Chemistry of New Particle Growth in Mixed Urban and Biogenic Emissions - Insights From CARES

Atmos. Chem. Phys.
, 14, 6477–6494, 2014

www.atmos-chem-phys.net/14/6477/2014/
doi:10.5194/acp-14-6477-2014
© Author(s) 2014. CC Attribution 3.0 License.
Chemistry of new particle growth in mixed urban and biogenic

emissions – insights from CARES
A. Setyan1,* , C. Song2 , M. Merkel3 , W. B. Knighton4 , T. B. Onasch5 , M. R. Canagaratna5 , D. R. Worsnop5,6 ,
A. Wiedensohler3 , J. E. Shilling2 , and Q. Zhang1
1 Department of Environmental Toxicology, 1 Shields Ave., University of California, Davis, CA 95616, USA
2 Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richmond, WA 99352, USA
3 Leibniz Institute for Tropospheric Research, 04318 Leipzig, Germany
4 Montana State University, Bozeman, MT 59717, USA
5 Aerodyne Research Inc., Billerica, MA 01821, USA
6 Department of Physics, University of Helsinki, 00014 Helsinki, Finland
* now at: Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf, Switzerland
Correspondence to: Q. Zhang ([email protected])
Received: 29 December 2013 – Published in Atmos. Chem. Phys. Discuss.: 23 January 2014
Revised: 20 May 2014 – Accepted: 26 May 2014 – Published: 1 July 2014
Abstract. Regional new particle formation and growth C2 H3 N+ , and C2 H4 N+ ) that are indicative of the presence
events (NPEs) were observed on most days over the Sacra- of alkyl-amine species in submicrometer particles enhanced
mento and western Sierra foothills area of California in significantly during the NPE days, suggesting that amines
June 2010 during the Carbonaceous Aerosols and Radia- might have played a role in these events. Our results also in-
tive Effect Study (CARES). Simultaneous particle measure- dicate that the bulk composition of the ultrafine mode organ-
ments at both the T0 (Sacramento, urban site) and the ics during NPEs was very similar to that of anthropogenically
T1 (Cool, rural site located ∼ 40 km northeast of Sacra- influenced secondary organic aerosol (SOA) observed in
mento) sites of CARES indicate that the NPEs usually oc- transported urban plumes. In addition, the concentrations of
curred in the morning with the appearance of an ultrafine species representative of urban emissions (e.g., black carbon,
mode at ∼ 15 nm (in mobility diameter, Dm , measured by CO, NOx , and toluene) were significantly higher whereas the
a mobility particle size spectrometer operating in the range photo-oxidation products of biogenic VOCs (volatile organic
10-858 nm) followed by the growth of this modal diame- compounds) and the biogenically influenced SOA also in-
ter to ∼ 50 nm in the afternoon. These events were gen- creased moderately during the NPE days compared to the
erally associated with southwesterly winds bringing urban non-event days. These results indicate that the frequently oc-
plumes from Sacramento to the T1 site. The growth rate curring NPEs over the Sacramento and Sierra Nevada re-
was on average higher at T0 (7.1 ± 2.7 nm h−1 ) than at T1 gions were mainly driven by urban plumes from Sacramento
(6.2 ± 2.5 nm h−1 ), likely due to stronger anthropogenic in- and the San Francisco Bay Area, and that the interaction of
fluences at T0. Using a high-resolution time-of-flight aerosol regional biogenic emissions with the urban plumes has en-
mass spectrometer (HR-ToF-AMS), we investigated the evo- hanced the new particle growth. This finding has important
lution of the size-resolved chemical composition of new par- implications for quantifying the climate impacts of NPEs on
ticles at T1. Our results indicate that the growth of new global scale.
particles was driven primarily by the condensation of oxy-
genated organic species and, to a lesser extent, ammonium
sulfate. New particles appear to be fully neutralized during
growth, consistent with high NH3 concentration in the re-
gion. Nitrogen-containing organic ions (i.e., CHN+ , CH4 N+ ,
Published by Copernicus Publications on behalf of the European Geosciences Union.

6478 A. Setyan et al.: Chemistry of new particle growth in mixed urban and biogenic emissions
1 Introduction the growth of new particles was found to be almost exclu-

sively driven by organics (Smith et al., 2008; Laaksonen et
New particle formation and growth processes are an impor- al., 2008; Ziemba et al., 2010; Pierce et al., 2012; Ahlm et
tant source of ultrafine particles in both clean and polluted al., 2012). In addition, it was found that in Pittsburgh, USA,
environments. A large number of studies reported the obser- despite high ambient SO2 concentrations, H2 SO4 contributes
vations of intensive new particle events at various locations, mainly to the early stage of the new particle growth, while
including urban areas (e.g., Brock et al., 2003; Dunn et al., the growth up to CCN sizes is mainly driven by secondary
2004; Stanier et al., 2004; Zhang et al., 2004a; Wu et al., organic aerosols (SOA), especially during late morning and
2007; Ahlm et al., 2012), remote sites (e.g., Weber et al., afternoon when photochemistry is more intense (Zhang et al.,
1999; Creamean et al., 2011; Vakkari et al., 2011; Pikridas et 2004a, 2005).
al., 2012), forested locations (e.g., Allan et al., 2006; Pierce SOA is a major component of fine particles globally
et al., 2012; Han et al., 2013), coastal sites (e.g., O’Dowd et (Zhang et al., 2007; Jimenez et al., 2009). Understanding
al., 2002; Wen et al., 2006; Liu et al., 2008; Modini et al., its roles in new particle formation and growth is important
2009), and polar regions (e.g., Komppula et al., 2003; Ko- for addressing aerosols’ effects on climate and human health.
ponen et al., 2003; Asmi et al., 2010). These events signifi- Recent studies found significantly enhanced SOA formation
cantly affect the number concentrations and size distributions rates in mixed biogenic and anthropogenic emissions (de
of particles in the atmosphere with important implications Gouw et al., 2005; Volkamer et al., 2006; Kleinman et al.,
for human health and climate (Spracklen et al., 2006; Bzdek 2008; Setyan et al., 2012; Shilling et al., 2013). However,
and Johnston, 2010; Kerminen et al., 2012). However, de- there is little known about the influence of the interactions
spite frequent observations, the chemical processes underly- of organic species from biogenic and anthropogenic sources
ing the formation and growth of new particles remain poorly on new particle growth. The Sacramento Valley in California
understood. is a place of choice to study this process. The Sacramento
New particle events occur in two steps, i.e., the formation metropolitan area lies in the Central Valley to the north of the
of nuclei, followed by the growth of the stable clusters to San Joaquin River delta and to the southwest of the forested
larger sizes by condensation of low-volatility compounds and Sierra Nevada mountains. The wind in this region is charac-
coagulation. For ambient measurements, the evolution of the terized by a very regular pattern, especially in summer (Fast
number-based particle size distribution is a main criterion for et al., 2012). Indeed, during the day, a southwesterly wind
identifying the onset of new particle events. Mobility particle usually brings air masses from the San Francisco Bay to the
size spectrometer (MPSS), also called scanning mobility par- Sacramento metropolitan area and pushes northeast to the
ticle sizer (SMPS), is the most widely used instrument to de- Sierra Nevada mountains (Dillon et al., 2002), promoting the
termine the particle number concentration and size distribu- transport of urban plumes from Sacramento and the bay area
tion during these events. The evolution of the chemical com- to forested regions where biogenic emissions are intense.
position of ultrafine particles during new particle formation The US Department of Energy (DOE) sponsored Carbona-
and growth is another piece of critical information needed for ceous Aerosols and Radiative Effects Study (CARES) that
understanding this process. For that purpose, aerosol mass took place in the Sacramento Valley in June 2010 was de-
spectrometer (AMS) (e.g., Zhang et al., 2004a; Allan et al., signed to take advantage of this regular wind pattern to bet-
2006; Ziemba et al., 2010; Creamean et al., 2011; Ahlm et ter understand the life-cycle processes and radiative proper-
al., 2012), chemical ionization mass spectrometer (CIMS) ties of carbonaceous aerosols in a region influenced by both
(e.g., Dunn et al., 2004; Smith et al., 2005, 2008, 2010; Joki- anthropogenic and biogenic emissions (Zaveri et al., 2012).
nen et al., 2012), Nano aerosol mass spectrometer (NAMS) Within the framework of CARES, a wide range of instru-
(e.g., Bzdek et al., 2011; Bzdek et al., 2012), and atmospheric ments were deployed between 2 and 28 June 2010 at two
pressure ionization time-of-flight (APi-TOF) mass spectrom- ground sites located in Sacramento (T0, urban site) and Cool,
eter (Lehtipalo et al., 2011; Kulmala et al., 2013) have been CA at the foothills of the Sierra Nevada mountains (T1, rural
successfully deployed in the field to study the chemical pro- site), to measure size-resolved chemical compositions, num-
cesses underlying atmospheric new particle events. ber size distributions, and optical and hygroscopic proper-
An important finding from previous studies is that organ- ties of aerosols, as well as trace gases and meteorological
ics and sulfates are usually involved in the growth of new data (Zaveri et al., 2012). One of the major observations dur-
particles up to sizes where they can act as cloud condensa- ing CARES was that particles were dominated by organics,
tion nuclei (CCN). The contribution of these two species to and that the formation of SOA was enhanced when anthro-
particle growth depends on the concentrations of the precur- pogenic emissions from the Sacramento metropolitan area
sors and meteorological conditions. For example, at urban or and the Bay Area were transported to the foothills and mixed
industrial locations where the SO2 mixing ratio is high, sul- with biogenic emissions (Setyan et al., 2012; Shilling et al.,
fate is an important contributor to the growth of new particles 2013).
(Brock et al., 2003; Zhang et al., 2004a; Yue et al., 2010; During CARES, new particle growth events were observed
Bzdek et al., 2012). At rural and remote locations, however, almost daily at both the T0 and T1 sites. Similarly, previous
Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

A. Setyan et al.: Chemistry of new particle growth in mixed urban and biogenic emissions 6479
studies conducted at the University of California Blodgett without size information. In the PToF mode, average mass
Forest Research Station, approximately 75 km to the north- spectra were acquired for 92 size bins covering 30–1500 nm
east of Sacramento and 35 km to the northeast of the T1 site, (Dva ), allowing the determination of the size-resolved chem-
also reported the frequent occurrence of NPEs (Lunden et ical composition. W-mode data was recorded exclusively in
al., 2006; Creamean et al., 2011). In their study conducted MS mode.
from May to September 2002, Lunden et al. (2006) found The particle number size distribution was measured both
that the oxidation products of reactive biogenic compounds at T0 and T1 with a MPSS (also called SMPS) as described in
accounted for a significant portion of the particle growth. The Wiedensohler et al. (2012). The instrument used at T1 con-
study of Creamean et al. (2011), which took place in early sists of a Hauke-type differential mobility analyzer (DMA)
spring of 2009, found that sulfates and amines participated in and a condensation particle counter (CPC; TSI Inc., Shore-
the growth of new particles and that long-range transport of view, MN; model 3772), and used 210 Po as a radioactive
SO2 from Asia seemed to contribute to faster growth. These source for the neutralizer (Setyan et al., 2012). The MPSS
findings indicate that new particle formation and growth are was set to measure particles in the range 10–858 nm (in mo-
important processes in Northern California and are affected bility diameter, Dm ), divided into 70 logarithmically dis-
by regional anthropogenic and biogenic emissions as well as tributed size bins. MPSS data has been corrected to take into
by pollutants transported from Asia. Understanding to what account the DMA-CPC lag time, bipolar charge distribution,
extent these emissions may govern the NPEs requires mea- CPC efficiency, and diffusion loss. The SMPS deployed at
surements of size-resolved chemical compositions of the new T0 was a commercial instrument (TSI Inc.; model 3936),
particles. The main aim of the present paper is to examine the and was constituted of a 85 Kr neutralizer, a DMA (TSI Inc.;
evolution characteristics of new particles at the T0 and T1 model 3080 with the long column) and a CPC (TSI Inc.;
sites during CARES, with a focus on the evolution of size- model 3775). The instrument measured particles in the size
resolved particle chemical composition based on HR-ToF- range of 12–737 nm (in Dm ) divided into 115 size bins. Dif-
AMS measurements at T1. fusion loss correction was applied after the data inversion.
All dates and times reported in this paper are in Pacific Day-
light Time (PDT = UTC −7 h), which was the local time dur-
2 Experimental ing this study.
2.1 Sampling site and instrumentation 2.2 Data analysis
The T0 sampling site was located on the campus of Particle number concentration and size distribution have
the American River College in Sacramento (38◦ 390 0100 N, been used to identify new particle events in the atmosphere.
121◦ 200 4900 W, 30 m above sea level) and the T1 site was However, given that the new particles formed by nucleation
located on the campus of the Northside School at Cool have generally a diameter in the size range 1–3 nm, smaller
(38◦ 520 1600 N, 121◦ 010 2200 W, 450 m above sea level). Sacra- than the smallest size measured by our MPSSs, we were
mento is the capital of California, with 480 000 inhabitants not able to observe the new particle formation themselves
in the city and 2.5 million people living in the metropolitan during the present study, but only the growth of the newly
area. Cool is a small town (2500 inhabitants) surrounded by formed particles that are larger than 10 nm. For this reason,
very large forested areas, and located ∼ 40 km northeast of we will not use the terms “nucleation” or “new particle for-
Sacramento at the Sierra Nevada foothills. mation” in the forthcoming discussion, but rather “new par-
In this paper, we report results of particle chemical com- ticle growth”. Each day for which complete MPSS data was
positions at T1, and particle number size distributions at available was classified as new particle event (NPE) day if the
both T0 and T1. Size-resolved chemical composition of non- particle number concentration in the size range 12–20 nm in-
refractory submicron aerosols (NR-PM1 ) were measured at creased by more than 800 particles cm−3 , and if this increase
T1 using an Aerodyne HR-AMS (DeCarlo et al., 2006; Cana- was accompanied by the increase of the modal diameter dur-
garatna et al., 2007). A detailed discussion on its opera- ing the following hours. These two conditions allowed us
tion during the present study was presented in Setyan et to distinguish NPEs from primary emissions from vehicles,
al. (2012). Briefly, the HR-AMS was equipped with a stan- which also produce small particles but are usually observed
dard aerodynamic lens, described in Zhang et al. (2004b), as occasional spikes in the time series of the particle num-
and allowing the transmission of particles in the range ∼ 30– ber concentration in the range 12–20 nm. In addition, each
1500 nm (in vacuum aerodynamic diameter, Dva ). The in- growth event was considered as “strong” if the increase of
strument was operated alternatively in V- and W-mode ev- the particle number concentration in the range 12–20 nm was
ery 2.5 min. In V-mode, data was recorded in mass spectrum higher than 1500 particles cm−3 , and “weak” if the increase
(MS) mode and particle time-of-flight (PToF) mode. The MS was lower than this threshold. A summary of the new parti-
mode was used to obtain average mass spectra and determine cle growth events observed during this study is provided in
the concentration of the species in submicrometer particles Table 1.
www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

