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HomeMy WebLinkAboutAkutan geothermal report Appendix A 2014 Appendix A USGS Report: Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 U.S. Department of the Interior U.S. Geological Survey Scientific Investigations Report 2013–5231 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 Cover. View to the southeast of the main stem of Hot Springs Creek, showing the outflow from the group A hot springs (lower far right edge of image) and steam from group B hot spring (near center). U.S. Geological Survey photograph by Deborah Bergfeld, July 28, 2012. Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 By Deborah Bergfeld, Jennifer L. Lewicki, William C. Evans, Andrew G. Hunt, Kinga Revesz, and Mark Huebner Scientific Investigations Report 2013–5231 U.S. Department of the Interior U.S. Geological Survey U.S. Department of the Interior SALLY JEWELL, Secretary U.S. Geological Survey Suzette M. Kimball, Acting Director U.S. Geological Survey, Reston, Virginia: 2014 For more information on the USGS—the Federal source for science about the Earth, its natural and living resources, natural hazards, and the environment, visit http://www.usgs.gov or call 1–888–ASK–USGS. For an overview of USGS information products, including maps, imagery, and publications, visit http://www.usgs.gov/pubprod To order this and other USGS information products, visit http://store.usgs.gov Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. Although this information product, for the most part, is in the public domain, it also may contain copyrighted materials as noted in the text. Permission to reproduce copyrighted items must be secured from the copyright owner. Suggested citation: Bergfeld, D., Lewicki, J.L., Evans, W.C., Hunt, A.G., Revesz, K., and Huebner, M., 2014, Geochemical investigation of the hydrothermal system on Akutan Island, Alaska, July 2012: U.S. Geological Survey Scientific Investigations Report 2013–5231, 20 p., http://dx.doi.org/10.3133/sir20135231. ISSN 2328-0328 (online) iii Contents Abstract ...........................................................................................................................................................1 Introduction.....................................................................................................................................................1 Methods...........................................................................................................................................................3 Site Descriptions ............................................................................................................................................3 Hot Springs.............................................................................................................................................3 Other Waters .........................................................................................................................................8 Gas Vents ...............................................................................................................................................8 Results .............................................................................................................................................................9 Water and Gas Chemistry ....................................................................................................................9 Discharge ...............................................................................................................................................9 Discussion .......................................................................................................................................................9 Hot-Spring Water Geochemistry ........................................................................................................9 Hot-Spring Geothermometry .............................................................................................................12 Gases at Akutan ..................................................................................................................................12 Thermal Chloride Flux.........................................................................................................................15 Change in the Akutan Hydrothermal System .................................................................................16 Summary........................................................................................................................................................16 Acknowledgments .......................................................................................................................................18 References Cited..........................................................................................................................................18 Figures 1. Topographic map of northeastern part of Akutan Island, showing locations of caldera and modern cinder cone of Akutan Volcano, flank fumarole field, and Akutan village ........................................................................................................................2 2. Photos showing features in Hot Springs valley. Aerial photograph of Hot Springs valley, with steam plume visible from group C hot spring. Vent-type hot spring in group A. Pool-type hot spring with gas bubbles in group B ...........................8 3. Scatterplots showing positive correlation between Cl concentration and other components in Akutan hot-spring waters and negative correlation between Cl and Mg concentrations ........................................................................................13 4. Plots of isotopic composition and chloride concentrations for Akutan hot springs and local cold creek water in 2012. δD versus δ18O values of hot springs and cold creek water relative to World Meteoric Water Line. Cl concentration versus δ18O values in hot-spring water, showing positive correlation ..............................14 5. Ternary N2-He-Ar diagram for gas samples collected at Akutan Volcano in 1981, 1996, and 2012 ...............................................................................................................15 6. Scatterplots showing differences in water chemistry for Akutan hot springs in 1980–81 and 2012 ....................................................................................................................17 7. Schematic cross section of hydrothermal system on Akutan Island ..........................................18 iv Tables 1. Sample-collection parameters, chemical analyses and isotope values for waters from Akutan Volcano, Alaska sampled during 1996 and 2012..................................4 2. Sample locations, gas chemistry and noble-gas data for degassing features around Akutan Volcano, Alaska, sampled during 2012 ........................................................10 3. Chloride concentrations and stream discharges used to determine geothermal flux and heat output from hot springs along sections of Hot Springs Creek near Akutan Volcano, Alaska, in 1981 and 2012.....................................................................12 Conversion Factors SI to Inch/Pound Multiply By To obtain Length centimeter (cm)0.3937 inch (in.) meter (m)3.281 foot (ft) kilometer (km)0.6214 mile (mi) Area square meter (m2)0.0002471 acre square meter (m2)10.76 square foot (ft2) square kilometer (km2)0.3861 square mile (mi2) Volume liter (L)1.057 quart (qt) liter (L)0.2642 gallon (gal) Flow rate liter per second (L/s)15.85 gallon per minute (gal/min) Mass gram (g)0.03527 ounce, avoirdupois (oz) kilogram (kg)2.205 pound avoirdupois (lb) metric tonnes per day (t/d)1.102 tons per day (ton/d) Energy joule (J)0.0000002 kilowatthour (kWh) Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows: °F=(1.8×°C)+32 Vertical coordinate information