©2012 Society of Economic Geologists, Inc.

Economic Geology, v. 107, pp. 1669–1694

Submarine Magmatic-Hydrothermal Systems at the
Monowai Volcanic Center, Kermadec Arc
MATTHEW I. LEYBOURNE,1,†,* ULRICH SCHWARZ-SCHAMPERA,2 CORNEL E. J. DE RONDE,1 EDWARD T. BAKER,3
KEVIN FAURE,1 SHARON L. WALKER,3 DAVID A. BUTTERFIELD,4 JOSEPH A. RESING,4 JOHN E. LUPTON,5
MARK D. HANNINGTON,6 HAROLD L. GIBSON,7 GARY J. MASSOTH,1,8 ROBERT W. EMBLEY,5
WILLIAM W. CHADWICK, JR.,9 MALCOLM R. CLARK,10 CHRISTIAN TIMM,1 IAN J. GRAHAM,1 AND IAN C. WRIGHT11
1 GNS Science, P.O. Box 30-368, Lower Hutt, New Zealand
2 Bundesanstalt für Geowissenschaften und Rohstoffe, Stilleweg 2, 30655 Hannover, Germany
3 Pacific Marine Environmental Laboratory, National Oceanic and Atmospheric Administration,
7600 Sand Point Way NE, Seattle, Washington 98115-6349
4 JISAO, University of Washington, 7600 Sand Point Way NE, Seattle, WA 98115-6349
5 Pacific Marine Environmental Laboratory, National Oceanic and Atmospheric Administration,
2115 S.E. OSU Drive, Newport, Oregon 97365-5258
6 Department of Earth Sciences, University of Ottawa, Ottawa, Ontario, Canada K1A 0E8
7 Mineral Exploration Research Centre, Department of Earth Sciences, Laurentian University, Sudbury, Ontario, Canada P3E 2C6
8 Mass-Ex3 Consulting LLC, 2100 Lake Washington Boulevard N, Renton, WA 98056
9 Hatfield Marine Science Center, Oregon State University, Newport, Oregon
10 National Institute of Water and Atmospheric Research, Greta Point, Wellington 6241, New Zealand
11 National Oceanography Centre, Southampton, University of Southampton Waterfront Campus,
European Way, Southampton SO14 3ZH, United Kingdom

Abstract
The Monowai volcanic center is located at the midpoint along the ~2,530-km-long Tonga-Kermadec arc sys-
tem. The Monowai volcanic center is comprised of a large elongate caldera (Monowai caldera area ~35 km2;
depth to caldera floor 1,590 m), which has formed within an older caldera some 84 km2 in area. To the south
of this nested caldera system is a large composite volcano, Monowai cone, which rises to within ~100 m of the
sea surface and which has been volcanically active for the past several decades. Mafic volcanic rocks dominate
the Monowai volcanic center; basalts are the most common rock type recovered from the cone, whereas
basaltic andesites are common within the caldera. Hydrothermal plume mapping has shown at least three
major hydrothermal systems associated with the caldera and cone: (1) the summit of the cone, (2) low-tem-
perature venting (<60°C; Mussel Ridge) on the southwestern wall of the caldera, and (3) a deeper caldera
source with higher temperature venting that has yet to be observed. The cone summit plume shows large
anomalies in pH (a shift of −2.00 pH units) and δ3He (≤358%), and noticeable H2S (up to 32 μm), and CH4
(up to 900 nm). The summit plume is also metal rich, with elevated total dissolvable Fe (TDFe up to 4,200
nm), TDMn (up to 412 nm), and TDFe/TDMn (up to 20.4). Particulate samples have elevated Fe, Si, Al, and
Ti consistent with addition to the hydrothermal fluid from acidic water-rock reaction. Plumes extending from
~1,000- to 1,400-m depth provide evidence for a major hydrothermal vent system in the caldera. The caldera
plume has lower values for TDFe and TDMn, although some samples show higher TDMn concentrations than
the cone summit plume; caldera plume samples are also relatively gas poor (i.e., no H2S detected, pH shift of
−0.06 pH units, CH4 concentrations up to 26 nm). The composition of the hydrothermal plumes in the caldera
have higher metal contents than the sampled vent fluids along Mussel Ridge, requiring that the source of the
caldera plumes is at greater depth and likely of higher temperature. Minor plumes detected as light scattering
anomalies but with no 3He anomalies down the northern flank of the Monowai caldera most likely represent
remobilization of volcanic debris from the volcano flanks.
We believe the Monowai volcanic center is host to a robust magmatic-hydrothermal system, with significant
differences in the style and composition of venting at the cone and caldera sites. At the cone, the large shifts
in pH, very high δ3He% values, elevated TDFe and TDFe/TDMn, and the H2S- and CH4-rich nature of the
plume fluids, together with elevated Ti, P, V, S, and Al in hydrothermal particulates, indicates significant mag-
matic volatile ± metal contributions in the hydrothermal system coupled with aggressive acidic water-rock
interaction. By contrast, the caldera has low TDFe/TDMn in hydrothermal plumes; however, elevated Al and
Ti contents in caldera particulate samples, combined with the presence of alunite, pyrophyllite, sulfide miner-
als, and native sulfur in samples from Mussel Ridge suggest past, and perhaps recent, acid volatile-rich vent-
ing and active Fe sulfide formation in the subsurface.
† Corresponding author: e-mail, matthew.leybourne@alsglobal.com

*Present address: ALS Geochemistry, 2103 Dollarton Highway, Vancouver, BC, Canada V7H 0A7.

0361-0128/12/4078/1669-26 1669

1670 LEYBOURNE ET AL.

Introduction subcontinent and, as such, is potentially influenced by sub-
HYDROTHERMAL systems have long been studied on mid- duction of continentally derived sediments and the Hikurangi
ocean ridges (MOR) to better understand heat flow and plateau (Fig. 1; de Ronde et al., 2007).
chemical fluxes to the oceans from oceanic crust and the By contrast, the hydrothermal system at the large Monowai
upper mantle. The contribution of hydrothermal systems as- volcanic center has received less attention. It, too, is charac-
sociated with submarine volcanic arcs has only begun to re- terized by an even larger caldera (~35 km2; Monowai caldera);
ceive greater attention in the past decade (de Ronde et al., however, it also has a large cone (Monowai cone) south of the
2001, 2008; Baker et al., 2008). As part of this effort to un- caldera and is dominated by mafic volcanic rocks (Graham et
derstand arc volcanism and hydrothermal processes, the Ker- al., 2008; Timm et al., 2011) versus the typically dacitic lavas
madec arc northeast of New Zealand has been systematically of Brothers (Wright and Gamble, 1999; de Ronde et al.,
surveyed for evidence of hydrothermal activity (de Ronde et 2005). The Monowai caldera is thus atypical of large oceanic
al., 2001, 2007; Baker et al., 2003). These surveys have docu- and continental calderas, which tend to be dominated by sili-
mented that ~70% of the submarine volcanic centers along cic rocks (e.g., Lipman, 1992; Stix et al., 2003). The setting
the Kermadec arc are presently hydrothermally active, but to (i.e., far from a continental influence) and rock chemistry
date only one of these centers, Brothers volcano, has been the (mafic) therefore provide an excellent opportunity to study
focus of detailed study (see Fig. 1 for location). Brothers is the hydrothermal chemistry of an arc hydrothermal system
host to at least two major hydrothermal systems, the NW that is in significant contrast to the well-studied Brothers
caldera site, which is characterized by high-temperature volcano.
(~300°C), focused black smoker venting with Cu-Au−rich The study of submarine arc hydrothermal systems is im-
massive sulfide mineralization, and the cone site with diffuse portant, not only to better understand heat and chemical
venting of lower temperature (<122°C) gas-rich acidic vent fluxes to the oceans, but also in terms of ore deposit-forming
fluids (de Ronde et al., 2005, 2011). The hydrothermal sys- processes. Arc volcanoes provide better analogs to ancient
tems at Brothers provide clear evidence for direct magmatic volcanogenic massive sulfide (VMS) deposits on land than do
contributions to the hydrothermal fluids and are thus similar MOR systems because arc volcanoes are more likely to be
to systems on several subaerial volcanic islands along the Ker- preserved and large ancient VMS are typically associated with
madec arc, including White, Raoul, and Curtis Islands. Broth- convergent margin rocks (e.g., Hannington et al., 2005;
ers volcano is situated relatively close to the New Zealand Piercey, 2011). Furthermore, there is controversy over the ex-
tent to which direct magmatic inputs contribute to volatile
and metal loads of sea-floor VMS mineralization at MORs,
whereas the greater depth range and generally shallower na-
Monowai ture of arc hydrothermal systems provides better insights into
26°S how magmatic fluids contribute to sea-floor hydrothermal
South Fiji
Basin systems (e.g., Stanton, 1991; Hannington et al., 1995; Yang
and Scott, 2002; Beaudoin and Scott, 2009).
This paper presents a synthesis of the current understand-
28°
gh

ing of a large hydrothermal system located at a submarine arc
Tr o u

ch

volcanic center, based primarily on hydrothermal plume data,
ren
vre

but supplemented with data from vent fluids, bathymetric
ga T
Ha

30° mapping, submersible observations, and recovered rock and
mineralized samples. Here, we seek to characterize the
To n

Monowai hydrothermal systems and determine the extent to
which magmatic volatiles influence the chemistry of the
ec

hydrothermal plumes and the potential for subsea-floor VMS
ad

32°
mineralization.
rm
Ke

The Monowai Volcanic Center
Brothers
34° The Monowai volcanic center lies at the northern end the
Kermadec arc, itself the southern portion of the ~2,500-km-
long Kermadec-Tonga arc formed by the subduction of the
Pacific Plate westward underneath the Australia Plate (Fig.
36° 1). Volcanic rocks have been recovered from the Monowai
caldera and cone, as well as several smaller satellite cones
(Fig. 2). Samples were recovered by dredging during SO-135
Inactive Site
White Is.
Active Site
and NZAPLUME III (Haase et al., 2002; Graham et al.,
2008) and during dives made by the manned submersible
38° TVZ
Pisces V and the remotely operated vehicle ROPOS (Embley
176° 178°E 180° 178°W 176° 174° et al., 2006; Schwarz-Schampera et al., 2007). Graham et al.
FIG. 1. Location and tectonic setting of the Monowai volcanic center at
(2008) defined two caldera structures at Monowai, namely, a
the northern end of the Kermadec arc. Map shows the hydrothermally active larger, older caldera in which a younger, but deeper and hy-
submarine volcanic centers (red dots). drothermally active caldera has formed (Fig. 2). At present, in

0361-0128/98/000/000-00 $6.00 1670

2008). Tangaroa (Sept/Oct 2004) 177°15. 2005). 2). Proximal to the of parasitic cones around the rim of the Monowai caldera and southwest wall of the Monowai caldera there are two subpar- a small cone in the center of the caldera (Fig.00 1671 . the entire volcanic center also appears to forming events or one continuous event..0'S T0 4D -14 V04D-16 V04D-15 Monowai Cone V04D-14 25°55. Ronde et al.0'S T04D-07 Depth Contours: 50m 0 1 2 4 250m Kilometers SIMRAD EM300 multibeam bathymetry NIWA vessel R. KERMADEC ARC 1671 CTD vertical cast CTD tow 25°45. and ver- tical casts. where hydrothermal ac- cones are clearly affected by faulting (Fig. 2) and predate tivity in the caldera is presently focused (Fig.0'W FIG. The older the main Monowai cone and most recently formed caldera caldera has the largest volume of any caldera in the northern (Graham et al.0'S T0 4 D- 15 9 D-0 T04 V04D-13 Mussel Ridge TVG Monowai V0 D-1 V0 T0 Caldera 4D 2 4D 4 -0 -0 8 8 25°50.0'W 177°10. CDTO tow-yos. which comes 0361-0128/98/000/000-00 $6. The parasitic allel ridges. Light-gray dashed lines are the outlines of the two caldera structures. showing the locations of TV Grabs (TVG). 3).V. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS. 2008). de unclear whether these calderas represent two discrete caldera.0'W 177°5. There are a number be similarly elongated (Graham et al. MONOWAI VOLCANIC CENTER. 2... Bathymetry collected by Simrad EM300 on the R/V Tangaroa in 2004. including Mussel Ridge. The Monowai cone. it is (as is Brothers volcano in the southern Kermadec arc. Inset map shows location of Monowai (red square) on the Kermadec arc. the absence of any age constraints on the volcanic rocks. (2008). Bathymetric map of Monowai volcanic center. as identified by Graham et al. The active caldera is elongated NW-SE part of the Kermadec arc. at the northern limit of New Zealand’s exclusive economic zone (EEZ).

160 -177. 0361-0128/98/000/000-00 $6.170 B 0.0 0.5 Resurgent T04D-14 cone -177.04 T04D-08 NW of Monowai 0 1 km cone plume 0.175 -177.150 -177.08 0. The ΔNTU scale applies to all panels.6 0.5 Depth (km) 1.0 5.00 Depth (km) 0. proximal to Mussel Ridge.220 -177.120 C 0.190 -177.2 2. crossing the resurgent cone.200 -177.00 1672 .8 0.0 0.210 -177. NW-SE profile between the Monowai cone and caldera.180 -177.140 -177.145 Longitude (°E) FIG. 3.0 0.165 -177. NW-SE profile across the SW portion of the caldera. ΔNTU A 0.10 0. C.06 0.4 0.0 West caldera plume 0 1 km 1.130 -177.180 -177. Particle plume distributions at Monowai volcanic center during the NZAPLUME III survey in 2004. NW-SE profile through the long axis of the caldera.1672 LEYBOURNE ET AL.185 -177.5 Depth (km) 1. The saw- toothed tow-path of the CTDO during tow-yos is shown (light gray lines).00 -177.5 0 1 km T04D-15 -177.170 -177. B.0 West caldera plume 1. Locations of the tow-yos are shown in Figure 2.195 -177.02 1.50 0.00 0. A.155 -177.

830 E 0.890 -25. Monowai has been re.. NZAPLUME III cruise while aboard the R/V Tangaroa.00 1673 .. KERMADEC ARC 1673 D 0.0 -25. 3. Sam- caldera basaltic-andesites are common.830 -25. CH4. crossing Mussel Ridge.790 -25.840 -25. For more details on American Submarine Ring of Fire) in 2005 (Embley et al.170−1.4 Cone NW flank upper plume 0.. see Timm et al.. isotopes. 2008).6 Cone NW flank plume 0. the The majority of rocks collected from Monowai are mafic in 2005 Pisces V cruise on the R/V Ka`imikai-o-Kanaloa. Chadwick et the major element and mineralogical characteristics of the al. N-S profile across the Monowai cone.) D. 2004). the rock geochemistry.0 0. whereas at the 2007 MANGO 192-2 ROPOS cruise on the R/V Sonne. particulate 0361-0128/98/000/000-00 $6. 1980. 2012).050 m). Wright et al. By contrast to the cone. to within ~100 m of the sea surface.5 T04D-09 Resurgent 0 1 km cone -25. 2008. helium Monowai is truly dominated by basalts and basaltic-andesites. with rare andesites. NE-SW profile across the caldera..400 m) is below the depth of the observed vents (~1.800 -25.050−1. If pling conditions and analytical methods for pH. the Monowai caldera Methods was only recently discovered by swath mapping during the Samples used in this study were collected during the 2004 NZAPLUME III cruise. the NZASRoF (New Zealand weighted mean SiO2 contents of ~55%. MONOWAI VOLCANIC CENTER. 1999).860 -25. where recovered III (New Zealand American PLUme Mapping Expedition) in samples are basaltic to basaltic-andesite to andesite with 2004 (de Ronde et al.. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS.2 Depth (km) 0. recently has been vol. Restricted circulation below the sill depth will most likely prevent dissipation of the caldera plume. total dissolvable Fe (TDFe) and Mn (TDMn). (e.8 T04D-07 0 1 km 1. cone are entirely basaltic with weighted mean SiO2 contents visited by several research cruises.0 0. and the MANGO cruise in 2007 (Schwarz-Schampera et al.. Leybourne et al.880 -25. (2011).900 -25.910 -25.820 -25.0 West caldera plume 1.770 -25. Note that a large portion of the caldera plume (~1.. and the composition. E. (2008) described canically active for over 30 years (Davey.760 Latitude (°S) FIG.870 -25. 2007). which compares to the calderas.g.850 -25.810 -25.5 Depth (km) 1. the cone is dominantly basaltic. 2006). whole-rock analyses. indicating that there is a deeper source of venting than sampled by Pisces V or ROPOS.780 -25. Graham et al. filtered it is then a relatively large mafic caldera by global standards Fe (DFe) and Mn (DMn). (Cont. including NZAPLUME of ~50%. with low-temperature diffuse rocks collected from the Monowai volcanic center during venting discovered there in 1998 during the SO-135 cruise by NZAPLUME III and noted that samples from the Monowai the R/V Sonne (Stoffers et al.

