Description: Dissolved methane and high resolution bathymetry surveys were conducted over the Rock Garden region of Ritchie Ridge, along the Hikurangi margin, eastern New Zealand. Multibeam bathymetry reveals two prominent, northeast trending ridges, parallel to subduction along the margin, that are steep sided and extensively slumped. Elevated concentrations of methane (up to 10 nM, 10× background) within the water column are associated with a slump structure at the southern end of Eastern Rock Garden. The anomalous methane concentrations were detected by a methane sensor (METS) attached to a conductivity‐temperature‐depth‐optical backscatter device (CTDO) and are associated with elevated light scattering and flare‐shaped backscatter signals revealed by the ship's echo sounder. Increased particulate matter in the water column, possibly related to the seepage and/or higher rates of erosion near slump structures, is considered to be the cause of the increased light scattering, rather than bubbles in the water column. Methane concentrations calculated from the METS are in good agreement with concentrations measured by gas chromatography in water samples collected at the same time. However, there is a c. 20 min (c. 900 m) delay in the METS signal reaching maximum CH4 concentrations. The maximum methane concentration occurs near the plateau of Eastern Rock Garden close to the edge of a slump, at 610 m below sea level (mbsl). This is close to the depth (c. 630 mbsl) where a bottom simulating reflector (BSR) pinches out at the seafloor. Fluctuating water temperatures observed in previous studies indicate that the stability zone for pure methane hydrate in the ocean varies between 630 and 710 mbsl. However, based on calculations of the geothermal gradients from BSRs, we suggest gas hydrate in the study area to be more stable than hydrate from pure methane in sea water, moving the phase boundary in the ocean upward. Small fractions of additional higher order hydrocarbon gases are the most likely cause for increased hydrate stability. Relatively high methane concentrations have been measured down to c. 1000 mbsl, most likely in response to sediment slumping caused by gas hydrate destabilisation of the sediments and/or marking seepage through the gas hydrate zone.

Description: The Monowai volcanic center is located at the midpoint along the ~2,530-km-long Tonga-Kermadec arc system. 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-temperature 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 magmatic 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 minerals, and native sulfur in samples from Mussel Ridge suggest past, and perhaps recent, acid volatile-rich venting and active Fe sulfide formation in the subsurface.

Description: Brothers volcano, which is part of the active Kermadec arc, northeast of New Zealand, forms an elongate edifice 13 km long by 8 km across that strikes northwest-southeast. The volcano has a caldera with a basal diameter of ~3 km and a floor at 1,850 m below sea level, surrounded by 290- to 530-m-high walls. A volcanic cone of dacite rises 350 m from the caldera floor and partially coalesces with the southern caldera wall. Three hydrothermal sites have been located: on the northwest caldera wall, on the southeast caldera wall, and on the dacite cone. Multiple hydrothermal plumes rise ~750 m through the water column upward from the caldera floor, originating from the northwest caldera walls and atop the cone, itself host to three separate vent fields (summit, upper flank, northeast flank). In 1999, the cone site had plumes with relatively high concentrations of gas with a ΔpH of −0.27 relative to seawater (proxy for CO2 + S gases), dissolved H2S up to 4,250 nM, high concentrations of particulate Cu (up to 3.4 nM), total dissolvable Fe (up to 4,720 nM), total dissolvable Mn (up to 260 nM) and Fe/Mn values of 4.4 to 18.2. By 2002, plumes from the summit vent field had much lower particulate Cu (0.3 nM), total dissolvable Fe (175 nM), and Fe/Mn values of 0.8 but similar ΔpH (−0.22) and higher H2S (7,000 nM). The 1999 plume results are consistent with a magmatic fluid component with the concentration of Fe suggesting direct exsolution of a liquid brine, whereas the much lower concentrations of metals but higher overall gas contents in the 2002 plumes likely reflect subsea-floor phase separation. Plumes above the northwest caldera site are chemically distinct, and their compositions have not changed over the same 3-year interval. They have less CO2 (ΔpH of −0.09), no detectable H2S, total dissolved Fe of 955 nM, total dissolved Mn of 150 nM, and Fe/Mn of 6.4. An overall increase in 3He/4He values in the plumes from R/RA = 6.1 in 1999 to 7.2 in 2002 is further consistent with a magmatic pulse perturbing the system. The northwest caldera site is host to at least two large areas (~600 m by at least 50 m) of chimneys and sub-cropping massive sulfide. One deposit is partially buried by sediment near the caldera rim at ~1,450 m, whereas the other crops out along narrow, fault-bounded ledges between ~1,600 and 1,650 m. Camera tows imaged active 1- to 2-m-high black smoker chimneys in the deeper zone together with numerous 1- to 5-m-high inactive spires, abundant sulfide talus, partially buried massive sulfides, and hydrothermally altered volcanic rocks. 210Pb/226Ra dating of one chimney gives an age of 27 ± 6 years; 226Ra/Ba dating of other mineralization indicates ages up to 1,200 years. Formation temperatures derived from Δ34Ssulfate-sulfide mineral pairs are 245° to 295° for the northwest caldera site, 225° to 260°C for the southeast caldera and ~260° to 305°C for the cone. Fluid inclusion gas data suggest subsea-floor phase separation occurred at the northwest caldera site. Alteration minerals identified include silicates, silica polymorphs, sulfates, sulfides, Fe and Mn oxide and/or oxyhydroxides, and native sulfur, which are consistent with precipitation at a range of temperatures from fluids of different compositions. An advanced argillic assemblage of illite + amorphous silica + natroalunite + pyrite + native S at the cone site, the occurrence of chalcocite + covellite + bornite + iss + chalcopyrite + pyrite in sulfide samples from the southeast caldera site, and veins of enargite in a rhyodacitic sample from the northwest caldera site are indicative of high-sulfidation conditions similar to those of subaerial magmatic-hydrothermal systems. The northwest caldera vent site is a long-lived hydrothermal system that is today dominated by evolved sea-water but has had episodic injections of magmatic fluid. The southeast caldera site represents the main upflow of a relatively well established magmatic-hydrothermal system on the sea floor where sulfide-rich chimneys are extant. The cone site is a nascent magmatic-hydrothermal system where crack zones localize upwelling acidic waters. Each of these different vent sites represents diverse parts of an evolving hydrothermal system, any one of which may be typical of submarine volcanic arcs.

