Atmospheric organic hazes are common in planetary bodies in our solar system and likely exoplanet atmospheres as well. In addition, geochemical data support the existence of an organic haze in the early Earth's atmosphere. Much of what is known about organic haze formation derives from studies of Saturn's moon Titan. It is believed that on Titan ions play an important role in haze formation. It is possible, by using Titan as an analog for the Archean Earth, to consider that an Archean haze could have formed by similar processes. Here, we examine the anion chemistry that occurs during laboratory simulations of early Earth haze formation and measure the composition of gaseous anions as a function of O2 mixing ratio. Gaseous anion composition and relative abundances are measured by an atmospheric pressure interface time-of-flight mass spectrometer and are compared to previous photochemical haze mass loading measurements. Numerous anions are observed spanning from mass-to-charge ratio 26 to 246, with a majority of the identified anions containing carbon, hydrogen, nitrogen, and/or oxygen. A shift in the anion composition occurs with increasing the precursor O2 mixing ratio. With 0–20 ppmv O2 in CH4/CO2/N2 mixtures, ions contain mostly organic nitrogen, with CNO− being the most intense ion peak. As the precursor O2 is increased to 200 and 2000 ppmv, inorganic nitrogen ions become the dominant chemical group, with NO3− having the most intense ion signal. The clear shift in the ionic composition could be indicative of a modification to the gas-phase chemistry that occurs in the transition from an anoxic atmosphere to an oxygen-containing atmosphere, with potential astrobiological significance.
Get full access to this article
View all access options for this article.
References
1.
AndersonJ.G., MargitanJ.J., and KaufmanF. (1974) Gas phase recombination of OH with NO and NO2. J Chem Phys, 60:3310–3317.
2.
ArneyG., Domagal-GoldmanS.D., MeadowsV.S., WolfE.T., SchwietermanE., CharnayB., ClaireM., HébrardE., and TrainerM.G. (2016) The pale orange dot: the spectrum and habitability of hazy Archean Earth. Astrobiology, 16:873–899.
3.
ArnoldI. and ComesF.J.Temperature dependence of the reactions O(3P) + O3 → 2O2 and O(3P) + O2 + M → O3 + M. Chem Phys, 42:231–239.
4.
AtakanB., KocisD., WolfrumJ., and NelsonP. (1992) Direct investigations of the kinetics of the reactions of CN radicals with N atoms and 3CH2 radicals with NO. 24th Symp Int Combustion, 24:691–699.
5.
BarnesI., SolignacG., MelloukiA., and BeckerK.H. (2010) Aspects of the atmospheric chemistry of amides. ChemPhysChem, 11:3844–3857.
6.
BeaumontV. and RobertF. (1999) Nitrogen isotope ratios of kerogens in Precambrian cherts: a record of the evolution of atmosphere chemistry?. Precambrian Res, 96:63–82.
7.
BerryJ.L., UgelowM.S., TolbertM.A., and BrowneE.C. (2019a) Chemical composition of gas phase positive ions during laboratory simulations of Titan's haze formation. ACS Earth Space Chem, 3:202–211.
8.
BerryJ.L., UgelowM.S., TolbertM.A., and BrowneE.C. (2019b) The influence of gas-phase chemistry on organic haze formation. Astrophys J Lett, 885:L6.
9.
BorduasN., AbbattJ.P.D., and MurphyJ.G. (2013) Gas phase oxidation of monoethanolamine (MEA) with OH radical and ozone: kinetics, products, and particles. Environ Sci Technol, 47:6377–6383.
10.
BorduasN., da SilvaG., MurphyJ.G., and AbbattJ.P.D. (2015) Experimental and theoretical understanding of the gas phase oxidation of atmospheric amides with OH radicals: kinetics, products, and mechanisms. J Phys Chem A, 119:4298–4308.
11.