000-m-high T04D-15 Monowai cone.66 (Fig. but lower than most of those on the southern-Kermadec arc (de Ronde et al. Hydrother- mal plumes within the Monowai caldera have shifts of up to 800 −0. Plumes were found at the summit (~130-m 1. 2). 5).0V. FIG.06 pH units over background (Fig. TDFe and pH covary (Fig. whereas samples from the caldera (>1. In the caldera. A series Depth (m) of five CTDO tow-yos and seven vertical casts were con- ducted across the caldera and cone structures (Fig. All LSS data.5 8.0 ~600 m on the northern flank (Fig. the venting sources are too shallow to account for the vertical extent of 1. diffuse venting sources are located along 800 the easternmost (inner) of a series of ridges forming the west- ern wall of the caldera. where H2S concentrations in plumes sam- ples are <10 μm (de Ronde et al.000 TDFe and particulate (PFe) concentrations. 5A).0 0. Venting at the sum- mit is particularly intense. shifts of this magnitude are common on hydrother. Although the caldera plume has a smaller pH shift than the cone summit Monowai caldera plume. 5).00 1674 . expressed as a m) have smaller LSS and pH shifts. 3D). pH data. no apparent pH shift and no Mn. abundant T04D-08 V04D-16 hydrothermal sources were found on the 1.00 pH units)..) 0361-0128/98/000/000-00 $6. There is a positive correlation between and pH (up to −2. implying that there are deeper vents V04D-14 within the caldera that have not yet been observed.5 Total dissolvable Fe and Mn: TDFe and TDMn concentra- pH tions for the Monowai cone hydrothermal plume samples are also elevated. All where pH decreases rapidly with only relatively small in.2 0. (The particle plume at 600-m depth has power law function where PFe = 5.0 8. 1. as noted in the text. Monowai caldera plume ries of plumes that filled the western and northern sectors of the 500-m-deep caldera (Fig. i. 1. up to −2. The highest H2S Monowai cone flanks Monowai caldera concentrations are in excess of those recorded for the most Background hydrothermally active volcano along the Kermadec arc.5 7.03·TDFe0. 6. Plumes above the cone summit site have the largest shifts 400 in pH recorded along the Kermadec arc. Table 1) in vertical casts. Results Monowai cone summit plume Hydrothermal plumes 400 CTDO results: The CTDO results show that the Monowai volcanic center hosts the most extensive hydrothermal system found in the northern segment of the Kermadec arc. V04D-15 thermal activity associated with the cone in the center of the T04D-07 caldera has been detected. A.200 the caldera plumes. large-scale. 4B). vent fluid and gas compositions. B 0 pH: The pH values for hydrothermal plumes associated with both the Monowai cone and caldera display reflect dif- Monowai cone summit ferent chemical compositions with analyses based on discrete plume samples collected by the vertical casts and tow-yos (Figs. Zoom to better show the caldera plume.6 0. 4A). 4) and TDFe concentrations (Fig. 2005). No hydro. depth for the vertical there appears to be a threshold value of ~1.600 depth) and associated with small satellite cones at ~400 and 0. These hydrothermal vents form a se..600 Brothers volcano. commonly reaching maximum Light Scattering (ΔNTU) light-scattering sensor (LSS) NTU levels (5. Key features are that shallow samples from the cone (<100 m) have large shifts in LSS (up to 5 V) creases in TDFe. 4.. South of the caldera. C. However. plume mally active volcanoes along the mid-Kermadec arc.4 0. and sulfur isotopes A 0 are described in detail in the Appendix.e. with concentrations ranging Monowai cone from below detection (~1 μm) to 32 μm.200 Inset C Hydrogen sulfide: Hydrogen sulfide was only detected in plumes over the Monowai cone.000-nm TDFe casts and tow-yos over the Monowai volcanic center. 5A). 2001. B. 4. analyses. Light scattering sensor (LSS) and pH vs. However. 2007).1674 LEYBOURNE ET AL.0 7. again coincident with the largest pH and H2S anomalies (Fig.0 6. Plume samples with the largest shifts in pH also have the highest ΔNTU val- Depth (m) ues (Fig. 3).00 pH units relative to background seawater (Fig.8 1. 5B).

There is a strong dependence of TDFe on pH in the shallow plume over the sum- mit cone. TDMn (nM) 0361-0128/98/000/000-00 $6. Note 0. pH vs.70 7. 5C. PFe vs. showing the relationships between pH and 1 plume metals. 5C). although the caldera plume has the highest TDMn concen- trations.85 7. Also note that plume 0. 7). 6). TDFe (nM) tween DFe and TDFe (DFe = 0.400 1. r2 = 0. The deeper 10 FIG. but little to no correlation within the flank plumes or the caldera plume as the latter are considered not of hydrothermal origin (see text). Plots of hydrothermal plume samples from tow-yos and casts across the caldera and cone. with little change in corresponding TDMn concen- trations. Elevated TDFe and TDMn concentrations characterize the 100 cone summit plume.1 the strong correlation between particulate and TDFe. Most of the plume samples from 1 the caldera and cone are elevated in TDFe (with respect to 1 10 100 1.1 1 10 100 samples from the Monowai cone have the most elevated TDMe concentra- tions.200 Monowai cone flanks Monowai caldera 6.) 100 PFe (nM) The summit plume of the Monowai cone is characterized by elevated TDMn concentrations of up to 412 nm (Fig. 5. 4. whereas the caldera plume has higher TDFe (nM) TDMn concentrations relative to the TDFe. DFe = 40−81% 1. TDMn concentrations rapidly increase r2 = 0. 10 For the whole Monowai volcanic center data set. B. TDMn.00 7.345.50 Monowai cone 1. MONOWAI VOLCANIC CENTER.000 TDFe (nM) B 1. Depth profiles for TDFe and TDMn demonstrate that the plumes have different chemical characteristics (Fig.00 0. C however. TDFe vs.50 8. C.80 7.000 7.00 6. There is a strong positive correlation be. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS.027·TDFe1. TDFe. TDFe concentrations increase from background concentrations to ~100 nm.000 TDFe. B). TDFe. coincident with anomalously elevated CH4 (see Fig. DFe = <5−41% TDFe). A.813). whereas for TDFe <500 nm. the ratio DFe/TDFe increases with decreasing TDFe concentration (for TDFe >500 nm. KERMADEC ARC 1675 C 800 A 8. Thereafter. up to 775 nm (Fig. (Cont.75 with little change in TDFe.90 pH FIG.00 1675 . 6A.75 7.000 seawater values).000 pH Depth (m) 7.1 1 10 100 1.50 1.

23 26.93 15 15 Oct 01 2004 3:25:49 557.43 3.30 34.01 34.2 1054 4.97 34.15 13 13 Oct 01 2004 3:19:25 801.41 4.38 4.96 34.82 27.4 4.11 34.90 34.4 696 7.21 across 4 4 Oct 03 2004 6:50:52 1062.43 3.96 27.45 34.5 1309 3.9 1161 4. TABLE 1.43 27.92 27.09 34.39 4.6 1051 4.2 1207 4.8 1265 4.34 parallel 2 25 Oct 04 2004 9:22:14 1171.58 34.87 34.5 1080 4.19 34.60 35.42 4.99 34.1 899 5.1 1035 4.4 1264 4.98 27.86 26.34 9 21 Oct 04 2004 10:10:58 1276.2 684 7.95 27.21 27.4 553 8.33 11 1 Oct 03 2004 20:25:22 1097.1 1129 4.30 9 8 Apr 08 2005 20:16:12 1139.00 27.08 27.30 14 2 Oct 03 2004 20:33:08 963.31 7 15 Apr 08 2005 20:13:08 1170.7 1191 4.96 27.37 4.19 15 23 Oct 03 2004 20:35:00 907.43 3.96 27.97 27.50 27.08 34.56 25.17 34.2 599 8.07 34.41 4.42 4.26 Ridge 7 9 Oct 03 2004 11:37:30 1010.48 16.50 8.38 34.1 1140.24 27.25 34.31 34.97 27.34 7 5 Oct 04 2004 10:07:37 1338.95 27.88 18 18 Oct 03 2004 20:46:00 452.28 15 26 Apr 08 2005 20:27:22 957.43 3.17 0361-0128/98/000/000-00 $6.39 3.5 4.03 26.08 34.12 34.92 27.42 4.41 4.53 27.25 west 9 7 Oct 03 2004 11:45:32 909.85 11.33 7 22 Oct 03 2004 7:15:30 1472.99 12.39 6.14 34.74 27.9 1175 4.35 across 3 5 Oct 01 2004 1:07:43 1139.41 26.82 34.42 4.41 4.92 34.4 1129 4.38 4.27 34.7 804 6.25 34.53 19 19 Oct 03 2004 20:50:38 250.98 27.11 34.03 14 14 Oct 01 2004 3:22:19 696.39 34.09 34.43 3.2 1132 4.0 1108 4.33 6 6 Oct 01 2004 1:45:10 986.00 V04D-12 1 15 Oct 03 2004 11:30:28 1082.43 3.40 4.33 9 7 Oct 03 2004 20:22:53 1128.05 34.33 caldera 5 3 Oct 01 2004 6:23:56 1060.33 cone in 4 4 Oct 01 2004 6:20:37 1154.34 7 5 Oct 03 2004 20:21:41 1127.6 1077 4.0 824 5.8 1115 4.42 4.43 3.04 34.40 4.43 3.97 34.5 794 6.4 496 11.1 1001 4.4 1224 3.42 7.05 17 11 Oct 03 2004 20:42:37 604.87 27.42 4.02 34.23 27.34 wall 5 28 Oct 04 2004 9:53:40 1276.21 34.29 7 22 Oct 01 2004 6:28:29 856.77 27.93 27.85 27.34 6 6 Oct 03 2004 20:20:05 1155.91 27.03 27.43 7.93 27.96 11 9 Oct 01 2004 6:36:01 504.87 35.2 1090 4.38 27.35 Over 2 10 Oct 01 2004 6:14:41 1288.87 27.37 5.22 7 1 Oct 01 2004 1:49:32 1154.48 34.02 34.35 34.17 27.6 1053.25 34.8 1334 4.7 795 6.05 34.29 12 12 Oct 01 2004 3:16:55 904.28 13 28 Apr 08 2005 20:21:49 1100.34 5 17 Oct 03 2004 20:17:59 1197.7 978 4.42 4.61 35.94 12 12 Oct 03 2004 11:53:49 499.79 27.34 11 1 Oct 04 2004 10:23:03 1196.33 wall 4 4 Oct 03 2004 20:17:25 1197.11 27.36 27.6 1101.40 4.03 27.41 4.37 35.43 3.43 3.1676 LEYBOURNE ET AL.61 34.06 34.31 34.28 Over 3 28 Oct 03 2004 11:32:54 1063.55 17.43 3.65 13 13 Oct 03 2004 11:57:42 300.32 west 3 22 Oct 04 2004 9:28:57 1142.28 27.66 12 12 Oct 01 2004 6:39:52 304.12 27.23 27.4 1457.22 27.97 34.43 3.04 26.01 34.8 1209 3.11 9 7 Oct 01 2004 6:31:46 689.06 34.43 3.30 11 9 Oct 01 2004 2:37:40 1089.42 4.6 1186 4.4 249 17.45 34.53 35.30 27.15 16 16 Oct 03 2004 20:38:23 810.43 3.23 27.1 4.53 17 8 Oct 01 2004 3:33:31 310.31 27.15 34.29 34.29 12 12 Apr 08 2005 20:19:15 1118.90 26.06 34.38 4.5 4.42 4.6 1040 4.2 449 12.3 500 10.45 7.33 6 6 Oct 03 2004 7:08:00 1111.1 1158 4.06 27.85 27.29 6 6 Oct 01 2004 6:24:09 1061.12 34.4 302 16.52 34.30 13 13 Oct 03 2004 20:29:50 1048.06 34.33 34.33 caldera 3 3 Oct 03 2004 20:06:51 1124.38 6.07 27.0 1185 4.32 12 12 Oct 03 2004 20:29:10 1048.99 27.9 1040.31 26.9 1145 4.9 1326 3.38 6.3 902 5.00 12.81 16 16 Oct 01 2004 3:29:17 452.31 caldera 4 4 Oct 04 2004 9:41:31 1218.80 V05A-01 1 3 Apr 08 2005 20:01:30 1235.06 34.33 9 17 Oct 01 2004 2:09:24 1049.97 27.89 27.34 V04D-08 1 23 Oct 01 2004 6:12:20 1321.38 3.7 1088 4.35 T04D-15 1 13 Oct 04 2004 9:18:19 1346.4 1144 4.58 34.02 34.6 1561 3.97 34.4 1160 4.37 5.86 34.90 27.9 950 4.43 3.30 caldera 5 17 Oct 03 2004 6:53:40 1151.02 26.1 308 16.30 34.05 27.00 1676 .6 1039 4.51 16.02 27.43 3.8 1118 4.06 34. Hydrothermal Plume Samples from Tow-Yos Bottle Depth Temp Salinity position Nisken Date Time Pressure m °C PSU θ σθ T04D-09 1 23 Sep 30 2004 23:10:54 831.43 3.29 34.36 5.0 974.2 896 5.98 34.00 34.42 4.97 27.6 955 5.2 1118 4.99 34.43 3.32 4.59 8.3 1052 4.19 27.35 central 3 5 Oct 01 2004 6:17:12 1185.55 25.48 26.99 T04D-14 1 3 Oct 03 2004 6:33:14 1049.36 5.13 caldera 11 1 Oct 03 2004 11:49:44 701.39 3.7 1073 4.50 27.00 27.5 1114 4.4 449 12.2 1276 3.82 10.7 849 5.31 4 25 Apr 08 2005 20:06:57 1220.41 4.17 27.90 27.8 1039 4.37 4.08 NE-SW 2 10 Oct 01 2004 0:59:32 1576.43 3.2 298 16.82 25.39 3.48 16.6 4.30 NW-SE 3 28 Oct 03 2004 6:48:23 983.32 NW 2 25 Oct 03 2004 20:06:21 1124.5 1144 4.00 5 28 Oct 01 2004 1:34:53 1169.95 V04D-13 1 22 Oct 03 2004 19:51:07 1086.04 34.02 34.18 26.31 6 10 Apr 08 2005 20:10:09 1201.2 1186 4.87 27.91 27.43 3.15 34.2 691 7.32 caldera 4 4 Oct 01 2004 1:19:12 800.27 Mussel 5 26 Oct 03 2004 11:35:09 1044.8 3.37 5.43 3.09 34.

