Iodine-initiated new particle formation (I-NPF) has long been recognized in
coastal hotspot regions. However, no prior work has studied the exact
chemical composition of organic compounds and their role in coastal
I-NPF. Here we present an important complementary study to the ongoing
laboratory and field research on iodine nucleation in the coastal atmosphere.
Oxidation and NPF experiments with vapor emissions from real-world coastal
macroalgae were simulated in a bag reactor. On the basis of comprehensive
mass spectrometry measurements, we reported for the first time a variety of
volatile precursors and their oxidation products in gas and particle phases
in such a highly complex system. Organic compounds overwhelmingly dominated
over iodine in the new particle growth initiated by iodine species. The
identity and transformation mechanisms of organic compounds were proposed in
this study to provide a more complete story of coastal NPF from low-tide
macroalgal emission.
Introduction
Coastal new particle formation (NPF) may be driven by daytime low-tide
emission of iodine species from macroalgae fully or partially exposed to the
air. The phenomenon was reported in hotspot locations of west Europe,
Australia and polar regions (O'Dowd et al., 2002; Heard et al., 2006;
McFiggans et al., 2010; Whitehead et al., 2009; Sipilä et al., 2016;
Allan et al., 2015; Baccarini et al., 2020; Beck et al., 2021). On the
southeast coastline of China, we reported intense iodine-initiated NPF based
on particle number size distribution and iodine measurements
(Yu et al., 2019).
To simulate iodine-initiated NPF (I-NPF) in controlled laboratory
conditions, I2 or CH2I2 vapor was usually photolyzed in the
presence of ozone to provide nucleation precursors (Burkholder et al.,
2004; Jimenez et al., 2003; Monahan et al., 2012; Saunders and Plane, 2005;
O'Dowd et al., 2004; Gómez Martín et al., 2020; He et al., 2021;
Huang et al., 2022; Gómez Martín et al., 2022). Ashu-Ayem et al. (2012), Monahan et al. (2012), McFiggans et al. (2004), Sellegri et al. (2005) and Sellegri et al. (2016) also
investigated NPF from the vapors emitted by real-world macroalgal
specimens or seawater in laboratory chamber or apparatus. However, the focus
of all the above studies was emission rate, oxidation mechanisms or nucleation
pathways of iodine species. For example, positive correlations between
particle concentrations and I2 or CH2I2 mixing ratios were
usually observed (Burkholder et al., 2004; Jimenez et al., 2003; Sellegri
et al., 2005; Monahan et al., 2012). Kinetic studies in a flow tube or a CERN
CLOUD chamber proposed the clustering of iodine oxides (IxOy) or
iodine oxoacids (HIO3, HIO2) as nucleation mechanisms on the basis
of photoionization time-of-flight mass spectrometry (TOF-MS; Gómez Martín et al.,
2020), atmospheric pressure interface TOF (APi-TOF) and nitrate chemical ionization mass spectrometer (nitrate-CIMS)
measurements (He et al., 2021; Gómez Martín et al., 2022).
Organic compounds have also been suggested to be involved in coastal NPF
(Vaattovaara et al., 2006; Yu et al., 2019). Huang et al. (2022) and Saunders et al. (2010) investigated
the effect of uptake of meso-erythritol, glyoxal, dimethylamine and oxalic
acid on the growth of iodine oxide nanoparticles. However, no prior work has
investigated the exact chemical identity of organic compounds (other than
iodomethane) and their role in I-NPF. The role of biogenic terpenes and
anthropogenic aromatics in continental NPF has been recognized for a long
time (Donahue et al., 2013). Their ozonolysis or photochemistry
products have been investigated in depth using electrospray ionization
mass spectrometry (ESI-MS) and, more recently, CIMS instruments (Nguyen et al., 2010;
Kundu et al., 2017, 2012; Faxon et al., 2018; Wang et al.,
2020; Riva et al., 2017; Yan et al., 2020; Ehn et al., 2014). It is very
likely that certain volatile organic compounds (VOCs) emitted mutually with
iodine or iodinated methane from coastal biota or biologically active sea
surface may also be involved in the coastal I-NPF process and promote the growth
of iodine particles.
