,* +,,2,+, / +, -., Department of Environmental Studies, School of Social Information Studies, Otsuma Women s University, Karakida +0, 20*+ + -

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1 J Hot Spring Sci /2,+1,*,**3 + +, -,,* +,,2,+, / Environmental Geochemical Characteristics and Sources of Organic Components in Hydrothermal Environments, Japan + Kusatsu and Yunotsu Hot Spring Sources +, - Genki I M ATSUMOTO, Takayuki S ATO, Hideyuki N AGASHIMA,, Kenji SUGIMORI and Tetsuo TAKEMURA Abstract Organic components in sediment samples from Kusatu hot spring sources (Shirahatanoyu, Yubatake and Sainokawara, etc) in Gunma Prefecture, and deposit samples from Yunotsu hot spring source in Shimane Prefecture were studied to clarify their environmental geochemical features, sources and thermal stresses Total organic carbon (TOC) and total nitrogen (TN) contents in sediment samples from Kusatsu hot spring sources ranging from */02, 2- and **,+ * +/+, respectively, were relatively low, while TOC/TN weight ratios of the samples ranging from 3 +- to +*3 were very high Environmental geochemical 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 and Yubatake-+ samples are largely derived from vascular plant debris, while Yubatake-,,,*02/*, 1 + Department of Environmental Studies, School of Social Information Studies, Otsuma Women s University, Karakida, 1 +, Tama-shi, Tokyo,*02/*, Japan +0, 20*+ + - Department of Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka + -, Shinjuku-ku, Tokyo +0, 20*+, Japan +0, 20*+ + - Department of Biology, Faculty of Science, Tokyo University of Science,Kagurazaka + -, Shinjuku-ku, Tokyo +0, 20*+, Japan +-2/* /,+ +0 Department of Biology, Toho University Faculty of Medicine, Omori-nishi /,+ +0, Ohta-ku, Tokyo +-2/*, Japan + +,,

2 Sainokawara-+ and Sainokawara-, samples are mainly attributed to unicellular red alga ( Cyanidium caldarium) TOC and TN contents in deposit samples from Yunotsu hot spring source ranging from **3 to + / and **+3 to *1*, respectively, were very low, revealed that deposits were mainly composed of inorganic substances Very low TOC/TN weight ratios (,/- -0* ) along with high relative abundance of branched ( iso- and anti-iso-) alkanoic acids showed that organic components in the samples are mainly originated from thermophilic 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 TOC TN TOC */02, 2- TOCTN 3 + +*3 + + TOC **3 + / TOCTN,/- -0* po : + Matsumoto et al, +321,,**- ; Peters et al,,**/ ; Bachtel et al,,**1 ; Medeiros and Simoneit,,**2 218

3 /2,**3 Matsumoto et al, +32+, +32,,,** ; Matsumoto, +33- ;,**2, / - b, no no Matsumoto and Watanuki +33* Matsu- moto and Watanuki, +33, +1 ah +1 bh / ah + bh +1bH Matsumoto and Watanuki, +33*, +33,,,+ +,,** m / 3/ ph + 1, +,** ,+ +,**/ 0/3,** +,*1- Lmin +331 ;,**2,**1 1 0 ph, Fig +, Photo +, Photo, +,** 3 0,**-,** Fig +, Photo - -*,, + *- g -/ ml ++*, TOC TN 219

4 Fig + Sampling sites of sediment samples from Kusatsu hot spring (Fuse and Nagashima,,**2) in Gunma Prefecture, and deposit samples from Yunotsu hot spring in Shimane Prefecture TC TS cm - TOC, TN, TC TS Fisons Photo + Yubatake hot spring source in Kusatsu hot NA,/** Automatic Elemental Analyzer / +* mg spring, Gunma Prefecture mg +2**, Q, -* m-mm id, 1* TC TS 0M ++*, TOC TN 220

5 /2,**3, Matsumoto et al ,,**- Matsumoto and Watanuki +33, 2*, +0* / mm id, +** / +, Photo, Sainokawara hot spring source in Kusatsu Matsumoto et hot spring, Gunma Prefecture al,,**- +, TMS,/ N, OBis trimethylsilylacetamide J&W DB /, -* m *,/ mm id, + mm JEOL JMS K3 Gas Chromatograph-Mass Spectrometer, GC-MS GC-MS 1* +,* -* min, +,* -,* Photo - Deposit at Motoyu source of Yunotsu hot spring, Shimane Prefecture 2min -- -* +, mlmin,,2* GC-MS -**,/* 1* ev, *-** ma, +,** V Matsumoto et al, +313, +32, ; Matsumoto and Watanuki, +33, TIC GC-MS * 2 0/ * Table + W 0/ *, -* 2 ph +3-,,+ +33/ +331,**2 221

