Fluxes of Volatiles (H2O, CO2, N2, Cl, F) from Arc Volcanoes INVITED
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Geochemical Journal, Vol. 42, pp. 21 to 38, 2008 INVITED REVIEW Fluxes of volatiles (H2O, CO2, N2, Cl, F) from arc volcanoes TOBIAS P. FISCHER* Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, NM 87131-1116, U.S.A. (Received June 6, 2007; Accepted September 10, 2007) This review gives an overview of the estimates of volatile emissions from arc and mid-ocean ridge volcanoes to the atmosphere and hydrosphere with particular focus on H2O, CO2, N2, Cl and F. The gas compositions of high temperature ° (>500 C) fumaroles are compiled and used to derive magmatic H2O/SO2, CO2/SO2, HCl/SO2 and HF/SO2 ratios on an arc- by-arc basis to obtain new estimates of major volatile fluxes from arcs globally. The estimate of F flux from arcs is two orders of magnitude smaller than the amount of F released from mid ocean ridges whereas the arc Cl flux exceeds the ridge flux. An important observation is that globally the water budget of subduction zones seems to be balanced and the amount of water degassed through arc volcanism is within the estimates of the amount of water released from the slab below the volcanic front. Recent work that focused on the Central American arc shows that detailed knowledge of the subduction input compositions, coupled with gas emission studies is critical to further constrain the fate of volatiles during the subduction processes. Keywords: volcanoes, fluxes, water, halogens, sources Although a large number of SO flux measurements INTRODUCTION 2 using the Correlation Spectrometer (COSPEC) have been Volatiles are transferred from the Earth’s mantle to made since the instrument was first pointed at a volcano the atmosphere, the hydrosphere and crust through erup- (Mt. Mihara, Japan) by Moffat et al. (1972) and Stoiber’s tive and non-eruptive subaerial and submarine volcanic first estimate of global volcanic SO2 (Stoiber and Jepsen, activity. Volatiles are also recycled from the surface back 1973), there are still large data gaps particularly for vol- to the Earth’s mantle via subduction. Quantification of canoes in remote areas. This is certainly improving with volatile degassing through volcanoes and estimation of better satellite remote sensing technology (Bluth et al., their source components (mantle vs. surface) bears fun- 1993; Khokhar et al., 2005) and smaller, cheaper ground- damental information on a number of issues in the Earth based instruments such as the mini DOAS (Galle et al., sciences ranging from the evolution of the Earth’s atmos- 2002). Because SO2 is the easiest gas to measure remotely phere to the potential origin of geochemical (high abundance in the plume, low atmospheric back- heterogeneities in the mantle. Noble gases are a critical ground and strong absorption in the UV), its global vol- part of estimating the fluxes of other volatiles to the at- canic flux has been comparatively well constrained. This mosphere by combining, for example, the mid-ocean ridge is also true for CO2 where recent estimates generally fall 3 3 (MOR) He flux of Craig et al. (1975) with the CO2/ He within the range of earlier ones. The flux estimates of ratio of oceanic basalt to arrive at MOR CO2 flux (Marty other major volatiles, still vary by several orders of mag- and Jambon, 1987). The application of noble gases to nitude (H2O) or have not received much attention (HCl, constraining the sources and fluxes of volatiles from sub- HF). duction zones has recently been reviewed by Hilton et al. The purpose of this review is to provide the reader (2002). Deriving subduction volatile fluxes from melt with an overview of the work that has been done in the inclusion studies combined with magma emplacement field of volatile flux estimates from volcanoes. Gas chem- rates has recently been reviewed by Wallace (2005) and istry from high temperature (>500°C), magmatic Kerrick (2001) reviewed the present and past fumaroles world-wide (1970’s to 2002) is compiled to nonanthropogenic CO2 flux from the solid Earth. determine representative, magmatic H2O/SO2, CO2/SO2, N2/SO2, HCl/SO2 and HF/SO2 ratios on an arc-by-arc basis for new estimates of H2O, CO2, N2, HCl and HF *E-mail address: [email protected] fluxes. The water flux, in particular, is discussed in more Copyright © 2008 by The Geochemical Society of Japan. detail with implications for the water cycle in subduction 21 90° 145° 160° 105° 50° Kamchatka 30° Alaska Cascades Ryuku