Atmospheric chemistry

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Atmospheric chemistry is a branch of atmospheric science that studies the chemistry of the Earth's atmosphere and that of other planets. This multidisciplinary approach of research draws on environmental chemistry, physics, meteorology, computer modeling, oceanography, geology and volcanology, climatology and other disciplines to understand both natural and human-induced changes in atmospheric composition. Key areas of research include the behavior of trace gasses, the formation of pollutants, and the role of aerosols and greenhouse gasses. Through a combination of observations, laboratory experiments, and computer modeling, atmospheric chemists investigate the causes and consequences of atmospheric changes.

Contents

Atmospheric composition

Visualisation of composition by volume of Earth's atmosphere. Water vapour is not included as it is highly variable. Each tiny cube (such as the one representing krypton) has one millionth of the volume of the entire block. Data is from NASA Langley. Atmospheric composition Langley.svg
Visualisation of composition by volume of Earth's atmosphere. Water vapour is not included as it is highly variable. Each tiny cube (such as the one representing krypton) has one millionth of the volume of the entire block. Data is from NASA Langley.
The composition of common nitrogen oxides in dry air vs. temperature Dry Air NOx Composition vs Temperature.svg
The composition of common nitrogen oxides in dry air vs. temperature
Chemical composition of atmosphere according to altitude. Axis: Altitude (km), Content of volume (%). Chemical composition of atmosphere accordig to altitude.png
Chemical composition of atmosphere according to altitude. Axis: Altitude (km), Content of volume (%).

The composition and chemistry of the Earth's atmosphere is important for several reasons, but primarily because of the interactions between the atmosphere and living organisms. Natural processes such as volcano emissions, lightning and bombardment by solar particles from corona changes the composition of the Earth's atmosphere. It has also been changed by human activity and some of these changes are harmful to human health, crops and ecosystems.

Average Composition of Dry Atmosphere (mole fractions)
GasDry air per NASA
Nitrogen, N278.084%
Oxygen, O2 [2] 20.946%
Minor Constituents (mole fractions in ppm)
Argon, Ar9340
Carbon dioxide, CO2430
Neon, Ne18.18
Helium, He5.24
Methane, CH41.9
Krypton, Kr1.14
Hydrogen, H20.53
Nitrous oxide, N2O0.34
Xenon, Xe0.087
Nitrogen dioxide, NO2up to 0.02
Ozone, O3, in summerup to 0.07
Ozone, O3, in winterup to 0.02
Sulphur dioxide, SO2up to 1
Iodine, I20.01
Water
Water vapour*Highly variable (about 0–3%);
typically makes up about 1%
Notes
The mean molecular mass of dry air is 28.97 g/mol. The content of the gas may undergo significant variations from time to time or from place to place. The concentration of CO2 and CH4 vary by season and location.

Trace gas composition

Besides the major components listed above, the Earth's atmosphere contains many trace gas species that vary significantly depending on nearby sources and sinks. These trace gasses include compounds such as CFCs/HCFCs which are particularly damaging to the ozone layer, and H2S which has a characteristic foul odor of rotten eggs and can be smelt in concentrations as low as 0.47 ppb. Some approximate amounts near the surface of some additional gasses are listed below. In addition to gasses, the atmosphere contains particles such as aerosol, which includes examples such as droplets, ice crystals, bacteria, and dust.

GasComposition (ppt by volume unless otherwise stated)
Carbon monoxide, CO40-200 ppb p39 [3]
Nitric oxide, NO16 [4]
Ethane, C2H6781 [4]
Propane, C3H8200 [4]
Isoprene, C5H8311 [4]
Benzene, C6H611 [4]
Methanol, CH3OH1967 [4]
Ethanol, C2H5OH75 [4]
Trichlorofluoromethane, CCl3F237 p41 [3]
Dichlorodifluoromethane, CCl2F2530 p41 [3]
Chloromethane, CH3Cl503 [4]
Bromomethane, CH3Br9–10 p44 [3]
Iodomethane, CH3I0.36 [4]
Carbonyl sulfide, OCS510 p26 [3]
Sulfur dioxide, SO270–200 p26 [3]
Hydrogen sulfide, H2S15–340 p26 [3]
Carbon disulfide, CS215–45 p26 [3]
Formaldehyde, H2CO9.1 ppb p37, polluted [3]
Acetylene, C2H28.6 ppb p37, polluted [3]
Ethene, C2H411.2 ppb p37, polluted [3]
Sulfur hexafluoride, SF67.3 p41 [3]
Carbon tetrafluoride, CF479 p41 [3]
Total gaseous mercury, Hg0.209 p55 [3]