To test this hypothesis, we conducted oxidation and NPF experiments with
vapor emissions from real-world coastal macroalgae in a bag reactor. A suite
of mass spectrometric methods including inductively coupled plasma MS
(ICP-MS), gas chromatography MS (GC-MS), iodide-CIMS and ESI-orbitrap MS
were applied to measure vapor precursors, gaseous products and particulate
products during the NPF process. Mass concentrations of total organic carbon
(TOC) and total iodine (TI) of new particles were compared to evaluate the
relative importance of organics and iodine in new particle growth. The
identity and transformation mechanisms of organic compounds were identified
to provide a more complete story of coastal NPF from low-tide macroalgal
emission. Our study is thus complementary to prior laboratory and field
studies of I-NPF but has an emphasis on organics.
ExperimentsExperimental apparatus and sample collection
Similar to a potential aerosol mass (PAM) oxidation flow reactor, a bag
reactor was designed to provide an oxidizing environment for simulating
atmospheric oxidation processes of algae-emitted VOCs. The bag reactor was
made from 75 µm thick fluorinated ethylene propylene (FEP) Teflon
(1.2 m × 1.5 m, flat dimension). The volume of the bag at full
inflation was determined experimentally to be about 200 L. The bag was
suspended vertically (Fig. 1) and kept in the dark or directly exposed to
room light of a fluorescent lamp. Before each experiment, the bag was purged
for several hours to reduce background particle concentrations to below 1 cm-3.
Schematic of experimental setup. Solid line: air flows. Dashed
lines: sent for offline chemical analysis.
Undaria pinnatifida, a common brown seaweed species found in the Xiangshan Gulf on the east China coast, was
collected from local intertidal zone and stored at -10 ∘C until the
experiments. A quantity of 2 kg macroalgae was put in a 20 L Pyrex glass bottle that was
filled with ∼ 1 L natural seawater. The specimens were
partially exposed to the air to simulate tidal emersion of macroalgae. A
flow of particle-free ultra-high-purity (UHP) air blew algae-emitted VOCs
out of the bottle and merged with a diluting air flow before entering the
bag reactor.
Two types of experiments were conducted. In the three ozonolysis
experiments, ozone (O3) was generated by UHP air flowing
through a 5 W 185 nm UV lamp. The O3 flow was fed just before the
bag reactor was fully inflated. Final O3 concentration in the bag
reactor was measured to be ∼ 500 ppbv using an ozone analyzer
(Model 49i, Thermo-Fisher Scientific Inc.). RH was estimated to be 10 % in
the bag reactor assuming 0.3 L min-1 water-saturated VOC flow was diluted by 2.7 L min-1 dry-air flow. In an additional OH-enhanced experiment, the O3/ VOC
mixture flow was directed through a 254 nm UV light before entering the bag
reactor. OH radicals were produced via the reaction O3+hv→ O2+O(1D) and O(1D) + H2O → 2OH. Integrated OH
exposure time was determined by a SO2 decay experiment to be 2.4 d in
the experimental apparatus assuming an ambient average OH concentration of 1.5×106 molecules cm-3 (see Supplement Sect. S1).
Other oxidants may include O(3P) that resulted from the quenching of
O(1D) (Li et al., 2015). Because the purpose of this study
is to identify gas and particle products of algae-emitted VOCs in the
simulated NPF event, a significantly higher oxidation level in the bag reactor
than the atmosphere should not change the conclusions in the article. Wall loss,
aerosol yield, reaction rate and other kinetic factors in the bag reactor
were also not evaluated.
The bag reactor was first operated in a static mode to monitor the time
evolution of gaseous products and particle size. In the static mode, the bag
was first filled to full inflation with the VOC / O3 flows. The flows
were then shut down; a scanning mobility particle sizer (SMPS; model 3936,
TSI Inc., Shoreview, MN, USA) and an Aerodyne iodide-CIMS pulled two flows
of 0.3 and 1.8 L min-1 out of the bag, respectively. The
SMPS measured the particle number size distribution from 14 to 600 nm.
