PUBLICATIONS
Journal of Geophysical Research: Atmospheres
RESEARCH ARTICLE
10.1002/2015JD024245
Key Points:
• Size-resolved particulate amine salts
are first characterized in China
• The frequent NPF events in hot
summer might be associated with
the abundant amines
• The mass fraction of amines in new
particles was strongly correlated with
total aerosol acidity
Supporting Information:
• Figures S1 and S2 and Table S1
Correspondence to:
X. Ye and J. Chen,
yexingnan@fudan.edu.cn;
jmchen@fudan.edu.cn
Citation:
Tao, Y., X. Ye, S. Jiang, X. Yang, J. Chen,
Y. Xie, and R. Wang (2016), Effects of
amines on particle growth observed
in new particle formation events,
J. Geophys. Res. Atmos., 121, 324–335,
doi:10.1002/2015JD024245.
Received 23 SEP 2015
Accepted 3 DEC 2015
Accepted article online 29 DEC 2015
Published online 7 JAN 2016
©2015. American Geophysical Union.
All Rights Reserved.
TAO ET AL.
Effects of amines on particle growth observed
in new particle formation events
Ye Tao1, Xingnan Ye1, Shuqing Jiang1, Xin Yang1, Jianmin Chen1, Yuanyuan Xie1, and Ruyu Wang1
1
Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and
Engineering, Fudan University, Shanghai, China
Abstract Particle size distributions in the range of 0.01–10 μm were measured in urban Shanghai in the
summer of 2013 using a Wide-range Particle Spectrometer (WPS). Size-segregated aerosol samples were
collected concurrently using a Micro-Orifice Uniform Deposit Impactor (MOUDI), which aided our in-depth
understanding of the new particle formation (NPF) mechanism in the polluted Yangtze River Delta area.
During the observations, 16 NPF events occurred at high temperatures (~34.7°C) on clear and sunny days.
In the ammonium-poor PM1.0 (particulate matter less than 1.0 μm), sulfate and ammonium accounted for
92% of the total water-soluble inorganic species. Six aminiums were detected in these MOUDI samples,
among which the group of diethylaminium and trimethylaminium (DEAH+ + TMAH+) was the most abundant.
The very high level of aminiums (average concentration up to 86.4 ng m
3 in PM1.8), together with highly
acidic aerosols, provided insight into the frequent NPF events. The high mass ratio of total aminiums to
NH4+ (>0.2 for PM0.056) further highlighted the important role of amines in promoting NPF. The concentration
of DEAH+ + TMAH+ in new particles below 180 nm was strongly correlated with aerosol phase acidity,
indicating that acid-base reactions dominated the aminium formation in NPF events. The unexpected
enhancement of DEAH+ + TMAH+ on a nonevent day was attributed to the transportation of an SO2 plume.
Our results reveal that the heterogeneous uptake of amines is dominated by the acid-base reaction mechanism,
which can effectively contribute to particle growth in NPF events.
1. Introduction
As the dominant source of aerosol particles in the global atmosphere, new particle formation (NPF) may
significantly influence the global radiation balance and climate change [Penner et al., 2004; Pirjola et al., 2002].
Based on a global aerosol microphysics model, Global Model of Aerosol Processes, Merikanto et al. [2009]
estimated that 45% of the global low-level cloud condensation nuclei (CCN) at 0.2% supersaturation result
from nucleation. NPF consists of cluster formation (nucleation) and the subsequent growth of freshly
nucleated particles [Kulmala et al., 2004]. Several nucleation mechanisms have previously been proposed. The
most basic nucleation mechanism is the binary nucleation of H2SO4 with water vapor, first proposed by
Doyle [1961], which can predict the nucleation rates under some extreme conditions, such as the remote free
troposphere. The subsequently developed ternary nucleation model of H2SO4 – NH3
H2O has been successfully
used to explain NPF in the Eastern United States [Gaydos et al., 2005]. However, neither the binary nucleation of
H2SO4
H2O nor the ternary nucleation of H2SO4
H2O involving ammonia could explain all the particle
growth rates observed in the field [Kirkby et al., 2011; Weber et al., 1997]. Smith et al. [2010] observed a considerable
amount of aminium salts in nanoparticles (8–10 nm) during NPF events, suggesting that amines significantly
contribute to new particle formation. To date, the important role of amines in nucleation has been confirmed
by field measurements, laboratory studies, and computational calculations [Almeida et al., 2013; Bzdek et al.,
2010; Creamean et al., 2011; Erupe et al., 2011; Yu et al., 2012; Zhang et al., 2012b].
Apart from nucleation, aminium salts were also found in Aitken and accumulation mode particles [Facchini et al.,
2008; Müller et al., 2009; VandenBoer et al., 2011]. However, their source and formation mechanism have not
been fully explored. Laboratory experiments by Angelino et al. [2001] and Murphy et al. [2007] suggested that
the formation of aminium salts through acid-base reactions might contribute to the significant presence of
amines in ambient particles. Qiu et al. [2011] found that amines could displace ammonia from ammonium salts
or neutralize acidic sulfate and contribute to particle growth. Numerical simulations by Barsanti et al. [2009]
further suggested that amines can participate in the growth of new particles via salt formation, and their study
highlighted the requirement for experimental studies to verify their conclusion.
SIZE DISTRIBUTION OF PARTICULATE AMINES 324
 Journal of Geophysical Research: Atmospheres 10.1002/2015JD024245

