Bulletin of Glaciological Research ,1 (,**3) +ῌ/ῌJapanese Society of Snow and Ice

1Measurements of peroxide concentrations in precipitation and dew water in Toyama,Japan
Koichi WATANABE, Mikiko AOKI, Nagisa EDA, Yukiko SAITO, Yuki SAKAI, Syoko TAMURA,Mari OHATA, Manami KAWABUCHI, Ayumi TAKAHASHI, Nobuko MIYASHITAand Keiko YAMADA
Department of Environmental Systems Engineering, College of Technology, Toyama Prefectural University,/+2* Kurokawa, Imizu, Toyama 3-3ῌ*-32, Japan(Received March +1, ,**3; Revised manuscript accepted April ,,, ,**3)

AbstractMeasurements of the peroxide concentrations in precipitation were conducted in Imizu City,
Toyama Prefecture, Japan, from July ,**/ to March ,**3 and in dew water in the autumn of ,**2.
The peroxide concentrations in the precipitation samples exhibited a range from below the level ofdetection,῍*.+ mM, to +3* mM with strong seasonal variations. The peroxide concentrations during
the winter were higher in rainwater than in the snow, perhaps because rain and snow have di#erent
processes of scavenging peroxides from the atmosphere. The concentrations of peroxides in dewwater in Imizu City ranged from *.2 to -.0 mM from September to November in ,**2. At lower sites,
the peroxide concentrations were signiﬁcantly lower in dew water than in rainwater, however, higher
concentrations in dew water, 0/ mM, were detected at Murododaira (,./* m a.s.l.), near the summit ofMt. Tateyama.

+.

Introduction

Hydrogen peroxide, H,O,, considered an important oxidant of SO,, S(IV), in atmospheric liquid water,
has been found to be highly soluble in cloud and fog
droplets or aqueous aerosols (Watanabe et al., +330).
The reaction between H,O, and S(IV) in water dropletsis very rapid and is independent of the pH. The
reaction between O- and S(IV), on the other hand, does
not occur under conditions below pH / (Martin andDamschen, +32+). Organic hydroperoxides, ROOH,
are thought to play an important role in the oxidationof S(IV) as well as that of H,O, (Lind et al., +321).
Therefore, the concentration of total peroxides (H,O,ῌROOH) in the aqueous phase is a useful indicator ofoxidation capacity. Moreover, peroxides, as well asO-, may contribute to vegetation damage (Hewitt andTerry, +33,; Kume et al., ,**+). Peroxide concentrations are mainly dependent on the meteorological conditions, e.g. UV radiation, temperature and humidity, and the concentrations of atmospheric pollutants(Sakugawa et al., +33*). Large seasonal variations in
the concentrations of peroxides in the atmospherehave been observed (Sakugawa and Kaplan, +323;
Watanabe and Tanaka, +33/).

Peroxide concentrations in precipitation andcloud water have been measured, especially in theUnited States and Europe (Gunz and Ho#mann, +33*).
Preliminary studies on peroxide in rain and cloudwater in central parts of Japan have been reported(Watanabe et al., +333; ,**+a; ,**+b; ,**/; ,**0). However, there is still a shortage of such data on peroxides
in East Asian countries. Up to now, no long-term observation of peroxides has been performed in Japan.
Moreover, peroxide concentrations have rarely beenmeasured in dew water. Recently, O- concentrationsin the background troposphere have signiﬁcantly increased over East Asian countries, including Japan(Akimoto et al., +33.). The increase in O- may accelerate the formation of peroxides in the atmosphere;
therefore, measurements of peroxides are importantto estimate environmental conditions.
In this paper, the concentrations of peroxides inprecipitation, including snowfall and dew water inToyama, Japan and the characteristics of peroxideconcentrations are examined. The preliminary results of peroxide measurement in dew water near thesummit of Mt. Tateyama are also discussed.

2,.

