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INSTYTUT CHEMII FIZYCZNEJ PAN

Probing the formation and transformation of secondary

organic aerosol in the atmosphere using

hyphenated mass spectrometry

Rafał Włodzimierz Szmigielski, Ph.D.

Résumé covering the scientific profile and scientific achievements prepared in

connection to the application for a scientific degree of doktor habilitowany

Warszawa, February 2, 2016

Résumé by Rafal Wlodzimierz Szmigielski, 2016

2

A. Name and Surname

Rafał Włodziemierz Szmigielski

B. Obtained degrees and diplomas with mentioning their name, places and dates of

their receiving as well as a title of the doctoral thesis

2003 – 1999: Institute of Organic Chemistry Polish Academy of Sciences, Warszawa

o Ph.D. study: Ph.D. dissertation on "Synthesis of N-alkoxymethylated amides and sulfon-

amides and fragmentation studies of these derivatives with mass spectrometry” carried

out under the supervision of Prof. Dr. Witold Danikiewicz; Ph.D. received summa cum

laude on January 6, 2004.

1999 – 1994: Faculty of Chemistry, Warsaw University of Technology, Specialization:

Technology of Organic Synthesis, Warszawa

o M.Sc. study: M.Sc thesis on "Study on regioselectivity of [4+2] cycloaddition reactions

between oxazole derivatives and acetylenic agents" carried out under the supervision of

Dr. Tadeusz Mizerski; graduation with honors on October 14, 1999.

C. Information on hithero employment in research centers

Now – 2009: Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa

o Now – 2011: Assistant professor and head of Environmental Chemistry Group (group

members: one post-doctoral researcher, one senior research fellow, two Ph.D.

candidates, M.Sc. students, B.Sc. students).

o Research interests cover (i) chemical and kinetic evaluation of dark/UV-induced

aqueous-phase oxidation reactions of biogenic organic compounds (e.g., isoprene,

Z-3-hexenal) leading to atmospheric secondary organic aerosol (SOA); (ii) application

of tandem mass spectrometry and ion mobility mass spectrometry for the identification

and structural elucidation of the unknown components of ambient and laboratory-

generated secondary organic aerosol; (iii) identification of bio-active organic compounds

underlying insect-tree and insect-insect interactions (chemo-informatics) – cooperation

with the forest industry.

o Development of hitherto scientific collaboration with the University of Antwerp

(Prof. Prof. M. Claeys and F. Blockhuys), University of Ghent (Prof. Dr. W. Meanhaut),

U.S. Environmental Protection Agency (Dr. M. Jaoui) and North Carolina University at

the Chapel Hill (Dr. J. Surratt).

o 2010 – 2009: Assistant professor in Group of Aerosol Physico-chemistry and Modelling

(head: Prof. Dr. L. Gmachowski).


3

2009 – 2005: University of Antwerp, Department of Pharmaceutical Sciences, Antwerp,

Belgium

o Post-doctoral research stay in Bio-organic Mass Spectrometry Group

(head: Prof. Dr. Magda Claeys) within a framework of Intra-European Marie Curie

project (6th

FP-People; Nr 39787; acronym: SOAMASS) as well as two international

projects: Formation Mechanisms Marker Compounds and Source Apportionment for

Biogenic Atmospheric Aerosols; Nr. SD/AT/02A; Akronim: BIOSOL and

Characterization of Oxidation Products of Isoprene in Biogenic Rural Aerosols;

Nr SPO23091999).

o Research focused on (i) application of liquid and/or capillary gas chromatography and

ion trap mass spectrometry, for qualitative assessment of biogenic SOA; (ii) organic

synthesis of reference compounds for structural assignments.

o The research developed in a close cooperation with the U.S. Environmental Protection

Agency (Dr. T. Kleindienst), California Institute for Technology (Prof. Dr. J. Seinfeld),

Paul Scherrer Institute (Prof. Dr. U. Baltensperger) and the University of Ghent

(Prof. Dr. W. Meanhaut).


o Research associate in Organic Mass Spectrometry Group (head: Prof. W. Danikiewicz).

o Scientific interests: (i) probing the non-covalent complex formation of organic

molecules, using atmospheric pressure ionization mass spectrometry, (ii) synthesis of

organic compounds for the pharmaceutical industry; (iii) GC/MS and GC/MS/MS

qualitative and quantitative analyses of organic compounds in various matrices and the

interpretation of their mass spectra.


o Ph.D. candidate in Organic Mass Spectrometry Group.

1999: Faculty of Chemistry, Warsaw University of Technology, Specialization: Technology

of Organic Synthesis, Warszawa

o Junior assistant in the Department of Organic Chemistry (head: Prof. Dr. D. Buza).

o Teaching fundamentals of organic chemistry in the student seminars, supervising the lab

work of B.Sc. students.

D. Indication of the scientific achievement in accordance with the article 16 section 2

of the act on scientific degrees and the scientific title and degrees and title in the

arts from March 14, 2003 (Dz. U. nr 65, sec. 595 with changes):

a) Title of the scientific/artistic achievement,

Probing the formation and transformation of secondary organic aerosol in the atmosphere

using hyphenated mass spectrometry


4

b) (author/authors, title/titles of publication, year, and name of the printing house),

H1 paper

Szmigielski R., Cieslak, M., Rudziński J.K.,Maciejewska B. (2012): Identification of

volatiles from Pinus silvestris attractive for Monochamus galloprovincialis using a SPME-

GC/MS platform. Environmental Science and Pollution Research, 19, 2860-2869, DOI

10.1007/s11356-012-0792-5.

IF(2014) = 2.828

IF(5-letni) = 2.920

Number of citation = 2

I am the main author of the research concept, I designed and optimized the experimental

setup, I carried out most of experiments and GC/MS analyses, I interpreted results obtained,

including interpretation of mass spectra, I wrote the manuscript, prepared answers for

reviewers and corresponded with the Editor. I assess my contribution at a level of 75%.

H2 paper

Szmigielski R., Vermeylen R., Dommen J., Metzger A., Maenhaut W., Baltensperger U.,

Claeys M. (2010): The acid effect in the formation of 2-methyltetrols from

the photooxidation of isoprene in the presence of NOx. Atmospheric Research, 98(2-4),

183-189.

IF(2014) = 2.844

IF(5-letni) = 2.872


I am a co-author of a research concept, I made the majority of analytical measurements for

SOA samples generated in the PSI smog-chamber from isoprene – as a precursor,

I interpreted the data and proposed fragmentation patterns, I contributed to the writing of

a manuscript and I took part in the discussion with reviewers on their comments and

suggestions. I assess my contribution at a level of 65%.


5

H3 paper

Szmigielski R., Surratt D.J., Vermeylen R., Szmigielska K., Kroll J.H., Ng N.L., Murphy

S.M., Sorooshian A., Seinfeld J.H., Claeys M. (2007): Characterization of 2-methylglyceric

acid oligomers in secondary organic aerosol formed from the photooxidation of isoprene

using trimethylsilylation and gas chromatography/ion trap mass spectrometry. Journal of

Mass Spectrometry, 42(1), 101-116.

IF(2014) = 2.379

IF(5-letni) = 2.649


I am a co-author of a research idea, I conducted the majority of analytical work, including

sample preparation, mass spectrometric analyses, for isoprene SOA generated in CALTECH

chamber, I interpreted data, including reading mass spectra and proposing fragmentation

pathways, I contributed to the writing of a manuscript and to the answering reviewers’

comments. I assess my contribution at a level of 70%.

H4 paper

Claeys M., Szmigielski R., Kourtchev I., Veken P., Vermeylen R., Maenhaut W., Jaoui M.,

Kleindienst T.E., Lewandowski M., Offenberg J.H., Edney E.O. (2007): Hydroxydi-

carboxylic acids: markers for secondary organic aerosol from the photooxidation of

alpha-pinene. Environmental Science & Technology, 41(5), 1628-1634.

IF(2014) = 5.330

IF(5-letni) = 6.326


I am a co-leader of a research concept, I carried out the majority of analytical measurements

for EPA chamber-generated alpha-pinene SOA and ambient aerosol, I interpreted raw data,

including ion trap mass spectra, I designed and executed the synthesis of authentic standards,

and I contributed to the manuscript writing. I assess my contribution at a level of 60%.

H5 paper

Szmigielski R., Surratt D.J., Gómez-Gonzalez Y., Veken P., Kourtchev I., Vermeylen R.,

Blockhuys F., Jaoui M., Kleindienst T.E., Lewandowski M., Offenberg J.H., Edney E.O.,

Seinfeld J.H., Maenhaut W., Claeys M. (2007): 3-Methyl-1,2,3 butanetricarboxylic acid:

An atmospheric tracer for terpene secondary organic aerosol. Geophysical Research Letters,

34, L24811, DOI: 10.1029/2007GL031338.

IF(2014) = 4.196

IF(5-letni) = 4.410



6

I am a co-author of a research concept, I performed the majority of GC/MS i LC/MS

analyses (over 95%) for EPA chamber-generated alpha-pinene SOA and ambient aerosol,

I interpreted the data obtained, including ion trap mass spectra, I designed and run the

synthesis of 3-methyl-1,2,3-butanotricarboxylic acid – as a key authentic standard,

I contributed to the writing of a manuscript and to the addressing reviewers’ remarks.

I assess my contribution at a level of 60%.

H6 paper

Szmigielski R. (2013): Chemistry of organic sulfates and nitrates in the urban atmosphere:

Rozdział w książce NATO Science for Peace and Security Book, Series C. “Disposal of

dangerous chemicals in urban areas and mega cities”, Springer, 211-225, ISBN 9400750366.

IF(2014)/(5-letni) = 0 (monography)


H7 paper

Szmigielski R. (2015): Evidence for C5 organosulfur secondary organic aerosol components

from in-cloud processing of isoprene: role of reactive SO4 and SO3 radicals. Atmospheric

Environment, xx, DOI:10.1016/j.atmosenv.2015.10.072 (in press – state at the end of

January, 2016).

IF(2014) = 3.281

IF(5-letni) = 3.780



7

Scientometric data for a monothematic cycle of H1 – H7 papers:

Summary impact factor = 20.858

Averaged impact factor = 2.980

Total citation number = 275

data according to Web of Knowledge Core Collection

® – updated in February 2, 2016

c) Description of the scientific/artistic objective of above mentioned paper/papers and

obtained results along with description of their possible application

Description of the research efforts conducted to probe the formation and transformation of

secondary organic aerosol in the atmosphere using hyphenated mass spectrometry, I will present

in compliance with the following structure:

1. Introduction to the research...................................................................................................8

2. Research objectives.............................................................................................................16

3. Analysis of atmospheric secondary organic aerosol precursors..........................................17

4. Secondary organic aerosol formation from isoprene photo-oxidation in

the atmosphere.....................................................................................................................19

5. Secondary organic aerosol formation from α-pinene photo-oxidation in

the atmosphere.....................................................................................................................27

6. Secondary organic aerosol formation from aqueous-phase processing in

the atmosphere.....................................................................................................................38

7. Conclusions and perspectives..............................................................................................42


8

1. Introduction to the research

The presented report (habitation thesis) covers selected scientific papers H1-H7 released

in a period of 2007 and 2015, which are concerned with the chemistry of organic aerosol in

the atmosphere. An emphasis is put to fill the gaps in understanding of the aerosol formation

and growth from biogenic precursors.

