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Insitute of Physical Chemistry Polish Academy of Sciences. Laboratory research on aqueous reactions of isoprene with inorganic radicals. Inna Kuznietsova Lech Gmachowski, Krzysztof J. Rudzinski. Why ?. interaction and transformation of atmospheric trace compounds - PowerPoint PPT Presentation
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Laboratory research Laboratory research on aqueous reactions on aqueous reactions
of isoprene of isoprene with inorganic radicalswith inorganic radicals
Inna KuznietsovaInna Kuznietsova
Lech Gmachowski, Krzysztof J. RudzinskiLech Gmachowski, Krzysztof J. Rudzinski
Insitute of Physical ChemistryInsitute of Physical Chemistry Polish Academy of SciencesPolish Academy of Sciences
22
Why ?Why ?
• interaction and transformation of atmospheric interaction and transformation of atmospheric trace compounds trace compounds
• formation of secondary organic aerosols formation of secondary organic aerosols
(SOA)(SOA)
33
SOSO22
• anthropogenic sources (80 TgS/year)anthropogenic sources (80 TgS/year) combustion of fossil fuels
vehicles, aircraft, ships, vehicles, aircraft, ships, power stations, industrial boilerspower stations, industrial boilers
industry ores smelting, scrubbing natural gasores smelting, scrubbing natural gas
• natural sources natural sources (12 TgS/year)(12 TgS/year) volcanic eruptions oxidation of organic materials in soils atmospheric oxidation of dimethylsulfide rainforests
44
Autooxidation of SAutooxidation of SIVIV
Mn(III) + SOMn(III) + SO332-2-
/HSO/HSO33-- Mn(II) + SOMn(II) + SO3 3
- -
Mn(II)Mn(II) Mn(III)Mn(III)SSIVIV, O, O22
2 SO2 SO332-2- /2 HSO /2 HSO33
- - + O+ O22 2 SO2 SO442-2- /2 HSO /2 HSO44
2-2- SOSO33•-•-,,SOSO44
•-•- , , SOSO55•-•-
SOSO332-2- / HSO / HSO33
-- SOSO22 + H + H22OO
55
IsopreneIsoprene
Sources:Sources:• Plants Plants • Sea phytoplanktonSea phytoplankton• Microbes Microbes • Animals and humansAnimals and humans• Biomass burningBiomass burning• Combustion and evaporation of fuelsCombustion and evaporation of fuels• Cigarette smokingCigarette smoking• Chemical technology Chemical technology
(2-methyl-1,3-butadien)(2-methyl-1,3-butadien)
66
Importance of isopreneImportance of isoprene
• Emission 500 TgC/yearEmission 500 TgC/year
• High reactivity (OHHigh reactivity (OH••, NO, NO33••, O, O33))
• Precursor of Secondary Organic AerosolsPrecursor of Secondary Organic Aerosols
• Influence on formation photochemical smogInfluence on formation photochemical smog
• Influence on autooxidation SInfluence on autooxidation SIVIV
77
Gas-phase transformations of isopreneGas-phase transformations of isoprene
R
•
R•, OR•, O33
R•
R•
R•
R•R•
••OHOH
NONO33••
NONO
Cl•Cl•
SOSO33••
(....)(....)
R •
R•
R
•
R
•
OOO
88
Typical gas-phase productsTypical gas-phase products
aldehydesaldehydesketonesketones
3-methyl furan3-methyl furandiolsdiols
hydroxynitrateshydroxynitratesdinitratesdinitrates
peroxynitratesperoxynitratesperoxyacetyl nitrates (PAN)peroxyacetyl nitrates (PAN)methacrolyl nitrate (MPAN)methacrolyl nitrate (MPAN)
OH
OH
ONO2
OOH
O
OO
NO
O
O
O
OO
NO
O
O
99
Heterogeneous and aqueous-phase Heterogeneous and aqueous-phase transformations of isoprenetransformations of isoprene
hydroxyacetonshydroxyacetons
2-methyltetraols2-methyltetraols
hydroxycarboxyl acidshydroxycarboxyl acids
dicarboxy acidsdicarboxy acids
sulfate-nitrate esters sulfate-nitrate esters
sulfate esterssulfate esters
nitrate estersnitrate esters
keto acidsketo acids
OHOH
OH
OHOH OH
OH
O
CH3 OH
OO
OHO
OHOH
SOH
O
O
OHO
OH
N
SOH
O
O
O O
1010
25 25 ooC C pH = 4.5pH = 4.5÷÷8.68.6
NaNa22SOSO3 3 + Na+ Na22SS22OO5 5 + O+ O22
IsopreneIsoprene
MnSOMnSO44UVUV
[O[O22],],pHpH
[iso], [S(IV)][iso], [S(IV)]
ESI-MSESI-MS(offline)(offline)
Experimental setupExperimental setup
1111Wavelength, nmWavelength, nm
Recorded UV spectra of a reacting solutionRecorded UV spectra of a reacting solution A
bsor
banc
e, a
.u.
