provide an overview of the ATTREX flights, examples of measurements from the flights, and plans for modeling/analysis of the ATTREX dataset.

Airborne↗

Concerns for Ozone Recovery

Reactive halogen gases containing chlorine (Cl) or bromine (Br) can destroy stratospheric ozone via catalytic cycles. The main sources of atmospheric reactive halogen are the long-lived synthetic chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), carbon tetrachloride (CCl4), methyl chloroform (CH3CCl3), and bromine-containing halons, all of which persist in the atmosphere for years. These ozone-depleting substances are now controlled under the Montreal Protocol and its amendments. Natural methyl bromide (CH3Br) and methyl chloride (CH3Cl) emissions are also important long-lived sources of atmospheric reactive halogen. Rising concentrations of very-short-lived substances (VSLSs) with atmospheric lifetimes of less than half a year may also contribute to future stratospheric ozone depletion. A greater concern for ozone layer recovery is incomplete compliance with the Montreal Protocol, which will impact stratospheric ozone for many decades, as well as rising natural emissions as a result of climate change.

VSLS↗

Overview of the NASA Airborne Tropical TRopopause EXperiment (ATTREX)

The NASA Airborne Tropical TRopopause EXperiment (ATTREX) is a series of airborne campaigns focused on understanding physical processes in the Tropical Tropopause Layer (TTL) and their role in atmospheric chemistry and climate. ATTREX is using the high-altitude, long-duration NASA Global Hawk Unmanned Air System to make in situ and remote-sensing measurements spanning the Pacific. A particular ATTREX emphasis is to better understand the dehydration of air as it passes through the cold tropical tropopause region. The ATTREX payload contains 12 in situ and remote sensing instruments that measure water vapor, clouds, multiple gaseous tracers (CO, CO2, CH4, NMHC, SF6, CFCs, N2O), reactive chemical compounds (O3, BrO, NO2), meteorological parameters, and radiative fluxes.ATTREX flight series have been conducted in the fall of 2011 from Armstrong Flight Research Center (AFRC) in California, in the winter of 2013 from AFRC, and in the winterspring of 2014 from Guam. The first two flight series provided extensive sampling of the central and eastern Pacific, whereas the last flight series permitted sampling in the western Pacific. The sampling strategy has primarily involved repeated ascents and descents through the depth of the TTL (about 13-19 km). Over 100 TTL profiles were obtained on each flight series. The ATTREX dataset includes TTL water vapor measurements with unprecedented accuracy, ice crystal size distributions and habits. The cloud and water measurements provide unique information about TTL cloud formation, the persistence of supersaturation with respect to ice, and dehydration. The plethora of tracers measured on the Global Hawk flights are providing unique information about TTL transport pathways and time scales. The meteorological measurements are revealing dynamical phenomena controlling the TTL thermal structure, and the radiation measurements are providing information about heating rates associated with TTL clouds and water vapor.This presentation will provide an overview of the ATTREX flights, examples of measurements from the flights, and plans for modelinganalysis of the ATTREX dataset.

Jensen, Eric J.↗

Faster Tropical Upper Stratospheric Upwelling Drives Changes in Ozone Chemistry

Tropospheric trends in long-lived source gases N2O and the chlorofluorocarbons (CFCs) cause trends in O3 through changes in their reactive product gases. Transport affects the product gases because it controls the distribution of the long-lived source gases. We find that large changes in tropical upwelling 10-5 hPa since 2012 have strengthened the northern branch of the upper stratospheric (UpS) transport circulation, dramatically altering the abundances of N2O and its odd nitrogen product gases, NOx and HNO3. Increased upwelling is connected to stronger and more frequent Quasi-Biennial Oscillation easterly winds at 10 hPa and above. We use simulations with and without time varying MERRA2 meteorology to quantify the impact of dynamical changes on O3 loss via the NOx and ClOx cycles. We find that dynamical impacts on these cycles explain the mid-stratospheric tropical O3 increase and Arctic UpS O3 decrease since 2005.

Middle atmosphere chemistry and composition↗

Faster Tropical Upper Stratospheric Upwelling is Driving Changes in Ozone Chemistry

Trends in N2O and the chlorofluorocarbons (CFCs) cause trends in O3 through changes in their reactive product gases, NOx and ClOx, but transport plays an important role because it controls the distribution of the long‐lived source gases that produce ozone‐destroying radicals. In this study we show that increased tropical upwelling 10‐5 hPa from 2013‐2021 has changed upper stratospheric (UpS) composition and shifted the balance of O3 loss processes. We use N2O, HNO3, NOx, temperature and O3 data from the Aura Microwave Limb Sounder (MLS) and the SCI‐Sat Atmospheric Chemistry Experiment Fourier Transport Spectrometer (ACE‐FTS) over a 16‐year period to show how changes in reactive nitrogen species affected gas phase ozone chemistry above 30 hPa between June 2013‐May 2021 compared to the previous 8 years, June 2005‐May 2013. We use 2 simulations of the Global Modeling Initiative (GMI) chemistry transport model (CTM), with and without time varying MERRA2 meteorology, to understand how dynamical changes during this 16‐yr period affected O3 through changes in loss via the NOx and ClOx cycles. We also identify the role that the quasi‐biennial oscillation (QBO) in tropical zonal winds plays in the UpS composition changes. We find large increases in tropical upwelling and poleward transport in the northern branch of the UpS transport circulation since 2013 that dramatically increased the abundance of the N2O and its odd nitrogen product gases, NOx and HNO3. O3 loss by NOx in the Arctic UpS increased due to dynamically driven composition change, explaining the observed weak O3 recovery in that region since 2005. The increased upwelling also drove decreases in tropical NOx, leading to increased tropical O3 from 12‐6 hPa.