Atmospheric aerosol, referred to as „pył zawieszony” in the Polish academic literature,

is defined as fine liquid and/or solid particles suspended in ambient air with aerodynamic

diameters below 100 µm. At the molecular level these particles are complex chemical mixture

of dynamically changing physico-chemical properties that affect the mankind and its

environment. In the global scale, aerosol is behind climatic changes having a strong effect on

the Earth’s radiation balance and the formation of cloud condensation nuclei.1-3

On the other

hand, ambient particulate matter has a direct influence on our health and the quality of our

lives, as indicated by numerous epidemiological studies. There is a clear tendency of

increasing numbers of cardiovascular and/or lung diseases, including asthma and allergy, in

correlation with decreasing sizes of particles.4 The rapidly growing population of the planet

along with industrial developments, increasing transportation and biomass burning are behind

long-lasting smog episodes that occur more and more frequently.5 During these events

the aerosol mass concentration is rapidly peaking, including respirable PM2.5 and PM1

fractions, i.e. fractions containing aerosol particles of diameters lower than 2.5 µm and 1 µm,

respectively, which worsen the air quality, disturb the comfort of the live and markedly

reduce the visibility. Phenomena of the aerosol particle formation (aerosol events) occurring

at various points of the Earth are exemplified in Fig.1.

Fig. 1. Atmospheric aerosol particles in practice: a) record smog event in Beijing – November 2015

(PM2.5 aerosol concentration ~ 600 µg/m3); b) oppressive smog event in Cracow – September 2015; c) fine

aerosol formed over forested mountainous region (Beskid Śląski, Poland); d) aerosol particulate matter from

savanna wild fires in Africa; e) aerosol particles from the outbreak of the Eyjafjallajökull volcano (Island) –

April 2010; f) aerosol air pollution in Indonesia due to agriculture fires – June 2013.

a)

b)

c)

d)

e)

f)


9

In Poland smog episodes have increasingly become a serious social and political

problem and the awareness of the detrimental effect of the air aerosol pollution is still

insufficient when compared to western countries and the U.S.6

A lack of the sufficient knowledge on the formation, chemical composition and

physico-chemical properties of the atmospheric aerosol has been fueling scientific activities

for years. These include research efforts carried out by researchers representing different

disciplines ranging from chemistry, physics and the environmental engineering to medical

sciences and mathematical modelling. It arises from a direct effect of airborne particulate

matter on the atmosphere, climate as well as the biosphere and its inhabitants.

Despite the intense research, there is only a minor fraction of the atmospheric aerosol,

i.e., up to 10-15%, to be equivocally identified. In contrast to the inorganic fraction, where

most of molecular components, i.e., sulfate and nitrate salts of potassium/sodium, ammonium

and heavy metal cations were identified, the composition of the organic fraction is poorly

characterized.7 Aerosol measurements conducted at different sites over the globe clearly

indicate a dominant contribution of the organic fraction to the aerosol mass (Fig. 2).8

This fraction is made up of thousands of chemical species, covering an array of molecular

masses, volatility, polarity and eco-toxicology, the origin of which in the atmosphere is by far

not recognized.9

Fig. 2. Total aerosol mass concentrations (in µg x m-3

) and the contribution of inorganic and organic fractions to

ambient aerosol masses measured over the northern Earth’s hemisphere using aerosol mass spectrometry.8

In terms of the aerosol origin, there are two key sources:

Direct sources, such as volcanic eruptions, rock erosion, sand storms, see salt

spray (direct natural sources), as well as fossil fuel burning, forest fires and

industrial emissions (direct anthropogenic sources).


10

In all of examples mentioned above, organic components of aerosol particles, also regarded to

as primary organic aerosol (POA), enter the lower atmosphere, where they undergo further

chemical evolution, i.e., aging, leading to particles of more complex entity.

Indirect (secondary) sources

In the case of secondary sources, aerosol components, also regarded to as secondary organic

aerosol (SOA), form in the atmosphere as a result of a complex reaction network from volatile

organic precursors. A number of different volatile organic compounds have been assessed as

SOA precursors. In the context of the atmospheric chemistry the most relevant turned out to

be non-methane hydrocarbons fulfilling an isoprene rule. These include isoprene (C5H8),

monoterpenes (C10H16), sesquiterpenes (C15H24) and oxygenated derivatives thereof, which

are emitted by plants due to vegetation.10

According to field- and laboratory measurements

along with the mathematical box modelling, the global plant vegetation releases every year as

high as 1200 Tg of these biogenic precursors. For comparison, the total emission from

anthropogenic sources, including fossil fuel burning and industrial releases constitutes only

100 Tg, thus an order of magnitude less.11-13

Table 1 summarizes key representatives of bio-

genic volatile organic compounds (BVOC) – as SOA precursors, along with their vapor

pressures and estimated lifetimes in the atmosphere against ambient oxidants, such as

hydroxyl radicals, nitrate radicals and ozone.

Tab. 1. Comparison of key representatives of biogenic volatile organic compounds (BVOC) – as SOA

precursors, along with their vapor pressures and estimated lifetimes in the atmosphere.

Biogenic SOA

precursor

Vapor pressure*

in Pa

(T = 298 K)

Estimated

emission13-15

in Tg x year-1

Atmospheric lifetime

against reaction

with**

w min

HO. O3 NO3

.

Hemiterpene (C5H8) (Estimated total emission 350 – 800 Tg x year-1

)13-15

isoprene 7.32 x 10

4 350 – 800 84 1872 96

* Data retrieved from available physico-chemical databases: PubChem (http://pubchem.ncbi.nlm.nih.gov), NIST

Chemistry WebBook (http://webbook.nist.gov/chemistry) and SciFinder (https://scifinder.cas.org).

** Reactivity determined assuming: [OH] = 2.0×106 molecules x cm

−3 (average 24h concentration),

[O3] = 7 x 1011

molecules x cm−3

(average 24h concentration), [NO3] = 2.5 x 108 molecules x cm

−3 (average

night concentration).16

http://pubchem.ncbi.nlm.nih.gov/

http://webbook.nist.gov/chemistry


11

Tab. 1. (continued) Comparison of key representatives of biogenic volatile organic compounds (BVOC) – as

SOA precursors, along with their vapor pressures and estimated lifetimes in the atmosphere.

Biogenic SOA

precursor

Vapor pressure*

in Pa

(T = 298 K)

Estimated

emission13-15

in Tg x year-1

Atmospheric lifetime

against reaction

with**

w min

HO. O3 NO3

.

Monoterpene (C10H16) (Estimated total emission 127 – 177 Tg x year-1

) 13-15

alpha-pinene

6.33 x 102 45 – 70 156 276 12

beta-pinene

3.90 x 102 15 – 25 108 1560 30

d-limonene

1.90 x 102

7 – 15 48 120 6

Sesquiterpene (C15H24) (Estimated total emission 18 – 25 Tg x year-1

) 13-15

beta-caryophyllene

1.33 x 100

4 – 7 42 2 3

Oxygenated hydrocarbon (Estimated total emission 94 – 260 Tg x year-1

) 15

alpha-

terpineol

5.64 x 10-1

2 – 3 61 54 190

* Data retrieved from available physico-chemical databases: PubChem (http://pubchem.ncbi.nlm.nih.gov), NIST

Chemistry WebBook (http://webbook.nist.gov/chemistry) and SciFinder (https://scifinder.cas.org).

** Reactivity determined assuming: [OH] = 2.0×106 molecules x cm

−3 (average 24h concentration),

[O3] = 7 x 1011

molecules x cm−3

(average 24h concentration), [NO3] = 2.5 x 108 molecules x cm

−3 (average

night concentration).16

http://pubchem.ncbi.nlm.nih.gov/

http://webbook.nist.gov/chemistry


12

Data from the Table 1 clearly indicate that isoprene – 2-methylobuta-1,3-diene – is

a key isoprenoid hydrocarbon in the atmospheric chemistry since its total emission rate

exceeds more than a half of total mass of all BVOCs released by forest eco-systems. A short

lifetime of isoprene in the atmosphere (estimated from minutes to hours) in conjunction with

the presence of a reactive carbon carbon double bond in its molecular skeleton makes

isoprene a leading BVOC aerosol precursor.17-20

Plant chamber measurements revealed that

isoprene emissions are a typical signature of broad-leaf plant species, such as oaks, birches,

maples and elms. It was evidenced that the average isoprene concentration in the boundary

layer ranges from 1 to 10 ppbv (i.e., from 3 to 30 µg x m-3

),10

and the emission phenomenon

is linked to a self-defense mechanisms developed by plants during their evolution against

environmental pollution, biotic stresses induced by parasites and pests as well as abiotic

stresses induced by intense solar radiation, low temperatures, droughts, strong winds etc.21,22

Alpha-pinene – (1S,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-2-ene – a chiral bicyclic

alkene containing a reactive four-membered ring residue is the second significant secondary

organic aerosol precursor.23

The emission of the compound estimated at the level of

45 – 70 Tg x year-1

is a fingerprint of conifer eco-systems (pines, spruces etc.). Typically,

alpha-pinene concentrations recorded over a forest canopy ranges from 0.1 to 50 ppbv

(0.5 - 300µg x m-3

) depending on the weather conditions, seasons and a geographical

position.24

The presence of a carbon carbon double bond makes isoprene and alpha-pinene highly

reactive organic species in the lower atmosphere (troposphere) with ambient oxidants,

including ozone (O3), inorganic radicals (mainly: HO., NO3, SO4

-.) and primary gaseous

pollutants, such as: sulfur dioxide (SO2) and nitrogen oxides (NOx). These processes might

occur both in a gas-phase, aqueous-phase as well as in heterogenic systems, for instance on

a surface of SOA particles, that lead to a vast number of oxygenated polar offspring

characterized by increasingly lower vapor pressures. New polar products formed could

condense on pre-existing aerosol particles, e.g., inorganic seeds, and/or spontaneously form

novel SOA particles, both inducing aerosol episodes in the atmosphere. The spontaneous

SOA particle formation might happen when oligomers and/or polymers form from BVOC

oxidative degradation. These processes are schematically shown in Fig. 3. In this context

the Earth’s atmosphere could be regarded as a great chemical vessel, where numerous

oxidation reactions occur, preferentially at carbon carbon double bond residues.25


13

Fig. 3. Schematic representation of the Earth’s lower atmosphere network, where SOA particle formation

and growth occur (taken from the paper H6).

