Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23

www.elsevier.com/locate/chemolab

Study of pollutants in precipitation (rain and snow) transported long

distance to west coasts of Japan Islands using oblique rotational
factor analysis with partially non-negative constraint
Toru Ozeki a,b,*, Toshihiro Ihara a, Nobuaki Ogawa c
a
Hyogo University of Teacher Education, Shimokume 942-1, Yashiro-cho, Kato-gun, Hyogo 673-1494, Japan
b
CREST (Core Research for Evolutional Science and Technology) of JST (Japan Science and Technology Corporation), Japan
c
Faculty of Engineering and Resource Science, Akita University, Tegata Gakuen-cho, Akita 010-8502, Japan

Received 6 January 2005; received in revised form 5 May 2005; accepted 9 May 2005
Available online 14 October 2005

Abstract

In recent years, acidic precipitation (rain and snow) is receiving global interest, especially in East Asia where a rapid industrialization and an
economic growth have been observed. In Japan, heavy acidification of precipitation in winter has been observed at areas close to west coasts of the
Japan Islands and is related to the long distance transportation of the acidic pollutants across the Sea of Japan. In order to characterize
transportation process of the pollutants and the seasonal and regional variations of the transportation, the precipitation samples were collected at
nine areas from north to south of Japan in the period from July 2000 to June 2001 and the compositions of the precipitation samples were analyzed
by a chemometrical method developed by our group ‘‘Oblique Rotational Factor Analysis with Partially Non-Negative Constraint (ORFA-
PNNC)’’. It consists of the Principal Component Analysis and the oblique rotation of the composition matrix based on the non-negative constraint.
Our method has a very distinctive feature that the non-negative constraint is exempted from the hydrogen ion so as to take the neutralization
reactions among the acidic pollutants and alkaline pollutants into account. Furthermore, in this study, the normalization of the concentration data
of the samples was incorporated into the analysis to extract the feature of ions with small concentration such as potassium ion and nitrous ion.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Factor analysis; Oblique rotation; Chemical constraints; Non-negativity; Normalization; Acid precipitation (rain and snow); Long-distance transportation
of pollutants

1. Introduction quantities such as pH, electric conductivity, concentrations of

In recent years, acidic precipitation (rain and snow) is receiving
global interest. In Japan, heavy acidification of precipitation has
been observed in winter at areas close to west coasts of the Japan
Islands and is related to the long distance transportation of the
acidic pollutants across the Sea of Japan [1 –9].
Our group started the study of acidic precipitation in Japan
at 1991. In the study, we have had a vast amount of
compositional data of precipitation samples for that a week
base collection of precipitation only gives 52 sets of data a year
for each sampling place and one data set contains at least 11
* Corresponding author. Hyogo University of Teacher Education, Shimo-
kume 942-1, Yashiro-cho, Kato-gun, Hyogo 673-1494, Japan. Tel.: +81 795
44 2201.
E-mail address: ozeki@sci.hyogo-u.ac.jp (T. Ozeki).
0169-7439/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemolab.2005.05.012
major nine ions (Na+, K+, NH4+, Mg2+, Ca2+, SO42, NO3, Cl,
NO2). A usual way to study the trends of dissolved pollutants
is one by one comparison of two quantities of precipitation
samples. However, in many cases, such a comparison is
cumbersome and time-consuming and several important
information may be lost on the way of analysis. For such
reason, statistical approaches such as PCA are quite frequently
utilized in this field. However they have limit to analyze
natures of the compositional data because of their unrealistic
assumption such as orthogonal relationships among the
extracted factors. So, our group has developed a new approach
of oblique rotational factor analysis based on chemically
meaningful non-negative constraint [10 – 18]. However, in our
conventional study using compositional data of real precipita-
tion samples, pretreatment of data such as normalization has
not been discussed seriously since we have had no much
16 T. Ozeki et al. / Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23

value measured by a pH meter (Horiba M-8L) with a combined

type glass electrode (Horiba 6328). EC was measured by a
conductivity meter (Horiba C-172). The concentrations of the
major nine ions were measured by an ion chromatograph
system (Dionex 2000i). For cation analysis, a separation
column CS12 and a suppressor CSRS were used, and for
anion analysis an AS4A and an ASRS were used, respectively.
The water used was Milli-Q water after doubly distillation.
Reagents used were all of analytical grade. The chemical
analysis was carried out according to the recommendations of
the Japan Environment Agency [19].

