carbonyl sulfide

Carbonyl sulfide is the most abundant sulfur compound naturally present in the atmosphere, at {{val|0.5|0.05|ul=ppb}}, because it is emitted from oceans, volcanoes and deep sea vents. As such, it is a significant compound in the global sulfur cycle. Measurements on the Antarctica ice cores and from air trapped in snow above glaciers (firn air) have provided a detailed picture of OCS concentrations from 1640 to the present day and allow an understanding of the relative importance of anthropogenic and non-anthropogenic sources of this gas to the atmosphere.{{cite journal | last1 = Montzka | first1 = S. A. | last2 = Aydin | first2 = M. | last3 = Battle | first3 = M. | last4 = Butler | first4 = J. H. | last5 = Saltzman | first5 = E. S. | last6 = Hall | first6 = B. D. | last7 = Clarke | first7 = A. D. | last8 = Mondeel | first8 = D. | last9 = Elkins | first9 = J. W. | title = A 350-year atmospheric history for carbonyl sulfide inferred from Antarctic firn air and air trapped in ice | year = 2004 | journal = Journal of Geophysical Research | volume = 109 | issue = D18 | pages = 22302 | id = eid D22302 | doi = 10.1029/2004JD004686 | bibcode = 2004JGRD..10922302M | s2cid = 1261238 | url = https://escholarship.org/content/qt17j6m436/qt17j6m436.pdf?t=n6lm7g }} Some carbonyl sulfide that is transported into the stratospheric sulfate layer is oxidized to sulfuric acid.{{cite journal | title = The possible importance of COS for the sulfate layer of the stratosphere | author-link = Paul Crutzen | author = Crutzen, P. | journal = Geophysical Research Letters | year = 1976 | volume = 3 | issue = 2 | pages = 73–76 | doi = 10.1029/GL003i002p00073 | bibcode = 1976GeoRL...3...73C }} Sulfuric acid forms particulate which affects energy balance due to light scattering.{{cite book | last = Seinfeld | first = J. | title = Atmospheric Chemistry and Physics | publisher = J. Wiley | location = London | year = 2006 | isbn = 978-1-60119-595-1 }} The long atmospheric lifetime of COS makes it the major source of stratospheric sulfate, though sulfur dioxide from volcanic activity can be significant too. Carbonyl sulfide is also removed from the atmosphere by terrestrial vegetation by enzymes associated with the uptake of carbon dioxide during photosynthesis, and by hydrolysis in ocean waters.{{cite journal | last1 = Campbell | first1 = J. E. | last2 = Carmichael | first2 = G. R. | last3 = Chai | first3 = T. | last4 = Mena-Carrasco | first4 = M. | last5 = Tang | first5 = Y. | last6 = Blake | first6 = D. R. | last7 = Blake | first7 = N. J. | last8 = Vay | first8 = S. A. | last9 = Collatz | first9 = G. J. | last10 = Baker | first10 = I. | last11 = Berry | first11 = J. A. | last12 = Montzka | first12 = S. A. | last13 = Sweeney | first13 = C. | last14 = Schnoor | first14 = J. L. | last15 = Stanier | first15 = C. O. | title = Photosynthetic Control of Atmospheric Carbonyl Sulfide During the Growing Season | journal = Science | year = 2008| volume = 322 | issue = 5904 | pages = 1085–1088 | doi = 10.1126/science.1164015 | pmid = 19008442 | bibcode = 2008Sci...322.1085C| s2cid = 206515456 | url = http://www.escholarship.org/uc/item/82r9s2x3 }}{{cite journal | last1 = Kettle | first1 = A. J. | last2 = Kuhn | first2 = U. | last3 = von Hobe | first3 = M. | last4 = Kesselmeier | first4 = J. | last5 = Andreae | first5 = M. O. | title = Global budget of atmospheric carbonyl sulfide: Temporal and spatial variations of the dominant sources and sinks | journal = Journal of Geophysical Research | year = 2002 | volume = 107 | issue = D22 | pages = 4658 | doi = 10.1029/2002JD002187 | bibcode = 2002JGRD..107.4658K | doi-access = free }}{{cite journal | last1 = Montzka | first1 = S. A. | last2 = Calvert | first2 = P. | last3 = Hall | first3 = B. D. | last4 = Elkins | first4 = J. W. | last5 = Conway | first5 = T. J. | last6 = Tans | first6 = P. P. | last7 = Sweeney | first7 = C. | year = 2007 | title = On the global distribution, seasonality, and budget of atmospheric carbonyl sulfide (COS) and some similarities to CO₂ | journal = Journal of Geophysical Research | volume = 112 | issue = D9 | id = eid D09302 | pages = 9302 | doi = 10.1029/2006JD007665 | bibcode = 2007JGRD..112.9302M }} Loss processes, such as these, limit the persistence (or lifetime) of a molecule of COS in the atmosphere to a few years.

