Access to this full-text is provided by Copernicus Publications on behalf of European Geosciences Union.
Content available from Atmospheric Chemistry and Physics
This content is subject to copyright.
Atmos. Chem. Phys., 21, 10625–10641, 2021
https://doi.org/10.5194/acp-21-10625-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
Mediterranean nascent sea spray organic aerosol
and relationships with seawater biogeochemistry
Evelyn Freney1, Karine Sellegri1, Alessia Nicosia1,a, Leah R. Williams2, Matteo Rinaldi3, Jonathan T. Trueblood1,
André S. H. Prévôt4, Melilotus Thyssen5, Gérald Grégori5, Nils Haëntjens6, Julie Dinasquet7,8,b,
Ingrid Obernosterer8, France Van Wambeke5, Anja Engel9, Birthe Zäncker9, Karine Desboeufs10, Eija Asmi11 ,
Hilkka Timonen11, and Cécile Guieu12
1Université Clermont Auvergne, CNRS, Laboratoire de Météorologie Physique (LaMP), 63000 Clermont-Ferrand, France
2Aerodyne Research, Inc., Billerica, Massachusetts, USA
3National Research Council of Italy, Institute of Atmospheric Sciences and Climate (CNR-ISAC), Bologna, Italy
4Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland
5Aix-Marseille Université, Université de Toulon, CNRS, IRD, Mediterranean Institute of Oceanography,
UM110, 13288 Marseille, France
6School of Marine Sciences, University of Maine, Orono, ME 04469, USA
7Marine Biology Research Division, Scripps Institution of Oceanography, La Jolla, CA 92037, USA
8CNRS, Sorbonne Université, Laboratoire d’Océanographie Microbienne, UMR7621, 66650 Banyuls-sur-Mer, France
9GEOMAR, Helmholtz Centre for Ocean Research Kiel, 24105 Kiel, Germany
10Université de Paris, Univ. Paris Est Créteil, CNRS, Laboratoire Interuniversitaire des Systèmes Atmosphériques, IPSL,
Paris, France
11Atmospheric Composition Research, Finnish Meteorological Institute, Helsinki, 00101, Finland
12Sorbonne Université, CNRS, Laboratoire d’Océanographie de Villefranche, LOV, 06230 Villefranche-sur-Mer, France
anow at: National Research Council of Italy, Institute of Atmospheric Sciences and Climate (CNR-ISAC), Bologna, Italy
bnow at: Center for Aerosol Impacts on Chemistry of the Environment,
CASPO, Scripps Institution of Oceanography, UCSD, La Jolla, CA 92037, USA
Correspondence: Evelyn Freney (evelyn.freney@uca.fr)
Received: 25 April 2020 – Discussion started: 23 June 2020
Revised: 22 March 2021 – Accepted: 30 March 2021 – Published: 14 July 2021
Abstract. The organic mass fraction from sea spray
aerosol (SSA) is currently a subject of intense research.
The majority of this research is dedicated to measurements
in ambient air. However a number of studies have recently
started to focus on nascent sea spray aerosol. This work
presents measurements collected during a 5-week cruise in
May and June 2017 in the central and western Mediterranean
Sea, an oligotrophic marine region with low phytoplankton
biomass. Surface seawater was continuously pumped into
a bubble-bursting apparatus to generate nascent sea spray
aerosol. Size distributions were measured with a differen-
tial mobility particle sizer (DMPS). Chemical characteriza-
tion of the submicron aerosol was performed with a time-
of-flight aerosol chemical speciation monitor (ToF-ACSM)
operating with 10 min time resolution and with filter-based
chemical analysis on a daily basis. Using positive matrix fac-
torization analysis, the ToF-ACSM non-refractory organic
matter (OMNR) was separated into four different organic
aerosol types, identified as primary OA (POANR), oxidized
OA (OOANR), methanesulfonic acid type OA (MSA-OANR),
and mixed OA (MOANR). In parallel, surface seawater bio-
geochemical properties were monitored providing informa-
tion on phytoplankton cell abundance and seawater particu-
late organic carbon (1 h time resolution) and seawater sur-
face microlayer (SML) dissolved organic carbon (DOC) (on
a daily basis). Statistically robust correlations (for n > 500)
were found between MOANR and nanophytoplankton cell
abundance, as well as between POANR, OOANR, and particu-
Published by Copernicus Publications on behalf of the European Geosciences Union.
10626 E. Freney et al.: Mediterranean nascent sea spray organic aerosol
late organic carbon (POC). Parameterizations of the contribu-
tions of different types of organics to the submicron nascent
sea spray aerosol are proposed as a function of the seawater
biogeochemical properties for use in models.
1 Introduction
Oceans cover approximately 70 % of the Earth’s surface, and
sea spray emissions contribute up to 6 kt yr−1of particulate
matter, making them a major source of primary aerosol in
the atmosphere (Lewis and Schwartz, 2004). The majority
of the mass associated with sea spray emissions is in the
form of coarse-mode sea salt particles. However, it is now
well known that the submicron fraction of marine emissions
is also important and contains a significant portion of or-
ganic compounds (Facchini et al., 2008). This organic frac-
tion tends to be highest during phytoplankton bloom events
(O’Dowd et al., 2004). Although the organic fraction of the
aerosol population represents little mass, the high number
concentration of these aerosol particles makes them a signif-
icant contributor to the potential cloud condensation nuclei
concentration (Burrows et al., 2014). Organics in sea spray
have also been shown to contribute to potential marine ice
nuclei (McCluskey et al., 2017). Understanding how the or-
ganic fraction of marine aerosol particles transfer to the at-
mosphere is essential to help identify the contribution of the
marine aerosols to the Earth’s radiative budget.
In general, sea spray aerosol is generated through bubble
bursting after wave breaking at the ocean surface, a process
that has been described in early publications (Blanchard and
Woodcock, 1980). Once bubbles burst, film and jet droplets
are ejected into the atmosphere and dry to leave aerosol par-
ticles as residuals containing the different constituents of the
bulk seawater and surface microlayer. The size distribution
of this sea spray aerosol (SSA) extends from the fine par-
ticle range, with diameters <100 nm, to the super-micron
range (up to 3 µm). The super-micron range is known to be
mainly composed of refractory NaCl and different MgCO3
or (Mg)2SO4species, while the submicron fraction tends to
be enriched with organic compounds (O’Dowd et al., 2004).
Traditionally, measurements in and around the marine
boundary layer were made using offline filter measurements
followed by laboratory-based analysis using either ion chro-
matography or organic carbon and elemental carbon anal-
ysis. However, over the last decade, there has been a sig-
nificant increase in the number of studies deploying online
aerosol mass spectrometry methods, including laser ablation
mass spectrometry (Dall’Osto et al., 2019) and thermal va-
porization followed by electron impact ionization methods
(Giordano et al., 2017; Ovadnevaite et al., 2011; Schmale
et al., 2013). The aerosol mass spectrometer (AMS, Aero-
dyne Research, Inc.) and aerosol chemical speciation mon-
itor (ACSM, Aerodyne Research, Inc.) are examples of the
latter type and are widely used instruments to monitor the
chemical composition of submicron particulate matter in the
atmosphere. The design of this instrument is optimized to in-
vestigate the non-refractory fraction (defined as material that
vaporizes at 600 ◦C) of aerosol mass in the atmosphere. In the
majority of atmospheric environments, the submicron frac-
tion of the aerosol is dominated by non-refractory organic
and inorganic species. In marine environments, aerosol mass
spectrometry has been used to better characterize the chem-
ical properties of ambient marine aerosol particles, from the
Atlantic (Ovadnevaite et al., 2011) to Antarctic coastal en-
vironments (Schmale et al., 2013; Giordano et al., 2017).
Using a combination of high-resolution aerosol mass spec-
trometry and positive matrix factorization analysis, different
marine organic aerosols have been identified including sec-
ondary marine organic aerosols, organic aerosols containing
methanesulfonic acid (MSA), and organic aerosols associ-
ated with amino acid (AA). The latter were thought to be pri-
marily linked to local sea life emissions at the measurement
site (Schmale et al., 2013).
Most of these studies measured ambient aerosol already
modified through atmospheric chemical and physical pro-
cesses. Current knowledge on the source and evolution of
nascent sea spray organic emissions is still limited. This is
attributed to the natural variability of marine organic aerosol
and to the lack of high-temporal-resolution studies at the
ocean–atmospheric interface. A limited number of studies
have focused directly on the composition of nascent sea spray
aerosol particles emitted from wave action in controlled sim-
ulation chambers (Wang et al., 2015; Collins et al., 2016)
or through dedicated bubble-bursting experiments in ambi-
ent environments (Bates et al., 2012, 2020; Dall’Osto et al.,
2019; Park et al., 2019). These studies in controlled envi-
ronments identified the presence of aliphatic-rich and amino-
acid-rich organic aerosols related to different phases of phy-
toplankton blooms (Bates et al., 2012; Wang et al., 2015).
Dall’Osto et al. (2019) identified an amino acid contribu-
tion in both nascent sea spray aerosol and ambient aerosols.
Park et al. (2019) observed that sea salt aerosol production
was positively correlated with organic compounds in the wa-
ter, notably dissolved organic carbon, marine microgels, and
chlorophyll a(chl a). However, in all of these studies, sam-
ples were collected at point intervals and were not able to
provide information on the evolution of aerosol physical and
chemical properties over a large spatial area. In addition to
this, previous studies do not provide measurements of seawa-
ter composition, making it impossible to provide the quanti-
tative link between seawater biogeochemistry and the SSA
organic composition.
In this work, we characterized the chemical composi-
tion of the nascent sea spray submicron aerosol contin-
uously generated from an underway seawater system on
the R/V Pourquoi Pas? over a 5-week campaign in the
Mediterranean Sea. The Mediterranean Sea is a low-nutrient
low-chlorophyll (LNLC) environment and was characterized
Atmos. Chem. Phys., 21, 10625–10641, 2021 https://doi.org/10.5194/acp-21-10625-2021
E. Freney et al.: Mediterranean nascent sea spray organic aerosol 10627
by oligotrophic conditions along the whole field campaign
(Guieu et al., 2020a). Understanding the formation of nascent
sea spray aerosols in such an LNLC system can provide valu-
able information and be extrapolated to other oligotrophic
environments.
2 Methodology
2.1 The PEACETIME oceanographic campaign
The French research vessel, the R/V Pourquoi Pas?, was
deployed for a 5-week-long period from 10 May to
10 June 2017 on the Mediterranean Sea, as part of the project
PEACETIME (ProcEss studies at the Air-sEa Interface after
dust deposition in The Mediterranean sea). The ship track
(Fig. 1) started and ended in La Seyne-sur-Mer, France. The
ship traveled clockwise, covering latitudes in the Mediter-
ranean Sea from 35 to 42◦and longitudes from 0 to 21◦.