6 Table + Water temperature, ph, total organic carbon (TOC) and total nitrogen (TN) concentrations in sediment samples from Kusatsu hot spring sources Sample Water temp/ ph TOC/ TN/ TOC/TN Remarks Shirahatanoyu 243,4+0,4, *4*,+ +*3 Sediment Kusatsuo W /*4*,4+/ *4/1 *4*-* +34, Sediment Yubatakeo+ /*43,4+/ +4+0 *4*,1,40 Sediment Yubatakeo, /40,4++ ND ND ND Pebbles with attached algae Sainokawarao+ -4/,4+2 ND ND ND Pebbles with attached algae Sainokawarao, -*42,4** ND ND ND Pebbles with attached algae Rurinoike 142,4,+,42, *4+,,,40 Sediment Oninochagama 0/4* *, *4*,, 042 Sediment Tourounoikeo *41, *4* Sediment Tourounoikeo, 4/ +43-,42- *4+/ Sediment ND : Not determined Table, Total carbon (TC), total sulfur (TS), TOC, TN and total inorganic carbon (TIC) concentrations in + deposit samples from Yunotsu hot spring source* Sample TC/ TS/ TOC/ TN/ TIC/ TIC/TC/ TOC/TN TS/TOC Yo *4/++ +4/ *41*,4,/ /34- -4,3 *4-- Yo, +43/ *4,22 *43,2 *4,/2 +4*- /,4/ -40* *4-+, Yo- a* *4-0 *4*1/ *4*3 3 * /,4/- +4/, Yo- b* *4-- *4*12 / *4*,0 *4, 14, -4,2 *43-, Yo- c* *4+ *4*1 *4*00 *4*,0 *4-2-41,4// +4+, + * Samples were taken on,2 November,**0 Water temperature and ph were 3 and 0 *1, respectively, * -a, -b and - c are top ( + cm), middle ( + cm) and inner ( + cm) layers, respectively Cyanidium caldarium Tilden Geitler Galdieria sulphuraria Galdieri Pinnuralia braunii var amphicephala,**/ ph 0 *1 Table, Photo - -, TC, TOC, TN, TIC TS TOC TN */1, 2- **,+ * +/+ Table + W TOC */1,,,* - + Williams et al, +33- ; Matsumoto et al,,***,,**-,/ Meyers and Ishiwatari, +33- / 0, / 11Nishi- mura, ,,**0 TOC TOCTN 3 + +*3 Table + TOCTN * Matsumoto 222

7 /2,**3 Fig, Mass chromatogram (m/z /1) of hydrocarbons obtained from Rurinoike sediment of Sainokawara source in Kusatsu hot spring sources Arabic figures on the peaks denote carbon chain length of n-alkanes i : Isoprenoid akanes et al,,***,,**- ;,**0 TOC TN TC, TS, TOC, TN TIC TCTOC * **1 * /++ **3 + / **+3 * 1* *,,,/ Table, TC TIC /,/ 20 / TOC Table, Yo- - Y o-a, Y o-b, Yo-c TOCTN,/- -0* Matsumoto et al,,***,,**- ;,** mz /1 noc noc no noc noc +1,3 +/, ioc io C Fig,,* -* mz /1 no no noc no C +* noc noc noc noc noc Table - * +1,/,0,1,3, +,,, noc C caldarium +1 Nagashima et al, +320 ioc ioc ioc no UCMH -* +/ +3,* 223

8 Table - Normal and acyclic isoprenoid alkanes found in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot spring source Alkane Yo+ Yo, YonoShort +/ Shirahatanoyu *4- *403 +4/+ * /3,4,/ ,, 4+0 *4* *4* *4,0 *4*1 *4*1 / / 04/+ Kusatsu Yunotsu -4*+,4+3-34, * -40,4*1 34*1,4+2,42* +4*, *4* +24* *4/3,4* /+,4*+ 43, 4/1 +/4*/ KusatsuoW Yubatakeo+ Yubatakeo,* + Sainokawarao+* + kawara-,* + Saino- Rurinoike Oninochagama Tourounoikeo+ Tourounoikeo,,4-*,42/ -4*+,40- -4/3 noshort/ 43* +/43* *42 0,41+ //4/ +3410,, /4, / +422,343 nolong,*,+,,,-,,/,0,1,2,3 -* -+ -, / * ,40* * / / ,* -4/+ +4/ +42- *41, *43 *4-0 41, 40- / / / *4+, -40,4/3 4/0 *40* +4,1 *422 *41, *40* *4/- *4*/ *4++ *41,43/ * / ,42/ *, / *42+ *4/+ *4-0 *4,/ *4+1 *4+, *43,,4*3,4,2 042,, ,40, -4-1,400-4+, , *43+ *40/ *4-3 *4,1 *4,+ *4+0 * ,4/+,41+ 04/2,423-4/ , *42* *4/3 *4* *4-, *4,+ *4,+ nolong/ 3,40* *, 0*4+0 2,411 /,42+,4+0 /043- Isoprenoid i+3 i,* i-* *4/, * ,43*,4,/ *4*, *4*3 *4,- * *4-3 *4,/ Isoprenoid/, *4+- *4-3,4/1, *+ 4/0,42/ 14- * UCMH* - / /,4* Total/ +* +* +* +* +* +* +* +* +* +* +* +* +* nolong/noshort /,*14/ *4/3 *41/ , / ,42/ +43*,4+* -4*1,41/ 421,4/ 4+0,4/2 04* *, /4, /4 / ,43*,4-/ ,+ *40- *40+ *430 *422 *40, * /4/* , /,4, 040,4* *420 *40 *4/ *4,1 *4,+ *4+- *4*3 +4,3 342* +40, *41+ +4*- *4/ * ,* *2 +4/+ *40* +4/ *43 *41- *4-0 *4+2 *41- *4, *,42-4,2,4, 40*,4*1 0400, ,,4/1 0432,4+2,422 +4,/ +4*2 *41 +4/3 *40/,41,4*3-4*, -4*3 43+ / * /4+* -4*, -43/ +4-,43- *400,4*+ * / *4,, * /+ *, /41* 14-* +,4,/ /3-401,43,,43,,4/+,4/ , ,4, / ,1 *40, *433 *4,1 *41-4/0-421 *, *4+, *4*/ +4-/ *4*1 *4,2 *4* *4, *4+2 *40+ * /,4,+ -401, ,4-3,4-+ +4,+ *43+ *41 *4-/ *4+0 *4*0 *4*0 *4*, * /4/, ** / , -4*2,4/2,4,/ ,40,4+* -4++,43, 4*0,4/-, /,42+ -4* ,+ CPIH (C+1oC-/)* *43* 4/, -4,* +400 /4+, *42,,4-* *42 +4-/ +4/+ +4*0 * + Pebbles with attached algae *, Squalane may be present * - Unresolved complex mixture of hydrocarbons * Carbon preference index for noalkanes 224