BunkanA.J., MikovinyT., NielsenC.J., WisthalerA., and ZhuL. (2016) Experimental and theoretical study of the OH-initiated photo-oxidation of formamide. J Phys Chem A, 120:1222–1230.
12.
CableM.L., HörstS.M., HeC., StocktonA.M., MoraM.F., TolbertM.A., SmithM.A., and WillisP.A. (2014) Identification of primary amines in Titan tholins using microchip nonaqueous capillary electrophoresis. Earth Planet Sci Lett, 403:99–107.
13.
CoatesA.J., CraryF.J., LewisG.R., YoungD.T., WaiteJ.H.Jr., and SittlerE.C.Jr. (2007) Discovery of heavy negative ions in Titan's ionosphere. Geophys Res Lett, 34:L22103.
14.
CoatesA.J., WellbrockA., LewisG.R., JonesG.H., YoungD.T., CraryF.J., WaiteJ.H., JohnsonR.E., HilleT.W., and Sittler, JrE.C. (2010) Negative ions at Titan and Enceladus: recent results. Faraday Discuss, 147:293–305, discussion 379–403.
15.
CoustenisA., AchterbergR.K., ConrathB.J., JenningsD.E., MartenA., GautierD., NixonC.A., FlasarF.M., TeanbyN.A., BezardB., SamuelsonR.E., CarlsonR.C., LellouchE., BjorakerG.L., RomaniP.N., TaylorF.W., IrwinP.G.J., FouchetT., HubertA., OrtonG.S., KundeV.G., VinatierS., MondelliniJ., AbbasM.M., and CourtinR. (2007) The composition of Titan's stratosphere from Cassini/CIRS mid-infrared spectra. Icarus, 189:35–62.
16.
CoustenisA., JenningsD.E., NixonC.A., AchterbergR.K., LavvasP., VinatierS., TeanbyN.A., BjorakerG.L., CarlsonR.C., PianiL., BampasidisG., FlasarF.M., and RomaniP.N. (2010) Titan trace gaseous composition from CIRS at the end of the Cassini-Huygens prime mission. Icarus, 207:461–476.
17.
CroweS.A., DøssingL.N., BeukesN.J., BauM., KrugerS.J., FreiR., and CanfieldD.E. (2013) Atmospheric oxygenation three billion years ago. Nature, 501:535–539.
18.
CubisonM.J. and JimenezJ.L. (2015) Statistical precision of the intensities retrieved from constrained fitting of overlapping peaks in high-resolution mass spectra. Atmos Meas Tech, 8:2333–2345.
DemingB., PagonisD., LiuX., DayD., TalukdarR., KrechmerJ., de GouwJ. A., JimenezJ. L., and ZiemannP. J. (2019) Measurements of delays of gas-phase compounds in a wide variety of tubing materials due to gas-wall interactions. Atmos Meas Tech, 12:3453–3461.
21.
DeWittH.L., TrainerM.G., PavlovA.A., HasenkopfC.A., AikenA.C., JimenezJ.L., McKayC.P., ToonO.B., and TolbertM.A. (2009) Reduction in haze formation rate on prebiotic Earth in the presence of hydrogen. Astrobiology, 9:447–453.
22.
DodonovaN.Y. (1966) Activation of nitrogen by vacuum ultraviolet radiation. Russ J Phys Chem, 40:523–524.
23.
Domagal-GoldmanS.D., KastingJ.F., JohnstonD.T., and FarquharJ. (2008) Organic haze, glaciations and multiple sulfur isotopes in the Mid-Archean Era. Earth Planet Sci Lett, 269:29–40.
24.
DuaS. and BowieJ.H. (2003) Formation of cyanate (OCN) and fulminate (ONC) radicals from anionic precursors in the gas phase: a joint experimental and theoretical study. J Phys Chem A, 107:76–82.
25.
DucluzeauA.L., van LisR., DuvalS., Schoepp-CothenetB., RussellM.J., and NitschkeW. (2009) Was nitric oxide the first deep electron sink?. Trends Biochem Sci, 34:9–15.