China is suffering severe pollution from fine particulates, partly due to its rapid increase in fossil fuel
consumption and the large emissions of SO2 and NOx [Kirkby et al., 2011; Wang et al., 2012]. Recently, Guo
et al. [2014]demonstrated that a series of severe urban haze events was caused by NPF and the subsequent
continuous growth of the particles. The role of H2SO4 in NPF was highlighted in highly polluted North China
and in the Yangtze River Delta (YRD) area [Wang et al., 2011; Xiao et al., 2015; Yue et al., 2010]. However, to the
best of our knowledge, the characteristics of particulate amines during NPF events have not been reported.
In this study, size-segregated aerosol samples were collected with a cascade sampler during a period with a
high occurrence of NPF. Six aliphatic amines along with typical inorganic ions were characterized by ion
chromatography. The aminium mass fraction distributions and the effects of amines on new particle growth
are investigated.

2. Experiment
Size-segregated aerosol samples were collected approximately 7 m above the ground on the roof of the
Environment Building on the main campus of Fudan University (31.3°N, 121.5°E) from 15 July to 9 August
2013, using a 10-stage Micro-Orifice Uniform Deposit Impactor (MOUDI, Model 110, MSP Corp., USA). The
campus is located in one of the subcenters of Shanghai, which is a representative urban area influenced
by a wide mixture of emission sources. The MOUDI was operated at a flow rate of 30 L min
1, with 50% cutoff
points of 18, 10, 5.6, 3.2, 1.8, 1.0, 0.56, 0.32, 0.18, 0.1, and 0.056 μm in aerodynamic diameter for the sampling
inlet and 10 collection stages. Eleven quartz fiber substrates (47 mm, Whatman 1851–865) were mounted
on the collection stages, as well as on the MOUDI backup. The substrates were pretreated at 450°C for
6 h before sampling to remove all possible organic contaminants. The sampling typically started at 18:00
and ended at 17:00 the next day. All samples were transferred to 50 mm clean petri dishes and then were
maintained at
28°C until analysis.
The continuous monitoring of air quality and meteorological conditions was performed at our observation
supersite, previously reported by Yin et al. [2015]. The number size distribution of particles between 0.01
and 10 μm was measured using a Wide-range Particle Spectrometer (WPS, Model 1000XP, MSP Corporation,
USA). The PM1.0 (particulate matter less than 1.0 μm) mass loading was recorded using a Thermo Scientific™
5030 SHARP Monitor.
Half of each filter was ultrasonically extracted with 6 mL deionized water (18.2 MΩ cm). The extracts were
analyzed using a Metrohm 883 Ion Chromatograph (IC). Six anions (F
, Cl
, Br
, NO3
, SO42
, and PO43
) were
separated using a Metrosep A Supp 5-250/4.0 column. A Metrosep C4-250/4.0 column was used to separate
six inorganic cations (Li+, Na+, NH4+, K+, Ca2+, and Mg2+) and six protonated amines, including monomethy-
laminium (MMAH+), monoethylaminium (MEAH+), dimethylaminium (DMAH+), monoethanolaminium (MEOH+),
triethanolaminium (TEOH+), diethylaminium (DEAH+), and trimethylaminium (TMAH+) (see examples in
Figure S1 in the supporting information). The amines are denoted with an appended H+ because the particulate
amines should be protonated, and they existed as aminium salts [VandenBoer et al., 2011]. Because TMAH+
and DEAH+ were not separated on the Metrosep C4-250/4.0 column, the coeluting pair is referred to as
DEAH+ + TMAH+ in this study. Ethylamine and an inorganic potassium ion were not fully separated, which
may affect the ethylamine determination in the presence of high concentrations of potassium ions. All results
were corrected with field blanks.
The evaluation of the IC measurements is shown in Table S1. The corresponding detection limits for major
inorganic ions were 0.59 for Na+, 0.63 for NH4+, 1.65 for K+, 3.33 for Ca2+, 2.07 for Mg2+, 0.47 for Cl
, 0.93
for NO3
, and 0.68 for SO42
in ng mL
1. The detection limits for aminiums were 0.59 (MMAH+), 1.03
(MEAH+), 1.37 (DMAH+), 1.12 (MEOH+), 1.13 (TEOH+), and 0.61 (DEAH+ + TMAH+) in ng mL
1. The correlation
coefficients for all calibration curves were better than 0.999, and the recovery test yielded values within 93%
to 107% for all aminium ions.

