BulletinofGlaciologicalResearch22（2005）51づ5

5ノ◎JapaneseSocietyofSnowandIce

Measurementsol＝peroxideconcentrationsinprecipitationinToyamaandinthesnow
PitatMurododaira．nearthesummitofMt．Tateyama
KoichiWATANABE．AyumitWAl．NozomiTAKEDAandYusakuTAKEBE

DepartmentofEnvironmentalSystemsEngineering，CollegesofTechnology，ToyamaPrefecturalUniversity，Kosugi−maChi，Toyama9390398，Japan（ReceivedSeptember8，2004；RevisedmanuscriptreceivedNovember8，2004）

Abstract
MeasurementsoftheperoxideconcentrationsinprecipitationwereconductedatKosugl−maChiin

ToyamafromJune2002toJanuary2004andinthesnowpitatMurododaira，nearthesummitofMt．
Tateyama，inApri12004．TheconcentrationsofperoxidesintheprecipitationsamplesatKosugi−maChi
exhibitedarangefrombelowthelevelofdetection（＜0．1FLM）to67FLM．Theperoxidesconcentrations

weremuchhigherfromsummertoearlyautumn than thosefromlateautumn toearlysprlng．The
concentrationsofperoxidesinthesnowpitatMurododairarangedfrombelowthelevelofdetection

to2．6FLM．Thelevelofperoxidesdecreasedwithdepth．Post−depositionallossofperoxidesmighthave
OCCurred．

1．lntroduction
Hydrogen peroxide（H202）isconsidered to bean
importantoxidantofSO2（S（IV））inatmosphericliquid

been reported（Watanabe etal．，1999；2001a；2001b）．

However，thereisashortageofsuchdataonperoxides
in East Asian countries．LongTterm PerOXide data
Were nOtObtainedinJapan．Peroxideconcentrations

Water．Hydrogenperoxidehasbeenfoundtobehighly
SOlublein cloudandfogdropletsoraqueousaerosoIs

havealsobeenmeasuredinpolarsnowsamples（Nef−teletalリ1984；1995；Kamiyama and Nakayama，1992；
Kamiyama etal．，1996；Watanabe etal．，1998）．Meas−

Very rapid andindependent of the pH．The reactional．，1984）．Indiscussingperoxidesinthepastfromice（Yoshizumietal．，1984；Watanabeetal．，1996）．The re−action between H202and S（IV）in water dropletsis
between O3and S（IV），On the other hand，does noturementsofperoxidesinanicecoremaybeusefulfor
understanding past atmospheric oxidation（Neftelet

COre analysIS，itisnecessary to considerthe transfer

OCCurunderconditionsbelowpH5（MartinandDam− PrOCeSSeSin the air to snow and post−depositionalSChen，1981）．Organichydroperoxides（ROOH）aretho−ught to play animportant rolein the oxidationofS

modification（Nefteletal．，1995）．Thepost，depositional

lossofperoxidesalsowasobservedinthesnowpitsin（IV），aS Wellas H202（Lindetal．，1987）．Therefore，the the polar regions（Motoyama etal．，2001）．Snowis
COnCentrationoftotalperoxides（H202＋ROOH）inthe SeVeralmetersdeepin the highmountainsofJapan．

aqueous phaseis a usefulindicator of the oxidation

However，meaSurementSOfperoxidesinsnowathigh

Peroxideconcentrationsaremainlydependentonthe

precipitation，including snow fa11in Toyama andin

CapaCity．Moreover，PerOXides，aSWellasO3，mayCOnTelevations havenotbeen madeinJapan．
In this paper，the concentrations ofperoxidesin
tributetovegetationdamage（HewittandTerry，1992）．
meteorologicalconditions（UVradiation，temperaturethesnowpitatMurododaira，nearthesummitofMt．
andhumidity）andtheconcentrationsofatmospheric
TateyamainJapan，arepreSented，andthecharacter−pollutants（Sakugawaetal．，1990）．Largeseasonalvar− isticsofperoxideconcentrationsareexamined．