9 11.057 7.021 7.0 0.004 1.8 1.2 3.2 5.9 4.5 70.9 13.023 7.016 8.734 73.477 7.013 7.7 0.9 0.7 4.979 2.5 0.78 5.4 0.9 0.896 17.1 0.894 -0.206 7.9 11.2 1.4 2.770 127.8 5.23 0.757 68.1 2.7 64.151 22.0 42.4 2.924 0.058 7.95 0.40 5.0 1.799 42.0 3.9 0.88 0.075 7.9 174.100 7.168 4.777 67.6 1.7 72.2 1.2 1.852 38.898 34.13 1.727 187.608 3.3 17.7 0.8 6.057 7.6 16.063 7.350 3.141 7.08 0.9 7.9 2.840 3.835 4.0 1.772 55.466 3.795 154.54 0.75 0.5 3.909 0.0 0.7 2.754 3.9 42.259 3.1 66.0 41.2 0.464 3.092 7.241 7.7 3.6 1.0 14. KERMADEC ARC 1677 and Vertical Casts over the Monowai Cone and Caldera 3He 4He LSS TDFe TDMn DFe DMn TDFe/ CH4 (ccSTP/g) (ccSTP/g) δ3He H2S DFe/ DMn/ V pH nM nM nM nM TDMn (nM) (× 10–14) (× 10–8) (%) (μm) TDFe TDMn 0.41 0.3 73.29 0.2 6.4 0.18 5.720 657.054 2.024 7.127 7.7 3.405 3.6 71.9 4.71 0.138 18.175 18.7 0.767 79.5 1.89 0.6 14.127 1.9 3.015 8.979 2.750 19.35 5.751 46.2 3.0 1.259 4.0 171.8 3.770 87.113 7.172 20.8 5.0 4.9 55.961 1.776 95.4 0.809 103.039 9.150 17.5 3.969 1.045 4.144 4.196 18.78 6.198 7.0 57.15 6.4 7.60 5.2 6.47 6.0 1.107 7.8 2.227 4.0 2.4 24.4 10.900 4.103 7.780 77.3 9.19 0.6 0.05 6.593 3.6 0.061 7.4 7.027 8.870 26.061 7.790 143.013 8.917 4.30 6.4 16.0 176.1 0.66 7.7 0.0 171.0 2.091 7.38 6.1 3.024 7.2 0.766 118.104 7.7 66.5 10.1 3.770 116.66 0.767 49.178 18.0 0.95 5.8 0.855 41.3 18.974 4.6 3.84 0.7 16.8 1.20 6.81 0.6 0.799 7.795 130.174 21.768 126.761 3.246 7.189 24.12 6.4 1.922 0.230 7.7 0.025 7.2 3.3 0.773 48.798 4.112 15.00 1677 .7 61.6 1.764 92.8 26.0 50.28 5.763 4.38 0.600 3.56 5.0 775.98 0.4 23.6 5.139 7.767 56.8 2.774 129.407 3.8 36.721 713.1 0.495 3.996 3.772 20.967 2.95 5.145 4.077 7.95 0.8 2.7 2.6 8.9 0.6 29.819 4.9 4.0 0.875 4.8 8.131 7.754 177.126 7.2 1.7 0.8 5.7 2.083 8.018 7.03 0.85 0.040 7.037 7.5 56.100 13.9 2.026 4.5 64.0 7.13 0.97 0.3 2.052 7.4 14.7 2.823 51.760 401.769 133.158 0.53 0.78 0.8 1.1 2.09 5.2 133.826 -0.8 1.777 139.929 0.099 7.281 3.9 10.1 4.1 0.1 3.6 0.886 4.5 1.8 2.226 7.63 6.87 5.5 0.138 23.023 7.827 120.6 3.048 4.5 71.2 5.083 4.0 3.73 7.6 0.717 4.057 1.734 84.019 7.26 7.7 1.845 0.4 27.0 1.1 0361-0128/98/000/000-00 $6.849 4.245 7.6 3.8 0.4 0.8 65.65 0.2 5.875 99. MONOWAI VOLCANIC CENTER.8 7.067 12.39 5.765 4.2 0.032 7.105 17.023 4.146 7.094 7.94 0.8 0.975 1.4 27.6 0.011 5.8 125. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS.1 4.9 0.1 2.767 84.16 0.134 8.85 6.6 7.074 8.053 7.4 2.7 0.6 2.113 2.016 7.233 7.1 1.0 12.0 8.45 0.072 7.727 193.135 7.5 94.9 2.7 5.31 0.9 3.6 22.1 39.4 2.4 4.621 4.1 0.44 6.103 16.8 17.3 1.3 1.26 6.104 7.06 0.2 2.3 0.7 68.54 0.90 0.0 5.033 7.3 0.2 0.8 57.3 92.329 4.988 5.677 4.0 13.68 5.9 3.31 0.814 81.194 24.8 1.562 3.9 29.1 1.6 1.5 2.948 0.888 7.5 2.765 119.3 4.3 52.54 5.769 44.890 0.5 16.3 3.8 4.9 0.89 6.812 7.1 0.18 0.9 0.9 5.89 0.3 2.9 6.1 0.05 0.3 9.258 7.779 115.010 5.05 5.0 0.637 3.4 1.917 5.640 3.471 3.745 290.2 5.94 5.865 22.0 7.0 138.1 9.900 4.8 1.76 5.0 15.605 4.027 7.835 38.126 1.12 5.136 16.0 6.001 4.66 6.87 5.5 0.27 0.3 4.7 67.08 0.092 15.0 0.481 4.5 0.5 74.5 0.82 0.258 7.758 131.70 6.8 2.0 5.9 3.058 7.817 -0.77 5.049 7.0 0.0 25.1 0.37 6.565 4.111 7.07 0.0 16.0 0.159 7.727 131.2 64.2 5.965 0.1 0.2 37.8 0.0 68.766 114.6 22.3 27.238 7.5 1.2 1.539 3.925 10.069 7.9 0.772 136.104 0.24 5.3 4.2 0.141 19.8 1.5 0.361 7.38 6.4 0.2 5.7 1.1 5.6 1.0 755.810 36.779 72.

50 34.35 34.45 27.37 6.33 V04D-16 1 13 Oct 04 2004 6:34:57 636.75 10.44 7.93 34.03 34.9 695 6.04 12.51 35.78 26.32 Over 2 25 Oct 04 2004 0:51:22 138.45 7.70 19 19 Sep 30 2004 18:45:14 409.23 24.6 146 19.88 34.12 26.36 34.02 34.81 26.99 26.59 and greater 4 4 Sep 30 2004 7:17:57 642.6 504 10.51 8.5 637 7.89 35.22 24.32 main 3 3 Oct 04 2004 0:51:53 138.3 18 21.96 25.3 150 19.04 0361-0128/98/000/000-00 $6.3 716 6.85 17 8 Sep 30 2004 18:38:38 576.68 19.0 108 20.26 34.44 7.51 26.01 east cone 7 1 Sep 30 2004 17:58:43 749.46 7.52 34.92 11.45 V04D-07 1 22 Sep 30 2004 13:17:37 129.24 cone 5 28 Sep 30 2004 13:21:43 80.02 26.95 26.06 11 17 Sep 30 2004 7:43:41 682.69 19.68 19.93 12 12 Sep 30 2004 8:37:02 685.23 35.91 35.5 81 20.09 34.43 7.65 27.69 19.49 over lesser 3 11 Sep 30 2004 7:07:51 490.51 8.5 460 12.39 6.0 812 5.88 cone 5 26 Oct 04 2004 6:38:36 630.2 80 20.4 677 7.67 26.40 6.19 26.99 34.97 12.88 25.27 34. Bottle Depth Temp Salinity position Nisken Date Time Pressure m °C PSU θ σθ 17 19 Apr 08 2005 20:31:49 819.66 35.5 597 8.91 25.81 V04D-14 1 22 Oct 04 2004 0:50:53 138.66 34.4 647 7.20 24.3 137 19.39 6.28 34.36 5.64 25.97 15 15 Sep 30 2004 18:34:40 653.73 35.35 25.53 8.7 502 9.6 626 8.38 main 3 3 Oct 04 2004 3:59:42 146.16 35.10 34.69 19.13 34.4 632 7.52 21.9 578 8.86 35.2 762 6.12 9 3 Sep 30 2004 7:39:50 816.36 26.6 328 15.38 35.13 25.06 34.9 605 8.52 8.90 35.42 15 23 Sep 30 2004 9:26:19 134.91 35.99 11 1 Oct 04 2004 1:01:12 55.83 11 9 Sep 30 2004 13:26:36 34.22 24.27 35.4 631 7.54 34.38 cone 4 4 Oct 04 2004 4:01:25 134.9 133 19.3 55 21.90 flank 3 22 Oct 04 2004 6:37:15 652.34 Over 2 2 Sep 30 2004 13:18:02 129.2 605 8.15 25.37 34.43 25.7 721 6.84 25.95 24.1 605 8.4 532 10.43 26.51 25.49 21.77 10.95 13 15 Sep 30 2004 8:39:32 609.45 16.14 26.31 5.20 7 5 Oct 04 2004 0:58:30 81.34 main 3 5 Sep 30 2004 13:19:43 109.05 19 11 Apr 08 2005 20:38:57 505.59 8.03 9 7 Sep 30 2004 18:05:17 726.24 16 16 Sep 30 2004 9:51:24 185.88 25.2 129 19.72 19.34 T04D-07 1 24 Sep 30 2004 6:50:02 609.71 35.5 807 5.39 26.3 118 19.30 26.6 762 7.2 110 20.57 34.71 35.37 6.50 8.60 8.00 26.07 34.51 34.78 25.21 26.32 7 5 Oct 04 2004 4:04:35 130.60 9.70 19.63 20.5 184 19.9 130 19.82 12 12 Oct 04 2004 6:45:09 501.69 cone and 4 4 Sep 30 2004 17:20:40 768.95 27.32 5 15 Oct 04 2004 4:01:36 133.8 129 19.97 35.87 9 21 Oct 04 2004 6:41:55 601.2 110 20.20 26.38 6.6 134 20.80 18 18 Sep 30 2004 18:41:10 536.54 21.69 19.69 25.9 638 8. TABLE 1.68 19.46 35.00 7 1 Sep 30 2004 13:24:24 56.68 19.20 27.35 26.45 34.22 35.20 34.55 8.70 19.72 34.68 20.19 34.2 487 11.33 9 28 Oct 04 2004 4:06:29 117.02 13 13 Sep 30 2004 18:29:23 749.75 21 13 Apr 08 2005 20:47:54 119.3 137 19.84 10.21 35.83 26.0 133 19.37 5.20 6 6 Oct 04 2004 0:55:47 111.80 35.49 21.81 15 15 Sep 30 2004 13:29:57 7.73 34.99 14 14 Sep 30 2004 18:31:06 722.08 26.96 24.45 7.87 16 16 Sep 30 2004 18:36:39 601.29 27.36 15.35 34.67 20.8 572 9.3 604 8.88 6 6 Oct 04 2004 6:40:26 610.80 35.10 34.85 34.7 744 6.44 27.88 25.0 163 19.83 25.86 11 1 Oct 04 2004 6:43:16 582.13 26.88 cones 5 28 Sep 30 2004 7:23:26 578.29 26.19 34.3 497 11.67 20.93 35.3 703 7.3 163 19.7 899 5.43 17 8 Sep 30 2004 9:53:12 151.3 625 8.99 9 28 Oct 04 2004 0:58:59 81.92 27.92 35.22 35.59 19.51 8.67 19.3 56 21.88 14 14 Sep 30 2004 9:24:28 164.87 25.4 648 8.97 26.69 19.60 26.2 34 21.56 7 1 Sep 30 2004 7:30:44 330.65 26.99 26.78 25.2 406 13.93 over small 6 6 Sep 30 2004 17:55:35 700.51 8.7 117 19.40 T04D-08 1 23 Sep 30 2004 16:30:43 906.42 34.23 24.3 680 7.37 5.66 13 17 Oct 04 2004 6:49:52 301.59 26.69 19.89 34.26 25.85 V04D-15 1 13 Oct 04 2004 3:57:56 164.31 cone 4 4 Oct 04 2004 0:52:43 130.48 7.59 9.4 7 21.5 81 20.26 34.9 129 19.69 19.81 6 6 Sep 30 2004 7:27:41 463.0 596 8.26 25.28 27.8 810 6.9 450 12.28 35.69 19.73 19.1678 LEYBOURNE ET AL.28 35.50 7.29 5 26 Oct 04 2004 0:55:35 111.89 N-S 2 2 Sep 30 2004 6:53:35 453.0 573 9.06 26.48 26.12 NW-SE 2 10 Sep 30 2004 16:35:00 708.5 146 19.87 7 5 Oct 04 2004 6:40:43 610.00 1678 .90 on north 2 25 Oct 04 2004 6:35:30 637.14 35.81 13 13 Sep 30 2004 13:28:21 18.87 25.98 35.63 20.04 26.22 26.62 20.6 299 16.17 35.02 11 9 Sep 30 2004 18:24:15 813.01 34.50 7.9 129 19.89 35.89 25.43 34.49 21.70 25.67 20.95 caldera 5 28 Sep 30 2004 17:41:47 642.86 35.05 34.49 7.8 744 6.10 13.48 25.53 35.06 12 12 Sep 30 2004 18:26:57 768.96 between 3 5 Sep 30 2004 16:47:54 507.98 35.66 35.2 137 19.24 35.32 6 6 Oct 04 2004 4:04:23 129.49 Over 2 25 Oct 04 2004 3:59:17 146.86 26.03 26.93 of main 4 4 Oct 04 2004 6:38:22 630.

025 8.0 13.7 0.024 7.091 3.04 5.498 3.893 2.857 0.81 1.7 2.97 0.6 7.0 0.2 0.5 5.4 4.477 3.026 7.087 7.129 7.0 0.024 72.038 7.894 7.009 7.44 0.44 0.6 1.82 0.0 19.3 2.11 4.863 38.20 32.254 2.7 0.016 18.29 10.3 3.0 2289 285 13.0 0.981 0.8 0.7 2.7 1.9 33.3 0.011 7.63 1.9 1.1 0.99 5.998 5.62 5.7 2.525 3.873 17.2 2.981 284.531 3555.7 1.188 8.3 3.847 161.042 7.989 7.7 0.22 5.826 -0.05 0.5 2.0 2.3 0.894 381.4 4.0 115.018 7.046 8.00 0.4 0.0 2.7 2.0 1.31 5.01 0.1 2.988 7.375 3.02 1.021 7.009 2583.343 3.924 16.199 4.032 8.3 411.0 2.85 2.587 7.8 3.0 218.9 0.5 4.288 3.33 0.049 7.4 10.8 1.412 1452.0 2202 241 17.049 8.7 30.2 39.6 5.3 2.042 4.526 3.1 5.64 5.650 6.037 7.607 3.933 0.965 0.019 7.5 3.54 5.3 106.00 1679 .6 2.67 5.10 0.387 9.3 12.337 5.6 5.810 357.894 6.902 21.9 0.976 2.0 385.1 1.8 1.905 580.26 5.6 3.8 3.910 1.8 0.944 6.1 0.354 7.7 5.0 386.812 4.0 1.77 21.36 5.912 2.038 8.090 7.0 262.978 13.57 5.3 2.6 444.015 7.7 1.3 4.8 1.8 34.1 4.5 25.45 0.6 -0.04 0.8 0.) 3He 4He LSS TDFe TDMn DFe DMn TDFe/ CH4 (ccSTP/g) (ccSTP/g) δ3He H2S DFe/ DMn/ V pH nM nM nM nM TDMn (nM) (× 10–14) (× 10–8) (%) (μm) TDFe TDMn 0.02 0.5 1.865 259.84 5.918 80.1 0.538 3.9 9.942 7.859 31.614 4.6 19.04 0.970 1.942 21.880 0.856 106.34 34.84 0.3 1.323 3.043 8.0 14.894 6.5 2.6 1.571 3.536 3.979 513.64 0.903 73.0 0.255 0.007 8.536 3.7 2.2 3.920 11.8 2.46 5.208 4178.9 0.902 8.33 0.237 947.237 2.3 4.8 2.001 0.91 0.5 1.4 0.158 1.4 2.2 6.3 30.894 6.038 8.53 1.3 24.3 7.023 8.957 1.3 895.928 195.047 8.77 48.2 0.849 6.288 6.1 8.663 4.89 0.1 2.0 725 419 2.196 0.8 0.04 62.00 5.3 246.011 7.9 3.3 9.2 2.566 3.296 413.39 5.7 0.911 0.905 9.019 7.051 7.031 7.8 2.6 2. MONOWAI VOLCANIC CENTER.90 24.396 3.9 1.5 2.293 0.41 5.2 0.044 8.639 3.3 361.2 0.223 1.99 0.0 14.4 259.3 0.0 412.759 247.898 941.9 0.909 71.3 0.574 3.6 0.6 1.5 12.1 1.561 3670.578 3.50 22.40 0.855 3660.186 7.871 126.029 7.2 0.949 0.851 -0.0 82.859 142.02 0.885 0.90 49.814 11.0 114.242 7.079 8.0 1.0 0.96 10 4.672 3.0 1.246 4.9 398.7 10.013 7.995 2.988 9.10 0361-0128/98/000/000-00 $6.258 2.0 0.1 2.63 5.3 0.945 2320.7 250.014 7.048 8.545 7.978 0.6 0.2 4.074 7.23 32. KERMADEC ARC 1679 (Cont.046 8.8 4.422 319.998 0. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS.02 0.587 3.881 24.858 -0.459 7.945 1.880 52.6 2.0 242.088 7.015 8.6 2.080 7.288 896.576 3.893 3.0 127 20.0 526 98 12.945 0.0 2.3 1.7 1.441 75.937 1.3 27.020 1.1 2.188 42.1 0.0 8.12 5.257 2.71 5.3 16.27 2.4 4.059 7.909 89.1 3.9 3.082 7.9 2.08 4.1 2.2 28.982 3.397 7.260 7.1 7.0 16.050 7.1 3.05 5.9 2.904 2.289 5.57 5.4 212.012 7.081 7.952 1.420 3.8 3.30 14.81 0.226 0.224 0.0 10.965 3.2 4.09 2.36 0.4 0.423 7.981 1.5 2.7 0.7 12.5 2.449 7.887 17.8 1.413 7.9 0.812 16.8 2.022 8.0 263.1 0.127 8.3 2.7 0.047 8.4 1.084 -0.366 320.371 7.678 169.1 84.1 8.15 5.8 0.03 5.6 6.0 131.1 2.8 33.964 1.013 7.897 12.2 1.6 0.3 5.4 1.894 6.895 17.861 96.3 5.902 2.197 1.595 3.07 0.5 4.5 42.901 1046.

