In organic chemistry, peroxyacyl nitrates (also known as Acyl peroxy nitrates, APN or PANs) are powerful respiratory and eye irritants present in photochemical smog. They are nitrates produced in the thermal equilibrium between organic peroxy radicals by the gas-phase oxidation of a variety of volatile organic compounds (VOCs), or by aldehydes and other oxygenated VOCs oxidizing in the presence of NO2. [1] [2] [3]
They are good markers for the source of VOCs as either biogenic or anthropogenic, which is useful in the study of global and local effects of pollutants. [4] [5]
PANs are secondary pollutants, which means they are not directly emitted as exhaust from power plants or internal combustion engines, but they are formed from other pollutants by chemical reactions in the atmosphere. Free radical reactions catalyzed by ultraviolet light from the sun oxidize unburned non-methane [6] : 2679 hydrocarbons to aldehydes, ketones, and dicarbonyls, whose secondary reactions create peroxyacyl radicals. The most common peroxyacyl radical is peroxyacetyl, which can be formed from the free radical oxidation of acetaldehyde, various ketones, or the photolysis of dicarbonyl compounds such as methylglyoxal or diacetyl.
These react reversibly with nitrogen dioxide (NO2) to form PANs: [6] : 2680
Night-time reaction of aldehydes with nitrogen trioxide is another possible source. [6] : 2680
Since they dissociate quite slowly in the atmosphere into radicals and NO2, PANs are able to transport these unstable compounds far away from the urban and industrial origin. This is important for tropospheric ozone production as PANs transport NOx to regions where it can more efficiently produce ozone.
Peroxyacetyl nitrate is the most prevalent peroxyacyl nitrate (75–90% of total atmospheric emissions), [6] : 2681 followed by peroxypropionyl nitrate (PPN). [7] Peroxybenzoyl nitrate (PBzN) [7] and methacryloyl peroxynitrate (MPAN) [4] have also been observed. The composition of PANs in a particular region depends heavily on which hydrocarbons are present in the atmosphere, with the exception of peroxyacetyl nitrate, which is able to be produced from a range of precursors. [4] : 7624
PANs are both toxic and irritating, as they dissolve more readily in water than ozone. They are lachrymators, causing eye irritation at concentrations of only a few parts per billion. At higher concentrations they cause extensive damage to vegetation. PANs are mutagenic, [7] and are considered potential contributors to the development of skin cancer.[ citation needed ]
Carbon monoxide is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simplest carbon oxide. In coordination complexes, the carbon monoxide ligand is called carbonyl. It is a key ingredient in many processes in industrial chemistry.
Smog, or smoke fog, is a type of intense air pollution. The word "smog" was coined in the early 20th century, and is a portmanteau of the words smoke and fog to refer to smoky fog due to its opacity, and odor. The word was then intended to refer to what was sometimes known as pea soup fog, a familiar and serious problem in London from the 19th century to the mid-20th century, where it was commonly known as a London particular or London fog. This kind of visible air pollution is composed of nitrogen oxides, sulfur oxide, ozone, smoke and other particulates. Man-made smog is derived from coal combustion emissions, vehicular emissions, industrial emissions, forest and agricultural fires and photochemical reactions of these emissions.
Peroxyacetyl nitrate is a peroxyacyl nitrate. It is a secondary pollutant present in photochemical smog. It is thermally unstable and decomposes into peroxyethanoyl radicals and nitrogen dioxide gas. It is a lachrymatory substance, meaning that it irritates the lungs and eyes.
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.
Nitrogen dioxide is a chemical compound with the formula NO2. One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, NO2 is an intermediate in the synthesis of nitric acid, millions of tons of which are produced each year, primarily for the production of fertilizers.
Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that contain only nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.
In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups. The nitro group is one of the most common explosophores used globally. The nitro group is also strongly electron-withdrawing. Because of this property, C−H bonds alpha (adjacent) to the nitro group can be acidic. For similar reasons, the presence of nitro groups in aromatic compounds retards electrophilic aromatic substitution but facilitates nucleophilic aromatic substitution. Nitro groups are rarely found in nature. They are almost invariably produced by nitration reactions starting with nitric acid.
Volatile organic compounds (VOCs) are organic compounds that have a high vapor pressure at room temperature. They are common and exist in a variety of settings and products, not limited to house mold, upholstered furniture, arts and crafts supplies, dry cleaned clothing, and cleaning supplies. VOCs are responsible for the odor of scents and perfumes as well as pollutants. They play an important role in communication between animals and plants, such as attractants for pollinators, protection from predation, and even inter-plant interactions. Some VOCs are dangerous to human health or cause harm to the environment, often despite the odor being perceived as pleasant, such as "new car smell".
Non-methane volatile organic compounds (NMVOCs) are a set of organic compounds that are typically photochemically reactive in the atmosphere—marked by the exclusion of methane. NMVOCs include a large variety of chemically different compounds, such as benzene, ethanol, formaldehyde, cyclohexane, 1,1,1-trichloroethane and acetone. Essentially, NMVOCs are identical to volatile organic compounds (VOCs), but with methane excluded. Methane is excluded in air-pollution contexts because it is not toxic. It is however a very potent greenhouse gas, with low reactivity and thus a long lifetime in the atmosphere. An important subset of NMVOCs are the non-methane hydrocarbons (NMHCs).
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.
Autoxidation refers to oxidations brought about by reactions with oxygen at normal temperatures, without the intervention of flame or electric spark. The term is usually used to describe the gradual degradation of organic compounds in air at ambient temperatures. Many common phenomena can be attributed to autoxidation, such as food going rancid, the 'drying' of varnishes and paints, and the perishing of rubber. It is also an important concept in both industrial chemistry and biology. Autoxidation is therefore a fairly broad term and can encompass examples of photooxygenation and catalytic oxidation.
Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by absorption of light or photons. It is defined as the interaction of one or more photons with one target molecule that dissociates into two fragments.
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.
In chemistry, a photoinitiator is a molecule that creates reactive species when exposed to radiation. Synthetic photoinitiators are key components in photopolymers.
Nitrogen trioxide or nitrate radical is an oxide of nitrogen with formula NO
3, consisting of three oxygen atoms covalently bound to a nitrogen atom. This highly unstable blue compound has not been isolated in pure form, but can be generated and observed as a short-lived component of gas, liquid, or solid systems.
Barbara J. Finlayson-Pitts is a Canadian-American atmospheric chemist. She is a professor in the chemistry department at the University of California, Irvine and is the Director of AirUCI Institute. Finlayson-Pitts and James N. Pitts, Jr. are the authors of Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications (1999). She has been a member of the National Academy of Sciences since 2006 and is the laureate for the 2017 Garvan–Olin Medal. In 2016 she co-chaired the National Academy of Science report "The Future of Atmospheric Chemistry Research"
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).
Jennifer G. Murphy is a Canadian environmental chemist and an associate professor at the University of Toronto. She is known for her research how air pollutants such as increased reactive nitrogen affect the global climate.
Iodine nitrate is a chemical with formula INO3. It is a covalent molecule with a structure of I–O–NO2.
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.