Results from a suite of hydrology and biogeochemistry
measurements performed on board are given in Guieu et
al. (2020a). In addition to standard seawater temperature (T)
and salinity (S) measurements, the concentrations of a wide
range of chemical and microbiological parameters were
monitored hourly. Several plankton functional groups were
identified, including Synechococcus,Prochlorococcus, na-
noeukaryotes, coccolithophore-like plankton, cryptophyte-
like plankton, and microphytoplankton. The sea surface tem-
perature (T) showed a gradual increase from the start to the
end of the campaign from 19 to 23 ◦C. Sea surface salin-
ity (S) varied from 36 to 39 PSU (practical salinity units), in-
creasing from east to west. The sampling region was charac-
teristic of open sea (average depth 2750 m ±770 m along the
transect). The sea was calm to moderately rough throughout
the sampling period, with conditions always remaining be-
low Beaufort 4. Wind speed varied between 10 and 20 m s−1.
Total chlorophyll a(chl a) and particulate organic car-
bon (POC) were also measured. In line with the olig-
otrophic state of the Mediterranean Sea during this period,
the POC concentrations were highest at the most northern
latitudes and gradually decreased along the ship transect
(Fig. 1a), while the chl aconcentration remained stable and
low (0.07 ±0.013 mg m−3) throughout the sampling period
(Fig. 1b).
2.2 Surface seawater analysis
2.2.1 Flow cytometry
Phytoplankton cells were counted with 1 h time resolu-
tion using an automated Cytosense flow cytometer (Cyto-
buoy, NL) connected to a continuous-clean-pumping under-
way seawater system, as described in Thyssen et al. (2010)
and Leroux et al. (2017). Particles were brought within a
laminar-flow-filtered seawater sheath fluid and detected with
forward scatter (FWS) and side scatter (SWS) as well as flu-
orescence in the red (FLR >652 nm) and orange (FLO 552–
652 nm) ranges in the size range of 1 to 800 µm. Two trigger
levels were applied for the distinction between highly con-
centrated picophytoplankton and cyanobacteria groups (trig-
ger level FLR 7.34 mV, sampling at a speed of 4 mm3s−1
and analyzing 0.65 ±0.18 cm3) and less concentrated nano-
and microphytoplankton (trigger level FLR 14.87 mV, at a
speed of 8 mm3s−1and analyzing 3.57 ±0.97 cm3). Differ-
ent sets of 2D projections were plotted in Cytoclus®soft-
ware to manually gate phytoplankton groups. To follow sta-
bility of the flow cytometer, 2 µm red fluorescing polystyrene
beads (Polyscience) were regularly analyzed. The use of sil-
ica beads (1, 2, 3, 5, and 7 µm in diameter, Bangs Laboratory)
for size-retrieving estimates from FWS were used to separate
picoplankton from nanoplankton clusters.
2.2.2 Chlorophyll aand POC
From the underway seawater system, chl awas derived
from the particulate absorption spectrum line height at
676 nm (Boss et al., 2013) after the relationship was
adjusted to PEACETIME chl aderived from HPLC
(chl a=194.41 ×line_height1.131). POC was estimated from
particulate attenuation at 660 nm using an empirical relation-
ship specific to PEACETIME (POC =1405.1×cp(660)−
52.4), which was slightly higher than the literature value
likely due to the small dynamic range (1.27 higher on aver-
age for the range observed; Cetinic et al., 2012). Particulate
attenuation and absorption of surface water were measured
continuously with a WET Labs spectral absorption and at-
tenuation meter using a flow-through system similar to the
setup described in Slade et al. (2010). Both the chl aand the
POC were obtained with a time resolution of 1 min.
2.3 Surface microlayer (SML) sampling and analysis
2.3.1 Sampling
Surface microlayer SML sampling was conducted twice a
day from a zodiac using a 50 cm ×26 cm silicate glass plate
sampler (Harvey, 1966; Cunliffe and Wurl, 2014) with an ef-
fective sampling surface area of 2600 cm2considering both
sides. For sampling, the zodiac was positioned 0.5 nmi away
from the research vessel and into the wind direction to avoid
contamination. The glass plate was immersed perpendicular
to the sea surface and withdrawn at ∼17 cm s−1. SML sam-
ples were removed from the plate using a Teflon wiper (Cun-
liffe and Wurl, 2014) and collected in an acid-cleaned and
rinsed bottle. Prior to sampling, all equipment was cleaned
with acid (10 % HCl), rinsed in Milli-Q water, and copiously
rinsed with seawater directly before samples were taken.
https://doi.org/10.5194/acp-21-10625-2021 Atmos. Chem. Phys., 21, 10625–10641, 2021
10628 E. Freney et al.: Mediterranean nascent sea spray organic aerosol
Figure 1. The ship track in the Mediterranean Sea during the PEACETIME expedition. The trajectory is colored by (a) POC and (b) chl a.
2.3.2 DOC analysis
The concentration of dissolved organic carbon (DOC) was
determined in samples filtered online (Sartoban © 300;
0.2 µm filters). Subsamples of 10 mL (in duplicate) were
transferred to pre-combusted glass ampoules and acidified
with H3PO4(final pH =2). The sealed glass ampoules were
stored in the dark at room temperature until analysis. DOC
measurements were performed on a Shimadzu TOC-V-CSH
(Benner and Strom, 1993). Prior to injection, DOC samples
were exposed to CO2-free air for 6 min to remove inorganic
carbon. A 100 µL aliquot of sample was injected in tripli-
cate, and the analytical precision was ±2 %. Standards were
prepared with acetanilide. Analysis of DOC was performed
on both SML and the underlying seawater sampled from the
zodiac.
2.4 Sea spray generation and analysis
2.4.1 General setup
The sea spray generator has been characterized and deployed
in a number of previous studies, and full details are re-
ported in Schwier et al. (2015). Briefly, it consists of a 10L
glass tank, fitted with a plunging jet system for the water.
A particle-free air-flushing system is placed perpendicular to
the water surface at a distance of 1 cm to send a constant air-
flow across the surface of the water to replicate the effects
of wind on the surface (13 m s−l). The sea spray generator
was supplied with a continuous flow of seawater collected at
a depth of 5 m by an underway seawater circulating system
operated with a large peristaltic pump (Verder®VF40 with
EPDM hose). The wastewater was evacuated downstream of
the sampling location to avoid any contamination.
The aerosol instrumentation included a time-of-flight
aerosol chemical speciation monitor (ToF-ACSM, Aerodyne
Research, Inc.), a custom-made differential mobility particle
sizer (DMPS) coupled with a condensation particle counter
(CPC, model 3010, TSI), and an impactor (Dekati, PM1) for
collecting submicron particulate matter for offline ion chro-
matography and chemical analysis. All three sampled from
the headspace above the seawater in the tank. A silica gel
dryer was connected to the output of the chamber, which
was subsequently connected to a flow dispatcher having three
outputs of equal length (<50 cm), one to the ToF-ACSM,
one to the DMPS, and one to the impactor. The aerosol rel-
ative humidity was measured continuously and varied from
20 % to 40 % (Fig. S1 in the Supplement). The total sampling
line length after the sea spray generator was approximately
2 m with a sampling flow of 5 L min−1giving a residence
time of less than 30 s. A schematic of the sampling setup is
shown in Fig. S2. Regular tests were performed to ensure
that the system was airtight and free from external aerosol
influences.
2.4.2 Aerosol physical and chemical properties
Size distribution measurements
Particle size distribution and number concentration measure-
ments were obtained using the DMPS. Measurements were
provided approximately every 10min for 25 different size
bins ranging from 10 nm up to 500 nm. The size distribution
was relatively constant throughout the measurement period,
giving a principal size mode at 110 nm and a second mode
at 300 nm. This size distribution is characteristic of the bub-
bler seawater generation method (Schwier et al., 2015) and is
similar to that from other nascent seawater aerosol generators
(Bates et al., 2012) and to that observed in the clean marine
boundary layer (Yoon et al., 2007). Although the size distri-
bution remained constant, the absolute number concentration
varied by a factor of 3 over the sampling period. Details of
these changes in aerosol number concentration as well as the
Atmos. Chem. Phys., 21, 10625–10641, 2021 https://doi.org/10.5194/acp-21-10625-2021
E. Freney et al.: Mediterranean nascent sea spray organic aerosol 10629
associated cloud condensation nuclei activity are detailed in
Sellegri et al. (2021).
Offline PM1filter analysis
In parallel to the online aerosol physical and chemical mea-
surements, the generated nascent sea spray aerosol particles
were also sampled onto PM1quartz filters in the impactor.
Aerosol samples were stored in airtight containers and were
transported to the laboratory for analysis following the field
campaign. In the laboratory, aerosol samples were extracted
in Milli-Q water by sonication (30 min) for analysis of the
water-soluble components. Extracts were analyzed by ion
chromatography for the quantification of the main inorganic
ions (Sandrini et al., 2016). An IonPac CS16 3 ×250 mm
Dionex separation column with gradient MSA elution and
an IonPac AS11 2×250 mm Dionex separation column with
gradient KOH elution were deployed for cations and anions,
respectively. The contributions of the estimated ssSO4 (sea
salt SO4), ssK, ssMg, ssCa, and ssCl were calculated based
on the seawater theoretical ratio (Seinfeld and Pandis, 2016).
These ratios are 0.25 for SO4, 0.06 for K, 0.12 for Mg,
and 0.04 for Ca. The remaining non-sea-salt (nss) fraction
of the inorganic aerosol was within the measurement error of
the instrument.
The water-soluble organic carbon (WSOC) content of the
extracts was quantified using a total organic carbon (TOC)
thermal combustion analyzer (Shimadzu TOC-5000A) (de-
tection limit (DL) =1.9 µgC/filter). Measurements of the to-
tal carbon (TC) content were performed on a filter punch cut
before water extraction by a thermal combustion analyzer
equipped with a furnace for solid samples (Analytik Jena,
multi NC2100S; Rinaldi et al., 2007) (DL =37.9 µgC/filter).
For the organic carbon (OC) analysis, the punch was acid-
ified before analysis to remove inorganic carbon from TC
and obtain OC. This process included positioning the punch
in the instrument sample container, covered with 40µL of
H3PO4(20 %w/w) and left under oxygen flow, at room tem-
perature, for ca. 5 min to allow the volatilization of carbon-
ates as carbon dioxide (CO2). The process was monitored
online by nondispersive infrared (NDIR) spectroscopy CO2
detector: when the CO2level went back to baseline condi-
tions, the vessel was placed into the furnace (950 ◦C) for the
OC analysis.
The water-insoluble organic carbon (WIOC) is not mea-
sured directly but is derived from the difference between
WSOC and OC. As mentioned, the measurements of OC
and WSOC are made with two different instruments with
that for WSOC having a much lower limit of detection (DL).