It is worth noting that the contribution of BVOC sources in atmospheric processes of new

SOA particle formation and growth, in particular these from respirable fractions,

predominates rural and/or semi-rural regions. In regard to isoprene and alpha-pinene –

as SOA precursors, processes of their atmospheric decomposition are also relevant for

urbanized regions with green belts (e.g., parks, city forests etc.). The reactions leading to

novel SOA components could be catalyzed by acidic centers available on a surface of aerosol

particles and/or atmospheric waters. In the troposphere, oxidation reactions could also be

induced by the Sun-light irradiation, predominantly from a UV wavelength region, or could

occur under dark conditions. The latter case is particularly relevant for the night-time

chemistry.26,27

During last a few years it has been observed tremendous advances in the scientific work

regarding the understanding of phenomena of the aerosol formation and growth in the

atmosphere, both ambient and at workplaces. Numerous ambient measurements carried out at

various forested regions in Europe and the U.S. made it possible to identify a number of novel

SOA components, some of which serving as marker compounds for the characterization of the

aerosol origin, and consequently – for an inventory of pollution sources. A comprehensive

data set on this subject is provided by two recent review articles, one by Hallquist et al.,3

second by Noziere et al.28

Very useful in this direction are simulation experiments conducted

in a laboratory framework, including photo-oxidation in smog chamber experiments and/or

aqueous-phase simulation experiments, where SOA mass forms under strictly controlled

conditions from selected organic precursor(s) in the presence of radical species and/or ozone

as well as salt seed spray – as condensation nuclei. The organic aerosol formed is regarded as


14

laboratory-generated SOA, and the SOA composition is far simplified when linked to

the composition of ambient aerosol. In papers H2 – H7, which constitute a key base of my

habilitation essay, this approach was applied as a tool for the evaluation of SOA formation

mechanisms from isoprene and alpha-pinene, as atmospherically-relevant volatile organic

precursors.

Detailed account on the qualitative and/or quantitative characterization of secondary

organic aerosol, both ambient and laboratory-generated, requires sensitive, reliable and

reproducible analytical methods. Mass spectrometry is a method of choice here since allows

one for a robust detection of SOA components of a vast range of molecular masses ranging

from small molecules, such as methacrylic acid, to oligomers and/or polymers, such as

HULIS (HUmic-LIke Substances).29,30

The selection of an appropriate ionization technique

is an absolute must.31

For instance, electron ionization method (EI) applied to the

characterization of laboratory-generated isoprene aerosol under high NOx conditions (paper

H3) will remain unsuitable for the determination of monoesters of sulfuric(VI) acid, which

recently have been reported as key components of a polar fraction of urban aerosol (papers H6

– H7). In the latter case, electrospray ionization (ESI) was applied as a soft ionization

technique owing to the enhanced polarity and thermolability of the analyte. For the sake of

complex composition of atmospheric aerosol, which could roughly contain > 10000 different

compounds32

, the hyphenated mass spectrometry offers a reliable analytical methodology for

determination of SOA composition, mechanisms of marker formations as well as detection of

volatile SOA precursors.28

The paper H1 addresses the latter problem and is concerned with

the detection of volatile trace organics, which is released by plant material using gas

chromatography mass spectrometry (GC/MS) with a prior pre-concentration of the analyte.

The application of the hyphenated organic mass spectrometry, including GC/MS and

LC/MS equipped with tandem analyzers, such as an ion traps and/or triple quadruples and

ionization sources, such as EI and/or ESI, allowed one for determination and structural

elucidation of isomeric 2-methyltetrols (molecular weight, MW 136), C5 alkene triols

(MW 118) and 2-methylglyceric acid (MW 120), as well as organosulfate and/or

organonitrate derivatives thereof33-35

– as essential markers of isoprene-derived SOA.

Historically significant here are isomeric 2-methyltetrols, which form in the troposphere as a

result of isoprene oxidation by hydroxyl radicals.36,37

The addition of the latter to the isoprene

reactive centers (i.e., unsaturated carbon carbon bonds) results in the advent of an organic C5

radical, which undergoes further gas-phase processing via a row of reactive intermediates

(Fig. 4). Estimates done by Claeys and co-workers revealed that a year production of

2-methylterols in the atmosphere from the photo-oxidation of isoprene ranges from

2 to 4 Tg.38

It was also evidenced that isoprene-derived tetrols might form from isoprene

through aqueous-phase processing in the presence of hydrogen peroxide under non-

photochemical conditions.39

The further fate of 2-methylotetrols in the atmosphere as well as

detailed analysis of their formation has been a topic of vital scientific discussions. It should be

stressed that other unknown SOA components that results from the processing of isoprene, as

well as discovery of alternative routes of these processes that lead to great aerosol load in the

atmosphere remain a scientific challenge. Papers H2-H3 and H6-H7 address these challenges.


15

Fig. 4. Mechanisms of gas-phase isoprene photo-oxidation leading to stereoisomeric 2-methyltetrols.

These species serve as key markers of isoprene secondary organic aerosol.

A capacity of tandem mass spectrometers, including a variety of scanning modes, such

as precursor ion map scanning, product ion map scanning and a neutral loss scanning, using

triple quads analyzers, as well as MSn experiments, using ion trap technology, makes it

possible to address the molecular characterization of the organic aerosol composition through

a detailed fragmentation study of the detected analyte. This is often a way to differentiate

between isomeric SOA components that result from the processing of isobaric volatile

precursors, such as monoterpenes, in the atmosphere.40

In addition, the acquisition of

the accurate mass data with high resolution mass spectrometers, such as Time of Flight (ToF)

mass spectrometers, enables to infer the elemental composition of the analyzed SOA

components.41

The development of the analytical methodology for the screening of the

ambient and/or laboratory-generated aerosol using these ultrasensitive instruments made it

possible to identify and quantify marker compounds of monoterpene SOA that form as

a consequence of photo-oxidation processes of alpha-pinene, beta-pinene and D-limonene –

significant (after isoprene) C10 biogenic volatile precursors of secondary organic aerosol in

the atmosphere.40,42,43

Among firmly identified monoterpene SOA markers with hyphenated

organic mass spectrometry are there the following polar species: terpenylic acid (MW 172),

diaterpenylic acid acetate (MW 232), pinonic acid (MW 184).44

(Fig. 5)

OH.

HO2

OH

.

HO2

.

.

O2

[M]

rodnik nadtlenkowy rodnik alkoksylowy

3.

4.

/

2-metylotreitol (2R, 3R)

+ izomer (2S, 3S)

+

.

1.

.

2-metyloerytrytol (2S, 3R)

+ izomer (2R, 3S)

izopren

.

2. O2 / [M]


16

Fig 5. Chemical structures of alpha-pinene SOA markers identified with hyphenated mass spectrometry.

For instance, recently discovered terpenylic acid and organosulfate of nitro-oxypinenadiole

serve as useful markers of freshly formed alpha-pinene SOA, whereas 3-methyl-1,2,3-

trimethylbutanotricarboxylic acid (MBTCA) and 3-hydroxyglutaric acid – as markers of

processed (aged) alpha-pinene SOA. The research on the structural elucidation of the latter

markers is reported in papers H3-H4. A catalogue of ambient SOA markers is not completed

yet and discovery of novel aerosol markers, enabling to evaluate processes of the aerosol

particle formation in the atmosphere, is a driver for pursuing further research.28

This scientific

initiative is particularly crucial in Poland, where the research on the chemical SOA

characterization has been vaguely pursued! Novel unravel markers will allow one for gaining

insights into aerosol sources and the underlying mechanisms of SOA formation and

transformation (aging).

2. Research objectives

A concise literature survey stated above indicates gaps in the knowledge on the

chemistry of secondary organic aerosol particles in the atmosphere from organic trace gases.

Not only does it refer to the identification of unknown SOA volatile precursors but also it

deals with the assessment of SOA composition, properties and time evolution. The aim of the

presented habilitation report is to deliver experimental data on the formation of secondary

organic aerosol from isoprene and alpha-pinene – as biogenic volatile precursors. In particular

a key scientific objective is to construct the analytical methodology based on hyphenated

organic mass spectrometry for screening of novel SOA precursors as well as novel markers of

isoprene and alpha-pinene SOA.

kwas

cis-pinonowy

MW 184

kwas

10-hydroksypinonowy

MW 200

kwas

cis-norpinowy

MW 172

kwas

terpenylowy

MW 172

octan kwasu

diaterpenylowego

MW 232

kwas

cis-pinowy

MW 186

kwas

2-hydroksyterpenylowy

MW 188

kwas

terebowy

MW 158

organosiarczan

nitrooksypinanediolu

MW 295

ester kwasu

pinowego

MW 358


17

3. Analysis of atmospheric secondary organic aerosol precursors

The knowledge behind processes of tropospheric SOA formation requires detailed and

updated information on chemical profiles of organic volatile precursors, which enter

a boundary layer from various terrestrial sources. Laboratory research accompanied by field

measurements and calculations with complex mathematical models clearly indicate that

biogenic organic compounds (BVOC), including isoprenoid hydrocarbons, are predominant

SOA precursors. The assessment of emission inventories of aerosol volatile precursors along

with the search for unknown reactive volatile organics is one of the utmost important

scientific topic of the atmospheric chemistry.3 The H1 paper embarks on this subject.

In the H1 paper, I provided results of my research on the detection and identification of

biogenic volatile organics released from the bark of the young branches of the Scots pine trees

(Pinus silvestris, L). The hitherto field studies of the emission profiles from the Scots pines

were conducted either over a forest canopy or within coniferous boreal forest eco-systems.

The reported data provide the information about total emission fluxes, including emissions

from single sources, such as other plant species, lichens, fungi, soil, litter as well as emissions

conditioned by animals (chiefly pest pheromones) and natural fires.24,45,46

It was revealed that

monoterpenes, including Δ3-carene i α-pinene, are the major contributors to the emission

fluxes from forests dominated by P. silvestris (ca. 60-85%). A more precise catalogue of

volatile organics is provided with plant chamber experiments and/or laboratory Teflon bag

enclosures, where emissions from P. silvestris could be analyzed directly from needle-, root-

and branch levels.10,47,48

Indirect data on BVOC emission profiles from the Scots pines arise

from the analysis of essential oils obtained with Deryng steam destination.49,50

Reported

inventories of Scots pine oils are prevalent by isoterpenoid hydrocarbons and available

compositions clearly alter depending on the age of the pine tree, selected plant material and

destilation conditions. It turns out that monoterpenes, such as Δ3-carene (ca. 20-40%) and

α-pinene (ca. 20-40%) are key components with a distinct contribution from sesquiterpenes,

such as β- caryophyllene i Δ–cadinene (ca. 15-25%).