3. Results and Discussion

3.1. New Particle Formation Events
The size distribution of the number concentration of particles between 10 and 500 nm during the sampling
period is presented in Figure 1. Data between 29 July and 1 August were missing due to an electrical fault.

TAO ET AL. SIZE DISTRIBUTION OF PARTICULATE AMINES 325

 Journal of Geophysical Research: Atmospheres 10.1002/2015JD024245

Figure 1. Time series of the concentrations of O3, SO2, PM1.0, NTotal, and particle number size distributions during the sampling period.

The diffusion loss in the 3 m long copper sample tubing (4 mm inner diameter) was corrected using a particle
loss calculator (http://www.mpch-mainz.mpg.de/~drewnick/PLC). The criteria for NPF events followed
the protocol proposed by Kulmala et al. [2012], which is characterized by a burst of nucleation mode particles
and the subsequent growth process that lasts for several hours. During the measurement period from 15 July
to 9 August, 16 new particle formation events were identified from the typical “banana shape” particle size
evolutions. Moreover, the typical consecutive 10 day NPF events occurred from 16 to 25 July. A recent report
by An et al. [2015] showed that 10 NPF events were captured in approximately 20 days in the summer of 2012
in Nanjing, another megacity in the YRD area, suggesting that frequent NPF events during the summer might
be a common occurrence in this cluster of cities.

The meteorological data are presented in Figure S2. The mean temperature, relative humidity (RH), wind
speed, and PM1.0 mass loading during NPF events were 34.7°C, 49%, 2.9 m s
1, and 20.9 μg m
3, respectively,
indicating that NPF was more likely to occur under lower RH, a light breeze and with lower surface area of
preexisting aerosols. Strong atmospheric NPF at the same site was also found during the winter [Xiao et al.,
2015]. In contrast to their winter campaign, the NPF events in the summer occurred much more frequently.
A similar trend was found in Nanjing by comparing the reported NPF events in the summer and in the winter
[An et al., 2015; Herrmann et al., 2014]. The high NPF frequency in the hot summer should be highlighted
because the highest NPF frequency was often found in other seasons [Kanawade et al., 2012; Vehkamaki
et al., 2004; Wu et al., 2007].

Our observations revealed that all NPF events started in the late morning at approximately 9:00–10:00 and
that this was followed by a growth process of at least 3 h (Figure 1). Generally, the nucleation mode (10–20 nm)
particles burst from less than 500 cm
3 before the event to more than 4000 cm
3 when NPF occurred, whereas
the Aitken mode (20–100 nm) particles increased approximately tenfold during the rapid growth process.
Particles less than 100 nm in size accounted for more than 90% of the total number concentration of particles.
Based on the contour plot of the particle size distributions obtained from WPS, NPF primarily affected the
particle population below 200 nm.

3.2. Size-Resolved Water-Soluble Inorganic Species and Aminiums

Table 1 summarizes the average concentrations of major inorganic ions and aminiums during the observation
period. In this study, the cutoff size of 1.8 μm is chosen to categorize fine-mode and coarse-mode particles.
PM1.0 particles collected by MOUDI are obtained by summing the five lowest MOUDI collection stages and

TAO ET AL. SIZE DISTRIBUTION OF PARTICULATE AMINES 326

 Journal of Geophysical Research: Atmospheres 10.1002/2015JD024245

Table 1. MOUDI Size-Resolved Particulate Water-Soluble Inorganic Species and Aminiums During the Entire Observation
a
(Mean Concentration With 1 Standard Deviation)
Species PM1.0 PM1.8 PM10 PM18

3
Sum of inorganic ions (μg m ) 10.66 ± 4.85 12.30 ± 5.50 17.99 ± 6.19 18.82 ± 6.39
+
3
Na (μg m ) 0.11 ± 0.10 0.18 ± 0.11 0.63 ± 0.39 0.65 ± 0.38
+
3
NH4 (μg m ) 2.25 ± 1.14 2.49 ± 1.28 2.58 ± 1.33 2.60 ± 1.34
+
3
K (μg m ) 0.15 ± 0.07 0.17 ± 0.09 0.21 ± 0.09 0.22 ± 0.10
2+
3
Ca (μg m ) 0.04 ± 0.09 0.06 ± 0.11 0.87 ± 0.40 1.01 ± 0.47
2+
3
Mg (μg m ) 0.03 ± 0.07 0.04 ± 0.07 0.12 ± 0.09 0.12 ± 0.08