The bag reactor was then operated in a dynamic mode for a few hours to
collect enough particles for offline chemical analysis. In the dynamic mode,
the VOC / O3 flow of 3 L min-1 was fed to the bag continuously, while the
SMPS and a vacuum pump (GAST Group Ltd.) pulled sample flows of 0.3 and 2.7 L min-1, respectively, out of the bag reactor. This resulted in an overall
residential time of 67 min for the O3/ VOC mixture in the fully
inflated bag. The particles in the 2.7 L min-1 sample flow were collected onto a
Zefluor® PTFE membrane filter mounted in a filter inlet for
gases and aerosols (FIGAERO) for iodide-CIMS analysis or, alternatively,
onto 47 mm diameter double quartz fiber filter pack mounted in a filter
holder for ESI-orbitrap MS, ICP-MS and TOC analysis. The front filter of the
double-filter pack collected the particles and also adsorbed some volatile
species as positive artifacts, while the back filter placed downstream of the
front filter was supposed to adsorb the same amount of volatile species as
the front filter.
Chemical analysis
Before the ozonolysis experiments, the algae-emitted VOCs in the bag reactor
were collected by a 6 L pre-evacuated stainless-steel canister (Entech
Instruments, Inc., Simi Valley, CA, USA) and analyzed using a quadrupole
GC-MS system (model TH-300B, Wuhan Tianhong Instruments Co. Ltd., Wuhan,
China). The algae-emitted VOCs, as well as their gaseous and particulate
products, were also measured by the FIGAERO-iodide-CIMS. Iodide-adduct
chemical ionization is well suited for measuring oxygenated or acidic
compounds with minimal fragmentation. More details of the GC-MS and
FIGAERO-iodide-CIMS measurements can be found in Sect. S2. The
theory and design of the two instruments were described by Wang
et al. (2014) and Lopez-Hilfiker et al. (2014).
The particles collected on quartz fiber filters were sent for offline
quantification of TOC and TI, as well as non-target analysis of organic
compounds using ESI-orbitrap MS. The front and back filters were treated,
separately, following the procedure as below: the filter was ultrasonicated
twice with 10 mL water and acetone nitrile solvent mixture (v:v=1:1).
Ultrasonication time and power were 20 min and 150 W. The extract was
filtered by a 0.2 µm PTFE syringe filter and evaporated in a rotary
evaporator to 0.5 mL. After being centrifuged for 30 min at 12 000 rpm, the
supernatant was collected for TI analysis by Agilent 1100 HPLC-7900 ICP-MS
(Agilent Technologies, Santa Clara, CA, USA) and TOC analysis by a TOC
analyzer (Model TOC-5000A, Shimadzu, Japan). TI or TOC in the particles was
obtained by subtracting the amount on the back filter from that on the front
filter. Nontarget analysis of organic compounds in the supernatant was
conducted using a Q Exactive hybrid Quadrupole-Orbitrap mass spectrometer
(Thermo Scientific, Bremen, Germany). The supernatant was directly infused
by a syringe pump and ionized in negative ESI source. All the ions in the
m/z range from 50 to 500 Th were scanned with a mass resolution of 70 000.
The chemically sound CHO molecular formulas were computed with a mass
tolerance of ±2 ppm for these ions. Only the compounds that existed
solely in the front filter or with ion intensity in the front filter higher
than that in the back filter by a factor of 3 were regarded as the organic
compounds in the particle phase (Wang et al., 2017).
Results and discussion
No particles formed in the absence of room light or O3 (see Supplement Fig. S1). Therefore, light was on throughout the experiments reported in the
article. In the static mode experiments, we could not observe gas-phase
products until 48 min after O3 injection. New particles larger than
14 nm were observed only 58 min after O3 injection. Afterwards, new
particles began to grow to form a typical banana-shape particle size
spectrum (Fig. 2a). This relatively long waiting time was likely due to
the buildup of O3 and oxidation products. Time zero of Fig. 2 was
thus set as the time when gaseous products first appeared.
Time evolution of particle number size distribution (a) and
relative intensities of gaseous molecules and radicals (b–f); the fractions
of organic compounds grouped by O and C atom numbers in the selected time
points (g–h) in a typical ozonolysis experiment (static mode). Time zero was
set as the time when gaseous products first appeared.
Macroalgal emission
It is of particular interest to know what VOCs are emitted from coastal
macroalgae. They are potential precursors of iodine particle nucleation and
growth. The canister sampling followed by GC-MS analysis showed that the top
nine non-CHO compounds with highest TIC (total ion chromatogram) peak areas (Table 1) are C5
alkanes, C10α-pinene, and halogenated C1, C3 and C5
alkanes. The top 10 CHO compounds are C2–C6 alcohols and carbonyls
with saturated or unsaturated carbon chain.