9 /2,**3 unresolved complex mixture of hydrocarbons UCMH,**0 UCMH /, + no + +* Table - ioc ioc io C, UCMH 1-0 -* mz +3+ Fig -,, SC C +1 ah,+ bh Table +1 ah,+ b H-* +1 ah,+ bh C Matsumoto and Watanuki, +33* Y- -* : + +3,* -+ -/ Fig - Mass chromatogram (m/z +3+ ) of triterpanes obtained from Rurinoike sediment of Sainokawara source in Kusatsu hot spring sources + : +2 a (H) o,,,,3, -* otrisnorneoohopane, :,,,,3, -* otris- norhop o+1 (,+) oene - : +1 a(h) o,,,,3, -* otrisnorhopane : +1 b(h) o,,,,3, -* otrisnorhopane / : +1 a(h),,+ b(h) o-* onorhopane 0 : Hop o+1 (,+) oene 1 : +1 b(h),,+ a(h) o-* onormoretane 2 : +2a (H) ooleanane 3 : +1 a(h),,+ b(h) ohopane +* : Neohop o+- ( +2 ) oene ++ : C-* : + Hopene +, : C-* : + Hopene +- : (,, S) o+1 a(h),,+ b(h) o-* ohomohopane + : (,, R) o+1 a(h),,+ b(h) o-* ohomo- hopane +/ : +1 b(h),,+ b(h) ohopane +0 : (,, S) o+1 a(h),,+ b(h) o-*, -+ obishomohopane +1 : (,, R) o +1 a(h),,+ b(h) o-*, -+ obishomohopane +2 : (,, S) o+1 a(h),,+ b(h) o-*, -+, -, otrishomohopane +3 : (,, R) o+1 a (H),,+ b (H) o-*, -+, -, otrishomohopane,* : (,, S) o+1 a (H),,+ b (H) o-*, -+, -,, --o Tetrakishomohopane,+ : (,, R) o+1 a(h),,+ b(h) o-*, -+, -,, -- otetrakishomohopane,, : (,, S) o+1a (H),,+ b(h) o-*,-+,-,,--,- opentakishomohopane,- : (,, R) o+1 a(h),,+ b(h) o-*,-+,-,,--,- open- takishomohopane 225

10 Table Triterpanes, triterpenes and moretanes found in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot spring source Kusatsu Yunotsu Compound Shirahatanoyu KusatsuoW Yubatakeo+ Yubatakeo,*, Sainokawarao+*, kawarao,*, noike Oninochagama Tourou- Saino- Rurinoikeo+ Tourounoikeo, Yo+ Yo, Yo-* - Composition/* + + : +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 +2 :(,,S)o+1a (H),,+b(H)o-*, -+, -,o Trishomohopane +3 :(,,R)o+1a (H),,+b(H)o-*, -+, -,o Trishomohopane,* :(,,S)o+1a (H),,+b(H)o-*, -+, -,, --o Tetrakishomohopane,+ :(,,R)o+1a (H),,+b (H)o-*, -+, -,, --o Tetrakishomohopane,, :(,,S)o+1a (H),,+b (H)o-*, -+, -,, --, -o Pentakishomohopane,- :(,,R)o+1a (H),,+b(H)o-*, -+, -,, --, -o Pentakishomohopane 4*, *4,, -4* * -4/3 +4/ * , +4*1-42,42, *43 04+* *4+1, /43* +4/2 34/ -4/ / ,0 43 *4+ -4, * * / 142/ / 04-* *43- / *,4-0,40/ *43/ +4,/, *,4+3,*4-1 /410 4/+ -42, 14+0,42, +43* +4,1, *410-4** +4-0 *40- +* * -4*2-4/1 *433,4+*,4-/ +4*3,4,*,4-/ +04,2 * * ,4, +,4+1,4/ 042, /422,42* 41-,43/ 40/ -4-, -42* ,/ *430-4*0 4/+ 4*2,43-,4+3, ,4/* +4-, 1401 *40-,4/1 +410, , / -4*+ +41,4+* , -4,+ -4*0,4,/ ,4*, +4*- ++40* * ,4* *2,4/+ +4// -40, *41,, ,4*,,4*/ +4, -4/ ,/,4++,413,421 +4,2 * *2 34+3,412 *43- *4/ /- 14,2, /, *, /4,2 +4,1 +4// +*4/ *4 24/1 +*4-2, ,3-4,* +40, +4, +4+ *42+ * /4** *43/ ,/,4+* , * *4,,4+* *4,2 +24, *2 *4/2 +, /4-,4+, 24*, /42- *43* 40, / *42-,42 +4,/ , ,3, ** +4,* 14/ * / -4+, *4/3,41- *432 +/4+1,4+/ +4+0 *4/ , +/4-,4*2 141* /43* *42 /4+ -4/ (,,S/,,R)o+1a (H),,+b (H)o-*oHomohopane (,,S/,,R)o+1a (H),,+b (H)o-*,-+oBishomohopane (,,S/,,R)o+1a (H),,+b (H)o-*, -+, -,o Trishomohopane (,,S/,,R)o+1a (H),,+b (H)o-*, -+, -,, --o Tetrakishomohopane (,,S/,,R)o+1a (H),,+b (H)o-*, -+, -,, --, -o Pentakishomohopane +4, ,, +4,2 +4,/ +40/ /3 *41 +4/3 +4/, , +4-* +4-1 *4+1 +4/- +4+3,4/1 +4/, +4/ *, , *4+2-4** +40/ +4*+ +41 *43 +4/, +4,, +4*3 +4*, +4/ *4/* *4/1 +4*- * * +4,/ +4, * / +42* /0 +4/- +4/ +4-* +43 * + Arabic figures corrrespond peak numbers in Fig - *, Pebbles with attached algae * - Not detected 226

