EnvironmentalGeochemicalCharacteristicsandSourcesofOrganicComponentsinHydrothermalEnvironments,Japan ΰΊ̮Ῐ̯ῑῦ̮῜ῥῑ̮Ῐ̯ῖ̮̮ῠῢ̯῏̮Ὶῐ̮῎῔Ῑῗ

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Abstract

Environmental Studies, School of Social Information Studies, Otsuma Women’s University, Karakida

ulty of Science, Tokyo University of Science, Kagurazaka , Shinjuku-ku, Tokyo , Japan.

ATSUMOTO ATO AGASHIMA

UGIMORI AKEMURA

ology, Faculty of Science, Tokyo University of Science,Kagurazaka , Shinjuku-ku, Tokyo Department of , Tama-shi, Tokyo , Japan.

Department of Chemistry, Fac- Department of Bi- , Japan.

Department of Biology, Toho University Faculty of Medicine, Omori-nishi , Ohta-ku, Tokyo , Japan.

Organic components in sediment samples from Kusatu hot spring sources (Shirahatanoyu,

from . . and . . , respectively, were relatively low, while TOC/TN weight

and Yubatake- samples are largely derived from vascular plant debris, while Yubatake- , Yubatake and Sainokawara, etc.) in Gunma Prefecture, and deposit samples from Yunotsu

J. Hot Spring Sci.

hot spring source in Shimane Prefecture were studied to clarify their environmental geo- chemical features, sources and thermal stresses. Total organic carbon (TOC) and total nitrogen (TN) contents in sediment samples from Kusatsu hot spring sources ranging ratios of the samples ranging from . to were very high. Environmental geochem- ical features of organic compounds, in addition, revealed that organic components are derived from microorganisms, such as bacteria and algae, vascular plant debris in various ratios, and are derived from human activity. Especially, Shirahatanoyu, Oninochagama

Genki I. M , Takayuki S , Hideyuki N , Kenji S and Tetsuo T

. Kusatsu and Yunotsu Hot Spring Sources

Environmental Geochemical Characteristics and Sources of Organic Components in

Hydrothermal Environments, Japan

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acids showed that organic components in the samples are mainly originated from thermo- Sainokawara- and Sainokawara- samples are mainly attributed to unicellular red alga

( ).

TOC and TN contents in deposit samples from Yunotsu hot spring source ranging from . to . and . to . , respectively, were very low, revealed that de- posits were mainly composed of inorganic substances. Very low TOC/TN weight ratios ( . . ) along with high relative abundance of branched ( - and -) alkanoic philic bacteria.

Thermally epimerized triterpanes and steranes were found both in Kusatsu and Yunotsu hot spring samples with various thermal maturities. They suggest strongly that organic components in the samples are a ected by thermal stresses in the long period of time, together with some influences of petroleum products pollution by human activities, such as heavy oils, lubricants and asphalts.

Key words : Kusatsu hot spring source, Yunotsu hot spring source, sediment, organic components, hydrothermal environments, thermal stress

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Photo Deposit at Motoyu source of Yunotsu hot spring, Shimane Prefecture.

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Table Water temperature, pH, total organic carbon (TOC) and total nitrogen (TN) concentrations in sediment samples from Kusatsu hot spring sources

Table Total carbon (TC), total sulfur (TS), TOC, TN and total inorganic carbon (TIC) concentrations in deposit samples from Yunotsu hot spring source*

Samples were taken on November . Water temperature and pH were . and . , respectively.

Sample Water temp./ pH TOC/ TN/ TOC/TN Remarks

Shirahatanoyu Sediment

Kusatsu W Sediment

Yubatake Sediment

Yubatake ND ND ND Pebbles with attached algae

Sainokawara ND ND ND Pebbles with attached algae

Sainokawara ND ND ND Pebbles with attached algae

Rurinoike Sediment

Oninochagama Sediment

Tourounoike Sediment

Tourounoike Sediment

ND : Not determined.

Sample TC/ TS/ TOC/ TN/ TIC/ TIC/TC/ TOC/TN TS/TOC

Y Y Y a*

Y b*

Y c*

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* a, b and c are top ( cm), middle ( cm) and inner ( cm) layers, respectively.

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. Table W TOC .

. . Williams ; Matsumoto ,

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TOC TN . Table TOC TN

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Cyanidium caldarium Galdieria

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Sainokawara source in Kusatsu hot spring sources. Arabic figures on the peaks denote Fig. Mass chromatogram (m/z ) of hydrocarbons obtained from Rurinoike sediment of

carbon chain length of n -alkanes. i : Isoprenoid akanes.