Bulletin of Glaciological Research

Methods

Sampling of precipitation (rain and snow) anddew water was performed on the roof of the building(,* m above the ground level) at the College of Technology, Toyama Prefectural University (+/ m a.s.l.) in
Imizu City, Toyama, Japan. Precipitation samples
were collected in a +*** ml Teﬂon bottle (+** mm ID)
from July ,**/ to March ,**3. Unfortunately, precipitation could not be collected from March to October in ,**0. In the autumn of ,**2, dew water was
sampled during the nighttime on a + m, Teﬂon sheet
on foaming polystyrene. Dew water was also collected at Murododaira (,./* m a.s.l.), near the summitof Mt. Tateyama, at *ῌ- H JST on +, September, ,**2.
The sampling times for precipitation and dew watercollection were usually within . hours. The peroxide
concentrations in rainwater and dew water were measured immediately after collection. Snow samples
were melted at room temperature and immediatelyanalyzed. Figure + is a map of Japan showing thelocations of Toyama Prefectural University and Mt.
Tateyama. In this paper, the sampling sites, Toyama
Prefectural University and Murododaira, Mt. Tateyama,are described as Imizu City and Murododaira, respectively.

Fig. +. Map showing the locations of Toyama Prefectural University, Imizu City, and Mt. Tateyamain Toyama, Japan.

Peroxide concentrations were measured by theﬂuorometric method, using p-hydroxyphenyl acetic
acid and peroxidase reagents (Lazrus et al., +32/;
Kamiyama and Nakayama, +33,) as described in detailby Watanabe et al. (,**/). We also determined individual peroxides using HPLC separation (Kok et al., +33/).
The concentrations of organic hydroperoxides, suchas methylhydroperoxide (MHP), were less than /ῌ oftotal peroxide concentrations (Watanabe, unpublished data). Therefore, H,O, is considered a main
component of peroxides in this study.

-.
-.+

Results and discussion

Peroxide concentrations in precipitation
A summary of the concentrations of peroxides inprecipitation in Imizu City from July ,**/ to March,**3 is shown in Table +. The peroxide concentrations
ranged from below the level of detection,ῌ*.+ mM, to+3* mM, and the concentrations were signiﬁcantly
higher from May to October than from November toApril. Time series of the peroxide concentrations arepresented in Fig. ,. The concentrations of chemical
constituents seemed to be a#ected by the amounts ofprecipitation, which, unfortunately, could not be measured. High peroxide concentrations,῍+** mM, which
may result in serious damage to vegetation (Kumeet al., ,**+), were sometimes observed, indicating thatbackground concentrations of peroxides may be increasing in the troposphere over Japan.
The peroxide concentrations in Imizu City from,**/ to ,**3 are plotted for each month in Fig. -.
There were strong seasonal variations in peroxide
concentrations. From summer to early autumn, theperoxide concentrations were much higher than thosefrom late autumn to spring (Table +). As mentioned
above, peroxides are important SO, oxidants. The
capacity for in which SO, oxidation seems to be much
lower in winter than in summer. There may be a
condition [H,O,]ῌ[SO,] (Oxidant Limitation) in the atmosphere during the cold season. Similar seasonalvariations in peroxides have also been measured in
the gas phase (Sakugawa and Kaplan, +323; Watanabeand Tanaka, +33/). Peroxides are mainly producedby photochemical reactions (Sakugawa et al., +33*);
therefore, the formation of peroxides in the atmosphere is accelerated during the summer season.
However, peroxide concentrations in precipitation
may be dependent on not only gaseous peroxide concentrations but also scavenging processes from theatmosphere.
The peroxide concentrations in the rain and snow
in Imizu City during the winter months are shown inFig. .. Peroxide concentrations were usually higher
in rain than in snow, and relatively high concentrations of peroxides were detected in rainwater. Thescavenging processes of H,O,, the main component ofWatanabe et al.

Table +. Summary of the peroxide concentrations in the precipitation in Imizu City from July ,**/ to March,**3. N and BDL denote the number of samples and values below the detection limit,῍*.+ mM, respectively.

Fig. ,. Time series of the peroxide concentrations in precipitation in Imizu City from ,**/ to ,**3.
Measurements of peroxides in precipitation could not be performed from March to October in ,**0.