Note that the three major plume sources (cone summit.200 plume Monowai cone Monowai cone flanks Monowai caldera 1. 600-m depth on cone flank.1680 LEYBOURNE ET AL.01 0.000 0. and (D) TDFe/TDMn. and caldera) have different chemical characteristics.600 0.1 1 10 100 1. (B) TDMn. 0361-0128/98/000/000-00 $6.1 1 0.000 TDFe (nM) TDMn (nM) C 0 D Monowai cone summit plume 400 Depth (m) 800 Monowai caldera 1.00 1680 .1 1 10 100 LSS (ΔNTU) TDFe/TDMn FIG. 6.001 0. See text for details.600 0.1 1 10 100 1. (C) LSS. A 0 B Monowai cone summit plume 400 Depth (m) 800 Monowai caldera 1. Depth plots for (A) TDFe.200 plume 1.

methane. reaching a maximum of 26 nm (Fig. 7). <0. 6D). Fig.200 plume 0 2 4 6 8 10 1. MONOWAI VOLCANIC CENTER.200 plume Monowai cone Monowai cone flanks Monowai caldera Background 1 1. most samples with >100-nm TDMn having essentially 100% 7A). δ3He. KERMADEC ARC 1681 plume on the cone is characterized by elevated TDFe values. anomaly in TDMn and only subtle increases in TDFe (Fig. 3). with regional background. (B) total dissolvable metals vs.00 1681 . Similar to Fe and Mn.600 0. plumes at 600. CH4. there are no coinci- son. By contrast.600 1 10 100 1. the LSS anomaly at ~600-m (Fig. Plots of hydrothermal plume samples from tow-yos and casts across the Monowai caldera and cone. The CH4 concentrations associated with the cone sum- of the Mn in dissolved (i. showing the relationships between (A) depth vs. Samples from the caldera are also elevated in CH4 over the 6). significantly above background for this depth (≤2 nm). Several plume samples from the Monowai cone summit plume have anomalously elevated CH4 concentrations. (Table 1.e. ranging up to 895 nm summit plume are higher than for the caldera. although many samples from the cone and caldera sites are also elevated over a regional (nonhydrothermal) background. 7). TDFe/TDMn values for the plume are elevated over seawater.and 800-m depth on the north flank of the dent CH4 anomalies with LSS anomalies at ~450 m on the cone have the highest TDFe/TDMn values. Methane (CH4): CH4 concentrations for the cone summit but background TDMn values. Although the plume at ~450-m depth is clearly vis. mit are among the highest yet observed associated with a sub- A 0 Monowai cone summit plume 400 Depth (m) 800 Monowai caldera 1.1 1 10 100 0.1 1 10 100 TDFe/TDMn δ3He (%) FIG. DMn is in all cases >40% of TDMn. Inset to (A) shows the 1σ deviation for CH4 background concentrations along the entire arc. this plume has no associated nm. 0361-0128/98/000/000-00 $6. depth on the Monowai cone has CH4 concentrations up to 15 ible in the LSS data (Fig. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS.000 CH4 (nM) B 1000 C 0 Monowai cone summit plume 400 100 CH4 (nM) Depth (m) 800 10 Monowai caldera 1. By contrast. and (C) depth vs.. in excess of 20 cone flanks (Fig. By compari. 7.4 μm) form.

07 78. Particulate Fe concentrations are tight fit (R = 0. Total wt Vol Depth TSM Na Mg Al Si P S(total) S NV SV Location Sample name (μg) (L) (m) (μg/L) (nm) (nm) (nm) (nm) (nm) (nm) (nm) (nm) Monowai caldera T04D09 R5 N28 688 8.07 26.. caldera samples are all from depths >1.5 17.65 625 560.000 nm for the cone.86 2.59 235.90 750.09 –9.38 4492. de Ronde et al. cone samples commonly have elevated Ti con- and TDFe/TDMn (Fig.1 Monowai cone V04D14 R5 N26 986 2.g.e. 2005).69 4351.45 133 1247.7 Monowai caldera V04D12 R7 N9 373 8. Within the et al..13 314.88 100.46 622.56 54.600 nm at the cone and from 70 RA. rang- tight bottles had an average 3He/4He ratio of (after correction ing from 0. Zn.98 57.24 49.50 113. and 0.75 –35. de Ronde et al. and 0.00 0.9.39 1364.20 75. S V = volatile S 0361-0128/98/000/000-00 $6.81 –45. whereas caldera samples are δ3He values: The δ3He values at the Monowai cone and all <7 nm.12 142.23 213.6 29.15 1039 97.69 2. 2005).73 283.2 27.11 12.32 46.83 53.39 18.23 92.99964) with a slope corresponding to R = 6. 2007).99 6.18 14. Total sulfur concentra- Monowai caldera hydrothermal plume.01 1136. madec arc (e. respectively.2 32.13 32.23 42.45 262.96 77.43 5115.000 m (Table 2).86 117. With the exception of the summit plume at the cone There are some key differences between the two sample sets.91 998. there is generally an inverse relationship between CH4 For example.69 415.2 Monowai cone V04D15 R3 N3 1618 2.6 Monowai cone V04D16 R5 N26 3729 6.21 bd Monowai cone T04D07 R9 N3 301 8.10 403..4 Monowai caldera T04D14 R5 N17 401 8. site.53 154. (Table 2).2 87.4 nm.05 19.73 46.53 38.45 1141 47.35 1072 76.28 9.95 455 16.98 48.9 60.27 8.14 73. particulate Mn is less variable within all samples. el- 3He/4He ratio in air.06 35.1 34.09 10. centrations ranging up to 74 nm.65 1160 79.00 19372. The CH4 concentrations of the caldera plume at both the caldera and cone CTDO tow-yos and vertical casts Monowai are higher than all other plumes along the Ker.7 Monowai caldera V04D12 R1 N15 331 4.04 14.51 109.3 62.69 –3.19 0.0 29.55 1426.2 162.32 194.. Fig. The plumes along the highest total S concentrations for the caldera are more than flanks of the Monowai cone are not anomalous with respect an order of magnitude lower (Table 2).1 21. including those at Brothers (e. de were analyzed for samples with elevated ΔNTU values from Ronde et al.60 0.57 93.45 137 112..9 30.34 212.79 19.58 11.6 Notes: bd = below detection.8 28.66 225. the particulate samples from Monowai is variable.02 22.37 –8.85 129 540..4 0.15 1117 85.55 674 24.49 94.61 151.12 50.78 67.6 Monowai caldera V04D12 R3 N28 588 6.8 Monowai caldera T04D09 R9 N17 394 6.18 2.66 48.. Particulate Compositions. ranging from 2 to 2.25 146 719. 7C).09 389.29 66.61 bd 17..33 4012.00 0.96 9.82 4.40 24.1 Monowai caldera T04D09 R7 N1 475 5.0 Monowai caldera V04D13 R5 N17 659 7.04 45.52 1091.47 428.8 103.21 96.23 457.75 62.4 Monowai caldera T04D14 R7 N22 440 8.78 574.35 130 338.64 224..15 134 26.. Although no vent fluid samples were collected at the to 160 nm at the caldera.00 19372.65 358.00 0.15 117 2581.25 1039 63.23 86.11 262. with the most elevated values as.4 Monowai cone V04D15 R5 N15 8049 6.95 bd Monowai cone T04D07 R11 N17 207 8.48 18. 7B).76 –3. whereas madec arc.4 69. ranging termination of the end-member R/RA value.83 2903.17 53.6 33. These 3He/4He values of 6. 3.37 –6.02 –10. By con- caldera.17 43. TSM = total suspended material. The cone values for Fe are among Monowai cone. The speciation of S in to 3He (Fig.1 270.77 –8.42 96. where RA is the from essentially 0 to 100% of the total S as volatile S (i.58 11.32 25. These Ti concentrations are higher than most vol- caldera range up to 358%.25 110 438. several vent fluid samples were collected by the highest along the Kermadec arc. TABLE 2. with increasing percent volatile S as the total S from the four vertical casts over the Monowai cone gave a concentrations increase. S NV = nonvolatile sulfur.21 –10. In comparison.17 518. seawater samples tions are variable for both the cone and caldera sites and with elevated LSS values have δ3He values up to 17% above range up to 20. Monowai particulates have relatively for air addition) 7.47 352. A linear regression fit to all the samples emental S).96 52.7 Pb (175% higher. 2007).89 206. with known VMS.60 20. 2007).5 25.67 121.45 3.25 1458 53.56 0.87 118.14 393. higher than particulates from plumes along the MORs (Baker sent the highest values along the Kermadec arc.09 10. at the same depth (Table 1.63 67.65 809 34.18 37.5 80.6 Monowai cone V04D07 R2 N2 1000 1.g.55 73. ~15 Zn (385% higher). These repre.30 224.54 1181.12 133.25 1001 45.66 136.98 480.42 395. trast.3 79.78 60.12 1289.06 3. 2003. and Pb concentrations with maximum concentra- are similar to that recorded for other volcanoes along the Ker.87 13.2 1.96 1.91 5641.14 9.21 238.65 4487.4 Monowai caldera V04D13 R9 N7 612 7.000 nm PFe (de Ronde et al.1 25.19 776.25 1034 70.57 –128.00 0.43 1271. Cone samples come from <200-m depth.65 3651. has up to ~5 nm Cu (218% Particulates: Particulates from the hydrothermal plumes higher).e. tions of 2.9 14.36 bd 3.53 4.99 559.8 Monowai caldera T04D14 R1 N3 385 7.52 35.0 Monowai cone V04D15 R8 N28 10713 4. 7C).94 variable.36 147.25 79.49 1139.55 49.9 Monowai cone T04D08 R9 N7 1801 7.69 22.54 –5. By contrast.44 454.11 48. Regressing 3He against 4He permits the de.3 Monowai cone T04D07 R3 N11 145 8. The Monowai caldera samples collected with gas.40 98.95 1309.74 1.16 1960.91 –4. <10% δ3He for samples with low LSS values recorded to date for the Kermadec arc. de Ronde et al. Brothers.00 1682 .74 36.00 4.54 90.3.35 46.65 721 235.45 1144 87.0 Monowai caldera V04D13 R13 N13 792 8. the Macauley cone has submersible and ROV in 2005 and 2007 in the Monowai in excess of 3.05 66.15 4.41 107.7 Monowai caldera V04D12 R5 N26 508 7.87 18.65 1040 50. canic rock samples collected along the Kermadec arc and sociated with the cone summit plume (Fig.37 41.55 50.1682 LEYBOURNE ET AL.0 Monowai cone V04D14 R1 N22 275 2. marine arc.95 1053 84.28 1812.1 to 8 nm.2 RA.82 45.71 33.59 140.23 48.89 318.23 92.23 137.48 20.30 107.36 8138.26 13.2 34.0 Monowai cone T04D07 R15 N23 219 8.2 RA low Cu.98 bd 3.62 443.74 140.2 Monowai cone T04D07 R1 N24 139 8.2 14.51 4.16 5737.15 608 17.4 Monowai cone V04D07 R1 N22 795 2.9 to 7.3 32.85 1186 83.31 286. the highest particulate S background values (i. 7).