Interestingly, a literature survey showed a lack of data on the emission profile from the

bark of the Scot pines. This prompted me to pursue the research on the elaboration of a facile

analytical method for screening of volatile SOA precursors from the bark of the Scot pines

and the equivocal identification of single volatile components. To address the challenge,

I invented and constructed an experimental module with an inlet dedicated for

the introduction of solid-phase microextraction (SPME) fibers coated with polymer materials

of the 100 m diameter (visual representation is given in Fig. 6).


18

Fig. 6. A representative SPME-

GC/MS profile of volatiles released

from the Pinus silvestris bark, and

chemical structures of the identified

compounds 1–12. An inset shows a

snapshot of a designed experimental

module used in the research.

The role of SPME fibers is to

uptake and concentrate (i.e., to

extract) of volatile organic

compounds – released from the

bark of young P.silvestris at

low concentration level – as a

consequence of complex equili-

brium processes of the mass

transfer between the gas phase

and the surface of a solid fiber

through the absorption and/or

adsorption phenomena.51

It was not until the 90’ last century that the solid-phase

microextraction has increasingly become popular analytical method for the sample

preparation in various fields, such as medicine52

, biology53

and environmental sciences54

, due

to the simplicity of the method and its compatibility with hyphenated mass spectrometry, both

GC/MS and LC/MS.55

The approach applied in the H1 paper has come down to the quenching

of volatile SOA precursors – released from the P. silvestris fresh bark – in a dynamic mode

through sending a clean air through the headspace of an experimental module. A flow rate of

the air appeared to be a key variable. In a serious of runs, I could evidence that a flow rate of

10 mL x min-1

SPME-extracted samples were the most suitable for mass spectrometric

analysis (achieved signal to noise ratio > 90 in total ion current mode). Moreover, I could

achieve the satisfactory reproducibility of the analyte samples. The molecular identification of

individual BVOC components emitted by fresh bark samples I carried out using

the comparison of their chromatographic and mass spectrometric behaviors with that obtained

for available authentic standards. Additional structural evidences of the analyzed BVOC

mixture I could retrieve by a detailed interpretation of the corresponding EI mass spectra,

which in some cases were also supported by Willey mass library screening. All measurements

I conducted using a capillary gas chromatography coupled to either a single quad mass

spectrometer, equipped in the EI ionization source (GC/EI-sQ MS), or independently –

a flame ionization detector (GC/FID). The representative total ion current gas chromatogram,

recorded for the SPME-pre-concentrated BVOC sample of the P. silvestris fresh bark, along

with firmly identified chemical structures is shown in Fig. 6.

A critical analysis of the data obtained allowed me to conclude that of all identified

components of the P. silvestris bark, volatiles 1-9 (Fig. 6) might serve as crucial precursors en

route to secondary organic aerosol. It arises from the fact that these species feature high or

medium-high vapor pressures (above 10-1

Pa at 298 K) and additionally – bear reactive

residues in their molecules. My conclusion was partially supported by earlier results obtained


19

during smog-chamber photo-oxidation experiments with selected biogenic volatiles.56,57

Quantitation data obtained from GC/FID profiles indicated that the major contribution to

a flux of emitted biogenic trace gases from bark material is provided by sesquiterpene

hydrocarbons (ca. 48%), including α-longipinene, longifolene, E-β-farnesene i γ-cadinene,

with a minor load from monoterpenes (ca. 25%), including α-pinene, Δ3-carene i limonene,

and oxygenated hydrocarbons (ca.15%).

4. Secondary organic aerosol formation from isoprene photo-oxidation in

the atmosphere

A high emission rate of isoprene greatly shapes of the ambient aerosol physico-

chemistry and has a profound effect on the SOA chemical composition and transformation.

Tremendous research efforts undertaken during a last decade at laboratory- and/or field levels

revealed that isoprene oxidative decomposition at the atmospheric boundary layer affords

a vast offspring of low volatility products that significantly contribute to the organic SOA

fraction, in particular respirable PM1 and PM2.5 ones. The thermo-optical determination of

OC/EC parameters, i.e., a ratio of the organic carbon (OC) to the inorganic carbon (EC), for

numerous ambient- and laboratory-generated aerosol samples clearly proved isoprene-derived

products as meaningful contributors to the organic carbon. Depending on the origin of SOA

samples, calculated values of the contribution may vary from a few to several mass per cents.

A literature review suggests that a catalogue of relevant isoprene SOA components has

only been partially recognized, alike chemical mechanisms leading to these compounds.

It mainly concerns to the search of unknown isoprene SOA markers, which might me

supportive for precise assessments of the isoprene SOA contribution to ambient aerosol

masses in the atmosphere, and consequently – allow one for inventorying sources of local air

pollution and setting a policy of air pollution control.

In the H2 paper I reported results obtained during my studies on the effect of acidic

SOA particles on the formation and yield of 2-methyltetrols from the photo-oxidation of

isoprene. A breakthrough evidence on the detection and structural determination of

2-methyltetrols in fine ambient aerosol was provided by Claeys et al.38

who studied

the composition the Amazon rainforest aerosol. The discovery of abundant quantities of

isoprene-derived tetrols in the SOA phase launched intensive forthcoming research studies

on chemical mechanisms of 2-methyltetrol formation from isoprene – as a volatile precursor.

In my studies on the formation of atmospherically-relevant 2-methyltetrols, I utilized

smog chamber-produced isoprene SOA samples. It was possible thank to a scientific

collaboration with Swiss researchers from Paul Scherrer Institute in Villigen. Isoprene aerosol

mass was generated from gas-phase photo-oxidation of isoprene (2 ppm) under high

concentrations of nitrogen oxides NOX (NO, 500 ppb; NO2, 500 ppb). These conditions

reflected an urban atmosphere typical of big cities with green areas impacted by fossil fuel

burning and/or biomass burning processes. In contrast to the conventional work, we did not

apply an inorganic aerosol seed spray, as we interested in pristine isoprene oxidation products.

After a few hours of the UV-irradiation that mimic the atmospheric photochemistry, a gaseous

chamber content, containing these products, were transferred through a quartz-fiber filter,


20

surface of which was intentionally treated with a minute quantity (ca. 35 µg) of sulfuric(VI)

acid – a typical source of Brønsted acidic centers in the troposphere (Fig. 7A). The GC/ion

trap MS total ion current chromatogram registered for the trimethylsililated (TMS-ated)

extract of the isoprene SOA material form the filter was shown in Fig. 7B.

Fig. 7. A) Schematic representation of the experiment for generation of isoprene aerosol; B) GC/ion trap MS

total ion current chromatogram obtained for the TMS-ated extract of the sulfuric acid-treated quartz fiber filter

collected in an isoprene photo-oxidation experiment carried out in the presence of NOx.

Based on the comparison of chromatographic and mass spectral (both first order MS and MSn,

n = 2, 3) profiles recorded for peaks eluting at 38.3 min and 39.0 min with that of available

for authentic standards, I could firmly identify both products as 2-methyltreitol and

2-methylerythrytol, respectively. The quantitation analysis of these SOA components revealed

a significant increase of 2-methyltetrols (ca. 90 times increase) in comparison to the parallel

experiments with a non-treated quartz-fiber filter. A similar result I could also obtain

interpreting the OC/EC data for both samples. Both findings clearly demonstrated that

the isoprene SOA yield increases with the particle acidity. Another relevant achievement of

the H2 paper was to identify novel isoprene SOA markers. A detailed interpretation of

the GC/MS and GC/MSn data revealed the presence of novel SOA components that come off

a GC column prior to 2-methyltetrols (retention time range 32-33.5 min in Fig. 7B). Detailed

interpretation of the corresponding mass spectra, recorded both in the electron ionization

mode EI and the chemical ionization with methane as a reagent gas CI(CH4), allowed me to

assign the structure of these novel isoprene SOA components as tautomers of 4-hydroxy-1,3-

dioxo-2-methylbutane (Fig. 8). The discovery of these aerosol components was a great

achievement of the H2 paper since it allowed for extending the knowledge on the isoprene


21

SOA formation through delivery of mechanistic insights into isoprene secondary organic

aerosol, including the formation of 2-methyltetrols.

Fig. 8. A) Mass spectral data for TMS-ated enol tautomers of 4-hydroxy-1,3-dioxo-2-methylbutane (on the left –

first order mass spectrum and on the right – MS/MS spectrum) along with B) proposed fragmentation

mechanisms.

The second relevant data provided in the H2 paper was to propose the formation mechanism

for the identified 4-hydroxy-1,3-dioxo-2-methylbutane and 2-methyltetrols under acidic

conditions and in the presence of NOx. The proposed routes included the addition of hydroxy

radicals to an isoprene C=C bond system, disproportionation of resulting peroxyradicals,

formation of nitrate derivatives and hydrolysis thereof (Fig. 9).

Fig. 9. Proposed formation mechanism of 4-hydroxy-1,3-dioxo-2-methylobutane – novel marker of isoprene

SOA and a key gas-phase intermediate en route to 2-methyltetrols.

B)

A)


22

I proposed that formation of 2-methyl-1,4-dihydroxy-3-oxy-1-butene in the experiment,

where a gaseous reaction mixture generated in a high-NOx isoprene photo-oxidation

experiment is passed over a sulfuric acid-treated filter, can thus be readily explained by acid-

catalyzed hydrolysis of C5-nitrooxypolyols. The acid effect is behind the formation of

2-methylterols, accordingly.

In the H3 paper, I continued the study on the chemical composition of isoprene SOA

under an urban-impacted forested environment, where NOx is present. An emphasis was put

to the identification of novel aerosol components, including oligomeric species, interpretation

of their mass spectra and discussion of formation mechanisms. My research was conducted in

the collaboration with researchers from the California Institute of Technology in Pasadena

(California, U.S.), as a part of a big international project on the formation and properties of

isoprene secondary organic aerosol in the polluted and remote atmosphere.33

The SOA

samples were generated in a Caltech smog chamber facility from isoprene (500 ppb) in the

presence of high concentration of nitrogen oxides (NO, 805 ppb; NO2, 30 ppb) that reflect

anthropogenically-impacted environments. The major atmospheric sources of NOx (NOX =

NO + NO2) are fossil fuel burning processes, which predominate in big cities and

industrialized regions with heavy transportation, coal fueled-power plants, incinerators etc.

Teflon filters with deposited aerosol masses were subjected to the solvent extraction,

followed by a trimethysililation protocol. Alike in H2 paper, TMS-ation of the analyte

enabled to analytically transform acidic protons of hydroxyl and carboxyl groups into

appropriate sililated ethers and esters, which are far more volatile than their precursors.

GC/ion trap MS total ion current chromatogram obtained for TMS-ated SOA produced

from the photo-oxidation of isoprene under high-NOx conditions in the Caltech smog chamber

is depicted in Fig. 10.