Although the quantification of WSOC was always possible,
some samples had OC concentrations <DL, assuming that
OC =WSOC (and WIOC =0) would be incorrect and would
result in significant error in the estimate of total OC. There
could be a significant amount of WIOC that we cannot quan-
tify because of the lower sensitivity of the OC analysis. For
this reason, we presented WIOC and OC data only for sam-
ples that have both quantifiable OC and WSOC.
The amount of inorganic carbon varies between 12 % and
71 % of TC, and thus the acidification process for sea spray
is an important step to follow for OC measurements. Or-
ganic carbon was converted to organic mass using conver-
sion factors of 1.4 for the conversion of WIOC to WIOM
and 1.8 for the conversion of WSOC and WSOM (Facchini
et al., 2008). Although filters were only collected on a daily
basis, they provided valuable information on the refractory
component of the aerosol population. In order to compare
filter measurements with volume concentrations measured by
the DMPS, filter volume concentrations were calculated from
the measured mass concentrations using a density value of
1.2 g cm−3for organic matter and a density of 2.165 g cm−3
for the other remaining components, SO4, chl, Na, and Cl as-
suming a density for sea salt (Seinfeld and Pandis, 2016).
These concentrations compared well with those from the
DMPS (Fig. S3).
ToF-ACSM
The ToF-ACSM is based on the same operating principles
as the aerosol mass spectrometer (Drewnick et al., 2009).
The ToF-ACSM contains a critical orifice, a PM1aerody-
namic lens to focus submicron particles into a narrow beam
that flows into a differentially pumped vacuum chamber, a
standard vaporizer heated to 600 ◦C to vaporize particles, an
electron-emitting tungsten filament (70 eV) to ionize the va-
por, a compact time-of-flight mass analyzer (ETOF, Tofw-
erk AG, Thun, Switzerland), and a discrete dynode detector
(Fröhlich et al., 2013). It does not have the ability to size
aerosol particles but has the advantage of being more com-
pact and more robust for continuous observations than the
AMS (Fröhlich et al., 2013). The ToF-ACSM alternates be-
tween sampling ambient air and sampling through a filter in
order to subtract the signal due to air.
During this experiment the ToF-ACSM was operated in
a 2 min filter and 8 min sample mode with a measure-
ment every 10 min. The aerodynamic lens transmits parti-
cles between 70 and 700 nm, making the ACSM approx-
imately a PM1measurement. The non-refractory particle
material (NR-PM) is defined similarly as in DeCarlo et
al. (2006) as aerosol particles that are vaporized using the
600 ◦C resistively heated vaporizer and detected during the
instrument sampling interval. The relative ionization effi-
ciency for NH4was 3.12 and for SO4was 0.8, determined
from calibrations with ammonium nitrate and sulfate. How-
ever, considering that the measured SO4concentrations rep-
resent sea salt (ss) SO4, we adjusted the relative ionization
efficiency (RIE) of SO4to 0.3 so that the mass concentration
of SO2−
4from the ACSM agrees with that of the filters during
the periods when filter and ACSM total mass concentrations
were in agreement (before 30 May; see Fig. S3).
https://doi.org/10.5194/acp-21-10625-2021 Atmos. Chem. Phys., 21, 10625–10641, 2021
10630 E. Freney et al.: Mediterranean nascent sea spray organic aerosol
The temperature of the vaporizer and the size range do not
permit efficient detection of sea salt particles with the ToF-
ACSM. However, in situations of high sea salt concentra-
tions, detection of sea salt ions and related halides have been
reported (Bates et al., 2012; Giordano et al., 2017; Ovad-
nevaite et al., 2011; Schmale et al., 2013; Timonen et al.,
2016). Likewise, in this study mass spectral signals associ-
ated with sea salt were observed. In addition, the contribution
from chloride was very high (72 % of the total mass). In some
quadrupole ACSM instruments, negative Cl peaks are some-
times observed (Tobler et al., 2020) due to slow evaporation
of refractory material from the vaporizer relative to the 30s
switching time between filter and sample. This tends to over-
estimate the filter measurement and underestimate the sam-
ple measurement and can lead to negative values for the dif-
ference. However, during these measurements with the ToF-
ACSM, negative Cl was not observed likely because of the
long switching times.
The typical signature peaks for sea salt aerosol in our in-
strument were confirmed by atomizing pure aerosol particles
generated from sea salt solution (Biokar, synthetic sea salt,
lot: 0017475), passing the particles through a silica gel dryer
and into the ToF-ACSM instrument. In the default fragmen-
tation table used to assign the signals at individual m/z’s to
chemical species (Allan et al., 2004), peaks associated with
sea salt were identified as organic aerosol fragments. In or-
der to better represent the measured aerosol composition, we
modified the standard fragmentation table by introducing a
sea salt species that includes m/z fragments at m/z 23 (Na+),
m/z 35 and 37 (35Cl−,37 Cl−), 58 and 60 (Na35Cl, Na37 Cl),
and 81 and 83 (NaCl2, NaCl37Cl). For m/z 81, there is over-
lap with an SO4fragment, and a correction suggested by
Schmale et al. (2013) was applied (Eq. 1). This correction
accounted for less than 10 % of the signal at m/z 81 and 3 %
of the total sulfate signal.
frag_SO4[81] = 81 −frag_organic[81] − 0.036 ×frag_Na[23](1)
Quantification of sea salt is difficult in the ToF-ACSM as a
result of inefficient vaporization and a nonlinear contribution
to the Na+signal from surface ionization on the vaporizer.
Therefore, in this work we do not attempt to quantify the sea
salt fraction, but instead we use the mass spectral information
to separate it from the organic aerosols. A standard collection
efficiency (CE) of 0.5 was applied to all data obtained from
the ACSM (Middlebrook et al., 2012). Regular particle-free
sampling periods were performed to ensure that there was no
buildup of material on the vaporizer and that the sampling
setup was leak-free.
Positive matrix factorization (PMF)
In order to identify the different organic aerosols present in
the sea spray from primary seawater, unconstrained positive
matrix factorization, using the SoFi interface (Canonaco et
al., 2013), was performed on the ToF-ACSM organic mass
spectra. The ToF-ACSM gives unit mass resolution (UMR)
mass spectra, so it is not possible to distinguish between salt
and non-salt ions at a given m/z. A decision was made to re-
move all sea-salt-related ions from the organic mass spectral
data matrix, giving a total of 116 m/z from 0 up to 150. We
are aware that removing the m/z’s associated with NaCl (23,
35, 37, 58, 60, 81, and 83) will also remove contributions
from organics at these m/z’s. However, the organic contribu-
tions at these m/z values are small relative to the rest of the
organic MS and are typically a factor of 10 smaller than sea
salt in the ACSM signal.
During sampling, the ToF-ACSM was run with a 2 min fil-
ter and 8 min sample cycle. When sampling with long times
between filters, any drift in sensitivity can result in a dif-
ference signal that is an artifact. This is especially true for
those signals with a high background (e.g., from air at m/z 29
from 15NN), and when measuring low concentrations of or-
ganic mass (as is the case during this experiment). In PMF
solutions including m/z 29, one of the factors contained pre-
dominantly m/z 29, and the time series was noisy and flat.
Down-weighting m/z 29 (by ×100) did not help distribute
the signal at m/z 29 into the other organic factors. There-
fore, since m/z 29 was only contributing to noise and not
to chemical information, we removed it. The PMF solutions
were explored up to six factors, as a function of f-peak val-
ues from −1 to +1 (Figs. S4 to S10). The four-factor solution
was chosen, based on correlations with reference mass spec-
tra. The correlations for the three- and five-factor solutions
are illustrated in the Supplement (Figs. S5, S6, S9, and S10).
The four identified factors, as well as their mass spectral fin-
gerprints and time series, will be discussed in the following
sections.
3 Results and discussions
3.1 Time evolution of the chemical composition of
nascent sea spray
Mass concentrations of aerosol chemical composition ob-
tained from the submicron offline filter measurements are
listed in Table 1. The soluble inorganic species concentra-
tions were mostly found with proportions similar to the ref-
erence average seawater composition (Seinfeld and Pandis,
2016). However, enrichment in K+(69 % of which was not
explained by the average seawater composition) and a slight
enrichment of Ca2+were measured toward the end of the
campaign (17 % of Ca2+was not explained by reference
seawater composition from 28 May onward). In contrast,
the magnesium was slightly depleted (20 % less than ex-
pected in reference seawater composition) but less towards
the end of the campaign. Filter-based organic matter (OM)
was evenly split between WIOM (9 % ±0.5 % of total mass)
and WSOM (6 % ±6 % of total mass), which contrasts with
previous studies where organic matter in ambient marine
Atmos. Chem. Phys., 21, 10625–10641, 2021 https://doi.org/10.5194/acp-21-10625-2021
E. Freney et al.: Mediterranean nascent sea spray organic aerosol 10631
Figure 2. Time series of the fractional contribution of different species to the ToF-ACSM signal, as well as the total mass concentrations
measured by the ACSM (black), and the missing fraction relative to the DMPS measurement (FRefrac) in grey.
Table 1. Concentrations of different chemical species in PM1pri-
mary seawater aerosols measured using offline analysis of filters
and online measurements from the ACSM. The cited uncertainty
represents 1σ.
Offline analysis of filters % Non-refractory PM1%
(µg m−3) (ACSM) (µg m−3)
ssSO2−
41.22 ±0.48 5.3 % SO40.78 ±0.34 9.5 %
Sea salt−17.54 ±7.1 76.4 % NO30.02 ±0.02 0.2 %
ssCa2+
−0.18 ±0.07 0.8 % NH40.04 ±0.11 0.5 %
ssK+0.03 ±0.01 0.13 % Sea salt 6.7±5 82 %
Mg+0.59 ±0.23 2.6 % Org 0.67 ±0.26 8.2 %
WIOM 2.02 ±0.12 8.77 %
WSOM 1.39 ±1.3 6.06 %
aerosol was almost exclusively composed of WIOM (Fac-
chini et al., 2008). However, these previous studies were con-
ducted during phytoplankton bloom events of the North At-
lantic Ocean, where POC is usually enhanced. Considering
that the Mediterranean Sea is characterized by oligotrophic
conditions during PEACETIME, it could explain the rela-
tively low contributions of WIOM.
The chemical composition of SSA measured by the ACSM
is shown in Fig. 2 and listed in Table 1 and was primarily
composed of sea salt aerosol (determined from the signals at
m/z 23 (Na+), m/z 35 and 37 (35Cl−,37 Cl−), m/z 58 and
60 (Na35Cl, Na37 Cl), and m/z 81 and 83 (NaCl2, NaCl37Cl),
representing 82 % ±61 %), followed by SO4at 9.5 % and or-
ganic matter at 8.2 %. The variability in the different chemi-
cal compositions throughout the sampling is thought to be a
result of the differing associated contributions of refractory
compounds (Ca2+, Mg+, K+, etc.) in the sea salt sample.