middle atmosphere chemistry and composition↗

Low-GWP Refrigerants Status and Outlook

Refrigeration - including air conditioning (AC) – contributes substantially to the modern life of the 21st century and its economy. The food cold chain, air conditioning, healthcare and energy are examples of sectors for which refrigeration is indispensable. About 5 billion refrigeration systems – of different types and sizes– operate worldwide in different applications [1]. The dominant share of equipment providing refrigeration operate on the vapor-compression-cycle principle and use fluorocarbon refrigerants. Concerns about the environmental safety have become the driving force for refrigerant changes within the last 35 years. The phased-out schedule of stratospheric-ozone-depleting fluids was first formulated by the Montreal Protocol (MP) in 1987 and was made more stringent during the follow-up international meetings [2]. The affected chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) refrigerants were largely replaced by hydrofluorocarbons (HFCs).The 2016 Kigali Amendment to the MP [3] responses to the concerns about the Earth climate change. The refrigeration and AC sectors are attributed with about 7.8 % of global greenhouse gas emissions [4]. This contribution comes in the form of direct effect, which is related to refrigerant emissions from refrigeration systems (37 %), and in the form of indirect effect, which is related to CO2 emissions from fossil fuel power plants producing electricity to power refrigeration systems (63 %) [4]. The Kigali Amendment aims at reducing the direct effect. The effect a given molecule has on the climate change is quantified in a simplified manner by its Global Warming Potential (GWP), a relative index referencing the effect produced to that of the same mass of carbon dioxide released to the atmosphere. By definition, GWP of carbon dioxide is equal to one.While HFC refrigerants have on average a lower GWP than the CFCs and HCFCs they replaced, they are still potent greenhouse gases (GHGs). The Kigali Amendment phases down the use of HFCs by imposing a schedule for reducing a weighted GWP value to be implemented by a country through the year 2047 (Figure 1). It provides four paths depending on the country location and category assigned in the MP, and also prescribes a method for establishing the baseline consumption used for calculating GWP reductions. For developing countries, it is expected to bring the weighed GWP across all refrigeration applications down to about 300 from the baseline value of about 2000. The implementation of Kigali Amendment aims at reducing the future warming due to HFCs from the range of 0.3 °C to 0.5 °C to less than 0.1 °C [5]. While this reduction may seem to be small, it must be viewed in the context of the 2015 Paris Agreement [6], which calls for holding global warming to well below 2 °C and pursuing to limit global warming to 1.5 °C relative to pre-industrial levels [6]. Considering that average global temperatures reached 1 °C above pre-industrial levels for the first time in 2015 [7], the Earth is already within 1 °C of the “2 °C limit”.The low-GWP requirement narrows the pool of fluids that can be considered for application as a refrigerant [8]. This Informatory Note discusses low-GWP refrigerant options for major applications and presents their selection merits.

Yana Motta, Samuel↗

Atmospheric Transformation of Refrigerants: Current Research Developments and Knowledge Gaps

Refrigerants have evolved through the years to reduce their global warming potential while providing sufficient cooling in refrigeration systems. Replacements for hydrofluorocarbons (HFCs) and chlorofluorocarbons (CFCs) are the hydrofluoroolefins (HFOs), which contain reactive double bonds that decrease the atmospheric lifetime of fluorinated compounds. However, the transformation of unsaturated fluorinated compounds in the atmosphere could generate persistent pollutants, particularly trifluoroacetic acid (TFA) which is the simplest Perfluoroalkyl carboxylic acids (PFCAs). Understanding the transformation of refrigerants is critical in assessing their contribution to atmospheric levels of TFA and their impact on watersheds and human health. This article will present the reactivity of the refrigerants, atmospheric oxidation source, and sink processes of fluorinated refrigerants under daytime conditions, particularly the variability of TFA from refrigerants. Moreover, the discussion will suggest experimental procedures that can quantify the low concentration (~parts per trillion) of TFA generated from the transformation of HFOs. New state-of-the-art techniques such as chemical ionization mass spectrometers (HR-CIMS) will be assessed in providing high temporal resolution (minutes to hourly) to fully capture the atmospheric sources and variability of TFA. Likewise, local, regional, and global concentrations of TFA accounted from the oxidation of refrigerants will be examined. This will include data from both experimental procedures and simulation models. Participation of TFA in critical atmospheric processes such as new particle formation will also be included in this study. Lastly, overall knowledge gaps related to the oxidation products and their dispersion in the environment will be summarized to guide future research needs.

Salvador, Christian↗

Southern Polar Ozone in MERRA-2

MERRA-2 provides a good representation of the year-to-year variations and the long-term changes in total ozone column over Antarctica for the entire data record, beginning in 1980. When MLS data are introduced into MERRA-2 in 2004, agreement with independent data improves compared to earlier years when the SBUV observations were assimilated.

MERRA-2↗

A Comparison of Measurements from ATMOS and Instruments Aboard the ER-2 Aircraft: Halogenated Gases

We compare the mixing rations of N 2 O, CFC-11, CFC-12, CCI 4 , SF 6 , and HCI in the mid-latitude stratosphere measured by the ATMOS Fourier transform spectrometer with in situ measurements acquired aboard the NASA ER-2 aircraft during November 1994. Good agreement is found between ATMOS and in situ correlations of CFC-11, CFC-12, and SF 6 with N 2 O. ATMOS observations of CCI 4 are approx. 15 percent higher than the ER-2 data, but within the systematic uncertainties.

N2O↗