Chemosphere 45 (2001) 887891

www.elsevier.com/locate/chemosphere

Pinonaldehyde and some other organics in rain and snow in

central Japan
Hikaru Satsumabayashi
a
c

a,*

, Hiroshi Nishizawa a, Yoko Yokouchi b,

Hiromasa Ueda c

Nagano Research Institute for Health and Pollution, Amori, Nagano 380-0944, Japan
b
National Institute for Environmental Studies, Tsukuba, Ibaraki 305-0053, Japan
Disaster Prevention Research Institute, Kyoto University, Uji, Kyoto 611-0011, Japan
Received 27 September 2000; accepted 1 December 2000

Abstract
Solvent-extractable organic compounds in the rain and snow collected at local cities in the mountainous region in
central Japan, were analyzed by GC/MS and GC. Pinonaldehyde (2,2-dimethyl-3-acetyl-cyclobutyl-ethanal), an atmospheric reaction product of a-pinene, was detected in the rain and snow for the rst time, and n-alkanes (C17 C33 ),
fatty acids (C8 C23 ), and benzoic acid were also detected as major organic components. Concentrations of pinonaldehyde, C17 C33 n-alkanes, C8 C11 fatty acids, C12 C23 fatty acids and benzoic acid ranged between <0.0213, 0.1035,
0.555.7, 4.219 and <0.026.0 lg/l, respectively. Their composition showed some dierence in summer and winter. In
summer, fatty acids and benzoic acid were more abundant, while pinonaldehyde and n-alkanes were much less. Higher
photochemical reactivity and higher bioactivity in summer could explain these seasonal changes except for pinonaldehyde, which would suer from further oxidation in the atmosphere after its photochemical production from a-pinene.
Predominance of pinonaldehyde and C12 C23 fatty acids in the rain and snow showed a remarkable contrast to nalkanes in aerosol phase, which were the most abundant components. It indicated that oxygenated products from
biogenic compounds might be important as cloud condensation nuclei in forest areas. 2001 Elsevier Science Ltd. All
rights reserved.
Keywords: Rain; Snow; Organic matter; Pinonaldehyde; Biogenic; Photochemical reaction

1. Introduction
A number of organic compounds have been detected
in the atmospheric aerosols and shown to attain onethird in total weight occasionally. In such aerosols, in
addition to the primary anthropogenic/biogenic compounds, their photochemical reaction products are also
widely distributed (Appel et al., 1980; Yokouchi and

Corresponding author. Fax: +81-26-224-3415.

E-mail address: satsumabayashi@nagano-eikouken.or.jp
(H. Satsumabayashi).

Ambe, 1986; Satsumabayashi et al., 1990). Since the

aerosols are mostly removed from the atmosphere by the
precipitation process (rain or snow), the composition of
organic compounds in the aerosols might be reected in
rain and snow. Several studies have shown that compositions in rain and the aerosols are similar (Sempere
and Kawamura, 1994; Imai and Kawamura, 2000).
Reaction products of monoterpenes, major biogenic
volatile organic compounds, are known to contribute to
particulate organics in forest areas and could be important for cloud-condensation-nuclei formation (Went,
1960; Kavouras et al., 1998, 1999). Among them, pinonaldehyde, which is produced through photochemical

0045-6535/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
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H. Satsumabayashi et al. / Chemosphere 45 (2001) 887891

reaction of a-pinene (Yokouchi and Ambe, 1985;

Hatakeyama et al., 1991), has been detected in aerosols
in considerable amounts, typically in several tens of ng/
m3 (Yokouchi and Ambe, 1985; Satsumabayashi et al.,
1990, 1991; Kavouras et al., 1998, 1999; Yu et al., 1999).
Therefore, it has been our great concern as to how much
pinonaldehyde is present in the precipitation.
In this paper, we will report the organic composition
including pinonaldehyde in the rain and snow samples
collected at local cities in the mountainous region in
central Japan, focusing on its seasonal change and its
dierence from the composition in the aerosols.
2. Experimental
Rain and snow samples were collected at two local
sites, Nagano (360 m altitude) and Okaya (790 m altitude) in the central Japan having population of 360 000
and 60 000, respectively. Sampling was made in December 1986 and January 1987 at Nagano and from
June to September 1989 and from November 1989 to
January 1990 at Okaya (see the rst column of Table 1).