, ;

TOC TN

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Table - Normal and acyclic isoprenoid alkanes found in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot spring source

KusatsuYunotsu AlkaneShirahata- noyuKusatsuoWYubatakeo+Yubatakeo,*+Saino- kawarao+*+Saino- kawara-,*+Ruri- noikeOnino- chagamaTourou- noikeo+Tourou- noikeo,Yo+Yo,Yo- noShort +/ +0 +1 +2 +3

*4.- *403 +4/+ *43. +4-- +4/3 ,4,/ -403 .4,, .4+0

*4*. *4*. *4,0 *4*1 *4*1 /4++ +401 .1411 +40/ 04/+

-4*+ ,4+3 -34,0 -4+1 143*

-40. ,4*1 34*1 ,4+2 ,42*

+4*, *4.* +24*. *4/3 ,4*2 +401 +4-0 14-0 +4/+ ,4*+

.43, .4/1 +/4*/ .4.- 04-+

,4-* ,42/ -4*+ ,40- -4/3 /41* 14-* +,4,/ 04-3 24++

*4+, *4*/ +4-/ *4*1 *4,2 -43+ /4/, 240+ 04** /423

noShort/ῌ.43*+/43**4.20,41+//4/.+3410,,4+-+-43+-/4,2+.4-2-341/+422,343. noLong ,* ,+ ,, ,- ,. ,/ ,0 ,1 ,2 ,3 -* -+ -, -- -. -/ -0 -1 -2 -3 .*

+4-- +410 ,40* .40+ .4+0 141* 0400 +.43/ 1422 +.431 /43. 24.3 -4,* -4/+ +4./ +42- *41, *4.3 *4-0 *4** *4**

.41, .40- /400 0423 /4-3 043. .4/3 34+- -421 +*4+, -4.0 ,4/3 .4/0 *40* +4,1 *422 *41, *40* *4/- *4** *4**

*4*/ *4++ *41. ,43/ 0422 ++4*1 +.4+1 34+/ +.4-0 +,42/ 342. 0430 .4-* ,4-2 +4-/ *42+ *4/+ *4-0 *4,/ *4+1 *4+,

*43, ,4*3 ,4,2 042, ,403 -422 ,40, -4-1 ,400 -4+, +420 +42, *43+ *40/ *4-3 *4,1 *4,+ *4+0 *4+2 *4** *4**

+411 ,4/+ ,41+ 04/2 ,423 -4/3 -4-+ .4-- -4+1 -4-0 ,4+. +423 +4+- *42* *4/3 *4.* *4-, *4,+ *4,+ *4** *4**

,4+* -4*1 ,41/ .421 ,4/. .4+0 ,4/2 04*1 -421 34*, /4,- 142+ /4.. /4++ .4++ ,43* ,4-/ +4-0 +4,+ *40- *40+

*40- -4-2 +4-1 /4/* +423 242. ,4-0 +0411 -4-- +14./ ,4,. 04.0 ,4*3 +40- *420 *40. *4./ *4,1 *4,+ *4+- *4**

342* +40, *41+ +4*- *4/0 +4+- *4.1 +4-1 24,* +41- +4*2 +4/+ *40* +4./ *4.3 *41- *4-0 *4+2 *4** *4** *4**

-4.3 -4+* ,42- .4,2 ,4., .40* ,4*1 0400 ,4+1 240, ,4/1 0432 ,4+2 ,422 +4,/ +4*2 *41. +4/3 *40/ *4** *4**

-4*, -4*3 .43+ /433 24-2 142+ 240- 24+* 040+ .4-3 /4+* -4*, -43/ +4-. ,43- *400 ,4*+ *4-0 +4-/ *4,, *43+

.402 .4/3 -401 ,43, ,43, ,4/+ ,4/. .43. -4+- .4++ ,42- -4.3 ,4,1 +421 +4/3 +4++ +4,1 *40, *433 *4,1 *4.1

*4*. *4,. *4+2 *40+ *411 +43/ ,4,+ -401 ,42+ -412 ,4-3 ,4-+ +4,+ *43+ *4.1 *4-/ *4+0 *4*0 *4*0 *4** *4**

.400 -4., -4*2 ,4/2 ,4,/ +43+ +432 ,4.0 ,4+* -4++ ,43, .4*0 ,4/- ,422 .4.1 +4.1 -4./ ,42+ -4*. +410 *4**

noLong/ῌ3,40*114+0334-3-0423.+42311411104.3--4*,0*4+02,411/,42+,.4+0/043- Isoprenoid i+3 i,* i-*

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hopane. : (H), (H) Hopane. : ( S) (H), (H) , Bishomohopane. : ( R) (H), (H) , Bishomohopane. : ( S) (H), (H) , , Trishomohopane. : Tetrakishomohopane. : ( R) (H), (H) , , , Tetrakishomohopane. : ( S) (H), (H) , , , , Pentakishomohopane. : ( R) (H), (H) , , , , Pen- Fig. Mass chromatogram (m/z ) of triterpanes obtained from Rurinoike sediment of Sainokawara source in Kusatsu hot spring sources. : (H) , , trisnorneoohopane. : , , tris- norhop ( ) ene. : (H) , , trisnorhopane. : (H) , , trisnorhopane. :

(H), (H) norhopane. : Hop ( ) ene. : (H), (H) normoretane. : (H) oleanane. : (H), (H) hopane. : Neohop ( ) ene. : C Hopene. :

C Hopene. : ( S) (H), (H) Homohopane. : ( R) (H), (H) Homo-

( R) (H), (H) , , Trishomohopane. : ( S) (H), (H) , , ,

takishomohopane.