History

Schematic of chemical and transport processes related to atmospheric composition Atmosphere composition diagram-en.svg
Schematic of chemical and transport processes related to atmospheric composition

The first scientific studies of atmospheric composition began in the 18th century when chemists such as Joseph Priestley, Antoine Lavoisier and Henry Cavendish made the first measurements of the composition of the atmosphere. [5]

In the late 19th and early 20th centuries, researchers shifted their interest towards trace constituents with very low concentrations. An important finding from this era was the discovery of ozone by Christian Friedrich Schönbein in 1840. [6]

In the 20th century atmospheric science moved from studying the composition of air to consider how the concentrations of trace gasses in the atmosphere have changed over time and the chemical processes which create and destroy compounds in the air. Two important outcomes were the explanation by Sydney Chapman and Gordon Dobson of how the ozone layer is created and maintained, and Arie Jan Haagen-Smit’s explanation of photochemical smog. Further studies on ozone issues led to the 1995 Nobel Prize in Chemistry award shared between Paul Crutzen, Mario Molina and Frank Sherwood Rowland.


In the 21st century the focus is now shifting again. Instead of concentrating on atmospheric chemistry in isolation, it is now seen as one part of the Earth system with the rest of the atmosphere, biosphere and geosphere. A driving force for this link is the relationship between chemistry and climate. The changing climate and the recovery of the ozone hole and the interaction of the composition of the atmosphere with the oceans and terrestrial ecosystems are examples of the interdependent relationships between Earth's systems. [7] A new field of extraterrestrial atmospheric chemistry has also recently emerged. Astrochemists analyze the atmospheric compositions of our solar system and exoplanets to determine the formation of astronomical objects and find habitual conditions for Earth-like life. [8]

M15-162b-EarthAtmosphere-CarbonDioxide-FutureRoleInGlobalWarming-Simulation-20151109.jpg
Carbon dioxide in Earth's atmosphere if half of anthropogenic CO2 emissions [9] [10] are not absorbed
(NASA simulation; 9 November 2015)
15-233-Earth-GlobalAirQuality-2014NitrogenDioxideLevels-20151214.jpg
Nitrogen dioxide 2014 - global air quality levels
(released 14 December 2015) [11]

Methodology

Observations, lab measurements, and modeling are the three central elements in atmospheric chemistry. Progress in atmospheric chemistry is often driven by the interactions between these components and they form an integrated whole. For example, observations may tell us that more of a chemical compound exists than previously thought possible. This will stimulate new modeling and laboratory studies which will increase our scientific understanding to a level where we can explain the observations. [12]

Observation

Field observations of chemical systems are essential to understanding atmospheric processes and determining the accuracy of models. Atmospheric chemistry measurements are long term to observe continuous trends or short term to observe smaller variations. In situ and remote measurements can be made using observatories, satellites, field stations, and laboratories.

Routine observations of chemical composition show changes in atmospheric composition over time. Observatories such as the Mauna Loa and mobile platforms such as aircraft ships and balloons (e.g. the UK's Facility for Airborne Atmospheric Measurements) study chemical compositions and weather dynamics. An application of long term observations is the Keeling Curve - a series of measurements from 1958 to today which show a steady rise in the concentration of carbon dioxide (see also ongoing measurements of atmospheric CO2). Observations of atmospheric composition are increasingly made by satellites by passive and active remote sensing with important instruments such as GOME and MOPITT giving a global picture of air pollution and chemistry. [13]

Surface observations have the advantage that they provide long term records at high time resolution but are limited in the vertical and horizontal space they provide observations from. Some surface based instruments e.g. LIDAR can provide concentration profiles of chemical compounds and aerosols but are still restricted in the horizontal region they can cover. Many observations are available online in Atmospheric Chemistry Observational Databases [14]

Laboratory studies

Laboratory studies help understand the complex interactions from Earth’s systems that can be difficult to measure on a large scale. Experiments are performed in controlled environments, such as aerosol chambers, that allow for the individual evaluation of specific chemical reactions or the assessment of properties of a particular atmospheric constituent. [15] A closely related subdiscipline is atmospheric photochemistry, which quantifies the rate that molecules are split apart by sunlight, determines the resulting products, and obtains thermodynamic data such as Henry's law coefficients.

Laboratory measurements are essential to understanding the sources and sinks of pollutants and naturally occurring compounds. Types of analysis that are of interest include both those on gas-phase reactions, as well as heterogeneous reactions that are relevant to the formation and growth of aerosols. Commonly used instruments to measure aerosols include ambient and particulate air samplers, scanning mobility particle sizers, and mass spectrometers. [16]

Schematic of a one-dimensional column model depicting the movement and transformation of aerosols. Box Model Diagram Atmospheric Chemistry.jpg
Schematic of a one-dimensional column model depicting the movement and transformation of aerosols.