Fig. 10. GC/ion trap MS data obtained for a trimethylsilylated extract of isoprene high-NOx SOA. Peak

identifications: 1, 2-methylglyceric acid (2-MG); 2a, 2-MG linear dimer; 2a-Ac1 and 2a-Ac2, 2-MG linear dimer

mono-acetates; 3a, 2-MG linear trimer; 3b, 2-MG branched trimer. The peak eluting at 36.10 min is not

discussed in the present report and was tentatively identified as 2-hydroxymethyl-3-ketopropanoic acid.

For the purposes of the structural elucidation of the major components of generated isoprene

SOA, I applied the following methods of organic mass spectrometry:


23

Deuterium labelling (introduction of trideuteromethylsilil residues, TMS-D9, to

unknown molecules from analyzed SOA mixtures),

Ethylation followed by trimethysililation (a way for the identification of ester

moieties),

Analyzes of MS2 i MS

3 ion maps acquired for diagnostic ions from the first

order EI spectra,

Organic synthesis of authentic standards.

The 1 component of generated SOA, with partially retained isoprene skeleton, I firmly

identified as 2,3-dihydroxy-2-methylpropionic acid, 2-MG (2-methyloglyceric acid). This

compound was reported before as an abundant isoprene-related component of ambient

aerosol37,58,59

and smog chamber-generated SOA.60-64

Analysis of the product ion maps

recorded for diagnostic ions from the molecular ion region, i.e., [M – CH3]+ (m/z 321), [M –

(CH3 + CO)]+ (m/z 293) ions (Fig. 11A) allowed me for the confirmation of the presence of

the carboxylic group in the molecule. Thorough evaluation of fragmentation routes for

the most abundant ion in the 2-MG mass spectrum (m/z 219), which forms from the molecular

ion of a TMS-ated derivative (m/z 306) in the alpha cleavage process, led me to infer the

presence of a 1,2-dihydroxy-2-methyletyl residue in the analyzed molecule (Fig. 11B). The

molecular mass assignment of the component 1 from generated isoprene SOA, I could infer

from the analyses of relevant fragment ions in mass spectra of trimethylsililated (m/z 409, 336

and 321) as well as ethylated/trimethylsililated derivatives (m/z 365, 292 and 277).

Fig. 11. A) MS2 ion trap spectra recorded for two diagnostic ions of a TMS-ated derivative of 2-MG along with

B) proposed fragmentation pathways. All fragmentation channels confirmed by ion trap MS/MS measurements

are indicated by asterisk. In parenthesis are given mass shifts observed for a TMS-D9 derivative.

B)

A)


24

By a detailed interpretation of ion trap mass spectra, I assigned the structure of

the 2a component as a product of 2-MG self-esterification (2-MGAD), where an ester group

was formed by a terminal hydroxyl group from 2-MG molecule (linear ester). Based on mass

spectra of trimethylsililated and ethylated/trimethylsililated derivatives, in particular

diagnostic [M – CH2O]+.

ions at m/z 480 and 436, respectively as well as the m/z 393

fragment ion, I firmly excluded an ester linkage with the participation of the secondary

hydroxyl group of 2-MG (branched ester). A solid proof of this hypothesis I provided by

comparison of the EI ion trap mass spectra and chromatographic retention indices of

synthesized 2-MGAD, both linear and branched, with that of the 2a component. Both linear

and branched 2-MGADs I obtained by the aqueous-phase oxidation of methacrylic acid with

hydrogen peroxide. The analysis of a molecular ion region, including a characteristic set of

[M + TMS]+ (m/z 583), [M – CH3]

+ (m/z 495) i [M – (CH3 + CO)]

+ (m/z 467) ions confirmed

the molecular weight of the compound (MW 510). The newly characterized isoprene SOA

component has been reported in earlier laboratory and field studies, e.g. as a component of

the ambient aerosol collected over the southwestern U.S. area (Research Triangle Park region,

North Carolina), however its structure and formation mechanism remained unknown.60,65

Chromatographic peaks denoted as 2a-Ac1 i 2a-Ac2 (Fig. 10) I assigned to trimethyl-

sililated linear 2-MGAD esters, where one of available hydroxyl groups were substituted by

acetyl residues. The presence of these components I could rationalized by taking into account

a fact that isoprene photo-oxidation under high NOx concentration results in the formation of

acetic acid.33

The molecular assignment of acetylated linear 2-MGAD ester structures was

possible using a detailed interpretation of EI and CI(CH4) mass spectra. The presence of

a unique [M – CH3CO2H]+.

ion at m/z 420 in the EI mass spectrum of the only one isomer,

suggested me a way to differentiate between either isomer. The presence of the ion,

I explained by the capacity of the 2a-Ac2 isomer for the 1,3-elimination of acetic acid from

its molecular ion, otherwise impossible for the 2a-Ac1 isomer (Fig. 12). In the latter case the

hydrogen atom necessary for the 1,3-elimination reaction is not available. The 1,2-elimination

process, engaging a hydrogen atom adjacent to the acetyl group (2a-Ac1 isomer), was not

observed, likely due to an unfavorable molecular geometry in the transition state.

Fig. 12. Mechanism proposed for the formation of m/z 420, an ion characteristic of the TMS derivative of

the 2-MG dimer mono-acetate bearing an acetyl group at the terminal hydroxymethyl group of the non-

carboxylic acid-containing 2-MG residue (2a-Ac2). Parts of the molecule engaged in the elimination process

were circled.


25

A proof confirming the structure of the acetate derivative bearing an acetate residue on

a secondary hydroxyl group I could deliver by the analysis of ion trap-induced fragmentation

processes recorded for another useful [M – CH2O]+.

ion at m/z 450. The latter ion results from

the TMS group transfer via the McLafferty-like rearrangement followed by the ketene

(CH2=C=O) elimination (Fig. 13) and fingerprints the 2a-AC1 isomer only.

Fig. 13. The m/z 480 → m/z 450 → m/z 408 transition as a probe for the evaluation of the position of an acetyl

residue in the molecular skeleton of the trimethylsililated derivative of 2-MGAD acetate (2a-Ac1) formed in the

isoprene high NOx SOA experiment.

Molecular structures of the 3a and 3b components I solved as isomeric diesters of

2-methylglyceric acid (2-MGAT) based on the interpretation of their ion trap mass spectra.

The molecular mass of the unknown species (MW 480) I inferred from the CI(CH4) mass

spectra, which displayed a set of characteristic adduct ions, namely [M + H]+ (m/z 481), [M +

C2H5]+ (m/z 509), [M + C3H7]

+ (m/z 523) and [MH – CH4]

+ (m/z 465). Subtle differences in

the product- and precursor ion mass spectra recorded for the abundant m/z 393 ion, which

forms from 2-MGAT molecular ions via the α-cleavage process, led me to probe their

structures. I observed that the m/z 393 MS2 ion trap mass spectrum of one isomeric 2-MGAT

diester revealed the same profile as the product ion trap spectrum of m/z 393 ion originating

from the synthesized 2-MGAD ester (Fig. 14). This observation led me to the conclusion that

the 2-MGAT diester that appears in the chromatogram at the retention time of 60.01 min

(Fig. 10) contains an inner branched 2-MG residue. Another specific fingerprint of

the branched diester 3b was the m/z 596 ion, which results from the M+.

ion (m/z 684) through

an intramolecular interaction of the trimethylsililated hydroxyl group of a branched 2-MG

residue and the trimethylsililated hydroxyl group. This interaction results in the neutral loss of

trimethylsilane (CH3)4Si (88 u) and was not observed in case of the 3a isomer diester.

Moreover, based on fragmentation behaviors, I suggested that the structure of the second

isomeric diester (product 3a) is a linear combination of 2-methylglyceric acid residues, where

terminal hydroxyl groups play a crucial role. The raised hypothesis could be justified by the

analysis of chromatographic behaviors of either isomer. The linearity of the 3a product is

consistent with its late chromatographic elution on a GC apolar stationary phase compared to

the behavior of a branched diester (product 3b).


26

Fig. 14. MS2 ion trap spectra recorded for m/z 393 fragmentation ions originating from the isomeric TMS-ated

diester 3b (mass spectrum on the left), and for comparison – from the TMS-ated branched 2-methylglyceric

diester obtained synthetically (mass spectrum on the right). Both precursors at m/z 393 originate from molecular

ions of TMS-ated derivatives via ion trap-induced α-cleavage processes.

The interpretation of mass spectral data reported in the H3 paper allowed me for

a detailed characterization of polar isoprene SOA components, including 2-methylglyceric

acid and oligomers thereof. The relative contribution of these oligomeric products in the SOA

mass I was able to determine using a quantitative LC/MS analysis with an electrospray

ionization source and the use of internal surrogate standards. The results obtained and

reported in a concomitant paper33

(not included in a structure of my habilitation thesis)

evidenced that oligomeric isoprene SOA components account for ca. 22-34% of isoprene

aerosol mass.

In the last phase of my research, I proposed likely routes to rationalize the chemical

composition of the organic aerosol formed from the photo-oxidation of isoprene under high

NOx conditions. The advent of the 2-MG acid in a series of performed mimic experiment

I linked to the intermediary formation of methacrolein. The latter C4 intermediate seems to be

far more reactive than the starting isoprene, and thus in the presence of hydroxy radicals

undergoes efficient oxidation in the gas-phase to from the 2-MG acid (Fig. 15). It worth of

future efforts to address a scientific question if a transition of methacrolein to 2-MG acid

proceeds straightforward or is accompanied by unknown intermediate(s).

The likely formation of 2-MG acid oligomers occurs in the aerosol phase, and to my

knowledge was reported for the first time in the H3 paper. Recently, evidence was provided

that the aerosol-phase esterification of 2-MG acid might be a favored atmospheric process in

terms of the kinetics and chemical equilibria.66


27

Fig. 15. Postulated formation pathways of the major isoprene SOA components, i.e., 2-methylglyceric acid and

oligoesters thereof formed in Caltech smog chamber experiments under the high NOx regime. Structures of

photo-oxidation products were firmly identified using ion trap mass spectrometry.

5. Secondary organic aerosol formation from α-pinene photo-oxidation in

the atmosphere

Alpha-pinene is considered as a second relevant (just after isoprene) biogenic volatile

organic compound emitted to the atmosphere in a large scale. Its short atmospheric lifetime

against ambient oxidants, such as hydroxyl radicals, ozone, NO3 radicals, estimated from

minutes to a few hours (vide Tab. 1), makes the compound a pivotal precursor of ambient

secondary organic aerosol. The α-pinene oxidation at a tropospheric boundary layer gives rise

to a complex SOA mixture with the time-varying composition. Despite an intense research

work, the composition of the α-pinene aerosol is far from being completely recognized.