19 0.039 0.2 180.93 0.1 2.10 0.19 0.15 0.013 bd 0.009 bd 89.7 0.28 0.49 0. centrations close to zero as would be expected for an undiluted Monowai Caldera and Cone Plumes SV Cl K Ca Ti V Cr Mn Fe Ni Cu Zn As Rb Sr Ba W Pb Bi (%) nM nM nM nM nM nM nM nM nM nM nM nM nM nM nM nM nM nM 93.026 0.1 195.5 20.079 89.8 304.024 bd 22.09 bd 0.0 0.10 1177.34 0.8 0.7 3.45 0.32 1.76 129.7 0.25 bd 6.341 0.050 0.17 0.56 1.42 2.036 0.018 0.0 1.81 4.7 122.09 2.3 0.9 bd 0.25 bd bd 0.31 0.0 16.4 0.0 1.7 1.15 0. to 4 mmol/kg and H2S/heat values near 20 nmol/J.9 0.28 0.107 0.33 6.0 1.69 4.47 bd 0. with Na/Cl and Vent fluid chemistry K/Cl values as low as 84% of the seawater ratio in one sample. and the surveyed area has a high also enriched up to 1.1 6.18 0.9 15.10 2. H2S.029 0.3 175.30 0.55 0.71 0.33 mmol/kg).64 4.1 mmol/kg (i.28 137.9 77.9 0. local background sea- biomass dominated by hydrothermal vent-associated species water of 57 μmol/kg).106 bd 55.01 0.06 3.7 3.019 0.31 0.3 49.21 0.2 1. Trace elements are also enriched in Monowai vent fluids.4 3. i.057 bd 51. with two values near 0.022 bd 0.32 2.84 1063.83 1368.024 bd 0.18 0.4 4.020 0.27 0.490 μmol/kg (cf.8 0. 92 to >99% of mea.16 0.05 1.77 0.1 24.55 2.59 0.17 2.31 0. CH4 (21.16 0.5 mmol/kg).5 0.5−38. ranging from 0.0 86.24 0.07 2.31 111.0 0.3 3. MONOWAI VOLCANIC CENTER. Manganese con- from the Monowai cone.78 bd 0. near 25°48' S and 177°10' W (see ellipse in Fig.4 1. and the measured Mg/Cl ratio is as low as 95 percent of the measured seawater value.0 1.9 3.32 0.97 47.61 0.104 0.3 0.49 0.19 bd bd 0.53 0.02 0.10 0.21 bd 2. Table 4). with measured concentrations up andesitic pillows and pillow tube lavas that are typically cov.035 0.08 bd 0.20 bd 0.020 0.79 1.29 7.015 bd 0.09 1.38 18.109 0.02 bd 0.2 2.28 108.7 2.142 bd 77.84 1.5 0.23 69.08 0.41 0.170 Iron concentrations are low.3 and Four dives were carried out on the Mussel Ridge vent site 5.6 1.24 0.043 bd 87..93 0.48 0.73 445.050 bd bd 78.47 0.8 274.8 103. although We will first consider the measured fluid properties before no vent fluids sampled at the Monowai caldera have Mg con- considering the properties of a putative zero Mg end fluid.12 0.6 1.1 1.88 0.04 0. less than seawater values.43 bd 0.41 0.7 12.0 23.1 0.03 0.32 0.76 0.4 35. Several different vents were sampled at depths between 1.9.3 0.7 3.64 0.28 bd bd 0.7 0.042 0.039 bd 0.09 0.31 0.3 5.62 0.90 427.0 1.70 0.049 100.61 bd 0.38 2.12 2.2 29.9 bd 1.07 bd 1. ity.35 1.29 121.28 0.2 39.29 8.28 3.12 1. KERMADEC ARC 1683 Sea-floor observations For fluids with temperature >10°C.06 1.67 230.7 0.33 2.054 0. 2006).2 μmol/kg and 1.153 0.09 1.05 1.42 1.5 3.20 0.27 0.65 284.24 0.68 2.15 bd bd 0.0 2.51 0.9 0. Dissolved silica is (<60°C) is commonplace.1 12.57 0.0 1.14 0. and the lithodid crabs. CO2 (6.84 0.0 3.227 0.28 0. fluids are moderately gas rich with measured concentrations imum vent fluid temperatures were 57°C in 2005 and 42°C in of 3He (0.05 0.4 2.31 0.00 1683 .15 bd bd 0.13 0.15 0.025 bd 0.32 0. Max. The near-linear trends of Si.53 0.8 1.20 0.1 22.05 bd 0.5 bd 1.38 0.2 1.01.7 0.026 0. Alvinocaris niwa and Alvinocaris longirostris. owing to its ongoing volcanic activity. with a 1-km2 area over Mussel Ridge on the western side of the Ca/Cl values up to 122% of the measured seawater ratio.01 0.27 0.27 bd 0.386 bd 0.04 bd 0.3 0.10 3.050 m.0 1.01 0.76 2.4 0.50 0.2 3.0 2.3 2.9 53.66 0.45 0..021 bd 0.0 1. respectively.4 0.6 0.39 0.4 8.05 0. The fluids all have high Mg concentrations.24 0.06 bd 0.30 2. bathymodiolid pled and two of those sites yielded samples with low chlorin- mussels (Bathymodiolus manusensis).23 0.3 4.94 1.20 bd 2.05 bd 0.1 5.e.10 0.5 12.9 0. many ered by bottom current.42 0. and 2007.8 194.72 0.1 0.022 0. the low-temperature fluids. Vent fluids from the Monowai caldera were collected from Calcium is enriched above seawater in all vent samples.9 0.9 0.35 0.67 0.21 0.09 2.6 3. 2).73 0.71 bd 0.0 8.030 0361-0128/98/000/000-00 $6.15 bd 0.016 0.036 0.1 0. Several different vent sites were sam- such as the tubeworm Lamellibrachia juni.45 0.6 0.09 2.27 0.44 0.09 1.7 230.8 8.3 to 5.27 0.4 155. and Fe/Mn values No high-temperature vents were observed during the Pisces V are generally near 0. centrations range from 25 to 417μmol/kg.5 160.7 3.0 3.4−9.68 0.35 0. Hydrogen sulfide is highly enriched in dives showed that this ridge is dominated by basalt to basaltic.008 bd 0.9 58.94 10.28 7.06 2.034 0.5 9. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS.057 0.0 114. Thus. caldera.15 bd 0.44 0.4 6.10 0.77 139.33 118.0 0.2 14.74 0.37−1.5 0.6 0. The vent (2005) and ROPOS (2007) dives in the Monowai caldera.71 84.7 3.0 0. The other notable taxa were alvinocarid chlorinity very close to seawater values (Table 3).033 0.47 0.35 0.158 0.89 141.029 bd 0. Mg is lower shrimps.22 bd 0.6 85.9 5.71 75.41 0.6 1.0 28.8 2.39 0.8 1.032 0.68 pmol/kg).7 0.62 0.028 bd 72.5 5.0 to 52.2 4. suggest that there may be a zero Mg fluid at depth.17 0.06 0.3 0.4 215.3 22.32 0. These than ambient seawater.2 0.0 21.2.06 1.02 0.36 2607.74 bd 0.49 77. ranging from 48.81 0.27 0.5 12.13 1. Sodium and potassium are also depleted.84 0. and nu. reworked rippled sediment. 8) sured ambient seawater where Mg = 52.7 μmol/kg.0 0.60 0.5 0. An additional five sites had Paralomis hirtella..6 0.0 10.47 0.6 bd 2.0 3.2 0.141 0.4 130.25 0. the pH is between 5.40 0.09 156.1 1.40 0.2 0.3 196.3 120.05 bd 0.05 bd bd 0.29 0.88 0.77 0.1 4.01 0.09 0.30 11.5 0.1 2.1 0.647 0.9 644.39 0.4 0.0 11.10 bd 1.73 0.47 19.04 bd 0. than seawater values in all samples. No attempts were made to sample vent fluids with one anomalous sample at 70 μmol/kg.5 0.11 0.65 0.5 2.27 0.93 122.0 147.2 74.7 2.08 bd bd 0.016 bd 0.43 0.1 1.5 1.0 1.081 bd 62.02 0. of the fluids have a measured excess of total dissolved sulfur merous talus piles and scarps.1 0.3 41.64 29. and SO4 with Mg (Fig.048 0. with all of the samples having sulfate concentrations less within the caldera using Pisces V (Embley et al.02 0.4 0.3 205. Low-temperature venting (H2S + SO4) relative to ambient seawater.4 679.1 78.6 0.08 bd 0.60 bd 2.e.30 0.0 1.010 bd 0.

1979. Mussel Ridge.00 6.168317 177.40 539.3 kg) Fe form a separate trend from the remaining near-seawater chlo- rinity fluids. Long distinctly lower than seawater sulfate. but significantly.4 441.24 26. There is sig- nificant scatter in all of the other measured components.30 48. and smectite are also present.20 5. 517.9 96.9 0..52 537 540 Hydrothermal alteration at Mussel Ridge kg) Many samples of hydrothermally altered rock collected (μmol/ (μmol/ (mM/ 26.803762 25. and Li concentrations.68 27. which have variable LSS. Lat Pyrite.78 27.47 5. 9. 3−7): (1) the Monowai cone summit plume. as 1431 1431 1470 983 1032 833 537 886 974 118 230 925 408 57 kg) Si well as anhydrite. natroalunite. pyrophyllite.0 424. Ca-titr. Vent Discussion Plume fluids and particulates 9-Apr-05 9-Apr-05 9-Apr-05 8-Apr-05 9-Apr-05 9-Apr-05 9-Apr-05 9-Apr-05 9-Apr-05 10-Apr-05 7-Apr-05 Date There are three different plume types evident from the CTDO tow-yos and vertical casts (Figs..4 385.39 5. has a large pH shift— Type HFS HFS HFS HFS HFS HFS HFS HFS HFS HFS HFS MS MS MS larger than any pH shift observed to date on the Kermadec arc—and is Fe rich.804113 25.24 515.07 48.61 8. Native sulfur occurs as cement for lapilli ash parti- 5.29 536. The low chlorinity fluids 0.804156 25.002 0.03 11.5 371.167917 177.65 5.00 9. alteration crusts.803958 25.77 27.e. so analyzed 163.167 (mM/ (μmol/ (μmol/ (mol/ mol) perature (Edmond et al.001 0.52 26.167795 177.33 kg) member Na. Figure 8 shows that there are at least two possible mixing trends.168579 samples (n = 5) have δ34S values ranging from 1.006 0.8 457.35 28.167917 177.71 9.168317 177. 1987).27 538.804113 25.8 70.6 conservative mixing of a single high-temperature end mem- not kg) ber does not explain the data.43 11.86 9.006 0. and (3) several other HFS 1 f/piston HFS 20 piston HFS 22 piston Sample name HFS 18 f/bag HFS 16 f/bag HFS 11 f/bag HFS 14 f/bag HFS 6 piston HFS 5 piston plumes.168283 177. no pH.4‰ (Table 6).1684 LEYBOURNE ET AL.13 538.805783 25.g. Traces of magnetite and chalcopyrite.53 5.3 0.806963 sive precipitates of native sulfur are given in Table 5.21 52.027 0. We believe these Monowai cone flank 0361-0128/98/000/000-00 $6. weakly altered basalts and basaltic andesites.0 30. Na mmol/kg Si at zero Mg) low chlorinity end-member fluid (Verma. Given that extrapolation of the normal chlo- 11. vuggy silica-type).804113 25. cau- kg) tion is required when interpreting results from the projected TABLE 3.18 27.2 1.168283 177.803996 25. Amorphous silica. (2) the Monowai caldera plume.3 417.16 26.804156 25.31 26.15 10.64 5. 2008). geothermometers based on the alkali metals do not yield meaningful results.4 2.55 527.12 12.9 441.00 1684 .5 0. fine-grained cristobalite.6 0.016 0.77 6.3 256.89 26.5 75. The δ34S value of the pyrite is uniform at −8.41 9.21 7.1 25.803958 25.275 0. Seyfried.0 441. Mn. strongly altered and mineralized basaltic andesites. MS Blue MS Blue CH4.12 10. Given the uncertainties in estimates of end- 48.5 102.42 50.79 518.97 Using different geothermometers for dissolved silica in kg) K equilibrium with quartz yields a temperature of ~320° to 350°C for the last equilibration of the extrapolated (16. 9). and natrojarosite are intergrown with pyrite and marcasite (Fig. 600-.21 rinity fluids to zero Mg yields ~25 mmol/kg dissolved Si.28 9. SO4 kg) 2 for location) show disseminated sulfide mineralization.79 7.30 49.44 11.2 61. and TDFe anomalies.68 pH cles.2 to 2.44 9. The 1141 1141 1141 1166 1166 1166 1171 1157 1157 1143 1143 1079 1025 1052 composition of texturally well-preserved glass fragments. barite.30 9.22 49.41 5.168 2.02 10.27 9. and especially He anomalies.167773 177.68 28. Composition of Vent Fluids and Ambient Seawater..13 from the caldera during the 2007 Mango 192-2 cruise (see Fig.34 26. and mas- 25.47 11.25 9.13 52.93 11.17 12.7 kg) Cl titr Mg-titr.2 to 11.167917 177. Alunite 177.42 9.167773 177. Depth T which remain after breakdown of rock-forming minerals.803996 25.804837 25.5 0.5 424.0 459. In extensively altered samples. the rock is completely replaced by silica-alunite-pyrite (±pyrophyllite) assemblages (dec deg W) (dec deg S) (m) (°C) 52 52 52 44 43 35 56 26 32 6 9 25 13 3 (i.72 12.31 517.007 0.7 433.08 52.169449 177. Monowai Caldera (Pisces V) end members.168973 177.803958 25.47 11.0 165. including those at ~450-.168317 177. which is gas rich.44 50.4 0.40 10.89 51.06 50.8‰ (Table 6).9 455.3 425. K. The δ34S value of the native sulfur separate samples range from 1.9 (mM/ (mM/ (mM/ (mM/ 431.40 52.4 4.6 450.88 5.30 49.78 26.5 0.3 5. and 800-m depth on HFS 19 bag HFS 8 bag MS White the north flank of the Monowai cone.4 0. acid sulfate-type) or silica phases (e. Al- teration is particularly pronounced along cracks and fissures 3537 4017 3869 3169 3306 2590 684 769 1363 1 130 1054 685 0 H2S kg) within the rocks. 9-Apr-05 MCa10b 9-Apr-05 MCa10b 9-Apr-05 MCa10b AmbSW MCa10 MCa10 MCa11 MCa12 MCa8 MCa8 MCa8 MCa2 MCa9 MCa9 abbr. which is Dive characterized by a relatively small pH anomaly but has the 614 614 614 614 614 614 613 614 614 614 614 614 615 612 largest TDMn anomaly together with elevated LSS and CH4 compared to background seawater. and native sulfur from TV grab samples were analyzed for their sulfur isotope composition. alunite.4 0.3 430.002 0.61 10.3‰.91 9.4 168.20 538. Mn Fe/Mn hydrothermal end-member water-rock reaction at high tem- 0.007 0.07 541.62 518.72 6.004 0.

Fe/Al and P/Al of volcanic rock geochemistry from along the Kermadec. Mussel Ridge.73 pH fluids... 2011.g. Bennett et al. gen concentration. or that the vent fluids are more fractionated from each other. the greater sol- ids along MORs (Massoth et al. Statham et al. marcasite). the ence oxidation rates (Statham et al. and/or mass wasting events.7 pH units. and secondary mineral formation (e.00 pH units is higher (more acidic) than that at West Mata gressive water-rock reaction by more magmatic-hydrothermal (−1. with recent experimental work on active the Lower cone has higher pH and lower Fe/Mn owing to in- vent sites showing that microbial interaction may also influ..244 10. Whereas Fe is oxidized rapidly (min. 1992) and H2S and SO2 (Resing et al.3 2.e. higher TDFe/TDMn for the Monowai cone plume compared 2008). 1990. the differential fluid-mobil- cone plume.174 7.. one explanation for the high SO2-rich) source fluid at the Monowai cone. solubility.8 P5-614 GT2 Monowai 52 0.4 3. lowest pH values) and form a gen- and age of the plume.4 0. and most molar Fe/Mn ~35. will precipitate as a sulfide.5 9. implying that the plume samples at al.209 9. which is a highly acidic vol- rocks due to elevated magmatic gases. ity of Fe and Mn. differing pH-redox systematics. vent fields have fluids with different pH and Fe/Mn values. and (3) rapid dissolution of fresh volcanic rock by SO2.. erally positive correlation with host-rock molar Fe/Mn (e. the higher prob- the greater magnitude of the pH shift and H2S plume anom..4 6. is consistent with less dilution and a highly acidic (CO2. arc volcanoes and Seward. The pH shift for the Monowai cone summit plume of to those from the Monowai caldera may be the result of ag- −2. alaban- alies for the Monowai cone plume compared to the Brothers dite). the R/Ra values correct to a fairly uniform R/Ra correction even though the empirical values vary more widely LSS plumes are probably not hydrothermal in origin. 2011).and nontronite). 2009). dissolution.. 2003. utes to hours..19 47. 2005).096 4.9 P5-614 GT11 Monowai 52 0..89 7.. SO2. 2011). Resing et al. and Brothers cone (−0.5 7. two distinct dation is in part controlled by ambient pH and dissolved oxy.81 111 34. not Mn (e. 1990). 2005.e. 2010). that has undergone more water/rock reaction (lower water/ ated hydrothermal systems: (1) enhanced alteration of host rock ratio) than the cone summit.52 169 26.19 45.16 46.59 caldera mussel R1043 GT10 Monowai 42 0. 2005). Wysoczanski et al.14 47. with both having similar TDFe concentrations.. Resing et al. The particulate samples from the Monowai cone have ele- 2003). For example. Ti. Kadko et al..g..03 7. 2008.2 R1043 GT7 Monowai 24.9 6. 10)...88 7. typically higher than else- rich magmatic fluids (Butterfield et al. For example. 2003). 2011)..0 6. Wysoczanski et al. less There are several other ways in which Fe and Mn might be dilution by ambient seawater). (2) exsolution of an Fe-rich brine phase (Massoth et al. Vent Gas Compositions.2 6. values are in excess of whole-rock values (using whole-rock Tonga arc shows that felsic rocks along the arc have an average data from Graham et al. Timm et al. whereas ubility of Mn sulfides and Mn chloride complexes (Gammons MORs typically have Fe/Mn values of 2 to 4. i.66 91.63 7. caldera plume samples exhibit TDMn values higher than the with maximum values variable over time. 2008. Monaowai Caldera [He4] [Ne] Vent T Total [gas] Total [gas] He:Ne R/Ra R/Ra Mg empirical empirical Dive no. madec arc with the most elevated TDFe/TDMn values also Iron and Mn concentrations vary as a function of dilution have the highest ΔpH (i. MONOWAI VOLCANIC CENTER. The plumes from the Ker- 1 Volcano on the Mariana arc (Walker et al.. Mn oxidation occurs over Massoth et al. Resing et al....29 50. face (Massoth et al. at the Brothers cone.8 P5-614 GT6 Monowai 46 0... TDMn relative to TDFe for hydrothermal plume samples at Hydrothermal vent fluids associated with arc volcanoes the caldera site is precipitation of Fe sulfides in the subsur- commonly have elevated Fe/Mn values compared to vent flu.3 70 11. fig. KERMADEC ARC 1685 TABLE 4. Monowai were either sampled closer to the source (i. but ranging from ~6 cone summit plume. A compilation where along the Kermadec arc.. including: incongruous mineral CO2. 6D) and at the Brothers NW caldera..5 6. Furthermore. and Al contents. 2012). buffering by water-rock reaction. pyrite. months to a year or more terplay between pH. 2011.42 125 13.. However.. For example.19 50. creased water-rock reaction (de Ronde et al. at the typically high Fe/Mn of the fluids.9 11.3 4..44 pH units. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS. 2012).g. 2011. be associated with Fe-rich magmatic volatiles (de Ronde et de Ronde et al.234 10.g. NW Rota 1 (−0. 2007.e. 2007).6 0. there is a complex in- significantly longer time frames. Timm et al.257 11.00 1685 . Three processes could ac.. whereas mafic and intermediate rocks likely reflect remobilization of rock material during eruption have molar Fe/Mn ~44 (Graham et al. The rate of Fe oxi.55 118 10.g. and Fe (Cowen et al. The fact that the Monowai Monowai cone (Fig.. 2011). 2005). ID Site (°C) (ccSTP/g) (mmol/g) (empirical) (corrected) (mmol/kg) (nmol/kg) (nmol/kg) P5-613 GT7 Monowai 53. is consis- to 18. vated Fe. ability that Fe (e. as has been observed at NW Rota.8 5.4 6.2 (de Ronde et al. 1996) compared to Fe sulfides would lower the commonly have significantly higher Fe/Mn. Thus... Si.. Wysoczanski 0361-0128/98/000/000-00 $6.92 caldera mussel mkr 8 Notes: R/Ra corrected is derived by taking the actual measured R/Ra empirical and subracting out the air helium component based on the He/Ne ratio. tent with diffuse fluids venting at moderate pH from a source count for elevated Fe and TDFe/TDMn ratios of arc-associ. and/or H2S rich at the Monowai cone. similar to the Brothers cone (de Ronde et al. 2003.1 23 9.54 7..9 0.77 7.344 15.6 22..22 43. including CO2 (Sed. e.3 6. canic vent and more directly connected to a magmatic source. although the elevated TDFe concentrations may also units. yet have lower TDFe values.95 7. 2008.2 P5-613 GT10 Monowai 57. 2011).. wick et al. However.