Rain and snow samples were collected in a stainless

steel vessel (220  380 mm2 ) which had been washed
with pure water and acetone before use. Samplings at
Nagano and Okaya were done on the roofs of buildings
at heights of 13 and 7 m above ground level, respectively. Each sample was poured into a clean glass bottle,
added with a few ll of chloroform, and stored at 4C
prior to analysis.
Neutral and weakly acidic compounds were extracted
from the water sample (0.21.0 l) with dichloromethane
(CH2 Cl2 ) (50 ml  2). The CH2 Cl2 extract was concentrated into 1 ml at a temperature below 40C. After a
small portion of the concentrate was subjected to GC
and GC/MS analysis for pinonaldehyde and n-alkanes,
it was treated with 1 ml of diazomethane/ether to esterify
carboxylic acids. More acidic compounds in the remaining water samples (100 ml) were extracted by the
following steps: alkalication with 1 N KOH (pH 10),
evaporation to dryness at a temperature below 70C,
acidication with 0.8 ml of concentrated HCl, and extraction with 50 ml of CH2 Cl2 . The CH2 Cl2 extract was
evaporated, and esteried with 1 ml of diazomethane/
ether and then concentrated to 0.1 ml with nitrogen gas

Table 1
Concentrations of organic compounds in rain and snow
Sample

Precipitation
(mm)

Type

4
11

Concentration (lg/l)
Pinonaldehyde

C17 C33
n-alkanes (CPIa )

C8 C11
Fatty acids

Snow
Snow

13
3.4

35 (0.87)
1.2 (1.57)

1.4
3.4

6.4
4.7

6.0
1.7

2
8

Snow
Snow

2.5
1.4

1.2 (1.19)
0.51 (1.77)

2.0

4.7

1.6

Okaya, 1989
1516 June
16 June
5 July
810 July
1113 July
21 July
22 July
56 August
2627 August
23 September

23
31
10
76
83
3
24
42
52
14

Rain
Rain
Rain
Rain
Rain
Rain
Rain
Rain
Rain
Rain

0.61
1.0
4.1
0.76
4.8
4.1
0.16
n.d.b
1.4
4.0

0.10 (2.39)
0.13 (2.35)
0.31 (1.93)
0.10 (3.38)
0.24 (3.69)
2.2 (2.51)
0.74 (2.49)
0.28 (1.35)
0.13 (1.25)
0.93 (3.09)

1.1
1.9
0.60
1.5
5.7
1.7
2.6
1.4
4.6
1.3

6.8
11
6.9
9.6
12
19
11
4.2
12
7.2

0.09
0.18
0.17
0.31
1.3
1.1
0.02
0.54
0.54
0.17

Okaya, 19891990
28 November
14 December
15 December
2425 December
10 January
1517 January

5
12
12
15
11
7

Nagano, 19861987
2729 December
29 December5
January
56 January
1217 January

C12 C23
Fatty acids

Rain
4.3
0.26 (1.94)
1.1
6.0
Snow
2.8
1.4 (2.08)
1.2
6.4
Snow
6.7
1.2 (1.84)
1.4
4.7
Snow
0.79
0.91 (1.18)
1.3
7.6
Rain
1.7
1.7 (5.82)
0.55
5.7
Snow
5.2
2.0 (1.65)
1.8
7.6
P
P
a
Carbon preference index of n-alkanes: CPI ( amount of odd-carbon C17 C33 )/( amount of even-carbon C18 C32 ).
b
Not detected.