:

unresolved complex mixture of hydrocarbons UCMH

UCMH .

Table i C i C

i C UCMH .

m z Fig. S C C

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Matsumoto and Watanuki, Y

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o o o o o

o o o

o o o o o o

o o o o o o

o o o o

o o o o o o

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a

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Table . Triterpanes, triterpenes and m oretanes found in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot spring sourc e

KusatsuYunotsu CompoundShirahata- noyuKusatsuoWYubatakeo+Yubatakeo,*,Saino- kawarao+*,Saino- kawarao,*,Ruri- noikeOnino- chagamaTourou- noikeo+Tourou- noikeo,Yo+Yo,Yo-*- Composition/ῌ*+ +:+2a(H)o,,,,3,-*oTrisnorneohopane ,:,,,,3,-*oTrisnorhopo+1(,+)oene -:+1a(H)o,,,,3,-*oTrisnorhopane .:+1b(H)o,,,,3,-*oTrisnorhopane /:+1a(H),,+b(H)o-*oNorhopane 0:Hopo+1(,+)oene 1:+1b(H),,+a(H)o-*oNormoretane 2:+2a(H)oOleanane 3:+1a(H),,+b(H)oHopane +*:Neohopo+-(+2)oene ++:C-*:+Hopene +,:C-*:+Hopene +-:(,,S)o+1a(H),,+b(H)o-*oHomohopane +.:(,,R)o+1a(H),,+b(H)o-*oHomohopane +/:+1b(H),,+b(H)oHopane +0:(,,S)o+1a(H),,+b(H)o-*,-+oBishomohopane +1:(,,R)o+1a(H),,+b(H)o-*,-+oBishomohopane

.4*, *4,, -4*- +4+2 +14-* -4/3 +4/. *413 +-43, +4*1 -4.2 ,42, 24+0 041. *43. 04+* .4+2

-4++ *4+1 ,43+ +4+0 +14.- .4.+ +41+ +403 +/43* +4/2 34/. -4/2 0433 /41. +4+0 .4+2 -4,0

.43. *4.+ -4,. *42+ +143. -4-- +4.- *402 +.40+ +4-/ 142/ -402 142/ 04-* *43- /4.3 -4--

+4-* ,4-0 ,40/ 3420 +*43/ +4,/ ,4.- *4** ++43* ,4+3 ,*4-1 /410 .4/+ -42, 14+0 ,42, +43*

+4,1 ,431 +413 -4-2 +*410 -4** +4-0 *40- +*430 .4+1 .-4-3 *4** .43* -4*2 -4/1 *433 ,4+*

,4-/ +4*3 ,4,* ,4-/ +04,2 *43+ +410 *40- +.4+0 ,4., +,4+1 ,4/. 042, /422 ,42* .41- ,43/

+4,2 *43- +4.3 +4*2 34+3 ,412 *43- *4/+ 24-3 +4/- .14,2 ,400 -431 -4+3 +41/ ,400 +421

+4*, /4,2 +4,1 +4// +*4/1 04.2 +43- +423 *4.. *4** 24/1 +*4-2 ,4-1 04.2 24,3 -4,* +40,

+4,. +4.+ *42+ *4+3 .43+ .431 *4** *4** /4** *43/ 0-4.. 04,/ ,4+* +4-0 *4** +4,. *403

-41. *4,. ,4+* *4,2 +24,- -4+2 +4*2 *4/2 +,4++ -43+ +/4.- ,4+, 24*, /42- *43* .4.0 ,420

+41/ *42- ,42. +4,/ +04-. .40, +4+0 +4.0 ++4,3 ,402 +-4** +4,* 14/1 .430 +4*3 04-2 .4+/

-4+, *4/3 ,41- *432 +/4+1 ,4+/ +4+0 *4/. +-4+3 +42, +/4-. ,4*2 141* /43* *42. /4+. -4./

ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ ῌ +2:(,,S)o+1a(H),,+b(H)o-*,-+,-,o Trishomohopane.40/-4-,-42*+413+401-4,/+42++4-.*430-4*0.4/+.4*2ῌ +3:(,,R)o+1a(H),,+b(H)o-*,-+,-,o Trishomohopane,43-,4+3,4--+4-0*4**,4/*+4-,1401*40-,4/1+410,402ῌ ,*:(,,S)o+1a(H),,+b(H)o-*,-+,-,,--o Tetrakishomohopane-4.1-4,.-4+0+4-/*4**-4*++4.1,4+*+4.--4+,-4,+-4*0ῌ ,+:(,,R)o+1a(H),,+b(H)o-*,-+,-,,--o Tetrakishomohopane,4,/+40-+431+4--*4**,4*,+4*-++40**4.2+423-4+1,4*2ῌ ,,:(,,S)o+1a(H),,+b(H)o-*,-+,-,,--,-.o Pentakishomohopane-402-4*2,4/++4//*4**-40,+403+433*41,,4+1+431-4--ῌ ,-:(,,R)o+1a(H),,+b(H)o-*,-+,-,,--,-.o Pentakishomohopane-43-,4*,,4*/+4.,*4**-4/.+4+0-431+4,/,4++,413,421ῌ (,,S/,,R)o+1a(H),,+b(H)o-*oHomohopane (,,S/,,R)o+1a(H),,+b(H)o-*,-+oBishomohopane+4,+ +4.0+4,, +4,2+4,/ +40/+4+2 +4.2+4/3 *4.1+4+0 +40*+4,/ +4.,*4-0 +432+4/. +42*+4-2 +4/0+4/- +4/.+4-* +4.3ῌ ῌ (,,S/,,R)o+1a(H),,+b(H)o-*,-+,-,o Trishomohopane+4/3+4/,+40-+4-,ῌ+4-*+4-1*4+1+4/-+4+3,4/1+4/,ῌ (,,S/,,R)o+1a(H),,+b(H)o-*,-+,-,,--o Tetrakishomohopane+4/.+433+40++4*,ῌ+4.3+4.,*4+2-4**+40/+4*++4.1ῌ (,,S/,,R)o+1a(H),,+b(H)o-*,-+,-,,--,-.o Pentakishomohopane*43.+4/,+4,,+4*3ῌ+4*,+4./*4/**4/1+4*-*41++4+0ῌ *+ArabicfigurescorrrespondpeaknumbersinFig.-.*,Pebbleswithattachedalgae.*-Notdetected.

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cholestane. : ( R) (H), (H), (H) Cholestane. : ( R) Ethyl (H), (H) diacholestane.

: ( R) Methyl (H), (H), (H) cholestane ( R) methyl (H), (H), (H) cholestane.

S) Methyl (H), (H) diacholestane. : ( R) Methyl (H), (H) diacholestane. : ( S) (H), (H) Cholestane. : ( S) (H), (H), (H) Cholestane ( R) methyl (H), (H) dia-

: ( S) Ethyl (H), (H) diacholestane. : ( S) Methyl (H), (H), (H) cholestane.

lestane. : ( S) Ethyl (H), (H), (H) cholestane. : ( R) Ethyl (H), (H), (H) kawara in Kusatsu hot spring sources. : ( S) (H), (H) Diacholestane. : ( R) (H), (H)

: ( S) Methyl (H), (H), (H) cholestane. : ( R) Methyl (H), (H), (H) cho- cholestane ( R) ethyl (H), (H), (H) cholestane. : ( S) Ethyl (H), (H), (H)

Mass chromatogram (m/z ) of steranes and diasteranes obtained from Rurinoike sediment of Saino-

(H), (H), (H) Cholestane. : ( S) Methyl (H), (H) diacholestane ( R) (H), Fig.

Diacholestane. : ( S) (H), (H) Diacholestane. : ( R) (H), (H) Diacholestane. : (

cholestane. : ( R) Ethyl (H), (H), (H) cholestane.

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Table / Steranes and diasteranes found in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot sprring source

KusatsuYunotsu CompoundShirahata- noyuKusatsuoWYubatakeo+Yubatakeo,*,Saino- kawarao+*,,*-Saino- kawarao,*,Ruri- noikeOnino- chagamaTourou- noikeo+Tourou- noikeo,Yo+Yo,Yo-*- Composition/ῌ*+ +:(,*S)o+-b(H),+1a(H)oDiacholestane ,:(,*R)o+-b(H),+1a(H)oDiacholestane -:(,*S)o+-a(H),+1b(H)oDiacholestane .:(,*R)o+-a(H),+1b(H)oDiacholestane /:(,*S)o,.oMethylo+-b(H),+1a(H)odiacholestane 0:(,*R)o,.oMethylo+-b(H),+1a(H)odiacholestane 1:(,*S)o/a(H),+.a(H),+1a(H)oCholestane

.40. ,43+ *41+ ,43* ,4., +4/- 04/+

.4.0 -4-0 *42. ,4*, +432 +402 040/

-400 -4*0 +40+ +4*. ,4.+ -4,1 /412

+*4*, *4** *4** *4** *4** *4** 24.*

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,4/1 ,40. +4+, -4+. +4/0 .4,/ 34+*

.42* .4., *412 ,4.1 ,4/1 /4-/ /4-2

*4** *4** *4** *4** *4** *4** 242.