In order to determine how representative the ACSM PM1
measurements were of the total PM1mass, the total ACSM
PM1mass concentration was converted into volume concen-
tration (dividing organic mass concentrations by a density
value of 1.2 g cm−3, and the other remaining components
SO4, Cl, and NaCl by 2.165 g cm−3(Seinfeld and Pandis,
2016). Contributions from NO3and NH4were less than 1 %
of the mass and were not included in the volume calculation.
The ACSM volume concentration was compared to the vol-
ume concentration measured by the DMPS, giving a correla-
tion (r) of 0.49 and slope (b) of 1.21 (Fig. 3). The variation in
the total sea spray mass concentration with time is a result of
the variability in the number of sea spray particles generated
from the sea spray generation device. The size distribution of
the aerosol remained stable throughout the experiment, but
the sea spray number emission flux is influenced by the vari-
ability in seawater biogeochemical properties. This is pre-
sented and discussed in detail in a companion paper (Selle-
gri et al., 2021), where we show a clear relationship between
the sea spray number concentrations generated in the bubble-
bursting system and the nanophytoplankton concentration of
the seawater, not only in the PEACETIME experiment but
also in other seawater types.
The agreement between the two instruments is relatively
good in the first part of the campaign, but the difference
between the ACSM-derived volume and the DMPS-derived
volume increases during the later parts of the campaign from
1 to 10 June (Fig. 3). We ruled out the possibility that the
high fraction of inorganics in the SSA led to an accumu-
lation of refractory or semi-refractory material on the va-
porizer and a corresponding decrease in the ability to mea-
sure non-refractory material by examining the background
(filter) signals. Figure S11 shows the background signal at
m/z 58 (NaCl+) as a function of time; this signal varies as a
function of total mass loading but does not progressively in-
crease over time. Similarly, particle-free sampling periods at
the start and the end of the field campaign show that m/z 58
background levels dropped to comparably low values. There-
fore, we conclude that overloading of the ACSM by refrac-
tory, or semi-refractory slowly vaporizing, material did not
occur, and the missing mass is due to increased refractory
content. The fraction of missing mass, FRefrac, is estimated
as the difference between the DMPS volume and ACSM vol-
ume divided by the DMPS volume and is shown as the grey
area in Fig. 2. The latter period of the field campaign corre-
sponds to a change in seawater type with more inputs from
https://doi.org/10.5194/acp-21-10625-2021 Atmos. Chem. Phys., 21, 10625–10641, 2021
10632 E. Freney et al.: Mediterranean nascent sea spray organic aerosol
Figure 3. Comparison between the ACSM and the DMPS volume concentration (cm−3, m−3).
the Atlantic Ocean and a corresponding decrease in practi-
cal seawater salinity (Fig. S13). It is possible that during this
sampling period, the seawater contains higher fractions of
refractory material that are less efficiently measured by the
ACSM. An additional means to estimate the missing mass is
to subtract the total ACSM mass loading from the total mass
measured on the filters. Comparing this estimation of missing
mass to the different species measured on the filters shows
the best correlations with Mg2+, Ca2+, and SO2−
4(Fig. S14).
This might suggest that the ability of the ACSM to measure
NaCl particles depends on how NaCl is associated with other
compounds in the sea spray.
The PM1mass concentrations of WSOM and WIOM cal-
culated from the filters were additionally compared with the
total OM measured from the ACSM (OMACSM) (Fig. S14).
The OMACSM represented on average 27% of the total fil-
ter OM. In the following section, we analyze in more detail
the different organic aerosol species present in the SSA sam-
ples and determine to what extent they are related to seawater
biogeochemical properties.
3.2 Marine organic aerosol speciation
As explained in Sect. 2 (Methodology), PMF was used to
separate organic factors. Based on the correlations with ref-
erence mass spectra and on observations of the temporal
variations, we chose a four-factor solution. These factors
include an oxidized organic aerosol (OOANR), similar to
ambient reference OOA (Ng et al., 2010), somewhat oxi-
dized OA containing mixed amino acid and fatty acid sig-
natures (mixed OA, MOANR), primary organics containing
aliphatic signature peaks as well as several peaks correspond-
ing to fatty acids signatures (POANR), and a methanesulfonic
acid-like OA (MSA-OANR) (Phinney et al., 2006). The av-
erage composition for two distinct time periods, the mass
concentrations as a function of time, and the mass spec-
tra are shown in Fig. 4. The fractional contribution of each
factor to the total mass as a function of time is shown in
Fig. S7. The correlations of each of the identified factors
with reference mass spectra are illustrated in Fig. S8. The
OOANR contributed 51 % ±2 % to OA and had signature
peaks with high m/z 44 and m/z 28 and correlated with
an OOA reference mass spectrum (r=0.98). It did not con-
tain any other m/z values that might suggest a contribution
from other species. The O/C ratio of the OOANR fraction
was 1.6 (calculated using the method described in Cana-
garatna et al., 2015), which is significantly higher than the
average O/C ratio of LV-OOA found in terrestrial ambi-
ent aerosols (0.8) (Canagaratna et al., 2015). High O/C ra-
tios have been reported in ambient studies where carbonate
species were thought to be measured by the ACSM (Bozzetti
et al., 2017; Vlachou et al., 2019) and additionally have been
associated with aerosols subjected to aqueous phase process-
ing (Canagaratna et al., 2015). It is also possible that the PMF
analysis wrongly attributed excess m/z 44 to OOA at the ex-
pense of other species such as the MSA-OANR discussed be-
low. This would impact the reported absolute concentrations
of the OOANR vs. the MSA-OANR.
The second most dominant species was defined as a mixed
organic aerosol (MOANR). This factor contributed to 15 %
of the total OANR at the start of the campaign and then in-
creased to 28 % and 35 % later on in the campaign (Fig. 4a).
This MOANR factor contained several mass peaks associated
with amino acids (AAs) reported in reference mass spec-
tral signatures of leucine and valine (Schneider et al., 2011).
AA signature peaks were identified at m/z 41, 70, 98, 112,
115, 117, 119, and 131 and were similar to signature peaks
that had been identified in previous studies by Schmale et
al. (2013) in ambient marine aerosols and by Schneider et
al. (2011) during a series of laboratory studies on differ-
ent AAs. Similar marker m/z’s were present for fatty acid
species such as palmitic and oleic acid (Alfarra et al., 2004).
The MOANR factor had an O/C of 0.53 and an H/C of 1.39,
hence much less oxidized than the OOANR type. These val-
ues are intermediate between those often calculated for low-
volatility and semi-volatility OOANR in the ambient atmo-
sphere (Canagaratna et al., 2015) and are similar to those
Atmos. Chem. Phys., 21, 10625–10641, 2021 https://doi.org/10.5194/acp-21-10625-2021
E. Freney et al.: Mediterranean nascent sea spray organic aerosol 10633
Figure 4. (a) The contribution of the different organic factors during
different periods of the PEACETIME ship campaign (identified by
the grey bars at the top of b). (b) The mass concentrations of each
factor (OOANR, MOANR, POANR, and MSA OANR) as a function
of time. (c) The mass spectra of the factors.
identified by Schmale et al. (2013) for an amino-acid-type
aerosol (O/C 0.35 and H/C 1.65) detected in an ambient ma-
rine aerosol.
The third most prominent factor was identified as a pri-
mary organic aerosol (POANR) and contributed 26 % to the
total organics at the start of the campaign, decreasing to 9 %
near the end of the campaign (Fig. 4a). This factor con-
tained typical aliphatic signatures and had little contribution
from m/z 44. The mass spectral signature of the POANR fac-
tor correlated well with reference mass spectra of leucine
(r=0.56) and valine (r=0.51) but also with fatty acid mass
spectra of oleic (r=0.69), palmitic acid (r=0.74), and hy-
drocarbon organic aerosol (HOA) (r=0.78). The O/C ratio
of this POANR was 0.1 and the H/C was 1.64, which is typi-
cal for values of primary organic aerosol in the ambient atmo-
sphere. The POANR factor identified in this work, as well as
the H/C ratio (1.64), was similar to the aliphatic-rich organic
aerosol species measured in contained wave chamber exper-
iments during a phytoplankton bloom (Wang et al., 2015).
Once the bloom passed the H/C of these aerosol particles
decreased, and it was hypothesized that the primary organ-
ics were transformed through microbial activity in the water.
During the PEACETIME campaign, the POANR factor had
higher concentrations at the start of the field campaign and
then later decreased. This decrease in POANR was accompa-
nied by an increase in the more oxidized MOANR (Fig. 4b).
The last factor, MSA-OANR; contributed 6 % ±1 %, con-
tained typical signature peaks at m/z 65, 79, and 96; and
correlated with reference mass spectra of MSA (r=0.34)
(Fig. S8). This mass spectrum is similar to that identified by
Timonen et al. (2016) in Antarctica. However, unlike previ-
ously measured ambient MSA-like species (Schmale et al.,
2013), it contained little or no oxygenated peaks at lower
masses (m/z 43, 44, 45), making it impossible to calculate
an O/C ratio. As mentioned above, it is possible that, given
the low temporal variability, the m/z 44 was incorrectly at-
tributed by the PMF analysis, resulting in an excess m/z 44
in OOA and missing m/z 44 in MSA-OANR. The H/C ra-
tio of 1.12 was similar to 1.2 measured by Ovadnevaite et
al. (2011) but lower than the reported 1.6 by Schmale et
al. (2013) for MSA-OANR, both detected in ambient aerosol.
The presence of an MSA-OA in nascent sea spray gener-
ated in the present study suggests that this compound is al-
ready present in the seawater and not only produced from
gas-phase DMS emissions and oxidation in the atmosphere.
The Mediterranean Sea experiences a high level of radiation
(MerMex Group, 2011) and could also explain the presence
of MSA-like compounds from DMS oxidation within the
seawater. Precursor species of MSA exist in seawater, such
as dimethylsulfoniopropionate; however, the available refer-
ence mass spectra of this compound (determined using liquid
chromatography MS) contain m/z values at 63, 73, and 135,
none of which are visible in our organic spectra (Swan et
al., 2017; Spielmeyer and Pohnert, 2010). Therefore, we be-
lieve that the MSA-OANR species measured in these seawa-
ter samples resembles MSA more than one of its precursor
species.
AAs containing OA have been measured at a number of
coastal sites, and their formation in the ambient atmosphere
is similar to that of MSA, where the AAs are formed from
the gas-phase partitioning of amines such as trimethylamine
or dimethylamine into the particulate phase (Facchini et al.,
2008). These AA OA signatures were detected during mea-
surements made on the east coast of America, in the Arc-
tic (Dall’Osto et al., 2019), and also during controlled wave
and bubble-bursting chamber experiments (Dall’Osto et al.,
2019; Decesari et al., 2019; Kuznetsova et al., 2005; Wang et
al., 2015).