Modeling

Models are essential tools for interpreting observational data, testing hypotheses about chemical reactions, and predicting future concentrations of atmospheric chemicals. To synthesize and test theoretical understanding of atmospheric chemistry, researchers commonly use computer models, such as chemical transport models (CTMs). CTMs provide realistic descriptions of the three-dimensional transport and evolution of the atmosphere. [7] Atmospheric models can be seen as mathematical representations that replicate the behavior of the atmosphere. These numerical models solve the differential equations governing the concentrations of chemicals in the atmosphere.

Depending on the complexity, these models can range from simple to highly detailed. Models can be zero-, one-, two-, or three-dimensional, each with various uses and advantages. Three-dimensional chemical transport models offer the most realistic simulations but require substantial computational resources. These models can be global e.g. GCM, simulating the atmospheric conditions across the Earth, or regional, e.g. RAMS focusing on specific areas with greater resolution. Global models typically have lower horizontal resolution and represent less complex chemical mechanisms but they cover a larger area, while regional models can represent a limited area with higher resolution and more detail. [18]

A major challenge in atmospheric modeling is balancing the number of chemical compounds and reactions included in the model with the accuracy of physical processes such as transport and mixing in the atmosphere. Two simpliest types of models include box models and puff models. For example, box modeling is relatively simple and may include hundreds or even thousands of chemical reactions, but they typically use a very crude representation of atmospheric mixed layer. [17] This makes them useful for studying specific chemical reactions, but limited in stimulating real-world dynamics. In contrast, 3D models are more complex, representing a variety of physical processes such as wind, convection, and atmospheric mixing. They also provide more realistic representations of transportation and mixing. However, computational limits often simply chemical reactions and typically include fewer chemical reactions than box models. The trade-off between the two approaches lies in resolution and complexity.

To simplify the creation of these complex models, some researchers use automatic code generators like Autochem or Kinetic PreProcessor. These tools help automate the model-building process by selecting relevant chemical reactions from databases based on a user-defined function of chemical constituents. [19] Once the reactions are chosen, the code generator automatically constructs the ordinary differential equations that describe their time evolution, greatly reducing the time and effort required for model construction.

Differences between model prediction and real-world observations can arise from errors in model input parameters or flaws representations of processes in the model. Some input parameters like surface emissions are often less accurately quantified from observations compared to model results. The model can be improved by adjusting poorly known parameters to better match observed data [7] . A formal method for applying these adjustments is through Bayesian Optimization through an inverse modeling framework, where the results from the CTMs are inverted to optimize selected parameters. This approach has gained attention over the past decade as an effective method to interpret large amounts of data generate by models and observations from satellites.

One important current trend is using atmospheric chemistry as part of Earth system models. These models integrate atmospheric chemistry with other Earth system components, enabling the study of complex interactions between climate, atmospheric composition, and ecosystems.

Applications

Atmospheric chemistry is a multidisciplinary field with wide-ranging applications that influence environmental policy, human health, technology development, and climate science. Examples of problems addressed in atmospheric chemistry include acid rain, ozone depletion, photochemical smog, greenhouse gasses and global warming. By developing a theoretical understanding, atmospheric chemists can test potential solutions and evaluate the effects of changes in government policy. Key applications include greenhouse gas monitoring, air quality and pollution control, weather prediction and meteorology, energy and emissions, sustainable energy development, and public health and toxicology. Green atmospheric chemistry research prioritizes the sustainable, safe, and efficient use of chemicals, which led to government regulations minimizing the use of harmful chemicals like CFCs and DDT. [20]

Advances in remote sensing technology allow scientists to monitor atmospheric chemical composition from satellites and ground-based stations. Instruments such as the Ozone Monitoring Instrument (OMI) and Atmospheric Infrared Sounder (AIRS) provide data on pollutants, greenhouse gasses, and aerosols, enabling real-time monitoring of air quality [21] [22] .

Atmospheric chemistry is vital for evaluating the environmental impacts of energy production, including fossil fuels and renewable energy sources. By studying emissions, researchers can develop cleaner energy technologies and assess their effects on air quality and climate. Atmospheric chemistry also helps quantify the concentration and persistence of toxic substances in the air, including particulate matter and volatile organic compounds (VOCs), guiding public health measures and exposures assessments.

