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At least 163 records · Page 9

Increasing CO2 Coupled with Other Anthropogenic Perturbations: Effects on Ozone and Other Trace Gases

The GSFC 2D interactive chemistry-radiation-dynamics model has been used to study the effects on stratospheric trace gases of past and future CO2 increases coupled with changes in CFC'S, methane, and nitrous oxide. Previous simulations with the GSFC model showed that the stratospheric cooling calculated to result from doubling atmospheric CO2 would lead, in the absence of a growth of other anthropogenic gases, to a decrease in upper stratospheric NO(y) of roughly 15%. This work has been extended to simulate changes in stratospheric chemistry and dynamics occurring between the years 1960 and 2050. The simulations have been carried out with and without changes in CO2. In the low latitude upper stratosphere ozone is predicted to be 10% greater in 2050 than in 1990 when increased CO2 is included, compared with an increase of only 2% without the inclusion of CO2. In the low latitude lower stratosphere, ozone is predicted to decrease by about 1% between 1990 and 2050 when CO2 changes are taken into account, in contrast to an approximate 3% increase when they are not. The simulated behavior of water vapor is another example of the coupled responses. Between 1990 and 2050 low latitude water vapor is predicted to increase by 4% and 2% in the upper and lower stratosphere, respectively, without the inclusion of CO2 increases. with the inclusion of CO2 changes, the water vapor increases are predicted to be roughly 12% and 8%, for the upper and lower stratosphere, respectively.

Rosenfield, J. E.↗

BOREAS TF-7 SSA-OBS Tower Flux and Meteorological Data

The BOREAS TF-7 team collected meteorological data as well as energy, carbon dioxide, water vapor, methane, and nitrous oxide flux data at the BOREAS SSA-OBS site. The data were collected from 24-May to 19-Sep-1994. The data are available in tabular ASCII files.

Hall, Forrest G.↗

In Situ Measurements of N2O and CH4 During SOLVE on the ER-2 Using a New Tunable Diode Laser Instrument

This report is the final report for Cooperative Agreement NCC2-1105: 'In Situ Measurements of N2O and CH4 during SOLVE on the ER-2 using a new tunable diode laser instrument.' The tasks outlined in the proposal are listed below with a brief comment. The publications and the conference presentations are listed. Finally the important publications are attached. The Cooperative Agreement made possible a research effort to produce high precision and high accuracy in situ measurements of methane and nitrous oxide on the ER-2 during the SOLVE field campaign and to analyze these measurements. These measurements of CH4 and N2O were of utmost importance to studies of the ozone losses in the Arctic winter and spring. The concentrations measured over a large spatial and temporal range allowed the separation of the dynamical and chemical ozone loss. The most important results of the SOLVE program were contained in two scientific papers. This Cooperative Agreement allowed the participation of the Argus instrument in the program and the analysis of the data.

Jost, Hansjurg↗

Argus: a new instrument for the measurement of the stratospheric dynamical tracers, N2O and CH4

We describe here a new instrument for the simultaneous, in situ measurement of the stratospheric tracer molecules, nitrous oxide (N2O) and methane (CH4). Argus is unique in its small size making it well suited for limited payload atmospheric research platforms. Argus employs second harmonic spectroscopy using tunable lead-salt diode lasers emitting in the mid-infrared. We first explain the Argus design philosophy followed by detailed descriptions of the instrument's optical, mechanical, and thermal sub-systems. Argus employs an in-flight calibration system providing real time calibrations and tightly constrained uncertainty estimates of the returned data. Data analysis is carried out using non-linear least-squares model fits to the acquired second harmonic spectra. A sampling of Argus data acquired on a recent stratospheric research campaign in the Arctic winter is presented.