26.
FerrisJ.P., SanchezR.A., and OrgelL.E. (1968) Studies in prebiotic synthesis iii. synthesis of pyrimidines from cyanoacetylene and cyanate. J Mol Biol, 33:693–704.
27.
FleuryB., CarrascoN., GautierT., MahjoubA., HeJ., SzopaC., HadamcikE., BuchA., and CernogoraG. (2014) Influence of CO on Titan atmospheric reactivity. Icarus, 238:221–229.
28.
FleuryB., CarrascoN., MillanM., VettierL., and SzopaC. (2017) Organic chemistry in a CO2 rich early Earth atmosphere. Earth Planet Sci Lett, 479:34–42.
29.
GansB., Boyé-PéronneS., BroquierM., DelsautM., DouinS., FellowsC.E., HalvickP., LoisonJ.-C., LuccheseR.R., and GauyacqD. (2011) Photolysis of methane revisited at 121.6 nm and at 118.2 nm: quantum yields of the primary products, measured by mass spectrometry. Phys Chem Chem Phys, 13:8140–8152.
30.
GansB., PengZ., CarrascoN., GauyacqD., LebonnoisS., and PernotP. (2013) Impact of a new wavelength-dependent representation of methane photolysisbranching ratios on the modeling of Titan's atmospheric photochemistry. Icarus, 223:330–343.
31.
GautierT., SebeeJ.A., LiX., PinnickV.T., GrubisicA., LoefflerM.J., GettyS.A., TrainerM.G., and BrinckerhoffW.B. (2017) Influence of trace aromatics on the chemical growth mechanisms of Titan aerosol analogues. Planet Space Sci, 140:27–34.
32.
GoldblattC., LentonT.M., and WatsonA.J. (2006) Bistability of atmospheric oxygen and the Great Oxidation. Nature, 443:683–686.
33.
GuptaP.K., SinghK., DixitC.K., SinghN., SharmaC., SahaiS., JhaA.K., SinghD.P., TiwariM.K., and GargS.C. (2007) Spatial distribution in aerosol mass and size characteristics between Delhi and Hyderabad during land campaign in February 2004. Indian J Radio Space, 36:576–581.
34.
GuptaS., OchiaiE., and PonnamperumaC. (1981) Organic synthesis in the atmosphere of Titan. Nature, 293:725–727.
35.
HampsonJr., R.F. and GarvinD. (1975) Chemical kinetic & photochemical data for modelling atmospheric chemistry. Nat Bureau Stand Note. 866.
36.
HancockG. and HealM.R. (1992) Temperature dependences of CH2 (ã1A1) removal rates by Ar, NO, H2, and CH2CO in the range 295–859 K. J Phys Chem, 96:10316–10322.
37.
Haqq-MisraJ.D., Domagal-GoldmanS.D., KastingP.J., and KastingJ.F. (2008) A revised, hazy methane greenhouse for the Archean Earth. Astrobiology, 8:1127–1137.
38.
HasenkopfC.A., BeaverM.R., TrainerM.G., DewittH.L., FreedmanM.A., ToonO.B., McKayC.P., and TolbertM.A. (2010) Optical properties of Titan and early Earth haze laboratory analogs in the mid-visible. Icarus, 207:903–913.
39.
HeC., HörstS.M., RiemerS., SebreeJ.A., PauleyN., and VuittonV. (2017) Carbon monoxide affecting planetary atmospheric chemistry. Astrophys J Lett, 841:L31.
40.
HeC., HörstS.M., LewisN.K., MosesJ.L., KemptonE.M.-R., MarleyM.S., MorleyC.V., ValentiJ.A., and VuittonV. (2019) Gas phase chemistry of cool exoplanet atmospheres: insight from laboratory simulations. ACS Earth Space Chem, 3:39–50.
41.