.4.. -4/0 *40. ,40. -41. ,4., 04,+

.42. -4+2 ,42+ ,4,, 34+. *4** ++4/,

14-3 ,4+* *4** *4** *4** ,24-2 /40-

-4/3 ,403 *42+ ,43. ,41+ -4-+ /430

ῌ ῌ ῌ ῌ ῌ ῌ ῌ 2:(,*S)o,.oMethyl-+-b(H),+1a(H)odiacholestane ῍(,*R)o/a(H),+.b(H),+1b(H)ocholestane.430-431/40234-3ῌ.4+1-4//*4**.4*/24+3-4--.4,*ῌ 3:(,*S)o/a(H),+.b(H),+1b(H)oCholestane ῍(,*R)o,.omethylo+-a(H),+1b(H)odiacholestane-4./+43--41,340*ῌ-40,-4,/*4**/4*2-4//-4/0-43.ῌ +*:(,*R)o/a(H),+.a(H),+1a(H)oCholestane ++:(,*R)o,.oEthylo+-b(H),+1a(H)odiacholestane +,:(,*S)o,.oEthylo+-a(H),+1b(H)odiacholestane +-:(,*S)o,.oMethylo/a(H),+.a(H),+1a(H)ocholestane

14-3 043- ,4/0 -4-,

3400 040. ,4-/ ,4,2

/400 /4,. .4,. -4*2

2430 24.. *4** *4**

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/4+0 /4,, *400 +420

.4,. 04-, +403 -41,

-.431 *4** *4** *4**

-433 0411 ,4-, ,413

+,4*. *4** *4** *4**

*4** *4** *4** *4**

14*2 1433 ,4** .41.

ῌ ῌ ῌ ῌ +.:(,*R)o,.oMethylo/a(H),+.b(H),+1b(H)ocholestane῍ (,*R)o,.omethylo/b(H),+.a(H),+1a(H)ocholestane.4+,/43./4-,*4**ῌ-4*104+2*4**0420/40+,4*2/4,+ῌ +/:(,*S)o,.oMethylo/a(H),+.b(H),+1b(H)ocholestane +0:(,*R)o,.oMethylo/a(H),+.a(H),+1a(H)ocholestane +1:(,*S)o,.oEthylo/a(H),+.a(H),+1a(H)ocholestane

-4/+ -40/ 2401

.4,0 041, 24,0

341, ,403 34*2

*4** *4** +.401

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/41, /42/ 14/+

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.4./ ,43* +,4,2

*4** 04// -4.2

*4** *4** 0433

.41/ .4*3 242.

ῌ ῌ ῌ +2:(,*R)o,.oEthylo/a(H),+.b(H),+1b(H)ocholestane῍ (,*R)o,.oethylo/b(H),+.a(H),+1a(H)ocholestane34/,24-.34.0+040+ῌ++4,.242-*4**+*4,034.-+.4.234-*ῌ +3:(,*S)o,.oEthylo/a(H),+.b(H),+1b(H)ocholestane ,*:(,*R)o,.oEthylo/a(H),+.a(H),+1a(H)ocholestane24/, ++413/4+. +-4/.14./ 142,*4** +-43+ῌ ῌ242. ++41/042/ +*4/+*4** /04+314./ 14+1/4*1 +,4-0343* +04+/14/, 24-,ῌ ῌ Relativeabundanceof(,*R)o/a(H),+.a(H),+1a(H)osterane/ῌ C,1 C,2 C,3 (,*S/,*R)o,.oEthylo/a(H),+.a(H),+1a(H)ocholestane

-,4. +04* /+40 *41.

-,4- ,,4/ ./4, *40+

-/4* +040 .24- +4+0

-34, *4* 0*42 +4*/

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-243 ,+4, -343 *4,2

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-04- ,+4* .,41 +4*0

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in Kusatsu hot spring sources. Arabic figures on the peaks denote carbon chain length of alkaoic acids.

Fig. Mass chromatogram (m/z ) of fatty acids obtained from Rurinoike sediment of Sainokawara source

i : a : m : n : Carbon chain length : number of unsaturation.

n iso. anti-iso.

Table

m z m z Fig. C C

Fig.

Table

Table

TIC m/z , m/z , m/z , m/z , m/z Fig.

Table

o m p

p cis p trans cis

trans

/ 1.

,1 ,3

o /2 ,**3

0 -

+,3 ,+/ 0

/ - ,. / -

,. ,. / - ,.

/ - ,. /

- ,. ,. / - ,.

0

1 ,.

0 ,.

1 .