The largest man-made sources of carbonyl sulfide release include its primary use as a chemical intermediate and as a byproduct of carbon disulfide production; however, it is also released from automobiles and their tire wear,{{cite journal | vauthors = Pos W, Berreshein B| title = Automotive tire wear as a source for atmospheric OCS and CS2 | journal = Geophysical Research Letters| year = 1993 | volume = 1 | issue = 9 | pages = 815–818 | doi = 10.1029/93GL00972 |bibcode = 1993GeoRL..20..815P }} coal-fired power plants, coking ovens, biomass combustion, fish processing, combustion of refuse and plastics, petroleum manufacture, and manufacture of synthetic fibers, starch, and rubber.{{cite web | url = http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@DOCNO+6127 | title = Carbonyl Sulfide CASRN: 463-58-1 | work = Hazardous Substances Data Bank | publisher = National Library of Medicine }} The average total worldwide release of carbonyl sulfide to the atmosphere has been estimated{{when|date=August 2021}} at about 3 million tons per year, of which less than one third was related to human activity. It is also a significant sulfur-containing impurity in many fuel gases such as synthesis gas, which are produced from sulfur-containing feedstocks.{{cite book |doi=10.1002/14356007.a12_169.pub2|chapter=Gas Production |title=Ullmann's Encyclopedia of Industrial Chemistry |year=2006 |last1=Hiller |first1=Heinz |last2=Reimert |first2=Rainer |last3=Marschner |first3=Friedemann |last4=Renner |first4=Hans-Joachim |last5=Boll |first5=Walter |last6=Supp |first6=Emil |last7=Brejc |first7=Miron |last8=Liebner |first8=Waldemar |last9=Schaub |first9=Georg |last10=Hochgesand |first10=Gerhard |last11=Higman |first11=Christopher |last12=Kalteier |first12=Peter |last13=Müller |first13=Wolf-Dieter |last14=Kriebel |first14=Manfred |last15=Schlichting |first15=Holger |last16=Tanz |first16=Heiner |last17=Stönner |first17=Hans-Martin |last18=Klein |first18=Helmut |last19=Hilsebein |first19=Wolfgang |last20=Gronemann |first20=Veronika |last21=Zwiefelhofer |first21=Uwe |last22=Albrecht |first22=Johannes |last23=Cowper |first23=Christopher J. |last24=Driesen |first24=Hans Erhard |isbn=3527306730 }}

Carbonyl sulfide is present in foodstuffs, such as cheese and prepared vegetables of the cabbage family. Traces of COS are naturally present in grains and seeds in the range of 0.05–0.1 mg/kg.

Carbonyl sulfide has been observed in the interstellar medium (see also List of molecules in interstellar space), in comet 67P{{cite web|last1=Rosetta Blog|title=OMET'S FIREWORK DISPLAY AHEAD OF PERIHELION|url=http://blogs.esa.int/rosetta/2015/08/11/comets-firework-display-ahead-of-perihelion/|website=blogs.esa.int |publisher=European Space Agency|access-date=11 August 2015}} and in the atmosphere of Venus, where, because of the difficulty of producing COS inorganically, it is considered a possible indicator of life.{{cite journal | title = Astrobiology: the Case for Venus | last = Landis | first = G. A. | journal = Journal of the British Interplanetary Society | volume = 56 | issue = 7–8 | year = 2003 | pages = 250–254 | url = https://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/20030067857_2003079552.pdf |bibcode = 2003JBIS...56..250L }}

Carbonyl sulfide is used as an intermediate in the production of thiocarbamate herbicides.{{cite web | url = http://www.epa.gov/chemfact/s_carbns.txt | title = Chemical Summary for Carbonyl Sulfide | date = 2013-07-19 | publisher = U.S. Environmental Protection Agency }}