Major volatile organic compounds emitted by macroalgae as potential
NPF precursors, sorted by TIC peak area measured by GC/MS or MS peak
intensity measured by the iodide-CIMS.
The iodide-CIMS is more sensitive to more oxygenated or acidic compounds and
thus complementary to the GC-MS measurement. The 76 organic precursors
detected by the iodide-CIMS before ozone addition were characterized by
C1,2,3,6 and O2-3 formulas (Fig. 3a). The top seven compounds with
highest ion intensities were CH2O2, C2H4O2,
C3H6O3, C6H10O3, C2H6O2,
C4H8O2 and C6H12O3, which accounted for
82.5 % of total ion intensity. They are C1–C6 mono-carboxylic
acids, hydroxyl carboxylic acids or oxo-carboxylic acids with two to three oxygen
atoms (Table 1). Their carbon atom numbers are in general consistent with
the VOCs detected by GC-MS.
Oxygen and carbon atom number distributions of potential VOC
precursors (a), gaseous products (b) and particulate products measured by the
iodide-CIMS (c), as well as the particulate products measured by
ESI-orbitrap MS (d) in a typical ozonolysis experiment (dynamic mode).
Hatched bars indicate the fractions of organic formulas observed in both gas
and particle phases by the iodide-CIMS.
Integrated ion intensities of inorganic molecules and radicals in
the gas phase (static mode) and particle phase (dynamic mode) measured by
the iodide-CIMS in a typical ozonolysis experiment. The ions were color-coded according to their elemental composition. For each ion cluster, the parent
neutral molecule is on the left-hand side of the middle dot, while the
clustering ion I- or NO3- is on the right-hand side. Those
without a clustering ion are shown as bare anions.
Relatively high signals of NO3- and HNO3I- were observed
before the addition of ozone to the bag reactor. They were likely HNO3
or nitrate vaporized from algal specimens or natural seawater. Because
NO3- and HNO3I- were also observed in the particle phase
during the NPF (Fig. 4), we assume HNO3 was also an important
precursor of particle formation.
Gaseous productsGaseous inorganic molecules and radicals
Being different from the nitrate-CIMS, our iodide-CIMS did not detect nucleating
clusters of iodine oxides or oxyacids after the addition of ozone. Instead,
dozens of new inorganic molecules or radicals were observed as clusters with
I-, NO3- or deprotonated ions in the gas or particle phase
(Fig. 4). We grouped these species by elemental composition and
investigated their role in the NPF by observing how their gaseous ion
intensities evolved during the NPF event in the bag reactor (Fig. 2b–f).
Cl, I, Cl2and ClI in the gas phase. The intensities of I and Cl
increased ca. 10 min before 14 nm particles appeared and decreased as
the particles grew up (Fig. 2b). Based on prior work of Burkholder et
al. (2004), Jimenez et al. (2003) and O'Dowd et al. (2004), we suggested the
photolysis of CH2Cl2, CHBrCl, CH3I and C3H7I was
the source of halogen atoms (e.g., CH3I +hv→ CH3+ I),
although we could not exclude the photolysis of other precursors like
I2 and HOI that are invisible to GC-MS and the iodide-CIMS. There was a
time lag of 20–25 min between the appearances of Cl and I and those of
ClI and Cl2, which probably resulted from anion exchange reactions
of Cl ⋅ I- and I ⋅ I- with Cl atoms.
IO2, IO and ClIO in the gas phase. These species showed a similar time
evolution to I and Cl atoms (Fig. 2c). They could be from the reactions
between I, ClI and O3 (Saiz-Lopez et al.,
2014). Sequential oxidation and aggregation reactions might have formed
other halogen oxides (Gómez Martín et al.,
2013), but they might not be detectable by the iodide-CIMS.