See also

Related Research Articles

<span class="mw-page-title-main">Ozone depletion</span> Atmospheric phenomenon

Ozone depletion consists of two related events observed since the late 1970s: a steady lowering of about four percent in the total amount of ozone in Earth's atmosphere, and a much larger springtime decrease in stratospheric ozone around Earth's polar regions. The latter phenomenon is referred to as the ozone hole. There are also springtime polar tropospheric ozone depletion events in addition to these stratospheric events.

<span class="mw-page-title-main">Ground-level ozone</span> Constituent gas of the troposphere

Ground-level ozone (O3), also known as surface-level ozone and tropospheric ozone, is a trace gas in the troposphere (the lowest level of the Earth's atmosphere), with an average concentration of 20–30 parts per billion by volume (ppbv), with close to 100 ppbv in polluted areas. Ozone is also an important constituent of the stratosphere, where the ozone layer (2 to 8 parts per million ozone) exists which is located between 10 and 50 kilometers above the Earth's surface. The troposphere extends from the ground up to a variable height of approximately 14 kilometers above sea level. Ozone is least concentrated in the ground layer (or planetary boundary layer) of the troposphere. Ground-level or tropospheric ozone is created by chemical reactions between NOx gases (oxides of nitrogen produced by combustion) and volatile organic compounds (VOCs). The combination of these chemicals in the presence of sunlight form ozone. Its concentration increases as height above sea level increases, with a maximum concentration at the tropopause. About 90% of total ozone in the atmosphere is in the stratosphere, and 10% is in the troposphere. Although tropospheric ozone is less concentrated than stratospheric ozone, it is of concern because of its health effects. Ozone in the troposphere is considered a greenhouse gas, and as such contribute to global warming. as reported in IPCC reports. Actually, tropospheric ozone is considered the third most important greenhouse gas after CO2 and CH4, as indicated by estimates of its radiative forcing.

<span class="mw-page-title-main">Paul J. Crutzen</span> Dutch climatologist (1933–2021)

Paul Jozef Crutzen was a Dutch meteorologist and atmospheric chemist. In 1995, he was awarded the Nobel Prize in Chemistry alongside Mario Molina and Frank Sherwood Rowland for their work on atmospheric chemistry and specifically for his efforts in studying the formation and decomposition of atmospheric ozone. In addition to studying the ozone layer and climate change, he popularized the term Anthropocene to describe a proposed new epoch in the Quaternary period when human actions have a drastic effect on the Earth. He was also amongst the first few scientists to introduce the idea of a nuclear winter to describe the potential climatic effects stemming from large-scale atmospheric pollution including smoke from forest fires, industrial exhausts, and other sources like oil fires.

Trace gases are gases that are present in small amounts within an environment such as a planet's atmosphere. Trace gases in Earth's atmosphere are gases other than nitrogen (78.1%), oxygen (20.9%), and argon (0.934%) which, in combination, make up 99.934% of its atmosphere.

<span class="mw-page-title-main">Cooperative Institute for Research in Environmental Sciences</span> Research institute

The Cooperative Institute for Research in Environmental Sciences (CIRES) is a research institute that is sponsored jointly by the National Oceanic and Atmospheric Administration (NOAA) Office of Oceanic and Atmospheric Research (OAR) and the University of Colorado Boulder (CU). CIRES scientists study the Earth system, including the atmosphere, hydrosphere, cryosphere, biosphere, and geosphere, and communicate these findings to decision makers, the scientific community, and the public.

<span class="mw-page-title-main">Carbon tetrafluoride</span> Chemical compound

Tetrafluoromethane, also known as carbon tetrafluoride or R-14, is the simplest perfluorocarbon (CF4). As its IUPAC name indicates, tetrafluoromethane is the perfluorinated counterpart to the hydrocarbon methane. It can also be classified as a haloalkane or halomethane. Tetrafluoromethane is a useful refrigerant but also a potent greenhouse gas. It has a very high bond strength due to the nature of the carbon–fluorine bond.

In atmospheric chemistry, NOx is shorthand for nitric oxide and nitrogen dioxide, the nitrogen oxides that are most relevant for air pollution. These gases contribute to the formation of smog and acid rain, as well as affecting tropospheric ozone.

<span class="mw-page-title-main">Max Planck Institute for Chemistry</span> Research institute in Mainz, Germany

The Max Planck Institute for Chemistry is a non-university research institute under the auspices of the Max Planck Society in Mainz, Germany. It was created as the Kaiser Wilhelm Institute for Chemistry in 1911 in Berlin.