3
Cl (μg m ) 0.02 ± 0.02 0.03 ± 0.03 0.26 ± 0.32 0.30 ± 0.35


3
F (μg m ) 0.03 ± 0.05 0.04 ± 0.05 0.05 ± 0.06 0.05 ± 0.06


3
NO3 (μg m ) 0.45 ± 0.23 0.66 ± 0.28 3.18 ± 0.95 3.48 ± 1.05
2

3
SO4 (μg m ) 7.57 ± 3.39 8.63 ± 3.85 10.08 ± 4.13 10.38 ± 4.18
+ x+
Equivalent ratio (NH4 /ΣM ) 13.4 ± 9.5 8.9 ± 6.1 1.8 ± 1.0 1.6 ± 0.8
+ 2


Molar ratio (NH4 /(2SO4 + NO3 )) 0.73 ± 0.09 0.69 ± 0.10 0.52 ± 0.12 0.50 ± 0.11

3
Sum of aminiums (ng m ) 72.3 ± 24.7 86.4 ± 30.8 114.6 ± 43.3 116.9 ± 44.4
+
3
MEOH (ng m ) 0.8 ± 0.9 0.9 ± 1.1 1.3 ± 1.7 1.4 ± 1.7
+
3
MMAH (ng m ) 7.7 ± 5.0 8.9 ± 6.1 9.9 ± 6.9 10.0 ± 7.0
+
3
MEAH (ng m ) 9.7 ± 12.7 11.5 ± 17.4 15.7 ± 26.4 16.2 ± 27.8
+
3
DMAH (ng m ) 13.4 ± 6.5 15.7 ± 7.9 20.1 ± 10.7 21 ± 11.4
+
3
TEOH (ng m ) 7.7 ± 5.6 10.5 ± 7.7 20.6 ± 13.7 21.2 ± 14.2
+ +
3
DEAH + TMAH (ng m ) 32.9 ± 14.9 38.8 ± 17.0 47.0 ± 19.9 47.1 ± 20.1
a x+ + 2+ 2+ +
ΣM is the sum of K , Mg , Ca , and Na .

the backup filter. Similarly, PM1.8, PM10, and PM18 are determined by summing the MOUDI size bins with cutoff
sizes less than 1.8, 10, and 18 μm, respectively. The concentrations of Li+ and Br
were not considered because
they were rarely detected. The major water-soluble species in PM1.0 were SO42
and NH4+, which together con-
tributed approximately 92% of the total inorganic ionic species. In contrast, the concentrations of the major
water-soluble species in the coarse particles (PM1.8–18) followed the sequence of NO3
> SO42
> Ca2+ > Na+.
The pollution from secondary inorganic aerosols varied daily, with the highest concentration of sulfate in
PM1.8 exceeding 15 μg m
3, whereas the lowest was less than 4 μg m
3. However, the average concentration
of fine-mode sulfate in this study was considerably lower than that in previous studies [Pathak et al., 2009;
Wang et al., 2006], possibly due to the implementation of flue gas desulfurization in coal-fired power plants
[Wang et al., 2013; Zhao et al., 2013].
Regardless of heavy traffic and high NOx emissions, the concentration of fine-mode nitrate was less than a tenth
that of sulfate. It is interesting to note that 80% of nitrate was in the coarse mode, which is in contrast to the fact
that 85% of sulfate was in the fine particles, suggesting different formation mechanisms between secondary
sulfate and nitrate aerosols. Heavy fine-mode nitrate pollution in urban Shanghai has been reported in many
studies [Du et al., 2011; Shi et al., 2014; Tao et al., 2014]. The remarkably lower amount of nitrate in PM1.8 indi-
cated that the formation of ammonium nitrate during the period of continuous hot weather was suppressed.
Due to its low thermodynamic stability, the formation of ammonium nitrate via homogeneous neutralization
between ammonia and nitric acid preferentially occurs in ammonia-rich areas and at low temperatures. The
ratio of the equivalents of ammonium to the sum of other cations decreased from 8.9 in fine particles to
1.6 in PM18 because there was a negligible amount of coarse-mode ammonium. The dominant cations in
particles larger than 1.8 μm were Ca2+ and Na+, suggesting that the coarse-mode nitrate predominantly existed
as Ca(NO3)2 and NaNO3. Gaseous HNO3 prefers to react with alkaline species, such as sea salt and mineral aerosols,
when homogeneous reactions with ammonia are unavailable:

NaClðaq; sÞ þ HNO3 ðgÞ → NaNO3 ðaq; sÞ þ HClðgÞ (1)

CaCO3 ðsÞ þ HNO3 ðgÞ → CaðNO3 Þ2 ðaq; sÞ þ H2 Oðaq; gÞ þ CO2 ðgÞ (2)

The production and escape of gaseous HCl in the former reaction is called the well-known phenomenon of
“displacement of Cl
.” The mass ratio of Cl
to Na+ in coarse-mode particles was approximately 0.65, which is
much less than that in seawater (1.80), supporting the aforementioned coarse-mode nitrate formation mechanism.