INO2, ClNO2and INO3. INO2 and ClNO2 were
detected in the gas phase with similar time evolution with halogen atoms and
halogen oxides (Fig. 2d). INO3 was found in both gas and particle
phases. INO2 and INO3 were usually thought to form upon the
reactions I + NO2+ M → IONO + M and IO + NO2+ M → IONO2+ M in the atmosphere (Saiz-Lopez et al., 2012),
which seems to be unlikely in our bag reactor because NO2 was not
added. Considering NO3- was ubiquitous in the bag reactor of our
experiment, it is likely that INO2 and INO3 formed via
I2O2+ NO3-→ IO3-+IONO and
I2O3+ NO3-→ IO3-+ IONO2. These
reaction pathways have been supported by theoretical calculation and flow
tube mass spectrometry experiments (Gómez Martín et al., 2022, 2020). ClNO2 was likely to form upon
similar reaction between Cl2O2 and NO3- in the bag
reactor.
HIO, HIO2and HIO3. HIO3 seems to be the end product of
the above intermediates because its gas-phase ion intensity kept on increasing
during new particle growth (Fig. 2e). Based on this fact, we assume that
HIO3 could be from I2O5+ H2O → 2HIO3 or
I2Oy+ NO3-→ IO3-+ INOy. On the
other hand, HIO3 was not detected in the particle phase by the iodide-CIMS,
which is contrary to the offline analysis of the quartz filter by HPLC-ICP-MS
showing that total iodine was mostly dominated by IO3- peak. We
speculate that HIO3 might have been dehydrated to I2O5 under
thermal desorption temperature up to 180 ∘C in FIGAERO. The
signals of IO-, IO2- and HIONO3- (corresponding to
HIO and HIO2) were found in the particle phase but not in the gas phase. He
et al. (2021) proposed HIO2 formation via
I-+ H2O + O3→ HIO2 or
I2O2+ H2O →HIO + HIO2. With limit experimental
evidence of our work, the exact formation pathways of HIOx remain to
be explored in future.
CH3SO3H, S2-, S3-and SO3-. We
observed methane sulfonic acid (CH3SO3H, MSA) in both gas and
particle phases. Gaseous MSA increased in the beginning but decreased after
new particles appeared (Fig. 2f). Apparently, our measurement suggested
MSA contributed to the growth of new particles, but it is unknown if it also
participated in nucleation. We suggested S2-, S3- and
SO3- ions observed in the particle phase were thermal
decomposition products of MSA.
We note that CH3I vapor was added as an ion source reagent to the ion
molecule reactor (IMR) of the iodide-CIMS. It is likely that this extra
CH3I in the IMR might obscure the interpretation of the observed iodine
containing clusters. We believed that the ion source reagent CH3I should
have relatively small interference with inorganic iodine compounds from the
bag reactor, on the basis of two facts: (1) the ion source reagent CH3I was
added directly from the permeation tube into the IMR. Without photolysis, the ion
source reagent CH3I in the IMR should not become a source of I and
IxOy. (2) The concentration of the ion source reagent CH3I and
its potential products should be quite constant as long as O3 was
present in the IMR, which was not supported by the variable signals of I,
ClI, IO2, IO, ClIO, HIO3, INO2 and INO3 in Fig. 2.
Gaseous organic products
After ozone addition, a gradual transformation from C1–C3
precursors to C5–C8 gaseous products was observed during the NPF
process (Fig. 2h). In the meanwhile, the oxygen atom number of the
compounds increased from two–three to four–seven (Fig. 2g). The formation of compounds
with more carbon atoms than the parent VOCs is unlikely in the gas phase,
except bimolecular reactions of stabilized Criegee intermediates (SCIs) that
typically form upon alkene ozonolysis. Similar to isoprene ozonolysis
(Riva et al., 2017; Inomata et al., 2014), we propose the SCI addition
mechanism can also explain the transformation observed in our case: (1) C4 SCIs formed upon the ozonolysis of CHO precursors with C=C double
bonds (e.g., those observed by GC-MS in Table 1), and (2) the insertion of
C4 SCIs into carboxylic acid precursors (e.g., those observed by the CIMS
in Table 1) produced oligomeric hydroperoxides. An example is shown in
Scheme 1 for the reactions of most abundant ethyl vinyl carbinol
(C5H10O), ozone and formic acid (CH2O2), but the same
mechanism is also applicable for ethyl vinyl ketone (C5H8O) and
other abundant C2–C5 carboxylic acids and hydroxyl carboxylic
acids. As a result, a series of gaseous oligomeric hydroperoxides,
C5H10O5, C6H10O5, C6H12O5,
C7H12O6, C7H14O6, C8H14O5,
C8H16O6, C8H16O5 and C9H16O6,
were observed with high intensity by the iodide-CIMS.