is referenced to the World Geodetic System of 1984 (WGS 84). Horizontal coordinate information is referenced to the World Geodetic System of 1984 (WGS 84). Altitude, as used in this report, refers to distance above the vertical datum. v Abbreviations ASMW Air-saturated meteoric water DIC Dissolved inorganic carbon EFHSC East fork of Hot Springs Creek FF Flank fumarole field Q Discharge RC/RA 3He/4He corrected for atmospheric air TI Thermal influx VPBD Vienna Pee Dee Belemnite VSMOW Vienna Standard Mean Ocean Water WMWL World Meteoric Water Line Chemical unit abbreviations J/g Joules per gram mS/cm millisiemens per centimeter μS/cm microsiemens per centimeter MW megawatts Chemical symbols and chemical species abbreviations Ar Argon B Boron Br Bromine; bromide (Br–) Ca Calcium CH4 Methane Cl Chlorine; chloride (Cl–) CO2 Carbon dioxide δ13C 13C/12C in sample compared to that of a standard reference rock δ18O 18O/16O in sample compared to that of standard mean ocean water δD 2H/1H in sample compared to that of standard mean ocean water H2 Molecular hydrogen H2O Water H2S Hydrogen sulfide HCO3 Bicarbonate (HCO3 –) He Helium 3He Helium-3 atom K Potassium Li Lithium Mg Magnesium N2 Molecular nitrogen Na Sodium Si Silicon SiO2 Silica SO4 Sulfate vi Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 By Deborah Bergfeld, Jennifer L. Lewicki, William C. Evans, Andrew G. Hunt, Kinga Revesz, and Mark Huebner Abstract We have studied the geochemistry of the hot springs on Akutan Island in detail for the first time since the early 1980s. Springs in four discrete groups (A-D) along Hot Springs Creek showed generally higher temperatures and substantially higher Na, Ca, and Cl concentrations than previously reported, and total hot-spring discharge has also increased markedly. The springs now account for a heat output of ~29 MW, about an order of magnitude more than in 1981. Gas samples from the hot springs and from a fumarolic area on the flank of Akutan Volcano show high 3He/4He ratios (>6.4 RA) after correction for air contamination and reveal a common magmatic heat source. Hot-spring gases are unusually rich in N2, Ar, and CH4, suggesting that the water has boiled and lost CO2 during upflow beneath the flank fumarole field. Gas geothermom- etry calculations applied to the flank fumarole field implies temperatures of 200–240 °C for the reservoir, and Na-K-Ca geothermometry implies temperatures near 180 °C for the out- flow waters that feed the hot springs. The results of our study confirm the existence of a substantial geothermal resource on the island. Introduction Akutan Volcano is an active stratovolcano in the east- central Aleutian Islands that has erupted at least 27 times since the late 1700s (Finch, 1935; Byers and Barth, 1953; Waytho- mas, 1999). The most recent eruption, in 1992, was followed by a seismic crisis in March 1996 (McGimsey and others, 1995; Waythomas and others, 1998). The summit caldera, at an elevation of 1,100 m, contains an active cone and ice- covered lakes (Waythomas and others, 1998). During our site visit in July 2012, we observed degassing from fumaroles and steaming ground on the cone. Surface expressions of the hydrothermal system on Akutan Island include a ~5,000-m2 fumarole field (Motyka and others, 1988) on the northeast flank of the volcano, at an elevation of ~400 m, and a series of hot springs that dis- charge at elevations close to sea level along lower parts of the northeast-trending Hot Springs valley (fig. 1). Additional warm water discharges from diffuse seeps at the mouth of Hot Springs Bay. Reconnaissance surveys of the hot springs on Akutan Island began as early as 1953 (Byers and Barth, 1953). The first detailed geochemical and geophysical investigations to assess geothermal potential occurred during the early 1980s (Motyka and Nye, 1988). Motyka and others (1988) catego- rized the hot springs as belonging to one of five groups (A-E, fig. 1) from southwest to northeast. Between 1980 and 1983, Motyka and coworkers collected water and gas samples from the springs and made discharge and load measurements of the creek above and below the hot-spring inputs; they also collected gas from the flank fumarole field. Additional inves- tigations at Akutan took place in 1996, several months after the seismic crisis (Symonds and others, 2003a, b). Studies at Akutan beginning in 2009 were related to renewed interest in geothermal development of the Akutan hydrothermal system for use by the City of Akutan and other population centers on the island. (Kolker and Mann, 2009; Kolker and others, 2012). That work included geochemical sampling, geophysical studies, and the drilling of two small-diameter temperature- gradient wells in Hot Springs valley (Kolker and others, 2012) but no new investigation of the hot-spring chemistry. We report here the results of a 5-day survey of the hydro- thermal system on Akutan Island during July 2012. Samples of gas and water were collected from the hot springs, and gas was collected from fumaroles on the flank of the volcano and from an area of acid-altered steaming ground on the cone. Fuma- roles were also present on the cone but not readily accessible. We made discharge measurements on the main stem of Hot Springs Creek and two of its tributaries (fig. 1). 2 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 3 MILES3 KILOMETERS001 MILE1 KILOMETER00ALASKAAkutan54° 10’166° 00’165° 50’FFRFFmodern cinder conecalderaHot Springs BayHot Springs BayHot Springs CreekHot Springs BayAkutan Village1,5001,0001,0002,0002,0002,5003,0003,5004,0003,0001,0005005003,0001,5001,5001,0001,5002,0002,500SGSDBACE414181311512152016T21317910500500Flank fumarole fieldLake IceLand-surface contour–Shows altitude of land surface in feet above NGVD 29. Contour interval 500 feetFault–Dashed where inferred, dotted where concealed Tributary gaging siteCreek sampling site location and numberGaged Not gaged Sample sites and 2012 sample numbers Hot spring group A Hot spring group B Hot spring group C Hot spring group DHot spring group E, tidal zone seepEXPLANATIONT18153512217500Figure 1. Topographic map of northeastern part of Akutan Island (after Richter and others, 1998), showing locations of caldera and modern cinder cone of Akutan Volcano, flank fumarole field, and Akutan village. A, B, C, D, and E, hot spring groups defined by Motyka and others (1988) and retained in this study. FF, flank fumarole field; S, snow sample location; R, rain sample location; SG, area of summit gas discharge. Site Descriptions 3 Methods General information on sample collection and analytical techniques was presented by Bergfeld and others (2011). We used digital meters to measure water temperature, specific conductance and pH at each water-sampling site. Sampling- site locations were determined by using a handheld Global Positioning System device. Whenever possible, hot-spring waters were collected from the spring orifice, but at springs with deep pools we collected from the side of the pool. We collected two samples of filtered (0.45 µm) water in plastic bottles for bulk chemistry (including major ions and trace metals), and two samples of raw water in glass bottles for stable isotope (δD, δ18O) analysis and for determination of alkalinity at all of the springs and most of the creeks. At five springs we collected an additional sample of filtered water, using a 0.1-µm filter specifically for determination of Al concentrations. Samples for cation analysis were acidified in the field to pH <2, using ultrapure nitric acid. Alkalinity titrations were performed by using sulfuric acid and a digital titrator. The titrations were typically performed on the day of sample collection, but when this procedure was impossible, the sample was stored in a refrigerator. At five of the hot springs we collected a 60-mL water sample for determination of dissolved inorganic carbon (DIC) concentration. The water was collected in a syringe and injected into a preweighed