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Geochemicaljourn Al,Vol.28,Pp.263To287,1994 O Xyg

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Geochemicaljourn Al,Vol.28,Pp.263To287,1994 O Xyg GeochemicalJourn al,Vol.28,pp.263to287,1994 O x y g en, h y d ro ge n, a n d s ulfu r isoto p e syste m atics o f th e crater la k e syste m o f P o ~s V olc a n o, C osta R ic a G ARY L. R OW E, Jr.* Departm entofG eosciences, The Pennsylvania State University, University Park, PA 16802,U.S.A. (Received M ay 6,1993,･Accepted April 24, 1994) O xygen, hydrogen, and sulfurisotope data for fluids and m inerals associated with the craterlake of po~s Volcano, Costa Rica, are interp reted in the context ofthe chem ical and hydrologic stru cture ofthe volcano.Oxygen and hydrogenisotope dataw ere obtained forrain,spring,and riverw ater,Iow-tem perature fum arole condensates, and acid brines collected from the hotcraterlake before its disappearance in A pril 1989. Flank river and spring w aters whose solute com positions have been m odified by volcanic and hydrotherm al activity have, with one exception,isotopic com positions similar to local m eteoric water. Acid chloride-sulfate brines ofthe sum m it craterlake are extrem ely enriched in 180 with respectto local m eteoric water;in the m ost enriched brines 180 shifts are greaterthan 200100.The 180 shiftisrelatedto a kinetic isotope effectassociated with theintense evaporation atthe surface ofthelake. These sam e brines exhibit only m inim alshiftsin theirD/H ratios. The apparentlack ofdeuterium fractionation in the brines is attributed to an increase in the flux ofisotopically light steam into the craterlake and/or a decrease in the deute rium fractionation factor for evaporation that occurs atthe surface ofthe lake. The decrease in deuterium fractionation is correlated with large increases in lake-brine acidity and dissolved solids con- centration thatpreceded the disappearance ofthe lake. Sulfurisotope data are presented for H2S and S02 gas collected from low tem perature fum aroles;dis- solved sulfatein spring,river, and craterlake w aters;and native sulfur and gypsum found in the acid lake and active crater area. As02-H2s forlow tem perature gasesis approxim ately 240100indicating an equilibra- tiontem peratureof165'C. As04-H2S forlow temperatu re H2S andlake brine sulfateisapproxim ately 230100, allindicating subsurface equilibration occured at 265'C. The H2S and native sulfur are both highly de- pleted in 34S (834S = -8to -1Ioloo). 634S valuesof34S-depleted H2S and 34S-enriched sulfate in lake brine are produced by disproportionation ofS02 released by the shallow m agm a body.N ative sulfuris form ed bythe oxidation of34S-depleted H2S by non-sulfu r-bearing oxidantssuch as atm ospheric oxygen and ferric iron. M ass-balance calculations indicate that sulfitolysis of polythionic acids could also result in the deposition of significant quantities ofnative sulfur.Im plications ofthe isotopic com position of present- day fluids observ ed at Po~s V olcano with respectto the isotope system atics of acid-sulfate ore deposits are considered. the isotope system atics of crater lakes and their INTRODUCTION associated hydrotherm al system s is driven by Crater lakes hosted by active volcanos repre- econom ic, scientific, and hazard m itigation con- sent unique geochem icalenvironm ents. Such lakes cern s. For instance, stable isotope data are com - are the s urface expression ofhigh-level geotherm al m only used to evaluate the econom ic potential of system s and act as condensers for fluids and gases geotherm al system s associated with active volca- re leased by sh allow m agm a bodies (Giggenbach, nos (e.g., Traineau et al., 1989; Giggenbach and 1974; Bran tley et al., 1987, 1993). R esearch into C or ales, 1992). G eochem ical processes that oc- *Presentaddress' U.S. GeologicalSurvey. Water Resources Division,975 West ThirdAve.,Columbus, OH 43212, U.S.A. 263 264 G. L. Rowe, Jr. cur in shallow, volcano-hosted hydrotherm al sys- 1). po~s lavas are calc-alkaline basalts and tem s are considered to be analogousto those that andesites; deposits exposed in the sum m it area and occur during the form ation of epitherm al acid active crater are com posed of approxim ately equal sulfate precio us m etal deposits(H ayba et al.,1985; volum es oflava and w eathered pyroclastic m ate- Stoffgren, 1987; Rye etal., 199 2; H edenquist and rial (Prosser and C ar, 1987). Eruptive activity in A oki, 1991; Rye, 1993; H edenqu ist et al., 1993). historic tim es has been confined to the active crater The role of acid fluids generated by crater-lak e and consists of continuous low -level