11 /2,**3 mz,+1 Fig,* S/ ah+ ah+1ah C C,1,3 Table /,* R, / a H + a H +1a H Matsumoto and Watanuki, +33* Y+,* R, +- bh +1aH + Y-, TIC mz 1 Fig / 1 no noc noc no +0, noc noc C C C +, C noc noc +2 +0,, noc noc : noc noc, +0 : + +2 : + +0 Table 0 Matsumoto et al,,** no C /0 10* / +0 no Fig Mass chromatogram (m/z,+1) of steranes and diasteranes obtained from Rurinoike sediment of Sainokawara in Kusatsu hot spring sources + : (,* S) o+- b(h), +1 a(h) odiacholestane, : (,* R) o+- b(h), +1a(H) o Diacholestane - : (,* S) o+- a(h), +1 b(h) odiacholestane : (,* R) o+- a(h), +1 b(h) odiacholestane / : (,* S) o, omethyl o+- b(h), +1a(H) odiacholestane 0 : (,* R) o, omethyl o+- b(h), +1a(H) odiacholestane 1 : (,* S) o / a(h), + a(h), +1a(H) ocholestane 2 : (,* S) o, omethyl o+- b(h), +1 a(h) odiacholestane (,* R) o/ a(h), + b (H), +1b(H) ocholestane 3 : (,* S) o/ a(h), + b(h), +1 b(h) ocholestane (,* R) o, omethyl o+- a(h), +1b(H) odia- cholestane +* : (,* R) o/ a(h), + a(h), +1 a(h) ocholestane ++ : (,* R) o, oethyl o+- b(h), +1a(H) odiacholestane +, : (,* S) o, oethyl o+- a(h), +1 b(h) odiacholestane +- : (,* S) o, omethyl o/ a(h), + a(h), +1a(H) ocholestane + : (,* R) o, omethyl o/ a(h), + b(h), +1 b(h) ocholestane (,* R) o, omethyl o/ b(h), + a(h), +1a(H) ocholestane +/ : (,* S) o, omethyl o/ a(h), + b(h), +1 b(h) ocholestane +0 : (,* R) o, omethyl o/ a(h), + a(h), +1a(H) ocho- cholestane (,* R) o, oethyl o/ b(h), + a(h), +1 a(h) ocholestane +3 : (,* S) o, oethyl o/ a(h), + b(h), +1b(H) o lestane +1 : (,* S) o, oethyl o/ a(h), + a(h), +1 a(h) ocholestane +2 : (,* R) o, oethyl o/ a(h), + b(h), +1b(H) o cholestane,* : (,* R) o, oethyl o/ a(h), + a(h), +1a(H) ocholestane 227

12 Table / Steranes and diasteranes found in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot sprring source Kusatsu Yunotsu Compound Shirahatanoyu KusatsuoW Yubatakeo+ Yubatakeo,*, Sainokawarao+*,, * - kawarao,*, Saino- noike chagama Onino- Rurinoikeo, Tourounoikeo+ Tourou- Yo+ Yo, Yo-* - Composition/* + + :(,*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 2 :(,*S)o,oMethyl-+-b (H), +1a (H)odiacholestane (,*R)o/a (H), +b (H), +1b (H)ocholestane 3 :(,*S)o/a (H), +b (H), +1b (H)oCholestane (,*R)o,omethylo+-a (H), +1b (H)odiacholestane +* :(,*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 + : (,*R)o,oMethylo/a (H), +b (H), +1b(H)ocholestane (,*R)o,omethylo/b (H), +a (H), +1a (H)ocholestane +/ :(,*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 +2 : (,*R)o,oEthylo/a (H), +b (H), +1b(H)ocholestane (,*R)o,oethylo/b (H), +a (H), +1a (H)ocholestane +3 :(,*S)o,oEthylo/a (H), +b (H), +1b (H)ocholestane,* :(,*R)o,oEthylo/a (H), +a (H), +1a(H)ocholestane 40,43+ *41+,43*,4, +4/- 04/ *42,4*, / * *,4+ -4,1 /412 +*4*, 24* / // 4*/ ,* -4/ , 340* -40, -4,/ /4*2-4// -4/ ,4/0-4-, ,4-/,4,2 /400 /4, 4, -4* , /43 /4-, -4* /40+,4*2 /4,+ -4/+ -40/ ,0 041, 24,0 341,,403 34* /, , *4, * 24/, /4+ +-4/ 14/ 142, +-43+,4/1,40 +4+, /0 4,/ 34+* /4+0 /4,, * // / 42* 4, *412,41,4/1 /4-/ /4-2 4, 04-, , /41, /42/ 14/+ 042/ +*4/ / /0 *40,40-41,4, 04, ,4-,,413 4/,43* +,4,2 14/ ,42+,4,, /, +,4* 04// -42 /4*1 +, ,4+*,24-2 / * +04+/ -4/3,403 *42+,43, /430 14*2 1433,4** 41 41/ 4* /, 24-, Relative abundance of (,*R)o/a (H), +a (H), +1a (H)osterane/ 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* , *4* 0*42 +4*/,-42,,4, /4+ *433,*40,24 /+4* * *4* 0+40,24,*41 /+4* ,+4, -343 *4,2 *4* *4* +**4* * ,+4*,41 +4*0 * + Arabic figures corrrespond peak numbers in Fig *, Pebbles with attached algae * - Not detected 228