evacuated glass tube through a rubber septum and acidified in the field by injecting 0.5 mL of 6N HCl. No spring produced a vigorous gas upflow, but four springs had sufficient gas discharge to allow for sample collec- tion into an evacuated tube. The gas was collected by con- necting the sample bottle to the neck of a funnel and placing the mouth of the funnel over the bubble train. Narrow-gauge tubing was threaded through the funnel into the neck of the sample bottle, attached to a syringe, and used to pump away trapped atmospheric gas. After the atmospheric components were purged, the small tubing was removed, and the bottle was opened and allowed to fill. At two of the group A hot springs we collected a second aliquot of gas for analysis of noble-gas ratios including 3He/4He. These samples were collected in a copper tube sealed at both ends with refrigeration clamps. Three types of gas samples were collected from fuma- roles and steaming ground on the flanks and cone of Akutan Volcano. At some sampling sites, the gas was collected into empty evacuated bottles, using a funnel or metal tube to focus the gas flow. Before opening the sample bottle, we flowed gas through the collection apparatus to purge any trapped atmospheric gas. Gas collected in evacuated bottles was used for determination of bulk chemistry (for example, CO2, CH4, CO, H2) and for determination of the δ13C composition of CO2 and CH4. When a sufficient quantity of steam condensed in the bottles, the water was sent for δD and δ18O analysis. We also collected gas in evacuated bottles containing 4N NaOH solution. This method was used for determinations of bulk chemistry, concentrations of trace-gas species, and H2S, which might not be preserved in the evacuated bottles. A third set of gas samples was collected in copper tubes for analysis of noble-gas ratios. Discharge was measured at four sites, using a standard USGS wading rod and pygmy meter. The sites include Hot Springs Creek above the group A hot-spring inputs and below the group D inputs, a tributary containing the outflow from group A hot springs, and a tributary flowing from the east side of the valley that discharges into Hot Springs Creek (fig. 1). Water samples collected at three of the discharge-measurement sites were used to calculate the flux of dissolved constituents. Chemical analyses of gas and water samples were deter- mined at USGS laboratories in Menlo Park, Calif. Gases were analyzed by using gas chromatographs equipped with thermal- conductivity and flame-ionization detectors. Water samples were analyzed for anions by ion chromatography, and for cations by argon plasma optical-emission spectrometry. Stable isotope analyses of waters, steam, DIC, CO2, and CH4 were performed by mass spectrometry at the USGS Stable Isotope Laboratory in Reston, Va. Noble-gas ratios were determined by mass spectrometry at the USGS Noble Gas Laboratory in Denver, Colo. Reported 3He/4He ratios are corrected for minor amounts of air and are given as RC/RA values. Site Descriptions Hot Springs On the basis of the map by Motyka and others (1988), the layout of the hot springs in 2012 was apparently much like that in the 1980s. In this report, we retain their nomenclature for the hot-spring groups (fig. 1). Group E waters are thermal seeps in the intertidal zone that discharge diffusely and mix with seawater. We report the water chemistry for one group E site in table 1 but omit additional discussion of those data. Hot-spring groups A through D occur along a ~850-m section of lower Hot Springs valley at elevations close to sea level (fig. 1; table 1). Most of the hot springs discharge from the northwest side of Hot Springs Creek (fig. 2A). Some hot springs discharge from shallow discrete vents along the margin of volcaniclastic deposits (fig. 2B), and others originate on the valley floor and collect in pools that drain into the creek (fig. 2C). Water temperatures ranged from 60 °C to ~100 °C, with the higher temperatures at vent-type springs. The uppermost hot springs (group A, fig. 1) consist of two vents and a pool that are closely clustered and dis- charge into a small tributary stream on the west side of Hot Springs Creek. We collected water from all three hot springs (AKU12-01, AKU12-02, AKU12-03, table 1), and gas from the pool and the lowermost vent (AKU12-01 and AKU12-03, respectively). Water in the pool was cool enough to support aquatic plants, but the flow was sufficient that the surface of the pool was clear. 4 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 Table 1. Sample-collection parameters, chemical analyses and isotope values for waters from Akutan Volcano, Alaska, sampled during 1996 and 2012. [All analyses in milligrams per liter except as noted. Stable isotope values in per mil (‰) relative to Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation (VSMOW-SLAP) for δD and δ18O or relative to Vienna Pee Dee Belemnite-Space Vacuum Epitaxy Center (VPDB-SVEC) for δ13C; ---, no data. Water geothermometers: chalcedony (TCH) and quartz conductive (TQC) from Fournier (1981); Na-K-Ca (TNKC) from Fournier and Truesdell (1973). Datum for Universal Transverse Mercator (UTM) coordinates is referenced to WGS84 zone 3U. Analytical uncertainties ±5 percent at 1σ level for major species; 0.2 and 2 per mil at 2σ level for δ18O and δD, respectively] Sample number Description Date Easting (meters) Northing (meters) Elevation (meters) Temp. (°C) Cond. (µS/cm)pH δ18O (‰) δD (‰) Hot springs AKU12-01 Group A pool 07/25/2012 444006 6000806 18 60.5 1,920 6.44 -9.2 -69 AKU12-02 Group A upper vent 07/25/2012 443989 6000805 16 84.3 3,200 6.33 -8.6 -69 AKU12-03 Group A lower vent 07/25/2012 444032 6000819 18 94.0 3,050 7.00 -8.7 -69 AKU12-04 Group B upper pool 07/25/2012 444132 6000890 19 76.8 2,300 6.67 -8.9 -69 AKU12-11 Group B lower pool 07/27/2012 444255 6001052 14 75.2 1,472 6.49 -9.3 -69 AKU12-05 Group C geysering vent 07/25/2012 444349 6001222 18 100.8 3,240 6.69 -8.4 -67 AKU12-13 Group C east bank vent 07/27/2012 444461 6001338 18 73.0 1,836 6.88 -9.2 -69 AKU12-14 Group C west bank vent 07/27/2012 444339 6001217 18 99.5 2,670 6.65 -8.9 -69 AKU12-12 Group D vent spring 07/27/2012 444498 6001442 16 83.8 2,360 7.47 -8.9 -69 Cold waters AKU12-15 Upper Hot Springs Creek 07/28/2012 441925 5999860 73 5.3 55 7.49 -10.7 -74 AKU12-16 Hot Springs Creek, lower gage 07/29/2012 444721 6001526 54 10.5 266 6.86 ------ AKU12-18 Upper Hot Springs Creek at gage 07/29/2012 443357 6000037 31 5.8 60.2 7.02 ------ AKU12-19 Snow 07/30/2012 439151 5996100 505 ---33.4 --------- AKU12-20 East Fork Hot Springs Creek 07/30/2012 444634 6001377 16 5.7 115 6.71 ------ AKU12-21 Rain; Akutan Harbor 07/29/2012 449488 5998752 10 --------------- Other AKU12-17 Seep on beach 07/29/2012 444833 6001800 8 49.4 14,400 5.79 -6.3 -46 1996 Akutan waters AK-01 Vig. bubbling spring 7/27/1996 ---------97.4 2,490 6.89 -9.2 -69 AK-08 Green pool 7/30/1996 ---------60.6 1,250 6.94 -9.6 -67 AK-11 Small green pool 7/30/1996 ---------64.2 2,470 6.49 -9.5 -65 AK-02 Acidic water in fumarole field 7/28/1996 ---------90.7 2,290 2.50 -8.4 -57 Site Descriptions 5 Table 1. Sample-collection parameters, chemical analyses and isotope values for waters from Akutan Volcano, Alaska, sampled during 1996 and 2012.