8. Extrapolation of Na and K to zero Mg con- centration yields negative end members and is inconsistent with conservative mixing of a zero Mg end member with seawater.5 515 510 4. 545 8.000 27.1686 LEYBOURNE ET AL.5 525 520 5. 0361-0128/98/000/000-00 $6.600 14 13 1.000 28.000 26.5 535 530 Cl (mM) pH 6.0 1.0 1.200 12 Si (μM) Ca (mM) 800 11 400 10 0 9 10 500 8 400 Mn (μM) Fe (μM) 6 300 4 200 2 100 0 0 47 48 49 50 51 52 53 47 48 49 50 51 52 53 Mg (mM) Mg (mM) FIG.5 0 26. Plots of selected vent fluid chemical variables vs.0 H2S (μM) SO4 (mM) 3.5 2.5 5. The low-chloride fluids may be the result of subsea-floor phase separation or addition of a magmatic vapor phase. one with near-seawater chloride and one with low chloride.000 27.00 1686 . Mg for the Monowai caldera.5 4.5 Low Cl 540 Normal Cl Seawater 7.000 28. Trends suggest mixing between sea- water and two distinct low Mg fluids.

Mineralogical characterization of samples from the Monowai volcano. C. E. Close inter- growths of pyrite with natroalunite (samples 26TVG02 and 26TVG01IV).00 1687 . SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS. F: Intergrowths of marcasite and pyrite in a ma- trix of amorphous silica and alunite (sample 26TVG01). D. KERMADEC ARC 1687 A B C D E F FIG. as viewed by SEM. A. Natrojarosite crys- tals as open-space fillings (sample 26TVG02I). Natroalunite in SiO2-rich matrix (sample 26TVG01I). MONOWAI VOLCANIC CENTER. 0361-0128/98/000/000-00 $6. B. 9.

0 bl bl V ppm 265 242 259 252 5. Ho ppm 1.2 2.87 6. Dy ppm 4.10 0.77 n.4 0.d.33 Cl wt % 0.g.5 9. Notes: n.0 Sb ppm 0.3 3.d. n.5 3.3 n. n.4 19 9.0 13 9.5 7. 1. are well in excess of typical values from MORs and arc sys- Although the plumes at the Monowai caldera are less acidic tems elsewhere (all <1 nm.72 55.d.d.d. Co ppm 30 26 30 21 bl Cr ppm 8 20 12 5.d.13 MnO wt % 0.03 1.0 3.0 Tl ppm 0.09 50.d.d. 3.6 bl Zn ppm 110 52 62 31.72 1. Pr ppm 1.10 0. 0.5 14 6.0 n.4 9.d. U ppm 0.6 nm) Baker et al.7 8. bd = below detection et al.0 13 4. Lu ppm 0.34 9. 1.d. Least Altered.d. Tm ppm 0.86 99.24 8. Nd ppm 9.d.d.4 2.12 n.0 3.0 bl Ni ppm 7.01 0.d..01 Al2O3 wt % 14. n.48 5.40 0.6 5.5 Y ppm 28 16 18 14.20 3. n.31 K2O wt % 0..36 2.35 0. As ppm 6. 0361-0128/98/000/000-00 $6. Northern Kermadec Island Arc.32 0.d.75 n.97 1.81 99.28 2. contents of the particulates from the caldera site (2.3 n.d.d.3 6.d.59 0.8 4.30 0.00 1688 .0 bl Mo ppm 3.55 0. SW Pacific Basalt-andesite Basalt-andesite Basalt-andesite glass least-altered mineralized Alteration crust Native sulfur n=7 n = 15 n = 21 n=5 n=3 SiO2 wt % 55.72 99.1 n.6 6. Gd ppm 4.96 Au ppb bl bl 69 n.3 bl bl Sc ppm 35 30 32 29 1.25 1.0 Zr ppm 66 58 66 68.2 n.0 bl bl Th ppm 0. TABLE 5.9 6. 2003.47 0.44 2. n. n. n.7 Ta ppm 3. n. Ag ppm bl bl bl n.14 0.d. The addition of metals like Al and Ti typically and Fe rich than the cone summit plume (Figs.11 0. n.d.2 2.2 0.1 4. Composition of Volcanic Glass.d.57 98.08 0. and Mineralized Basalts and Basaltic Andesites.01 bl LOI wt % 0.27 4.d. n.91 5.85 51. Er ppm 3.7 n.7 n.00 MgO wt % 3.0 9. 6.0 Bi ppm n.54 0.d.08 16.75 5.3 1.d.d.3 Pb ppm 5.08 0.1 n.5 4.34 4.d.8 10 22 11 4.85 4. 4.47 n.0 5.16 CaO wt % 7.79 n.d. 2012).17 0. 5. Hf ppm 5. 1. 7). Sm ppm 3.32 15. n.6 bl 5.d.23 0.6 bl 3. Tb ppm 0.0 n. = not determined.d.4 9.8 3.d.6 n. and Alteration Crusts and Native Sulfur Precipitates from the Mussel Ridge.21 n.d.1 n.d.43 10.3 4. table 1).5 Rb ppm 8.6 4. n.d.5 Cs ppm 3.77 99.30 bl n.25 3.72 14.2 5. n. 0.41 n. Ce ppm 10.1 8.07 4.d.02 0.9 n.8 5.49 n.02 Total wt % 99.03 0.95 1.19 0.41 0.d.0 3.39 0.8 4. Yb ppm 3.36 3.7 3. n.12 0.09 P2O5 wt % 0.0 1. the Ti considered immobile in sea-floor hydrothermal systems (e.d.0 n.4 bl bl Sr ppm 208 384 287 605 6.d.1 0. Monowai Caldera. n.d.7 n.. see Baker et al.18 Fe2O3 wt % 12.0 Sn ppm bl 3.d.14 0.d.1 n.1688 LEYBOURNE ET AL.07 0.5 Ba ppm 158 167 165 169 9.5 bl Cu ppm 103 94 140 67 11 Ga ppm 18 15 16 12 bl Ge ppm 1. n.d..53 0.41 0.d.0 La ppm 3.d.0−6.0 Nb ppm 3.48 0.d.d.14 Na2O wt % 3. n. Eu ppm 1. 2003) indicates aggressive water-rock reaction.91 0.62 TiO2 wt % 1.d.5 2.35 15.01 S wt % 0.15 0. n.

respectively. 1995).. overall high TDFe/TDMn. Applying the sulfate (alunite)-sul- Sample no.. Giggenbach et Monowai summit cone plume likely results from the influ. The alteration and mineralization patterns for recov. ribas et al.. there is not fit this trend (e.9 +1. elevated TDFe.2 300°C (Table 6).. but the of Fe to the hydrothermal system. 1979). with postmixing reac- The range of isotopic compositions of the sulfide (pyrite). acid sulfate in the normal chlorinity fluids). of −8. the caldera plumes also ap. Yang and Scott.. Timm et al.8 +2.. The extrapolation of dissolved silica in vent 0361-0128/98/000/000-00 $6. 1996. Ar- Thus. δ34S Values for Different Sulfur Minerals and Species in Altered sulfur in sea-floor hydrothermal systems. therefore. Based on the large shifts in sulfides are still relatively enriched in 32S. 2003. high degree of mixing between zero Mg end members and temperature alteration. 2008). 2011) or subsea-floor boiling. pear to be the product of venting of magmatic-hydrothermal The vent fluids recovered from the caldera are not hot fluids. tionation is documented for Mussel Ridge. in combination with tween the low chlorinity fluids and the near-seawater fluids the occurrence of native sulfur. The vent fluids are rel- als in sea-floor hydrothermal systems and the role of mag. The 2007). nite pairs of highly altered samples have average δ34S values thermal system. the consequently give evidence for the presence of magmatic Macauley and Brothers volcanoes were the only systems volatiles. Huston et al..3 27TVG02A +2. Although sampled fluids at Mussel than normal Cl fluids. This frac- from particles for hydrothermal mobility of Al. 2007. going hydrothermal-magmatic system. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS. Phase separation in the sub- fluids were responsible for the prevailing alteration at one surface would require temperatures in excess of 320°C for time (Schwarz-Schampera et al. magmatic vapor phase (Reeves et al. 9. Fig.2 pyrite (−8.. Showing Heavier S Isotopes in Alu. 2001.2 pyrite and isotopically heaviest alunite are from different sub- samples of TVG 26. The hydrothermal systems at the Monowai cone are trapolation of Na and K to zero Mg yields very low or nega- gasrich. and evidence fates are enriched in 34S (Ohmoto and Rye. 1995.4 and +7. The platy habit of alunite has been interpreted as an indication of a large magmatic vapor component in the fluid system (Fig. resulting in the coprecipitation of sulfide. 2005. 8) may indicate injection of a plumes cannot be the present venting at Mussel Ridge. Due to kinetic effects during disproportionation. Mn. KERMADEC ARC 1689 TABLE 6. MONOWAI VOLCANIC CENTER.. de nated by seawater (92−99% based on Mg).1 +11. The observed low chloride content of some gressive water-rock reaction and the source(s) of the caldera Mussel Ridge vent fluids (Fig. Wysoczanski et al. 1 The isotopic values of native S are close to the magmatic δ34S signature The intergrowth of sulfides and sulfates (primarily alunite) for island-arc volcanic. but other major elements do Ridge show low temperature and near-neutral pH. and there is supporting evidence for this characteristic acid-sulfate alteration assemblages.. perature end member may exist in the subsurface. 2011). tions resulting in a loss of Fe and a change in the major ele- sulfate (alunite). native S in Monowai samples may have is consistent with cogenetic precipitation and suggests the formed by direct condensation of magmatic SO2 presence of variable oxidation states of sulfur. As noted above. Butterfield et al. Magmatic SO2 disproportionates to H2SO4 and H2S Influence of magmatic metals and volatiles or native S. The linear trends Ronde. H2SO4 dissociates at low ence of magmatic volatiles (i. sites and five other sites with near-seawater chlorinity. (2007) topes commonly reflect the disproportionation process.100 m. 8).e.g.5 using the isotopically lighter alunite (>500°C). K. of dissolved silica and Mn versus Mg suggest that a high-tem- Beaudoin et al.5‰) yields a temperature of formation of around 26 TVG s +2.. the where magmatic fluids were clearly implicated in the addition full equilibrium fractionation may not be obtained. 2012. unrealistically high temperatures are derived 26 TVG 01 +11. suggest that the hydrothermal that is consistent with vapor-liquid partitioning (Butterfield et fluids at the Monowai caldera at one time were highly acidic al.9‰. 2000.. and Ba. Na and K yield negative end members mineralogical evidence that higher temperature. 1990. native High Fe/Mn values and large differences in pH in the S. The low-temperature vents over the shallow Monowai cone strongly resembles the plume (<60°C) sampled in the caldera include two low chlorinity at the dominantly mafic NW Rota-1 system (Resing et al. whereas the sul- pH.2 −8. de Ronde et al. Note that the 27TVG02B +1. Si. Ti. where pyrite-alu- we suggest that the Monowai cone is also a magmatic-hydro.. and suggested that along the southern and mid-Kermadec arc.5 +1. and sulfate minerals (Kusakabe et al. which are distinct from the vents sampled at Mussel enough or acidic enough to explain the elevated Ti or ΔpH of Ridge. mixing trends for some major elements show a difference be- ered rocks and sulfide-sulfate material. seawater-like fluids below the sea floor. similar to Brothers and other more felsic systems tive concentrations and casts doubt on the use of the zero Mg along the arc (de Ronde et al.. juvenile fluids exsolved from temperature to produce acid. most likely reflect- Basaltic Andesites from Mussel Ridge. 2007. atively low temperature (<60°C) and clearly heavily domi- matic volatiles in the formation of ore deposits (e. al..9‰) and 26 TVG x −8. the plumes in the caldera are also the product of ag.00 1689 . which leads to the formation of degassing magma). Ca trends are lower for low Cl fluids and relatively oxidized. Sulfur iso- from recovered altered rock samples. e. ing variable contributions from reduced seawater sulfate and nite Separates and Extremely Light S Isotopes for Pyrite Concentrates1 a deeper magmatic source. The alteration boiling at the average vent depth of 1. the caldera plumes but still provide information about the on- There is continued discussion regarding the source of met.g. The low vent assemblage silica-alunite-pyrite (±pyrophyllite) and changes temperatures and high Mg concentrations could indicate a in whole-rock chemistry (Table 5) are consistent with high. 2007) and the plume end member at Mussel Ridge..9 +1.g. but ex- 2012). and native sulfur is typical of volcanic-derived ment chemistry. Pyrite (‰) Alunite (‰) Native Sulfur (‰) fide (pyrite) geothermometer of Ohmoto and Lasaga (1982) to the widest range in δ34S values for alunite (+7..