Fig. -. Seasonal variations of the peroxide concentrations in precipitation in Imizu City. The peroxide concentrations from ,**/ to ,**3 are plottedfor each month.

peroxides, from the atmosphere may di#er between
rain and snow. Watanabe et al. (,**/) reported thatthe concentrations of peroxides were much higher inrainwater in Imizu City than in snowfall at Murododaira in April ,**-.According to Sigg et al. (+33,), thedi#usional growth of snow is an important process in
H,O, scavenging. There is no fractionation between
H,O, and H,O during di#usional growth. On theother hand, H,O, may be preferentially absorbed byFig. .. The peroxide concentrations in rain (῎) andsnow (ῌ) in Imizu City from December ,**1 toJanuary ,**2 (upper panel) and December ,**2 toJanuary ,**3 (lower panel).

3

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Bulletin of Glaciological Researchrain droplets because of the high solubility of H,O,, forwhich Henry’s law constant is high. Henry’s law constant is given by Lind and Kok (+320) as follows:H῍T῎ῑexp῍AῌT῏B῎ῌ
where H (T) is Henry’s law constant (M atm῏+), T is theambient temperature (K), Aῑ00,+ and Bῑ++. Whenthe ambient temperature is +*ῒ, Henry’s law constantis about ,..ῐ+*/ (M atm῏+). Similar phenomena wereobserved at Murododaira in a snow pit in which relatively high peroxide concentrations were sometimes
detected in the granular snow layers (Watanabe et al.,,**/; ,**2). Granular snow is formed by the percolation of snowmelt water or rainwater, and peroxides
might have dissolved in the surface snowmelt water.

centrations of peroxides in dew water may be low.
On the other hand, peroxide concentrations at highmountainous sites in the air are higher in the nighttime than in the daytime (Watanabe et al., +33/). It isnatural that peroxides in dew water were muchhigher at Murododaira than in Imizu City. Kume et al.
(,**+) reported that high concentrations of H,O, in
dew water resulted in serious damage to vegetationand that OH radicals formed by Fenton’s reaction of
H,O, in the liquid phase after sunrise could damage
vegetation. To evaluate the e#ects of peroxides onhigh-altitude ecosystems, further measurements ofperoxides in dew water at mountainous sites such as
Murododaira are required.

Acknowledgments-.,

Peroxide concentrations in dew water
A summary of the measured peroxide concentrations in dew water in Imizu City and at Murododairain the autumn of ,**2 is shown in Table ,. The concentrations of peroxides in the dew water sampled in
Imizu City were *.2ῌ-.0 mM. The peroxide concentrations in the dew water in Imizu City were the same as
the H,O, concentrations in dew water in HigashiHiroshima City, where Sakugawa et al. (,**0) reported
that the peroxide concentrations ranged from below
the level of detection to -./ mM from April +331 toDecember +332. The peroxide concentrations may besigniﬁcantly lower in dew water than in rainwater atlower sites. The highest concentrations, 0/ mM in thedew water, were detected at Murododaira (Table ,).
Dew water is usually seen under calm conditionsin the nighttime and absorbs soluble gases, such asperoxides, in the ambient air. Gaseous peroxide
concentrations are very low from nighttime to earlymorning at low-altitude sites (Sakugawa and Kaplan,+323; Watanabe and Tanaka, +33/). When the windspeed is low and a boundary layer is developed, peroxide concentrations decrease rapidly after sunset(Watanabe and Tanaka, +33/). As a result, the con-Table ,. Summary of the concentrations of peroxides
in dew water in Imizu City and at Murododaira.

.

The authors thank the members of Toyama Prefectural University, the Ministry of the Environment,Toyama Prefecture, Tateyama Kurobe Kanko Inc. and
Murodo-sanso for their support of this study. Thiswork was supported in part by a Grant-in-Aid for
Scientiﬁc Research from the Ministry of Education,
Culture, Sports, Science and Technology (No. +2-+**,,and No. ,*-+*++-) and by funds from the Kajima Foundation Research Grant.

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