—Continued [All analyses in milligrams per liter except as noted. Stable isotope values in per mil (‰) relative to Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation (VSMOW-SLAP) for δD and δ18O or relative to Vienna Pee Dee Belemnite-Space Vacuum Epitaxy Center (VPDB-SVEC) for δ13C; ---, no data. Water geothermometers: chalcedony (TCH) and quartz conductive (TQC) from Fournier (1981); Na-K-Ca (TNKC) from Fournier and Truesdell (1973). Datum for Universal Transverse Mercator (UTM) coordinates is referenced to WGS84 zone 3U. Analytical uncertainties ±5 percent at 1σ level for major species; 0.2 and 2 per mil at 2σ level for δ18O and δD, respectively] Sample number δ13C-DIC (‰)Al As B Ba Br Ca Cd Cl Co CO3 Cr Cu Hot springs AKU12-01 ---<0.03 0.76 14.0 0.04 1.6 37.4 0.01 530 <0.006 0 <0.006 <0.006 AKU12-02 ---<0.055 1.51 25.1 0.05 3 61.8 0.02 980 <0.011 0 <0.011 <0.011 AKU12-03 -10.7 <0.055 1.50 23.4 0.04 2.8 41.0 0.02 920 <0.011 0 <0.011 <0.011 AKU12-04 -11.6 <0.055 1.16 18.1 0.02 2.1 45.1 0.01 700 <0.011 0 <0.011 <0.011 AKU12-11 -11.7 <0.03 0.55 10.1 0.05 1.2 39.1 <0.006 410 <0.006 0 <0.006 <0.006 AKU12-05 -9.9 <0.055 1.69 25.2 0.04 3.3 73.2 0.02 1100 <0.011 0.1 <0.011 <0.011 AKU12-13 ---<0.03 0.57 12.1 0.26 1.5 96.5 <0.006 510 <0.006 0.1 <0.006 <0.006 AKU12-14 ---<0.055 1.22 17.9 0.04 2.7 52.1 0.01 880 <0.011 0 <0.011 <0.011 AKU12-12 -11.4 <0.055 0.63 16.2 <0.011 2.5 64.5 <0.011 800 <0.011 0 <0.011 <0.011 Cold waters AKU12-15 ---0.01 <0.001 0.01 0.01 0.0039 5.3 <0.001 3.6 <0.001 0 <0.001 <0.001 AKU12-16 ---0.01 0.05 1.20 0.01 0.16 11.7 <0.001 58 <0.001 0 <0.001 <0.001 AKU12-18 ---0.01 <0.001 0.01 0.01 0.006 6.0 <0.001 4.3 <0.001 0 <0.001 <0.001 AKU12-19 ---0.05 <0.001 0.01 0.002 0.0014 0.57 <0.001 6.8 <0.001 ---<0.001 0.005 AKU12-20 ---<0.005 0.00 0.13 0.01 0.026 10.0 <0.001 13 <0.001 ---<0.001 <0.001 AKU12-21 ---------------0.057 ------12 ------------ Other AKU12-17 <0.25 0.36 6.30 <0.05 23 209.5 <0.05 7,300 <0.05 0 <0.05 <0.05 1996 Akutan waters AK-01 ---0.10 1.30 14.1 ---2.24 32.0 ---623 ---0 ------ AK-08 ---0.07 0.325 5.31 ---0.89 27.8 ---252 ---0 ------ AK-11 ---0.13 0.87 10.2 ---1.42 52.7 ---426 ---0 ------ AK-02 ---25.1 0.0051 0.059 ---<0.02 26.0 ---3.66 ---0 ------ 6 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 Table 1. Sample-collection parameters, chemical analyses and isotope values for waters from Akutan Volcano, Alaska, sampled during 1996 and 2012.—Continued [All analyses in milligrams per liter except as noted. Stable isotope values in per mil (‰) relative to Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation (VSMOW-SLAP) for δD and δ18O or relative to Vienna Pee Dee Belemnite-Space Vacuum Epitaxy Center (VPDB-SVEC) for δ13C; ---, no data. Water geothermometers: chalcedony (TCH) and quartz conductive (TQC) from Fournier (1981); Na-K-Ca (TNKC) from Fournier and Truesdell (1973). Datum for Universal Transverse Mercator (UTM) coordinates is referenced to WGS84 zone 3U. Analytical uncertainties ±5 percent at 1σ level for major species; 0.2 and 2 per mil at 2σ level for δ18O and δD, respectively] Sample number F Fe HCO3 K Li Mg Mn Mo Na NH4 Ni NO3-N1 PO4-P1 Hot springs AKU12-01 0.4 0.86 111 29.2 0.94 5.84 0.24 <0.006 325 <0.006 0.1 <0.1 AKU12-02 0.5 0.03 111 49.2 1.72 4.55 0.25 <0.011 578 ---<0.011 0.1 <0.1 AKU12-03 0.7 0.03 97 48.0 1.62 2.93 0.18 <0.011 557 ---<0.011 0.4 <0.1 AKU12-04 0.6 1.10 111 38.6 1.25 4.03 0.25 <0.011 434 ---<0.011 0.1 <0.1 AKU12-11 0.4 1.70 128 26.1 0.63 8.04 0.51 <0.006 246 ---<0.006 0.2 <0.1 AKU12-05 0.8 0.04 44 51.4 1.56 2.04 0.16 <0.011 636 ---<0.011 0.3 <0.1 AKU12-13 0.3 0.75 134 32.9 0.64 17.1 0.75 <0.006 228 ---<0.006 <0.1 <0.1 AKU12-14 0.6 0.35 42 40.5 1.27 3.89 0.26 <0.011 494 ---<0.011 0.1 <0.1 AKU12-12 0.5 <0.022 81 37.8 1.14 4.47 0.05 <0.011 452 ---<0.011 <0.1 <0.1 Cold waters AKU12-15 0.03 0.04 16 0.34 <0.001 0.86 0.02 <0.001 3 ---<0.001 0.02 <0.01 AKU12-16 0.06 0.35 35 3.17 0.08 2.02 0.10 <0.001 33 ---<0.001 0.01 <0.01 AKU12-18 0.04 0.03 18 0.38 <0.001 1.00 0.02 <0.001 4 ---<0.001 0.02 <0.01 AKU12-19 0.01 0.03 ---0.82 <0.001 0.50 0.03 <0.001 4 ---<0.001 0.03 <0.01 AKU12-20 0.04 0.33 ---0.68 0.00 2.12 0.08 <0.001 9 ---<0.001 <0.01 <0.01 AKU12-21 0.074 ------------------------------0.89 <0.065 Other AKU12-17 bdl <0.1 69 137 1.51 610 0.28 <0.05 3,578 <0.05 <1 <1 1996 Akutan waters AK-01 0.81 0.08 176 39.2 1.40 2.74 0.15 ---433 0.99 ---<0.05 --- AK-08 0.41 <0.01 117 15.0 0.48 2.90 <0.01 ---184 0.55 ---0.35 --- AK-11 0.60 1.66 159 27.6 0.83 5.79 0.35 ---266 1.33 ---<0.02 --- AK-02 0.22 41.0 0 2.59 <0.01 8.92 0.71 ---14.1 12.8 ---<0.02 --- Site Descriptions 7 Table 1. Sample-collection parameters, chemical analyses and isotope values for waters from Akutan Volcano, Alaska, sampled during 1996 and 2012.—Continued [All analyses in milligrams per liter except as noted. Stable isotope values in per mil (‰) relative to Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation (VSMOW-SLAP) for δD and δ18O or relative to Vienna Pee Dee Belemnite-Space Vacuum Epitaxy Center (VPDB-SVEC) for δ13C; ---, no data. Water geothermometers: chalcedony (TCH) and quartz conductive (TQC) from Fournier (1981); Na-K-Ca (TNKC) from Fournier and Truesdell (1973). Datum for Universal Transverse Mercator (UTM) coordinates is referenced to WGS84 zone 3U. Analytical uncertainties ±5 percent at 1σ level for major species; 0.2 and 2 per mil at 2σ level for δ18O and δD, respectively] Sample number Rb Se SiO2 SO4 Sr Zn TDS Cation Anion Balance TCH(°C) TQC(°C) TNKC(°C) Hot springs AKU12-01 0.15 <0.006 122 22 0.39 <0.012 1,202 17.4 17.3 0.9%123 148 181 AKU12-02 0.26 <0.011 155 31 0.69 <0.022 2,004 30.1 30.2 -0.3%140 163 184 AKU12-03 0.26 <0.011 158 37 0.56 0.025 1,891 27.9 28.4 -1.5%141 164 188 AKU12-04 0.19 <0.011 147 29 0.58 <0.022 1,534 22.7 22.2 2.0%146 160 184 AKU12-11 0.14 <0.006 161 17 0.47 <0.012 1,050 14.2 14.1 0.8%136 166 184 AKU12-05 0.30 <0.011 169 54 1.14 <0.022 2,165 33.0 33.0 0.1%129 169 181 AKU12-13 0.13 <0.006 134 28 0.95 <0.012 1,198 17.1 17.2 -0.4%142 154 192 AKU12-14 0.22 <0.011 140 43 0.83 <0.022 1,721 25.6 26.5 -3.2%133 157 180 AKU12-12 0.20 <0.011 141 41 0.85 <0.022 1,643 24.4 24.8 -1.7%133 157 178 Cold waters AKU12-15 <0.01 <0.001 7 5.5 0.03 <0.002 42 0.5 0.5 3.6%--------- AKU12-16 0.01 <0.001 21 6.7 0.10 0.005 172 2.3 2.4 -2.8%--------- AKU12-18 <0.01 <0.001 8 5.3 0.04 0.002 47 0.6 0.5 8.1%--------- AKU12-19 <0.01 <0.005 0.28 1.1 0.01 0.064 14 0.3 --------------- AKU12-20 <0.01 <0.001 15 3.2 0.05 0.008 53 1.1 --------------- AKU12-21 ---------5.7 --------------------------- Other AKU12-17 <0.5 <0.05 116 970 4 <0.1 13,024 217.3 224.5 -3.3%--------- 1996 Akutan waters AK-01 ------175 49.0 0.42 ---1,552 21.9 22.2 -1.4%149 171 188 AK-08 ------88.6 33.0 0.31 ---729 10.1 10.0 1.2%103 131 168 AK-11 ------126 36.0 0.52 ---1,118 15.7 15.9 -1.4%126 151 182 AK-02 ------121 662 0.11 ---918 11.6 13.9 -18.0%122 148 34 1Nitrate is reported as milligrams per liter nitrogen; phosphate reported as milligrams per liter phosphorus. 8 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 The hot springs in groups B, C, and D (fig. 1) discharge into the main stem of Hot Springs Creek. We sampled gas and water at two pools in group B ~200 m apart (AKU12-04, AKU12-11, table 1). Some pools of thermal water along the B-C traverse were either shallow and muddy or stagnant and choked with mats of vegetation. Given time constraints, these waters were not sampled. No significant gas was discharging at any of the hot springs below group B (fig. 1). All of the samples collected downstream of the group B hot springs were from vents. We sampled three group C hot springs along the edge of the creek (AKU12-05, AKU12-13, AKU12-14) and a single group D hot spring (AKU12-12) that discharged close to the creek. Two of the group C hot springs on the west side of Hot Springs Creek were boiling. At one site, the boiling water created a small geyser that fountained to ~40 cm, with a highly visible steam cloud. The water filled its basin and roiled violently for more than a minute before draining away. The fill-drain cycle repeated within 5 to 10 minutes. Other Waters Creek waters were collected concurrently with gaging at Hot Springs Creek below the hot springs (AKU12-16, table 1) at a tributary that flows in from the east (AKU12-20; denoted as the east fork of Hot Spring Creek [EFHSC] by Motyka and others, 1988) and at Hot Springs Creek above Hot Springs valley (AKU12-18, fig. 1). We also collected creek water above the upper gage site (AKU12-15), two samples of precipitation that included “old” snow on the northwest flank of an unnamed peak ~4 km southeast of the summit caldera, and a rain sample along the coast in the village