Kuril Is. Aleutian Japan Izu-Bonin Central America Colombia 0° Banda Java Kermadec New Zealand 30° 60° Fig. 1. Arcs that have high temperature (>400°) fumaroles with data compiled in Table 1. Italy is not shown. Modified from Hilton et al. (2002). zones. After discussing global volatile emissions, the re- volatile ratios to arrive at fluxes of gases other than SO2. view focuses on some recent studies done in the Central Extrapolation of both types of estimates to global emis- American arc, that provide tighter constrains on both the sions is still burdened with large uncertainties and ac- input into the subduction zone and the output through counting for extreme point source emissions, such as the volcanoes. 18 × 106 tons emitted from Miyakejima volcano, Japan from 2000 to 2003 (Kazahaya et al., 2004) remains a chal- lenge. This is true particularly for species other than SO2, GLOBAL VOLCANIC VOLATILE FLUXES 3 CO2 and He which are affected by hydrothermal or Quantifying volcanic volatile fluxes, in particular for seawater contributions (H2O, Cl and F), air contamina- greenhouse gases such as CO2, is critical for studies that tion (N2, Ar, Ne), or are extremely variable in volcanic are concerned with global element cycles. Berner and emissions (H2, CH4 and CO). Despite these uncertainties, Lasaga, (1989) note that calculating the rate of degassing current knowledge of volcanic volatile emissions allows of CO2 due to igneous and metamorphic process is a ma- for careful incorporation of these data into global ele- jor problem when modeling the global carbon cycle. Al- ment cycles. though CO2 degassing from volcanic arcs, mid-ocean ridges and to a lesser extent plumes is now relatively well Volatile fluxes from volcanic arcs constrained (within a factor of about two), the CO2 flux Correlation spectrometers (COSPEC) are the stand- from continental rifts remains largely unknown. Most ard instruments used to measure volcanic SO2 fluxes from global volcanic volatile flux estimates rely a) on magma volcanoes. These instruments were first developed in the emplacement rates, degrees of melting coupled with 1960s to measure pollution emitted from industrial and known or estimated volatile abundances in the source re- chemical plants (as SO2 and NO2), but their utility for gion of the melts or b) on sporadic point measurements volcanic flux measurements was recognised shortly there- of gas emissions rates (SO2) from erupting or passively after. The COSPEC was first used at Mt. Mihara volcano, degassing volcanoes coupled with measured or estimated Japan, in April 1971. Today, COSPEC measurements re- 22 T. P. Fischer Table 1. Gas chemistry of high temperature fumaroles world-wide (mol% total gas) and gas ratios used in flux calculations Volcano Mount St Helens Augustine Momotombo Momotombo Poas Galeras Galeras Arc Cascades Aleutians C. America C. America C. America N. South Am. N. South Am. T (°C) 710 870 844 747 940 358 642 Date 1982 May-2002 1981 Feb-1993 1991 Ref. Symonds et al., 1994 Symonds et al., 1990 Giggenbach, 1996 Elkins et al., 2006 Rowe et al., 1992 Goff and McMurtry, 2000 Giggenbach, 1996 H2O (%) 98.9 84.77 95.05 96.25 95 89.6 91.5 CO2 0.88 2.27 2.38 2.53234906 1.35 7.8312 5.98 SO2 0.27 6.98 0.7 0.2334981 2.83 1.2792 0.8415 H2S 0.49 0.53976 0.5725 HCl 0.15 1.01 0.35 0.52757577 0.38 0.3848 0.716 HF 0.03 0.086 0.029 0.03838822 0.015 0.038064 0.062 H2 0.4 0.54 0.87 0.35167164 0.9 0.23712 0.285 CH4 0.00003 <0.00003 0.0004 0 CO 0.003 0.016 0.025 0.01121797 0.012 0.0136 NH3 7.2133E-05 0.0029744 N2 0.12 0.11 0.08 0.05528918 0.1 0.047944 0.041 Ar 0.000025 0.0025 0.00010983 9.36E-05 O2 <0.00005 0 He 0.00005 0.000156 0.0003 Total 100.75 95.78 99.97 100.00 100.58 99.96 100.01 CO2/SO2 3.259 0.325 3.400 10.845 0.477 6.122 7.106 median 3.250 0.320 3.400 6.614 mean 3.250 4.907 6.614 STD 3.086 0.492 HCl/SO2 0.556 0.145 0.500 2.259 0.134 0.301 0.851 median 1.197 0.576 mean 3.250 0.965 0.576 STD 0.656 0.275 N /SO 0.441 0.001 0.114 0.218 0.035 0.035 0.049 Volatile fluxesfromvolcanoesVolatile 23 2, exc 2 median 0.127 0.042 mean 0.441 0.123 0.042 STD 0.053 0.007 H2O/SO2 366.3 12.1 135.8 412.2 33.6 70.0 108.7 median 0.320 135.7 89.3 mean 193.8 89.4 STD 113.1 19.3 HF/SO2 0.111 0.012 0.041 0.164 0.005 0.029 0.073 median 0.320 0.041 0.052 mean 0.070 0.052 STD 0.048 0.022 24 Fischer P. T. Table 1. (continued) Volcano Satsuma Iwojima Satsuma Iwojima Usu Showa Shinzan Tokachi Unzen Arc Japan Japan Japan Japan Japan Japan T (°C) 885 880 690 800 505 818 Date Nov-93 1992 Ref.