Abs
orba
nce,
a.u
.
Initial concentrations, mM:MnSO4 SIV C5H8 O2 pH0.01 1.04 0.07 0.25 6.7
Time, substrates
Time, products
1212
Changes of OChanges of O22 concentration concentration and pHand pH
1313
Decreasing of SDecreasing of SIVIV and isoprene with time and isoprene with time
1414
Identification of productsIdentification of products
Mass / chargeMass / charge
Inte
nsity
, cp
sIn
tens
ity,
cps OSO3
OHOSO3
OOSO2
O
OSO2
OH
1515
Structures of the productsStructures of the products
OSO3
O
OSO3
OH
OSO2
OH
OSO2
O
1616
Reaction of isoprene withReaction of isoprene with SOSO44••--
CH2 CH
CH2
CH3
CH2 CH
CH2
CH3
O2
CH2 CH
CH2
CH3 O O
O S
O
O
O S
O
O
O
CH2 CH
CH2
CH3 O
O S
O
O
O S
O
O
CH2 CH
CH2
CH3 O
CH2 CH
CH
CH3 O
O2
O
OH
O S O
O
O
O S
O
O
O
H+
O2
O S
O
OH
O S
O
OH
O
•
+ +
OSO3•
OSO3
OSO3
OSO3 OSO3
faster
slowerOSO3
_
_
_
_ _
_
1717
pHo= 8.31 pHo= 5.8pHo= 6.9
time, s
0 2000 4000
[O2]/
[O2] o
0,0
0,5
1,0
time, s
0 3000 6000 9000
[O2]/
[O2] o
0,0
0,5
1,0
time, s
0 1000 2000
[O2]/
[O2] o
0,0
0,5
1,0
Influence of isoprene on autooxidation of SInfluence of isoprene on autooxidation of S IVIV
in solution of different acidityin solution of different acidity
experiments without experiments without isoprenisoprene (blue) and with isoprene (red)e (blue) and with isoprene (red)
2SO32- /2HSO3
- + O2 2SO42- /2HSO4
2-
Rudziński et.al.2007 Proc. 6th Conf. Urban Air Quality, Cyprus
1818
Take-Home-MessagesTake-Home-Messages
• AqueousAqueous--phase reactionphase reactionss of isoprene with of isoprene with
ssulfoxyulfoxy radicals can be radicals can be a a source of atmospheric source of atmospheric
organosulfatesorganosulfates and and organosulforganosulfiitestes
• Influence of isoprene on aciditification of Influence of isoprene on aciditification of
atmospheric watersatmospheric waters
• Interaction of biosphere and atmosphereInteraction of biosphere and atmosphere
1919
Thank youThank you for your attentionfor your attention
2020
Mn(II) (+ O2, S(IV))→ Mn(III)Mn(II) (+ O2, S(IV))→ Mn(III)
SS22OO882–2– → SO → SO44
•–•– + SO + SO44•–•–
Mn(III) + SOMn(III) + SO332–2– → Mn(II) + SO → Mn(II) + SO33
•–•–
SOSO33•–•– + O + O22 → SO → SO55
•–•–
SOSO55•–•– + SO + SO33
2–2– → SO → SO552–2– + SO + SO33
•–•–
SOSO55•–•– + SO + SO33
2–2– → SO → SO442–2– + SO + SO44
•–•–
SOSO55•–•– + HSO + HSO33
–– → HSO → HSO55–– + SO + SO33
•–•–
SOSO55•–•– + HSO + HSO33
–– → SO → SO442–2– + SO + SO44
•–•– + H + H++
SOSO44•–•– + SO + SO33
2–2– → SO → SO442–2– + SO + SO33
•–•–
SOSO44•– •– + HSO + HSO33
–– → SO → SO442–2– + SO + SO33
•–•– + H + H++
HSO5– + HSO3
– → SO42– + SO4
2– + 2 H+
SO52– + SO3
2– → SO42– + SO4
2–
SO5•– + Mn(II) → SO5
2– + Mn(III)
SO5•– + Mn(II) → SO4
2– + Mn(III) (+ OH–)
SO4•– + Mn(II) → SO4
2– + Mn(III)
SO5•– + SO5
•– → SO4•– + SO4
•– + O2
SO4•– + S2O8
2– → SO42– + S2O8
•–
SO3•– + SO3
•– → S2O62–
SO4•– + SO4
•– → S2O82–
SO5•– + SO5
•– → S2O82– + O2
11
22
33
44
5-15-1
5-25-2
5-1a5-1a
5-2a5-2a
66
6a6a
77
7a7a
8-18-1
8-28-2
99
1010
1111
1212
1313
1414
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