of Akutan (AKU12-19 and AKU12-21, respectively, fig. 1). Gas Vents We observed gas discharging at several sites on the modern cinder cone within the summit caldera, the most accessible of which was a steeply sloping area of acid-altered ground (SG, fig. 1). A few spots had a focused discharge, but the overall discharge was weak across a broad area encrusted with sulfur-bearing minerals. The ground surface was dry, but the steam upflow created muddy conditions under the first few centimeters of crust. The area of degassing vents on the flank of the volcano (FF, fig. 1) was described in earlier studies as containing “geo- thermal fumaroles,” distinct from the “volcanic fumaroles” on the summit cone (Motyka and others, 1993). This area is larger and more active than the degassing sites on the cone. Large plumes of steam discharge from fumaroles and roiling mud pots, rivulets of acidic water flow through the area, and the ground surface is acid-altered with little vegetation. In 2012, we observed evidence of a recent mudflow from the lower part of the active area down into a ravine. The 2012 sampling sites included a vent fumarole with a strong focused discharge and a drowned fumarole, herein called a frying pan. A B C Figure 2. Photos showing features in Hot Springs valley. A, Aerial photograph of Hot Springs valley, with steam plume visible from group C hot spring. View northwestward. B, Vent- type hot spring (AKU12-02) in group A. C, Pool-type hot spring with gas bubbles (AKU12-04) in group B. Discussion 9 Results Water and Gas Chemistry The locations and chemical data for waters sampled in 2012 are listed in table 1, which includes four previously unpublished analyses of Akutan waters collected by R.B. Symonds in 1996. The 1996 data lack precise coordinates, and so we cannot relate the results to a specific hot-spring group. The hot springs are composed of neutral-chloride geothermal waters (Goff and Janik, 2000) and have Cl concentrations ranging from 410 to 1,100 mg/L, with Na as the main cation. In comparison, the local meteoric waters show a mixed cation composition and have Cl and SO4 concentrations as high as 12.0 and 5.7 mg/L, respectively, greater than for typical continental precipitation (Root and others, 2005) but much lower than in the hot springs. The water in EFHSC contained 13 mg/L Cl, just slightly greater than in the rain sample. The Cl concentration in Hot Springs Creek at the lower gage (downstream of all the hot springs and the confluence with EFHSC) was 58 mg/L, demonstrating a considerable flux of geothermal chloride contributed from the springs. The δD and δ18O values of the spring waters range from -69 to -67 per mil and from -9.3 to -8.4 per mil, respectively, relative to Vienna Standard Mean Ocean Water (VSMOW), in comparison with the values of –74 and –10.7 per mil, respectively, of creek water (table 1). DIC concentrations of waters in the five sampled hot springs are relatively low (0.5–3.7 µmol CO2/mg H2O), with δ13C-DIC values ranging from -11.7 to -9.9 per mil relative to Vienna Pee Dee Belem- nite (VPDB). The chemical compositions of the collected gases are diverse (table 2). Gas from the crater and the hot-spring pools has high N2 and Ar concentrations. In general, these samples are not air contaminated; only one sample (AK12-01, table 2) contained significant oxygen. Gas from the pools is distinguishable from crater gas by having high CH4 and low H2S concentrations. Gas from the group A vent hot spring (AKU12-03) is similar to that from the flank fumarole field in its high CO2 and much lower N2 concentrations. He concen- trations are generally low in all gas samples. He isotopes in the gas from group A hot springs and the flank fumarole have RC/RA ratios >6.4 that show strong inputs of 3He from a mag- matic source. Discharge Discharge measurements on Hot Springs Creek above and below the hot springs, on a small tributary to Hot Springs Creek that receives the discharge of the group A hot springs, and on EFHSC near the confluence with Hot Springs Creek (fig. 1) are listed in table 3. The upstream discharge in Hot Springs Creek was 890 L/s, and the downstream discharge was 1,348 L/s. The discharge of EFHSC was 245 L/s, suggesting that the hot springs could add as much as ~200 L/s to the flow of Hot Springs Creek. Discussion Hot-Spring Water Geochemistry Chloride is a useful tracer of source fluids because it behaves conservatively and Cl concentrations are low in meteoric water and relatively high in the hot springs. Our results indicate that large variations in Cl concentrations occur within each hot-spring group and that pool waters typi- cally have lower Cl concentrations than the waters in vent hot springs (table 1). We observed no correlation between Cl concentrations and the locations of springs along the flowpath of Hot Spring Creek. In contrast, strong positive correlations (R2 = 0.86–0.99) exist between Cl and Br, Na, B, Li, and specific conductance (fig. 3). The strong correlations between Cl and the conservative species Br and B suggest that all of the hot-spring waters are varyingly diluted from a common source that is not seawater. Concentrations of less conservative species, such as SO4, Si, and Ca, correlate somewhat with Cl but are more scattered. Waters in high-temperature geothermal systems typically have low Mg contents (Nicholson, 1993). The water from a group C vent hot spring that discharges from the east side of the creek is unusual in that it had relatively high Mg con- centrations (AKU12-13, table 1). Excluding that site, a clear negative correlation exists between Mg and Cl in the spring waters (R2 = 0.80, fig. 3). Extrapolation of the Mg trendline to zero suggests that the source fluid has a Cl concentration of ~1,300 mg/L. Figure 3A shows that the δ18O values of hot-spring waters are shifted to the right of the World Meteoric Water Line (WMWL) by ~1.0 to 1.5 per mil. Although such a shift could indicate a component of magmatic water, similar shifts have been observed in numerous geothermal systems with neutral-chloride waters and result from oxygen-isotope exchange between the reservoir rocks and hydrothermal fluids (Craig, 1963; Sheppard, 1986). Typically, no correla- tive change occurs in δD values because rocks contain little deuterium, and the hydrogen-isotope systematics are buffered by the water (Craig, 1963; Sheppard, 1986). Examination of the hot-spring waters on Akutan Island shows slight differences in the isotopic composition of pools and vents. Water in the geysering spring has the highest δD and δ18O values and is an outlier relative to the other hot springs. These high values could result from vigorous boil- ing and loss of isotopically light steam. Water in the pools has slightly lower δ18O values than that in most vent hot springs. The shift cannot be a function of evaporation, which would raise δD and δ18O values, and likely indicates that the pools are mixed with slightly more meteoric water than the vent hot springs. We note that, except for the geysering spring, the waters have a limited range of δD values, from –69.4 to –68.6 per mil. We can extrapolate back to the WMWL and derive an estimate of –9.95 to –9.80 per mil for the δ18O con- tent of the cold groundwater that dilutes the hot springs and pools (fig. 4A). 10 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 Table 2. Sample locations, gas chemistry and noble-gas data for degassing features around Akutan Volcano, Alaska, sampled during 2012.