A. Setyan et al.: Chemistry of new particle growth in mixed urban and biogenic emissions
www.atmos-chem-phys.net/14/6477/2014/
Table 1. Summary of the characteristics of new particle growth events observed at Sacramento (T0) and Cool (T1) in northern California.
T0 T1
Day Growth rate 1N/1t 1N12−20 nm NPEs Growth rate 1N/1t 1N12−20 nm 1Org40−120 nm 1SO42− 40−120 nm Wind NPEs
nm h−1 # cm−3 h−1 # cm−3 event nm h−1 # cm−3 h−1 # cm−3 µg m−3 h−1 µg m−3 h−1 event
2/6/2010 Incomplete SMPS data N/Aa Incomplete SMPS data 0.75 0.10 T0 → T1b N/A
3/6/2010 10.5 6.12 × 103 5.43 × 103 strong 4.1 2.56 × 103 3.35 × 103 0.98 0.32 T0 → T1 strong
4/6/2010 5.4 6.80 × 103 5.44 × 103 strong 12.5 6.14 × 103 1.70 × 103 Incomplete PToF data T0 → T1 strong
5/6/2010 10.9 9.57 × 103 3.77 × 103 strong 9.3 1.07 × 103 1.10 × 103 No PToF data T0 → T1 weak
6/6/2010 12.1 7.40 × 103 4.57 × 103 strong 8.8 2.98 × 103 1.01 × 103 Incomplete PToF data T0 → T1 weak
7/6/2010 10.1 6.40 × 103 4.83 × 103 strong 7.6 5.86 × 103 1.51 × 103 0.28 0.063 T0 → T1 strong
8/6/2010 4.1 5.64 × 103 4.28 × 103 strong 7.7 4.19 × 103 2.63 × 103 0.35 0.075 T0 → T1 strong
9/6/2010 7.3 1.21 × 104 1.18 × 104 strong 6.1 6.92 × 103 4.86 × 103 0.49 0.075 T0 → T1 strong
6/10/2010 6.5 7.76 × 103 1.44 × 103 weak 4.2 4.31 × 103 1.33 × 103 0.19 0.0 NW weak
6/11/2010 7.1 2.48 × 103 1.16 × 103 weak –c – – – – NW no NPE
12/6/2010 – – – no NPE Incomplete data NW N/A
13/6/2010 – – – no NPE – – – – – NW no NPE
14/6/2010 4.6 1.26 × 104 8.67 × 103 strong Incomplete data T0 → T1 N/A
15/6/2010 4.4 6.75 × 103 8.81 × 103 strong 3.8 4.52 × 103 3.29 × 103 0.27 0.095 T0 → T1 strong
16/6/2010 2.5 4.50 × 103 6.55 × 103 strong 3.6 1.59 × 103 1.35 × 103 – – NW weak
17/6/2010 – – – no NPE 2.9 2.28 × 103 8.08 × 102 0.19 0.0 NW weak
18/6/2010 6.7 3.56 × 104 8.25 × 103 strong 4.3 5.30 × 103 1.74 × 103 0.32 0.032 T0 → T1 strong
19/6/2010 3.4 2.60 × 104 9.55 × 103 strong 5.9 5.20 × 103 1.48 × 103 0.19 0.041 T0 → T1 weak
20/6/2010 4.1 8.69 × 103 6.02 × 103 strong 4.4 2.04 × 103 8.86 × 102 – – NW weak
21/6/2010 5.2 4.19 × 103 1.25 × 103 weak 9.5 1.96 × 103 9.89 × 102 0.17 0.0 NW weak
22/6/2010 7.6 1.51 × 104 5.03 × 103 strong Incomplete SMPS data 0.10 0.0 T0 → T1 N/A
23/6/2010 11.1 7.28 × 103 1.45 × 103 weak Incomplete SMPS data 0.17 0.060 T0 → T1 N/A
Atmos. Chem. Phys., 14, 6477–6494, 2014

24/6/2010 6.4 7.11 × 103 8.74 × 103 strong 7.6 8.28 × 103 2.27 × 103 0.64 0.13 T0 → T1 strong
25/6/2010 8.0 4.07 × 103 4.16 × 103 strong 4.7 3.15 × 103 9.77 × 102 0.31 0.0 T0 → T1 weak
26/6/2010 7.7 9.13 × 103 6.93 × 103 strong 5.3 1.81 × 103 8.26 × 102 0.27 0.11 T0 → T1 weak
27/6/2010 9.3 5.25 × 103 6.70 × 103 strong 5.6 1.34 × 103 1.01 × 103 0.11 0.0 T0 → T1 weak
28/6/2010 undefinedd – – T0 → T1 undefined
Mean 7.1 9.57 × 103 5.67 × 103 6.2 3.76 × 103 1.74 × 103
0.34 0.06
Std dev 2.7 7.62 × 103 2.90 × 103 2.5 2.09 × 103 1.09 × 103
0.24 0.08
Median 6.9 7.20 × 103 5.44 × 103 5.6 3.15 × 103 1.35 × 103
0.27 0.06
Min 2.5 2.48 × 103 1.16 × 103 2.9 1.07 × 103 8.08 × 102
0.10 0.0
Max 12.1 3.56 × 104 1.18 × 104 12.5 8.28 × 103 4.86 × 103
0.98 0.32
a “N/A” stands for not applicable.
b “T0 → T1” stands for T0 to T1 transport periods.
c “–” means that no increase was observed.
d “undefined” means that the MPSS data did not allow to determine whether a growth event took place or not, because of a change in the wind direction during the day.
6480
Figure 1. Time series of (a, d) wind direction colored by wind speed, (b, e) broadband solar radiation, temperature and relative humidity,
and (c, f) particle size distributions at the T0 and T1 sites.
The modal diameter(s) of each particle number size dis- 2.0x10

4
T0
tribution recorded during this study have been determined T1
with a multiple peak fitting tool available in Igor Pro 6.2.2.2
concentration [#/cm ]
3
1.5
Particle number
(WaveMetrics Inc., Lake Oswego, OR). All the size distribu-

tions were log normal. The growth rate (GR), which corre- 1.0
sponds to the increase of the modal diameter of newly formed
particles per time unit (nm h−1 ), has been calculated for each 0.5
individual growth event using Eq. (1):
0.0
1Dm 0 4 8 12 16 20 24
GR = , (1)
1t Hour of Day (PDT, UTC-7)
in which 1Dm is the difference of the modal diameter (nm) Figure 2. Diurnal patterns of particle number concentrations mea-
between the beginning of the growth and the period when sured at the T0 and T1 sites during NPE days.
the growth significantly slows down, and 1t is the duration
of the growth (h).
of 19 NPEs were identified at T1 (86 % of the time; Table 1),
eight of which were considered as “strong” and eleven as
3 Results and discussions “weak”. Most of the events (14 in total) occurred during pe-
riods of southwesterly wind that transported urban plumes
3.1 Evolution of particle number size distributions to the T1 site (i.e., T0 → T1), except for 5 events which oc-
during regional new particle events curred during northwesterly wind periods (Table 1). In ad-
dition, all eight strong NPEs occurred during the T0 → T1
The SMPS and MPSS were fully operational during 26 days periods (Table 1). At T0, 22 new particle events were identi-
at T0, and 22 days at T1, from 2–29 June 2010. The time se- fied, 18 of which were considered as “strong” and only four
ries of the particle number size distributions show that new events were “weak”.
particle events frequently occurred at both sites (Fig. 1), indi-
cating that these events occurred on a regional scale. A total

Figure 2 compares the average daily evolution patterns a) T0

Arrow length:
0.00
of particle number concentrations at the T0 and T1 sites 2
1 m/s
during NPE days. Generally, the increase of the parti- 100
Dm [nm]
6
cle number concentration during these events was signif- 4
icantly higher at T0 than at T1 (average 9.6 × 103 vs. 2
dN/dlogDm [#/cm ]
12000
3.8 × 103 # cm−3 h−1 , p < 0.05 with Student’s t test; Ta- 10
8000
b) T1
ble 1). The average (± 1σ ) growth rate of new particles was 4000
also higher at T0 (7.1 ± 2.7 nm h−1 vs. 6.2 ± 2.5 nm h−1 at 2
0
3
100
T1), but the difference was not statistically significant (i.e.,
Dm [nm]
6
4
p > 0.05 with Student’s t test). The growth rates given in Ta- 2
ble 1 correspond to the first hours of the observation, when 10
2- - + -
the increase of the modal diameter is linear. In fact, the Org SO4 NO3 NH4 Cl BC
Inorganics [µg/m ]
8
OA factors [µg/m ] Organics [µg/m ]

c) T1 1.2
3
growth rate is usually quite linear during the first 2–3 h and 6
0.8
4
slows down afterwards (Fig. 5a and 5c). One reason for the 0.4
2
decrease of the growth rate after a few hours may be that 0 0.0
3
when particles grow to a certain diameter, the condensation 5 Urban transport SOA
3
d) T1
Biogenic SOA
of additional species onto the surface of these particles will 4
Hydrocarbon-like OA
3
result in a very small increase of their sizes. The occurrence 2
of relatively stronger NPEs at T0 is likely due to the prox- 1
0
imity of emission sources of precursor species and a higher 00:00 04:00 08:00 12:00 16:00 20:00 00:00
anthropogenic influence. Indeed, the frequency as well as 6/26/10
Date & Time (PDT, UTC-7)
6/27/10
the growth rates observed during the present study were

much higher than those reported by Lunden et al. (2006) at Figure 3. Comparison of the time evolution of the particle size dis-
∼ 35 km northeast of T1 (frequency = 30 % of the time, av- tributions at the (a) T0 and (b) T1 sites on 26 June, along with the
hourly averaged wind direction (length of the arrows is proportional
erage growth rate = 3.8 ± 1.9 nm h−1 ), where the lower fre-
to the wind speed) for each site. Time series of (c) NR-PM1 species
quency and growth rates might be related to the fact that and BC, and (d) three different organic aerosol factors.
their site was located deeper into the forest and subjected
to relatively lesser anthropogenic influences from urban ar-
eas to the southwest (e.g., Sacramento and the San Francisco
Bay Area). The growth rates measured during the present An important observation of the present study is that NPEs
study are also much higher than those observed at Hyytiälä, began at T1 a few hours later than at T0, especially during
Finland, where NPEs have been extensively observed and days characterized with daytime T0 → T1 transport. A typi-
described over the past 15 years. Riipinen et al. (2011) re- cal example of this phenomenon occurred on 26 June (Figs. 3
port a median growth rate of 2.3 nm h−1 during the years and 4). According to Fast et al. (2012), a T0 to T1 transport
2003–2007, much lower than at T1 (6.2 nm h−1 ) and T0 occurred that day. Particles smaller than 20 nm (in Dm ) began
(7.1 nm h−1 ). NPEs at Hyytiälä are mainly driven by the pho- to increase slightly before 09:00 PDT at T0 (Fig. 3a), and an
tooxidation of biogenic precursors, and growth rates mea- Aitken mode appeared at the same time (Fig. 4). Then, dur-
sured in this kind of environment depend on the concentra- ing the following hours, the modal diameter increased slowly
tion and volatility of the condensing material (Pierce et al., up to ∼ 50 nm (in Dm ), likely due to condensation of low-
2011; Riipinen et al., 2011; Pierce et al., 2012; Riipinen et al., volatility compounds onto the surface of these new particles.
2012). The Sacramento and Sierra Foothill region, however, The increase of the modal diameter could also be due to co-
is influenced by both urban and biogenic emission sources. agulation, but this process is expected to be very slow for par-
Thus, the comparison between the growth rates at these dif- ticles in the Aitken mode. Thus, as shown in Fig. 3a, the evo-
ferent sites suggests that the degree of anthropogenic influ- lution of the particle number size distribution shows a “ba-
ence may be an important factor driving the growth rate. nana shape”, which is a typical observation for the growth
During the present study, all growth events began in the of new particles. At T1, the same phenomenon occurred at
morning, with the appearance of an Aitken mode observed ∼ 11:00 PDT, i.e., 2 h after T0 (Fig. 3b). This time delay is
with the MPSS between 09:00 and 12:00 (PDT). Particle consistent with the wind data recorded at T1 which indicate
growth lasted several hours, with size modes reaching their the sampling of air masses transported from the T0 direc-
maximum in the afternoon, typically after 15:00 PDT. The tion. The much lower concentrations of particles smaller than
modal diameters at the end of the growth in general peaked 20 nm between 09:00 and 11:00 PDT at T1 (Fig. 3b), com-
between 40–50 nm, but for several cases, the modal diame- pared with T0 (Fig. 3a), suggests that new particle forma-
ter did not reach 35 nm, especially for the weakest events or tion occurred much near and upwind of T0 and not close to
when a change in the wind direction was observed during the T1. In other words, the banana-shaped evolution pattern ob-
day (Fig. 1). served at T1 was likely independent of the emissions in the

