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Soot

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Emission of soot in the exhaust gas of a large diesel truck, without particle filters

Soot (/sʊt/ suut) is a mass of impure carbon particles resulting from the incomplete combustion of hydrocarbons.[1] Soot is considered a hazardous substance with carcinogenic properties.[2] Most broadly, the term includes all the particulate matter produced by this process, including black carbon and residual pyrolysed fuel particles such as coal, cenospheres, charred wood, and petroleum coke classified as cokes or char. It can include polycyclic aromatic hydrocarbons and heavy metals like mercury.[3]

Soot causes various types of cancer and lung disease.[4]

Terminology

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Definition

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Among scientists, exact definitions for soot vary, depending partly on their field.[5] For example, atmospheric scientists may use a different definition compared to toxicologists. Soot's definition can also vary across time, and from paper to paper even among scientists in the same field. A common feature of the definitions is that soot is composed largely of carbon based particles resulting from the incomplete burning of hydrocarbons or organic fuel such as wood. Some note that soot may be formed by other high temperature processes, not just by burning.[5] Soot typically takes an aerosol form when first created. It tends to eventually settle onto surfaces, though some parts of it may be decomposed while still airborne. In some definitions, soot is defined purely as carbonaceous particles, but in others it is defined to include the whole ensemble of particles resulting from partial combustion of organic matter or fossil fuels - as such it can include non carbon elements like sulphur and even traces of metal. In many definitions, soot is assumed to be black, but in some definitions it can be composed partly or even mainly of brown carbon, and so can also be medium or even light gray in colour.[5][6][7][8]

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Terms like "soot", "carbon black", and "black carbon" are often used to mean the same thing, even in the scientific literature, but other scientists have stated this is incorrect and that they refer to chemically and physically distinct things.[8][6][9]

Carbon black is a term for the industrial production of powdery carbonaceous matter which has been underway since the 19th century. Carbon black is composed almost entirely of elemental carbon. Carbon black is not found in regular soot - only in the special soot that is intentionally produced for its manufacture, mostly from specialised oil furnaces.[8][6]

Black carbon is a term that arose in the late twentieth century among atmospheric scientists, to describe strongly light absorbing carbonaceous particles which have a significant climate forcing affect - second only to CO2 itself as a contributor to short term global warming. The term is sometimes used synonymously with soot, but is now used preferentially in atmospheric science, though some prefer more precise terms like 'light-absorbing carbon'.[10] Unlike carbon black, black carbon is produced unintentionally. The chemical composition of black carbon is much more varied, and typically has a much lower proportion of elemental carbon, compared with carbon black.[8][6] In some definitions, black carbon also includes charcoal, a type of matter where the chunks tend to be too large to have an aerosol form as is the case with soot.[11]

Sources

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Soot as an airborne contaminant in the environment has many different sources, all of which are results of some form of pyrolysis. They include soot from coal burning, internal-combustion engines,[1] power-plant boilers, hog-fuel boilers, ship boilers, central steam-heat boilers, waste incineration, local field burning, house fires, forest fires, fireplaces, and furnaces. These exterior sources also contribute to the indoor environment sources such as smoking of plant matter, cooking, oil lamps, candles, quartz/halogen bulbs with settled dust, fireplaces, exhaust emissions from vehicles,[12] and defective furnaces. Soot in very low concentrations is capable of darkening surfaces or making particle agglomerates, such as those from ventilation systems, appear black. Soot is the primary cause of "ghosting", the discoloration of walls and ceilings or walls and flooring where they meet. It is generally responsible for the discoloration of the walls above baseboard electric heating units.

The formation and properties of soot depend strongly on the fuel composition, but may also be influenced by flame temperature.[13][14] Regarding fuel composition, the rank ordering of sooting tendency of fuel components is:[clarification needed] naphthalenesbenzenesaliphatics.[citation needed] However, the order of sooting tendencies of the aliphatics (alkanes, alkenes, and alkynes) varies dramatically depending on the flame type. The difference between the sooting tendencies of aliphatics and aromatics is thought to result mainly from the different routes of formation. Aliphatics appear to first form acetylene and polyacetylenes, which is a slow process; aromatics can form soot both by this route and also by a more direct pathway involving ring condensation or polymerization reactions building on the existing aromatic structure.[15][16]