Recent literature reviews suggest addressing the future research towards discovery of novel

α-pinene SOA markers (or chemical groups of markers), which would allow for better

quantification of fresh- and aged α-pinene SOA masses as well as for elaborating their

formation mechanisms.


28

The objective of the H4 paper was to elaborate an analytical methodology for targeting

of unknown components of ambient aerosol that forms over forested regions with prevalent

contribution from conifer eco-systems. Field measurements carried out at various points

revealed that ambient aerosol components originating from α-pinene oxidation arise in

appreciate concentrations ranging from several to several dozen nanograms per cubic meter,

although a number of them was not structurally identified or identified with false structures.

The presence of these species in ambient aerosol particles suspended over coniferous forests

let me raise the hypothesis that α-pinene might be their likely precursor. In the light of my

earlier studies (H1 paper) it becomes clear that α-pinene is a non-negligible BVOC released

by coniferous plant material, including the bark of young P.silvestris.

To verify an aforementioned hypothesis, I decided to undertake the study on

the characterization of the composition of smog chamber-generated α-pinene aerosol. In my

research I utilized aerosol samples produced in the 14.5 m3

EPA smog chamber facility from

α-pinene (313 ppb) photo-oxidation in the presence of ambient air and nitrogen oxides (NOx

313 ppb). This was feasible thank to the scientific collaboration with a research group from

the Environmental Protection Agency (EPA USA) in North Carolina. The α-pinene SOA was

subjected to the extraction, and alike in cases of H2-H3 papers – further trimethysililation to

enhance the volatility of the analyte and finally to a capillary GC/ion trap MS.

The representative total ion current chromatogram registered for the α-pinene SOA extract is

shown in Fig. 16 A. The resultant chromatogram features markedly a simplified profile

compared to a GC/MS profile obtained for ambient aerosol collected over Great Hungarian

Plain (K-puszta station) (Fig. 16B). It should be noted that laboratory-generated α-pinene

SOA reveals the same catalogue of unknown components (denoted as U1, U2 and U3 in

Figures 16 A and 16 B), which are also on display for the K-puszta ambient aerosol.

The result brought me to the conclusion that unknown components (U1, U2 and U3) of

ambient aerosol originate from the UV-induced degradation of α-pinene in the lower

troposphere.

Fig. 16. GC/ion trap MS profile of

TMS-ated extract of A) EPA chamber-

generated SOA, B) K-puszta ambient

aerosol. Inset reveals co-elution of the

unknown U1 component. Other

identified α-pinene aerosol components

1) succinic acid, 2) 2-MG, 3) glyceric

acid, 4) and 6) Z/E-2-methyl-1,3,4-

trihydroxybut-1-en, 5) 3-methyl-2,3,4-

trihydroxybut-1-en, 7) malic acid, 8)

norpinic acid, 9) 2-metylhtreitol, 10) 2-

methylerytrytol, 11) 2-hydroxyglutaric

acid, 12) pinonic acid, 13) octanoic

acid, 14) levoglucosan, 15) arabitol,

16) tetradecanoic acid, 17) glucose, 18)

mannitol, 19) sorbitol, 20) palmitic

acid, 21) glucose, 22) stearic acid, *)

unknown species

B)

A)


29

In the subsequent research, I made an effort to characterize the U1/U2/U3 aerosol

components with the application of organic mass spectrometric methods described in details

in previously discussed papers, i.e., H2-H3 paper. For the U1 component, I proposed

the structure of 3-hydroxyglutaric acid, albeit earlier evidence suggested a false structure of

3-isopropyl-1,2-dihydroxybutanol based on the fragmentary interpretation of EI mass

spectra.67

A starting point in my studies was an observation that the U1 compound was co-

eluting with another component of terpenoic (α-pinene) aerosol with already solved structure

of 2-hydroxyglutaric acid. The latter species was detected in a fine aerosol mass formed over

the Amazon rainforest.38

This brought me to the conclusion that the U1 α-pinene SOA

component is an isomer of 2-hydroxyglutaric acid. The comparison analysis of mass spectra

recorded for trimethylsililated derivatives of either hydroxyglutaric acids revealed striking

differences. However, a detailed interpretation of ion trap mass spectra, including

fragmentation cascades m/z 349 → m/z 259 → m/z 185 (confirmed for the U1 compound)

and 349 → m/z 321→ m/z 231 → m/z 203 (confirmed for 2-hydroxyglutaric acid), recorded

in the ion trap MS2 experiments, allowed me to differentiated between either acid. The useful

turned out to be the presence of diagnostic ions at m/z 333 i m/z 243 in the mass spectrum of

the U1 unknown α-pinene SOA component, which were absent in the mass spectrum of

2-hydroxyglutaric acid. The structural proposals of these ions along with their fragmentation

mechanisms are shown in Fig. 17. Evidently, the equivocal structural assignment for the U1

compound, I could provide through a comparison of chromatographic and mass spectral data

obtained for trimethylsililated derivatives of the unknown U1 species and that obtained for

3-hydroxyglutaric acid, as an authentic standard. The latter compound I obtained through the

art of organic synthesis. The synthesis entailed a canonical reduction of a carbonyl residue in

the molecule of 3-ketoglutaric acid with sodium borohydride (NaBH4).


30

Fig. 17. Proposed fragmentation pathways for the unknown U1 component of a C5 skeleton detected in ambient

(K-puszta) and laboratory-generated SOA from α-pinene at appreciated concentrations.

A detailed interpretation of the EI ion trap mass spectra of trimethylsililated and

ethylated derivatives led me to propose the structure of the unknown U2 α-pinene aerosol

component as 3-hydroxy-4,4-dimethylglutaric acid in contrast to previously reported a wrong

structure of 4-isopropyl-2,4-dihydroxyheksanolu.67

In my reasoning I took into account

the following ionic products that bear structural information: the m/z 287 ion, originating from

the [M – CH3]+

precursor ion via the loss of trimethylsilanol (TMSOH), the m/z 259 ion,

formed from the abundant m/z 287 ion via the CO elimination and the m/z 232 ion, which is

present in the EI mass spectrum due to the McLafferty’s rearrangement of the M+.

ion

(m/z 392) with a concomitant radical site-induced decomposition (Fig. 18). The latter ion

provided a unique structural data, since allowed to confirm the presence of the 1-carboxyl-

1,1,-dimethylmethylene moiety in the molecule of the U2 product. Taking into account the

structure of α-pinene – as a precursor, it is worth noting that a revised structure of the U2

product likely incorporates the (CH3)2C part of the dimethylcyclobutane ring.


31

Fig. 18. Proposed fragmentation pathways for the unknown U2 component with C7 skeleton detected in

laboratory-generated α-pinene SOA and K-puszta fine aerosol.

The U3 compound detected as the major component of the EPA smog chamber-

generated α-pinene SOA (Fig. 16) was previously reported as a relevant component of

ambient aerosol collected at different sites in Europe,37,68,69

Asia58,70,71

and the U.S.,72,73

as

well as related chamber experiments.65,74,75

The fragmentation pathways proved by product

ion maps recorded for relevant ions displayed in the first order mass spectrum of the U3

unknown, permitted me to assign for this component a structure of 2-hydroxy-4-isopropyl-

adypic acid (Fig. 19).


32

Fig. 19. Proposed fragmentation pathways for the unknown U3 component of a C9 skeleton detected in ambient

(K-puszta) and laboratory-generated SOA from α-pinene at appreciated concentrations.

Hitherto efforts made to elaborate the structure of the U3 component led to a C8 entity

of 3-carboxyheptanodinic acid as indicated by the interpretation of EI mass spectra recorded

for trimethylated and diazomethane-based methylated/trimethylsililated derivatives. In order

to verify the hypothesis, I subjected fine aerosol extracts (both ambient and laboratory-

generated) to the ethylation reaction followed by trimethylsililation one. I concluded that the

unknown molecule bears two carboxylic groups and one hydroxyl one. In addition, in the

chromatographic profile of the ethylated/trimethylsililated derivative, I could observe two

base line-separated peaks, which was consistent with the presence of two chiral centers in

the considered U3 molecule, and consequently – with a diastereoisomeric separation.

The analysis of a molecular ion region in the ion trap mass spectra of the ethylated/trimethyl-

sililated derivative and the trimethylsililated derivative of the U3 α-pinene SOA component,

in principle the [M – CH3]+ (m/z 317) and [M – OCH2CH3]

+ (m/z 287) ions of a mixed deriva-

tive, allowed me for inferring the molecular mass (MW 204). Interesting information

regarding the structure of the U3 molecule I retrieved from diagnostic ions at m/z 376 and

m/z 333 in the TMS-ated derivative. The analysis of the product ion mass spectra recorded for


33

these ionic precursors, pointed to the presence of an isopropyl moiety, as indicated by

a neutral loss of a C3H8 fragment (44 u) as well as combined losses of a C3H8 fragment (44 u)

and CO (28 u) for transitions M+.

(m/z 420) → m/z 376 and [M – CH3]+ (m/z 405) → m/z 333,

respectively. At this stage of my research I assumed that the U3 aerosol component bears

a close signature to the structure of the earlier discussed U1 compound, i.e., 3-hydroxyglutaric

acid, and thus proposed a structure of 3-hydroxy-5-isopropyladipic acid. In order to confirm

my assumptions I decided to design and execute the synthesis of the authentic standard.

The proposal of a synthetic strategy was based on Corey’s retrosynthetic analysis76

and

entailed two steps. First, I obtained tert-butyl 3-butenonate using commercially available

tert-butyl 2,2,2-trichloroacetaimide (TBTA) that was followed by the epoxidation of a double

bond with m-chloroperbenzoic acid (MCPBA) – Fig. 20A.

Fig. 20. Strategy of the synthesis of 3-hydroxy-5-isopropyladypic acid – as the authentic standard used in the

structural assignment of the U3 unknown of a C9 skeleton. Abbreviations: LHMDS – lithium hexamethyl-

disilazane; THF – tetrahydrofuran; TMCS – trimethylsilil chloride.

In a second step, I probed the reaction of an epoxide ring opening using nucleophilic

enolate anions generated from ethyl isovalerate (Fig. 20B). I noticed that on isolation a target

diaester, i.e., ethyl-tert-butyl 3-hydroxy-5-isopropyladipate, underwent a spontaneous

cyclization, as proved by 1H nuclear magnetic spectra, leading to a five-membered lactone

derivative (Fig. 20C). According to Baldwin’s rules this process was energetically favorited

(5-exo-Trig). Finally, required trimethylsililated and ethylated derivatives of 3-hydroxy-5-iso-

propyladypic acid, I obtained from an isolated lactone following trimethysililation and

ethylation protocols. The comparison of the EI ion trap mass spectra recorded for a trimethyl-

sililated (and separately – ethylated) authentic standard obtained synthetically with that

recorded for the U3 α-pinene SOA unknown, revealed a close similarity. However, profiles of

either spectrum differed in terms of relative abundancies of ions at the same m/z.