A proposed addition reaction involving stabilized Criegee intermediates in the gas phase.
Particulate productsRelative mass contribution of organic carbon and iodine to new
particles
In the dynamic-mode experiments, O3 in the bag reactor was kept at its
maximum concentration of 200 ppbv. With a prolonged residential time of 67 min,
the particles grew to 102±23 nm, which was measured by the SMPS at
the outlet of the bag reactor. The TOC and TI measurements show that organic
compounds contributed more particle mass than iodine, with a TOC / (I + TOC)
ratio of 96.1±2.9 % (Table 2).
Particle number concentration (N), mean diameter (Dp), total
organic carbon (TOC) and total iodine (TI) of new particles with a
residential time of 67 min in the bag reactor in the ozonolysis experiments
and OH-enhanced experiment (dynamic mode). Those of 10–56 nm new particles
collected by a nano micro-orifice uniform deposit impactor (nano-MOUDI; MSP,
Inc.) during an I-NPF event at a coastal site of Ningbo, China (Yu et al., 2019),
are also listed.
TOCTITOC / (TI + TOC)NDp(µg m-3)(µg m-3)(cm-3)(nm)Ozonolysis experiments45.6 ± 9.70.88 ± 0.3496.1 ± 2.9 %(5.58 ± 2.04) × 104102 ± 23OH-enhanced experiment125.39.592.9 %4.16×10573I-NPF event at a coastal site of China0.70.013598.2 %6.00×10516
In the OH-enhanced experiment (dynamic mode), more particulate products were
generated with enhanced oxidation capacity: TI in the particles increased by
a factor of 10.8, TOC increased by a factor of 2.7 and particle number
concentration increased by a factor of 7.4. On the other hand, particle size
decreased to 73 nm, and the TOC / (TI + TOC) ratio decreased to 92.9 % (Table 2).
These differences indicate that more iodine nuclei were produced with
enhanced oxidation capacity, probably via OIO + OH → HOIO2 (Plane et al., 2006) and O(3P) +CH3I → IO + CH3 (Teruel et al., 2004). Competitive uptake
of condensing organic vapors onto these iodine nuclei limited the growth of
individual new particles. Nevertheless, organic compounds overwhelmingly
dominated over iodine in the mass contribution to new particle growth.
The significant organic contribution observed in the laboratory condition is
generally consistent with the TOC / (I+TOC) ratio of 98.2 % in 10–56 nm new
particles collected during a coastal I-NPF event in China
(Yu et al., 2019), although TOC and TI during the field
event are 2 orders of magnitude lower than those in the bag reactor (Table 2). The mean diameter of new particles was observed to be only 16 nm during the
field event. But those small new particles are expected to grow into cloud condensation nuclei (CCN)
active sizes, given longer residence time and uptake of more condensing
vapors in the atmosphere (He et al., 2021).
Particulate organic products
In the end of a typical ozonolysis experiment (dynamic mode), 100 and 364
new formulas were observed in the gas and particle phases, respectively,
including 73 semivolatile organic compounds (SVOCs) that appeared in both gas and particle phases. Those
SVOCs accounted for 81 % and 20 % of total ion intensities of gaseous
and particulate products, respectively. Being different from unimodal atom
number distributions of gaseous products (Cmax= 7 and Omax= 5,
Fig. 3b), particulate products were characterized by distinct bimodal or
trimodal distribution of carbon number (Cmax= 8, 14 and 16, Fig. 3c)
and oxygen number (Omax= 4 and 8), implying possible dimer formation
via accretion reactions in the particle phase.