TAO ET AL. SIZE DISTRIBUTION OF PARTICULATE AMINES 327

 Journal of Geophysical Research: Atmospheres 10.1002/2015JD024245

In contrast, the equivalent of ammonium in PM1.0 was over tenfold higher than the sum of other cations,
indicating that ammonia was the dominant species to neutralize acidic sulfate and nitrate. Considering the
substantial contribution of ammonium to cations, the acidic characteristics of fine particles can be estimated
by the extent of the neutralization of sulfate and nitrate by ammonia [Pathak et al., 2009]. The equivalent ratio
of ammonium to the sum of sulfate and nitrate was much less than one (Table 1), indicating that PM1.0 was
significantly acidic. Highly acidic aerosols in Shanghai during the summer were previously reported by
Pathak et al. [2009], who attributed the formation of particulate nitrate to the hydrolysis of N2O5 on preexisting
aerosols. It should be highlighted that the lower molar ratio (NH4+/(2SO42
+ NO3
)) in particles larger than
1.8 μm did not cause particulate acidity because Ca2+ and Na+ rather than NH4+ were the dominant species
to balance anions in coarse-mode particles.
Six aminiums were detected in these MOUDI samples, although occasionally some of them were below the
detection limits of the instrument. In PM1.8, the total concentration of aminiums varied between 37.9 and
147.4 ng m
3, with an average of 86.4 ng m
3. The daily-averaged concentration of the sum of aminiums
in fine particles was higher than the maximum value measured in urban Toronto [VandenBoer et al., 2011].
A significant abundance of particle phase amines was also observed in the marine and terrestrial environments
[Facchini et al., 2008; Pratt et al., 2009]. Pratt et al. [2009] found that the particulate amines were more abundant
in the summer than in other seasons.
A variety of sources were found for atmospheric amines, such as sewage, heavy cooking, biomass burning,
and the ocean [Ge et al., 2011]. The mean ozone concentration during the entire observation period was
97 ± 69 μg m
3 (Figure 1), indicating strong atmospheric oxidation and high concentrations of OH and
NO3. According to the rate constants against different radicals reviewed by Ge et al. [2011], the atmospheric
life of amines is estimated as several hours under these high temperatures and concentrations of atmospheric
oxidants. The considerably high aminium mass loadings suggested larger emissions of amines or amine precur-
sors in this area. A typical alkali amine was reported to be nearly 40 times stronger than ammonia in nucleation
with H2SO4 [You et al., 2014]. Amines, together with ammonia, will further enhance the nucleation efficiency
through synergetic effects [Yu et al., 2012]. The abundant amines, together with precursors of acidic aerosols,
may be partially responsible for the observed frequent NPF events.
As shown in Table 1, TEOH+ was equally partitioned into fine- and coarse-mode particles, whereas other fine
aminiums were dominant in fine-mode particles. DEAH+ + TMAH+ was the most abundant aminium detected in
fine mode, followed by DMAH+. DEA is among the most favored amines to accumulate in the particulate phase
because the dissociation constant of diethylaminium sulfate is 1 order lower than that of dimethylaminium
sulfate and 2 orders lower than that of ethylaminium sulfate or methylaminium sulfate [Lavi et al., 2013].
TMA was found to be the most abundant amine in the atmosphere [Ge et al., 2011]. Generally, the concentration
of four alkyl aminiums in fine mode was largely dependent on their sources and dissociation constants for
aminium sulfate or nitrate salts. Although the MEAH+ concentration had a large uncertainty, the mean concen-
trations of MMAH+ and MEAH+ were in the range measured in Nanjing [Yang et al., 2005].
3.3. Size Dependence of Aminium Concentrations During NPF Events
There are 12 of 15 sets of MOUDI samples collected on NPF days. The size distributions of aminium mass loading
during NPF days are shown in Figure 2. The backup filter was not considered in the literature because the collec-
tion mechanism was filtration rather than impaction for the first to tenth stages, and it is very difficult to calculate
its collection efficiency [Contini et al., 2014; Fujitani et al., 2006]. The backup filter was easily contaminated with
sealing grease, which made it impossible to estimate the collection efficiency of the backup filter by considering
the particle size distribution from WPS measurements and the particle mass collected on the backup filter. For
convenience, we assume the lower cutoff size for the backup filter as 30 nm in this study. The geometric mean of
the two cutoff diameters is applied to each size range. Similar to secondary inorganic aerosols, the absolute
aminium concentration varied daily. However, the mass size distribution of DEAH+ + TMAH+, as well as DMAH+,
TEOH+, and MMAH+, displayed a similar trend on the 12 NPF days. In contrast, MEAH+ was not detected over
the entire size range in six sets of samples, whereas extraordinarily high concentrations were occasionally
observed in some collection stages. This abnormal feature partially originated from the interference from
potassium ions in the IC analytical method. In most cases, the amount of MEOH+ was close to the instrument
detection limit. Therefore, MEAH+ and MEOH+ are not discussed in later sections due to their large uncertainty.