[All gas compositions in volume percent; dashes, no data. Types: E, empty bottle; N, bottle containing NaOH solution. R/RA, 3He/4He ratio relative to air; RC/RA, 3He/4He ratio corrected for atmospheric components. Gas geothermometers: TD-P from D’Amore and Panichi (1980); TCO2-CH4 from Giggenbach (1996); TC1-C2 from Darling (1998). Datum for Universal Transverse Mercator (UTM) coordinates is referenced to WGS84 zone 3U. See Bergfeld and others (2011) for details on analytical uncertainties] Sample numberLocationDateEasting(meters)Northing(meters)Elevation(meters)TypeTemp(°C)CO2H2SHeH2CH4N2ArHot springsAKU12-01Group A pool07/25/12444006600080618E60.57.2<0.00050.00120.00022.486.41.19AKU12-03Group A lower vent07/25/12444032600081918E94.095.7<0.00050.00020.00160.613.450.11AKU12-04Group B upper pool07/25/12444132600089019E76.825.90.00560.00060.00549.463.61.04AKU12-11Group B lower pool07/27/12444255600105214E75.224.30.00120.00110.00106.767.81.11Akutan flankAKU12-09Flank fumarole07/26/124405506000347379E98.694.42.10.00090.670.222.570.005AKU12-09AFlank fumarole07/26/124405506000347379N98.694.61.70.00070.620.222.710.004AKU12-09BFlank fumarole07/26/124405506000347379N98.694.52.00.00080.650.232.600.004AKU12-10Flank frying pan07/26/124405476000367381E83.491.42.20.00080.590.214.870.034AKU12-10Flank frying pan07/26/124405476000367381N83.490.71.80.00080.590.226.560.059Akutan craterAKU12-07Crater site 207/26/1243631960002811070E95.014.82.10.00040.540.1781.30.89AKU12-08Crater site 307/26/1243632660002651082N95.013.30.60<0.0020.970.1383.81.06 Discussion 11 Table 2. Sample locations, gas chemistry and noble-gas data for degassing features around Akutan Volcano, Alaska, sampled during 2012. —Continued[All gas compositions in volume percent; dashes, no data. Types: E, empty bottle; N, bottle containing NaOH solution. R/RA, 3He/4He ratio relative to air; RC/RA, 3He/4He ratio corrected for atmospheric components. Gas geothermometers: TD-P from D’Amore and Panichi (1980); TCO2-CH4 from Giggenbach (1996); TC1-C2 from Darling (1998). Datum for Universal Transverse Mercator (UTM) coordinates is referenced to WGS84 zone 3U. See Bergfeld and others (2011) for details on analytical uncertainties] Sample numberO2COC2H6C3H8C4H10HClHFNH3R/RARc/RA40Ar/36ArT D-P(°C)T CO2-CH4(°C)T C1-C2(°C)Hot springsAKU12-012.8<0.0010.0083<0.0005<0.0005---------4.796.88297---------AKU12-030.177.8E-070.0086<0.0005<0.0005---------5.856.4929644163204AKU12-040.073.2E-070.02710.00090.0011---------------------------AKU12-110.05<0.0010.02690.00210.0011---------------------------Akutan flankAKU12-090.0623.6E-040.0015<0.0005<0.0005---------7.637.64297236199223AKU12-09A0.0023.7E-040.0017<0.0001<0.0020.00090.02530.026---------231199219AKU12-09B<0.033.9E-040.00160.0002<0.0020.00320.04970.001---------234198222AKU12-100.696.1E-040.0015<0.0005<0.0005---------0.967*0.835*295235200220AKU12-10<0.036.6E-040.0017<0.0001<0.0020.00490.0158<0.025---------232 199 218Akutan craterAKU12-070.14<0.001<0.0002<0.0005<0.0005---------1.412.09288---------AKU12-08<0.030.0011------0.03030.15820.001.803.80291---------*Air-contaminated sample. 12 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 Table 3. Chloride concentrations and stream discharges used to determine geothermal flux and heat output from hot springs along sections of Hot Springs Creek near Akutan Volcano, Alaska, in 1981 and 2012. [Q, stream discharge; ---, no data] Description 2012 1981 Sample number Cl (mg/L) Q (L/s) Cl (t/d) Sample number Cl (mg/L) Q (L/s) Cl (t/d) Upper Hot Springs Creek AKU12-18 4.3 890 0.33 ------------ Group A tributary ----1196 84 1.41 11 41 71 0.25 East fork Hot Springs Creek AKU12-20 13 245 0.3 ------------ Lower Hot Springs Creek AKU12-16 58 21,348 6.8 14 10 878 0.76 Geothermal Cl flux (corrected for background) ---------6.15 ------------ Average Cl 2012 hot springs (mg/L)---759 ------------------ Discharge of spring water (L/s)---93.8 ------------------ Enthalpy change (J/g)---305 ------------------ Heat output (MW)---28.7 ------------------ 1 Calculated from specific conductance. 2 Includes flow from the east fork of Hot Springs Creek, without which Q = 1,103 L/s. Enthalpy estimate is calculated by using the steam tables of Keenan and others, (1969). The strong correlation between Cl concentration and δ18O value (R2 = 0.958, fig. 4B) can also be used to derive informa- tion about the isotopic composition of thermal and nonthermal endmembers. As noted earlier, Mg and Cl concentrations in the springs suggest that the thermal end member has a Cl concentration of ~1,300 mg/L. Extrapolation of the Cl-δ18O trendline to a Cl concentration of 1,300 mg/L yields a δ18O value for this fluid of about -8.25 per mil, whereas extrapolat- ing the data to zero Cl gives a δ18O value of about -9.80 per mil for the cold groundwater, in agreement with the value derived from δD-δ18O relations (fig. 4A). These mixing lines (fig. 4A, B) reflect the isotopic composition of the cold ground- water more accurately than does the single cold creek sample that was analyzed. Hot-Spring Geothermometry The average temperatures estimated from silica and alkali geothermometers for the least diluted hot-spring waters, those with Cl concentrations of ≥800 mg/L, range from 129 °C to 188 °C (table 1). Using the quartz conductive geothermom- eter on the least diluted hot-spring water gives a maximum estimated temperature of 169 °C. Temperatures estimated from the Na-K-Ca thermometer (178–188 °C) of Fournier and Truesdell (1973) are less likely to be affected by dilution and closely agree with the measured downhole temperature of 182 °C at ~178 m in the thermal-gradient well TG-2, located near the group B hot springs (Kolker and others, 2012). The 1996 waters from sampling sites along Hot Springs Creek have lower Cl concentrations and Na-K-Ca temperatures of 168–188 °C. Gases at Akutan The composition of the gas on Akutan Island varies widely (table 2), and much of the variation likely results from shallow processes that greatly affect the final gas chemistry. He isotope ratios in five samples indicate that the degassing features at all sampling sites (summit crater, flank, lower Hot Springs valley) have some input of magmatic gas that is varyingly diluted with crustal gas before discharging. A sixth sample was badly air contaminated. The gas collected from the flank fumarole field on Akutan Volcano has high CO2 and H2S concentrations and relatively low concentrations of air-derived gas (table 2) and has more geothermal characteristics than the gas from other sites on Akutan Island. On a ternary He-Ar-N2 diagram (fig. 5), gas from the flank fumarole falls along a trend defined by gas from other Cascade Range and Aleutian Arc (CRAA) volcanoes (fig. 2; Symonds and others, 2003b). Gas from the flank fry- ing pan falls off the CRAA trend because of its higher N2 and Ar concentrations and shows some influence of air-derived components. Calculations using three gas geothermometers suggest equilibration temperatures for gas in the flank fuma- role field of ~200–240 °C (table 2). Gas from two sampling sites in the summit crater had elevated H2 and H2S concentrations similar to typical volcanic gas (table 2), whereas high N2 and Ar concentrations indi- cate that the deep-sourced component has been substantially diluted by the addition of atmospheric air (fig. 5). The absence of O2 indicates that the samples were not air contaminated during collection. Similar trends are evident for the composi- tion of summit and flank gases collected from fumaroles in Discussion 13 Trend line for the dilution of seawater Linear regression through measured valuesGroup A springs Group B springs Group C springs Group D springsEXPLANATION2,5001,5005003,5002,0001,0003,0000200 4000600 800 1,000 1,200Cl, in milligrams per literSpecific conductance, in microsiemens per centimeterR2=0.96020406010030500 200 400 600 800 1,000 1,200SO4, in milligrams per literCl, in milligrams per liter1.40.21.00.61.81.200.80.41.6Li, in milligrams per liter0600 800 1,000 1,200200 400R2=0.861Cl, in milligrams per liter6040201008050301009070200 4000600 800 1,000 1,200Ca, in milligrams per literCl, in milligrams per liter1062181484016120 200 400 600 800 1,000 1,200Mg, in milligrams per literR2=0.802Cl, in milligrams per liter100602018014080400160120SiO2, in milligrams per liter0600 800 1,000 1,200200 400Cl, in milligrams per liter200 40070010050030060004002000600 800 1,000 1,200Na, in milligrams per literR2=0.961Cl, in milligrams per liter30020100 200 400 600 800 1,000 1,200B, in milligrams per literSeawaterR2=0.891Cl, in milligrams per liter3.50.52.51.53.002.01.00600 800 1,000 1,200200 400Br, in milligrams per literR2=0.997SeawaterCl, in milligrams per literFigure 3. Scatterplots showing positive correlation between Cl concentration and other components in Akutan hot-spring waters and negative correlation between Cl and Mg concentrations. Solid trend lines are shown for specific conductance and Br, Na, B, and Li concentrations where linear regression of data yield R2 ≥0.86. Trend line in Mg-Cl plot is calculated by excluding one sample with anomalously high Mg concentration. 