Methane/analysis↗

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

Until recently, the stable isotopic composition of chemically and datively important stratospheric species, such as ozone (O3), carbon dioxide (CO2), nitrous oxide (N2O), and methane (CH4), was largely unexplored, despite indications from the few measurements available and theoretical studies that global-scale isotopic variations will provide a unique tool for quantifying rates of global-scale mass transport into, within, and out of the stratosphere and for understanding the mechanisms of chemical reactions involved in ozone production. The number and geographical extent of observations are beginning to increase rapidly, however, as access to the stratosphere, both directly and by remote-sensing, has increased over the last 10 years and as new analytical techniques have been developed that make global-scale isotope measurements by whole-air sampling more feasible. The objective of this study, begun in April 1999, is to incorporate into the Livermore 2D model the likely photochemical fractionation processes that determine the isotopic compositions of stratospheric CO2, N2O, CH4, and O3, and to use the model results and new observations from NASA field campaigns in 1996 and 1997 to investigate stratospheric chemistry and mass transport. Additionally, since isotopic signatures from the stratosphere are transferred to the troposphere by downward transport at middle and high latitudes, the isotopic compositions may also serve as sensitive tracers of stratosphere-totroposphere transport. Comparisons of model results with stratospheric and upper tropospheric observations from these campaigns, as well as with ground-based observations from new NOAA and NSF-sponsored studies, will help determine whether the magnitudes of the stratospheric fractionation processes are large enough to use as global-scale tracers of transport into the troposphere and, if so, will be used to help constrain the degree of coupling between the troposphere and the stratosphere.

Boering, Kristie A.↗

Measurements of Trace Gases Using a Tunable Diode Laser

This report is the final report for "Measurements of Trace Gases Using a Tunable Diode Laser." The tasks outlined in the proposal are listed below with a brief comment. The publications and the conference presentations are listed. Finally, the important publications are attached. The Cooperative Agreement made possible a research effort to produce high- precision and high-accuracy in-situ measurements of carbon monoxide, methane and nitrous oxide on the WB-57 during the CRYSTAL-FACE and pre-AVE field campaigns and to analyze these measurements. These measurements of CO and CH4 were of utmost importance to studies of the radiative effects of clouds. Some important results of the CRYSTAL-FACE program were contained in two scientific papers (attached). This Cooperative Agreement allowed the participation of the Argus instrument in the program and the analysis of the data.

Jost, Hans-Juerg↗

Net Influence of an Internally Generated Guasi-biennial Oscillation on Modelled Stratospheric Climate and Chemistry

A Goddard Earth Observing System Chemistry- Climate Model (GEOSCCM) simulation with strong tropical non-orographic gravity wave drag (GWD) is compared to an otherwise identical simulation with near-zero tropical non-orographic GWD. The GEOSCCM generates a quasibiennial oscillation (QBO) zonal wind signal in response to a tropical peak in GWD that resembles the zonal and climatological mean precipitation field. The modelled QBO has a frequency and amplitude that closely resembles observations. As expected, the modelled QBO improves the simulation of tropical zonal winds and enhances tropical and subtropical stratospheric variability. Also, inclusion of the QBO slows the meridional overturning circulation, resulting in a generally older stratospheric mean age of air. Slowing of the overturning circulation, changes in stratospheric temperature and enhanced subtropical mixing all affect the annual mean distributions of ozone, methane and nitrous oxide. Furthermore, the modelled QBO enhances polar stratospheric variability in winter. Because tropical zonal winds are easterly in the simulation without a QBO, there is a relative increase in tropical zonal winds in the simulation with a QBO. Extratropical differences between the simulations with and without a QBO thus reflect the westerly shift in tropical zonal winds: a relative strengthening of the polar stratospheric jet, polar stratospheric cooling and a weak reduction in Arctic lower stratospheric ozone.

stratosphere↗

Climate Change in New York State Updating the 2011 ClimAID Climate Risk Information Supplement to NYSERDA Report 11-18 (Responding to Climate Change in New York State)

In its 2013-2014 Fifth Assessment Report (AR5), the Intergovernmental Panel on Climate Change (IPCC) states that there is a greater than 95 percent chance that rising global average temperatures, observed since the mid-20th century, are primarily due to human activities. As had been predicted in the 1800s, the principal driver of climate change over the past century has been increasing levels of atmospheric greenhouse gases associated with fossil-fuel combustion, changing land-use practices, and other human activities. Atmospheric concentrations of the greenhouse gas carbon dioxide are now approximately 40 percent higher than in preindustrial times. Concentrations of other important greenhouse gases, including methane and nitrous oxide, have increased rapidly as well.

New York↗

Atmospheric Photochemistry

The upper atmosphere offers a vast photochemical laboratory free from solid surfaces, so all reactions take place in the gaseous phase. At 30 km altitude the pressure has fallen to about one-hundredth of that at ground level, and we shall, rather arbitrarily, regard the upper atmosphere as beginning at that height. By a little less than 100 km the pressure has fallen to 10(exp -3) mm Hg and is decreasing by a power of ten for every 15 km increase in altitude. Essentially we are concerned then with the photochemistry of a nitrogen-oxygen mixture under low-pressure conditions in which photo-ionization, as well as photodissociation, plays an important part. Account must also be taken of the presence of rare constituents, such as water vapour and its decomposition products, including particularly hydroxyl, oxides of carbon, methane and, strangely enough, sodium, lithium and calcium. Many curious and unfamiliar reactions occur in the upper atmosphere. Some of them are luminescent, causing the atmosphere to emit a dim light called the airglow. Others, between gaseous ions and neutral molecules, are almost a complete mystery at this time. Similar interesting phenomena must occur in other planetary atmospheres, and they might be predicted if sufficient chemical information were available.