,01 ,3- ,31 -,1 --2 1

o o o

o o

2

b b

b

a b a

b a b

ῌ ῌ

Table 0 Fatty acids found in sediment samples from Kusatu hot spring sources, and deposit samples from Yunotsu hot spring source

KusatsuYunotsu FattyacidShirahata- noyuKusatsuoWYubatakeo+Yubatakeo,*+Saino- kawarao+*+Saino- kawarao,*+Ruri- noikeOnino- chagamaTourou- noikeo+Tourou- noikeo,Yo+Yo,Yo- noShort +, +- +. +/ +0 +1 +2 +3

*4,. *4*, *4.- *4,* -343/ *4/* +,4*3 *4*3 ++4+- *4-3 -431 +4,/ --4+1 *43. +-4+, *4,, +/4/- *4-0 -4/0 +4,1 -*4-/ +4.. +,4-3 *4+3

*412 *4*2 +4/1 +4.- 0+4,1 ,400 +.4-/ *4+1 +4*3 *4*1 ,4,2 +4+1 1*4-2 +4,1 2433 *4*2 +40- *4+. ,+4*/ ,433 ..4/. *4/2 -4,1 *4*2 ,4.0 *4*2 /4+/ +4*2 -,4*- *42, 14.+ *4,/

,400 *4*2 ,40/ *423 ,04,/ ,4-1 +34*0 +4*+

-432 *4+- 1432 -411 -+4,/ *43. 04+3 *4,*

,4/0 *4++ /4+1 ,432 ,.4-* +4** /4.. *4-2 ,4/2 *4*2 /4/+ +4-, 0*4-0 +423 .413 *4+- ,403 *4+, /4.2 +4., 0*4.1 +430 .431 *4+- 24,. *4+0 24-, +4++ /04/2 +4,- .42+ *4+.

noShort/ῌ/-4/,0.4+20/4*32,4-+2/4--1.4,1.34-*/.431/.4...+43/10400114,/2*4/3 noLong ,* ,+ ,, ,- ,. ,/ ,0 ,1 ,2 ,3 -* -+ -, -- -.

04*/ *4.0 ,402 *40, -4+2 *4.1 +4,0 *4+, *400 *4-- *4-3 *4+0 *4,1 *4** *4**

,4+. *4-. -43* +4*+ 142- *42/ -4,* *4-3 +42+ *4-+ +4-2 *4+0 +4*/ *4*/ *4,.

+4*- *4,3 .41, +4-* 34*2 +4,, -40, *4/* +4/- *4-/ +4-, *4,0 *423 *4** *4**

*4.1 *4*. *4+, *4*/ *4-. *4*/ *4,- *4*, *4*/ *4*+ *4*+ *4** *4** *4** *4**

*4,+ *4*- *4+, *4*. *4,+ *4*- *4+* *4*+ *4*/ *4** *4** *4** *4** *4** *4**

*4-. *4*0 +4+. *4++ +410 *4*/ *4+1 *4*, *4*3 *4*, *4*2 *4*+ *4*/ *4** *4**

,411 *4.2 ++4.0 +4-, +,41. *433 .4*+ *4., ,4-+ *4-/ +433 *4+2 *43. *4*/ *4+3 -423 *42. /4+3 ,4.- 243+ +432 .40- *422 ,4/+ *41. ,4*. *4-* *41- *4*2 *4+2 +4/0 *4/. /41, *423 340, *4/1 ,4/* *4-0 +4,0 *4,, *43/ *4+* *4.+ *4*- *4*3 ,43- *42, ++43- +42, +.43+ +4-1 .4*3 *4/2 ,4-. *4.2 ,4*/ *4,* *42, *4*0 *4+0

*4.+ *4*. *4.- *4*- *4+- *4*+ *4*/ *4*+ *4*2 *4*+ *4*/ *4** *4** *4** *4**

*4.+ *4*- *4., *4*- *4++ *4*+ *4*. *4*+ *4*2 *4** *4** *4** *4** *4** *4**

*4/* *4*0 *4-3 *4*1 *4-/ *4*0 *4+0 *4*- *4+, *4*, *4+- *4*+ *4+* *4** *4**

noLong/ῌ+0401,.400,04+,+4.**413-423.*4,+-/4--,.42+..4/.+4,.+4+/,4** Branched i+- i+. i+/ i+0 i+1 a+- a+/ a+1

*4*+ *4*, *4,* *4+* *4*0 *4*+ *4*- *4*0

*4*1 *4.0 *4., -4,0 *401 *4+/ *4.3 +4-,

*4*3 *420 *433 +423 *4,. *4+- *4,+ *4.,

*4*+ *4+* *4,. .40. *4*2 *4+2 *4*2 *4/3

*4*+ *4++ *4+2 .4,- *4*0 *4+2 *4+- *402

*4*+ *4+* *4-- ,41/ *4++ *4*- *4.* *4/.