Benzoic
acid

0.29
0.53
n.d.b
0.35
0.10
0.21

H. Satsumabayashi et al. / Chemosphere 45 (2001) 887891

ow, and were subjected to the analyses for carboxylic

acids esteried. GC analysis was done with GC/FID
(Hewlett-Packard 5890) equipped with a SPB-5 (Supelco) fused silica capillary column (30 m long, 0.25 mm
i.d. and 0.25 lm thickness) in a splitless mode. The
column temperature was programmed to heat from
35C (1 min) to 280C at a rate of 8C/min and then
remained isothermal for 15 min (Satsumabayashi et al.,
1990). Organic compounds except for pinonaldehyde
were quantied with the authentic standard solutions in
CH2 Cl2 . Since pure pinonaldehyde was not available, it
was quantied by comparing the response with that for
methyl n-caprate standard and correcting its C number.
Identication of each compound was conrmed with
GC/MS analysis (JEOL, JMS AX505W).
Recoveries of authentic standards which were spiked
into 1.6 l distilled water were 7378% for C10 C23 fatty
acids, 62% for benzoic acid, and 83% or more for C16
C35 n-alkanes. In this paper, quantitative results are given without any correction for the recovery.
3. Results and discussion
3.1. Organics in rain and snow samples
Table 1 shows the concentrations of pinonaldehyde,
n-alkanes, fatty acids (short and long chains) and benzoic acid in the rain and snow samples collected at
Nagano and Okaya. Pinonaldehyde was detected in all
the samples except for the rain sample collected on 56
August 1989, and its concentration ranged from 0.16 to
13 lg/l, which often exceeded total n-alkanes or total
short-chain fatty acids. Such a detection of pinonaldehyde in rain or snow is considered to be the rst as far as
we know.
n-Alkanes with C17 C33 carbons were detected, and
their total concentrations were mostly in the range of

889

0.102.2 lg/l, but as high as 35 lg/l was found in the

snow sample from 2729 December 1986 at Nagano.
Their total abundance was generally consistent with the
observation in Tokyo, 0.427.9 lg/l for C15 C43 n-alkanes (Kawamura et al., 1994) and in Los Angeles, 0.21
2.6 lg/l for C17 C30 n-alkanes (Kawamura and Kaplan,
1986). The carbon preference index (CPI), the ratio of
the amount of odd-carbons numbered C17 C33 n-alkanes
to that of even-carbons numbered C18 C32 n-alkanes, is
also given for each sample in Table 1. The CPI is a
useful indicator for evaluation of anthropogenic
(CPI:1)/biogenic (CPI:5-10) contributions (Simoneit and
Mazurek, 1982; Simoneit, 1984; Kawamura and Kaplan,
1986; Kawamura et al., 1994). Although values of the
CPI obtained were highly variable (0.875.82), those in
winter samples were mostly lower than those in summer.
Short-chain fatty acids (<C11 ) are considered to be
derived from anthropogenic sources or photochemical
oxidation of hydrocarbons, whereas long-chain fatty acids (C12 C23 ) are likely to be of biogenic origin such as
bacterial and algal emission (Kawamura and Kaplan,
1986). Total concentration of short-chain fatty acids
ranged from 0.55 to 5.7 lg/l in Nagano and Okaya, and
were similar or a little lower than those at the urban area
in Los Angeles, 1.321 lg/l for C8 C11 fatty acids (Kawamura and Kaplan, 1986). On the other hand, longchain fatty acid concentration (4.219 lg/l) was a little
more abundant than that observed in Los Angeles
(1.48.3 lg/l for C12 C30 fatty acids). Fatty acids showed a
strong even/odd predominance in any of the samples and
C16 fatty acid (palmitic acid) was always most abundant.
Benzoic acid originates from automobile exhaust and
photochemical oxidations of aromatic hydrocarbons
(Kawamura and Kaplan, 1986). Concentration of benzoic acid in the rain and snow samples at Nagano and
Okaya ranged from <0.02 to 6.0 lg/l and was almost
equal or a little lower than that observed in the urban
area in Los Angeles (0.0610 lg/l).

Fig. 1. Concentrations of organic compounds in rain and snow (average values and ranges of variation). 1 Nagano/winter, 2 Okaya/
summer, 3 Okaya/winter. s-FAs: C8 C11 fatty acids. l-FAs: C12 C23 fatty acids.