HeinritziM., SimonM., SteinerG., WagnerA.C., KürtenA., HanselA., and CurtiusJ. (2016) Characterization of the mass-dependent transmission efficiency of a CIMS. Atmos Meas Tech, 9:1449–1460.
42.
HicksR.K., DayD.A., JimenezJ.L., and TolbertM.A. (2015) Elemental analysis of complex organic aerosol using isotopic labeling and unit-resolution mass spectrometry. Anal Chem, 87:2741–2747.
43.
HicksR.K., DayD.A., JimenezJ.L., and TolbertM.A. (2016) Follow the carbon: isotopic labeling studies of early Earth aerosol. Astrobiology, 87:822–830.
44.
HollandH. (2006) The oxygenation of the atmosphere and oceans. Phil Trans R Soc B, 361:903–915.
45.
HörstS.M., HeC., UgelowM.S., JellinekA.M., PierrehumbertR.T., and TolbertM.A. (2018a) Exploring the atmosphere of Neoproterozoic Earth: the effect of O2 on haze formation and composition. Astrophys J, 858:119.
46.
HörstS.M., YoonY.H., UgelowM.S., ParkerA.H., LiR., de GouwJ.A., and TolbertM.A. (2018b) Laboratory investigations of Titan haze formation: in situ measurement of gas and particle composition. Icarus, 301:136–151.
47.
HowardC.J. and EvensonK.M. (1974) Laser magnetic resonance study of the gas phase reactions of OH with CO, NO, and NO2. J Chem Phys, 61:1943–1952.
48.
ImanakaH. and SmithM.A. (2010) Formation of nitrogenated organic aerosols in the Titan upper atmosphere. PNAS, 107:12423–12428.
49.
IzonG., ZerkleA.L., ZhelezinskaiaI., FarquharJ., NewtonR.J., PoultonS.W., EigenbrodeJ.L., and ClaireM.W. (2015) Multiple oscillations in Neoarchaean atmospheric chemistry. Earth and Planet Sci Lett, 431:264–273.
JunkerC., SheahanJ.N., JenningsS.G., O'BrienP., HindsB.D., Martinez-TwaryE., HansenA.D.A., WhiteC., GarveyD.M., and PinnickR.G. (2004) Measurement and analysis of aerosol and black carbon in the southwestern United States and Panama and their dependence on air mass origin. J Geophys Res, 109:D13201.
52.
JunninenH., EhnM., PetäjäT., LuosujarviL., KotiahoT., KostiainenR., RohnerU., GoninM., FuhrerK., KulmalaM., and WorsnopD.R. (2010) A high-resolution mass spectrometer to measure atmospheric ion composition. Atmos Meas Tech, 3:1039–1053.
53.
KastingJ.F. (1990) Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere. Origins Life Evol Biosph, 20:199–231.
54.
KastingJ.F. (1993) Earth's early atmosphere. Science, 259:920–926.
55.
KastingJ.F. and WalkerJ.C.G. (1981) Limits on oxygen concentrations in the prebiological atmosphere and the rate of abiotic fixation of nitrogen. J Geophys Res, 86:1147–1158.
56.
KastingJ.F., ZahnleK., PintoJ., and YoungA. (1989) Sulfur, ultraviolet radiation, and the early evolution of life. Orig Life Evol Biosph, 19:98–108.
57.
KastingJ.F., PavlovA.A., and SiefertJ.L. (2001) A coupled ecosystem-climate model for predicting the methane concentration in the Archean atmosphere. Orig Life Evol Biosphere, 31:271–286.
58.
KumpL.R. (2008) The rise of atmospheric oxygen. Nature, 451:277–278.
59.
KurzweilF., ClaireM., ThomazoC., PetersM., HanningtonM., and StraussH. (2013) Atmospheric sulfur rearrangement 2.7 billion years ago: evidence for oxygenic photosynthesis. Earth Planet Sci Lett, 366:17–26.