Description

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The Intergovernmental Panel on Climate Change (IPCC) adopted the description of soot particles given in the glossary of Charlson and Heintzenberg (1995), "Particles formed during the quenching of gases at the outer edge of flames of organic vapours, consisting predominantly of carbon, with lesser amounts of oxygen and hydrogen present as carboxyl and phenolic groups and exhibiting an imperfect graphitic structure".[17]

Formation of soot is a complex process, an evolution of matter in which a number of molecules undergo many chemical and physical reactions within a few milliseconds.[1] Soot always contains nanoparticles of graphite and diamond, a phenomenon known as gemmy soot. Soot is a powder-like form of amorphous carbon. Gas-phase soot contains polycyclic aromatic hydrocarbons (PAHs).[1][18] The PAHs in soot are known mutagens[19] and are classified as a "known human carcinogen" by the International Agency for Research on Cancer (IARC).[20] Soot forms during incomplete combustion from precursor molecules such as acetylene. It consists of agglomerated nanoparticles with diameters between 6 and 30 nm. The soot particles can be mixed with metal oxides and with minerals and can be coated with sulfuric acid.[1][21]

Soot formation mechanism

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Many details of soot formation chemistry remain unanswered and controversial, but there have been a few agreements:[1]

  • Soot begins with some precursors or building blocks.
  • Nucleation of heavy molecules occurs to form particles.
  • Surface growth of a particle proceeds by adsorption of gas phase molecules.
  • Coagulation happens via reactive particle–particle collisions.
  • Oxidation of the molecules and soot particles reduces soot formation.

Hazards

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The black staining on the power car of this Midland Mainline InterCity 125 High Speed Train is the result of soot building up on the train's surface.

Soot, particularly diesel exhaust pollution, accounts for over one-quarter of the total hazardous pollution in the air.[12][22]

Among these diesel emission components, particulate matter has been a serious concern for human health due to its direct and broad impact on the respiratory organs. In earlier times, health professionals associated PM10 (diameter < 10 μm) with chronic lung disease, lung cancer, influenza, asthma, and increased mortality rate. However, recent scientific studies suggest that these correlations be more closely linked with fine particles (PM2.5) and ultra-fine particles (PM0.1).[1]

Long-term exposure to urban air pollution containing soot increases the risk of coronary artery disease.[23]

Diesel exhaust (DE) gas is a major contributor to combustion-derived particulate-matter air pollution.[12] In human experimental studies using an exposure chamber setup, DE has been linked to acute vascular dysfunction and increased thrombus formation.[24][25] This serves as a plausible mechanistic link between the previously described association between particulate matter air pollution and increased cardiovascular morbidity and mortality.

Soot also tends to form in chimneys in domestic houses possessing one or more fireplaces. If a large deposit collects in one, it can ignite and create a chimney fire. Regular cleaning by a chimney sweep should eliminate the problem.[26]

Soot modeling

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Soot mechanism is difficult to model mathematically because of the large number of primary components of diesel fuel, complex combustion mechanisms, and the heterogeneous interactions during soot formation.[1] Soot models are broadly categorized into three subgroups: empirical (equations that are adjusted to match experimental soot profiles), semi-empirical (combined mathematical equations and some empirical models which used for particle number density and soot volume and mass fraction), and detailed theoretical mechanisms (covers detailed chemical kinetics and physical models in all phases).[1]

First, empirical models use correlations of experimental data to predict trends in soot production. Empirical models are easy to implement and provide excellent correlations for a given set of operating conditions. However, empirical models cannot be used to investigate the underlying mechanisms of soot production. Therefore, these models are not flexible enough to handle changes in operating conditions. They are only useful for testing previously established designed experiments under specific conditions.[1]

Second, semi-empirical models solve rate equations that are calibrated using experimental data. Semi-empirical models reduce computational costs primarily by simplifying the chemistry in soot formation and oxidation. Semi-empirical models reduce the size of chemical mechanisms and use simpler molecules, such as acetylene as precursors.[1] Detailed theoretical models use extensive chemical mechanisms containing hundreds of chemical reactions in order to predict concentrations of soot. Detailed theoretical soot models contain all the components present in the soot formation with a high level of detailed chemical and physical processes.[1]