13 /2,**3 Fig / Mass chromatogram (m/z 1 ) of fatty acids obtained from Rurinoike sediment of Sainokawara source in Kusatsu hot spring sources Arabic figures on the peaks denote carbon chain length of noalkaoic acids i: iso a: anti-iso m: n: Carbon chain length : number of unsaturation Table 0 - mz +,3 mz,+/ Fig 0 C C,1,3 / - b, / -b,, / - b, / a- b, / a - b,, / a- b, Fig 0 Table 1, 0, Table 1 TIC m/z,01, m/z,3-, m/z,31, m/z -,1, m/z --2 Fig 1 oo mo po po cis po trans cis trans Table 2 229

14 Table 0 Fatty acids found in sediment samples from Kusatu hot spring sources, and deposit samples from Yunotsu hot spring source Fatty acid Yo+ Yo, YonoShort +, / Shirahatanoyu *4, *4*, *4- *4,* -343/ *4/* +,4*3 *4* * ,/ * , *4,, +/4/- *4-0 -4/0 +4,1 -*4-/ +4 +,4-3 *4+3 *412 +4/ ,1, / *4+1 Kusatsu Yunotsu +4*3 *4*1,4, *4-2 +4, *4+,+4*/,433 4/ *4/2-4,1,40 /4+/ +4*2 -,4*- *42, 14+ *4,/,400,40/ *423,04,/, *0 +4* * ,/ * *4,* KusatsuoW Yubatakeo+ Yubatakeo,* + Sainokawarao+* + kawarao,* + Saino- Rurinoike Oninochagama Tourounoikeo+ Tourounoikeo,,4/0 *4++ /4+1,432,4-* +4** /4 *4-2 noshort/ /-4/, /4*3 2,4-+ 2/4-- 14,1 34-* /431 /4 +43/ ,/ 2*4/3 nolong,*,+,,,-,,/,0,1,2,3 -* -+ -, */ *40,402 *40, -4+2 *41 +4,0 *4+, *400 *4-- *4-3 *4+0 *4,1,4+ *4- -43* +4* *42/ -4,* * * *4+0 +4*/ *4*/ *4, +4*- *4,3 41, +4-* 34*2 +4,, -40, *4/* +4/- *4-/ +4-, *4,0 *423 *41 *4* *4+, *4*/ *4- *4*/ *4,- *4*, *4*/ *4,+ *4*- *4+, *4* *4,+ *4*- *4+* *4*/ nolong/ +0401,400,04+, +4* * *4,+ -/4--,42+ 4/ +4, +4+/,4** Branched i+i+ i+/ i+0 i+1 a+a+/ a+1 *4*, *4,* *4+* *4*0 *4*- *4*0 *4*1 *40 *4, -4,0 *401 *4+/ *43 +4-, *4*3 *420 * *4, *4+- *4,+ *4, *4+* *4, 40 *4+2 *4/3 *4++ *4+2 4,- *4*0 *4+2 *4+- *402 Branched/ * /43, /4/3 4,1-40/ -4, ++4/ ,3 +/4-+ +4/0 Unsaturated +0 : + +2 : +a +2 : +b +2 :, +2 : - *4/ *4,0,4** +42, *4, *4, *423 *4,, *4* * *4+2 /4+, *4--,401 Unsaturated/, *4-1 24,3 +14/ ,3 /4*, /42+ 04,3,42/ Total/ +* +* +* +* +* +* +* +* +* +* +* +* +* nolong/noshort *4-+, * *4*/, *42+0 *40- *4/0 +4*0, 0 / *4*,/ *4- *4*0 +4+ * *4*/ *4+1 *4*, *4*3 *4*, *4*/ *4+* *4--,41/ *4++ *4*- *4* *4/ +43* +40 *40 *4/1,411 * , +,41 *433 4*+ *4,,4-+ *4-/ +433 *4+2 *43 *4*/ *4+3 *4*0 *421 +4/, *4,, *4*3 *4,0 * *, +4/1 * *42 /4+3, *422,4/+ *41,4* *4-* *41- *4+2 *4* *4-*,4*- *4,2 *4* *4*3 *4 *4+* 4,3 *420 +4,, +4/0 *4/ /41, * , *4/1,4/* *4-0 +4,0 *4,, *43/ *4+* *4+ *4*- *4*3 *4*1 *4* *, *42 *4, * , *40, +4*0,43- *42, , *3 *4/2,4- *42,4*/ *4,* *42, *4*0 *4+0 *4*0 *4+* +4/ 422 *4- *4+ *4-3 +4*/ +42/ +4,3 *43 *4-/ *4/3,4/2 /4/+ +4-, 0* *4+- *4+ *4* *4- *4*- *4+- *4*/ *4*/ *4-1 *4/ / 4/, *4* +42 *40* -41- *4+2 +4/ *4,2,403 *4+, /42 +4, 0* *4+- *4+ *4*- *4, *4*- *4++ *4* *4-, *4 04* +40, 4- *4*- +4/1 *4/+ 4,+ *4,, +4/- *4,/ 24, * , +4++ /04/2 +4,- 42+ *4+ *4/* *4*0 *4-3 *4*1 *4-/ *4*0 *4+0 *4*- *4+, *4*, *4+- *4+* *4,0 *4-3 14,,4--,4/* *4*1 *423 *422 +4,- *4/3 *4, *4+ *42 CPIF (C+oC-,)*,,,4/ +, / -*43 +24, /3 242* 140,,* ,/4/ * + Pebbles with attached algae *, Carbon preference index for noalkanoic acids 230