The hydrolysis of carbonyl sulfide is promoted by chromium-based catalysts:

:{{chem2|COS + H2O -> CO2 + H2S}}

This conversion is catalyzed in solution by carbonic anhydrase enzymes in plants and mammals. Because of this chemistry, the release of carbonyl sulfide from small organic molecules has been identified as a strategy for delivering hydrogen sulfide, which is gaseous signaling molecule.{{Cite journal |last1=Steiger |first1=Andrea K. |last2=Pardue |first2=Sibile |last3=Kevil |first3=Christopher G. |last4=Pluth |first4=Michael D. |date=2016-06-15 |title=Self-Immolative Thiocarbamates Provide Access to Triggered H₂S Donors and Analyte Replacement Fluorescent Probes |journal=Journal of the American Chemical Society |volume=138 |issue=23 |pages=7256–7259 |doi=10.1021/jacs.6b03780 |issn=0002-7863 |pmc=4911618 |pmid=27218691}}{{cite journal | last1 = Protoschill-Krebs | first1 = G. | last2 = Wilhelm | first2 = C. | last3 = Kesselmeier | first3 = J. | title = Consumption of carbonyl sulphide (COS) by higher plant carbonic anhydrase (CA) | journal = Atmospheric Environment | year = 1996 | volume = 30 | issue = 18 | pages = 3151–3156 | doi = 10.1016/1352-2310(96)00026-X |bibcode = 1996AtmEn..30.3151P }}

This compound is found to catalyze the formation of peptides from amino acids. This finding is an extension of the Miller–Urey experiment, and it is suggested that carbonyl sulfide played a significant role in the origin of life.{{cite journal |author1=Leman, L. |author2=Orgel, L. |author3=Ghadiri, M. R. |title=Carbonyl sulfide-mediated prebiotic formation of peptides |journal=Science |volume=306 |issue=5694 |pages=283–6 |year=2004 |pmid=15472077 |doi=10.1126/science.1102722 |bibcode = 2004Sci...306..283L |s2cid=11819295 }}

In ecosystem science, {{youtube|dbW236IDELo|What Carbonyl Sulfide Teaches Us About Earth's Biosphere}}. are increasingly being used to describe the rate of photosynthesis.{{Cite journal |last1=Campbell |first1=J. E. |last2=Berry |first2=J. A. |last3=Seibt |first3=U. |last4=Smith |first4=S. J. |last5=Montzka |first5=S. A. |last6=Launois |first6=T. |last7=Belviso |first7=S. |last8=Bopp |first8=L. |last9=Laine |first9=M. |date=April 2017 |title=Large historical growth in global terrestrial gross primary production |journal=Nature |volume=544 |issue=7648 |pages=84–87 |doi=10.1038/nature22030 |pmid=28382993 |bibcode=2017Natur.544...84C |osti=1398774 |s2cid=205255121}}{{Cite journal |last1=Yakir |first1=Dan |last2=Montzka |first2=Stephen A. |last3=Uri Dicken |last4=Tatarinov |first4=Fyodor |last5=Rotenberg |first5=Eyal |last6=Asaf |first6=David |date=March 2013 |title=Ecosystem photosynthesis inferred from measurements of carbonyl sulphide flux |journal=Nature Geoscience |volume=6 |issue=3 |pages=186–190 |doi=10.1038/ngeo1730 |bibcode=2013NatGe...6..186A |issn=1752-0908}}

Carbonyl sulfide was first described in 1841,{{cite journal | author = Couërbe, J. P. | title = Ueber den Schwefelkohlenstoff | journal = Journal für Praktische Chemie | year = 1841 | volume = 23 | issue = 1 | pages = 83–124 | doi = 10.1002/prac.18410230105 }} but was apparently mischaracterized as a mixture of carbon dioxide and hydrogen sulfide. Carl von Than first characterized the substance in 1867. It forms when carbon monoxide reacts with molten sulfur:

: {{chem2|CO +}} {{sfrac|1|8}} {{chem2|S8 -> COS}}

This reaction reverses above {{convert|1200|K|comma=off}}.