*4*+ *4*0 *421 +4/, *4,, *4*3 *4,0 *40-

*4*+ *4*. *4-* ,4*- *4,2 *4*. *4*3 *4..

*4*1 *4*3 +413 14*, *4.2 *4,. *4-2 +4-2

*4*0 *4+* +4./ .422 *4.- *4+. *4-3 +4*/

*4-1 *4/- 041. +40/ .4/, *4*. +42. *40*

*4-, *4.. 04.* +40, .4.- *4*- +4/1 *4/+

*4,0 *4-3 14,. ,4-- ,4/* *4*1 *423 *422

Branched/ῌ*4.2042-.42./43,/4/3.4,1-40/-4,.++4./24.3+04,3+/4-++.4/0 Unsaturated +0:+ +2:+a +2:+b +2:, +2:-

*4./ +142- 343+ *4** +4+.

*4,0 ,4** +42, *4** *4,.

*4,2 +4+- +4.- *423 *4,,

*4*- 24++ *4-0 *4** +421

*4+2 /4+, *4-- *4** ,401 +.43* +40. *4.0 *4** *4/1 +411 -4*, +4/1 *4** *4.2

*4+* .4,3 *420 *4** +4,, ,403 -4+3 +41- *40, +4*0 +42/ +4,3 *43. *4-/ *4/3 -41- *4+2 +4/. *4*2 *4,2 .4,+ *4,, +4/- *4*2 *4,/

+4,- *4/3 *4., *4+. *4.2

Unsaturated/ῌ,34--.4---430+*4-124,3+14/0042.04.134,3/4*,/42+04,3,42/ Total/ῌ+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4** noLong/noShort*4-+,*4-2.*4.*+*4*+1*4**3*4*/,*42+0*40.-*4./0+4*0,*4*+0*4*+/*4*,/ CPIF(C+.oC-,)*,,,4/+,40342+14/-*43+24,+-4004/3242*140,,*40+341,/4/ *+Pebbleswithattachedalgae.*,Carbonpreferenceindexfornoalkanoicacids.

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sediment of Sainokawara source in Kusatsu hot spring sources. ste : Cholesterol. sta : Choles- tanol. ste : -Methylcholesterol. sta : -Methylcholestanol. ste : -Ethylcholesterol. sta : Fig. Gas chromatogram (TIC) and mass chromatograms (m/z , ) of sterols found in Rurinoike

-Ethylcholestanol.

Table

Matsumoto and Hanya, a

TOC TN

Eartel and Hedges, ; Krishnamurthy ; Meyers and Ishiwatari,

; Matsumoto TOC TN .

Table TOC TN . .

Table TOC TN

W Tilden Geitler

Galdieri

-C

Table , Nagashima

C C

C C

p

p p

trans

p

et al., et al.,

C. caldarium G. sulphuraria

n

C. caldarium et

al.,

n n

,1 ,1

,2 ,. ,2 ,. ,3 ,. ,3

0 +,3 ,+/

,.

+1

,* -/

+/ +3

/2 ,**3

o

o o

2 o +32*

+/ .

+* +32/ +320

+33- ,**- , /- +*3

+ , /- - 0*

, +

,*

, +

+33/ +331 ,**2

+ ,

- +320

o o

- . ῌ

ῌ

ῌ

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Table 1 Sterols founds in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot spring source

KusatsuYunotsu SterolShirahata- noyuKusatsuoWYubatakeo+Yubatakeo,*+Saino- kawarao+*+Saino- kawarao,*+Ruri- noikeOnino- chagamaTourou- noikeo+Tourou- noikeo,Yo+Yo,Yo- Composition/ῌ Stenol Cholesto/oeno-bool(A) ,.oMethylcholesto/oeno-bool(B) ,.oEthylcholesto/oeno-bool(C)

+*41 .4* 104+

,-4- 24. ./4.

,14+ 241 .241

ῌ ῌ ῌ

ῌ ῌ ῌ

ῌ ῌ ῌ

04- +,4* 1,4-

+04/ .42 0-43

/41 +042 1*42

143 +,4+ 1+40

,04* -4. 004-

/-4- +40 .+41

-341 /42 ./4- Stanol /aoCholestano-bool(D) ,.oMethylo/aocholestano-bool(E) ,.oEthylo/aocholestano-bool(F)

*42 *41 141

,4, .40 +04*

-4* -4. 34+

ῌ ῌ ῌ

ῌ ῌ ῌ

ῌ ῌ ῌ

+4. -4/ .40

,4- ,4* +*40

*4. -4, -4*

+4+ -4. .4*

+4* +4/ +42

+40 *43 *42

,4, ,4- .41 Total/ῌ+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4** C,1oC,3sterolcomposition/ῌ C,1sterol(A῍D) C,2sterol(B῍E) C,3sterol(C῍F)

++4/ .41 2-41

,/4/ +-4* 0+4.