Finally, comprehensive models (detailed models) are usually expensive and slow to compute, as they are much more complex than empirical or semi-empirical models. Thanks to recent technological progress in computation, it has become more feasible to use detailed theoretical models and obtain more realistic results; however, further advancement of comprehensive theoretical models is limited by the accuracy of modeling of formation mechanisms.[1]

Additionally, phenomenological models have found wide use recently. Phenomenological soot models, which may be categorized as semi-empirical models, correlate empirically observed phenomena in a way that is consistent with the fundamental theory, but is not directly derived from the theory. These models use sub-models developed to describe the different processes (or phenomena) observed during the combustion process. Examples of sub-models of phenomenological empirical models include spray model, lift-off model, heat release model, ignition delay model, etc. These sub-models can be empirically developed from observation or by using basic physical and chemical relations. Phenomenological models are accurate for their relative simplicity. They are useful, especially when the accuracy of the model parameters is low. Unlike empirical models, phenomenological models are flexible enough to produce reasonable results when multiple operating conditions change.[1]

Applications

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Historically soot was used in manufacturing artistic paints and shoe polish, as well as a blackener for Russia leather for boots. With the advent of the printing press it was used in the printing ink well into the 20th century.[27]

See also

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References

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  1. ^ a b c d e f g h i j k l m n Omidvarborna; et al. (2015). "Recent studies on soot modeling for diesel combustion". Renewable and Sustainable Energy Reviews. 48: 635–647. Bibcode:2015RSERv..48..635O. doi:10.1016/j.rser.2015.04.019.
  2. ^ Kliment, Josef (2008). Carbon Black. Zlín: Czech Association of Industrial Chemistry. ISBN 978-80-02-02004-2.
  3. ^ "Black Carbon: A Deadly Air Pollutant". NoMorePlanet.com. 2020-09-13. Archived from the original on 2021-03-04. Retrieved 2020-11-01.
  4. ^
  5. ^ a b c Sipkens et all (2023). "Overview of methods to characterize the mass, size, and morphology of soot". Journal of Aerosol Science. 173. Bibcode:2023JAerS.17306211S. doi:10.1016/j.jaerosci.2023.106211.
  6. ^ a b c d Rituraj N, Kumar TA (2017). "The Toxicological Mechanisms of Environmental Soot (Black Carbon) and Carbon Black: Focus on Oxidative Stress and Inflammatory Pathways". Frontiers in Immunology. 8: 763. doi:10.3389/fimmu.2017.00763. PMC 5492873. PMID 28713383.
  7. ^ Petzold et all (2013). "Recommendations for reporting "black carbon" measurements". Atmospheric Chemistry and Physics. 13 (16): 8365–8379. Bibcode:2013ACP....13.8365P. doi:10.5194/acp-13-8365-2013. hdl:20.500.11850/71581.
  8. ^ a b c d Long CM, Nascarella MA, Valberg PA (2013). "Carbon black vs. black carbon and other airborne materials containing elemental carbon: physical and chemical distinctions". Environmental Pollution (journal). 181: 271–286. Bibcode:2013EPoll.181..271L. doi:10.1016/j.envpol.2013.06.009. PMID 23850403. the terms carbon black and soot have often been used interchangeably ... other terms like soot, elemental carbon, and graphitic carbon continue to be used synonymously with black carbon
  9. ^ Watson AY, Valberg PA (2001). "Carbon black and soot: two different substances". Journal of Occupational and Environmental Hygiene. 62 (2): 218–228. doi:10.1080/15298660108984625. PMID 11331994.