TAO ET AL. SIZE DISTRIBUTION OF PARTICULATE AMINES 328

 Journal of Geophysical Research: Atmospheres 10.1002/2015JD024245

Figure 2. Size distributions of six aminiums measured during NPF days. The solid line represents the average size distribution for
each aminium. Different symbols were used to represent the aminium concentrations in the 12 sets of MOUDI samples measured
on NPF days. The leftmost dc/dlogDp is uncertain due to the uncertainty of the collection efficiency on the backup filter.

The maximum concentration for each of the remaining four aminiums was observed in the MOUDI size bin of
0.56–1.0 μm, corresponding to the droplet mode range. This feature suggests that the aqueous uptake of
amines greatly contributes to aminium formation. Driven by the constants of Henry’s Law, water-soluble
amines can partition into cloud or fog droplets through direct dissolution. Particle partitioning becomes more
favorable when thermodynamically stable aminium salts are formed through neutralization with acidic ions
or displacement reactions between amines and ammonium. In-cloud formation and the transformation of air
pollutants were suggested to be more important in Shanghai due to the high level of low-cloud coverage
[Chan and Yao, 2008]. Laboratory and field investigations supported the idea that cloud and fog processing
could enhance the gas to particle conversion of amines [De Haan et al., 2009; Ervens et al., 2011; Rehbein et al.,
2011]. The uptake of amines on deliquesced particles is possibly another significant source of particulate
amines. The RH during the night varied between 60 and 80% during the observation period (Figure S2).
As mentioned above, the fine-mode sulfate and nitrate were not fully neutralized. Significant hygroscopic

TAO ET AL. SIZE DISTRIBUTION OF PARTICULATE AMINES 329

 Journal of Geophysical Research: Atmospheres 10.1002/2015JD024245

Figure 3. (a) Average aminium mass fractions as a function of particle size measured during NPF days. The leftmost mass
fraction is uncertain due to the uncertainty of grease contamination on the backup filter. (b) Average ratio of the sum of
all measured aminiums to ammonium as a function of particle size compared with ammonium concentration (error bar
represents 1 standard deviation).

growth can be expected to occur during the night because the deliquescence point of acidic sulfate is below
60% RH [Tang and Munkelwitz, 1993]. The aqueous phase of hygroscopic particles provided a favorable envir-
onment for amine adsorption and subsequent neutralization reactions with acidic aerosols. The promotion of
aminium formation by aqueous uptake was also reported by field observations at the same site by Huang
et al. [2012] and in Guangzhou by Zhang et al. [2012a], where amine-containing particles were enhanced
during high-RH episodes and fog events.
In addition to aqueous uptake, laboratory studies showed that particulate aminium salts were formed
by acid-base reactions between amines with sulfuric acid and nitric acid at lower RH [Yu et al., 2012]. Gas
phase amines could react directly with acidic compounds and contribute to the growth of submicron
aerosols [Qiu and Zhang, 2013]. Our results showed that the concentrations of DEAH+ + TMAH+, DMAH+, and
MMAH+ in condensation mode (0.1–0.56 μm) were second only to those in droplet mode (0.56–1.8 μm),
suggesting that the condensation on preexisting particles was an important mechanism of particulate
aminium formation. Similar to atmospheric ammonia, amines have the potential to form semivolatile and
nonvolatile aminium salts through neutralization reactions with acidic components. This mechanism should
be greatly strengthened during NPF events because sulfuric acid was well established as the key component
in triggering nucleus formation and contributing to the subsequent growth of nanoparticles [Sakurai et al.,
2005; Zhang et al., 2015].
Noticeably, it is easy to underestimate the important role of amines in the initial growth of freshly nucleated
particles from the mass size distribution of particulate amines because both nucleation and Aitken mode
particles have negligible mass, in contrast to their overwhelming dominance in the number concentration
of particles, especially during NPF events. The relative abundance of aminium salts is introduced in this study
and is expressed as the aminium mass fraction and mass ratio of total aminiums to NH4+. Figure 3 shows the
aminium mass fractions and the ratio of total aminiums to ammonium as a function of particle size. The error