This observation put forward an idea that a U3 structure could be also represented by other

structures, including positional isomeric forms of 3-hydroxy-5-isopropyladipic acid bearing

a hydroxyl group at a C-2 atom and an isopropyl group at a C-4 position. Further development

of my research in this field is included in the H5 paper.

C)

A)

B)


34

Another relevant achievement of the H4 paper is the proposal of the formation

mechanism for the U3 SOA component assigned to 2-hydroxy-4-isopropyladypipic acid in

the ambient atmosphere. Quantitative determination of the U3 component and other oxidation

product, including pinic acid, in the EPA smog chamber SOA extract using GC/MS method

revealed a sharp increase of the U3 concentration up to 12.3 µg x m-3

at the end of

the experiment, while the concentration of pinic acid (and pinonic acid) after 7h of photo-

oxidation was reportedly decreasing attaining a final level of 7µg x m-3

. These results

provided a strong argument that the formation of the U3 acid – as the major smog chamber-

generated SOA component – occurred at the expense of pinic acid. Thus, it means that the U3

compound, of the proposed structure of 2-hydroxy-4-isopropyladypipic acid, might be

regarded as a novel marker for aged α-pinene aerosol.

In a subsequent paper (H5 paper) I extended a scope of the research on the structural

assignment for the MW 204 α-pinene SOA (compound U3) based on more specific

GC/MS/MS and LC/MS/MS analyses along with the synthesis of the authentic standard.

A breakthrough was achieved through the accurate mass measurement data recorded for

a deprotonated ion of the U3 SOA component for ambient PM2.5 aerosol (sampling sites:

K-puszta/ Hungary + Birmingham, AL/U.S. + Centerville, AL/U.S. + Atlanta, GA/U.S.) and

EPA chamber-generated α-pinene SOA using electrospray ionization time of flight mass

spectrometry. A determined elemental composition of C8H11O6 unambiguously prompted me

to re-address its chemical structure. An experiment with diazomethane carried out for

the above mentioned aerosol samples indicated the presence of three carboxyl moieties in

the U3 molecular skeleton. The profile of the EI spectrum recorded for a trimethylated U3

derivative revealed a series of diagnostic ions: [M – OCH3]+ (m/z 215), [M – (OCH3 +

CH3OH)]+ (m/z 187), [M – (OCH3 + CH3COO + H)]

+ (m/z 155) and m/z 145/146 ions. The

latter ions are formed from the molecular ion of a U3 trimethyl ester via the McLafferty

rearrangement with a concomitant radical site-induced α-cleavage of a resultant distonic

radical cation. A discussed fragmentation sequence was shown in Fig.21.


35

Fig. 21. GC/MS data obtained for the chamber-generated α-pinene SOA (a-b) and the methylated synthesized

MBTCA (authentic standard) (c-d). Below is given a proposed fragmentation pattern for a trimethyl ester of

the U3 component with a revised C8 skeleton. (a) Total ion current chromatogram (TIC) for α-pinene/isoprene

SOA, (b) EI ion trap spectrum for compound eluting at 26.12 min, (c) TIC for MBTCA trimethyl ester, and (d)

EI ion trap spectrum for compound eluting at 26.15 min.

The presence of these ions in the EI ion trap mass spectrum allowed me to revoke the concept

of C8 tricarboxylic acid and propose for the unknown α-pinene SOA product the structure of

3-methyl-1,2,3-butanetricarboxylic acid (MBTCA). In the following step, I made an effort to

synthesize a MBTCA skeleton. Based on principles of Corey’s retrosynthes76

I proposed

a sequence of reactions (Fig. 22).

Fig. 22. Synthetic strategy for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) – the authentic standard used

for the structural assignment of the unknown U3 component. Abbreviation: LDA – lithium diisopropylamide.

LDA/THF

-78 0CA)

B)

MBTCA

12 M HCl aq

reflux


36

The first step entailed the construction of a molecular skeleton through a nucleophilic

substitution between ethyl 2-bromoisobutyrate and diethyl succinate in the presence of lithium

diisopropylamide (LDA) – as a base in dry THF solution (Fig. 21A). The isolated product

(triester) was ten subjected to acidic hydrolysis (Fig. 21B). The purity of a final product

I confirmed by the analysis 1H nuclear magnetic resonance spectrum. The registered EI and

ESI mass spectra for the synthesized MBTCA perfectly agreed to mass spectral data

registered for the MW 204 α-pinene SOA (compound U3) in ambient and chamber-generated

aerosol. A perfect agreement I also observed for normalized retention times in GC and LC

profiles. A key achievement described in the H5 paper was a firm structural elucidation of

the major component of secondary organic aerosol, which originates from the tropospheric

photo-oxidation of α-pinene.

In the H5 paper, I also postulated the formation mechanism for 3-methyl-1,2,3-butane-

tricarboxylic acid (MBTCA) in the atmosphere. A starting point was an assumption that

a reaction sequence starts from pinonic acid, which is a first row oxidation product of

α-pinene (or its isomer – β–pinene), and it is driven by the hydroxyl radical-based chemistry.

As indicated in an introduction part, pinonic acid is a well-known marker of fresh α-pinene

SOA since it characterizes fine aerosol particles at the early stage of their formation.

The assumption made was a logical conclusion from the smog chamber experiments, where

pinonic acid was detected in the early hours of photo-oxidation (paper H4). The proposed

reaction sequences is initiated by the HO. – induced deprotonation of pinonic acid followed

by a series of forthcoming radical decompositions of a carbocyclic skeleton, which are

enhanced by the NO → NO2 oxidation cycle (Fig. 23 i 24). A NO/NO2 cycle is a powerful

driver that controls the tropospheric gas-phase chemistry, including the formation of SOA

particles.77

A complex network of reactions towards MBTCA makes it a good candidate for a

novel marker of aged α-pinene SOA. The postulated mechanism allowed for the explanation

of other α-pinene SOA components, which were detected at elevated concentrations in

ambient and laboratory-generated organic aerosol, including 3-hydroxyglutaric acid and

3-hydroksy-2,2-dimethylglutaric acid – aerosol components discussed earlier (paper H4).


37

Fig. 23. Proposal of the formation mechanism for 3-methyl-1,2,3-butanotricarboxylic acid (MBTCA) in

the lower atmosphere. The early cis-pinonic acid is a first row photo-oxidation product of α-pinene (or β–pinene

isomer) controlled by the hydroxyl radical chemistry.

Fig. 24. Proposal of the formation mechanism for other α-pinene SOA markers, including 3-hydroxyglutaric acid

(U1) and 3-hydroxy-2,2-dimetyloglutaric acid (U2) discussed in the H4 paper. Labels (a) and (b) refer to

knots indicated in Fig.23.


38

6. Secondary organic aerosol formation from aqueous-phase processing in

the atmosphere

So far, the origin of various compounds representing different chemical classes in SOA

masses could have been rationalized by photo-oxidation reactions, which occur in the gas

phase followed by a gas-to-particle conversion of primarily oxidized products. These

processes afford an array of low-volatility products of increasing oxidation numbers that are

capable of aerosol particle formation. The concept of mechanisms relaying on the above

mentioned approaches was discussed in papers H2-H5.

However, significant SOA masses in the atmosphere could also result from other

reactions taking place on a surface or in the bulk of hydrometeors. A ubiquity of water

suspended in the ambient air (fog, rain cloud, deliquescent aerosol etc.) makes it an interesting

chemical system (reactor), where volatile precursors may react to form secondary organic

aerosol (Fig. 25).

Fig. 25. A conceptual scheme of aqueous-phase pro-

cesses (in-cloud processes) contributing to

the ambient SOA formation. Abbreviation: VOCs –

volatile organic compounds.

In contrast to gas-phase processes, aqueous-

phase reactions (in-cloud reactions) leading

to novel SOA components (denoted also as

aqSOA) are poorly recognized, and thus make

a great challenge for the atmospheric community.78

In the light of the mathematical

modelling, a global aqSOA production is estimated in a range of 20-30 Tg (for comparison,

an assessed total SOA load in the atmosphere ranges from 50 to 380 Tg per year).79

Of SOA components, monoesters of sulfuric(VI) acid, i.e., R‒OSO3H and nitric(V)

acid, i.e., R‒ONO2, referred also as organosulfates (OS) and organinitrates (ON), respectively

have recently become a relevant chemical class. The H6 paper (monography) addresses

a detailed account on the organosulfate/organonitrate formation through aqueous-phase

processes in the anthropogenically-impacted environments. In addition, an emphasis was

given to explain differences in the chemical reactivity between OS and ON against other SOA

and aqSOA components. In the H6 paper, I also presented results of my own study

on fragmentation reactions of organosulfates/organonitrates that are relevant for proper

understanding of their mass spectra.

Organosulfates constitute a group of polar aerosol components, which greatly contribute

to the SOA masses (i.e., up to 30%) depending on an aerosol origin. Despite great scientific

efforts made in a laboratory framework and in field measurements, only a small fraction of

organosulfates have been identified at the molecular level. The contribution of organonitrates

to a SOA load by far does not exceed 20%. For the sake of high polarity, and consequently –

a great affinity to the water phase, OS and ON enhances aerosol hydrophilic properties. Based

on the literature survey in conjunction with my own results from the quantum-chemical


39

calculations, I critically assessed the reactivity of these compounds in the gas- and aqueous-

phase. I observed that the OS reactivity in the aqueous-phase is mainly connected to

a disruption of a carbon oxygen single bond, while for ON – to an oxygen nitrogen bond.

A similar tendency is also applied to the gas-phase chemistry that allowed me to explain the

origin of diagnostic ions in electrospray mass spectra for either group. In the case of

organosulfates, an essential fragmentation route that leads to the characteristic HSO4-

fragment at m/z 97 is anchored to the heterolytic fission of a carbon oxygen bond.

The fragmentation mechanism of the process entails a syn-elimination reaction from

a deprotonated quasi-molecular ion, which in a principle reflects a Cope rearrangement.

Figure 26 shows an example of the process along with the ESI spectrum recorded for the MW

182 organosulfate, which has been recently detected in ambient fine aerosol at appreciable

concentrations. The proposal of the formation mechanism for the MW 182 OS from isoprene

in the atmospheric waters I thoroughly discussed in the H7.

Fig. 26. A) ESI negative ion product ion mass spectrum recorded for the [M – H]- ion from the isoprene-related

organosulfate (MW 182) with a triple quadruple mass spectrometry along with B) the fragmentation mechanism

explaining the formation of the most abundant ion at m/z 97 of a diagnostic value.