14 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 World Meteoric Water Linegeysering spring predicted range for cold groundwater dilution by groundwater thermal end memberR2=0.958Linear regression through measured values; dashed red where extrapolated Group A vents Group A pool Group B pools Group C vents Group D vent Cold creek EXPLANATION -11.0 -10.5 -10.0 -9.5 -9.0 -8.5 -8.0-76 -74 -72 -70 -68 -66 A B Cl, in milligrams per literδ18O per mil (SMOW)δD per mil (SMOW)δ18O per mil (SMOW) -11.0 -10.5 -10.0 -9.5 -9.0 -8.5 -8.0 0 200 400 600 800 1,000 1,200 100 300 500 700 900 1,100 1,300 Figure 4. Plots of isotopic composition and chloride concentrations for Akutan hot springs and local cold creek water in 2012. A, δD versus δ18O values of hot springs and cold creek water relative to World Meteoric Water Line. Horizontal lines show range of δD values in all hot-spring waters except that from geysering spring; vertical lines show range of δ18O values predicted for cold groundwater that dilutes hot springs. B, Cl concentration versus δ18O values in hot-spring water, showing positive correlation. Line of linear regression is extrapolated to 0 and 1,300 mg/L Cl to estimate δ18O values for groundwater diluting hot springs and for undiluted thermal fluid, respectively. SMOW, Standard Mean Ocean Water. Discussion 15 1996, although the amount of atmospheric dilution for the gas from the summit crater was lower than in 2012. A sample of gas from an acidic spring on the flank in 1981 is similar to the 2012 sample from the frying pan and plots along the atmo- spheric-dilution trend (Motyka and others, 1988). Altogether, it is reasonable to assume that the gases emitting from features on the flank and summit share a common deep magmatic source. The gas composition is consistent with a weak flow of gas to the summit crater within a permeable volcanic cone that acts as a chimney and allows atmospheric air to enter the system. As the mixed gas rises to the surface, it is heated, and atmospheric O2 is consumed in the process. Gas discharge from the hot springs in 2012 was weak and produced only small bubble trains that rose through the water. The 3He/4He ratios in gas from two of these hot springs demonstrate magmatic helium inputs, but the bulk gas com- position of most samples had high N2 and low CO2 concentra- tions (table 2) that are unlike most geothermal gas emissions (for example, Goff and Janik, 2000). High N2 concentrations have been a pervasive feature of the gas at the hot springs over the years. Gas from a group A hot spring in 1981 consisted of 10.3 volume percent CO2 and 76.7 volume percent N2 (Motyka and others, 1988). A vigorously degassing hot spring in 1996 contained 89.1 volume percent CO2 and 8.8 volume percent N2 (Symonds and others, 2003a). This sample is similar to the gas from the 2012 group A vent hot spring that had the highest CO2 concentration of any sample from the hot-spring area, but even this sample is low in gases (H2S, H2) that are typical of high-temperature geothermal systems. Thermal Chloride Flux Using mass balance with the discharge measurements and the Cl concentrations in waters from the creeks and springs, we can calculate the thermal influx (TI) to Hot Springs Creek. The flux of dissolved Cl (FCl) is calculated from stream- discharge measurements (Q) and the collocated Cl concentra- tions of the water [Cl], such that for each discharge point i: (FCl)i = Qi*[Cl]i. N2/100 10 x He Ar Air ASMW (5.8) (6.5) (6.9) (7.6) (7.2) (7.3) (3.8) (2.1)Cascade Range and Aleutian Arc trendYellowsto n e t r e n d (6.0-6.3) (7.1)The GeysersFUM FP 2012 Flank 2012 Summit 2012 Hot Springs valley 1996 Flank 1996 Summit 1996 Hot Springs valley 1981 Flank 1981 Hot Springs valley EXPLANATION Figure 5. Ternary N2-He-Ar diagram for gas samples collected at Akutan Volcano in 1981, 1996, and 2012. Pre-2012 data are from Motyka and others (1988) and Symonds and others (2003a). Numbers in parentheses, RC/RA ratios. Tielines on 2012 flank fumarole samples indicate that multiple samples were collected for chemistry and only one He sample was collected for isotopic analysis. Arrow indicates that flank and summit samples fall along a mixing line between deep-sourced gas and air. Trendlines are derived from data of Symonds (2003b) for Cascade Range and Aleutian Arc (CRAA), Bergfeld and others (2011) for Yellowstone National Park, and Lowenstern and others (1999) for The Geysers, Calif. ASMW, air-saturated meteoric water; FUM, flank fumarole, FP, frying pan. 16 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 We correct for the chloride in meteoric water above the group A hot springs (U) and for the input from EFHSC. Assuming that the remaining chloride in the downstream site (D) is provided from the hot spring system, TI = (FCl)D - ((FCl)U+ (FCl)EFHSC). These calculations indicate that a thermal influx of ~6.15 metric tonnes of chloride is released by the hot-spring system each day (t/d). We can refine our understanding of individual hot-spring inputs by using the discharge measurement for the tributary below the group A hot springs. Although we did not collect a water sample, the overall excellent correlation between specific conductance and Cl concentration of the hot springs (fig. 3) allows us to calculate a chloride flux for the group A hot-spring waters. Using a linear regression of Cl concentra- tion and specific conductance for all of the hot springs, we estimate that the tributary water with a specific conductance of 745 mS/cm had a Cl concentration of ~196 mg/L (table 3). The discharge of 84 L/s yields a chloride flux of ~1.4 t/d. The remaining 4.7 t/d of thermal influx is contributed below the group A hot springs. Change in the Akutan Hydrothermal System Comparison of the hot-spring water chemistry from the early 1980s through July 2012 shows large changes in the hydrothermal system on Akutan Island (fig. 6). In general, the concentrations of most dissolved components in each spring group were higher in 2012 than in the 1980s, and we specifi- cally note the high Ca, Cl, and Na concentrations in 2012. Excluding the intertidal springs, the maximum Cl concentra- tion was 424 mg/L in the early 1980s, 623 mg/L in 1996, and 1,100 mg/L in 2012 (table 1; Motyka and others, 1988, table 6-1). Only HCO3 and SO4 lack evidence of a consistent increase from the 1980s to 2012 (fig. 6). A maximum tem- perature of 84 °C was recorded for the hot springs in 1980, in comparison with 97.4 °C at a vigorously bubbling hot spring in 1996 and two hot springs with temperatures of >99 °C in 2012 (table 1). The discharge data for Hot Springs Creek from 1981 and 2012 are comparable, even though gaging locations are not identical. A direct comparison of discharge from the tributary below the group A hot springs is possible because the stream is short and places to make measurements are limited. Discharge from the tributary in 1981 was 71 L/s, in comparison with 84 L/s in 2012 (table 3). The July 1981 discharge of 878 L/s in lower Hot Springs Creek was obtained above the confluence with EFHSC, whereas the 2012 measurement (1,348 L/s) was obtained below. Subtracting the 2012 discharge of EFHSC (245 L/s) results in a discharge of 1,103 L/s in Hot Springs Creek above the confluence. Thus, the flow in both the