TAO ET AL. SIZE DISTRIBUTION OF PARTICULATE AMINES 330

 Journal of Geophysical Research: Atmospheres 10.1002/2015JD024245

+ + +
Figure 4. Size-segregated linear regressions between [H ]Total and the DEAH + TMAH concentration. Red dots represent
NPF days, red lines represent the corresponding linear regression results, and black dots represent non-NPF days.

bar represented by 1 standard deviation is used to qualify the dispersion of all samples collected on NPF days.
The relatively small standard deviations (Figure 3a) indicate that the difference among the data was not
statistically significant; thus, there was a similar mass fraction distribution on those NPF days. Although PM
below 56 nm could not be fully obtained due to the limitations of the MOUDI, the enhanced uptake of
DEA + TMA and DMA in nanoparticles (less than 100 nm) was easily identified from their size-resolved mass
fraction. Grease contamination increased the filter weight after sampling and subsequently caused an over-
estimation of the mass concentration for particles below 56 nm. Therefore, the mass fraction of aminium in
nanoparticles less than 56 nm was very likely underestimated. The actual contribution of amines to nucleation
and nanoparticle growth can be indicated by the ratio of aminiums to NH4+. Figure 3b illustrates the size
dependence of the mass ratio of total aminiums to NH4+. The coarse-mode aminiums may be sourced from
sea salt and crustal aerosols [Ge et al., 2011]. The reactive uptake of HNO3-aged aerosols was possibly another
important mechanism for coarse-mode aminium formation. The maximum mass ratio of aminiums to ammo-
nium appeared in the size bin of 5.6–10 μm, which did not represent the higher mass loading of aminiums. As
shown in Figure 3b, the size distribution of ammonium was bimodal, with one peak in the droplet mode size
range (maximum at 0.56–1.0 μm) and a secondary peak in the condensation mode size range (maximum at
0.18–0.32 μm), whereas the coarse-mode ammonium was negligible.
It is evident that the significant decrease of NH4+ was responsible for the increase of the mass ratio of coarse-
mode aminiums to ammonium. The mass ratio of total aminiums to NH4+ was larger than 0.2 for the particle
population smaller than 56 nm. This finding highlighted the important role of amines in promoting the
nucleation and initial growth of newly nucleated particles. Our result was also in accordance with the thermal
desorption chemical ionization mass spectrometer observation in an urban site in Tecamac, Mexico, in which
aminiums accounted for 47% of the detected nanoparticle cations between 8 and 10 nm in diameter [Smith
et al., 2010]. A noticeable feature is that the observed ratio of total aminiums to NH4+ decreased with the
increasing particle size within PM1.0, which is indicative of the decreasing uptake coefficient of amines. The
most plausible explanation is that amines gradually lost the competitive advantage when the Kelvin effect

TAO ET AL. SIZE DISTRIBUTION OF PARTICULATE AMINES 331

 Journal of Geophysical Research: Atmospheres 10.1002/2015JD024245

+ +
Figure 5. (a) The linear regression of DEAH + TMAH for 56–100 nm and 100–180 nm particles during NPF days. (b) Time
series of the SO2 concentration and PM1.0 mass loading during the SO2 episode.

became less important as the particle grew because the concentration of ammonia is 2–3 orders of magnitude
higher than that of amines in the typical atmosphere [Ge et al., 2011].

3.4. The Amine Chemistry in Aitken Mode

Laboratory studies showed that amines can contribute to particle growth through the displacement
of ammonia from ammonium salts or a neutralization reaction with acidic sulfate [Qiu et al., 2011]. To
understand the mechanism of amine partitioning during NPF events, a more detailed analysis between
aminium mass concentration and aerosol phase acidity was applied. 2[SO42
] + [NO3
]
[NH4+], briefly
noted as [H+]Total, is the parameter for the total aerosol acidity contributed by strong acids such as sulfuric
and nitric acids [Pathak et al., 2009; Squizzato et al., 2013]. Note that the [H+]Total defined in this study is
different from free H+ or pH. In contrast to the pH, which describes the hydrogen ion activity in aqueous
solution and is a critical parameter for chemical processes in liquid water, [H+]Total represents the capacity
of neutralization with alkaline species.
Figure 4 illustrates the linear regression between the size-segregated DEAH+ + TMAH+ concentration and
[H+]Total on NPF days. The red dots represent NPF days, and the black dots represent nonevent days. A strong
linear relationship was found for Aitken mode particles (56–100 nm) (Figure 4a, r2 = 0.94), indicating that
the reactive uptake of amines increased with increasing aerosol acidity. This finding provides clear evidence
that aminium salts in Aitken mode particles were predominantly formed through acid-base reactions. This
dependence on acidity was also observed for 100–180 nm particles (Figure 4b, r2 = 0.64), although the aerosol
acidity considerably decreased. In contrast, for particles larger than 180 nm (Figures 4c–4d), no linear correlation
was found between DEAH+ + TMAH+ and [H+]Total, suggesting different formation mechanisms. As shown in
Figure 1, particles in this size range were only slightly affected by the observed NPF events. This finding
strongly suggests that the reactive uptake on the newly formed acidic particles is one of the important
sources of particulate amines.
Interestingly, the DEAH+ + TMAH+ concentration for the condensation mode (100–180 nm) on nonevent days
strongly deviated from the aforementioned linear regression (shown in Figure 4b). The condensation mode
DEAH+ + TMAH+ was below the detection limit on 27 July and 6 August, in vivid contrast to NPF days.
Similarly, Makela et al. [2001] observed a 30-fold enhanced DMAH+ during NPF days compared with nonevent
days. Surprisingly, on another nonevent day, 26 July, the concentration of DEAH+ + TMAH+ was far above the
linear regression curve.