4 4 4
6x10 June 26 6x10 6x10
T0
dN/dlogDm
4 T1 00:00 4 4
[#/cm ]
08:00 16:00
3
2 2 2
0 0 0
4 4 4
6x10 6x10 6x10
dN/dlogDm
4 4 4
[#/cm ]
01:00 09:00 17:00
3
2 2 2
0 0 0
4 4 4
6x10 6x10 6x10
dN/dllogDm
4 4 4
cm ]
02:00 10:00 18:00

3
2 2 2
[#/c
0 0 0
4 4 4
6x10 6x10 6x10
dN/dlogDm
4 4 4
[#/cm ]
03:00 11:00 19:00

3
2 2 2
0 0 0
4 4 4
6x10 6x10 6x10
dN/dlogDm
4 4 4
[#/cm ]
04:00 12:00 20:00

3
2 2 2
0 0 0
4 4 4
6x10 6x10 6x10
Dm
4 4 4
dN/dlogD
[#/cm ]
05:00 13:00 21:00

3
2 2 2
0 0 0
4 4 4
6x10 6x10 6x10
dlogDm
4 4 4
[#//cm ]
06:00 14:00 22:00

3
2 2 2
dN/d
0 0 0
4 4 4
6x10 6x10 6x10
dN/dlogDm
4 4 4
[#/cm ]
07:00 15:00 23:00

3
2 2 2
0 0 0
2 4 6 8 2 4 6 2 4 6 8 2 4 6 2 4 6 8 2 4 6
10 100 10 100 10 100
Dm [nm] Dm [nm] Dm [nm]
Figure 4. Comparisons of the average particle number size distributions for each hour at T0 and T1 during June 26.
T1 area and mostly dependent on the emissions near T0 and This time delay between T0 and T1 was also observed dur-
upwind of T0. Further evidence for this pseudo Lagrangian ing the other events, and this is confirmed by comparing the
sampling is the observation of a sudden change in wind di- diurnal evolution profiles of particle number concentrations
rection at ∼ 14:30 at T0 that brought in a very clean air mass (Fig. 2) and size distributions at both sites (Fig. 5a and c).
associated with a sharp decrease of particle number concen- These observations indicate that new particle growth gen-
tration that lasted for ∼ 3.5 h (Fig. 3a). Particle concentra- erally occurred during T0 → T1 transport promoted by the
tion at T0 increased again at ∼ 18:00 PDT after a shift of the daytime southwesterly wind and that the new particle growth
wind direction back to southwesterly. A mirrored decrease events were generally more intense at T0 compared to those
of particle concentration, although less dramatically, was ob- at T1. Wind rose plot during NPEs (Fig. 6g) confirms that
served at 16:30 at T1, ∼ 2 h after the clean air mass event at these events usually occurred when the wind was coming
T0 (Fig. 3b). The increase of particle number concentration from the southwest, which corresponds to the location of the
occurred at T1 around 21:00 PDT, ∼ 3 h after the increase Sacramento metropolitan area. On the other hand, when an
occurred at T1, consistent with gradually decreasing wind NPE was not observed, the wind was coming mainly from
speed from 16:30 to 21:00 PDT. The wind direction at T1 re- the northwest and the west (Fig. 6h), bringing air masses
mained southwesterly during the entire afternoon (Fig. 3b).

2
NPE days Non-NPE days hicular emissions, due to the proximity of traffic, anthro-
T0 a) b)
100
pogenic emissions, and transport from the Bay Area. On the
8
other hand, the T1 site was more influenced by downslope
Dm [nm]
4
20x10
3
winds during the night, when a change in the wind direction
dN/dlogDm [#/cm ]
2
15 brought down more aged aerosols from the Sierra Nevada to
10
2 10 the foothills (Setyan et al., 2012).
T1 c) d)
100 5
3
8
3.2 Evolution of particle chemistry during new particle
Dm [nm]
6 0
4
growth
2
10
0 4 8 12 16 20 24 0 4 8 12 16 20 24
The evolution of particle chemistry during an NPE at T1
Hour of day (PDT, UTC-7) Hour of day (PDT, UTC-7) was studied in detail with an HR-ToF-AMS. As summa-
rized in Table 1, the increase of particle number concen-
Figure 5. Diurnal size distributions of the particle number concen-
tration at the (a, b) T0 and (c, d) T1 sites during NPE days (left
tration during NPE was accompanied by an increase of or-
panel) and non-NPE days (right panel). Black crosses correspond ganics and sulfate in ultrafine particles (40–120 nm in Dva ).
to the modal diameters fitted by log-normal distributions. The average (± 1σ ) increase of organics in that size range
was 0.71 (± 0.29) µg m−3 while that of sulfate was 0.10
NPE days Non-NPE days
Figure 5
(± 0.11) µg m−3 .
a) b)
Org 6 2
Figure 6 shows the diurnal size distributions of organic
4
matter, sulfate, and particle volume concentrations, along
Dva [nm]
2
dM/dlogDva [µg/m ]
1
100 with the wind rose plots during NPE days and non-event
6
4
0 days. The growth of new particles was mainly contributed by
c) d)
SO4
2-
6 sulfate and organics (Fig. 6a and c), but the increase of par-
4 0.2
Dva [nm]
ticle mass was observed by the AMS after 11:00 PDT, later
3
2
0.1
100 than the increase of number concentration according to the
6 00
0.0
4
e) f)
MPSS. This is because the smallest size measured by our
dV/dlogDm [µ
Vol 6
4 MPSS is 10 nm (in Dm ), while the transmission through the
2
Dm [nm]
2
AMS is significant only for particles larger than 30 nm (in
100 1
Dva ) (Jayne et al., 2000). Given that particle density at T1
µm /cm ]
6
3
4
0
was on average 1.4 during this study (Setyan et al., 2012),
3
0 4 8 12 16 20 24 0 4 8 12 16 20 24
g)
Hour of day (PDT, UTC-7)
h)
Hour of day (PDT, UTC-7) and assuming that they are spherical, the smallest particles
0 0
315
40
30 45 315 45 measured by the AMS correspond to ∼ 21 nm in Dm . Thus,
20
10 Wind speed (m/s)
0-1
the MPSS was the first instrument to detect the growth of
270 0 90 270 90
10 20 30 40 1-2
2-3
new particles, while the HR-ToF-AMS observed the growth
3+
225 135 225 135
2 or 3 h later, depending on the growth rate. A similar obser-
180 180
vation was reported during NPEs in Pittsburgh (Zhang et al.,
Figure 6. Diurnal size distributions of (a, b) Org, (c, d) SO2− 2004a). It is interesting to notice that organics, sulfate, and
4 , and 10
(e, f) particle volume concentrations, and (g, h) daytime wind rose particle volume exhibit qualitatively the same diurnal size
plots (08:00–20:00 PDT) for NPE days (left panel) and non-NPE distributions (Fig. 6). Indeed, they have a constant modal di-
days (right panel) at T1. ameter in larger particles during the entire day, and they in-
crease in ultrafine particles in the afternoon during the growth
events.
dominated by biogenic emissions (Setyan et al., 2012), thus The diurnal patterns of organics and sulfate in three differ-
reducing anthropogenic influences at T1. ent size ranges (40–120, 120–200, and 200–800 nm in Dva )
It is interesting to notice that the evolution of the parti- show that their afternoon increase occurred mainly in ultra-
cle number size distributions and concentrations during the fine particles (40–120 nm) while the increases in the rest of
evening and the night is not similar at T0 and T1. At T0, par- the sizes were moderate during NPE days (Fig. 7a and c).
ticle number concentration remains almost constant between In comparison, the diurnal profiles of both species were rel-
23:00 and 08:00 PDT (Fig. 2), while the mode is centered at atively flat and their concentrations much lower during the
∼ 35–40 nm (in Dm ) during this period (Fig. 5a). On the con- non-event days (Fig. 7b and d). Although both organics and
trary, particle number concentration decreases gradually at sulfate in ultrafine particles increased in the afternoon, the
T1 during night (Fig. 2), while the modal diameter increases increase of the organic mass in the 40–120 nm particles was
from 35 nm (at 21:00 PDT) up to 70 nm (at 08:00 PDT the on average 7 times higher than that of sulfate (see above
following day; Fig. 5c). This may be due to the fact that and Fig. 8d and e). Clearly, the growth of new particles
the T0 site was more influenced by nanoparticles from ve- was mainly driven by organics. This is in agreement with

a) Org, NPE days b) Org, Non-NPE days 2-

100 2.5 100 2.5 1400 a) Particle # NPE days 0.12 d) SO4 , 40-120 nm
200-800 nm 8-15 nm Non-NPE days
120-200 nm
Total mass [µg/m ]

80 2.0 80 2.0 1050 0.09
40-120 nm
% contribution
3
3
µg/m
#/cm
60 1.5 60 1.5 700 0.06
40 1.0 40 1.0 350 0.03

20 0.5 20 0.5
3
0 0.00
0 0.0 0 0.0 2.0 b) Urban transport SOA 1.00 e) Org, 40-120 nm
2- 2-
c) SO4 , NPE days d) SO4 , Non-NPE days
100 0.4 100 0.4 1.5 0.75
200-800 nm
3
120-200 nm
Total mass [µg/m ]
µg/m
µg/m
80 80 1.0 0.50
40-120 nm 0.3 0.3
% contribution
60 60
0.2 0.2 0.5 0.25
40 40
0.0 0.00
0.1 0.1
20 20 2.0 -2 + +
0.25
3
c) Biogenic SOA 1.5x10 f) CxHyN NH4
0 0.0 0 0.0 0.20
1.5
3
Org-eq µg/m
0 4 8 12 16 20 24 0 4 8 12 16 20 24 1.0
0.15
µg/m
µg/m
Hour of day (PDT, UTC-7) Hour of day (PDT, UTC-7)
1.0
0.10
3
0.5
0.5
Figure 7. Diurnal patterns of the concentrations of (a, b) Org and 0.05
(c, d) SO2−4 (black circles and lines, right y-axes) and the mass
0.0 0.0 0.00
0 4 8 12 16 20 24 0 4 8 12 16 20 24
fractions in the range 40–120, 120–200 and 200–800 nm (in Dva ,
Hour of day (PDT, UTC-7) Hour of day (PDT, UTC-7)
left y-axes) during NPE days (left panel) and non-NPE days (right
panel) at T1.
Figure 8. Diurnal patterns of (a) particle number concentration (10–
15 nm), (b) urban transport SOA, (c) biogenic SOA, (d) SO2− 4 (40-
120 nm in Dva ), (e) Org (40–120 nm in Dva ), and (f) N-containing
organic ions (= CHN+ + CH4 N+ + C2 H3 N+ + C2 H4 N+ ) and am-
monium during NPE (solid symbols) and non-NPE (open symbols)
previous studies, which also emphasized the key-role of or- days at T1.
ganics in the growth of new particles up to CCN sizes (Laak-
sonen et al., 2008; Smith et al., 2008; Ziemba et al., 2010;
Zhang et al., 2011; Ahlm et al., 2012; Pierce et al., 2012; amines likely played an important role in the formation of
Riipinen et al., 2012). new particles in the Sacramento and Sierra foothills region.
Another important observation is the substantial increase Due to the high contribution of organics to submicron
of the signals of four nitrogen-containing ions (i.e., CHN+ , aerosol mass in the region, positive matrix factorization
CH4 N+ , C2 H3 N+ , and C2 H4 N+ ) in submicron particles dur- (PMF) analysis was performed on the high resolution mass
ing the new particle growth periods (Fig. 8f). On average, the spectra of the AMS to investigate the sources and processes
concentration of these ions during NPE days was 2.4 times of organic aerosols (Setyan et al., 2012). Briefly, three dis-
the concentration observed during non-NPE days (Fig. 11). tinct factors were determined, including a biogenically influ-
Since these Cx Hy N+ ions are generally related to alkyl- enced SOA associated with the regional biogenic emissions
amine species (Ge et al., 2014), this class of compounds was (O / C ratio = 0.54, 40 % of total organic mass), an anthro-
likely involved in the growth of new particles. This is consis- pogenically influenced SOA associated with transported ur-
tent with previous findings in the atmosphere (e.g., Makela ban plumes (O / C ratio = 0.42, 51 %), and a hydrocarbon-like
et al., 2001; Smith et al., 2008, 2010; Bzdek et al., 2011; organic aerosol (HOA) mainly associated with local primary
Creamean et al., 2011; Laitinen et al., 2011). Recent studies emissions (O / C ratio = 0.08, 9 %). Details on the determi-
have found that sulfuric acid–amine clusters are highly sta- nation and validation of these three OA types are given in
ble and that even trace amount of amines (e.g., a few ppt) Setyan et al. (2012). It is important to clarify here that the
can enhance particle formation rates by orders of magnitude biogenic SOA and urban transport SOA identified at T1 do
compared with ammonia (Zollner et al., 2012; Almeida et not correspond to SOAs formed from 100 % anthropogenic
al., 2013). The importance of gas-phase amines in the gen- or biogenic precursors. In fact, the so-called biogenic SOA
eration of organic salts involved in the formation of new was found in air masses with dominant biogenic influence
particles was also confirmed by thermodynamic modeling and little anthropogenic influence, while the urban transport
study (Barsanti et al., 2009). Based on the mass spectrom- SOA was found in air masses characterized as urban plumes
etry fragmentation patterns of amine standards analyzed in mixed with the continuously present biogenic emissions in
our lab (Ge et al., in preparation), the average concentration the region. These observations are consistent with radiocar-
of aminium (R1 R2 R3 N+ , where R1 , R2 , R3 are either H or bon analysis of fine particulate matter, which has shown that
an alkyl group) is estimated to be approximately 1/10th that modern carbon worldwide often contributes > 70 % of the
of ammonium at T1 during this study (Fig. 8f). Although we total carbon, particularly downwind of urban areas (Glasius
are unable to directly assess the importance of amines in new et al., 2011; Schichtel et al., 2008 and references therein).
particle formation based on this study, our results suggest that