15 /2,**3 Fig 0 Gas chromatogram (TIC) and mass chromatograms (m/z +,3,,+/) of sterols found in Rurinoike sediment of Sainokawara source in Kusatsu hot spring sources,1 ste : Cholesterol,1sta : Cholestanol,2 ste :,-Methylcholesterol,2 sta :,-Methylcholestanol,3 ste :,-Ethylcholesterol,3sta :,-Ethylcholestanol po po po trans Table 2 po Matsumoto and Hanya, +32* a - TOCTN +/ +* Eartel and Hedges, +32/ ; Krishnamurthy et al, +320 ; Meyers and Ishiwatari, +33- ; Matsumoto et al,,**- TOCTN,/- +*3 Table + TOCTN,/-- 0* Table, + TOCTN,* W, + C caldarium Tilden Geitler G sulphuraria Galdieri +33/ +331,**2 n-c +, +1 C caldarium Table -, Nagashima et al, +320 C C no,* -/ C C no +/

16 Table 1 Sterols founds in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot spring source Kusatsu Yunotsu Sterol Shirahatanoyu KusatsuoW Yubatakeo+ Yubatakeo,* + Sainokawarao+* Saino- Rurinoikeo+ Oninchagama Tourou- + kawarao,* + noike Oninchagama Tourounoikeo, Composition/ Stenol Cholesto/oeno-bool (A),oMethylcholesto/oeno-bool (B),oEthylcholesto/oeno-bool (C) Stanol /aocholestano-bool (D),oMethylo/aocholestano-bool (E),oEthylo/aocholestano-bool (F) +*41 4* 104+ *42 *41 141, * /42 /4-,4,, / ,4-,4* +*40 / *42 *4-4, -4* 143 +, * Yo+ Yo, Yo-,-4-24 /4,4, * 04- +,4* 1, / 40,04* * +4/ +42 / *43 *42 Total/ +* +* +* +* +* +* +* +* +* +* C,1oC,3 sterol composition/ C,1 sterol (AD) ++4/ C,2 sterol (BE) 41 C,3 sterol (CF) 2-41,/4/ +-4* 0+4 -*4+ +,4+ / /4/ ,* * +/4 1/40 14* /43,4/, /*4* Ratio/ C,3/(C,1C,3 sterol)/ *40 0/42 3* ,4 234 /*40-41 /4/ Stanol/sterol/ C,1 stanol/sterol 14* C,2 stanol/sterol +42 C,3 stanol/sterol 34+ +*4*,24* +/42 +24,,40 /43 +,4+,34, +4, 14* +04, /4-,04* +,4,+42 / *4-,40-4* -40,4* /4,, * + Pebbles with attached algae Not determined 232

17 /2,**3 Fig 1 Gas chromatogram (TIC) and mass chromatograms (m/z,01,,3-,,31, -,1 and --2) of trimethylsilyl derivatives of phenolcarboxylic acids found in Rurinoike sediment of Sainokawara source in Kusatsu hot spring sources OHA : oohydroxybenzoic acid, MHA : mohydroxybenzoic acid, PHA : pohydroxybenzoic acid, cpca : pocoumaric acid ( cis), tpca : pocoumaric acid ( trans), VAA : Vanillic acid, SYA : Syringic acid, cfea : Ferulic acid ( cis), tfea : Ferulic acid ( trans) Matsumoto and Hanya, +32* b ; +332 ; Matsumoto et al,,**- no no no CPI carbon preference index for noalkanes, H Matsumoto, +32, a ;,**0 + CPIH, no CPI + +32, a;,**0 no CPI + / Matsumoto, H no CPI *2, /+ H CPI / H +, CPI + no Nishimura and Baker, +320 CPI + no H H H 233

18 Table 2 Phenolcarboxylic acids found in sediment samples from Kusatsu hot spring sources, and deposit samples from Yunotsu hot spring source Kusatsu Yunotsu Phenolcarboxylic acid Shirahatanoyu KusatsuoW Yubatakeo+ Yubatakeo,* + kawarao+* Saino- Sainokawarao,* + Rurinoike + Oninochagama Tourounoikeo+ Tourounoikeo, Composition/ oohydroxybenzoic acid mohydroxybenzoic acid pohydroxybenzoic acid pocoumaric acid (cis) pocoumaric acid (trans) Vanillic acid Syringic acid Ferulic acid (cis) Ferulic acid (trans) +40 * ,4*1,,41,4/* 24*+ *40* -4, * /,4/ * -4,0 34*/ -4* , 34, *4-* *4+1, , +34/1 +,431 *4-0 *4+* *4,, *421 *4/ *0 /4,+ +4/1 +4** * /3,,42,/4/ *3 +/43* +4*, * ,4-/,/4* -+4,1 14*+, / 4** -4+/ +,4+* ++4+/, *4/* +*4,0 +/4*3 Total +* +* +* +* +* +* +* +* +* +* +* +* +* Three components/ pohydroxybenzoic acid Vanillic acid Syringic acid, , , 234,0 +*4-0 * *0,+4- *40* Yo+ Yo, Yo- +42, ,,24-* -4/2 342,,42 / ,4+, +24*1 343+,*4+1 -/4/3 *41-41* / * *3, / 40, -42, 34+1 *4, *4/2-4, 24*/,+4,- +,4-- * *4/ *41/ -*41-34+* +0411,,4+ +4, 24** +* /4* ,, 0/4- +4-/, /0,4*1 *4-- /-4*0 040,, ,+ 34+,, ** , 0*4/+ +4/1 1-4+,04,* *400 /0413 *43,,4,3 * + Pebbles with attached algae 234