iationsintheconcentrationsofperoxideintheatmos−

phere have been observed（Sakugawa and Kaplan，1989；Watanabeand Tanaka，1995）．

Peroxide concentrations in precipitation and

2． Methods
PrecipitationsampleswerecollectedbyalOOOml

Teflonbottle（100mmID）ontheroofofthebuildingof
Cloud water have been measured，eSpeCially，in thethe college of Technology，Toyama PrefecturalUni一
United States and Europe（01szynaetal．，1988；GunzandHoffmann，1990）．Preliminarystudiesonperoxide VerSity at Kosugi−maChi，in Toyama，fromJune2002

inrainandcloudwaterincentralpartsofJapanhavetoJanuary2004．FigurelisamapofJapanshowingBulletin ofGlaciologlCalResearch

0204D6080Km

Fig．1．MapofJapanshowingthelocationsofToyamaPrefecturalUniversityandMt．Tateyama．

thelocations of Toyama PrefecturalUniversity andMt．Tateyama．The precipitation sampling was usu−

Peroxide concentrations were measured by thefluorometric method，uSing p−hydroxyphenylacetic
ally performed in the early afternoon when gaseousacid and peroxidase reagents（Lazrusetal．，1985；Ka−
peroxideisusua11yhigh（SakugawaandKaplan，1989； miyama and Nakayama，1992），aS describedin detail
WatanabeandTanaka，1995）．Samplingtimewaswith− byWatanabeetal．（1995）．Thefluorescencereagents，1in3hours．The concentrations of peroxidesin rain−
mlp−hydroxyphenylaceticacid（1．5×102M）inapho−
Water Were meaSuredimmediately after collection．
Sphate buffer（adjusted to pH7）andlmlperoxidase（50unitmrl）inaphosphatebuffer（adjustedtopH7），
Snowfall samples were melted at room temperature

andimmediatelyanalyzed．
The snow pit study was performed at Murodo，daira（36．60N，137．60E，2450m altitude），nearthesum−
mitofMt．Tateyama（Fig．1），On24−25Apri12004．The

SnOWCOVeratMurododairawasabout6mdeep．The
SamPlingintervalfor analysis was aboutlOcm．TheSnOW SamPles were transported to Toyama Prefec−
turalUniversityon25Aprilandpreservedinafreezer（一100c）．The measurements of peroxides were per−formed within one week．The preliminary snow pit
StudyforperoxidemeasurementsatMurododairawas

made on20−21Aprilin2003．Snow samples from thepit wa11were taken from the top to a depth ofl．5m
depth．Peroxide concentrationsalso were measured
within one week．

Wereaddedtothelmlliquidsample．Severalminutes

later，1mlNaOH（1N）wasaddedtostabilizethegener−
atedfluorescence．The amount offluorescencein theSOlution was determined by afluorescence spectro−

photometer（HitachiCorporation，ModelF−2500）．This

method determines the concentration of totalperox−ides（H202＋ROOH）．TodiscriminateH202fromROOH，Catalaseregenthasbeenused（Lazrusetal．，1985；Wat−anabeetal．，1995）．ROOH arealsoimportantoxidants
Of S（IV），therefore we measured only totalperoxides．

Tocalibrate，aStandardH202SOlutionwasmadefrom
a stock solution that was titrated with a standard

KMnO4SOlution．

ThepHandelectricconductivity（EC）inthesam−

plingsolutionweremeasuredwithapHmeterandanWatanabe etal．

ニラ、丁JTablel．Summary of the concentrations of peroxidesinprecipitation at Kosugi−maChi，Toyama．BDL denotes values
belowthedetectionlimit（＜0．1〃M）．
Date

PrecipitationformPeroxides山M）

14 June 2002

Rain

4110 July 2002

Rain

27

15 October 2002

Rain

6．2

8 November 2002

Rain

BDL

13 November 2002

Rain

0．20

27 November 2002

Rain，Snow

BDL

5 March 2003

Snow

0．43

5 April 2003

Rain

BDL

20 April 2003

Rain

22

13 June 2003

Rain

5020 June 2003

Rain

67

1 September 2003

Rain

3124 September 2003

Rain

60

23 October 2003

Rain

1．020 November 2003

Rain

BDL

12 December 2003

Rain

BDL

14 January 2004

SnowBDLEC meter，reSpeCtively．Unfortunately we could notmeasurethepHandECintheprecipitationsamplesat