NPE days Non‐NPE days
a) Number 8:00-10:00 b) Number
dN//dlogDva [#/cm ]
25000 8000
3
10:00-12:00
20000 12:00-14:00
6000
14:00-16:00
15000
16:00-18:00 4000
10000
5000 2000
0 0
2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7
100 1000 100 1000
3.0
dV//dlogDva [m /cm ]
c) Volume d) Volume
3
1.5
3
2.0
1.0
1.0
0.5
0.0 0.0
2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7
100 1000 100 1000
Dm [nm] Dm [nm]
2- 2-
0.6 e) SO4 f) SO4
0.20
0.4 0.15
0.10
0.2
g/m ]
3
0.05
dM/dlogDva [µg
0.0 0.00
2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7
100 1000 100 1000
4 g) Org 2.5 h) Org
2.0
3
1.5
2
1.0
1 0.5
0 00
0.0
2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7
100 1000 100 1000
Dva (nm) Dva (nm)
Figure 9. 2 h averaged size distributions of (a, b) particle number and (c, d) volume, (e, f) SO2−
4 , and (g, h) Org during NPE days (left panel)
and non-NPE days (right panel) between 08:00 and 18:00 PDT at T1.
As shown in Fig. 8, during NPE days, the mass concen- that sulfate involved in NPEs was usually under the form of
tration of urban transport SOA increased by more than a sulfuric acid, especially during the initial steps of the growth
factor of 2 (from 0.75 to 1.7 µg m−3 ) between 10:00 and (Brock et al., 2003; Zhang et al., 2004a; Yue et al., 2010;
16:00 PDT (Fig. 8b), whereas that of biogenic SOA in- Bzdek et al., 2012). However, northern California contains
creased only slightly by ∼ 10 % during that period (from very large agricultural regions with a lot of sources of am-
0.84–0.93 µg m−3 , Fig. 8c). This result underlines the key- monia, which could possibly neutralize sulfate in the ultra-
role played by the urban plumes from Sacramento in the fine mode. Using high mass resolution mass spectra acquired
NPEs at Sierra foothills. under PToF mode, we determined the size distributions of
Figure 9 shows the evolutions of the mass-weighted size ammonium and sulfate based on those of the NH+ 3 and SO ,
+
distributions of Org, SO2− 4 , and organic tracer ions and the which are the ions of ammonium and sulfate, respectively,
particle number distributions during daytime. The average with the highest signal-to-noise ratio (see supplementary ma-
size distributions of Org and SO2− 4 during NPE days show terial for details of this data treatment). As shown in Fig. 10,
significant increase of concentrations in the small mode despite relatively noisy data, the size distributions suggest
(Fig. 9e and g). On the other hand, the increases of the con- that sulfate was fully neutralized by ammonium in the en-
centrations of Org and SO2− 4 in ultrafine particles were all tire size range, including ultrafine particles. Moreover, we
negligible during non-event days (Fig. 9f and h). did not observe any difference in the sulfate neutralization
Another important parameter to determine was the neu- between NPE and non-NPE days or between different times
tralization of sulfate in the ultrafine mode during NPEs. We of the day. These results indicate that sulfate in ultrafine par-
already know from the mass spectral mode of the AMS that ticles was present in the form of ammonium sulfate and that
sulfate was fully neutralized in the bulk during the entire sulfuric acid was quickly neutralized after condensation.
study (Setyan et al., 2012). Many previous studies mentioned

Table 2. Summary of average value ± 1 standard deviation for meteorological parameters, particle phase species, and gaseous species during
new particle event (NPE) and non-NPE days at the T1 site between 08:00 and 18:00 PDT.
Parameter NPE days Non-NPE days

Meteorological data
Temperature (◦ C) 24.2 ± 4.4 25.0 ± 4.1
Relative humidity (%) 45.3 ± 12.6 27.1 ± 12.1
Solar radiation (W m−2 ) 702.9 ± 246.1 792.7 ± 200.4
Particle phase
Particle number (# cm−3 ) 9.4 × 103 ± 6.1 × 103 4.1 × 103 ± 1.9 × 103
Growth rate (nm h−1 ) 6.2 ± 2.5 –
Biogenic SOA (µg m−3 ) 0.90 ± 0.65 0.56 ± 0.27
Urban transport SOA (µg m−3 ) 1.2 ± 0.90 0.54 ± 0.44
HOA ( µg m−3 ) 0.16 ± 0.15 0.11 ± 0.08
SO2− −3
4 (µg m ) 0.39 ± 0.22 0.14 ± 0.10
− −3
NO3 (µg m ) 0.13 ± 0.08 0.054 ± 0.036
BC (µg m−3 ) 0.042 ± 0.028 0.027 ± 0.017
Trace gases (ppb)
Terpenes 0.058 ± 0.088 0.043 ± 0.034
Isoprene 1.40 ± 1.02 1.35 ± 0.80
MACR + MVK 0.98 ± 0.79 0.75 ± 0.50
Methanol 6.36 ± 3.12 5.36 ± 1.76
Acetone 1.90 ± 1.09 1.64 ± 0.42
Formaldehyde 2.71 ± 1.39 1.83 ± 0.81
Acetaldehyde 0.97 ± 0.47 0.71 ± 0.24
Acetic acid 0.98 ± 1.10 0.87 ± 0.43
Acetonitrile 0.18 ± 0.03 0.17 ± 0.02
Benzene 0.036 ± 0.029 0.031 ± 0.014
Toluene 0.060 ± 0.037 0.038 ± 0.019
O3 43.5 ± 14.2 46.2 ± 10.5
NOx 3.8 ± 3.3 2.7 ± 3.5
CO 130.1 ± 27.0 99.8 ± 19.8
3.3 Anthropogenic influence on new particle growth ing NPE days: 0.98 ± 0.79 ppb vs. 0.75 ± 0.50 ppb. These
events markers of oxidation are likely correlated with other semi-
volatile compounds co-generated during photo-oxidation,
which could condense onto the surface of particles and could
The average concentrations and diurnal patterns of VOCs,
be an important factor driving the growth of new particles.
trace gases (O3 , CO, NOx ), BC, and meteorological parame-
Moreover, the diurnal patterns of these compounds during
ters (temperature, relative humidity, and solar radiation) dur-
NPE and non-NPE days show a clear difference during the
ing NPE days and non-event days were compared (Fig. 11,
afternoon, whereas the differences are much smaller during
Figs. S3 and S4 in the Supplement, and Table 2). An im-
nighttime (Fig. S4 in the Supplement). This result stresses
portant difference between NPE and non-event days was
the influence of photochemistry on the formation and growth
the concentrations of photo-oxidation products (formalde-
of new particles.
hyde and acetaldehyde) and anthropogenic precursors (BC,
The average concentrations of isoprene were almost
CO and toluene), which were all significantly higher dur-
identical during NPE and non-event days (Fig. 11)
ing NPE days than during non-event days. Photo-oxidation
but the enhancements of anthropogenic species dur-
products were on average ∼ 50 % more concentrated on NPE
ing NPE days were more dramatic. The average con-
days (formaldehyde: 2.71 ± 1.39 ppb vs. 1.83 ± 0.81 ppb
centrations of BC (0.042 ± 0.028 µg m−3 during NPE
during non-NPE days; acetaldehyde: 0.97 ± 0.47 ppb vs.
days vs. 0.027 ± 0.017 µg m−3 during non-NPE days),
0.71 ± 0.24 ppb). The sum of methacrolein (MACR) and
CO (130 ± 27.0 vs. 99.8 ± 19.8 ppb), NOx (3.8 ± 3.3 vs.
methyl vinyl ketone (MVK), which are the first generational
2.7 ± 3.5 ppb), HOA (0.16 ± 0.15 vs. 0.11 ± 0.08 µg m−3 ),
products of isoprene oxidation, was also ∼ 20 % higher dur-

NH4+ SO42- served much higher RH during NPEs days than non-NPE
a 1.5 days. However, most of the previous studies reported NPEs
0.5
0.15 0.4 Figure 9
when the RH was low (Boy and Kulmala, 2002; Hamed et
1.0 al., 2007, 2011; Jeong et al., 2010; Guo et al., 2012). The
0.10 0.3 new
exact role of RH in NPEs is not clearly elucidated yet. Ac-
0.2 cording to Hamed et al. (2011), the anti-correlation between
0.5
0.05 RH and NPEs would simply be due to the fact that solar radi-
0.1 10:00 - 11:00
NPE days ation and photochemistry usually peak at noon when the RH
0 00
0.00 00
0.0 00
0.0 exhibits its lower value. However, in our case, this does not
8 9 2 3 4 5 6 7 8 9
100 seem to explain the different behavior of RH between NPE
and non-NPE days, since the weather was sunny during the
NH4
0.30 0.8 b 1.5
entire field campaign. A possible reason is that the RH was
dM/dlogDva [µg/m ]
3
0.25
+
meas
0.6 much lower during northwesterly wind periods (Setyan et al.,
0 20
0.20 10
1.0
sured
2012), during which we usually did not observe NPEs.
0.15 0.4 Figure 12 shows the average size-resolved mass spectra
/ NH4
0.10 0.5 of organics in 40–120 nm (Dva ) particles during NPE days
0.2
+
14:00 - 15:00 and non-event days, along with the mass spectra of bio-
predicted
0.05
NPE days
0.00 0.0 0.0
genic SOA and urban transport SOA reported in Setyan et
8 9 2 3 4 5 6 7 8 9 al. (2012). The average mass spectrum of organics before
100 the growth (i.e., between 08:00 and 10:00 PDT) was sub-
c 1.5 tracted in order to remove the influence of particles existing
0.20 0.5 before the start of the growth events. Therefore, the spectra
0.4 1.0 shown in Fig. 12 are the average mass spectra of organic mat-
0.15
0.3 ter that contributed to the growth of 40-120 nm particles be-
0.10
0.2
tween 10:00–16:00 PDT during NPE days (1OrgNPE 40−120 nm )
0.5
0.05 18:00
8 00 - 19:00
9 00
and during non-event days (1Orgnon-NPE
40−120 nm ), respectively. As
01
0.1
NPE days shown in Fig. 12a, the spectrum of 1OrgNPE 40−120 nm is dom-
0.00 0.0 0.0
8 9 2 3 4 5 6 7 8 9 inated by the signal at m/z = 44 (mostly CO+ 2 ), while that
100 Dva [nm] of m/z = 43 (mostly C2 H3 O+ ) is approximately 20 the half of
it. The spectrum of 1OrgNPE 40−120 nm is very similar to that
Figure 10. Size distributions of SO2− +
4 , NH4 and the ratio of urban transport SOA (r 2 = 0.95; Fig. 12b) but its cor-
of measured NH+ + q 2− q
4 to predicted NH4 (= 2 SO4 18/96) be- relation coefficient towards the spectrum of biogenic SOA
tween (a) 10:00–11:00 PDT, (b) 14:00–15:00 PDT, and (c) 18:00– is lower (r 2 = 0.87). On the other hand, the spectrum of
19:00 PDT during NPE days at T1. 1Orgnon-NPE
40−120 nm is very similar to that of biogenic SOA, as
shown by the scatterplot of Fig. 12d. We further performed
multilinear regression analyses to represent the mass spectra
of 1OrgNPE non-NPE
40−120 nm and 1Org40−120 nm , respectively, as the lin-
and toluene (0.060 ± 0.037 vs. 0.038 ± 0.019 ppb; Table 2)
ear combinations of the spectra of urban transport SOA and
were 30–60 % higher on NPE days. According to the Stu-
biogenic SOA. Based on this analysis, we estimated that dur-
dent’s t test, the difference between NPE and non-NPE
ing NPE days, ∼ 74 % of the organic mass that contributed
days was significant (i.e., p < 0.05) for all the anthro-
to the growth of ultrafine particles was SOA formed in ur-
pogenic species, except for NOx . The ozone concentra-
ban transport plumes. During non-event days, the growth of
tions, however, were very similar between two types of
ultrafine mode organics, which was much slower compared
days (46.2 ± 10.5 ppb during non-NPE vs. 43.5 ± 14.2 ppb).
during NPE, was primarily (∼ 76 % by mass) due to SOA
These results point out the importance of the anthropogenic
influenced by regional biogenic emissions.
influence on the formation and growth of new particles.
These results, coupled to the higher concentrations of an-
However, during a study undertaken at the Blodgett Forest
thropogenic compounds on NPE days suggest that the growth
Research Station, which is located ∼ 35 km on the north-
of new particles in the Sierra Nevada foothills was mainly
east of the present sampling site and ∼ 75 km downwind
driven by anthropogenic precursors transported from Sacra-
from Sacramento, Lunden et al. (2006) observed new par-
mento and that the growth was likely promoted by the inter-
ticle growth events when the degree of anthropogenic influ-
action between urban plumes and biogenic emissions. These
ence was significantly reduced.
observations may have important implications for our un-
The relative humidity (RH) was higher on NPE days
derstanding of SOA formation. For example, models used
(45 ± 13 %) compared to non-NPE days (27 ± 12 %). Sim-
to assess global SOA budget tend to underpredict the SOA
ilarly, Lunden et al. (2006) and Charron et al. (2007) ob-