In our experimental setup, the short time between particle
generation and analysis (less than 30 s) does not allow for the
formation of secondary aerosol through oxidation and parti-
https://doi.org/10.5194/acp-21-10625-2021 Atmos. Chem. Phys., 21, 10625–10641, 2021
10634 E. Freney et al.: Mediterranean nascent sea spray organic aerosol
Figure 5. Diurnal variation in the four PMF organic factors chosen to represent the measured non-refractory organic aerosol: average (circles)
and standard deviation (vertical bars) of the measurements by hour during the whole PEACETIME cruise. The underlying raw data are shown
with small dots.
tioning of gas-phase species into the particle phase. Since
these amino acid signatures are internally mixed with signa-
tures for several different species, we assume that they are
present in the organic matter of the seawater, similar to con-
clusions made by Dall’Osto et al. (2019).
Although very weak and within the measurement error,
OOANR, MSA-OANR, and MOANR factors had a similar di-
urnal variation with increases during the early hours of the
morning and again in the afternoon (Fig. 5). POANR showed
similar variation to the other species in the morning but a
second increase was not observed in the afternoon. A lack
of strong diurnal variation in MSA-OANR and OOANR indi-
cates that the secondary (oxygenated) nature of these com-
pounds might be a result of biological processing rather than
photochemical processes.
3.3 The sources and formation pathways of marine
organic aerosol species
In several large-scale climate models chl ais used as a
proxy of phytoplankton biomass to predict the organic frac-
tion of sea spray. In this study, the measured chl ain the
underway surface seawater was low and had little variability
(0.07±0.013 mg m−3), therefore making it difficult to extract
any significant relationship between our measured organic
mass fractions and the measured chl a. No significant cor-
relations were observed between the mass concentrations of
the OM (measured by either the ACSM (OMACSM) or on fil-
ters (OMfilter =WIOM +WSOM) and chl aconcentrations,
or between the fraction of these two organic classes to the
total sea spray mass and chl a(not shown). Therefore it is
important to identify other marker species or processes that
can be used to correctly link seawater chemical composition,
biological activity, and the organic fraction in the seawater
aerosol that can represent up to 15 % of the total submicron
sea spray mass in oligotrophic waters.
In a companion paper, we illustrate that the total number
of sea spray particles measured by the DMPS was corre-
lated to the nanophytoplankton cell abundance (NanoPhyto)
(r=0.33, n=501, p < 0.001) (Sellegri et al., 2021). The
hypothesis behind the dependence of the sea spray number
concentration on NanoPhyto is that organic matter released
by NanoPhyto influences the surface seawater (SSW) surface
tension and therefore the bubble lifetime that drives the num-
ber of film drops ejected to the atmosphere.
3.3.1 High-time-resolution correlations
In this section we will investigate the dependence of each of
the organic classes identified in sea spray on the SSW bio-
geochemical properties. The relationships of the total factor
mass concentrations and the fractional factor contributions to
the seawater biochemistry were investigated (Fig. 6).
MOANR was strongly linked to NanoPhyto (r=0.34),
as was MSA-OANR and OOANR but with less significance
(r=0.25). Therefore, these organic classes follow the to-
tal sea spray mass and number behavior, as illustrated in
Sellegri et al. (2021). The hypothesis of organic matter
influencing the surface tension of seawater, bubble life-
time, and the number of film drops is therefore linked to
this specific class of organic matter. Fatty acids, consistent
with the MOANR and OOANR spectra, have been reported
Atmos. Chem. Phys., 21, 10625–10641, 2021 https://doi.org/10.5194/acp-21-10625-2021
E. Freney et al.: Mediterranean nascent sea spray organic aerosol 10635
Figure 6. Pearson correlation coefficients for the four different organic factors (MOANR, POANR, OOANR, and MSA-OANR ) and their frac-
tion of the total sea spray mass (fMOA, fPOA, fOOA, and fOA) with several phytoplankton functional group abundances (cells per cubic cen-
timeter) (Synechococcus, picoeukaryotes, nanoeukaryotes (Nano-phyto), coccolithophore (coccolith), cryptophytes), total chl a(mg m−3),
and POC (mg m−3) in the sampled seawater during the whole campaign. Sample number =461. Correlations with absolute Rvalues <0.16
had Pearson’s two-tailed significance values lower than 0.001 and were therefore left blank.
to be enriched in the SML (Cunliffe et al., 2013), which
would explain their impact on the bubble-bursting process.
POANR species are instead significantly correlated with par-
ticulate organic carbon concentrations, POC (r=0.40), and
Coccolithophore-like abundance (r=0.38). A relationship
between Coccolithophore-like cell abundance and [POC] is
likely linked to the ability of the coccolithophores or similar
groups of phytoplankton to secrete large amounts of sticky
carbon which can result in the formation of gels and POC
(Engel et al., 2004). As the time variation in POANR does not
follow that of total sea spray mass, it is possible that POA is
not linked to film drop formation and is ejected into the at-
mosphere via a separate mechanism, such as jet drops. It was
recently shown by Wang et al. (2017) that jet drops can con-
tribute significantly to the population of submicron SSA (up
to 43 %). The jet-drop-originating SSA has a different chem-
ical composition than the film-drop-originating SSA and is
more influenced by the SML (Wang et al., 2017). The hy-
pothesis of POANR being linked to jet drops is supported by
its relationship to POC in SSW.
The time series of OOANR had positive relationships with
NanoPhyto (r=0.25), but also with coccolithophore-like
cell abundances (r=0.25) and POC (r=0.21), and hence
OOANR seem to have an intermediate behavior between
POANR and MOANR. All organic classes except MOANR
are anticorrelated to the classes of small phytoplankton (pi-
coeukaryotes and Synechococcus). This anticorrelation could
be the result of the competition for nutrients between these
small cells and the larger ones that rather drive the POC con-
tent.
Except for MOANR, all correlations for the absolute mass
of these different types of organic matter are also observed
when the fractional contribution of these species to the total
mass of SSA (determined from the DMPS) are considered,
although less significantly (lower part of Fig. 6). However,
for MOANR species, correlations with NanoPhyto no longer
hold if the fractional contribution of these species to the total
mass of sea spray is considered. Instead, fMOA is correlated
to picoeukaryotes and Synechococcus. This is likely due to
the strong anticorrelation of the fraction of all other organic
classes with these classes of small phytoplankton. At low
picoeukaryotes and Synechococcus cell abundances, fPOA,
fOOA, and fMSA-OA are higher, artificially decreasing the
proportion of fMOA to the rest of the organic matter.
3.3.2 Filter-based resolution correlations
Since the non-refractory organic components analyzed us-
ing the ACSM technique are only a fraction of the marine
organic mass, we investigate the relationships between off-
line filter-based organic compounds and seawater biogeo-
chemical properties. Filter-based organic fractions are also
compared to seawater properties at the filter sampling time
resolution. The organic mass concentration from filters is
correlated to the coccolithophore cell abundance (r=0.88,
n=13). The fraction of OM to total mass analyzed on fil-
ters (OMSS) was also correlated to coccolithophore cell
abundance (r=0.72, n=13) and POC (r=0.6, n=13).
https://doi.org/10.5194/acp-21-10625-2021 Atmos. Chem. Phys., 21, 10625–10641, 2021
10636 E. Freney et al.: Mediterranean nascent sea spray organic aerosol
Figure 7. Time series of the DOC enrichment factor (EF), POC concentrations, and PMF organic factors MOANR and POANR.
This indicates that the total organic matter present in sea
spray behaved similarly to the non-refractory POANR and
OOANR analyzed by the ACSM. Previous studies observed a
connection between seawater POC and SSA organic fraction.
Facchini et al. (2008) found that WIOM in SSA was related
to seawater POC derived from microgels. Furthermore, dur-
ing mesocosm bubbling experiments using Emiliania huxleyi
cultures and low heterotrophic prokaryote abundance counts,
O’Dowd et al. (2015) suggested that the aggregation of dis-
solved organic carbon (DOC) into POC in the form of insol-
uble gel colloids was the driving force behind the enrichment
of organic matter into submicron SSA. The authors hypoth-
esized that the organic fraction of SSA can be controlled ei-
ther by DOC or POC, depending on the biological state of
the waters.
Measurements of DOC in the SML and underlying seawa-
ter were performed daily, as well as surface seawater bacte-
rial total counts from daily surface water samples (5 m depth)
(the description of these methods is provided in Sect. S2).
DOC was slightly enriched in the SML compared to the
underlying seawater, with enrichment factors varying be-
tween 1 and 1.2 (Fig. 7). The filter-based total organic con-
tent of sea spray aerosol was not correlated to DOC or total
bacterial count in the SML and neither was OMSS. How-
ever we observe that MOANR was correlated to the enrich-
ment of DOC in the SML (r=0.55, n=9), suggesting again
that MOANR is likely linked to organic matter present in
the SML. The correlation between MOA and DOC enrich-
ment in the SML suggests that the fraction of DOC which
is enriched in the SML contains lipids and amino acids
found in the MOANR fraction. Although MOANR is an oxi-
dized organic class, it does not seem to be the result of the
bacterial production (BP) of organic matter in the seawa-
ter. Instead, we found a significant anticorrelation between
MOANR and bacterial production (r= −0.82, n=10), indi-
cating that MOANR could instead be consumed by this pro-
cess.
3.3.3 Predicting organic matter in sea spray from
seawater biogeochemical properties
By combining relationships between filter-based chemical
analysis, ACSM organic source apportionment, and seawater
properties, it is possible to propose a general relationship that
can be used to predict the different fractions of organic matter
in the nascent sea spray emitted from oligotrophic seawaters.
These different organic fractions may have different atmo-
spheric properties related to their climate impact, such as ice
nuclei properties (Trueblood et al., 2021). We chose to pa-
rameterize the organic fractions of sea spray rather than com-
puting organic mass fluxes, for an easier implementation in
models that already have an inorganic sea spray source func-
tion. However, as shown in the preceding section, the total
mass of sea spray is significantly influenced by SSW biology,
and we recommend that the biology-dependent sea spray
number flux modulation computed in Sellegri et al. (2021) is
applied before biology-dependent organic fractions are cal-
culated.
We initially examined the relationship with offline filter or-
ganic measurements of water-insoluble and water-soluble or-
ganic matter fractions (FWIOM and FWSOM, respectively)
with POC (Eqs. 2 and 3). These showed positive correlations
of both WIOM and WSOM with POC measurements.