Kosugi−maChi．The pH and EC were measured only
SnOWpitsamplesatMt．Tateyama．

3．Results and discussion
J．／．R〃■0．1イ（左−（、0〃（、ぐ〃JJてJJ山JJ∫わJ♪J■（で∫♪∫山JわJJわJ了 叩（川J（JAsummaryofthemeasuredperoxideconcentra−

tionsin precipitation（rainwaterand snowfall）at Ko−
Sugi−maChi，Toyama，fromJune2002toJanuary2004

isshownin Tablel．The concentrationsofperoxides

tochemicalreactions（Sakugawa etal．，1990）；there−

fore，theformationofperoxidesin theatmosphereis
acceleratedduringthesummerseason．Asmentioned

above，PerOXidesareimportantoxidantsforSO2．The
CapaCity of SO20Ⅹidationseemsto be muchlowerin
Winterthaninsummer．Theremaybeacondition［H202］＜［SO2］（OxidantLimitation）intheatmosphereduト

ingthecoldmonths．Theconcentrationsofperoxides
inmostoftheprecipitationsampleswerebelowdetec−
tionlimitin the cold seasons．Peroxides might havebeen consumed by SO2in the atmospheric droplets，especiallyln Winter．

exhibitedarangefrombelowthelevelofdetection（＜0．1pM）to67FLM．Theconcentrationsofchemicalcon− 、フ．ヱ 凸−「り．1イ（左〉（、…J（、ぐ〃け（JJわJJJわJ〃圧，∫Jい！ぐ♪′J（〜りJJ〃1）（J（トStituentsseemtobeaffectedbyanamountofprecipi−（∫〃汀（JCOuld not be measured．Thelevelof peroxides was
lower than thatin cloud water at high elevationsin

Rangesinperoxidesconcentrations，pHandECin
thesnowpitatMurododairaarepresentedinTable2．
The concentrations of peroxides ranged from below

WaternearthesummitofMt．Norikurawere3r180FLM

peroxideconcentrationsin thesnowpitin Apri12004

entsareusua11ycondensedincloud water．
There were strong seasonalvariations．The conT
Centrationsofperoxidesfromthesummertotheearly
autumn were much higher than those from the late

OfpHandECarealsopresented．TherangesinpHandtation．Unfortunately，the amounts of precIPitation

Japan．For example，perOXide concentrationsin fog thelevelofdetectionto2．6FLM．Averticalprofileofthe
insummer（Watanabeetalリ1999）．Chemicalconstitu−

autumn to the early spring．Similar seasonalvaria−

tionsofperoxideshavealsobeenmeasuredinthegas

phase（Sakugawa and Kaplan，1989；Watanabe andTanaka，1995）．Peroxidesaremainlyproducedbypho−

isshowninFig．2．Thesnowstratigraphyandprofiles
ECwerefrom4．6to5．5andfrom2to22〟S／cm，reSpeC−

tively．There was a weak relationship between theperoxideconcentrationsandthepH．AweaknegativeCOrrelation between the peroxides and the EC also
WaS Seen．The highest concentrations of peroxides
were seen at the top of the snow layer which wasCOmpOSed of new snow．Thelevels of peroxides de−Bulletin ofGlaciologlCalResearch

54

Table2．Rangesin peroxide concentrations，PH，and ECin the snow pitsat Murododairaon20−21
Apri12003and24¶25Apri12004．N and BDL denote the number of samples and values below
thedetectionlimit（＜0．1pM），reSpeCtively．
Date