degassing, hydrotherm al system s in the form ation of acid frequent geyser-like phreatic eruptions in the cra- sulfate ore deposits has also received attention ter lake, and rare phreato-m agm atic eruptions (R ow e, 1991; C hristenson and W ood, 1993). Fi- (Casert ano etal., 1983). nally, tem poral variations in the sul fur isotope A sm all but vigorous m agm atic-hydrotherm al com p osition of w ater collected from Y ugam a system at the sum m it of Po~s V olcano is charac- crater lake have been used to assess recent v olca- terized by (1) a hot, acid crater lake (300 m eters nic activity at K usatsu-Shirane V olcano, Japan in diam eter) w hose level, tem perature, and w ater (O hsaw a et al., 1993). chem istry vary sharp ly in response to changes in Th e purp ose ofthis paper is to sum m arize and rainfall,therm alpower output, and sum mitseismic interp ret oxygen, hydrogen, and sulfurisotope data activity (Brow n et al., 1989; R ow e et al., 1992a, rece ntly obt ained a t Po~s V olcano in the context b), and (2)the rem nants ofa 30-m eter-high pyro- ofa chemical and hydrologic m odel developed for clastic cone form ed during the last phreato-m ag- the sum mitcraterlake and associated hydr otherm al m atic eru ption of Po~s in 1953-54 (C asertano et system (R ow e et al., 1992a, 1994). These data al., 1983). This cone, on the southern edge ofthe p rovide insight into the geochem ical and hydro- pit crater occupied by the lake,is the site ofsub- logic processes associated w ith the form ation and aerial fum arolic activity of variable tem perature circulation of acidic chloride-sulfate brines ofthe and intensity (Casert ano et al., 1983, 1987; R ow e crater lake. The isotope data also provide infor- et al., 1992a). The crater-lake brines are am ong m ation regarding the origin of the sulfuric acid the m ost acidic natural w aters ever sam pled; pH responsible for the extrem e acidity of the lake ofthe acid-chloride-sulfate brines is usually near brin e,the origin of native sulfurin t he craterlake zero (T able 1). and its sedim ents, and the origin of the diverse Previous studies of the crater lake system solute com positions ofriversthat drain the flanks (C asertano et al., 1987; R ow e et al., 1992a) indi- of Po~s V olcano. Finally, im plications ofthe re- cate that hydrotherm alcirculation is driven by the sults of this study w ith resp ect to the isotopic release of heat and volatiles from a pipe-like system atics of epit herm al ore deposits are briefly m agm a body w hose upper m argin lies approxi- discussed. m ately 500 m beneath the floor ofthe active cra- ter(R ym er and Brow n, 1987, 1989). H eattransfer Geochemica/ and hydrogeologic structure of Pods is by a heat-pipe m echanism in w hich condensed Volcano hydr otherm al steam and seeping lake brines are 'po~s V olcano,along with the adjacent volcanic revaporized near the chilled upper part of the centers of Platanar-Porvenir, B arva, and lrazti- m agm a body to supply heatto the overlyingliquid- Turrialba, is part of the Q uaternary C ordillera dom inated convection cell (H urst et al., 1991; C entral ofcentral Costa Rica(Fig.1). The sum m it R ow e et al., 1992a). R ecycling of lake brine and area ofPo~s consists ofthree nested calderas and condensed steam is a key feature ofthe craterlake an active crater bordered by tw o com posite cones: hydrotherm al system : volatile fluxes calculated V on Frantzius to the north (E = 2639 m) and from pow er outputestim atesindicatethatlessthan B otos, the site of a 400 m eter diam eter cold 1Oolo ofthe heat su pplied to th e crater lake is de- freshw ater lake,to the south (E = 2708 m ) (Fig. rived by condensation ofm agm atic steam degassed O,H and S isotope system atics of Poas V olcano 265 84'20' 84'16' 84'12' ~ ~¥ 1¥~00;// 1o'16' ,., ｢r l ~ ~'d20'~ ¥ ' ¥o /i¥ ' b/: ~ ¥~( ~~ CERR r~ ¥b~i~) ' (/e '4 ~;' l: ( / ~ ~i ~Cl ~ l E'V / l ' {, ~ ~ 3~t, f~le I ¥ ~ :~f ' '~ '~ ¥ /./6;~] ¥,¥ 10'12' ~~ )!~.~;~2i¥ 4~i)~_~:~~ "~ "'A!/~:7n::~~ TZ~.~,1/;i1e~/f:~~{2 " / /~ ¥ ' / l ｢:l i /~ ' V ))~ <~ ~ / ( ( ' ( ~ ' 'IA~Inv ¥ / 5~ ~' .~1 ¥ - 9 T~ l l ' f ' ~ ~" VOpLCA (B~O ]NOES'j;~ ~: ( / j ~ IU~ / <:~~~~' ~.¥ . ~ t Ei /1 //l/ l ¥ prl 10'08' '/ // ' 7 2000 / OO l iI '>' *' *. /' .BAR~ *~ )// ' ~~-~:1"- + c! 11' ' / . , ~ p;oasIo ｢ ' ' / ｢' ' ' l'2Qb ~~ // COSTA' / l l'/ / /' RICAf (C'J . '. l l ' . pacific ocea" , ! ~ 10004' 85' 84" 83' o 2 4, KILO METERS EXPLANATIO N I l l RIO AGRIO W ATERSHED TYPE OF WATER SITES--nvmberedsites have com positionaldata availabie O Acidchloride-sulfate l Neutralsulfate El Acidsulfate C) Neutralbicarbo nate - 2000 - ELEVATION--in m etersabo vesealevel.
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