3.0
b) Ratio NPE Days / Non-NPE Days
2.5
2.0
1.5
1.0
0.5
VOCs O3, NOx CO BC NR-PM1
3 3
[ppb] [ppb] [ppb] [µg/m ] [µg/m ]
6 a) Averages -2
120 8:00-18:00 4x10
40 NPE Days 1.0
5 100 Non-NPE Days
3
30 0.8
4 80
0.6
3 60 x5 2
20
2 0.4
40 x10
10 x20 x20 1
x20
1 20 x20 0.2
0 0 0 0 0.0
Ac tic de
et K
Su OA
rm ce ol
lu e
Ac deh e
or OA
nz ile
AC pr s
R ene
o id
e
et eh e
on te
BC
Am Ni te
an nic OA
O
y N + um
x
3
O
ns
O
M Iso ne
To en
al yd
en
Ac ald ton
M MV
Fo A han
et ac
tra
lfa
Be nitr
e y
io
tS
sp S
i
Tr ge H
e
+
rp
m
Te
xH
an io
C
rb B
U
Figure 11. (a) Average concentrations of VOCs, O3 , NOx , CO, BC, NR-PM1 species, different factors, and N-containing organic ions (=
CHN+ + CH4 N+ + C2 H3 N+ + C2 H4 N+ ) between 08:00 and 18:00 PDT during NPE and non-NPE days at T1. (b) NPE days / non-NPE days
ratios for the same parameters.
a) 12 b)
12 MS-Org40-120 nm NPE days 2 2844
r = 0.95
NPE
MSUrban Transport SOA 10
10
signal
Slope = 0.93 ± 0.02

MS-Org40-1220 nm 8
8
% of total s
43
6 6 29
41 100
27
80
5539
4 4
m/z
42 60
40
2 2 3156 6726
57
53
15
69
18
309545
81
65
54
79
9
91
771 20
64 9
71
68
58
83
7050
85
52
82
78 51
12
38
84
96
63
98
60
99
7217
93
37
25
59
66
97
73
94
87
49
80
86
76
92
89
75
74
61
62
0 0 24
16
90
48
88
20
11
10
14
35
34
33
32
23
22
21
19
47
46
36
9
8
7
6
5
4
3
2
11340
10 20 30 40 50 60 70 80 90 100 0 2 4 6 8 10 12
m/z (amu) MSUrban Transport SOA
12 c)
MS-Org40-120 nm non-NPE days d)
10
non-NPE
2 28
44 43
10 MSbiogenic SOA r = 0.94
otal signal
8 Slope = 0.92 ± 0.02

8
MS-Org40-120 nm
29
6 6
100
% of to
4127
4 80
4 55
m/z
39 60
45
1842 40
2 2 67
31
26 15
56 69
1253
79
58 30 20
5737
81
91
71
77
54
65
50
96
64
85
63 68
52
70
7817
95
66
93
9983
59
8238
51
84
97
25
60
72
94
87
89
73
86
98
80
75
24
92
74
6113
0 0 16
76
62
49
48
90
88
20
19
47
46
11
10
9
8
7
6
5
4
3
2
1
14
23
22
21
35
34
33
32
36 40
10 20 30 40 50 60 70 80 90 100 0 2 4 6 8 10 12
m/z (amu) MSBiogenic SOA
Figure 12. Average mass spectra of (a) urban transport SOA and 1Org40−120 nm (i.e., organics that contribute to the growth of 40–120 nm
particles) during NPE days at T1, and (c) biogenic SOA and 1Org40−120 nm during non-NPE days at T1. Scatterplots that compare the mass
spectra of (b) urban transport SOA vs. 1Org40−120 nm during NPE days, and (d) biogenic SOA vs. 1Org40−120 nm during non-NPE days.
The data fitting of these two scatterplots was performed using the orthogonal distance regression (ODR).
concentrations. However, in a recent study, Spracklen et 4 Conclusions

al. (2011) used a model to estimate the global OA source, and
compared their results with worldwide AMS observations.
New particle growth events were frequently observed dur-
When they took into account anthropogenically controlled
ing the US DOE’s CARES campaign in northern California
biogenic SOA formation in their estimation of the global OA
in June 2010. Presented here is a description of these events
budget, it considerably reduced the bias between their model
observed with two MPSSs deployed at Sacramento (T0, ur-
and AMS observations.
ban site) and Cool (T1, rural site at the Sierra foothills).

Our results showed that these growth events took place on a References
regional scale, predominantly during periods of southwest-
ern flow that transports urban plumes and anthropogenic Ahlm, L., Liu, S., Day, D. A., Russell, L. M., Weber, R., Gentner,
emissions from the Sacramento metropolitan area and the D. R., Goldstein, A. H., DiGangi, J. P., Henry, S. B., Keutsch,
F. N., VandenBoer, T. C., Markovic, M. Z., Murphy, J. G., Ren,
San Francisco Bay Area near Carquinez Strait. Growth rates
X., and Scheller, S.: Formation and growth of ultrafine particles
were on average higher at T0 (7.1 ± 2.7 nm h−1 ) than at T1 from secondary sources in Bakersfield, California, J. Geophys.
(6.2 ± 2.5 nm h−1 ), but the difference is not statistically sig- Res., 117, D00V08, doi:10.1029/2011JD017144, 2012.
nificant. The evolution of the size-resolved chemical compo- Allan, J. D., Alfarra, M. R., Bower, K. N., Coe, H., Jayne, J. T.,
sition of these newly formed particles has been investigated Worsnop, D. R., Aalto, P. P., Kulmala, M., Hyotylainen, T., Cav-
in detail with a HR-ToF-AMS deployed at T1. Our results in- alli, F., and Laaksonen, A.: Size and composition measurements
dicate that the new particle growth was mainly driven by or- of background aerosol and new particle growth in a Finnish forest
ganics, with a small contribution of ammonium sulfate. For during QUEST 2 using an Aerodyne Aerosol Mass Spectrometer,
example, the average increase of the organic mass in ultra- Atmos. Chem. Phys., 6, 315–327, doi:10.5194/acp-6-315-2006,
fine particles (40-120 nm in Dva , which corresponds to 30– 2006.
85 nm in Stokes (volume equivalent) diameter, assuming no Almeida, J., Schobesberger, S., Kurten, A., Ortega, I. K.,
Kupiainen-Maatta, O., Praplan, A. P., Adamov, A., Amorim, A.,
internal voids, sphericity = 1, and density = 1.4 g cm−3 ) was
Bianchi, F., Breitenlechner, M., David, A., Dommen, J., Don-
0.71 µg m−3 during this period, approximately 7 times higher ahue, N. M., Downard, A., Dunne, E., Duplissy, J., Ehrhart,
than that of sulfate (0.10 µg m−3 ). Our results also indicate S., Flagan, R. C., Franchin, A., Guida, R., Hakala, J., Hansel,
that amines were enhanced significantly during the new par- A., Heinritzi, M., Henschel, H., Jokinen, T., Junninen, H., Ka-
ticle growth, suggesting that this class of compounds likely jos, M., Kangasluoma, J., Keskinen, H., Kupc, A., Kurten, T.,
played a role. The mass spectra of organics that contributed Kvashin, A. N., Laaksonen, A., Lehtipalo, K., Leiminger, M.,
to the growth of ultrafine particles during the growth peri- Leppa, J., Loukonen, V., Makhmutov, V., Mathot, S., McGrath,
ods of NPE days were very similar to the mass spectrum M. J., Nieminen, T., Olenius, T., Onnela, A., Petaja, T., Ric-
of anthropogenically influenced SOA from urban plume. cobono, F., Riipinen, I., Rissanen, M., Rondo, L., Ruuskanen,
In addition, during the NPE days, the concentrations of T., Santos, F. D., Sarnela, N., Schallhart, S., Schnitzhofer, R.,
photo-oxidation products (formaldehyde, acetaldehyde, sum Seinfeld, J. H., Simon, M., Sipila, M., Stozhkov, Y., Stratmann,
F., Tome, A., Trostl, J., Tsagkogeorgas, G., Vaattovaara, P., Vi-
of methacrolein and methyl vinyl ketone) and species rep-
isanen, Y., Virtanen, A., Vrtala, A., Wagner, P. E., Weingartner,
resentative of urban emissions (e.g., BC, CO, NOx , HOA,
E., Wex, H., Williamson, C., Wimmer, D., Ye, P. L., Yli-Juuti,
and toluene) were on average 50 % higher than during non- T., Carslaw, K. S., Kulmala, M., Curtius, J., Baltensperger, U.,
event days. These results suggest that the new particle growth Worsnop, D. R., Vehkamaki, H., and Kirkby, J.: Molecular under-
events were mainly driven by the transported urban plumes standing of sulphuric acid-amine particle nucleation in the atmo-
and that the growth of new particles was enhanced by the in- sphere, Nature, 502, 359–363, doi:10.1038/nature12663, 2013.
teractions between biogenic emissions and transported urban Asmi, E., Frey, A., Virkkula, A., Ehn, M., Manninen, H. E., Ti-
plumes. monen, H., Tolonen-Kivimaki, O., Aurela, M., Hillamo, R.,
and Kulmala, M.: Hygroscopicity and chemical composition of
Antarctic sub-micrometre aerosol particles and observations of
The Supplement related to this article is available online new particle formation, Atmos. Chem. Phys., 10, 4253–4271,
at doi:10.5194/acp-14-6477-2014-supplement. doi:10.5194/acp-10-4253-2010, 2010.
Barsanti, K. C., McMurry, P. H., and Smith, J. N.: The potential con-
tribution of organic salts to new particle growth, Atmos. Chem.
Phys., 9, 2949–2957, doi:10.5194/acp-9-2949-2009, 2009.
Boy, M. and Kulmala, M.: Nucleation events in the continental
Acknowledgements. This research was supported by the US boundary layer: Influence of physical and meteorological param-
Department of Energy (DOE), the Office of Science (BER), eters, Atmos. Chem. Phys., 2, 1–16, doi:10.5194/acp-2-1-2002,
Atmospheric System Research Program, grant No. DE-FG02-11 2002.
ER65293, the California Air Resources Board (CARB), Agreement Brock, C. A., Trainer, M., Ryerson, T. B., Neuman, J. A., Parrish,
No. 10-305, and the California Agricultural Experiment Station, D. D., Holloway, J. S., Nicks, D. K., Jr., Frost, G. J., Hübler,
Project CA-DETX-2102-H. G., Fehsenfeld, F. C., Wilson, J. C., Reeves, J. M., Lafleur, B.
G., Hilbert, H., Atlas, E. L., Donnelly, S. G., Schauffler, S. M.,
Edited by: J. Thornton Stroud, V. R., and Wiedinmyer, C.: Particle growth in urban
and industrial plumes in Texas, J. Geophys. Res., 108, 4111,
doi:10.1029/2002jd002746, 2003.
Bzdek, B. R., and Johnston, M. V.: New Particle Formation
and Growth in the Troposphere, Anal. Chem., 82, 7871–7878,
doi:10.1021/ac100856j, 2010.
Bzdek, B. R., Zordan, C. A., Luther, G. W., and John-
ston, M. V.: Nanoparticle Chemical Composition During New