group A tributary and Hot Springs Creek appears to be 20–25 percent higher in 2012 than in 1981. This increase in flow could simply be attributed to seasonal or interannual changes, but the large increase in stream Cl concentrations (table 3) is clear evidence of a large increase in the hydrothermal component in Hot Springs Creek. The Cl concentration in the group A tributary increased by a factor of ~5 between 1981 and 2012, and a similar increase occurred in Hot Springs Creek below the group D hot springs, from 10 mg/L in 1981 to 58 mg/L in 2012. Because of the additional dilution from EFHSC, the measured fivefold increase for lower Hot Springs Creek considerably underes- timates the actual change. As described earlier, the Cl con- centration in EFHSC was similar to precipitation, with little evidence of thermal inputs to this stream. Thus, the Cl concen- tration in the creek increased by a greater factor than in the hot springs, a result that can be explained only by an increase in hot-spring discharge rate. We can estimate the heat output associated with the chloride flux by using the average hot-spring temperature of 83 °C and average Cl concentration of 759 mg/L for the hot springs in 2012 (table 3). A thermal chloride flux of 6.15 t/d yields a hot-water discharge of 93.8 L/s. The enthalpy anomaly of this hot water relative to the annual land-surface temperature of 10 °C (Selkregg, 1976) is 305.5 J/g, yielding a heat output of 29 MW. This value is approximately an order of magnitude higher than the heat-discharge estimate of 2.2 to 4.1 MW from 1981 (Motyka and others, 1988). Summary The existing conceptual model of the geothermal system on Akutan Island (Kolker and others, 2012) places the reser- voir in the vicinity of the flank fumarole field, which caps an upflow zone. The rising hot water loses gas and steam before flowing laterally as an outflow plume northeastward, where it discharges at the springs in Hot Springs valley after varying dilution with groundwater (fig. 7). This model fits well with our new results, particularly the gas data. The most robust gas samples that were collected from the flank fumarole had a 3He/4He ratio (RC/RA=7.6) and N2-He-Ar concentrations typi- cal of other CRAA volcanoes (Symonds and others, 2003a, b). In contrast, the chemical compositions of the hot-spring gases are strongly influenced by shallow processes. Low CO2 concentrations in most samples reflects the previous loss of this gas in the flank fumarole field, allowing N2 and Ar from the diluting groundwater and CH4 from organic sources to dominate the gas composition. Although the gas compositions are reset by low-temperature processes and are not representa- tive of deep reservoir conditions, the similarity in the isotope compositions of He in the gas and C in DIC to those in the gas from the flank fumarole field, -11.2 to -10.8 per mil (Motyka and others, 1988), support a connection between the two areas through the envisioned outflow plume. Samples collected since 1981 indicate that flank fuma- roles provide the most reliable information on the deep reser- voir temperature. Kolker and others (2012) used a gas geother- mometer based on the ratios of CO2 and H2 to Ar (Powell and Summary 17 Figure 6. Scatterplots showing differences in water chemistry for Akutan hot springs in 1980–81 and 2012. A through D, hot-spring groups of Motyka and others (1988). Results for 1980s analyses with poor charge balance are omitted, and no comparisons of B and Br concentrations are made because recent changes in analytical procedures have greatly improved precision and detection limits. Diamonds, waters measured in this study; circles, compositions from Motyka and others (1988). Cumming, 2010) to propose reservoir temperatures well above 200 °C. We obtain a temperature range of 200–240°C by using three non-Ar-based gas geothermometers. Lower temperature estimates are obtained by applying solute geothermometers to the hot-spring waters, and these temperatures reflect the cool- ing and mixing that occur on the outflow path. Temperatures of 178–188 °C calculated from the Na-K-Ca geothermometer are consistent with a measured temperature of 182 °C from a thermal-gradient well in Hot Springs valley (Kolker and others, 2012). Results from our study document increasing concentrations of hydrothermal components in the spring waters and an increase in the volume of water discharging from the hot spring system. Taken together, these findings provide unequivocal evidence that large changes in the hydro- thermal system on Akutan Island have occurred over the past ~30 years. We estimate the heat output of the current hydro- thermal system at 29 MW, approximately an order of magni- tude higher than in the early 1980s (Motyka and others, 1988). We are unaware of any other neutral-chloride hydrothermal Hot spring group Hot spring groupSpecific conductance, in microsiemens per centimeter500 2,500 1,500 3,500 3,000 0 2,000 1,000Ca, in milligrams per literSiO2, in milligrams per liter100 60 20 180 140 80 40 0 160 120 100 20 60 0 80 40 C DA B C DA B C DA B Mg, in milligrams per liter1,200 200 600 1,000 0 800 400 Cl, in milligrams per literHCO3, in milligrams per literC DA B C DA B C DA B 20 40 60 10 0 30 50 SO4, in milligrams per literLi, in milligrams per liter1.0 0.6 0.2 1.8 1.4 0.8 0.4 0 1.6 1.2Na, in milligrams per liter700 600 300 0 200 100 400 C DA B C DA B C DA B 500 10 6 2 18 14 8 4 0 16 12 100 60 20 180 140 80 40 0 160 120 Hot spring group 18 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 Figure 7. Schematic cross section of hydrothermal system on Akutan Island. Cold groundwater infiltrates in summit region, feeding reservoir situated somewhere near flank fumarole field. Heat and gases are supplied to reservoir by underlying magmatic intrusion. Hot water rising from the reservoir boils, providing steam and gas to flank fumarole field. Degassed hot water forms an outflow plume that discharges in Hot Springs valley after varying dilution by cold groundwater. systems that have shown this kind of change. Many causes could be invoked, but a permeability enhancement somewhere in the system, such as in the outflow zone, would logically explain the increase in hot-spring discharge. It is tempting to link such a process to fault movement during the seismic crisis of March 1996, given that a hot spring sampled by Symonds later in that year had a higher Cl concentration than that reported by Motyka and others (1988). The infrequency of sampling may obscure the exact timing, but if the ten- fold increase in heat output dates back to 1996, it can hardly be considered a short-term transient, and so the increased heat resource available for power generation over a 30-year timespan may be much larger than indicated by the resource data of Motyka and others (1988). Acknowledgments We thank Colin Williams (USGS, Menlo Park, Calif.) and John Power (USGS, Alaska Volcano Observatory, Anchor- age) for supporting this project, and Michelle Coombs, Kristi Wallace, and Chris Waythomas (USGS, Alaska Volcano Observatory, Anchorage) for logistical assistance in plan- ning and executing the fieldwork. Additional thanks go to Timothy Brabets (USGS, Anchorage) for the loan of some gaging equipment. Helpful reviews of the manuscript were provided by Fraser Goff (New Mexico Institute of Mining and Technology, Socorro) and Cynthia Werner (USGS, Alaska Volcano Observatory, Anchorage). 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Manu- script approved September 16, 2013 20 Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012 Menlo Park Publishing Service Center, California Manuscript approved for publication December 5, 2013 Edited by George Havach and Claire Landowski Design and layout by Ron Spencer Bergfeld—Geochemical Investigation of the Hydrothermal System on Akutan Island, Alaska, July 2012—Scientific Investigations Report 2013–5231ISSN 2328–0328 (online) http://dx.doi.org/10.3133/sir20135231