Laboratory research on aqueous reactions of isoprene with inorganic radicals
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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

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Laboratory research on aqueous reactions of isoprene with inorganic radicals

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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

  • formation of secondary organic aerosols

    (SOA)


SO2

  • anthropogenic sources (80 TgS/year)

    combustion of fossil fuels

    vehicles, aircraft, ships,

    power stations, industrial boilers

    industry

    ores smelting, scrubbing natural gas

  • natural sources (12 TgS/year)

    volcanic eruptions

    oxidation of organic materials in soils

    atmospheric oxidation of dimethylsulfide

    rainforests


SO2 + H2O

SO32- / HSO3-

Mn(III)

SIV, O2

Mn(II)

Mn(II) + SO3  -

Mn(III) + SO32-/HSO3-

SO3•-,SO4•- , SO5•-

2 SO32- /2 HSO3- + O2

2 SO42- /2 HSO42-

Autooxidation of SIV


Isoprene

(2-methyl-1,3-butadien)

Sources:

  • Plants

  • Sea phytoplankton

  • Microbes

  • Animals and humans

  • Biomass burning

  • Combustion and evaporation of fuels

  • Cigarette smoking

  • Chemical technology


Importance of isoprene

  • Emission 500 TgC/year

  • High reactivity (OH•, NO3•, O3)

  • Precursor of Secondary Organic Aerosols

  • Influence on formation photochemical smog

  • Influence on autooxidation SIV


•OH

NO3•

R•, O3

NO

R•

Cl•

SO3•

(....)

Gas-phase transformations of isoprene


Typical gas-phase products

aldehydes

ketones

3-methyl furan

diols

hydroxynitrates

dinitrates

peroxynitrates

peroxyacetyl nitrates (PAN)

methacrolyl nitrate (MPAN)


Heterogeneous and aqueous-phase transformations of isoprene

hydroxyacetons

2-methyltetraols

hydroxycarboxyl acids

dicarboxy acids

sulfate-nitrate esters

sulfate esters

nitrate esters

keto acids


Na2SO3 + Na2S2O5 + O2

Isoprene

MnSO4

[O2],pH

ESI-MS

(offline)

[iso], [S(IV)]

UV

25 oC

pH = 4.5÷8.6

Experimental setup


Initial concentrations, mM:

MnSO4SIVC5H8O2pH

0.011.040.070.256.7

Time, substrates

Time, products

Recorded UV spectra of a reacting solution

Wavelength, nm

Absorbance, a.u.


Changes of O2 concentrationand pH


Decreasing of SIV and isoprene with time


Identification of products

Intensity, cps

Mass / charge


Structures of the products


Reaction of isoprene withSO4•-


Influence of isoprene on autooxidation of SIV

in solution of different acidity

2SO32- /2HSO3-+ O2

2SO42- /2HSO42-

experiments without isoprene (blue) and with isoprene (red)

Rudziński et.al.2007 Proc. 6th Conf. Urban Air Quality, Cyprus


Take-Home-Messages

  • Aqueous-phase reactions of isoprene with sulfoxy radicals can be a source of atmospheric organosulfates and organosulfites

  • Influence of isoprene on aciditification of atmospheric waters

  • Interaction of biosphere and atmosphere


Thank you

for your attention


7

1

S2O82– → SO4•– + SO4•–

SO52– + SO32– → SO42– + SO42–

7a

2

HSO5– + HSO3– → SO42– + SO42– + 2 H+

Mn(II) (+ O2, S(IV))→ Mn(III)

8-1

SO5•– + Mn(II) → SO52– + Mn(III)

Mn(III) + SO32– → Mn(II) + SO3•–

3

8-2

SO5•– + Mn(II) → SO42– + Mn(III) (+ OH–)

4

SO3•– + O2 → SO5•–

9

SO5•– + SO32– → SO52– + SO3•–

SO4•– + Mn(II) → SO42– + Mn(III)

5-1

5-2

SO5•– + SO32– → SO42– + SO4•–

SO5•– + SO5•– → SO4•– + SO4•– + O2

10

5-1a

SO5•– + HSO3– → HSO5– + SO3•–

11

SO4•– + S2O82– → SO42– + S2O8•–

12

SO3•– + SO3•– → S2O62–

SO5•– + HSO3– → SO42– + SO4•– + H+

5-2a

13

SO4•– + SO32– → SO42– + SO3•–

SO4•– + SO4•– → S2O82–

6

14

SO5•– + SO5•– → S2O82– + O2

6a

SO4•– + HSO3– → SO42– + SO3•– + H+


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