Particle Formation, Aerosol Sci. Technol., 45, 1041–1048, phys. Res.-Atmos., 116, D11302, doi:10.1029/2011jd015646,
doi:10.1080/02786826.2011.580392, 2011. 2011.
Bzdek, B. R., Zordan, C. A., Pennington, M. R., Luther, G. W., and Guo, H., Wang, D. W., Cheung, K., Ling, Z. H., Chan, C. K., and
Johnston, M. V.: Quantitative Assessment of the Sulfuric Acid Yao, X. H.: Observation of aerosol size distribution and new par-
Contribution to New Particle Growth, Environ. Sci. Technol., 46, ticle formation at a mountain site in subtropical Hong Kong,
4365-4373, doi:10.1021/es204556c, 2012. Atmos. Chem. Phys., 12, 9923–9939, doi:10.5194/acp-12-9923-
Canagaratna, M. R., Jayne, J. T., Jimenez, J. L., Allan, J. D., Al- 2012, 2012.
farra, M. R., Zhang, Q., Onasch, T. B., Drewnick, F., Coe, H., Hamed, A., Joutsensaari, J., Mikkonen, S., Sogacheva, L., Dal
Middlebrook, A., Delia, A., Williams, L. R., Trimborn, A. M., Maso, M., Kulmala, M., Cavalli, F., Fuzzi, S., Facchini, M. C.,
Northway, M. J., DeCarlo, P. F., Kolb, C. E., Davidovits, P., and Decesari, S., Mircea, M., Lehtinen, K. E. J., and Laaksonen,
Worsnop, D. R.: Chemical and microphysical characterization A.: Nucleation and growth of new particles in Po Valley, Italy,
of ambient aerosols with the aerodyne aerosol mass spectrome- Atmos. Chem. Phys., 7, 355–376, doi:10.5194/acp-7-355-2007,
ter, Mass Spectrom. Rev., 26, 185–222, doi:10.1002/mas.20115, 2007.
2007. Hamed, A., Korhonen, H., Sihto, S. L., Joutsensaari, J., Jarvinen,
Charron, A., Birmili, W., and Harrison, R. M.: Factors in- H., Petaja, T., Arnold, F., Nieminen, T., Kulmala, M., Smith, J.
fluencing new particle formation at the rural site, Har- N., Lehtinen, K. E. J., and Laaksonen, A.: The role of relative
well, United Kingdom, J. Geophys. Res., 112, D14210, humidity in continental new particle formation, J. Geophys. Res.-
doi:10.1029/2007JD008425, 2007. Atmos., 116, D03202, doi:10.1029/2010jd014186, 2011.
Creamean, J. M., Ault, A. P., Ten Hoeve, J. E., Jacobson, M. Z., Han, Y., Iwamoto, Y., Nakayama, T., Kawamura, K., Hussein, T.,
Roberts, G. C., and Prather, K. A.: Measurements of Aerosol and Mochida, M.: Observation of new particle formation over a
Chemistry during New Particle Formation Events at a Remote mid-latitude forest facing the North Pacific, Atmos. Environ., 64,
Rural Mountain Site, Environ. Sci. Technol., 45, 8208–8216, 77–84, doi:10.1016/j.atmosenv.2012.09.036, 2013.
doi:10.1021/es103692f, 2011. Jayne, J. T., Leard, D. C., Zhang, X. F., Davidovits, P., Smith,
DeCarlo, P. F., Kimmel, J. R., Trimborn, A., Northway, M. J., Jayne, K. A., Kolb, C. E., and Worsnop, D. R.: Development of
J. T., Aiken, A. C., Gonin, M., Fuhrer, K., Horvath, T., Docherty, an aerosol mass spectrometer for size and composition anal-
K. S., Worsnop, D. R., and Jimenez, J. L.: Field-deployable, ysis of submicron particles, Aerosol Sci. Technol., 33, 49–70,
high-resolution, time-of-flight aerosol mass spectrometer, Anal. doi:10.1080/027868200410840, 2000.
Chem., 78, 8281–8289, doi:10.1021/ac061249n, 2006. Jeong, C. H., Evans, G. J., McGuire, M. L., Chang, R. Y. W., Ab-
de Gouw, J. A., Middlebrook, A. M., Warneke, C., Goldan, P. batt, J. P. D., Zeromskiene, K., Mozurkewich, M., Li, S. M., and
D., Kuster, W. C., Roberts, J. M., Fehsenfeld, F. C., Worsnop, Leaitch, A. R.: Particle formation and growth at five rural and ur-
D. R., Canagaratna, M. R., Pszenny, A. A. P., Keene, W. C., ban sites, Atmos. Chem. Phys., 10, 7979–7995, doi:10.5194/acp-
Marchewka, M., Bertman, S. B., and Bates, T. S.: Budget of or- 10-7979-2010, 2010.
ganic carbon in a polluted atmosphere: Results from the New Jimenez, J. L., Canagaratna, M. R., Donahue, N. M., Prevot, A. S.
England Air Quality Study in 2002, J. Geophys. Res.-Atmos., H., Zhang, Q., Kroll, J. H., DeCarlo, P. F., Allan, J. D., Coe,
110, D16305, doi:10.1029/2004JD005623, 2005. H., Ng, N. L., Aiken, A. C., Docherty, K. S., Ulbrich, I. M.,
Dillon, M. B., Lamanna, M. S., Schade, G. W., Goldstein, A. H., Grieshop, A. P., Robinson, A. L., Duplissy, J., Smith, J. D., Wil-
and Cohen, R. C.: Chemical evolution of the Sacramento urban son, K. R., Lanz, V. A., Hueglin, C., Sun, Y. L., Tian, J., Laak-
plume: Transport and oxidation, J. Geophys. Res.-Atmos., 107, sonen, A., Raatikainen, T., Rautiainen, J., Vaattovaara, P., Ehn,
4045, doi:10.1029/2001jd000969, 2002. M., Kulmala, M., Tomlinson, J. M., Collins, D. R., Cubison, M.
Dunn, M. J., Jiménez, J.-L., Baumgardner, D., Castro, T., Mc- J., Dunlea, E. J., Huffman, J. A., Onasch, T. B., Alfarra, M. R.,
Murry, P. H., and Smith, J. N.: Measurements of Mexico Williams, P. I., Bower, K., Kondo, Y., Schneider, J., Drewnick,
City nanoparticle size distributions: Observations of new par- F., Borrmann, S., Weimer, S., Demerjian, K., Salcedo, D., Cot-
ticle formation and growth, Geophys. Res. Lett., 31, L10102, trell, L., Griffin, R., Takami, A., Miyoshi, T., Hatakeyama, S.,
doi:10.1029/2004gl019483, 2004. Shimono, A., Sun, J. Y., Zhang, Y. M., Dzepina, K., Kimmel,
Fast, J. D., Gustafson Jr, W. I., Berg, L. K., Shaw, W. J., Pekour, J. R., Sueper, D., Jayne, J. T., Herndon, S. C., Trimborn, A.
M., Shrivastava, M., Barnard, J. C., Ferrare, R. A., Hostetler, M., Williams, L. R., Wood, E. C., Middlebrook, A. M., Kolb,
C. A., Hair, J. A., Erickson, M., Jobson, B. T., Flowers, B., C. E., Baltensperger, U., and Worsnop, D. R.: Evolution of Or-
Dubey, M. K., Springston, S., Pierce, R. B., Dolislager, L., Ped- ganic Aerosols in the Atmosphere, Science, 326, 1525–1529,
erson, J., and Zaveri, R. A.: Transport and mixing patterns over 10.1126/science.1180353, 2009.
Central California during the carbonaceous aerosol and radiative Jokinen, T., Sipilä, M., Junninen, H., Ehn, M., Lönn, G., Hakala,
effects study (CARES), Atmos. Chem. Phys., 12, 1759–1783, J., Petäjä, T., Mauldin Iii, R. L., Kulmala, M., and Worsnop,
doi:10.5194/acp-12-1759-2012, 2012. D. R.: Atmospheric sulphuric acid and neutral cluster measure-
Ge, X., Shaw, S. L., and Zhang, Q.: Toward Understanding Amines ments using CI-APi-TOF, Atmos. Chem. Phys., 12, 4117–4125,
and Their Degradation Products from Postcombustion CO2 Cap- doi:10.5194/acp-12-4117-2012, 2012.
ture Processes with Aerosol Mass Spectrometry, Environ. Sci. Kerminen, V. M., Paramonov, M., Anttila, T., Riipinen, I., Foun-
Technol., 48, 5066–5075, doi:10.1021/es4056966, 2014. toukis, C., Korhonen, H., Asmi, E., Laakso, L., Lihavainen, H.,
Glasius, M., la Cour, A., and Lohse, C.: Fossil and nonfossil carbon Swietlicki, E., Svenningsson, B., Asmi, A., Pandis, S. N., Kul-
in fine particulate matter: A study of five European cities, J. Geo- mala, M., and Petäjä, T.: Cloud condensation nuclei production
associated with atmospheric nucleation: a synthesis based on ex-