3. Results of chemical analysis

3.1. Regional and seasonal variations of pH and hydrogen ion

concentration

The chemical compositions of the precipitation samples

Fig. 1. Location of sampling points of precipitation samples (July 2000 – June examined in this study have been reported elsewhere in
2001). Japanese [18]. Here, brief outline of their chemical composi-
tions is introduced for readers to know the natures of
attention in minor pollutant ions so far. In this study, we precipitation data. In Fig. 2, the three dimensional (3D) plots
focused the origin and incorporation process of two minor ions,
K+ ion and NO2 ion by taking normalization pretreatment into
account. The importance and validness of normalization is
reported in this paper.

2. Experimental

2.1. Sampling points and sampling method

In Fig. 1, location of the nine sampling points of precipitation

samples are shown (1:Fko, Fukuoka; 2:Hg, Yamaguchi-Hagi;
3:Yn, Tottori-Yonago; 4:Tt, Tottori-Kedaka; 5:Fki, Fukui-
Sabae; 6:Is, Ishikawa-Kahoku; 7:Ty, Toyama; 8:Ks, Niigata-
Kashiwazaki; 9:Ak, Akita). These places are all locating at
the western side of the main island of Japan called Honshu
and are close to a coastal line of the Sea of Japan from the
closest Tottori (4:Tt) of 200 m to the farthest Fukui (5:Fki) of
16.1 km.
In this study, a cylindrical container of the inner diameter 22
cm made of plastic was used as a sampling vessel because rain
and snow samples were expected. A polyethylene bag was set
inside the vessel and precipitation was collected for one week.
Even when no precipitation was occurred within a week, an old
polyethylene bag was replaced by a new one. In order to make
the experimental condition to the same, all precipitation
samples were delivered to Hyogo University of Teacher
Education and chemical analysis was carried out. Sampling
period was from July 2000 to June 2001.

2.2. Chemical analysis

Analyzed quantities are: pH, electric conductivity (EC),

concentrations of major nine ions (Na+, K+, NH4+, Mg2+, Ca2+,
SO42, NO3, Cl, NO2) and an amount of precipitation in a Fig. 2. Regional and seasonal variations of pH and H+ ion concentration (July
week. The concentration of H+ ion was converted from the pH 2000 – June 2001).
 T. Ozeki et al. / Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23 17

of regional and seasonal variations of pH (Fig. 2-A) and H+

ion concentration (Fig. 2-B) are shown. The H + ion
concentration is the monthly averaged concentration obtained
by dividing the sum of the depositions (product of concen-
tration of a week base precipitation sample and its precipi-
tation amount) by the total amount of precipitation at the
month. The H+ ion concentration of each precipitation sample
was converted from the pH value of the sample. The monthly
averaged pH value shown in Fig. 2-A was the one converted
from the monthly averaged H+ ion concentration. The
monthly averaged concentrations of ions shown below follow
the same definition.
As seen in Fig. 2, it is obvious that the pH values of the
precipitation samples in winter season from October 2000 to
February 2001 were low at any place and the monthly averaged
H+ ion concentrations were high. Especially the pH values of
the areas locating south rather than Ishikawa (6:Is) were lower
as compared to the areas locating north. When the difference
between the sum of the equivalent concentrations of acidic
substances and that of alkaline substances was compared with
the H+ ion concentration, a good agreement was observed
between them. [18] It means that the balance between acidic
pollutants and alkaline pollutants determines the pH of
precipitation. On the other hand, no large regional deviation
of precipitation amount was observed.