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H. Satsumabayashi et al. / Chemosphere 45 (2001) 887891

Fig. 1 shows the dierence of the abundance of each

organic group among the datasets from (1) Nagano/
winter, (2) Okaya/summer and (3) Okaya/winter. For
the winter samples, n-alkanes and benzoic acid were
found to be much more abundant in Nagano samples
(1) than in Okaya samples (3), while no signicant
dierence was found in pinonaldehyde and short- and
long-chain fatty acids. This observation as well as lower
CPI in Nagano samples suggests greater contribution
of anthropogenic sources on the snow samples in
Nagano. It is consistent with our expectation for winter
Nagano which is a mid-size city surrounded by high
mountains.
As for the dierence between the summer and winter
samples at Okaya, fatty acids (short- and long-chain)
and benzoic acid were more abundant in summer than in
winter, while n-alkanes and pinonaldehyde were more
abundant in winter. Higher photochemical reactivity
and higher bioactivity in summer could explain the increase of fatty acids and benzoic acid. The increase of nalkane in winter might be attributed to lower photochemical decay rate and more fuel combustion in wintertime. Pinonaldehyde was present at lower
concentrations in summer, and this is not consistent with
the presumption that higher emission of its precursor
compound (a-pinene) from plants and higher photochemical reactivity would produce more pinonaldehyde
in the atmosphere in summer. A possible explanation for
this nding is that pinonaldehyde is an intermediate
product and it would suer from further photochemical
reactions in the atmosphere (Kavouras et al., 1998,
1999), resulting in its lower concentration in summer.
3.2. Comparison with the organic composition in the
aerosols
Among the ve organic groups in Table 1 and Fig. 1,
long-chain fatty acids were the most abundant, followed
by pinonaldehyde, short-chain fatty acids, n-alkanes and
benzoic acid in the rain/snow samples. Such a composition diered signicantly from those found in the airborne aerosols. During the present observation periods,
aerosol samples were also collected for a week at Okaya
(Satsumabayashi et al., 2001). Fig. 2 shows the compositions of pinonaldehyde, n-alkanes, and fatty acids in
the rain and aerosol, both of which were collected on 28
November 1989 at Okaya. Remarkable dierences can
be seen between them: pinonaldehyde and long-chain
fatty acids were much more abundant components in the
rain sample, while n-alkanes were the most abundant
components in the aerosol. Similar dierences in the
compositions of organics were found in the other samples. This result suggests that pinonaldehyde and longchain fatty acids are more easily incorporated into rain
or snow than n-alkanes probably due to their higher
water absorptivity or solubility.

Fig. 2. Comparison of relative abundance of pinonaldehyde, nalkanes and C12 C23 fatty acids between rain and airborne
aerosol at Okaya on 28 November 1989.

3.3. Signicance of high-level pinonaldehyde

Pinonaldehyde in the aerosols has been found at the
concentration of 387 ng/m3 in several areas in central
Japan (Satsumabayashi et al., 1990, 2001). Aerosol
samples collected in summertime at more forested areas
compared to Okaya and Nagano (Satsumabayashi et al.,
1990), showed a diurnal variation of pinonaldehyde with
nighttime maximum, while in the aerosol samples collected in wintertime at Okaya and Nagano (Satsumabayashi et al., 2001) pinonaldehyde decreased at night.
Decrease of pinonaldehyde in the aerosol samples during daytime in summer has been considered due to further decomposition by photochemical reactions in the
atmosphere. Another possibility is insucient collection
eciency of volatile pinonaldehyde particles on the lters during summer daytime. These facts are consistent
with the present nding that pinonaldehyde in the rain
samples were less abundant in the summer samples.
Finding of high level of pinonaldehyde in the precipitation (rain or snow) in the present study, as well as
our previous detection of high concentration pinonaldehyde particles in the forest aerosols, indicates that
polar reaction products from biogenic organic compounds are likely to be playing an important role in
CCN formation. Since biogenic organic compounds
with higher polarity than pinonaldehyde are known to
be produced from the reactions of a-pinene or some
other compounds and would be distributed on regional
and global scale, further investigation of those photochemical products in the rain/snow samples would give
us important information on aerosol and precipitation
chemistry.
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