FWSOM =0.002[POC] − 0.0393r=0.55, n =19,
p < 0.01 (2)
FWIOM =0.002[POC] + 0.031r=0.54, n =12,
p < 0.05 (3)
Using the higher-time-resolution data obtained from the
ACSM, the non-refractory organic fraction of nascent sea
spray can also be predicted using three different equations,
with MSA-OANR being a negligible fraction of the total sea
spray mass:
Atmos. Chem. Phys., 21, 10625–10641, 2021 https://doi.org/10.5194/acp-21-10625-2021
E. Freney et al.: Mediterranean nascent sea spray organic aerosol 10637
Figure 8. Time series and correlation plots of each of the parameterizations (Eqs. 4 to 6) for the determination of the different organic
fractions in nascent SSA.
fPOA =0.0002[POC] − 0.001
r=0.31, n =459, p < 0.001 (4)
fOOA =0.0002[POC] + 0.02
r=0.20, n =478, p < 0.001 (5)
fMOA =4.5×10−6×(picoeukaryotes)+0.009
r=0.37, n =459, p < 0.001.(6)
These relationships apply to the ranges of POC and pi-
coeukaryotes measured during the PEACETIME cruise.
Hence they may be applicable to other oligotrophic waters. If
larger ranges of seawater biogeochemical properties are con-
sidered in the future, fractions of organic classes should be
parameterized as logarithmic laws asymptotic to 1, in order
to take into account the saturation of the organic fraction at
1 for the largest POC values.
Figure 8 shows the reconstruction of these organic factors
using the parameterizations determined in Eqs. (4) to (6).
The parameterizations correctly represent the absolute con-
centrations. However, the short-term variability is less well
represented, with correlations varying from 0.20 to 0.37. For
this sample size (n > 450) the significance of this correla-
tion is <0.001. These relatively low correlations suggest that
there are parameters other than POC influencing the emission
of these organic species, especially for OOA that is believed
to be more linked to the SML properties than to the bulk sea-
water. However, these parameterizations are useful to pro-
vide a first approximation of the organic matter exported to
the SSA and in this type of environment (LNLC) are a better
choice than using chl a.
4 Conclusions
The primary objective of this experiment was to study the re-
lationships between sea spray chemical properties and those
of seawater. This work presents a unique dataset, which de-
scribes the first deployment of a ToF-ACSM to character-
ize, in a continuous way, the organic fraction present in sea
spray aerosol generated from Mediterranean surface seawa-
ter. The non-refractory part of the organic content of sea
spray was characterized by low concentrations and low vari-
ability along a 4300 km transect. Yet, using a positive ma-
trix factorization on the ACSM organic mass spectra, it
was possible to extract signatures for fatty acids, amino
acids, and marine primary organic aerosols in non-refractory
nascent sea spray. We identified four organic classes: two
were composed of mixtures of amino acids and fatty acids
(a primary aerosol POANR and a slightly oxidized MOANR
factor), and two were identified as more oxidized organic
aerosol (OOANR and MSA-OANR). The POANR factor was
similar to that observed in wave chamber experiments and
correlated well with POC concentrations in the seawater, as
did the OOANR and MSA-OANR. The MOANR concentra-
tions had a different behavior and correlated well with the
nanophytoplankton cell abundance in the seawater, and also
with the total sea spray number concentration and DOC en-
richment in the surface microlayer. It is hypothesized that
MOANR is related to surface tension properties that influence
the bubble-bursting process and the resulting number of film
drops ejected to the atmosphere. In contrast, the fraction of
POANR, OOANR, and MSA-OANR classes is not connected
to the sea spray number concentration but is linked to POC of
https://doi.org/10.5194/acp-21-10625-2021 Atmos. Chem. Phys., 21, 10625–10641, 2021
10638 E. Freney et al.: Mediterranean nascent sea spray organic aerosol
the bulk surface seawater and more likely emitted with a dif-
ferent process such as through jet drops. Water-soluble and
water-insoluble organic matter measured using offline filter
analysis confirm this positive relationship between OM and
POC measurements. This suggests that the refractory, as well
as non-refractory, fractions of the particulate organic carbon
in the seawater are transferred to the sea spray.
This work illustrates the value of continuous aerosol
chemistry and physical characterization of the nascent sea
spray aerosol in parallel with other biogeochemical measure-
ments in surface seawater. It also illustrates that even un-
der oligotrophic conditions, seawater biogeochemical prop-
erties influence the type and concentration of marine organic
aerosols and therefore their ability to act as cloud condensa-
tion nuclei or ice nuclei. We provide a parameterization of the
different marine organic components of nascent sea spray as
a function of seawater biogeochemical properties typical for
oligotrophic conditions in LNLC regions of the ocean that
represent 60 % of the global ocean. Such parameterization
used in models should allow a better prediction of the impact
of living marine organisms on these properties in a future cli-
mate.
Data availability. Underlying research data are available at
https://doi.org/10.17882/75747 (Guieu et al., 2020b).
Supplement. The supplement related to this article is available on-
line at: https://doi.org/10.5194/acp-21-10625-2021-supplement.
Author contributions. CG and KD designed the PEACETIME
project. KS designed the experiments specifically used in this pa-
per. KS and AN performed the measurements aboard the ship. MT,
GG, NH, JD, IO, FVW, AE, and BZ were responsible for collecting
and analyzing the biogeochemical parameters in either the seawa-
ter or the surface microlayer. MR analyzed the offline filter mea-
surements. EF analyzed the ACSM data with input from LRW and
ASHP. EF and KS prepared the manuscript with contributions from
all authors.
Competing interests. The authors declare that they have no conflict
of interest.
Special issue statement. This article is part of the special issue “At-
mospheric deposition in the low-nutrient–low-chlorophyll (LNLC)
ocean: effects on marine life today and in the future (ACP/BG inter-
journal SI)”. It is not associated with a conference. This article is
also part of the special issue “CHemistry and AeRosols Mediter-
ranean EXperiments (ChArMEx) (ACP/AMT inter-journal SI)”. It
does not belong to a conference.
Acknowledgements. The underway optical instrumentation was
provided by Emmanuel Boss’s group funded by NASA Ocean
Biology and Biogeochemistry. We thank Oliver Grosso, Do-
minique Lefèvre, and Thibault Wagener for their contribution
to the continuous surface pumping system and the follow-up of
CytoSense during the cruise. More information on the PEACE-
TIME cruise can be found at https://doi.org/10.17600/17000300.
Sea2Cloud was endorsed by SOLAS. We thank the captain and the
crew of R/V Pourquoi Pas? for their professionalism and their work
at sea.
Financial support. This study is a contribution to the PEACETIME
project (http://peacetime-project.org, last access: 5 May 2021), a
joint initiative of the MERMEX and ChArMEx components sup-
ported by CNRS-INSU, IFREMER, CEA, and Météo-France as
part of the MISTRALS program coordinated by CNRS-INSU.
PEACETIME was endorsed as a process study by GEOTRACES
and is also a contribution to the IMBER and SOLAS international
programs. This work has also received funding from the Euro-
pean Research Council (ERC) under the European Union’s Hori-
zon 2020 research and innovation program (Sea2Cloud grant agree-
ment no. 771369).
Review statement. This paper was edited by Maria Kanakidou and
reviewed by two anonymous referees.
References
Alfarra, M. R., Coe, H., Allan, J. D., Bower, K. N., Boudries, H.,
Canagaratna, M. R., Jimenez, J. L., Jayne, J. T., Garforth, A.,
Li, S. M., and Worsnop, D. R.: Characterization of Urban and
Rural Organic Aerosols In the Lower Fraser Valley Using Two
Aerodyne Particulate Mass Spectrometers, Atmos. Environ., 38,
5745–5758, 2004.
Allan, J. D., Delia, A. E., Coe, H., Bower, K. N., Alfarra, M.
R., Jimenez, J. L., Middlebrook, A. M., Drewnick, F., Onasch,
T. B., and Canagaratna, M. R.: A generalised method for the
extraction of chemically resolved mass spectra from Aerodyne
aerosol mass spectrometer data, J. Aerosol Sci., 35, 909–922,
https://doi.org/10.1016/j.jaerosci.2004.02.007, 2004.
Bates, T., Quinn, P., Frossard, A., Russell, L., Hakala, J.,
Petäjä, T., Kulmala, M., Covert, D., Cappa, C., and Li,
S.: Measurements of ocean derived aerosol off the coast
of California, J. Geophys. Res.-Atmos., 117, D00V15,
https://doi.org/10.1029/2012JD017588, 2012.
Bates, T. S., Quinn, P. K., Coffman, D. J., Johnson, J. E., Upchurch,
L., Saliba, G., Lewis, S., Graff, J., Russell, L. M., and Behren-
feld, M. J.: Variability in Marine Plankton Ecosystems Are
Not Observed in Freshly Emitted Sea Spray Aerosol Over the
North Atlantic Ocean, Geophys. Res. Lett., 47, e2019GL085938,
https://doi.org/10.1029/2019GL085938, 2020.
Benner, R. and Strom, M.: A critical evaluation of the an-
alytical blank associated with DOC measurements by high
temperature catalytic oxidation, Mar. Chem., 41, 153–160,
https://doi.org/10.1016/0304-4203(93)90113-3, 1993.
Atmos. Chem. Phys., 21, 10625–10641, 2021 https://doi.org/10.5194/acp-21-10625-2021
E. Freney et al.: Mediterranean nascent sea spray organic aerosol 10639
Blanchard, D. C. and Woodcock, A. H.: The production, concen-
tration, and vertical distribution of the sea-salt aerosol, Ann.
NY. Acad. Sci., 338, 330–347, https://doi.org/10.1111/j.1749-
6632.1980.tb17130.x, 1980.
Boss, E., Picheral, M., Leeuw, T., Chase, A., Karsenti, E.,
Gorsky, G., Taylor, L., Slade, W., Ras, J., and Claustre, H.:
The characteristics of particulate absorption, scattering and at-
tenuation coefficients in the surface ocean, in: Contribution
of the Tara Oceans expedition, Meth. Oceanogr., 7, 52–62,
https://doi.org/10.1016/j.mio.2013.11.002, 2013.
Bozzetti, C., El Haddad, I., Salameh, D., Daellenbach, K. R.,
Fermo, P., Gonzalez, R., Minguillón, M. C., Iinuma, Y., Poulain,
L., Elser, M., Müller, E., Slowik, J. G., Jaffrezo, J.-L., Bal-
tensperger, U., Marchand, N., and Prévôt, A. S. H.: Or-
ganic aerosol source apportionment by offline-AMS over a
full year in Marseille, Atmos. Chem. Phys., 17, 8247–8268,
https://doi.org/10.5194/acp-17-8247-2017, 2017.
Burrows, S. M., Ogunro, O., Frossard, A. A., Russell, L. M., Rasch,
P. J., and Elliott, S. M.: A physically based framework for mod-
eling the organic fractionation of sea spray aerosol from bub-
ble film Langmuir equilibria, Atmos. Chem. Phys., 14, 13601–
13629, https://doi.org/10.5194/acp-14-13601-2014, 2014.