19 /2,**3 CPI +*0 +/+ UCMH Matsumoto, +32, a ;,**0 UCMH C C C C - Matsumoto and Watanuki, +33, ;,**0 C C CPI carbon preference index for noalkanoic acids CPI 0/3 -*3 +3 1,/ / Table 0 CPI no CPI Table - C +, +3,* + CPIA, H A A C C Matsumoto et al, +32, ; Volkman et al, +332 C C C O Leary, +32, ; Reddy et al,,***,,**- a,,**-b, Table 0 W, + + no Table 0 Matsumoto et al,,**- C C C 0/ 23, Table 1 C C C A +, +2,1,2,3,1,3,3,3,1,3-1 / /, Matsumoto et al, +32, ; Volkmann et al, +332 po po Matsumoto and Hanya, +32* a po Matsumoto et al, +313 ; Matsumoto, +32, b po W + +,, + po Table 2, 235 H,3,1,3

20 po -/ Seifert and Moldowan, +32+ ; Mackenzie et al, +32, ; Peters et al,,**/,, R,, S,, S,, R + / Seifert and Moldowan, +32+ ; Matsumoto et al, +321 C C,* R/ ah + ah +1aH,* S/ ah + bh +1bH,* R,* S,* S,* R +, Mackenzie et al, +32, ; Matsumoto et al, +321,1,3 Matsumoto et al, +321 ; Peters et al,,**/,, SC C +1 ah,+ bh,* S/ ah -/ + ah +1aHC C Table 1, Table 2,1,3,, S,, R+1 ah,+ b H -* +,+ + /3,* S,* R,o o/ ah + a H +1 a HC C *, Table 1, Table 2,1,3 Brault et al +322 East Pacific Rise +-N,, S,, RC + * +,* S,* RC + * -,,3,, S,, R + /,* S,* R +,,, R,, S 32 kjmol,* R,* S +1 kjmol Suzuki,

21 /2,**3 + TOC TN TOCTN + TOC TN TOCTN, noc no C +* noc noc +/ * +1,/ noc noc noc,0,1,3 + +* no C caldarium - noc noc +0, no noc noc C C +, C C noc noc noc noc noc ,,, +0 : + +2 : + a noc C C,1,3,, / po 0 +0, Bachtel, A, Gawlick, H-J, Gratzer, R, Tomaselli, M and Puttmann, W (,**1) : Molecular indicators of palaeosalinity and depositional environment of small scale basins within carbonate platforms : The Late Triassic Hauptdolomite Wiestalstausee section near Hallein (Northern Calcareous Alps, Austria) Org Geochem, -2, 3, +++ Brault, M, Simoneit, BRT, Marty, JC and Saliot, A ( +322) : Hydrocarbons in waters and particulate material from hydrothermal environments at the East Pacific Rise, +-N Org Geochem, +,,,*3,+3 237

22 Eartel, JR and Hedges, JI ( +32/ ) : Sources of sedimentary humic substances : Vascular plant debris Geochim Cosmochim Acta, 3,,*31,+*1,**2 : ph / *,**2 : Res Org Geochem,,-, /-1+ Krishnamurthy, RV, Bhattachary, SK and Kusumgar, S ( +320) : Palaeoclimatic changes deduced from C/ C and C/N ratios of Karewa lake sediments, India Nature, -,-, +/* +/, +- +, Mackenzie, AS, Brassell, SC, Eglinton, G and Maxwell, JR ( +32, ) : Chemical fossils : The geological fate of steroids Science,,+1, 3+ /* Matsumoto, G ( +32, a) : Comparative study on organic constituents in polluted and unpolluted inland aquatic environments-iv Indicators of hydrocarbon pollution for waters Water Res, +0, +/,+ +/,1 Matsumoto, G ( +32, b) : Comparative study on organic constituents in polluted and unpolluted inland aquatic environments-iii Phenols and aromatic acids in polluted and unpolluted waters Water Res, +0, //+ //1 Matsumoto, GI ( +33-) : Geochemical features of the McMurdo Dry Valley lakes Physical and Biogeochemical Processes in Antarctic Lakes Antarct Res Ser /3 (eds Green, W and Friedmann, EI), pp 3/ ++2, Amer Geophys Union, Wash DC,**0 : Matsumoto, GI, Fujimura, C, Minoura, K, Takamatsu, N, Takemura, T, Hayashi, S, Shichi, K and Kawai, T (,**-) : Paleoenvironmental changes in the Eurasian continental interior during the last +, million years derived from organic components in sediment cores (BDP-3and BDP- 32) from Lake Baikal Long Continental Records from Lake Baikal (ed Kashiwaya, K), pp 1/ 3, Springer-Verlag, Tokyo Matsumoto, G and Hanya, T ( +32* a) : Gas chromatographic-mass spectrometric identification of phenolic acids in recent sediments J Chromatogr, +3-, 233 Matsumoto, G and Hanya, T ( +32* b) : Presence of squalane in urban aquatic environment J Chromatogr, +3, +33,* Matsumoto, GI, Kosaku, S, Takamatsu, N, Akagi, T, Kawai, T and Ambe, Y (,***) : Estimation of paleoenvironmental changes in the Eurasian continental interior during the past / million years inferred from organic components in the BDP- 30 / + sediment core from Lake Baikal Lake BaikaloA Mirror in Time and Space for Understanding Global Change Processes (ed Minoura, K), pp ++3 +,0, Elsevier, Amsterdam Matsumoto, GI, Machihara, T, Suzuki, N, Funaki, M and Watanuki, K ( +321) : Steranes and triterpanes in the Beacon Supergroup samples from southern Victoria Land in Antarctica Geochim Cosmochim Acta, /+,,00-,01+ Matsumoto, GI, Nienow, JA, Friedmann, EI, Sekiya, E and Ocampo-Friedmann, R (,**) : Biogeochemical features of lipids in endolithic microbial communities in the Ross Desert (McMurdo Dry Valleys), Antarctica Cellar Molecular Biol /*, /3+ 0* +332 : 238