TAO ET AL. SIZE DISTRIBUTION OF PARTICULATE AMINES 332

 Journal of Geophysical Research: Atmospheres
Acknowledgments
This work was supported by the
National Natural Science Foundation of
China (21277027 and 21477020), the
Environmental Public Welfare Fund of
China (201409008), the National Science
and Technology Support Program of
China (2014BAC22B01), and the Science
and Technology Commission of
Shanghai Municipality (12DJ1400100).
Supporting data are included as two
figures and one table in an SI file; any
additional data related to the series of
size-segregated aminium concentrations
may be obtained from Ye (email:
yexingnan@fudan.edu.cn).
TAO ET AL.
10.1002/2015JD024245
Figure 5a illustrates the linear regression of the DEAH+ + TMAH+ concentration between 56–100 nm and
100–180 nm particles. The good correlation (r2 = 0.67) during NPF days suggests that the aminium salts
in these two-size ranges very likely shared the same source and formation mechanism. In contrast, there
was no correlation during nonevent days, which is indicative of different amine sources between the
Aitken and condensation modes.
A more detailed analysis of 26 July is presented in Figure 5b. A spike in the SO2 concentration was observed
in the early afternoon of 26 July, which indicated that a heavily polluted air mass passed through the
measurement site. Favored by strong atmospheric oxidation, as indicated from the high O3 concentration,
a large amount of H2SO4 would be produced from the oxidation of SO2. The highly acidic environment
would promote the neutralization reaction with amines and ammonia. The average PM1.0 mass loading
was close to 60 μg m
3 during the SO2 episode, which favored condensation growth on preexisting particles
while the NPF was suppressed. A large amount of aminium salts may be formed in the SO2-containing plume
before its arrival in Shanghai. Alternatively, heterogeneous reactions between amines and acidic sulfate on
preexisting particles may also be responsible for the enhancement of aminium salts.
4. Conclusions
NPF events occurred on 16 days in urban Shanghai during the summer observation period from 15 July to
9 August 2013. The new particles burst at approximately 9:00–10:00 A.M., which was followed by rapid growth
on clear and sunny days with high temperatures (~34.7°C), a significant difference from many observations.
With an average mass fraction of 92%, SO42
and NH4+ might be the most important inorganic species in these
highly acidic PM1.0 particles.
Six aminium salts were detected in these MOUDI samples collected during the observation period. Compared
with other urban sites, the average amine concentration of 86.4 ng m
3 in PM1.8 indicates larger emissions of
amines or amine precursors in this region. The abundant amines are very likely correlated to the observed
high NPF frequency. Among these aminiums, DEAH+ + TMAH+ was the most abundant. This result can be
explained by their thermodynamic stability and the abundance of precursors.
The mass ratio of total aminiums to NH4+ was larger than 0.2 for nanoparticles less than 56 nm. Our findings
provided insight into the important role of amines in promoting the nucleation and initial growth of newly
nucleated particles. The mass ratio decreased with increasing particle size, indicating that the uptake coefficient
of amines decreased as the particle size increased. The mass ratio increased in the coarse-mode range as the
amount of ammonium significantly decreased.
During NPF days, the concentration of DEAH+ + TMAH+ was linearly correlated with the aerosol phase acidity
for particles below 180 nm, corresponding to the size range of new particle formation and growth. This
indicates that acid-base reactions were the dominant mechanism of aminium formation in NPF events, which
can effectively contribute to new particle formation and growth. In the case of a highly polluted atmosphere,
DEAH+ + TMAH+ preferentially condensed on preexisting particles.
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