<span class="mw-page-title-main">Atmospheric chemistry observational databases</span> Aspect of atmospheric sciences

Over the last two centuries many environmental chemical observations have been made from a variety of ground-based, airborne, and orbital platforms and deposited in databases. Many of these databases are publicly available. All of the instruments mentioned in this article give online public access to their data. These observations are critical in developing our understanding of the Earth's atmosphere and issues such as climate change, ozone depletion and air quality. Some of the external links provide repositories of many of these datasets in one place. For example, the Cambridge Atmospheric Chemical Database, is a large database in a uniform ASCII format. Each observation is augmented with the meteorological conditions such as the temperature, potential temperature, geopotential height, and equivalent PV latitude.

<span class="mw-page-title-main">Atmospheric infrared sounder</span> Science instrument on NASAs Aqua satellite

The atmospheric infrared sounder (AIRS) is one of six instruments flying on board NASA's Aqua satellite, launched on May 4, 2002. The instrument is designed to support climate research and improve weather forecasting.

<span class="mw-page-title-main">Tropospheric ozone depletion events</span>

Tropospheric ozone depletion events are phenomena that reduce the concentration of ozone in the earth's troposphere. Ozone (O3) is a trace gas which has been of concern because of its unique dual role in different layers of the lower atmosphere. Apart from absorbing UV-B radiation and converting solar energy into heat in the stratosphere, ozone in the troposphere provides greenhouse effect and controls the oxidation capacity of the atmosphere.

A chemical transport model (CTM) is a type of computer numerical model which typically simulates atmospheric chemistry and may give air pollution forecasting.

<span class="mw-page-title-main">Greenhouse gas monitoring</span> Measurement of greenhouse gas emissions and levels

Greenhouse gas monitoring is the direct measurement of greenhouse gas emissions and levels. There are several different methods of measuring carbon dioxide concentrations in the atmosphere, including infrared analyzing and manometry. Methane and nitrous oxide are measured by other instruments. Greenhouse gases are measured from space such as by the Orbiting Carbon Observatory and networks of ground stations such as the Integrated Carbon Observation System.

Tectonic–climatic interaction is the interrelationship between tectonic processes and the climate system. The tectonic processes in question include orogenesis, volcanism, and erosion, while relevant climatic processes include atmospheric circulation, orographic lift, monsoon circulation and the rain shadow effect. As the geological record of past climate changes over millions of years is sparse and poorly resolved, many questions remain unresolved regarding the nature of tectonic-climate interaction, although it is an area of active research by geologists and palaeoclimatologists.

<span class="mw-page-title-main">SAGE III on ISS</span>

SAGE III on ISS is the fourth generation of a series of NASA Earth-observing instruments, known as the Stratospheric Aerosol and Gas Experiment. The first SAGE III instrument was launched on a Russian Meteor-3M satellite. The recently revised SAGE III was mounted to the International Space Station where it uses the unique vantage point of ISS to make long-term measurements of ozone, aerosols, water vapor, and other gases in Earth's atmosphere.

<span class="mw-page-title-main">Flash-gas (petroleum)</span>

In an oil and gas production, flash-gas is a spontaneous vapor that is produced from the heating or depressurization of the extracted oil mixture during different phases of production. Flash evaporation, or flashing, is the process of volatile components suddenly vaporizing from their liquid state. This often happens during the transportation of petroleum products through pipelines and into vessels, such as when the stream from a common separation unit flows into an on-site atmospheric storage tank. Vessels that are used to intentionally “flash” a mixture of gas and saturated liquids are aptly named "flash drums." A type of vapor-liquid separator. A venting apparatus is used in these vessels to prevent damage due to increasing pressure, extreme cases of this are referred to as boiling liquid expanding vapor explosion (BLEVE).

<span class="mw-page-title-main">Nadine Unger</span> Atmospheric chemistry researcher

Nadine Unger is a Professor of Atmospheric Chemistry at the University of Exeter. She has studied the role of human activities and forests on the Earth's climate.

Jennifer Logan is an atmospheric scientist known for her research on how human activities influence the atmosphere, particularly with respect to biomass burning and the ozone hole.

<span class="mw-page-title-main">John W. Birks</span> American professor at the University of Colorado Boulder

John W. Birks is an American atmospheric chemist and entrepreneur who is best known for co-discovery with Paul Crutzen of the potential atmospheric effects of nuclear war known as nuclear winter. His most recent awards include the 2019 Haagen-Smit Clean Air Award for his contributions to atmospheric chemistry and the 2022 Future of Life Award for discovery of the nuclear winter effect.

Randall V. Martin is a scientist, engineer, academic and author. He is the Raymond R. Tucker Distinguished Professor in the Department of Energy, Environmental, and Chemical Engineering, with a courtesy appointment in Computer Science and Engineering at Washington University in St. Louis, McKelvey School of Engineering.

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Further reading