isting literature and new results, Atmos. Chem. Phys., 12, 12037– Makela, J. M., Yli-Koivisto, S., Hiltunen, V., Seidl, W., Swi-
12059, doi:10.5194/acp-12-12037-2012, 2012. etlicki, E., Teinila, K., Sillanpaa, M., Koponen, I. K., Paatero,
Kleinman, L. I., Springston, S. R., Daum, P. H., Lee, Y. N., Nun- J., Rosman, K., and Hameri, K.: Chemical composition of
nermacker, L. J., Senum, G. I., Wang, J., Weinstein-Lloyd, J., aerosol during particle formation events in boreal forest, Tellus
Alexander, M. L., Hubbe, J., Ortega, J., Canagaratna, M. R., B – Chem. Phys. Meteorol., 53, 380–393, doi:10.1034/j.1600-
and Jayne, J.: The time evolution of aerosol composition over 0889.2001.530405.x, 2001.
the Mexico City plateau, Atmos. Chem. Phys., 8, 1559–1575, Modini, R. L., Ristovski, Z. D., Johnson, G. R., He, C., Surawski,
doi:10.5194/acp-8-1559-2008, 2008. N., Morawska, L., Suni, T., and Kulmala, M.: New particle for-
Komppula, M., Lihavainen, H., Hatakka, J., Paatero, J., Aalto, P., mation and growth at a remote, sub-tropical coastal location, At-
Kulmala, M., and Viisanen, Y.: Observations of new particle for- mos. Chem. Phys., 9, 7607–7621, doi:10.5194/acp-9-7607-2009,
mation and size distributions at two different heights and sur- 2009.
roundings in subarctic area in northern Finland, J. Geophys. Res., O’Dowd, C. D., Jimenez, J. L., Bahreini, R., Flagan, R. C., Seinfeld,
108, 4295, doi:10.1029/2002JD002939, 2003. J. H., Hameri, K., Pirjola, L., Kulmala, M., Jennings, S. G., and
Koponen, I. K., Virkkula, A., Hillamo, R., Kerminen, V.-M., and Hoffmann, T.: Marine aerosol formation from biogenic iodine
Kulmala, M.: Number size distributions and concentrations of the emissions, Nature, 417, 632–636, 2002.
continental summer aerosols in Queen Maud Land, Antarctica, J. Pierce, J. R., Riipinen, I., Kulmala, M., Ehn, M., Petäjä, T., Junni-
Geophys. Res., 108, 4587, doi:10.1029/2003jd003614, 2003. nen, H., Worsnop, D. R., and Donahue, N. M.: Quantification of
Kulmala, M., Kontkanen, J., Junninen, H., Lehtipalo, K., Manni- the volatility of secondary organic compounds in ultrafine par-
nen, H. E., Nieminen, T., Petäjä, T., Sipilä, M., Schobesberger, ticles during nucleation events, Atmos. Chem. Phys., 11, 9019–
S., Rantala, P., Franchin, A., Jokinen, T., Järvinen, E., Äijälä, M., 9036, doi:10.5194/acp-11-9019-2011, 2011.
Kangasluoma, J., Hakala, J., Aalto, P. P., Paasonen, P., Mikkilä, Pierce, J. R., Leaitch, W. R., Liggio, J., Westervelt, D. M., Wain-
J., Vanhanen, J., Aalto, J., Hakola, H., Makkonen, U., Ruuska- wright, C. D., Abbatt, J. P. D., Ahlm, L., Al-Basheer, W., Cz-
nen, T., Mauldin, R. L., Duplissy, J., Vehkamäki, H., Bäck, iczo, D. J., Hayden, K. L., Lee, A. K. Y., Li, S. M., Rus-
J., Kortelainen, A., Riipinen, I., Kurtén, T., Johnston, M. V., sell, L. M., Sjostedt, S. J., Strawbridge, K. B., Travis, M.,
Smith, J. N., Ehn, M., Mentel, T. F., Lehtinen, K. E. J., Laak- Vlasenko, A., Wentzell, J. J. B., Wiebe, H. A., Wong, J. P. S.,
sonen, A., Kerminen, V.-M., and Worsnop, D. R.: Direct Obser- and Macdonald, A. M.: Nucleation and condensational growth to
vations of Atmospheric Aerosol Nucleation, Science, 339, 943– CCN sizes during a sustained pristine biogenic SOA event in a
946, doi:10.1126/science.1227385, 2013. forested mountain valley, Atmos. Chem. Phys., 12, 3147–3163,
Laaksonen, A., Kulmala, M., O’Dowd, C. D., Joutsensaari, J., Vaat- doi:10.5194/acp-12-3147-2012, 2012.
tovaara, P., Mikkonen, S., Lehtinen, K. E. J., Sogacheva, L., Dal Pikridas, M., Riipinen, I., Hildebrandt, L., Kostenidou, E., Manni-
Maso, M., Aalto, P., Petaja, T., Sogachev, A., Yoon, Y. J., Li- nen, H., Mihalopoulos, N., Kalivitis, N., Burkhart, J. F., Stohl,
havainen, H., Nilsson, D., Facchini, M. C., Cavalli, F., Fuzzi, S., A., Kulmala, M., and Pandis, S. N.: New particle formation at a
Hoffmann, T., Arnold, F., Hanke, M., Sellegri, K., Umann, B., remote site in the eastern Mediterranean, J. Geophys. Res., 117,
Junkermann, W., Coe, H., Allan, J. D., Alfarra, M. R., Worsnop, D12205, doi:10.1029/2012jd017570, 2012.
D. R., Riekkola, M. L., Hyotylainen, T., and Viisanen, Y.: The Riipinen, I., Pierce, J. R., Yli-Juuti, T., Nieminen, T., Hakkinen,
role of VOC oxidation products in continental new particle for- S., Ehn, M., Junninen, H., Lehtipalo, K., Petaja, T., Slowik, J.,
mation, Atmos. Chem. Phys., 8, 2657–2665, doi:10.5194/acp-8- Chang, R., Shantz, N. C., Abbatt, J., Leaitch, W. R., Kerminen,
2657-2008, 2008. V. M., Worsnop, D. R., Pandis, S. N., Donahue, N. M., and Kul-
Laitinen, T., Ehn, M., Junninen, H., Ruiz-Jimenez, J., Parsh- mala, M.: Organic condensation: a vital link connecting aerosol
intsev, J., Hartonen, K., Riekkola, M. L., Worsnop, D. R., formation to cloud condensation nuclei (CCN) concentrations,
and Kulmala, M.: Characterization of organic compounds in Atmos. Chem. Phys., 11, 3865–3878, doi:10.5194/acp-11-3865-
10-to 50-nm aerosol particles in boreal forest with laser 2011, 2011.
desorption-ionization aerosol mass spectrometer and compari- Riipinen, I., Yli-Juuti, T., Pierce, J. R., Petaja, T., Worsnop, D. R.,
son with other techniques, Atmos. Environ., 45, 3711–3719, Kulmala, M., and Donahue, N. M.: The contribution of organics
doi:10.1016/j.atmosenv.2011.04.023, 2011. to atmospheric nanoparticle growth, Nature Geoscience, 5, 453–
Lehtipalo, K., Sipilä, M., Junninen, H., Ehn, M., Berndt, T., Kajos, 458, doi:10.1038/ngeo1499, 2012.
M. K., Worsnop, D. R., Petäjä, T., and Kulmala, M.: Observations Schichtel, B. A., Malm, W. C., Bench, G., Fallon, S., McDade,
of Nano-CN in the Nocturnal Boreal Forest, Aerosol Sci. Tech- C. E., Chow, J. C., and Watson, J. G.: Fossil and contempo-
nol., 45, 499–509, doi:10.1080/02786826.2010.547537, 2011. rary fine particulate carbon fractions at 12 rural and urban sites
Liu, S., Hu, M., Wu, Z., Wehner, B., Wiedensohler, A., in the United States, J. Geophys. Res.-Atmos., 113, D02311,
and Cheng, Y.: Aerosol number size distribution and new doi:10.1029/2007jd008605, 2008.
particle formation at a rural/coastal site in Pearl River Setyan, A., Zhang, Q., Merkel, M., Knighton, W. B., Sun, Y., Song,
Delta (PRD) of China, Atmos. Environ., 42, 6275–6283, C., Shilling, J. E., Onasch, T. B., Herndon, S. C., Worsnop, D. R.,
doi:10.1016/j.atmosenv.2008.01.063, 2008. Fast, J. D., Zaveri, R. A., Berg, L. K., Wiedensohler, A., Flow-
Lunden, M. M., Black, D. R., McKay, M., Revzan, K. L., Gold- ers, B. A., Dubey, M. K., and Subramanian, R.: Characterization
stein, A. H., and Brown, N. J.: Characteristics of fine particle of submicron particles influenced by mixed biogenic and anthro-
growth events observed above a forested ecosystem in the Sierra pogenic emissions using high-resolution aerosol mass spectrom-
Nevada Mountains of California, Aerosol Sci. Technol., 40, 373– etry: results from CARES, Atmos. Chem. Phys., 12, 8131–8156,
388, doi:10.1080/02786820600631896, 2006. doi:10.5194/acp-12-8131-2012, 2012.

Shilling, J. E., Zaveri, R. A., Fast, J. D., Kleinman, L., Alexander, lani, P., Laj, P., Aalto, P., Ogren, J. A., Swietlicki, E., Williams,
M. L., Canagaratna, M. R., Fortner, E., Hubbe, J. M., Jayne, J. P., Roldin, P., Quincey, P., Hüglin, C., Fierz-Schmidhauser, R.,
T., Sedlacek, A., Setyan, A., Springston, S., Worsnop, D. R., Gysel, M., Weingartner, E., Riccobono, F., Santos, S., Grüning,
and Zhang, Q.: Enhanced SOA formation from mixed anthro- C., Faloon, K., Beddows, D., Harrison, R., Monahan, C., Jen-
pogenic and biogenic emissions during the CARES campaign, nings, S. G., O’Dowd, C. D., Marinoni, A., Horn, H. G., Keck,
Atmos. Chem. Phys., 13, 2091–2113, doi:10.5194/acp-13-2091- L., Jiang, J., Scheckman, J., McMurry, P. H., Deng, Z., Zhao, C.
2013, 2013. S., Moerman, M., Henzing, B., de Leeuw, G., Löschau, G., and
Smith, J. N., Moore, K. F., Eisele, F. L., Voisin, D., Ghimire, A. Bastian, S.: Mobility particle size spectrometers: harmonization
K., Sakurai, H., and McMurry, P. H.: Chemical composition of of technical standards and data structure to facilitate high qual-
atmospheric nanoparticles during nucleation events in Atlanta, ity long-term observations of atmospheric particle number size
Journal of Geophysical Research: Atmospheres, 110, D22S03, distributions, Atmos. Meas. Tech., 5, 657–685, doi:10.5194/amt-
doi:10.1029/2005jd005912, 2005. 5-657-2012, 2012.
Smith, J. N., Dunn, M. J., VanReken, T. M., Iida, K., Stolzen- Wu, Z., Hu, M., Liu, S., Wehner, B., Bauer, S., Ma ßling, A.,
burg, M. R., McMurry, P. H., and Huey, L. G.: Chemical com- Wiedensohler, A., Petäjä, T., Dal Maso, M., and Kulmala,
position of atmospheric nanoparticles formed from nucleation M.: New particle formation in Beijing, China: Statistical anal-
in Tecamac, Mexico: evidence for an important role for organic ysis of a 1-year data set, J. Geophys. Res., 112, D09209,
species in nanoparticle growth, Geophys. Res. Lett., 35, L04808, doi:10.1029/2006jd007406, 2007.
doi:10.1029/2007GL032523, 2008. Yue, D. L., Hu, M., Zhang, R. Y., Wang, Z. B., Zheng, J., Wu, Z.
Smith, J. N., Barsanti, K. C., Friedli, H. R., Ehn, M., Kulmala, M., J., Wiedensohler, A., He, L. Y., Huang, X. F., and Zhu, T.: The
Collins, D. R., Scheckman, J. H., Williams, B. J., and McMurry, roles of sulfuric acid in new particle formation and growth in
P. H.: Observations of aminium salts in atmospheric nanoparti- the mega-city of Beijing, Atmos. Chem. Phys., 10, 4953–4960,
cles and possible climatic implications, Proc. Natl. Acad. Sci., doi:10.5194/acp-10-4953-2010, 2010.
107, 6634–6639, doi:10.1073/pnas.0912127107, 2010. Zaveri, R. A., Shaw, W. J., Cziczo, D. J., Schmid, B., Ferrare, R.
Spracklen, D. V., Carslaw, K. S., Kulmala, M., Kerminen, V. M., A., Alexander, M. L., Alexandrov, M., Alvarez, R. J., Arnott, W.
Mann, G. W., and Sihto, S. L.: The contribution of boundary P., Atkinson, D. B., Baidar, S., Banta, R. M., Barnard, J. C., Be-
layer nucleation events to total particle concentrations on re- ranek, J., Berg, L. K., Brechtel, F., Brewer, W. A., Cahill, J. F.,
gional and global scales, Atmos. Chem. Phys., 6, 5631–5648, Cairns, B., Cappa, C. D., Chand, D., China, S., Comstock, J. M.,
doi:10.5194/acp-6-5631-2006, 2006. Dubey, M. K., Easter, R. C., Erickson, M. H., Fast, J. D., Flo-
Spracklen, D. V., Jimenez, J. L., Carslaw, K. S., Worsnop, D. R., erchinger, C., Flowers, B. A., Fortner, E., Gaffney, J. S., Gilles,
Evans, M. J., Mann, G. W., Zhang, Q., Canagaratna, M. R., M. K., Gorkowski, K., Gustafson, W. I., Gyawali, M., Hair, J.,
Allan, J., Coe, H., McFiggans, G., Rap, A., and Forster, P.: Hardesty, R. M., Harworth, J. W., Herndon, S., Hiranuma, N.,
Aerosol Mass Spectrometer constraint on the global secondary Hostetler, C., Hubbe, J. M., Jayne, J. T., Jeong, H., Jobson, B. T.,
organic aerosol budget, Atmos. Chem. Phys., 11, 12109–12136, Kassianov, E. I., Kleinman, L. I., Kluzek, C., Knighton, B., Kole-
doi:10.5194/acp-11-12109-201, 2011. sar, K. R., Kuang, C., Kubátová, A., Langford, A. O., Laskin,
Stanier, C. O., Khlystov, A. Y., and Pandis, S. N.: Nucle- A., Laulainen, N., Marchbanks, R. D., Mazzoleni, C., Mei, F.,
ation events during the Pittsburgh air quality study: De- Moffet, R. C., Nelson, D., Obland, M. D., Oetjen, H., Onasch,
scription and relation to key meteorological, gas phase, T. B., Ortega, I., Ottaviani, M., Pekour, M., Prather, K. A., Rad-
and aerosol parameters, Aerosol Sci. Technol., 38, 253–264, ney, J. G., Rogers, R. R., Sandberg, S. P., Sedlacek, A., Senff,
doi:10.1080/02786820390229570, 2004. C. J., Senum, G., Setyan, A., Shilling, J. E., Shrivastava, M.,
Vakkari, V., Laakso, H., Kulmala, M., Laaksonen, A., Mabaso, D., Song, C., Springston, S. R., Subramanian, R., Suski, K., Tom-
Molefe, M., Kgabi, N., and Laakso, L.: New particle forma- linson, J., Volkamer, R., Wallace, H. W., Wang, J., Weickmann,
tion events in semi-clean South African savannah, Atmos. Chem. A. M., Worsnop, D. R., Yu, X. Y., Zelenyuk, A., and Zhang,
Phys., 11, 3333–3346, doi:10.5194/acp-11-3333-2011, 2011. Q.: Overview of the 2010 Carbonaceous Aerosols and Radiative
Volkamer, R., Jimenez, J. L., San Martini, F., Dzepina, K., Zhang, Effects Study (CARES), Atmos. Chem. Phys., 12, 7647–7687,
Q., Salcedo, D., Molina, L. T., Worsnop, D. R., and Molina, M. doi:10.5194/acp-12-7647-2012, 2012.
J.: Secondary organic aerosol formation from anthropogenic air Zhang, Q., Stanier, C. O., Canagaratna, M. R., Jayne, J. T.,
pollution: Rapid and higher than expected, Geophys. Res. Lett., Worsnop, D. R., Pandis, S. N., and Jimenez, J. L.: Insights into
33, L17811, doi:10.1029/2006gl026899, 2006. the chemistry of new particle formation and growth events in
Weber, R. J., McMurry, P. H., Mauldin, R. L., Tanner, D. J., Pittsburgh based on aerosol mass spectrometry, Environ. Sci.
Eisele, F. L., Clarke, A. D., and Kapustin, V. N.: New Particle Technol., 38, 4797–4809, doi:10.1021/es035417u, 2004a.
Formation in the Remote Troposphere: A Comparison of Ob- Zhang, Q., Worsnop, D. R., Canagaratna, M. R., and Jimenez, J.
servations at Various Sites, Geophys. Res. Lett., 26, 307–310, L.: Hydrocarbon-like and oxygenated organic aerosols in Pitts-
doi:10.1029/1998GL900308, 1999. burgh: insights into sources and processes of organic aerosols,
Wen, J., Zhao, Y., and Wexler, A. S.: Marine particle nucleation: Atmos. Chem. Phys., 5, 3289–3311, doi:10.5194/acp-5-3289-
Observation at Bodega Bay, California, J. Geophys. Res., 111, 2005, 2005.
D08207, doi:10.1029/2005jd006210, 2006. Zhang, Q., Jimenez, J. L., Canagaratna, M. R., Allan, J. D., Coe,
Wiedensohler, A., Birmili, W., Nowak, A., Sonntag, A., Weinhold, H., Ulbrich, I., Alfarra, M. R., Takami, A., Middlebrook, A.
K., Merkel, M., Wehner, B., Tuch, T., Pfeifer, S., Fiebig, M., M., Sun, Y. L., Dzepina, K., Dunlea, E., Docherty, K., De-
Fjäraa, A. M., Asmi, E., Sellegri, K., Depuy, R., Venzac, H., Vil- Carlo, P. F., Salcedo, D., Onasch, T., Jayne, J. T., Miyoshi,