Canagaratna, M. R., Jimenez, J. L., Kroll, J. H., Chen, Q., Kessler,
S. H., Massoli, P., Hildebrandt Ruiz, L., Fortner, E., Williams, L.
R., Wilson, K. R., Surratt, J. D., Donahue, N. M., Jayne, J. T.,
and Worsnop, D. R.: Elemental ratio measurements of organic
compounds using aerosol mass spectrometry: characterization,
improved calibration, and implications, Atmos. Chem. Phys., 15,
253–272, https://doi.org/10.5194/acp-15-253-2015, 2015.
Canonaco, F., Crippa, M., Slowik, J. G., Baltensperger, U.,
and Prévôt, A. S. H.: SoFi, an IGOR-based interface for
the efficient use of the generalized multilinear engine (ME-
2) for the source apportionment: ME-2 application to aerosol
mass spectrometer data, Atmos. Meas. Tech., 6, 3649–3661,
https://doi.org/10.5194/amt-6-3649-2013, 2013.
Cetini´
c, I., Perry, M. J., Briggs, N. T., Kallin, E., D’Asaro,
E. A., and Lee, C. M.: Particulate organic carbon and
inherent optical properties during 2008 North Atlantic
Bloom Experiment, J. Geophys. Res.-Oceans, 117, C06028,
https://doi.org/10.1029/2011JC007771, 2012.
Collins, D. B., Bertram, T. H., Sultana, C. M., Lee, C., Axson, J.
L., and Prather, K. A.: Phytoplankton blooms weakly influence
cloud forming ability of sea spray aerosol, Geophys. Res. Lett.,
43, 9975–9983, https://doi.org/10.1002/2016GL069922, 2016.
Cunliffe, M. and Wurl, O.: Guide to best practices to study the
ocean’s surface? Occasional Publications of the Marine Bio-
logical Association of the United Kingdom serie, Marine Bi-
ological Association of the United Kingdom for SCOR, Ply-
mouth, UK, 118 pp., http://hdl.handle.net/11329/261 (last ac-
cess: 1 June 2021), 2014.
Cunliffe, M., Engel, A., Frka, S., Gasparovic, B., Guitart, C., Mur-
rell, C., Salter, M., Stolle, C., Upstill-Goddard, R., and Wurl, O.:
Sea surface microlayers: A unified physiochemical and biologi-
cal perspective of the air-ocean interface, Prog. Oceanogr., 109,
104–116, https://doi.org/10.1016/j.pocean.2012.08.004, 2013.
Dall’Osto, M., Airs, R. L., Beale, R., Cree, C., Fitzsimons, M.
F., Beddows, D., Harrison, R. M., Ceburnis, D., O’Dowd,
C., and Rinaldi, M.: Simultaneous detection of alkylamines
in the surface ocean and atmosphere of the Antarctic sym-
pagic environment, ACS Earth Space Chem., 3, 854–862,
https://doi.org/10.1021/acsearthspacechem.9b00028, 2019.
DeCarlo, P. F., Kimmel, J. R., Trimborn, A. M., Jayne, J. T.,
Aiken, A. C., Gonin, M., Fuhrer,K., Horvath, T., Docherty, K.
S., Worsnop, D. R., and Jimenez, J. L.: A field-deployable
high-resolution time-of-flight aerosol mass spectrometer, Anal.
Chem., 78, 8281–8289, 2006.
Decesari, S., Paglione, M., Rinaldi, M., Dall’Osto, M., Simó, R.,
Zanca, N., Volpi, F., Facchini, M. C., Hoffmann, T., Götz,
S., Kampf, C. J., O’Dowd, C., Ceburnis, D., Ovadnevaite, J.,
and Tagliavini, E.: Shipborne measurements of Antarctic sub-
micron organic aerosols: an NMR perspective linking multiple
sources and bioregions, Atmos. Chem. Phys., 20, 4193–4207,
https://doi.org/10.5194/acp-20-4193-2020, 2020.
Drewnick, F., Hings, S. S., Alfarra, M. R., Prevot, A. S. H.,
and Borrmann, S.: Aerosol quantification with the Aero-
dyne Aerosol Mass Spectrometer: detection limits and ion-
izer background effects, Atmos. Meas. Tech., 2, 33–46,
https://doi.org/10.5194/amt-2-33-2009, 2009.
Engel, A., Delille, B., Jacquet, S., Riebesell, U., Rochelle-
Newall, E., Terbrüggen, A., and Zondervan, I.: Transparent ex-
opolymer particles and dissolved organic carbon production
by Emilianiahuxleyi exposed to different CO2concentrations:
a mesocosm experiment, Aquat. Microb. Ecol., 34, 93–104,
https://doi.org/10.3354/ame034093, 2004.
Facchini, M. C., Rinaldi, M., Decesari, S., Carbone, C., Finessi, E.,
Mircea, M., Fuzzi, S., Ceburnis, D., Flanagan, R., and Nilsson,
E. D.: Primary submicron marine aerosol dominated by insol-
uble organic colloids and aggregates, Geophys. Res. Lett., 35,
L17814, https://doi.org/10.1029/2008GL034210, 2008.
Fröhlich, R., Cubison, M. J., Slowik, J. G., Bukowiecki, N., Prévôt,
A. S. H., Baltensperger, U., Schneider, J., Kimmel, J. R., Go-
nin, M., Rohner, U., Worsnop, D. R., and Jayne, J. T.: The
ToF-ACSM: a portable aerosol chemical speciation monitor
with TOFMS detection, Atmos. Meas. Tech., 6, 3225–3241,
https://doi.org/10.5194/amt-6-3225-2013, 2013.
Giordano, M. R., Kalnajs, L. E., Avery, A., Goetz, J. D., Davis, S.
M., and DeCarlo, P. F.: A missing source of aerosols in Antarctica
– beyond long-range transport, phytoplankton, and photochem-
istry, Atmos. Chem. Phys., 17, 1–20, https://doi.org/10.5194/acp-
17-1-2017, 2017.
Guieu, C., D’Ortenzio, F., Dulac, F., Taillandier, V., Doglioli, A.,
Petrenko, A., Barrillon, S., Mallet, M., Nabat, P., and Des-
boeufs, K.: Introduction: Process studies at the air–sea inter-
face after atmospheric deposition in the Mediterranean Sea
– objectives and strategy of the PEACETIME oceanographic
campaign (May–June 2017), Biogeosciences, 17, 5563–5585,
https://doi.org/10.5194/bg-17-5563-2020, 2020a.
Guieu, C., Desboeufs, K., Albani, S., Alliouane, S., Aumont,
O., Barbieux, M., Barrillon, S., Baudoux, A.-C., Berline, L.,
Bhairy, N., Bigeard, E., Bloss, M., Bressac, M., Brito, J., Car-
lotti, F., de Liege, G., Dinasquet, J., Djaoudi, K., Doglioli, A.,
D’Ortenzio, F., Doussin, J.-F. Duforet, L., Dulac, F., Dutay, J.-C.,
Engel, A., Feliu-Brito, G., Ferre, H., Formenti, P., Fu, F., Gar-
cia, D., Garel, M., Gazeau, F., Giorio, C., Gregori, G., Grisoni,
J.-M., Guasco, S., Guittonneau, J., Haëntjens, N., Heimburger,
L.-E., Helias, S., Jacquet, S., Laurent, B., Leblond, N., Lefevre,
D., Mallet, M., Marañón, E., Nabat, P., Nicosia, A., Obernos-
terer, I., Perez Lorenzo, M., Petrenko, A., Pulido-Villena, E.,
https://doi.org/10.5194/acp-21-10625-2021 Atmos. Chem. Phys., 21, 10625–10641, 2021
10640 E. Freney et al.: Mediterranean nascent sea spray organic aerosol
Raimbault, P., Ridame, C., Riffault, V., Rougier, G., Rousselet,
L., Roy-Barman, M., Saiz-Lopez, A., Schmechtig, C., Sellegri,
K., Siour, G., Taillandier, V., Tamburini, C., Thyssen, M., Tovar-
Sanchez, A., Triquet, S., Uitz, J., Van Wambeke, F., Wagener, T.,
and Zaencker, B.: Biogeochemical dataset collected during the
PEACETIME cruise, SEANOE, https://doi.org/10.17882/75747,
2020b.
Harvey, G.: Microlayer collection from the sea surface: a new
method and intial results, Limnol. Oceanogr., 11, 608–613,
https://doi.org/10.4319/lo.1966.11.4.0608, 1966.
Kuznetsova, M., Lee, C., and Aller, J.: Characterization of the pro-
teinaceous matter in marine aerosols, Mar. Chem., 96, 359–377,
https://doi.org/10.1016/j.marchem.2005.03.007, 2005.
Leroux, R., Grégori, G., Leblanc, K., Carlotti, F., Thyssen, M.,
Dugenne, M., Pujo-Pay, M., Conan, P.,Jouandet, M.-P., Bhairy,
N., and Berline, L.: Combining laser diffraction, flow cytome-
try and optical microscopy to characterize a nanophytoplankton
bloom in the northwestern Mediterranean, Prog. Oceanogr., 163,
248–259, https://doi.org/10.1016/j.pocean.2017.10.010, 2017.
Lewis, E. R. and Schwartz, S. E.: Sea Salt Aerosol Production:
Mechanisms, Methods, Measurements and Models – a Critical
Review, in: Geophys. Monogr. Ser., AGU, Washington, D.C.,
USA, 413 pp., 2004.
McCluskey, C. S., Hill, T. C., Malfatti, F., Sultana, C. M., Lee, C.,
Santander, M. V., Beall, C. M., Moore, K. A., Cornwell, G. C.,
and Collins, D. B.: A dynamic link between ice nucleating parti-
cles released in nascent sea spray aerosol and oceanic biological
activity during two mesocosm experiments, J. Atmos. Sci., 74,
151–166, https://doi.org/10.1175/JAS-D-16-0087.1, 2017.
MerMex Group: Marine ecosystems’ responses to climatic and an-
thropogenic forcings in the Mediterranean, Prog. Oceanogr., 91,
97–166, https://doi.org/10.1016/j.pocean.2011.02.003, 2011.
Middlebrook, A. M., Bahreini, R., Jimenez, J. L., and Cana-
garatna, M. R.: Evaluation of composition-dependent collec-
tion efficiencies for the aerodyne aerosol mass spectrom-
eter using field data, Aerosol Sci. Tech., 46, 258–271,
https://doi.org/10.1080/02786826.2011.620041, 2012.
Ng, N. L., Canagaratna, M. R., Zhang, Q., Jimenez, J. L., Tian,
J., Ulbrich, I. M., Kroll, J. H., Docherty, K. S., Chhabra, P.
S., Bahreini, R., Murphy, S. M., Seinfeld, J. H., Hildebrandt,
L., Donahue, N. M., DeCarlo, P. F., Lanz, V. A., Prévôt, A. S.