In contrast to the gas-phase behavior of organosulfate, mass spectra of organonitrates are

dominated by a highly abundant ion at m/z 46, which could be explained by a homolytic

cleavage of an oxygen nitrogen bond that lead to the NO2+

charged species. This fragmenta-

tion channel has been recently applied for real-time ON measurements in ambient air using

aerosol mass spectrometry.80

The analysis of hitherto postulated pathways of the organosulfate formation from

volatile organic precursors in the lower atmosphere was another scientific topic discussed in

the H6 monographic paper. In a context of the atmospheric chemistry, aqueous-phase

processes have increasingly become accepted by environmental scientists to elucidate

the organosulfate (and organonitrate) origin in the SOA. This prompted me to launch a series

of experiments, which aimed at providing evidence on the formation of isoprene-derived

organosulfates through aqueous-phase processing of isoprene. So far, isoprene (and other

biogenic hydrocarbons) was considered irrelevant for the ambient aqueous chemistry owing to

their unfavorable Henry’s constant. However, based on earlier suggestions,81

in the H7 paper

A) B)


40

I provided experimental evidence that isoprene oxidation induced by sulfur-centered radicals,

SOx (where: x = 3 and 4) in the water solution leads to the formation of the essential fraction

of isoprene SOA. The latter radicals I generated in situ by the process of auto-oxidation of

sulfur(IV) inorganic species in the presence of the catalytic amount of transient metal ions.

The concept of the sulfur(IV) auto-oxidation, i.e., an oxidation reaction of tetra-valent sulfur

compounds, e.g., SO2 into six-valent ones, e.g., H2SO4 by means of dissolved oxygen in

atmospheric waters, was a subject of earlier broad studies,82-85

The process features a great

environmental relevance since it contributes to a mechanistic scheme of acid rain formation.

To mimic atmospheric aqueous-phase isoprene degradation, I applied aqueous aerosol

samples generated in a simulation experimental setup, where isoprene (5.44 ppm) was

introduced into diluted aqueous solutions, where manganese(II) ions-catalyzed auto-oxidation

of sulfate(IV) anions was running. The qualitative analyses of isoprene aqSOA samples

performed using liquid chromatography coupled to a QTRAP triple quadrupole mass

spectrometry, and additionally – using a Synapt GS2 high resolution mass spectrometry

equipped with a time-of-flight mass analyzer, showed the presence of isoprene-derived

organosulfur formation. A few of detected organosulfate SOA components were previously

determined in a number of environmental samples, including ambient aerosol, atmospheric

waters and laboratory-generated SOA.85-88

However, their complete identification and likely

formation mechanisms were not rationalized.

One of a key product detected in mimic aqueous SOA particles was the MW 182

organosulfate. This product was previously reported in ambient aerosol as an abundant

organic component based on mass spectrometric analyses. However, its origin and likely

structure(s) remained unknown.88

An essential achievement made in the H7 paper was to

solve and confirm the structure of the MW 182 OS as well as to propose the formation

mechanism from isoprene through aqueous-phase processing.

Fig. 27. A) The m/z 181 extracted ion liquid chromatograms registered for the MW 182 isoprene aqSOA (upper

panel) and ambient aerosol (bottom panel) collected at a rural site in Poland (Diabla Góra) along with B)

proposed fragmentation pathways.

The product ion mass spectra recorded for selected precursor ions from the negative ion ESI

mass spectrum of the 5.27 min retention time aqSOA component (Fig. 27 A), including

A) B)


41

fragmentation sequences: m/z 181 → m/z 151 → m/z 119 and m/z 181 → m/z 97, supported by

accurate mass measurements, allowed me to assign the m/z 181 OS as sulfate esters of

2-methylbut-2-en-1,4-diol with the sulfate group located at the C-1or C-4 position.

Comparison of extracted ion chromatograms (EIC) at m/z 181 from aqueous isoprene SOA

(Fig. 27 A – upper panel) with that obtained for ambient fine aerosol (Fig. 27 A – bottom

panel) (sampling site: Diabla Gora, Poland) demonstrated the presence of one isomer

(RT 5.27 min) in both samples.

The clear confirmation of a raised hypothesis I could provide by the comparison of

chromatographic and mass spectra behaviors of the MW 182 unknown with that of

a synthesized authentic standard. A designed synthesis embraced the reduction of dimethyl

citraconate to 2-methylbut-2-en-1,4-diol (first stage) followed by the sulfation of an isolated

diol with a minute drop of sulfuric(VI) acid or alternatively – with a SO3 x DMF complex

(second stage).

Fig. 28. Designed synthesis of the reference MW 182 organosulfate used for a structural assignment of

the unknown organosulfur component of secondary organic aerosol.

A profile of the synthesized in-solution standard equivocally confirmed the postulated

structure. Another organosulfur product identified in the aqueous simulation experiment was

the MW 180 organosulfur. The presence of an abundant the peak at m/z 97 in ESI mass

spectrum of a chromatographically separated aqSOA component provided evidence on

the presence of a O‒SO3H moiety. In addition, the CO elimination from quasi-molecular [M

– H] ion (m/z 179) along with another fragment ion [M – (H + SO3)]- (m/z 99) suggested a

carbonyl residue in the molecular skeleton of the MW 180 unknown. The presence of an

aldehyde residue I could confirm by nuclear magnetic resonance spectroscopy.

In the 1H NMR spectrum, recorded for aqueous isoprene SOA, I observed a downfield

doublet peak (δ = 9.86–9.89 ppm) with a vicinal coupling constant of 7.94 Hz typical of

unsaturated aldehydes. Overall, these data allowed me to assign the structure of 4-oxo-3-

methylbut-2-enol organosulfate to the MW 180 unknown component.

A relevant part of the H7 paper concerns the proposal of the formation mechanism for

either organosulfate in the atmospheric waters. Based on earlier evidence,85,89

I proposed that

a reaction sequence might be initiated by the addition of electrophilic SO4- radicals to

the isoprene unsaturated bonds in the aqueous bulk (Fig. 29).


42

Fig. 29. Proposal of the formation mechanism for atmospherically-relevant organosulfates of a C5 skeleton from

in-cloud isoprene processing.

The resulting carbonaceous radicals undergo stabilization through the addition of

molecular oxygen to afford alkyl peroxy radicals and further – to alkyloxy radicals via

the reduction pathway. In the final step, a radical reaction cycle is terminated through

the involvement of HSO3- species that leads to the MW 182 OS or – by dissolved oxygen that

leads to the MW 180 OS. Regardless of the branching, SO4 radicals were shown to be key

players behind isoprene aqueous transformations, providing another mechanism explaining

the fate of isoprene in the atmosphere.

Results obtained in the H7 paper demonstrated that in comparison to photo-oxidation

reactions, in-cloud oxidation processes of aerosol volatile precursors serve as alternative

routes leading to secondary organic aerosol. Currently, I have been extending the research in

this field in through my own research group with an emphasis put to the evaluation of novel

routes for SOA particle formation from green plant volatiles and biomass burning products.

7. Conclusions and perspectives

The aim of the presented habilitation thesis (report) was to deliver experimental data to

fill gaps in the understanding of secondary organic aerosol (SOA) formation in the lower

atmosphere. Discussed results cover the construction of analytical methods based on

hyphenated mass spectrometry, to search for novel SOA volatile precursors as well as to

identify unknown components of isoprene and α-pinene SOA that appear at appreciated

concentrations in ambient aerosol masses based on a detailed interpretation of mass spectra.

A relevant part of the research was concerned with proposals of chemical mechanisms for

isoprene and α-pinene transformations, which are behind the SOA formation in the gas- and

aqueous phases. The broad experimental material collected during realization of my research

(papers H1-H7) could be used for developing effective policies that improve air quality and


43

public health as well as to accurately predict the response of the climate system due to human

activities.

On the other hand, results obtained have been boosting further research activities of my

research group towards developments of analytical methodology based on organic mass

spectrometry for qualitative and quantitative assessment of SOA particle formation in the

troposphere. In principle, it concerns the research on poorly recognized in cloud SOA

formation from green leaf volatiles and volatiles released during biomass burning (laboratory

work), as well as field studies on the evolution of smog episodes in Poland over rural and

urban sites.

The essential research achievements delivered through a presented monothematic cycle

of publications include:

Development of a facile SPME-GC/MS method for determination of volatile

secondary organic aerosol precursors and the application of this method for

screening a volatile profile of the bark from Pinus silvestris (H1 paper).

Evidence of a strong acid effect on the efficiency of isoprene secondary organic

aerosol (isoprene SOA) formation, including the enhanced formation of

2-methylterols (reported isoprene SOA marker) and 4-hydroxy-1,3-dioxo-2-

methylbutan (novel isoprene SOA marker) (H2 paper).

Structural assignment of the major components of isoprene SOA, which forms in

a highly polluted atmosphere (high NOx concentration), as well as determination

of their mass spectrometric fragmentation pathways and formation mechanisms

in the atmosphere (H3 paper).

Identification of unknown components of ambient fine aerosol formed over

coniferous forests, as well as determination of their fragmentation pathways and

discovery of their volatile precursor – alfa-pinene (H4 paper).

Structural assignment and the formation mechanism for abundant MW 204 SOA

component that forms from alpha-pinene – as a volatile precursor (H5 paper).

Evaluation of atmospheric formation mechanisms, reactivity and mass

spectrometric behaviors of organosulfates and organonitrates – relevant group of

polar SOA components formed over anthropogenically-impacted environments

(H6 paper).

Evidence of the capability of secondary organic aerosol formation through

an aqueous-phase isoprene processing, as well as the structural assignment of

atmospherically-relevant C5 organosulfates (MW 182 and 180) along with

the their formation mechanisms (H7 paper).


44

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E. Account on other scientific (artistic) achievements

Below, there are given a concise compilation of my relevant scientific achievements.

A detailed account on this subject is provided in the attachment “Additional information”.

Number of papers: 30, including 28 from the so-called Philadelphia list and 1 textbook.

Total number of citations = 1900

Total number of citation without self-citations = 1840

Total impact factor = 121.47

Mean impact factor = 4.1886

Hirsch index, h = 13

data according to Web of Knowledge Core Collection

® – last update February 2, 2016

Up to now:

I have taken a lead in 5 projects, while I have been a principle investigator in 2 projects

and an investigator in 1 research project.

I presented results of my research in over than 28 international scientific conferences,

including 14 oral presentations and 17 poster presentations.

I have had 4 lectures on invitation.

I have reviewed one big international research project (COST) and 14 papers from the so-

called Philadelphia list.

I have been engaged in lecturing on organic chemistry to master students and

monographic lectures on the organic mass spectrometry for doctoral students.

I was a leading author of the educational/scientfic book “Chemisty on every day” for

students of secondary school and for general public.

instytut chemii fizycznej pan - ichf panichf.edu.pl/r_act/hab/szmigielski_autoreferat_en.pdf ·...

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