LeslieM.D., RidoliM., MurphyJ.G., and Borduas-DedekindN. (2019) Isocyanic acid (HNCO) and its fate in the atmosphere: a review. Environ Sci: Processes Impacts, 21:793–808.
62.
LevyM.E., ZhangR., ZhengJ., TanH., WangY., MolinaL.T., TakahamaS., RussellL.M., and LiG. (2014) Measurements of submicron aerosols at the California-Mexico border during the Cal-Mex 2010 field campaign. Atmos Environ, 88:308–319.
63.
LuH.-C., ChenK.-K., ChenH.-F., ChengB.-M., and OgilvieJ.F. (2010) Absorption cross section of molecular oxygen in the transition E at 38 K. Astron Astrophys, 520:A19.
64.
LyonsT.W., ReinhardC.T., and PlanavskyN.J. (2014) The rise of oxygen in Earth's early ocean and atmosphere. Nature, 506:307–315.
65.
Navarro-GonzalézR., McKayC.P., and MvondoD.N. (2001) A possible nitrogen crisis for Archaean life due to reduced nitrogen fixation by lightning. Nature, 412:61–64.
66.
NIST Computational Chemistry Comparison and Benchmark Database. NIST standard reference database number 101 20, August 2019. Editor: Russell D. Johnson III. Available online at http://cccbdb.nist.gov.
67.
NitschkeW. and RussellM.J. (2013) Beating the acetyl coenzyme A-pathway to the origin of life. Philos Trans R Soc Lond B Biol Sci, 368:20120258.
68.
PaulingL. (1975) The relative stability of isosteric ions and molecules. J Chem Educ, 52:577.
69.
PavlovA.A. and KastingJ.F. (2002) Mass-independent fractionation of sulfur isotopes in Archean sediments: strong evidence for an anoxic Archean atmosphere. Astrobiology, 2:27–41.
70.
PavlovA.A., BrownL.L., and KastingJ.F. (2001) UV shielding of NH3 and O2 by organic hazes in the Archean atmosphere. J Geophys Res, 106:23267–23287.
71.
SaganC. and ChybaC. (1997) The Early faint sun paradox: organic shielding of ultraviolet labile greenhouse gases. Science, 276:1217–1221.
72.
SaganC. and MullenG. (1972) Earth and Mars: evolution of atmospheres and surface temperatures. Science, 177:52–56.
73.
ScattergoodT.W., McKayC.P., BoruckiW.J., GiverL.P., Van GhyseghemH., ParrisJ.E., and MillerS.L. (1989) Production of organic compounds in plasmas: a comparison among electric sparks, laser-induced plasmas, and UV light. Icarus, 81:413–428.
74.
SebreeJ.A., SternJ.C., MandtK.E., Domagal-GoldmanS.D., and TrainerM.G. (2016) 13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: relevance to Titan. Icarus, 270:421–428.
75.
SebreeJ.A., RoachM.C., ShipleyE.R., HeC., and HörstS.M. (2018) Detection of prebiotic molecules in plasma and photochemical aerosol analogs using GC/MS/MS techniques. Astrophys J, 865:133.
76.
SeguraA., MeadowsV.S., KastingJ.F., CrispD., and CohenM. (2007) Abiotic formation of O2 and O3 in high-CO2 terrestrial atmospheres. Astron Astrophys, 472:665–679.
77.
ShibuyaT., RussellM.J., and TakaiK. (2016) Free energy distribution and hydrothermal mineral precipitation in Hadean submarine alkaline vent systems: importance of iron redox reactions under anoxic conditions. Geochim Cosmochim Acta, 175:1–19.
78.
ShumanN.S., HuntonD.E., and ViggianoA.A. (2015) Ambient and modified atmospheric ion chemistry: from top to bottom. Chem Rev, 115:4542–4570.
79.
StarkH., YatavelliR.L.N., ThompsonS.L., KimmelJ.R., CubisonM.J., ChhabraP.S., CanagaratnaM.R., JayneJ.T., WorsnopD.R., and JimenezJ.L. (2015) Methods to extract molecular and bulk chemical information from series of complex mass spectra with limited mass resolution. Int J Mass Spectrom, 389:26–38.