Massey, Harrie↗

Airborne Measurements of Western U.S. Wildfire Emissions: Comparison with Prescribed Burning and Air Quality Implications

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total non methane organic compounds, and PM1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM1 emission estimate (1530 +/- 570 Gg/yr) is over 3 times that of the NEI PM2.5 estimate and is also higher than the PM2.5 emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions.

measured oxygenated volatile organic compounds↗

Airborne In-Situ Measurements of Formaldehyde Over California: One Year of Results from the Compact Formaldehyde Fluorescence Experiment (COFFEE) Instrument

Formaldehyde (HCHO) is one of the most abundant oxygenated volatile organiccompounds (VOCs) in the atmosphere, playing a role in multiple atmosphericprocesses, such as ozone (O3) production in polluted environments. Due toits short lifetime of only a few hours in daytime, HCHO also serves astracer of recent photochemical activity. While photochemical oxidation ofnon-methane hydrocarbons is the dominant source, HCHO can also be emitteddirectly from fuel combustion, vegetation, and biomass burning. The CompactFormaldehyde FluorescencE Experiment (COFFEE) instrument was built forintegration onto the Alpha Jet Atmospheric eXperiment (AJAX) payload, basedout of NASAs Ames Research Center (Moffett Field, CA). Using Non-ResonantLaser Induced Fluorescence (NR-LIF), trace concentrations of HCHO can bedetected with a sensitivity of 200 parts per trillion.Since its first research flight in December 2015, COFFEE has successfullyflown on more than 20 science missions throughout California and Nevada.Presented here are results from these flights, including boundary layermeasurements and vertical profiles throughout the tropospheric column.Californias San Joaquin Valley is a primary focus, as this region is knownfor its elevated levels of HCHO as well as O3. Measurements collected inwildfire plumes, urban centers, agricultural lands, and on and off shorecomparisons will be presented. In addition, the correlation of HCHO to othertrace gases also measured by AJAX, including O3, methane, carbon dioxide,and water vapor will also be shown. Lastly, the implications of these HCHOmeasurements on calibration and validation of remote sensing data collectedby NASAs OMI (Aura) and OMPS (SuomiNPP) satellites will be addressed.

wildfire↗

Kiloton Class ISRU Systems for LO2/LCH4 Propellant Production on the Mars Surface

As part of the 2023 strategic analysis cycle to explore the trade space, the NASA Mars Architecture Team wanted to explore what it takes to produce in situ on Mars many hundreds of tons of propellants for a large all-chemical transportation system. The conceptual operations and design of the LO 2 /LCH 4 in situ resource utilization (ISRU) water acquisition, propellant production and liquification system was assigned to the NASA Compass concurrent engineering team with support from various NASA ISRU, cryogenic fluid management, and surface power experts. The conceptual point design examined one case producing 300 t of LO 2 /LCH 4 from the Mars atmosphere and delivered water in 20 months and storing the liquified propellants in a to-be-reused lander. Several of these large single-stage, all-chemical class large vertical landers would deliver the required ISRU equipment. The required 150 t of water stock for the ISRU system was traded between three options: delivered, pumped from subsurface ice deposits or extracted from surface soils. The large propellant production systems consist of atmospheric CO 2 collection scroll pumps, a combined solid oxide electrolysis and methanation system to convert the CO 2 and water into gaseous O 2 and CH 4 , and various dryers, scrubbers, and separators to remove the excess water, CO 2 and H 2 . The liquefaction system consisted of 90 K cryocoolers to provide cold Ne to the launch vehicle tanks to liquify these CH 4 and O 2 gases and store them as rocket propellants. The systems are deployed using a 6 t (payload) capable chassis derived from conceptual pressurized rover designs. In total, the propellant production and liquefaction systems required three propellant production pallets, two liquefaction pallets, two water tankers, and six 40 kW-fission surface power systems (FSPS) with cabling. All this equipment was found to notionally fit inside two- 75 metric ton payload capacity Mars ascent and landing vehicles (MALV). For the case where 150 t of water delivered from Earth, four cargo MALVs are required for the full system. The same is true when the 150 t of water is extracted through surface mining. For the borehole system, only 3 cargo MALVs are necessary. A comparison of approaches in terms of number of landers, number and type of elements, power and time is made.