3.2. Regional and seasonal variations of sea salt origin ions

Three dimensional plots of regional and seasonal variations

of the monthly averaged concentration of Na+ ion and K+ ion
are shown in Fig. 3. Concentration unit used here is ‘‘A equiv
L 1’’. Generally in the countries near or surrounded by seas,
most of Na+ ion, Cl ion and Mg2+ ion contained in
precipitation samples are ascribed to the sea salt origin ions.
In fact, the regional and seasonal variations of these ions are
very similar. Thus, in a field of chemists monitoring of acidic
precipitation in Japan, the pollutant ions are divided in two
groups; one is the sea salt origin denoted as Fss_ and the other is
the non sea salt origin denoted as Fnss_. In this case, it is usually
assumed that all of Na+ ion is sea salt origin and the sea salt
origin ions (ss-ions) maintain the composition same as that of
the standard sea water of the world (the Fss_ assumption).
Consequently, the concentration of ss-SO42 ion can be
estimated from the Na+ ion concentration of the sample and
that of nss-SO42 ion can be calculated by subtracting the ss
concentration (ss-SO42) from the total concentration of SO42
ion. However, the Fss/nss_ assumption is only an assumption.
One reason we have applied chemometrical approach is to
clarify whether this assumption is valid or not.
On the other hand, usually Na+ ion, Cl ion and Mg2+ ion
are regarded as the sea salt origin ions, but the regional and
seasonal variations of K+ ion shown in Fig. 3-B seem to be a
little bit different with that of Na+ ion shown in Fig. 3-A. There
is a possibility that a part of K+ ion was transported by different
routes with those of the sea salt origin. This point is the second
purpose to be examined in this work by using the chemome-
trical analysis.
Fig. 3. Regional and seasonal variations of Na+ ion concentration and K+ ion
concentration (July 2000 – June 2001).
3.3. Regional and seasonal variations of acidic ions and
alkaline ions
Three dimensional plots of regional and seasonal variations
of the monthly averaged concentration of NH4+ ion and nss-
Ca2+ ion are shown in Fig. 4. Similarly, those of nss-SO42 ion
and NO3 ion are shown in Fig. 5. It can be seen that these ions
have very high values at March and April. After consideration,
it was concluded that these increases were explained by the
transportation with Jet streams from the Continental China to
Japan Islands at these months [18]. Recently, Jet streams have
brought vast amount of Ca2+ ion as Eolian dust in spring to the
Japan Islands. The chemical and physical properties of Eolian
dust transported from the inland deserts of China have been
studied by Inoue et.al. [20,21].
On the other hand, it is observed in Figs. 4 and 5 that the
concentration of NH4+ ion and that of nss-SO42 ion are also
high in November to February (winter season) at all sampling
points. In winter season these sampling points have very strong
seasonal northwestern winds. Thus it is considered that an
acidic mixture of sulfuric acid and ammonium sulfate is
transported in winter by the winds and is contributing to the
18 T. Ozeki et al. / Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23

negative Constraint (ORFA-PNNC)’’ developed by our group

[10,12,17] was applied to the data set obtained for the
precipitation samples. Furthermore, the normalization pretreat-
ment of the compositional data was examined in this work. The
compositional data of 410 precipitation samples were used in
the following analysis.

4.1. Principal component analysis (PCA) [10,17]

The first step of the ORFA-PNNC is the same as the

conventional PCA [22 – 25]. The concentration of the following
nine ions (or ten ions) in equivalent unit — H+, Na+, K+, NH4+,
Mg2+, Ca2+, SO42, NO3, Cl (and NO2 in the case of ten
ions) —were used for the analysis. An element d ij of a data
matrix D is the equivalent of the j-th ion in the i-th sample.
This data matrix D is decomposed to the product of the
contribution matrix R and the composition matrix C. In the
composition matrix C, the composition of each independent
pure pollutant source is aligned as a row vector. In the
contribution matrix R, the contribution of each independent

Fig. 4. Regional and seasonal variations of NH+4 ion concentration and nss-Ca2+
ion concentration (July 2000 – June 2001).

acidification of winter precipitation. Yamamoto et. al. have

reported increase of SO2 emission inside China and its
transportation to the Japan Islands [8].
Several years ago, long distance transportation of only
sulfuric acid has been reported. But recent economical
development of China and Korea, especially increase of
automobiles, makes the emission of NOx increase [5,7].
Consequently, increase of long distance transportation of
NO3 ion has been proposed. In Fig. 6, the three dimensional
plot of regional and seasonal variations of the monthly
averaged concentration of another nitrogen compound NO2
ion is shown. The pattern of NO2 ion is, however, different
from that of NO3 ion. The discussion on transportation of
NO2 ion is the third purpose of this study by using
chemometrical analysis.