23 /2,** Matsumoto, G, Torii, T and Hanya, T ( +313) : Distribution of organic constituents in lake waters and sediments of the McMurdo Sound region in the Antarctic Mem Natl Inst Polar Res Spec Iss, +-, +*- +,* Matsumoto, G, Torii, T and Hanya, T ( +32+ ) : High abundance of long-chain normal alkanoic acids in Antarctic soil Nature,,3*, 02203* Matsumoto, G, Torii, T and Hanya, T ( +32, ) : High abundance of algal,-ethylcholesterol in Antarctic lake sediment Nature,,33, /, / Matsumoto, GI and Watanuki, K ( +33* ) : Geochemical features of hydrocarbons and fatty acids in sediments of the inland hydrothermal environments of Japan Org Geochem, +/, +33,*2 Matsumoto, GI and Watanuki, K ( +33, ) : Organic geochemical features of an extremely acid crater lake (Yugama) of Kusatsu-Shirane Volcano in Japan Geochem J,,0, Medeiros, PM and Simoneit, BRT (,**2) : Multi-biomarker characterization of sedimentary organic carbon in small rivers draining the Northwestern United States Org Geochem, -3, /, 1 Meyers, PA and Ishiwatari, R ( +33-) : Lacustrine organic geochemistryan overview of indicators of organic matter sources and diagenesis in lake sediments Org Geochem,,*, 2013** +33/ : /,0-* +331 : 0/ 3,,**2 : 0121 Nagashima, H, Matsumoto, GI and Fukuda, I ( +320) : Hydrocarbons and fatty acids in a hot spring alga Cyanidium caldarium Phytochemistry,,/,,--3,-+ Nishimura, M ( +311) : The geochemical significance in early sedimentation of geolipids obtained by saponification of lacustrine sediments Geochim Cosmochim Acta, +, ,- Nishimura, M and Baker, EW ( +320) : Poossible origin of n-alkanes with a remarkable evento-odd predominance in recent marine sediments Geochim Cosmochim Acta, /*,,33-*/ O Leary, WM ( +32, ) : Lipoidal contents of specific microorganisms CRC Handbook of Microbiology,, nd Ed, Vol IV Microbial composition : Carbohydrates, Lipids, and Minerals (eds Laskin AI and Lechevalier, HA), pp -3+ -, CRC Press, Boca Raton, FL Peters, KE, Walters, CC and Moldowan, JM (eds,,**/) : The Biomarker Guide, Vol +, Biomarkers and Isotopes in the Environment and Human History, Vol,, Biomarkers and Isotopes in Petroleum Exploration and Earth History, ++// p, Cambridge University Press, Cambridge Reddy, GSN, Aggarwal, RK, Matsumoto, GI and Shivaji, S (,***) : Arthrobacter flavus sp nov, a psychrophilic bacterium isolated from a pond in McMurdo Dry Valley, Antarctica Int J Sys Evol Microbiol, /*, +//- +/0+ Reddy, GSN, Prakash, JSS, Prabahar, V, Matsumoto, GI, Stackebrandt, E and Shivaji, S 239

24 (,**-a) : Kocuria polaris sp nov, an orange-pigmented psychrophilic bacterium isolated from an Antarctic cyanobacterial mat sample Int J Sys Evol Microbiol, /-, Reddy, GSN, Prakash, JSS, Srinivas, R, Matsumoto, GI and Shivaji, S (,**-b) : Leifsonia rubra sp nov and Leifsonia aurea sp nov, psychrophiles from a pond in Antarctica Int J Syst Evol Microbiol, /-, Seifert, WK and Moldowan, JM ( +32+ ) : Paleoreconstruction by biological markers Geochim Cosmochim Acta, /, 12-13,**- :,**- Suzuki, N ( +32 ) : Estimation of maximum temperature of mudstone by two kinetic prameters ; epimerization of sterane and hopane Geochim Cosmochim Acta, 2,,,1-,,2, Volkman, JK, SM Barrett, SI Blackburn, MP Mansour, EL Sikes and F Gelin ( +332) : Microbial biomarkers A review of recent research developments Org Geochem,,3, : -,+ Williams, DF Qui, L, Karabanov, E and Gvozdkov, A ( +33-) : Geochemical indicators of productivity and sources of organic matter in surficial sediments of Lake Baikal Rus Geol Geophys, -- ( +* ++ ), +++ +,/,**1 3,* 0* 240