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