4. Oblique rotational factor analysis with partially

non-negative constraint

In order to find answers to the above questions, the Fig. 5. Regional and seasonal variations of nss-SO2
4 ion concentration and
‘‘Oblique Rotational Factor Analysis with Partially Non- NO3 ion concentration (July 2000 – June 2001).
 T. Ozeki et al. / Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23
Fig. 6. Regional and seasonal variations of NO
2 ion concentration (July 2000 –
June 2001).
pollutant source to each precipitation sample is aligned as a
column vector.
D ¼ RC:
First, the covariance matrix Z is calculated by multiplying
the transpose of the data matrix D from the left of the data
matrix to estimate the number of the independent pollutant
sources.
Z ¼ t DD
By solving the Eigenvalue problem, an Eigenvalue matrix E
and an Eigenvector matrix Q are obtained. In our case, the
Jacobi method was applied for this purpose.
Z ¼ QEt Q
In this step, from the information of the cumulative contribu-
tion ratio and the number of the large Eigenvalues, the number
of pollutant sources n was estimated. Then Eigenvectors of that
number are extracted from the column vectors of the matrix Q
and are aligned as row vectors of a composition matrix C.
In this stage, the first factor represents the total degree of
pollution; and the second factor represents the difference of the
quality of pollution and the several elements of the composition
matrix C take negative values. It is clear that the negative
concentrations are meaningless. Sometimes, the Varimax
rotation has been applied in this stage to make the characters
of the factor axes clearer. [26,27] However, the Varimax
rotation keeps the orthogonal relationship between the axes.
Thus the Varimax rotation cannot delete all the negative
elements. In our analysis, the oblique rotation was introduced.
4.2. Oblique rotation with partially non-negative constraint
[10,17]
In this treatment, the oblique rotation is incorporated so that
all negative elements of the C are eliminated. What was done is
19
to replace the negative element of the composition matrix C by
zero. If the replaced matrix is denoted as Cx, a matrix T to
rotate the matrix C to Cx is optimized based on the least-square
method:
Cx ¼ TC ð4Þ
 1
T ¼ Cxt C Ct C ð5Þ
The rotation matrix T gives rise to a new matrix C*.
CT ¼ TC: ð6Þ
As compared to the original matrix C, the number of
negative elements of the C* is reduced. But the negative
elements still remain in C*. So the above procedure is repeated.
Finally the composition matrix C* with no negative elements is
obtained.
However, this non-negative constraint is excluded from the
elements of the H+ ion in our method. It is because a
neutralization reaction among the acidic pollutants and the
alkaline pollutants has to be taken into account [10,17]. In any
case, either of [H+] or [OH] is less than 10 7 mol L 1. When
the non-negative constraint is excluded from H+ ion, the
resultant concentration of H+ ion is interpreted as follows: If
ð1Þ
[H+] is positive, the value is regarded as [H+] itself. And if [H+]
is negative, then the value is regarded as [OH]. This treatment
of [H+] can include the neutralization reaction between OH
ion and H+ ion.
After the above oblique rotation, if the normalization
pretreatment of the data matrix D mentioned in Section 5.1
ð2Þ was not carried out before the PCA, then the sum of the
absolute values of row elements of the matrix C are normalized
so that the total amount of ions contained in each pollutant
source is the same, one equivalent. And if the normalization
pretreatment of the data matrix D was done, its de-normaliza-
ð3Þ tion treatment is performed first (see Section 5.1) and this
normalization of composition matrix C follows.
4.3. Calculation of the contribution [11,17]
By the above procedure, the composition matrix C is
obtained. Strictly speaking, the term ‘‘composition’’ means
‘‘the molar ratio of ions’’ in a pollutant group. Then next, the
contribution of the extracted factor is numerically evaluated.
Here again, strictly speaking, the term ‘‘contribution’’ means
‘‘concentrations of groups in a sample’’. In early stage of our
study, the contribution matrix R was obtained based on the
least square method.
1
R ¼ Dt CðCt CÞ ð7Þ
Then the relation among the elements can be written as
follows:
dij ¼ ~ rik ckj þ eij ð8Þ
k
Here, the residual error e ij takes positive and negative values;
namely it is random error. However, if we assume four
20 T. Ozeki et al. / Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23
pollutant factors, for example, it means that there are other
residual factors having positive contribution. Then the value of
(Ak r ik c kj ) in the right hand side of Eq. (8) should be smaller
than the value of the left hand side (d ij ). Namely the value of e ij
is positive or zero. Then the Eq. (8) should be rewritten as
follows:
dij  ~ rik ckj ð9Þ
k
In order to take this inequality relationship into account, we
have introduced the Simplex Tableau Algorithm of the Linear
Programming Method and the maximum set of contribution (~
r ij ) is calculated. The details of this algorithm can be seen
elsewhere [28,29].
The contribution of each pollutant source to a precipitation
sample is evaluated numerically by using the values of r ij . The
total reproduction ratio Trr is defined as:
!
 