A laboratory synthesis entails the reaction potassium thiocyanate and sulfuric acid:

: {{chem2|KSCN + 2 H2SO4 + H2O → KHSO4 + NH4HSO4 + COS}}

The resulting gas contains significant amounts of byproducts and requires purification.{{cite journal | title = The Chemistry of Carbonyl Sulfide | author = Ferm R. J. | journal = Chemical Reviews | year = 1957 | volume = 57 | issue = 4 | pages = 621–640 | doi = 10.1021/cr50016a002 }}

Hydrolysis of isothiocyanates in hydrochloric acid solution also affords COS.

Carbonyl Sulfide has the "rotten egg" odor characteristic of sulfides, although some sources suggest that the associated odor is due to impurities, and not present in the pure compound.CDC, Hydrogen Sulfide and Carbonyl Sulfide, [https://www.atsdr.cdc.gov/toxprofiles/tp114-c4.pdf 4. Chemical and Physical Information], p. 139. Retrieved 20 April 2025. The detectability threshold is estimated at 135µg/m$^3$.

As of 1994, limited information existed on the acute toxicity of carbonyl sulfide in humans and in animals. High concentrations (above 1000 ppm) can cause sudden collapse, convulsions, and death from respiratory paralysis. Occasional fatalities have been reported, practically without local irritation or olfactory warning. In tests with rats, 50% animals died when exposed to {{val|1400|u=ppm}} of COS for 90 minutes, or at {{val|3000|u=ppm}} for 9 minutes. Limited studies with laboratory animals also suggest that continued inhalation of low concentrations (around 50 ppm for up to 12 weeks) does not affect the lungs or the heart.

Carbonyl sulfide is a potential alternative fumigant{{Cite journal|last1=Bartholomaeus|first1=Andrew|last2=Haritos|first2=Victoria|year=2005|title=Review of the toxicology of carbonyl sulfide, a new grain fumigant|journal=Food and Chemical Toxicology|volume=43|issue=12|pages=1687–1701|doi=10.1016/j.fct.2005.06.016|pmid=16139940}} to methyl bromide and phosphine. In some cases, however, residues on the grain result in flavours that are unacceptable to consumers, such as in barley used for brewing.

{{reflist|30em}}

• {{cite journal | title = COS and C₃S₂: The Discovery and Chemistry of Two Important Inorganic Sulfur Compounds |author1=Beck, M. T. |author2=Kauffman, G. B. | journal = Polyhedron | year = 1985 | volume = 4 | issue = 5 | pages = 775–781 | doi = 10.1016/S0277-5387(00)87025-4 }}
• {{cite journal | title = Assessing a New Clue to How Much Carbon Plants Take Up

|author1=J. Elliott Campbell

|author2= Jürgen Kesselmeier

|author3= Dan Yakir

|author4= Joe A. Berry

|author5= Philippe Peylin

|author6= Sauveur Belviso

|author7= Timo Vesala

|author8= Kadmiel Maseyk

|author9= Ulrike Seibt

|author10= Huilin Chen

|author11= Mary E. Whelan

|author12= Timothy W. Hilton

|author13= Stephen A. Montzka

|author14= Max B. Berkelhammer

|author15= Sinikka T. Lennartz

|author16= Le Kuai

|author17= Georg Wohlfahrt

|author18= Yuting Wang

|author19= Nicola J. Blake

|author20= Donald R. Blake

|author21= James Stinecipher

|author22= Ian Baker

|author23= Stephen Sitch

| journal = EOS| year = 2017| volume = 98 | doi = 10.1029/2017EO075313 |doi-access= free

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• {{cite journal | title = Carbonyl sulfide: A review of its chemistry and properties |author1=Svoronos P. D. N. |author2=Bruno T. J. | journal = Industrial & Engineering Chemistry Research | year = 2002 | volume = 41 | issue = 22 | pages = 5321–5336 | doi = 10.1021/ie020365n }}

• [http://www.scripps.edu/newsandviews/e_20041011/ghadiri.html Carbonyl sulfide and origins of life]
• [http://mbao.org/altmet00/86wright.pdf Carbonyl sulfide as a potential fumigant]
• [https://web.archive.org/web/20060529015001/http://amsglossary.allenpress.com/glossary/search?id=carbonyl-sulfide1 Carbonyl sulfide in the atmosphere]

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Category:Inorganic carbon compounds

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Category:Oxides

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