-*4+ +,4+ /142

ῌ ῌ ῌ

ῌ ῌ ῌ

ῌ ῌ ῌ

141 +/4/ 1043

+241 042 1.4.

04+ ,*4+ 1-43

34* +/4. 1/40

.14* .43 .24+

/.43 ,4/ .,40

.+42 24+ /*4* Ratio/ῌ C,3/(C,1῍C,3sterol)/ῌ21431*400/42ῌῌῌ3*4313433,4.234./*40.-41/.4/ Stanol/sterol/ῌ C,1stanol/sterol C,2stanol/sterol C,3stanol/sterol

14* +.42 34+

242 -/4- ,04*

+*4* ,24* +/42

ῌ ῌ ῌ

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+24. ,,40 /43

+,4+ ,34, +.4,

14* +04, .4+

+,4. ,+42 /4-

-41 -*4- ,40

-4* -.40 ,4*

/4, ,240 34. *+Pebbleswithattachedalgae.Notdetermined.

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Fig. Gas chromatogram (TIC) and mass chromatograms (m/z , , , and ) of trimethylsilyl derivatives of phenolcarboxylic acids found in Rurinoike sediment of Sainokawara source in Kusatsu hot spring sources. OHA : Hydroxybenzoic acid, MHA : Hydroxybenzoic acid, PHA : Hydroxybenzoic acid, cPCA : Coumaric acid ( ), tPCA : Coumaric acid ( ), VAA : Vanillic acid, SYA : Syringic acid, cFEA : Ferulic acid ( ), tFEA : Ferulic acid ( ).

o m p

p cis p trans

cis trans

H

H

H H

H

H

H

H

Matsumoto

and Hanya, b ; ; Matsumoto

CPI carbon preference index for alkanes, Matsumoto, a ;

CPI

CPI

CPI Matsumoto,

a ;

CPI . .

CPI

CPI

Nishimura and Baker, CPI

et al.,

n n

n

n

n n

n

n

n

1 ,01 ,3- ,31 -,1 --2

o o o

o o

/2 ,**3

+32* +332 ,**-

o o

o

o

+32, ,**0

+ ,

o +

o + /

+32, ,**0

o * 2, / +

/

+ , +

o

+320

+ o

ῌ

ῌ

Table 2 Phenolcarboxylic acids found in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot spring source

KusatsuYunotsu PhenolcarboxylicacidShirahata- noyuKusatsuoWYubatakeo+Yubatakeo,*+Saino- kawarao+*+Saino- kawarao,*+Ruri- noikeOnino- chagamaTourou- noikeo+Tourou- noikeo,Yo+Yo,Yo- Composition/ῌ ooHydroxybenzoicacid moHydroxybenzoicacid poHydroxybenzoicacid poCoumaricacid(cis) poCoumaricacid(trans) Vanillicacid Syringicacid Ferulicacid(cis) Ferulicacid(trans)

+40. *42+ +24.2 ,4*1 ,,4.1 .,4/* 24*+ *40* -4.,

+42, +4+2 241- 14+, ,24-* -.4/2 342, ,4.2 /432

*4** *410 0433 .42/ ,.4/+ ..4+3 04.* -4,0 34*/

-4*3 141. 03422 +4., 34,3 24++ *4-* *4** *4+1

,42. 1401 .14.. 242, +34/1 +,431 *4-0 *4+* *4,,

+411 ,4+, +24*1 343+ ,*4+1 -/4/3 *41- .41* 043.

*421 *4/1 +3431 .4-2 +-4*0 /.4,+ +4/1 +4** .4-2

+4-0 +4*3 +34.+ 04/3 ,,42. ,/4/. -4+3 .4*3 +/43*

+4+/ *40. ++43. 14*3 ,140- --43/ .40, -42, 34+1

+4*, *4.0 ++4-0 ,4-/ ,/4*. -+4,1 14*+ ,40. +242/

.4** -4+/ +,4+* ++4+/ ,.4.. +34-+ *4/* +*4,0 +/4*3

*4,. *4/2 -.4., 24*/ ,+4,- +,4-- *4-+ 2421 +-430

*4/. *41/ -*41- 34+* +0411 ,,4+. +4,. 24** +*41. Total+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4**+**4** Threecomponents/ῌ poHydroxybenzoicacid Vanillicacid Syringicacid

,0412 0+40+ ++40+

+04.- 0/4*2 +24.2

+,4+. 1041. ++4+,

234,0 +*4-0 *4-2

124*0 ,+4-. *40*

--4,, 0/4.- +4-/

,04-0 1+4/0 ,4*1

.*4-- /-4*0 040,

,-40. 014,+ 34+.

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-143, 0*4/+ +4/1

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et al., et al.,

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p

et al., p

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