Trr ¼ ~i ~j ~k rik ckj = ~ ~ dij ð10Þ
i j
Finally, the contribution (concentration) of the k-th pollutant
source in the i-th sample is expressed as follows:
 
fi;k ¼ Trr rik = ~ rik : ð11Þ
k concentrations of K+ ion (5.11 A equiv L 1) and nitrous ion
5. Results of application of the ORFA-PNNC to the real
precipitation data set (2000 –2001)
5.1. Normalization pretreatment of the data matrix D
First, the number of extracted pollutant groups was
examined from one to four. Generally speaking, as the number
Fig. 7. Influence of normalization treatment in the case of 9 ions by 4 factors.
of the extracted factors increases, the character of the factor
changes from a form of combination of salts to that of single
ion. Chemically speaking, the ionic pollutant must have neutral
charge as a whole. Thus the check of ionic balance for each
extracted pollutant is important. In this study, however, several
ions such as organic acids or heavy metals have not been
measured. So, four pollutant groups were assumed in order to
make characterization of the nature of the pollutant groups
easy.
The compositions of the four extracted pollutant groups are
shown in Fig. 7-(I). The first pollutant group Fig. 7-(I)-4A of
the largest Eigenvalue contains Na+ ion and Cl ion of large
amount and is ascribed to the sea salt origin group. On the
other hand, the group 4C contains NO3 ion, SO42 ion, NH4+
ion and H+ ion (of positive value), and is considered as the
acidic pollutant consisted of sulfuric acid, nitric acid and their
ammonium salts. Additional two pollutant groups 4B and 4D
have H+ ion with negative values implying hydroxide ion.
Namely these two pollutant groups are alkaline groups. 4B is a
pollutant group characterized by Ca2+ ion and 4D is the one
characterized by NH4+ ion.
In this stage, normalization of concentrations of the data
matrix D was examined for ions. For the precipitation samples
collected in this work, the mean concentrations of Na+ ion and
Cl ion are very large, about 200 A equiv L 1. However, the
(0.47 A equiv L 1) are very small. Thus, if the raw
concentrations without normalization are used for analysis,
the natures of ions of small concentration are concealed by the
natures of ions of large concentration. Thus, the pollutant
groups extracted without normalization and those with
normalization were compared in this stage. For the normaliza-
tion, the raw concentrations were divided by the mean value of
each ion.
D4 ¼ DF ð12Þ
 T. Ozeki et al. / Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23 21

Fig. 8. Influence of normalization treatment in the case of 10 ions by 4 factors.