D. Manus Basin. the large shifts in pH. K.R.G. R. Furthermore. J.A. Ronde et al. the hydrothermal plume is less would not result in the observed excess total dissolved sulfur acidic and gas rich than over the Monowai cone. NOAA’s Undersea Research Program (NURP) provided richment in high-temperature fluid-associated metals (with funding for some of the transit time from Hawaii to New the exception of Zn). Fe/Mn.J. and 03G0192). v. sulfur over seawater in the fluids (Table 5) and is consistent with the alteration mineral assemblage and precipitation of Acknowledgments pyrite in the subsea floor. cooling. TDFe/TDMn values. G.. Funding for the SO192-2 sistent with venting of a strongly acidic. the more mafic character of the Monowai cone compared to Baker.T.. v. R. v. R. wysocki. 113. The fluids inferred to produce the The fate of fossil fuel CO2 in the oceans: New York. We interpret the Monowai cone as possessing a robust high and German. as at NW thermal system.W. G.. the heat source for the Monowai mura. Fones. E. As. R. Resing. De Ronde.. and NIWA. large underlying magma chamber. or Baker.. 4256−4278. Beaudoin. Beaudoin. J. G.H. Kelly. 749−758. and Culberson.. C. including Pb. implying el... intense plume over the summit of the Monowai cone are pro. The R/V Ka`imikai-o-Kanaloa provided ex- cone summit. consistent with in deep-sea hydrothermal plumes: Earth and Planetary Science Letters. An alternative and preferred theless has significant pH. 1990). CH4. C. p. and pyrite at jointly funded by New Zealand Government grants to GNS the low-temperature vents requires a previous episode of Science and NIWA.. 219 p.P. The NZAPLUME III cruise on the R/V Tangaroa was The prevalence of precipitated sulfur. C. alunite. MS study: Geochimica et Cosmochimica Acta. p.. P.. Tivey and two anonymous journal reviewers for construc- served at NW Rota-1 and West Mata. S. C.1690 LEYBOURNE ET AL. Connelly. 157−167. E.. We thank ciated with recent and ongoing volcanic activity.. 2011) and NW Rota-1 (Resing et al. Y. as recently suggested for Brothers volcano (de nite deposit. and namic state of marine systems.L.E. mersible and the RCV-150 remotely operated vehicle used on No vent fluids have been recovered from the Monowai this expedition.. R. Cunningham. and Scott. and the excellent performance of the ROPOS crew.J. 2007.R. 2008. gas. W. the composition of the plume is con. Gorton.A.and H2S-rich nature of the plume siderable uncertainty. and elevated Ti and Al in the particulates indicate sig- member silica would require reaction zone conditions of nificant magmatic volatile ± metal contributions to the hydro- 350°C and 300 bars (Von Damm.. length and tor. 45–61. The Submarine Ring of Fire 05 expedition was provided from the δ34S values for the pyrite-alunite minerals suggest venting NOAA VENTS Program. N.. The produce the caldera plumes.. Feely. indicating that the source of the high sulfidation scenario explains the excess of total dissolved deep plume has not been observed. and Zealand that made the entire expedition possible (there were Sn (Table 5).C. and Wright... 2009. hydrothermal con.C..H. 3175.. Naka- Mussel Ridge. Although both the tive comments that greatly improved the paper. At present... fluids. M.. Rota.. and isotope geochemistry of the Rodalquilar gold alu- the sea floor. from Mussel Ridge on the western wall of the caldera cannot version of SO2 to H2S. vent fluids recovered in the fluids. W. rich.. GNS Science. Pod- ences suggest either different pathways (i. D. Z..00 1690 .. high-temperature venting at this site. and Massoth. Such a reaction zone thermal system.. v. Lupton.. The Hawaii Undersea pyrite + alunite along with pyrophyllite (Fig. S. 2007). The distribution and stabilisation of dissolved Fe sulfidation magmatic-hydrothermal system. These differ- Arribas. 795−822. p. p. mineralized basaltic andesites from Mussel Ridge show en. 1977. Mo. Funding for the New Zealand American strongly acidic. Sb.and metal-rich MANGO cruise on the R/V Sonne was provided by the Ger- fluid comparable to vent fluids observed at NW Rota-1 (But.9-mmol/kg end. The presence of an alteration assemblage of alunite- with seawater and react with the crust at relatively high pyrophyllite-pyrite is consistent with relatively high tempera- water/rock ratio.J.to 0-mmol/kg Mg concentration involves con. J. Research Laboratory very capably operated the Pisces V sub- evated fluid temperatures (280°−300°C. v. Achterberg. Rytuba. 2011). E. man Federal Ministry of Education and Research (grant terfield et al. the NOAA Office of Ocean Explo- temperatures were at least 300°C. Massoth. eastern Manus Basin: Numerical modeling of a magmatic versus leached origin: ECONOMIC GEOLOGY. ODP Leg 193... Hydrogen ions and the thermody- to the sea floor resulting in significant mixing.. 104. 1995. but never- when mixed with seawater. 1991). elevated TDFe concentrations.J. geochronol- tuosity) for magmatic and hydrothermal fluids from depth to ogy.P. M.. A. Statharn.. I. 90. incomplete removal of Mg. reflecting input of magmatic-hydrothermal sulfidation system where magmatic gases with high SO2 mix fluids. Embley. Submarine hydrothermal venting on the southern Kermadec volcanic arc front (offshore New Zealand): Location and extent of particle plume (2011) for the Monowai volcanic center and consistent with signatures: Geological Society Special Publication. Pb in the PACMANUS sea-floor hydro- duced by magma degassing closer to the sea floor. cellent support for the operation. Geology.. Cu. resulting in enrichment of rock components ture venting and alteration. However. C. 0361-0128/98/000/000-00 $6. with a long fluid pathway Bates. 2008. combined with acidic water-rock reaction. and precipitation of iron sulfides. v... with SO2 driving acid alteration of the volcanic rocks..T. two separate magma chambers. as suggested by Timm et al 2003..e. as also ob. altered and ration and Research (OER).D.E. Bennett. metal sulfide precipitation. and 270.J. and Tosdal.M..R.O. S. and Halter. S. A. The elevated CH4/Mn. Reyes. PMEL con- Monowai cone and caldera hydrothermal systems are volatile tribution no. However. 9). de Ronde.G. 2069. there are clear and significant differences in the compo- REFERENCES sitions of the associated hydrothermal plumes. Rye. 141−161. in Anderson. Papua New Guinea: a LA-ICP- reaction. would produce a zero Mg and zero SO4 end member and Within the Monowai caldera. Y. CH4.J. consistent with apparently high-temperature several other legs of the expedition). JISAO contribution no. Mckee. fluid inclusions. Thanks are also due to the crew onboard FS Sonne TDMn and TDFe are consistent with magmatic inputs asso. M. p. and dissolved and particulate explanation is that Mussel Ridge is the expression of a high metal anomalies.P. Spain: ECONOMIC GEOLOGY.A.. Scott.H..I. Zajacz. Ef- but with a fluid pathway that is insufficiently long to result in fects of hydrothermal alteration on Pb in the active PACMANUS hydro- neutralization and precipitation due to continued water/rock thermal field. Au. fluids from 48. Walker. E. 71. and Malahoff.E. but the resulting 16. eds. Hydrothermal ac- caldera low-temperature fluids may be at the level of the tivity and volcano distribution along the Mariana arc: Journal of Geophysi- cal Research.

A.T.. M. Stability of manganese(II) chlo..A. K... J. Ohmoto.. Peckett. Baker.. S.E. Yuan. Chadwick..D.J. I.. Massoth. ridges: Geophysical Monograph 91..J.R.. v.P. G. G.. Evans. and water by flow injection analysis using in-line preconcentration and spec- Grant.. Gibson. M..E. 45. and Feely. and Craig. search.. Timm..E. G.A.A. Resing. Lilley.J. J. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS. 1980. and Ohba. Lupton.I. mental sulfur from active crater lakes: Journal of Volcanology and Geo- Feely.. S. H..J. in Hurd.A.W. C. R.A.J. Geophysics. V.M.. New Zealand: Earth and Leybourne.. Submarine hydrothermal activity and gold-rich mineralization at marine hydrothermal plumes of the southern Kermadec volcanic arc (New Brothers volcano. W.. Y. M. v. J. and Maenner. Enriched H2. Komoda.L. Ash-flow calderas as structural controls of ore de- Resing..E..W.I. Massoth. Feely. using flow-injection analysis with online preconcentration and spectropho- Giggenbach. Kusakabe... 359−369. G. Massoth. 1999.. 95.. E. Baker. Metal leaching and inorganic sulfate reduction in volcanic- chemistry. p.D. G.A. 2004. and Lasaga. Manus Basin. C. M.. Geophysics. Massoth. M.. 2001.L. and Spencer.E.L. 1990.. Wysoczanski. 39. 1977.L. Determination of iron in sea- Edmond. 2005. and de Ronde.. S..K. 144.. Lilley. 1097−1133. R.M. 2000. J. p.. D. R. ANNIVERSARY VOLUME.... v.D. Wright.. Geochemistry of hydrothermal ore depostis: New York.D.A. and Greene. 2002. A. Nakamura. rine venting of liquid carbon dioxide on a Mariana Arc volcano: Geochem- Ishibashi.. E. and sea-floor massive sulfide de Ronde. C. E. 3–12. p. activity along the mid-Kermadec arc. R. N. Fluid chemistry and isotopic characteristics of 1996 Gorda Ridge eruptive event: Deep-Sea Research II. solved manganese in a hydrothermal vent plume: Deep-Sea Research. 479−509. Graham... S.. Mixing. Sulfur isotopic magmatic contributions: Mineralogical Association of Canada..A. G.. 2003... G. Wiley... H... R... E. and participants. 26.O. ed.J. Physical and chemical processes of seafloor mineralization at mid-ocean Butterfield... Isotopes of sulfur and carbon. Wright.. New Zealand American Submarine Ring of Fire 2005—Kermadec arc sub. G..J. Worthington.. I. and Young. p. Walker.. Evolution of a submarine magmatic-hydrothermal sys- posits—recent work and future problems: U.. Schwarz-Schampera.. 1996. 193. Lupton. T. p. J. Lupton. Jonasson. K.. R. 75. Massoth.. 449−471. and Abiko.E. K.. 75 p. v. Soule.. 1982. Panorama district. R. C. v. R. element recycling. J. D. I. Cruise Report.D. J.R.. 287−307. Garbe-Schönberg. Part A: Oceanographic Research Papers. J. Resing.E. and Lilley. Zellmer.W. 1088−1123. enna Woods hydrothermal fields. Baker. R.G. Roe.A.. R.. P. and magma genesis R. W. Butterfield. L... p. 1990. v. South Pacific boiling and subsequent fluid-rock interaction: Journal of Geophysical Re. Butterfield. ica Acta. 541−584. The water- and rock within the White Island volcanic-hydrothermal system. B. Huston.J. J. Collier.A. M.H... 29.. The Monowai seamount: An active submarine volcanic hydrothermal plume: Earth and Planetary Science Letters. P. R.D. Faure.. southern Kermadec arc. tem: Brothers volcano.J. T.M..J..E. 2665–2682. v. Haase.. 0361-0128/98/000/000-00 $6. 46.F. p. R.L. and gas Hannington. Bannister.E. R. cruise “Northern-Kermadec arc: GNS Science. 1979. Dekov.. 9..M.S. Baker.. 1992. 2011. Lebon. fluids: Implications for the δS-34 variations of dissolved bisulfate and ele- de Ronde. R.I. 97. 1619−1637.E. J..M.. 1998. the sub-seafloor revealed by temporal and spatial variation in diffuse flow Geosystems. R.. I. C. R.. 2008. J.. Technical Note 15.E. B. p.. C. 2008.. Jr.. v.M. p.E..E. hydrothermal activity. E. R. 107. and Mottl. p..J.R.A. KERMADEC ARC 1691 Butterfield.. 100. Submarine hydrothermal Lupton.. I. 2012. 64. A.D. Kamenetsky. W. Geo. sulfur accumulation. B.. Kermadec arc: 1998–2007: Geo. American Geophysical Union. Resing. 2003. K. style.A. p. 803−806. v. Ronde. V. D.... D. R.. Gamo. E. R.J.J.. 1995. Lupton. F.J. B. M.T.. U. Greene. C. p. seawater. and Massoth. D. 267. E. J.A. and Lipman. Ishibashi. 1979. CH4. 12.. 1649–1668. Clark. C.. hydrothermal venting. physical Research Letters. E. D. Layton-Matthews. Ishibashi... Lupton. G. p. McDuff. Shinohara. 269–289. Q07007. v. R. 315−335.J. sulfates and sulfides in hydrothermal systems: Geochimica et Cosmochim- Embley.S..C. Geophysics. K. 1990. Massoth. Lup. Pichler.. J. Measures. v.R.C. C. 2001. Papua New Guinea: Gieskes. M...E. R.921. A. J. R. 19−40. 1992. 1995. M.. vents at Axial Volcano: Subseafloor Biosphere at Mid-Ocean Ranges..J. L. Davidson. p. Roe. Greene. K. D. Soong. High SO2 flux. NZAPLUME III Tontini. de Ronde. E. D. Chemically rich and diverse sub- 2011.... F. p.P.J.E.. M. G. 2007.. C. R. 99. C. tion (NOAA) Cruise Report. G......J... v.. C. Reyes.C. 509−567.J.K.. D. 2006.T.. Sparks. GEOLOGY. 3. New column chemical signature after the 1998 eruption of Axial Volcano: Geo- Zealand: Society of Economic Geologists Special Publication 10. S.C.. M. New Zealand: ECONOMIC v.T. M. M..J.. S.. centre on the Tonga-Kermadec ridge: New Zealand Journal of Geology and Kelley. S. 3645–3648. G..E. C. reaction and microbial activity in beneath the Kermadec arc-Havre trough: Geochemistry.W.. and Olson.W. 50. Faure. hosted massive sulfide mineral systems: Evidence from the paleo-Archean Cowen.895−12.. 1−19. D. mineralization at the Rumble II west mafic caldera: ECONOMIC GEOLOGY. Wright. 113. Sea-floor tec- fractionation at an erupting submarine volcano: Geology.J. and Brumsack.. and Rye.T. G. 1991. Kermadec volcanic arc..37.. p.. Baross. Faure. p. Dziak. Kinetics of reactions between aqueous Planetary Science Letters... major and minor elements in the ocean: the Galapagos data: Earth and Ohmoto. Feely.G.F. Lupton. Saccocia.. p. D.J. J.E. Geochem- ride complexes from 25° to 300°C: Geochimica et Cosmochimica Acta.. v. and Butterfield. Northeast Pual and Vi- 60. Planetary Science Letters. Kermadec arc..S. H.. S. J. Juan de Fuca Ridge: Subseafloor centers in the northern Kermadec-southern Tofua arc. Lilley. C. in Barnes. v. 63. Walsh. Geochimica et Cosmochimica Acta.. Lupton. tonics and submarine hydrothermal systems: ECONOMIC GEOLOGY 100TH Chadwick.. Ditchburn.C.L. H. lapses at Monowai submarine volcano. Lupton.E. Hannington.J. 60. Graham. Collier. S. Hyvernaud. and Lebon. Resing. 111−141. ton.E.J. and Petersen. v. Baker. p.J. physical Monograph Series.. p....W. v. de Ronde.G. J. J. Christenson. and Resing. 533−536. and 3He concentrations in hydrothermal plumes associated with the de Ronde.. tometric detection: Analytical Chemistry. Chemical methods for in.T. and Lebon. Forma.R. 2012.J. Rosenberg.. T.A.. C.E.... 8. Stoffers. K. Massoth. T. Measures.. 119−139. Takano. Gammons. G.J. C. New Zealand: Large-scale effects on W..C. Geological Survey Bulletin.. C. Scavenging rates of dis. Feely. Bach. W.R.D..C. Geology. Piercey. of volcanogenic massive sulfide deposits: Mineralium Deposita. 687−690.D. p. J.. E. mal plumes in the Galapagos Rift: Nature. 2011... and Roe.. v.. Lupton.. G.. v. 46. p. Brathwaite. K. H. and Groves.E. J.J. and Participants. Intra-oceanic subduction-related thermal Research. Drieberg. Mantle dynamics. de venting: Geochemistry.. de Ronde. and Lilley.. 23. J. G. Massoth... I. Zealand): Geological Society Special Publication 219. G..I. Fornari. Massoth. D.. Evans. Takano. T. G. Cyclic eruptions and sector col. 46. p. I. Huber.A. 2004. 2682–2687. seafloor hydrothermal system and associated VMS deposits: Potential for Kusakabe. Chan. Reyners. Weiss. v..F.. Sampling of marine particu. Ridge crest hydrothermal activity and the balances of the trophotometric detection: Marine Chemistry. Seewald.P.S.J. 4295−4311. D. and Massoth. ley. Reyes.M. 7. P.. M.. Hannington. 1727−1745. D.. v. Wright. Massoth.. and Baker.. Embley. L. p..R. J.M. Subma- de Ronde. Geophysics.W.. J.. Resing.J. v. D. Lebon. Structure and petrology of newly discovered volcanic hydrothermal emissions study vent field. Marine particles: Analysis and characterization.. J. Emb... J. Short effects in the disproportionation reaction of sulfur dioxide in hydrothermal Course Handbook 23... p. Proskurowski.. p. Chemical-reaction rates and entrainment within the Endeavor Ridge Davey. Determination of manganese in seawater v... Geosystems. P. K..E. A.... Brauhart.. Walker. Hannington.. v.G..C. p. 251–257... C. Western Australia: Geology. 46. v. J. S. v. J. R. v.. Lahr. 115−157. Walker. p. Ocean: Journal of Geophysical Research. Ditchburn. 2011. 2005. Shanks. tion of acid volcanic brines through interaction of magmatic gases. E.H. and Takai.. and role of magmatism in the formation late matter and analysis by X-ray fluorescence spectrometry. Lilley.L.. Munnik. I.. C. Herzig.. J. L1−L12. J.. R.E.J..J..E.D.T.... McDuff. Baker.-I. Craddock. Olson.L. terstitial water analysis aboard Joides Resolution: Ocean Drilling Program. 2006.J. marine volcanoes: National Oceanographic and Atmospheric Administra. I.. M. S. Wright.. New Zealand: Mineralium Deposita. Reymond. v. and M. T. istry of hydrothermal fluids from the PACMANUS.W. Reeves. 603–604.J.W. I. istry Geophysics Geosystems. Bray.. Wright. and Rosner. de Ronde. Smith. 1991. J.00 1691 . Lebon. Embley.. F. M. T.. p. P.W. The setting. Lupton. p..T. C. K. Nakamura.T.C.A. P...E.P. Geosystems. H. G. eds. Caratori de Ronde. v. MONOWAI VOLCANIC CENTER. O. G. p. J.J..M.. p.E. and Petersen. K.J. S. H. v.. 1995.. and Seward. Greene.. S. Kadko. Geochemistry of hydrothermal fluids from Axial Seamount Arculus. Sylva. Mantle helium in hydrother- de Ronde. Stoffers.