H., Dinar, E., Rudich, Y., and Worsnop, D. R.: Organic aerosol
components observed in Northern Hemispheric datasets from
Aerosol Mass Spectrometry, Atmos. Chem. Phys., 10, 4625–
4641, https://doi.org/10.5194/acp-10-4625-2010, 2010.
O’Dowd, C., Ceburnis, D., Ovadnevaite, J., Bialek, J., Stengel, D.
B., Zacharias, M., Nitschke, U., Connan, S., Rinaldi, M., Fuzzi,
S., Decesari, S., Facchini, M. C., Marullo, S., Santoleri, R.,
Dell’Anno, A., Corinaldesi, C., Tangherlini, M., and Danovaro,
R.: Connecting marine productivity to sea-spray via nanoscale
biological processes: Phytoplankton Dance or Death Disco?, Sci
Rep.-UK, 5, 14883, https://doi.org/10.1038/srep14883, 2015.
O’Dowd, C. D., Facchini, M. C., Cavalli, F., Ceburnis, D., Mircea,
M., Decesari, S., Fuzzi, S., Yoon, Y. J., and Putaud, J.-P.: Bio-
genically driven organic contribution to marine aerosol, Nature,
431, 676–680, https://doi.org/10.1038/nature02959, 2004.
Ovadnevaite, J., O’Dowd, C., Dall’Osto, M., Ceburnis,
D., Worsnop, D. R., and Berresheim, H.: Detecting
high contributions of primary organic matter to marine
aerosol: A case study, Geophys. Res. Lett., 38, L02807,
https://doi.org/10.1029/2010GL046083, 2011.
Park, J., Dall’Osto, M., Park, K., Kim, J.-H., Park, J., Park, K.-
T., Hwang, C. Y., Jang, G. I., Gim, Y., Kang, S., Park, S.,
Keun, Y., Yong, J., Jin, K., Yum, S. S., Simó, R., and Yoon,
Y. J.: Arctic Primary Aerosol Production Strongly Influenced by
Riverine Organic Matter, Environ. Sci. Technol., 53, 8621–8630,
https://doi.org/10.1021/acs.est.9b03399, 2019.
Phinney, L., Leaitch, W. R., Lohmann, U., Boudries, H., Worsnop,
D. R., Jayne, J. T., Toom-Sauntry, D., Wadleigh, M., Sharma, S.,
and Shantz, N.: Characterization of the aerosol over the subarctic
north east Pacific Ocean, Deep-Sea Res. Pt. II, 53, 2410–2433,
https://doi.org/10.1016/j.dsr2.2006.05.044, 2006.
Rinaldi, M., Emblico, L., Decesari, S., Fuzzi, S., Facchini, M.
C., and Librando, V.: Chemical characterization and source
apportionment of size-segregated aerosol collected at an ur-
ban site in Sicily, Water Air Soil Poll., 185, 311–321,
https://doi.org/10.1007/s11270-007-9455-4, 2007.
Sandrini, S., van Pinxteren, D., Giulianelli, L., Herrmann, H.,
Poulain, L., Facchini, M. C., Gilardoni, S., Rinaldi, M., Paglione,
M., Turpin, B. J., Pollini, F., Bucci, S., Zanca, N., and Dece-
sari, S.: Size-resolved aerosol composition at an urban and a
rural site in the Po Valley in summertime: implications for
secondary aerosol formation, Atmos. Chem. Phys., 16, 10879–
10897, https://doi.org/10.5194/acp-16-10879-2016, 2016.
Schmale, J., Schneider, J., Nemitz, E., Tang, Y. S., Dragosits, U.,
Blackall, T. D., Trathan, P. N., Phillips, G. J., Sutton, M., and
Braban, C. F.: Sub-Antarctic marine aerosol: dominant contri-
butions from biogenic sources, Atmos. Chem. Phys., 13, 8669–
8694, https://doi.org/10.5194/acp-13-8669-2013, 2013.
Schneider, J., Freutel, F., Zorn, S. R., Chen, Q., Farmer, D. K.,
Jimenez, J. L., Martin, S. T., Artaxo, P., Wiedensohler, A.,
and Borrmann, S.: Mass-spectrometric identification of primary
biological particle markers and application to pristine submi-
cron aerosol measurements in Amazonia, Atmos. Chem. Phys.,
11, 11415–11429, https://doi.org/10.5194/acp-11-11415-2011,
2011.
Schwier, A. N., Rose, C., Asmi, E., Ebling, A. M., Landing, W.
M., Marro, S., Pedrotti, M.-L., Sallon, A., Iuculano, F., Agusti,
S., Tsiola, A., Pitta, P., Louis, J., Guieu, C., Gazeau, F., and Sel-
legri, K.: Primary marine aerosol emissions from the Mediter-
ranean Sea during pre-bloom and oligotrophic conditions: cor-
relations to seawater chlorophyll a from a mesocosm study, At-
mos. Chem. Phys., 15, 7961–7976, https://doi.org/10.5194/acp-
15-7961-2015, 2015.
Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and
Physics: From Air Pollution to Climate Change, 3rd Edn., John
Wiley & Sons, Inc., Hoboken, New Jersey, USA, 2016.
Sellegri, K., Nicosia, A., Freney, E., Uitz, J., Thyssen, M., Gré-
gori, G., Engel, A., Zäncker, B., Haëntjens, N., Mas, S., Pi-
card, D., Saint-Macary, A., Peltola, M., Rose, C., Trueblood, J.,
Lefevre, D., D’Anna, B., Desboeufs, K., Meskhidze, N., Guieu,
C., and Law, C. S.: Surface ocean microbiota determine cloud
precursors, Sci. Rep., 11, 281, https://doi.org/10.1038/s41598-
020-78097-5, 2021.
Slade, W. H., Boss, E., Dall’Olmo, G., Langner, M. R., Loftin, J.,
Behrenfeld, M. J., and Roesler, C.: Underway and moored meth-
ods for improving accuracy in measurement of spectral partic-
Atmos. Chem. Phys., 21, 10625–10641, 2021 https://doi.org/10.5194/acp-21-10625-2021
E. Freney et al.: Mediterranean nascent sea spray organic aerosol 10641
ulate absorption and attenuation, J. Atmos. Ocean. Tech., 27,
1733–1746, https://doi.org/10.1175/2010JTECHO755.1, 2010.
Spielmeyer, A. and Pohnert, G.: Direct quantification of dimethyl-
sulfoniopropionate (DMSP) with hydrophilic interaction liq-
uid chromatography/mass spectrometry, J. Chromatogr. B, 878,
3238–3242, 2010.
Swan, H. B., Deschaseaux, E. S. M., Jones, G. B., and Eyre, B. D.:
Quantification of dimethylsulfoniopropionate (DMSP) in Acro-
pora spp. of reef-building coral using mass spectrometry with
deuterated internal standard, Anal. Bioanal. Chem., 409, 1929–
1942, https://doi.org/10.1007/s00216-016-0141-5, 2017.
Thyssen, M., Grégori, G., Grisoni, J.-M., Pedrotti, M., Mousseau,
L., Artigas, L. F., Marro, S., Garcia, N., Passafiume O.,
and Denis, M. J.: Onset of the spring bloom in the north-
western Mediterranean Sea: influence of environmental pulse
events on the in situ hourly-scale dynamics of the phy-
toplankton community structure, Front. Microbiol., 5, 387,
https://doi.org/10.3389/fmicb.2014.00387, 2010.
Timonen, H., Cubison, M., Aurela, M., Brus, D., Lihavainen, H.,
Hillamo, R., Canagaratna, M., Nekat, B., Weller, R., Worsnop,
D., and Saarikoski, S.: Applications and limitations of con-
strained high-resolution peak fitting on low resolving power mass
spectra from the ToF-ACSM, Atmos. Meas. Tech., 9, 3263–3281,
https://doi.org/10.5194/amt-9-3263-2016, 2016.
Tobler, A. K., Skiba, A., Wang, D. S., Croteau, P., Styszko, K.,
N˛ecki, J., Baltensperger, U., Slowik, J. G., and Prévôt, A. S. H.:
Improved chloride quantification in quadrupole aerosol chemical
speciation monitors (Q-ACSMs), Atmos. Meas. Tech., 13, 5293–
5301, https://doi.org/10.5194/amt-13-5293-2020, 2020.
Trueblood, J. V., Nicosia, A., Engel, A., Zäncker, B., Rinaldi, M.,
Freney, E., Thyssen, M., Obernosterer, I., Dinasquet, J., Belosi,
F., Tovar-Sánchez, A., Rodriguez-Romero, A., Santachiara, G.,
Guieu, C., and Sellegri, K.: A two-component parameterization
of marine ice-nucleating particles based on seawater biology and
sea spray aerosol measurements in the Mediterranean Sea, At-
mos. Chem. Phys., 21, 4659–4676, https://doi.org/10.5194/acp-
21-4659-2021, 2021.
Vlachou, A., Tobler, A., Lamkaddam, H., Canonaco, F., Daellen-
bach, K. R., Jaffrezo, J.-L., Minguillón, M. C., Maasikmets, M.,
Teinemaa, E., Baltensperger, U., El Haddad, I., and Prévôt, A.
S. H.: Development of a versatile source apportionment analy-
sis based on positive matrix factorization: a case study of the
seasonal variation of organic aerosol sources in Estonia, At-
mos. Chem. Phys., 19, 7279–7295, https://doi.org/10.5194/acp-
19-7279-2019, 2019.
Wang, X., Sultana, C. M., Trueblood, J., Hill, T. C., Malfatti, F.,
Lee, C., Laskina, O., Moore, K. A., Beall, C. M., and Mc-
Cluskey, C. S.: Microbial control of sea spray aerosol com-
position: a tale of two blooms, ACS Cent. Sci., 1, 124–131,
https://doi.org/10.1021/acscentsci.5b00148, 2015.
Wang, X., Deane, G. B., Moore, K. A., Ryder, O. S., Stokes, M.
D., Beall, C. M., Collins, D. B., Santander, M. V., Burrows, S.
M., Sultana, C. M., and Prather, K. A.: The role of jet and film
drops in controlling the mixing state of submicron sea spray
aerosol particles, P. Natl. Acad. Sci. USA, 114, 6978–6983,
https://doi.org/10.1073/pnas.1702420114, 2017.
Yoon, Y., Ceburnis, D., Cavalli, F., Jourdan, O., Putaud, J., Facchini,
M., Decesari, S., Fuzzi, S., Sellegri, K., and Jennings, S.: Sea-
sonal characteristics of the physicochemical properties of North
Atlantic marine atmospheric aerosols, J. Geophys. Res.-Atmos.,
112, D04206, https://doi.org/10.1029/2005JD007044, 2007.
https://doi.org/10.5194/acp-21-10625-2021 Atmos. Chem. Phys., 21, 10625–10641, 2021
Available via license: CC BY 4.0
Content may be subject to copyright.