80.
TrainerM.G., PavlovA.A., JimenezJ.L., McKayC.P., WorsnopD.R., ToonO.B., and TolbertM.A. (2004) Chemical composition of Titan's haze: are PAHs present?. Geophys Res Lett, 31:L17S08.
81.
TrainerM.G., PavlovA.A., DeWittH.L., JimenezJ.L., McKayC.P., ToonO.B., and TolbertM.A. (2006) Organic haze on Titan and the early Earth. PNAS, 103:18035–18042.
82.
TrainerM.G., JimenezJ.L., YungY.L., ToonO.B., and TolbertM.A. (2012) Nitrogen incorporation in CH4-N2 photochemical aerosol produced by far ultraviolet irradiation. Astrobiology, 12:315–326.
83.
TrainerM.G., SebreeJ.A., YoonY.H., and TolbertM.A. (2013) The influence of benzene as a trace reactant in Titan aerosol analogs. Astrophys J Lett, 766:L4.
84.
UgelowM.S., De HaanD.O., HörstS.M., and TolbertM.A. (2018) The effect of oxygen on haze analog properties. Astrophys J Lett, 859:L2.
85.
VuittonV., LavvasP., YelleR.V., GalandM., WellbrockA., LewisG.R., CoatesA.J., and WahlundJ.-E. (2009) Negative ion chemistry in Titan's upper atmosphere. Planet Space Sci, 57:1558–1572.
86.
WahlundJ.-E., GalandM., Müller-WodargI., CuiJ., YelleR.V., CraryF.J., MandtK., MageeB., WaiteJr., J.H., YoungD.T., CoatesA.J., GarnierP., ÅgrenK., AndréM., ErikssonA.I., CravensT.E., VuittonV., GurnettD.A., and KurthW.S. (2009) On the amount of heavy molecular ions in Titan's ionosphere. Planet Space Sci, 57:1857–1865.
87.
WaiteJr., J.H., YoungD.T., CravensT.E., CoatesA.J., CraryF.J., MageeB., and WestlakeJ. (2007) The process of tholin formation in titan's upper atmosphere. Science, 316:870–875.
88.
WangQ., ZhaoJ., DuW., AnaG., WangZ., SunL., WangY., ZhangF., LiZ., YeX., and SunY. (2016) Characterization of submicron aerosols at a suburban site in central. China Atmos Environ, 131:115–123.
89.
WolfE.T. and ToonO.B. (2010) Fractal organic hazes provided an ultraviolet shield for early Earth. Science, 328:1266–1268.
90.
WongM.L., CharnayB.D., GaoP., YungY.L., and RussellM.J. (2017) Nitrogen oxides in early Earth's atmosphere as electron acceptors for life's emergence. Astrobiology, 17:975–983.
91.
YamagataY. (1999) Prebiotic formation of ADP and ATP from AMP, calcium phosphates and cyanate in aqueous solution. Orig Life Evol Biosph, 29:511–520.
92.
YoonY.H., HörstS.M., HicksR.K., LiR., de GouwJ.A., and TolbertM.A. (2014) The role of benzene photolysis in Titan haze formation. Icarus, 233:233–241.
93.
YungY.L. and McElroyM.B. (1979) Fixation of nitrogen in the prebiotic atmosphere. Science, 203:1002–1004.
94.
ZahnleK., ClaireM., and CatlingD. (2006) The loss of mass-independent fractionation in sulfur due to a Palaeoproterozoic collapse of atmospheric methane. Geobiology, 4:271–283.
95.
ZerkleA.L., ClaireM.W., Domagal-GoldmanS.D., FarquharJ., and PoultonS.W. (2012) A bistable organic-rich atmosphere on the Neoarchaean Earth. Nat Geosci, 5:359–363.
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