E. Mackay.E. K.S. Statham.1692 LEYBOURNE ET AL..A. R. B08503.. Chadwick.C.M.. Universität Kiel. G. ity in hydrothermal seawater.. Feely. G. 2005.. The tectonomagmatic source of ore metals and volatile elements in and Planetary Sciences. and owissenschaften und Rohstoffe.. Langley.I. p. 1079−1100.L. and Geosystems.J. 1047−1061. R. M. 2009. 279−309. p.E.. C.. Wright. S. Lupton.. G. 2011. 1998−2004: Journal of Geophysical Research.. H. M. 2010. L. R. Chemistry of volcano. 56. L. I. Chadwick. Gibson.. 2011.. 82−95.. J... Caldera-forming processes and the origin of submarine Union. 2008. M... in hydrothermal plumes.. Ostertag-Henning.E.W.. Embley.T. C.. R.. K. Evans. 1986. W.L. de Ronde. ton. C.. C. and Party.MANGO. M. M... hydrothermal solutions from Pele’s Vents. Transactions American Geophysical Franklin.D. present. 43. and Tracey.. D. I. J. et al. v. Science. 31. 113. Mariana arc: Journal Cormany.W. C. Dunkin. E.A. p. K. and Woodhead. Bundesanstalt für Ge. and Scott.. CO2 and 3He Stoffers. and Rosenbauer.L. p. Cruise report Transport of fine ash through the water column at erupting volcanoes— Sonne 192/2 MANGO. E. ern Kermadec arc subduction system. K.. Quartz solubil- plication of alteration mineralogy to their assessment: Journal of Volcanol. Metaxis.L. 1998: Institut für Geowissenschaften. Metaxis.. 2004. 22 p. 92 p. Sheperd. M.T. Kermadec arc.T. J. 383.. and Lilley. Hannington. 735... Lup- analysis: Limnology & Oceanography. Ostertag.. 1983. Leybourne. 1991. and Lebon. Hyver- Sonne 192/2 . Evans. Status Report 2008 Wright. v..N. Indian Ocean: Earth and Planetary Science Letters..A. Dziak. J. ing quartz solubility for up to 0. Anger. Chadwick. Leybourne. v.. C.A... 4. implications for mid-ocean ridge CO2 flux: Earth Havre trough-Taupo Volcanic Zone: Tectonic. J.I. v. P. Q0AF01. 449–464. the Mariana arc: ECONOMIC GEOLOGY. Timm. Rauch. Sources of chalcophile and siderophile elements in Ker- Resing. Mueller. J.. p. C. 102.. A. the southern Kermadec arc: ECONOMIC GEOLOGY. Embley.T13B-2193.. M. Leybourne. Fiske.J. C.. S.L. Mas.. 11280/07: Hannover. and Gamble. D. E... W. ubility geothermometer: Computers and Geosciences.J. clastic deposits at a submarine volcano: NW Rota-1. volcanogenic massive sulfide deposits: Geology.. Young..P.. K.5 M NaCl solutions: American Journal of Sakamoto-Arnold. 77 p. M.W.. and Weternstroer.E. Schmidt.P.. Schmidt. Hannington.. Faure. Determina.. P. D. P.. Abstracts. I. Venting of acid-sul. thermal alteration processes at mid-ocean ridges: Annual Review of Earth 2012.C.B.L. J. p. Bischoff. naud. J. Mills. above submarine volcanoes of the Mariana arc: Geochemistry. arc volcanoes (SW Pacific): Caldera formation by effusive and pyroclastic M.t. an experimental study and equation describ- ogy and Geothermal Research.A..A. Creech. D. C. Nichols. W.. 1987. J. Lupton.D.. Gibson. v.. Geo- soth.. and Merle. 375−378.. Rotella. McMurtry... M. S. 31. Gibson. Walker.D. German. western Pacific: ECONOMIC GEOLOGY.S. ological Union Fall Meeting.G.. C. Kennedy.. Lupton.. 2007. and Connelly. Petrology of Philippine geothermal systems and the ap. Berichte-Reports 1. U. Hirdes. 12.A. v. Baker. G. Lupton.. of Geophysical Research. Hocking.I. p.T. Reyes. Stevens. Leybourne. 420−423. K. v. S. 226. 1990.... and Macdougall. M. Rubin.. S.. Kermadec-Tonga arc. D. Geophysics. J.J... and cold-welded copper tubin: EOS. V..W. M. Geochemical evolution of Monowai: new insights into the north- Resing.I..T. D.. A. Botz.L.J.... Stoffers. K.M. p. 207−227. H. M. Schipper. K. 41 p... 1527–1538. 1991. Bundesanstalt für Ge. SW Pacific: Geochemistry. M.C. 107.. 13 p.. K. v.... 2012. Sheperd.. 799−806. 236. C. magmatic and hydrothermal and Planetary Science Letters. Southern Kermadec submarine caldera Haase. Baker. processes.P. 894–890.. 2007. p. K. Wright. M. Leybourne. Langley. 977–1007. Collapse and reconstruction of Monowai submarine Sedwick.S. E.. Schwarz-Schampera. Hannington. W. p. Rauch. v. Butterfield. Lupton. Loihi Seamount. An ultratight fluid sampling system using Stix. J.. Wilson. and Beehler. 2008. J. Resing. I.. Understanding volcanic massive sulfides—past. Resing. Massoth. 107.J. Walker. Bannister. v... 1999. J.. 291.. 1992. Handler. 317−336. v.S. R.. 15. B. and Stewart.J. W. Gennerich.E. R. J. G.I. G. 10. 0361-0128/98/000/000-00 $6. Active submarine eruption of boninite in the northeastern Lau Basin: Na. de Ronde. p. BGR.L.00 1692 .. U. 97. p. Baker. v.. v..I.. Kermadec arc [abs. W.. Juniper.N. W. p. R. and Nakamura. tion of hydrogen sulfide in seawater using flow injection analysis and flow Walker.J.C. Qrtzgeotherm: An ActiveX component for the quartz sol- ture Geoscience. Verma. 2003... R...]: American Ge- owissenschaften und Rohstoffe. p. Eruption-fed particle plumes and volcani- Schwarz-Schampera. Lebon.. 2008. Rutkowski.. R. Adamson.. Cruise report Sonne 135. Geosystems. Reymond. K. J.E.. v. Stanton. Lebon. K. Greene.. v.. H. v.. Possible contribution of a metal-rich mag- and future: ECONOMIC GEOLOGY MONOGRAPH 8. p. New Zealand September 9−October 15. v. J. fate fluids in a high-sulfidation setting at NW Rota-1 submarine volcano on Timm. J. C.. Jr. Botz. Seyfried. A. C.. 1918−1925. Von Damm. O..H. 1996. C.J.D. 64.. Resing.G. R.E. S. 588−596. 1999.J. 3643−3667.. p. and Lupton. Chadwick.. Tamburri. Chemistry of hydrothermal plumes physics.. Henning.. Monowai cone. de Ronde... 161.E. R. 2008. C. and de Ronde. Leybourne. 10924/08: Hannover.. J. W. vent sites. J. Graham. p. Graham. v.. P.. Hocking.E. Juniper.H... S.A. Tracey. madec arc lavas: ECONOMIC GEOLOGY. M.R.R. v. eruption: Marine Geology.. J. Stevens. J. a... p. Hawaii: 113.. Magmatic degassing of volatiles and ore metals into a hydrother- and oxidation kinetics in hydrothermal plumes at the Kairei and Edmond mal system on the modern sea floor of the eastern Manus back-arc basin.W. Layton-Mathews. Johnson. M. Yang. R. Geochimica et Cosmochimica Acta.. Rutkowski... C.J. Jr. matic fluid to a sea-floor hydrothermal system: Nature. H... 34.-I. K. 1539–1556. v. M.. Experimental and theoretical constraints on hydro. v. p.H. K. Haase. C..E. U. Iron(II) distribution ——2002. Suva-Fiji-Wellingtn... D. Wysoczanski.R.. J. A...A.E. p. Baker. Baker. R.. de Ronde. I. Hirdes... R.. S.. BGR..J. M. M... p.

Precision is typically 2% for major elements (i. sus.. The syringes were placed in Niskin-style bottles and the CTDO instrumentation. 1999. Ni. The bottles were board and later onshore have determined that this method closed using silastic springs actuated by remote control. using an Orion Ross SureFlow com.4·10 . using a modification of the leuco-malachite samplers. using a Finnigan Delta E/DeltaPlus mass spec- the activity of H+ (for seawater. The water added to the 100 ml of seawater and vigorously agitated for 2 sampling bottles were maintained “trace metal clean” by min to reach equilibrium between the CH4 concentration in Teflon coating all wet surfaces and using noncontaminating the water and in the gas phase. alteration crusts (n = 5). Cl. Geowissenschaften und Rohstoffe (BGR). Pb. 1983). 2). Troilite. The results are reported relative to the Canyon Diablo units (Resing et al. Ge. ture. Cr. Cu. where ene (HDPE) bottles.01% Methane was analyzed onboard by head-space gas chro- full scale). typically the difference is trometer.2% in δ3He (Lupton et al. Shipboard determinations of H2S (1σ precision = green method of Resing and Mottl (1992). Methane concentrations are also cor- pended particulate matter composition. rected for temperature and atmospheric pressure at the time Helium samples were stored in 25-cm-long sections of Cu re. He- integrity (Young and Lupton.013 pH units (Bates and Culberson. ambient temperature. The lower limit of determination for dis- frigeration tubing cold-welded at both ends to insure sample solved CH4 is ~0. Hannover. and native sulfur separates (n = 11) were analyzed at Münster ments are recalculated to account for the effects of salinity on University. 2009). Al. Sulfide mineral separates were prepared by pan- 0. 5%) were made using the methylene blue colorimetric 0361-0128/98/000/000-00 $6. The light-scattering sensor (LSS.. carried out on polished thin sections using the Cameca Su- culating bath for 30 min prior to analysis. and 11% for sulfur sors) detects backscattered light from two modulated 880-nm (Resing et al. 1998). depth. KERMADEC ARC 1693 APPENDIX Methods Water column samples were collected during the 2004 Filters were analyzed for chemical composition of particu- NZAPLUME III cruise while aboard the R/V Tangaroa. cone (Fig.0005 V (0. which involves reaction major samplers by the PMEL Hydrothermal Fluid and of Fe with N. Seattle. optical) tow-yos Marine Environmental Laboratory (PMEL. and spigots. Sr). For samples highly enriched in metals (DMe) were collected after the passage of seawater helium (e. Metal sam. Forty ml of high-grade N2 was then tles attached to the towable profiling package. As. the 1σ precision for the 3He/4He the Niskin samplers into acid-cleaned high-density polyethyl. 1991). 2004) and with titanium gas-tight colorimetrically. Gieskes ning followed by handpicking under a binocular microscope. Subsamples for total dis. The reproducibility of the results is better than Total dissolvable Fe and Mn were measured by flow-injec. volcanic rocks and vent fluids) the helium iso- through 0.2‰..114 ± 0. 0.. 7% for trace elements (i. Mg. Experiments undertaken on- materials for O rings. 1991). V. Ca).. with temperature perprobe at BGR.. The pH electrodes were standardized ternational standards. Ti. of measurement. K. et al. Ba. The measured CH4 concentrations were then corrected topes. Feely et and vertical casts used a high-precision SeaBird 911plus CTD al. Si. MONOWAI VOLCANIC CENTER. and dissolved metals. and by Measurements of pH were made within an hour of retrieval total digestion inductively coupled plasma mass spectrometry of the CTDO on board. and were carried out over both the Monowai caldera and Na.4 μm polycarbonate membrane filters. Ontario. springs. where R = ples were acidified to pH 1.5 nm and analytical precision is ~5%. Sus. 3He/4He and R = (3He/4He) A Air = 1. Fe.4-μm pore size polycarbonate spectrometry (XRF) on fused disks at the Bundesanstalt für membranes.. light-emitting diodes. temperature.. The sulfur isotope ratios of pyrite. using a nondestructive thin-film technique at Pacific CTDO (conductivity. All gets). Ancaster. P. TDFe was determined using Vent fluids were collected using 750-ml titanium syringe the method of Measures et al. followed by CH4.001 pH units within a single CrCl2-HCl and precipitation as Ag2S. for extraction efficiency. lium isotopes were determined using a 21-cm-radius. SUBMARINE MAGMATIC-HYDROTHERMAL SYSTEMS. 1977). (ICP-MS) at BGR and at Actlabs. −6 pended particulate matter (SPM) and scanning electron mi. or collapsible ride with colorimetric detection. Discrete a water bath for at least 30 min to equilibrate the samples to water samples were collected in custom-built 19 L PVC bot. Seapoint Sen. and the trometry (Pd source and Mo. 0. alunite.9 using ultra-clean HCl.e. Preci- bination hydrogen ion selective electrode and an Orion sion and accuracy were checked on replicates and against in- (model 250) pH meter. Mn.g. Measurements of pH performed in this manner Sulfur was extracted from sulfide minerals by digestion in have replicate precision of ±0. TDMn was also determined bags (Butterfield et al. Zn.e. with a resolution of ±0. pH. Particle Sampler (HFPS) into PVC pistons. 2004). the late matter by X-ray primary and secondary emission spec- 2005 Pisces V cruise on the R/V Ka`imikai-o-Kanaloa. tope ratios are typically expressed as R/RA. (1995).005 pH sis. Electron microprobe analyses were daily and all samples were thermally equilibrated in a recir. dual solvable metals (TDMe) were collected on-deck directly from collector mass spectrometer. The has an extraction efficiency of 88% for a 100:40 H2O:N2 mix- first aliquot taken from the Niskin bottles was for helium iso. prior to isotope analy- cast or tow-yo and a daily precision of around ± 0.. total dissolvable metals. Ti.. 1977. Dissolved δ3He (%) = 100·[(R/RA) − 1]. compensation following pH measurements. tion analysis at GNS Science. and Co secondary tar- 2007 MANGO 192-2 ROPOS cruise on the R/V Sonne.00 1693 . and sul- Niskin samplers by vacuum filtration onto acid-cleaned and fur precipitates (n = 3) was determined by X-ray fluorescence preweighed 37-mm diameter. via a shielded transfer tube. All pH measure. The composition of altered and mineralized basalts and croscope samples were collected on-deck directly from the basaltic andesites (n = 43).N-dimethyl-p-phenylenediamine dihydrochlo. measurements is 0. The water-sampling rosette was configured to hold matography (Kelley et al.

K. content was measured manometrically and then fractions of precision = 5%) at PMEL. Na. method adapted for flow injection analysis (Sakamoto-Arnold gas-tight titanium samplers were connected directly to a et al. 1986). the where (Butterfield et al.. Lupton et al. analysis by mass spectrometry. The total gas and flame or graphite furnace atomic absorption (Fe and Mn.1694 LEYBOURNE ET AL. For gas analyses. or gas chromatography. 1σ precision = 5%). 2004. with The Interna. Mg and Ca. seagoing high-vacuum processing line and gases were sepa- termined onshore by ion chromatography using a Dionex rated from the fluid fraction by pumping through a trap DX500 (Cl. chilled to −60°C and into a calibrated volume. and Cl. More tional Association for the Physical Sciences of the Ocean complete details of the analytical methods are provided else- (IAPSO) seawater as the standard.. Br..5%) were also used for Ca. SO4. Titration methods (precision = the dry gas were sealed into glass ampoules for subsequent 0. 0361-0128/98/000/000-00 $6. Mg.00 1694 . 2006). Major and trace elements in vent fluids were de.