Samplingsnowlayers N

Peroxides山M）

pHEC山S／cm）

20−21Apri12003

0〜1．5mdepth

160．21′〜2．04．9′〜5．64〜452425 April 2004

0〜6．Omdepth59

BDL〜2．64．6〜5．52′｝22

山

仙（〝叫川と010

細仙lj

鵬．
餌払（〟訂細5j

畑‥‥‥‥‥‥
︵−こ一三
占川︵∈︶
一三
占山l︵j一⁝凸山ll

か餌∽仙相仙帥和∽

机

Fig．2．Snow stratigraphy and verticalprofiles of peroxide concentrations，pH，and ECin the snow pit at Murododaira，nearthesummitofMt．Tateyama，On2425Apri12004．

CreaSed with depth．The concentrations were below
the detectionlimitin most of the samples be10W4m（Fig．2）．The snow at thelowerlayers was deposited，When the photochemicalformation of peroxidesis
SuppreSSed．Alowlevelofperoxidesmighthavebeen

foundin the deposited snowfall；in addition，pOSt−

depositiona1loss of peroxides seemed to occur，inparticular，inthelowerlayers．However，detailsofthemechanism for theloss of peroxidesin the snow pit
arenotavailableatthispoint．
There arecomparable peroxide datain thesnow
pitin polarreglOnS．The peroxides concentrations at
Murododaira werelower than thosein snow samples

from thepit wallat NGRIP，Greenland（Motoyamaetal．，2001）．Siggetal．（1992）reportedthatahighconcen−

trationofH202intheairwasobservedduringsummer
at Summit，Greenland and the H202COnCentrationin
freshsnowsampleswasaround20FLM．Relativelyhighconcentrations of H202 were detected in the snow
layers deposited during summer and autumnin Gre，

daira on20Aprilin2003．Peroxide concentrationsin

theatmosphereareusuallylargeathighaltitude（Kle−inman and Daum，1991；Watanabe etal．，1995）．How−
ever，the concentrations of peroxides werel．OpM at
Murododaira but 22pM at Kosugi−maChi（Tablel）．

The main component of peroxides seems to be H202．
Scavenging processes of H202 frOm atmosphere may
be differentin rainwater and snowfall．According toSiggetal．（1992），thediffusionalgrowthofsnowisan

important process of H202SCaVenglng．Thereis nofractionation between H202 and H20 during diffーusionalgrowth．Ontheotherhand，H202maybepref−

erentially absorbed by rain droplets because of thehigh solubility of H202，for which Henryslaw con−Stantis high．The Henryslaw constantis glVen byLind and Kok（1986）asfo1lows：〃（T）＝eXp（A／T一β），

peroxidesatMurododairaweresimilartothoseinthe

WhereH（T）isHenry slawconstant（Matml），Tistheambient temperature（K），A＝6621and B＝11．WhentheambienttemperatureislOOc，theHenry slawcon−
stantisabout2．4×105（Matml）．

02in Svalbardwaschangedbyperocolationofsnow−

Acknowledgments

dairamight havealso beenmodifiedbysnowmelt．
Peroxide concentrations may be higherin rain−
Water thanin snowfall．We simultaneously collected

TheauthorsthankProfs．K．Kawada，H．Satake，K．
SuzukiandT．Iida，Drs．M．Igarashiand S．Matoba，K．
Kawashima and C．Natori，and the members of Toy−
ama University，Nagoya University，Sinsyu Univer−enland（Motoyamaetal．，2001）．Theconcentrationsof
SnOWpitsinSvalbard（Motoyamaetal．，2001）．TheH2
melt water after accumulation．Peroxides at MurodoT

rainwater at Kosugl−maChiand snowfallat Murodo−Watanabeetal．
Sity，andthesubcommitteeofsnowandicechemistry
fortheirsupportofthesnowpitstudyatMt．Tatey−
ama．Thiswork wassupportedinpartbyaGrant−in−
AidforScientificResearchfromtheMinistryofEdu−
Cation，Culture，Sports，Science and Technology（No．
16710011）．

55

inpolarsnow and theirrelation toatmosphericchemis−try．InIceCore StudiesofBiogechemicalCycles，NATO
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Sakugawa，H．and Kaplan，Ⅰ．R（1989）：H202and O3in theatmosphereofLosAngelesanditsvicinity：factorscon−
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