ISRU↗

Prediction of hydrodynamics and chemistry of confined turbulent methane-air flames with attention to formation of oxides of nitrogen

A formulation of the governing partial differential equations for fluid flow and reacting chemical species in a tubular combustor is presented. A numerical procedure for the solution of the governing differential equations is described, and models for chemical equilibrium and chemical kinetics calculations are presented. The chemical equilibrium model is used to characterize the hydrocarbon reactions. The chemical kinetics model is used to predict the concentrations of the oxides of nitrogen. The combustor consists of a cylindrical duct of varying cross sections with concentric streams of gaseous fuel and air entering the duct at one end. Four sample cases with specified inlet and boundary conditions are considered, and the results are discussed

Elghobashi, S.↗

Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

Levine, J. S.↗

Advanced oxygen-hydrocarbon Earth-to-orbit propulsion

Liquid oxygen/hydrocarbon (LO2/HC) rocket engine cycles for a surface to orbit transportation system were evaluated. A consistent engine system data base is established for defining advantages and disadvantages, system performance and operating limits, engine parametric data, and technology requirements for candidate engine systems. Preliminary comparisons of the engine cycles utilizing delivered specific impulse values are presented. Methane and propane staged combustion cycles are the highest LO2/HC performers. The hydrogen cooled LO2/methane dual throat engine was found to be the highest performing. Technology needs identified in the study include: high temperature turbines; oxidizer-rich preburners; LO2, methane, and propane cooling; methane and propane fuel-rich preburners; the HC fuel turbopump; and application of advanced composite materials to the engine system. Parametric sensitivity analysis data are displayed which show the effect of variations in engine thrust, mixture ratio, chamber pressure, area ratio, cycle life, and turbine inlet temperature on specific impulse and engine weight.

Obrien, C. J.↗

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope aud Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41º32'N, 120º5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4 2-, respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 oC, and higher than the values measured at orifices (77.3 to 90.0 oC). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The 13C fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 oC) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope and Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41 deg 32'N, 120 deg 5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4(2-), respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 C, and higher than the values measured at orifices (77.3 to 90.0 C). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The C-13 fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 C) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

Atmospheric Composition Change: Climate-Chemistry Interactions

Chemically active climate compounds are either primary compounds such as methane (CH4), removed by oxidation in the atmosphere, or secondary compounds such as ozone (O3), sulfate and organic aerosols, formed and removed in the atmosphere. Man-induced climate-chemistry interaction is a two-way process: Emissions of pollutants change the atmospheric composition contributing to climate change through the aforementioned climate components, and climate change, through changes in temperature, dynamics, the hydrological cycle, atmospheric stability, and biosphere-atmosphere interactions, affects the atmospheric composition and oxidation processes in the troposphere. Here we present progress in our understanding of processes of importance for climate-chemistry interactions, and their contributions to changes in atmospheric composition and climate forcing. A key factor is the oxidation potential involving compounds such as O3 and the hydroxyl radical (OH). Reported studies represent both current and future changes. Reported results include new estimates of radiative forcing based on extensive model studies of chemically active climate compounds such as O3, and of particles inducing both direct and indirect effects. Through EU projects such as ACCENT, QUANTIFY, and the AEROCOM project, extensive studies on regional and sector-wise differences in the impact on atmospheric distribution are performed. Studies have shown that land-based emissions have a different effect on climate than ship and aircraft emissions, and different measures are needed to reduce the climate impact. Several areas where climate change can affect the tropospheric oxidation process and the chemical composition are identified. This can take place through enhanced stratospheric-tropospheric exchange of ozone, more frequent periods with stable conditions favouring pollution build up over industrial areas, enhanced temperature-induced biogenic emissions, methane releases from permafrost thawing, and enhanced concentration through reduced biospheric uptake. During the last 510 years, new observational data have been made available and used for model validation and the study of atmospheric processes. Although there are significant uncertainties in the modelling of composition changes, access to new observational data has improved modelling capability. Emission scenarios for the coming decades have a large uncertainty range, in particular with respect to regional trends, leading to a significant uncertainty range in estimated regional composition changes and climate impact.

Atmosphere climate chemistry↗