ESI-Orbitrap MS differs from the FIGAERO-iodide-CIMS in its extraction method
(ultrasonic solvent extraction from quartz fiber filter vs. thermal desorption
from PTFE membrane filter), ionization source (electrospray ionization vs.
iodide-adduct chemical ionization) and MS-resolving power (70 000 vs. 4500). The
result showed that ESI-orbitrap MS and the FIGAERO-iodide-CIMS detected 336 and
364 organic formulas, respectively, in the particle phase. A total of 167 organic
formulas were commonly observed by both methods, which accounted for 87 %
and 54 % of total ion intensity of organic formulas by the two methods,
respectively (Fig. S2). As shown in Fig. 3c and d, the FIGAERO-iodide-CIMS
had better sensitivity toward the organic compounds with more oxygen atoms
(e.g., O ≥ 8) and carbon atoms (e.g., C ≥ 10). As a result, bimodal
carbon and oxygen atom number distributions were observed by
the FIGAERO-iodide-CIMS but not ESI-orbitrap MS.
The measurement by ESI-orbitrap MS provided more insights about the
formation mechanism of particulate products. We compared the 336 formulas
detected by ESI-orbitrap MS in our study with the 414 formulas of isoprene
ozonolysis secondary organic aerosol (SOA) products (Nguyen et al., 2010) and 922
formulas of α-pinene ozonolysis SOA products (Putman et
al., 2012) measured by the ESI-orbitrap MS. It was found that 72 % of the
formulas in this study can also be found in isoprene SOA, but only 39 %
can be found in α-pinene SOA. This seems to imply that some similar
alkene ozonolysis reactions occurred in our system and isoprene ozonolysis.
For such a highly complex system full of various algae-emitted precursors,
it is impossible to simply propose a reaction mechanism to explain the
formation of all particulate products, nor to list all reactions occurring
in the bag reactor. On the basis of particle-phase oligomer chemistry
(Seinfeld and Pandis, 2016), especially the well-understood
isoprene ozonolysis SOA chemistry (Nguyen et al., 2010; Inomata et al.,
2014; Riva et al., 2017), we suggest that a variety of accretion reactions
without uniform oligomerization pattern (e.g., esterification, aldol
condensation, hemiacetal reactions, peroxyhemiacetal formation and SCI
reactions) transformed Omax= 4 and Cmax= 8 multifunctional
monomers (like alcohols, carbonyls, hydroperoxides and carboxylic acids) to
Omax= 8 and Cmax= 14 or 16 dimers. As an example, we used two
simplified reaction equations to illustrate addition-type
cross-oligomerization between C6 and C8 monomers and
self-oligomerization of C8 monomers, respectively:
C6H6–12O3–6+C8H10–16O3–6⋅→C14H16–26O6–12C8H10–16O3–6+C8H10–16O3–6⋅→C16H20–32O6–12,
in which the C6 , C8, C14 and C16 formulas in the
equations are among the most abundant ones observed in the particle phase by
the iodide-CIMS.
Conclusions
Using a suite of mass spectrometers, we reported, for the first time, the
chemical compositions of volatile precursors emitted by real-world coastal
macroalgae and their gaseous and particulate oxidation products. In the
presence of room light and ozone, the photolysis of halogenated
C1,3,5 alkanes ends up as HIO3 and INO3. It was
most likely HIO3 initiated NPF and provided nuclei for the further
condensation of other products like MSA and CHO compounds. Gas-phase SCI
reactions and particle-phase accretion reactions transformed C1–C6
and O2–O3 precursors gradually to particulate products with
Cmax= 8, 14 and 16 and Omax= 4 and 8. As a result, organic
carbon was found to overwhelmingly dominate over iodine in the mass
contribution to the new particle growth. Although our instruments did not
allow for the detection of nucleating clusters of iodine oxides or oxyacids, our
study provided important complementary information to the ongoing laboratory
and field research on coastal I-NPF.
Data availability
All data related to figures and tables in this study have been archived and are available through the Zenodo data repository at
10.5281/zenodo.6965859 (Yu, 2022).
The supplement related to this article is available online at: https://doi.org/10.5194/acp-22-15413-2022-supplement.
Author contributions
HY designed the experiment. YW, XH and CX conducted the experiments. YW and
HY analyzed the data and wrote the manuscript. QW and XG reviewed and
revised the manuscript.
Competing interests
The contact author has declared that none of the authors has any competing interests.
Disclaimer
Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Financial support
This work was supported by the National Science Foundation of China (grant
nos. 41975831 and 42175131) and start-up research funding from the China
University of Geosciences.
Review statement
This paper was edited by James Allan and reviewed by two anonymous referees.
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