T., Shimono, A., Hatakeyama, S., Takegawa, N., Kondo, Y., Ziemba, L. D., Griffin, R. J., Cottrell, L. D., Beckman, P. J.,
Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demer- Zhang, Q., Varner, R. K., Sive, B. C., Mao, H., and Tal-
jian, K., Williams, P., Bower, K., Bahreini, R., Cottrell, L., bot, R. W.: Characterization of aerosol associated with en-
Griffin, R. J., Rautiainen, J., Sun, J. Y., Zhang, Y. M., and hanced small particle of number concentrations in a suburban
Worsnop, D. R.: Ubiquity and dominance of oxygenated species forested environment, J. Geophys. Res.-Atmos., 115, D12206,
in organic aerosols in anthropogenically-influenced Northern doi:10.1029/2009JD012614, 2010.
Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13801, Zollner, J. H., Glasoe, W. A., Panta, B., Carlson, K. K., McMurry,
doi:10.1029/2007GL029979, 2007. P. H., and Hanson, D. R.: Sulfuric acid nucleation: power de-
Zhang, X. F., Smith, K. A., Worsnop, D. R., Jimenez, J. L., Jayne, pendencies, variation with relative humidity, and effect of bases,
J. T., Kolb, C. E., Morris, J., and Davidovits, P.: Numerical Atmos. Chem. Phys., 12, 4399-4411, doi:10.5194/acp-12-4399-
characterization of particle beam collimation: Part II – Inte- 2012, 2012.
grated aerodynamic-lens-nozzle system, Aerosol Sci. Technol.,
38, 619–638, doi:10.1080/02786820490479833, 2004b.
Zhang, Y. M., Zhang, X. Y., Sun, J. Y., Lin, W. L., Gong, S.
L., Shen, X. J., and Yang, S.: Characterization of new parti-
cle and secondary aerosol formation during summertime in Bei-
jing, China, Tellus Ser. B-Chem. Phys. Meteorol., 63, 382-394,
10.1111/j.1600-0889.2011.00533.x, 2011.

Supplement of Atmos. Chem. Phys., 14, 6477–6495, 2014
http://www.atmos-chem-phys.net/14/6477/2014/
doi:10.5194/acp-14-6477-2014-supplement
© Author(s) 2014. CC Attribution 3.0 License.
Supplement of
Chemistry of new particle growth in mixed urban and biogenic emissions
– insights from CARES
A. Setyan et al.
Correspondence to: Q. Zhang ([email protected])

Supplemental material to:
Chemistry of new particle growth in mixed urban and biogenic
emissions - Insights from CARES
A. Setyan1,*, C. Song2, M. Merkel3, W. B. Knighton4, T. B. Onasch5, M. R. Canagaratna5,

D. R. Worsnop5,6, A. Wiedensohler3, J. E. Shilling2, Q. Zhang1,#
1
Department of Environmental Toxicology, 1 Shields Ave., University of California, Davis,
CA 95616, United States
2
Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory,
Richmond, WA 99352, United States
3
Leibniz Institute for Tropospheric Research, 04318 Leipzig, Germany
4
Montana State University, Bozeman, MT 59717, United States
5
Aerodyne Research Inc., Billerica, MA 01821, United States
6
Department of Physics, University of Helsinki, FI-00014 Helsinki, Finland
*
Now at: Empa, Swiss Federal Laboratories for Materials Science and Technology, CH-8600
Dübendorf, Switzerland
#
Corresponding author; Department of Environmental Toxicology, University of California,
Davis, CA 95616, United States; [email protected]; 530-752-5779
S1
Size distributions of ammonium and sulfate using high resolution data
Particle time-of-flight (PToF) data in AMS is usually used in unit mass resolution to
determine size distributions of species. However, during the present study, PToF data of
ammonium were too noisy and not usable to determine size distributions for short selected
periods. Therefore, in the present case, PToF data have been used in high resolution, in which
ammonium fragments had satisfactory signal to noise (S/N) ratios. First, 86 size bins recorded
in the PToF mode and covering 40-1400 nm (in Dva) have been grouped into 7 different size
ranges in order to increase the S/N ratio. Given that the PToF data processed in the PIKA
software is without DC markers applied, an eighth size range between 1400-2200 nm has
been used as a background signal to subtract the signals of the other size ranges (Fig. S1).
Then, for each size range, average high resolution mass spectra have been plotted, and the
signals of the ammonium and sulfate fragments having the best S/N ratios have been
integrated. For that purpose, we chose NH3+ (m/z 17) for ammonium and SO+ (m/z 48) for
sulfate (Fig. S1). The scatterplots of NH3+ vs. total ammonium and SO+ vs. total sulfate (Fig.
S2) have then been used to reconstruct the concentrations of ammonium and sulfate for each
of the 7 size ranges. Finally, these results have been used to reconstruct size distributions of
the two species in Hz, and converted to µg/m3 by scaling the size distributions to the
concentrations of these species in MS mode.
Figure S1. Average high resolution mass spectra between 14:00-15:00 during NPE days at T1
for particles in the range (a, b) 250-400 nm, (c, d) 1400-2200 nm, and (e, f) top MS minus
bottom MS, for m/z 17 (left panel) and m/z 48 (right panel).
a) b)
c) d)
e) f)
S2
Figure S2. Scatterplots of (a) NH3+ vs. total ammonium, and (b) SO+ vs. total sulfate for T1.
The data fitting was performed using the orthogonal distance regression (ODR).
a)
2
r = 0.997
Slope = 0.549 ± 0.000
600
NH3 [Hz]
Date & Time (PDT)

400
+
29.06.2010
25.06.2010
200 21.06.2010
17.06.2010
0
0 200 400 600 800 1000 1200 1400
Total ammonium [Hz]
200
b)
2
r = 0.997
Slope = 0.171 ± 0.000
150
SO [Hz]
Date & Time (PDT)

100 29.06.2010
+
25.06.2010
50 21.06.2010
17.06.2010
0
0 200 400 600 800 1000
Total sulfate [Hz]
Figure S3. Diurnal patterns of (a) temperature, (b) relative humidity, and (c) broadband solar
radiation during new particle event (NPE) days and non-NPE days at T1.
30
Temperature [°C]
a)
25
20
15 NPE days
Non-NPE days
10
80
Solar radiation [W/m ] Relative humidity [%]
60
40 b)
20
0
1000
2
800 c)
600
400
200
0
0 4 8 12 16 20 24
S3
Figure S4. Diurnal patterns of (a) isoprene, (b) terpenes, (c) sum of methacrolein (MACR)
and methyl vinyl ketone (MVK), (d) formaldehyde, (e) acetic acid, (f) acetaldehyde, (g)
benzene, (h) toluene, (i) black carbon, (j) CO, (k) O3, (l) NOx, and (m) condensation sink
during NPE and non-NPE days at T1.
3.0 0.25
2.5
(a) NPE days (b)
Non-NPE days 0.20
Terpenes [ppb]
Isoprene [ppb]
NPE days
2.0 Non-NPE days
0.15
1.5
0.10
1.0
0.5 0.05
0.0 0.00
0 4 8 12 16 20 24 0 4 8 12 16 20 24
3.0
(c) (d)
Formaldehyde [ppb]
MACR + MVK [ppb]
1.2
2.5
0.8 2.0
1.5
0.4 1.0
NPE days NPE days
0.5 Non-NPE days
Non-NPE days
0.0 0.0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
(e) (f)
Acetaldehyde [ppb]
1.2
Acetic acid [ppb]
1.2
0.8 0.8
0.4 0.4 NPE days

NPE days
Non-NPE days Non-NPE days
0.0 0.0
-2
0 4 8 12 16 20 24 0 4 8 12 16 20 24
8x10 (g) NPE days
(h)
Non-NPE days 0.12 NPE days
Benzene [ppb]
6
Toluene [ppb]
Non-NPE days
4 0.08
2 0.04
0 0.00
0 4 8 12 16 20 24 0 4 8 12 16 20 24
6x10
-2 (i) 140 (j)
5
BC [µg/m ]
120
3
CO [ppb]
4
3 100
2
1 NPE days NPE days
Non-NPE days 80
Non-NPE days
0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
60 NPE days
50
(k) 6
(l) Non-NPE days
5
NOx [ppb]
40
O3 [ppb]
4
30 3
20 Non-NPE days 2
10 NPE days
1
0 0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
-2
2.5x10 Hour of day (PDT, UTC-7)
(m)
Condensation sink [cm ]
2.0
-2
1.5
1.0
0.5 NPE days

Non-NPE days
0.0
0 4 8 12 16 20 24
S4
Figure S5. Time series of (a) broadband solar radiation and O3, (b) CO and NOx, (c) Org,
SO42-, NO3-, NH4+ and Cl-, (d) OA components, and (e) particle number concentration and
condensation sink at T1. Periods of T0 to T1 transport and northwesterly wind periods are
shaded in pink and green, respectively.
T0 T1 transport Northwesterly wind
1200 a) 80
Solar radiation
O3 [ppb]
60
[W/m ]
800
2
40
400
20
0 0
400
b) 20
NOx [ppb]
300
CO [ppb]
15
200 10
100 5
0
Org
12 c) 2-
AMS species
SO4
[µg/m ]
3
8 NO3
-
+
4 NH4
-
0 Cl
5 Urban Transport SOA
OA components
d)
4 Biogenic SOA
[µg/m ]
HOA
3
3
2
1
0
4
Condensation sink
2.5x10 e) 0.04
Particle number
2.0
conc. [#/cm ]
0.03
3
[cm ]
1.5
1.0 0.02
-2
0.5 0.01
0.0 0.00
6/3/10 6/8/10 6/13/10 6/18/10 6/23/10 6/28/10
Date & Time (PDT, UTC-7)
S5

Chemistry of New Particle Growth in Mixed Urban and Biogenic Emissions - Insights From CARES

Uploaded by

Copyright:

Available Formats

Chemistry of New Particle Growth in Mixed Urban and Biogenic Emissions - Insights From CARES

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chemistry of New Particle Growth in Mixed Urban and Biogenic Emissions - Insights From CARES

Uploaded by

Copyright:

Available Formats

Atmos. Chem. Phys.

, 14, 6477–6494, 2014

Chemistry of new particle growth in mixed urban and biogenic

Correspondence to: Q. Zhang ([email protected])

Published by Copernicus Publications on behalf of the European Geosciences Union.

1 Introduction the growth of new particles was found to be almost exclu-

Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

2.1 Sampling site and instrumentation 2.2 Data analysis

www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

Atmos. Chem. Phys., 14, 6477–6494, 2014

The modal diameter(s) of each particle number size dis- 2.0x10

(WaveMetrics Inc., Lake Oswego, OR). All the size distribu-

www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

Figure 2 compares the average daily evolution patterns a) T0

during NPE days. Generally, the increase of the parti- 100

icantly higher at T0 than at T1 (average 9.6 × 103 vs. 2

OA factors [µg/m ] Organics [µg/m ]

the growth rates observed during the present study were

Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

02:00 10:00 18:00

03:00 11:00 19:00

04:00 12:00 20:00

05:00 13:00 21:00

06:00 14:00 22:00

07:00 15:00 23:00

www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

a) Org, NPE days b) Org, Non-NPE days 2-

Total mass [µg/m ]

40 1.0 40 1.0 350 0.03

Total mass [µg/m ]

www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

Parameter NPE days Non-NPE days

www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

Slope = 0.93 ± 0.02

8 Slope = 0.92 ± 0.02

concentrations. However, in a recent study, Spracklen et 4 Conclusions

www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

www.atmos-chem-phys.net/14/6477/2014/ Atmos. Chem. Phys., 14, 6477–6494, 2014

Atmos. Chem. Phys., 14, 6477–6494, 2014 www.atmos-chem-phys.net/14/6477/2014/

Correspondence to: Q. Zhang ([email protected])

A. Setyan1,*, C. Song2, M. Merkel3, W. B. Knighton4, T. B. Onasch5, M. R. Canagaratna5,

Date & Time (PDT)

Date & Time (PDT)

0.4 0.4 NPE days

0.5 NPE days

You might also like