where F is a diagonal matrix having normalization coefficients

f jj as diagonal elements; the f jj is the inverse of the mean
concentration of j-th ion. A normalized data matrix D* was
applied in place of the original raw matrix D. If the
composition matrix obtained from the D* is denoted as C*,
de-normalization treatment is carried out to obtain the true
composition matrix CV.
CV ¼ C4F1 ð13Þ
where F 1 is a diagonal matrix having inverse of normalization
coefficients 1 / f jj as diagonal elements.
In Fig. 7, the compositions (I) of the four pollutant groups
are the ones without normalization obtained by using the
original D matrix. In this case, the data of 9 ions except for
nitrous ion were treated by 4 factors. On the other hand, the
compositions (II) and (II*) are the ones obtained by using the
normalized data matrix D*. The compositions (II) are the ones
reproduced after de-normalization treatment CV, but the
compositions (II*) are the transient ones before the de-
normalization treatment C*. Two final compositions (I) and
(II) are almost the same. But, when the transient compositions
(II*) are examined, the obvious contribution of K+ ion can be
seen in the first pollutant group 4A (namely, sea salt group) and
in the forth pollutant group 4D (namely, an alkaline pollutant
group characteristic to NH4+ ion). It means that the K+ ion is
brought to the sampling points along with two pollutant
groups.
On the other hand, Fig. 8 is the case that a data set consisted
of 10 ions including nitrous ion was analyzed in a similar
manner. When the transient composition Fig. 8-(II*) is
examined, the nitrous ion can be found in the second pollutant
group 4B, namely an alkaline pollutant group characterized by
the Ca2+ ion. It means that nitrous ion is coming to Japan along
with Ca2+ ion. Probably, NOx generated in urban areas of the
Continental China is adsorbed on the Eolian dust and is Fig. 9. Regional and seasonal variations of contribution of group 4A and group
transported to Japan. 4B (July 2000 – June 2001).
22 T. Ozeki et al. / Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23
Fig. 10. Regional and seasonal variations of contribution of group 4C and
group 4D (July 2000 – June 2001).
5.2. Features of the extracted four pollutant groups
5.2.1. The first pollutant group 4A (sea salt group)
The three dimensional (3D) plot of regional and seasonal
variations of the contribution of the first pollutant group 4A is
shown in Fig. 9-(A). The corresponding composition of this
group can be seen in Fig. 7-(I)-4A. All of Na+ ion, Cl ion,
Mg2+ ion and a part of SO42 ion are contained in this group.
The unit of the contribution (concentration) of Fig. 9-(A) is 100
A equiv L 1 as the sum of the composition is set to 1 equivalent
for each pollutant group as explained in Section 4.2. This
concentration unit is used throughout Figs. 9 and 10. The group
4A corresponds to the sea salt origin group and has very high
contribution to the precipitation samples, as a whole 64.0% of
the total equivalent concentration. From Fig. 9-(A) it can be
Table 1
The comparison of the equivalent ratio of ions in the standard sea water of the world and that of the group 4A extracted by this work when the content of sodium is
set to 1.000 equiv
H+ Na+
The standard sea water 0.000 (1.000)
This work 0.005 (1.000)
seen that the contribution is higher in winter season from
December to March. This sea salt group was brought by the
north-western seasonal wind blowing across the Sea of Japan.
As already mentioned, this group has a very good value of
ionic balance, 1.07 (Fig. 7-(I)-4A). In Table 1, the ratio of
composition of this group obtained by this work is compared
with the ratio of the standard sea water of the world [30]. These
are very close each other. So, we can say that the conventional
grouping of the pollutants, sea salt origin and non sea salt
origin (ss/nss), carried out so far seems adequate.
5.2.2. The second pollutant group 4B (an alkaline pollutant
group characteristic to Ca2+)
The three dimensional (3D) plot of regional and seasonal
variations of the contribution of the second pollutant group 4B
is shown in Fig. 9-(B). The corresponding composition of this
group can be seen in Fig. 7-(I)-4B. This group is the alkaline
pollutant group characteristic to Ca2+ ion. This group is
transported by Jet streams in spring from February to April.
The contribution of this group to precipitation samples is