  10. ^ Tami Bond; Robert W. Bergstrom (2020-09-13). "Light Absorption by Carbonaceous Particles: An Investigative Review". Aerosol Science and Technology. 40: 27–67. doi:10.1080/02786820500421521.
  11. ^ Burke M, Marín-Spiotta E, Ponette-González AG (2024). "Black carbon in urban soils: land use and climate drive variation at the surface". Carbon Balance and Management. 9 (1): 9. Bibcode:2024CarBM..19....9B. doi:10.1186/s13021-024-00255-3. PMC 10908174. PMID 38429441.
  12. ^ a b c Omidvarborna; et al. (2014). "Characterization of particulate matter emitted from transit buses fueled with B20 in idle modes". Journal of Environmental Chemical Engineering. 2 (4): 2335–2342. doi:10.1016/j.jece.2014.09.020.
  13. ^ Seinfeld, John H.; Pandis, Spyros N. (2006). Atmospheric Chemistry and Physics : From Air Pollution to Climate Change (2nd ed.). John Wiley & Sons. ISBN 0-471-72018-6.
  14. ^ Alfè, M.; Apicella, B.; Rouzaud, J.-N.; Tregrossi, A.; Ciajolo, A. (October 2010). "The effect of temperature on soot properties in premixed methane flames". Combustion and Flame. 157 (10): 1959–1965. Bibcode:2010CoFl..157.1959A. doi:10.1016/j.combustflame.2010.02.007.
  15. ^ Graham, S. C.; Homer, J. B.; Rosenfeld, J. L. J. (1975). "The formation and coagulation of soot aerosols generated in pyrolysis of aromatic hydrocarbons". Proc. R. Soc. Lond. A. 344: 259–285. doi:10.1098/rspa.1975.0101. JSTOR 78961. S2CID 96742040.
  16. ^ Flagan, R. C.; Seinfeld, J. H. (1988). Fundamentals of Air Pollution Engineering. Englewood Cliffs, NJ: Prentice-Hall. ISBN 0-13-332537-7.
  17. ^ Charlson, R. J.; Heintzenberg, J., eds. (1995). Aerosol Forcing of Climate. New York, NY: John Wiley & Sons. p. 406. ISBN 0-471-95693-7.
  18. ^ Rundel, Ruthann, "Polycyclic Aromatic Hydrocarbons, Phthalates, and Phenols", in Indoor Air Quality Handbook, John Spengleer, Jonathan M. Samet, John F. McCarthy (eds), pp. 34.1-34.2, 2001
  19. ^ Rundel, Ruthann, "Polycyclic Aromatic Hydrocarbons, Phthalates, and Phenols", in Indoor Air Quality Handbook, John Spengleer, Jonathan M. Samet, John F. McCarthy (eds), pp. 34.18-34.21, 2001
  20. ^ "Soots (IARC Summary & Evaluation, Volume 35, 1985)". Inchem.org. 1998-04-20. Retrieved 2013-12-04.
  21. ^ Niessner, R. (2014). "The Many Faces of Soot: Characterization of Soot Nanoparticles Produced by Engines". Angew. Chem. Int. Ed. 53 (46): 12366–12379. doi:10.1002/anie.201402812. PMID 25196472.
  22. ^ "Health Concerns Associated with Excessive Idling". Nctcog.org. Archived from the original on 2014-01-16. Retrieved 2013-12-04.
  23. ^ "Long-Term Exposure to Air Pollution and Incidence of Cardiovascular Events in Women" Archived 2007-02-02 at the Wayback Machine Kristin A. Miller, David S. Siscovick, Lianne Sheppard, Kristen Shepherd, Jeffrey H. Sullivan, Garnet L. Anderson, and Joel D. Kaufman, in New England Journal of Medicine February 1, 2007
  24. ^ Lucking, Andrew J.; et al. (2008). "Diesel exhaust inhalation increases thrombus formation in man". European Heart Journal. 29 (24): 3043–3051. doi:10.1093/eurheartj/ehn464. PMID 18952612.
  25. ^ Törnqvist, Håkan; et al. (2007). "Persistent Endothelial Dysfunction in Humans after Diesel Exhaust Inhalation". American Journal of Respiratory and Critical Care Medicine. 176 (4): 395–400. doi:10.1164/rccm.200606-872OC. PMID 17446340.
  26. ^ "Gr8fires". gr8fires.co.uk. 2015-02-22.
  27. ^ Surmiński, Janusz, "Węglarstwo leśne – sadza i potaż", Sylwan vol. 154 (3), 2010, pp. 182−186 (pdf file: www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=&cad=rja&uact=8&ved=2ahUKEwjD_-mOqOCCAxWzKEQIHc-7BIIQFnoECBcQAQ&url=https%3A%2F%2Fsummer-heart-0930.chufeiyun1688.workers.dev%3A443%2Fhttps%2Fbibliotekanauki.pl%2Farticles%2F1009503.pdf&usg=AOvVaw0K6o-KjiJN4ULbJqxQdDNx&opi=89978449)
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