higher in south-western part of Japan rather than that in north-
eastern part because many of Jet streams are passing southern
part of Japan Islands in this season. The value of ionic balance,
the ratio of total equivalent of anions to that of cations, is not
good, 0.55 (Fig. 7-(I)-4B), implying that some anions are
missing. The reason is probably that carbonate ion contained in
soil dust is not measured in this work. As mentioned in Section
5.1, this group contains the nitrous ion. It means that the
nitrogen oxide (NO2) generated in urban areas of the
Continental China is adsorbed on Eolian dust and is transported
to Japan Islands by Jet streams.
5.2.3. The third pollutant group 4C (an acidic pollutant group)
The three dimensional (3D) plot of regional and seasonal
variations of the contribution of the third pollutant group 4C is
shown in Fig. 10-(A). The corresponding composition of this
group can be seen in Fig. 7-(I)-4C. This group is the acidic
pollutant group consisted of sulfuric acid and ammonium
sulfate. It is considered that this group is transported by two
routes: namely, the transportation at March to April is the one
brought by Jet streams and the transportation in winter season
is the one brought by the northwestern seasonal wind. In
winter, an acidic pollutant group transported to the Japan
Islands is this group. It is clear from the Fig. 10-(A) that the
contribution of this group in winter was higher in south-
western part of Japan rather than that at Toyama (7:Ty). This
regional variation may be related to the location of Korean
Peninsula. The value of ionic balance is not good, 2.00 (Fig. 7-
(I)-4C), implying some cation is missing.
K+ NH+4 Mg2+ Ca2+ SO2
4 NO
3 Cl
0.022 0.000 0.226 0.044 0.121 0.000 1.166
0.017 0.002 0.201 0.051 0.112 0.003 1.246
 T. Ozeki et al. / Chemometrics and Intelligent Laboratory Systems 82 (2006) 15 – 23
5.2.4. The fourth pollutant group 4D (an alkaline pollutant
group characteristic to NH4+)
The three dimensional (3D) plot of regional and seasonal
variations of the contribution of the forth pollutant group 4D is
shown in Fig. 10-(B). The corresponding composition of this
group can be seen in Fig. 7-(I)-4D. This group is the alkaline
pollutant group characterized to the NH4+ ion. Contrary to the
second group 4B shown in Fig. 9-(B), this group had higher
contribution at north-eastern part of Japan rather than south-
western part. From the seasonal point of view, higher
contributions were seen from April to July, namely in early
summer. From the normalization pretreatment of the data
matrix, it was proposed that this group contained the K+ ion.
Consequently, this group seems related to biomass or agricul-
tural substances. The value of ionic balance is 0.29 (Fig. 7-(I)-
4D), implying some anion is missing. The reason is probably
that anions of organic acids contained in biomass or
agricultural substances were not measured in this work.
6. Conclusions
In this study, the precipitation samples collected at nine
points near the Sea of Japan during July 2000 – June 2001 were
analyzed by ‘‘Oblique Rotational Factor Analysis with Partially
Non-negative Constraint (ORFA-PNNC)’’ developed by our
group and four pollutant groups were extracted. From their
seasonal and regional variations, they were ascribed to a sea
salt origin group, an acidic pollutant group consisted of sulfuric
acid and ammonium sulfate, and two alkaline pollutant groups.
One of the alkaline groups was characterized by Ca2+ ion and
the other was characterized by NH4+ ion. In this study, it was
made clear that the contributions of north-western seasonal
winds and Jet streams were very large to the transportation of
these pollutant groups. Furthermore, the normalization pre-
treatment of the compositional data has offered the information
on the origins of K+ ion and that of NO2 ion. From this study,
it has been demonstrated that our factor analysis, ORFA-
PNNC, is powerful to extract pollutant groups contaminating
precipitation samples.
Acknowledgements
The present work was partly supported by funds from the
‘‘Nippon Life Insurance Foundation’’ in 1999 and in 2000
(Principal Investigator: Prof. Toru Ozeki, Hyogo University of
Teacher Education). This work was also partly supported by a
CREST1999 and 2000 (Core Research for Evolutional Science
and Technology). The authors express their thanks to these
supports.
23
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