Description: Clark volcano of the Kermadec arc, northeast of New Zealand, is a large stratovolcano comprised of two coalescing volcanic cones; an apparently younger, more coherent, twin-peaked edifice to the northwest and a relatively older, more degraded and tectonized cone to the southeast. High-resolution water column surveys show an active hydrothermal system at the summit of the NW cone largely along a ridge spur connecting the two peaks, with activity also noted at the head of scarps related to sector collapse. Clark is the only known cone volcano along the Kermadec arc to host sulfide mineralization. Volcano-scale gravity and magnetic surveys over Clark show that it is highly magnetized, and that a strong gravity gradient exists between the two edifices. Modeling suggests that a crustal-scale fault lies between these two edifices, with thinner crust beneath the NW cone. Locations of regional earthquake epicenters show a southwest-northeast trend bisecting the two Clark cones, striking northeastward into Tangaroa volcano. Detailed mapping of magnetics above the NW cone summit shows a highly magnetized “ring structure” ~350 m below the summit that is not apparent in the bathymetry; we believe this structure represents the top of a caldera. Oblate zones of low (weak) magnetization caused by hydrothermal fluid upflow, here termed “burn holes,” form a pattern in the regional magnetization resembling Swiss cheese. Presumably older burn holes occupy the inner margin of the ring structure and show no signs of hydrothermal activity, while younger burn holes are coincident with active venting on the summit. A combination of mineralogy, geochemistry, and seafloor mapping of the NW cone shows that hydrothermal activity today is largely manifest by widespread diffuse venting, with temperatures ranging between 56° and 106°C. Numerous, small (≤30 cm high) chimneys populate the summit area, with one site host to the ~7-m-tall “Twin Towers” chimneys with maximum vent fluid temperatures of 221°C (pH 4.9), consistent with δ34Sanhydrite-pyrite values indicating formation temperatures of ~228° to 249°C. Mineralization is dominated by pyrite-marcasite-barite-anhydrite. Radiometric dating using the 228Ra/226Ra and 226Ra/Ba methods shows active chimneys to be 〈20 with most 〈2 years old. However, the chimneys at Clark show evidence for mixing with, and remobilizing of, barite as old as 19,000 years. This is consistent with Nd and Sr isotope compositions of Clark chimney and sulfate crust samples that indicate mixing of ~40% seawater with a vent fluid derived from low K lavas. Similarly, REE data show the hydrothermal fluids have interacted with a plagioclase-rich source rock. A holistic approach to the study of the Clark hydrothermal system has revealed a two-stage process whereby a caldera-forming volcanic event preceded a later cone-building event. This ensured a protracted (at least 20 ka yrs) history of hydrothermal activity and associated mineral deposition. If we assume at least 200-m-high walls for the postulated (buried) caldera, then hydrothermal fluids would have exited the seafloor 20 ka years ago at least 550 m deeper than they do today, with fluid discharge temperatures potentially much hotter (~350°C). Subsequent to caldera infilling, relatively porous volcaniclastic and other units making up the cone acted as large-scale filters, enabling ascending hydrothermal fluids to boil and mix with seawater subseafloor, effectively removing the metals (including remobilized Cu) in solution before they reached the seafloor. This has implications for estimates for the metal inventory of seafloor hydrothermal systems pertaining to arc hydrothermal systems.

Description: The Woodlark Basin is one of the rare places on earth where the transition from continental breakup to seafloor spreading can be observed. The potential juxtaposition of continental rocks, a large magmatic heat source, crustal-scale faulting, and hydrothermal circulation has made the Woodlark Basin a prime target for seafloor mineral exploration. However, over the past 20 years, only two locations of active hydrothermalism had been found. In 2009 we surveyed 435 km of the spreading axis for the presence of hydrothermal plumes. Only one additional plume was found, bringing the total number of plumes known over 520 km of ridge axis to only 3, much less than at ridges with similar spreading rates globally. Particularly the western half of the basin (280 km of axis) is apparently devoid of high temperature plumes despite having thick crust and a presumably high magmatic budget. This paucity of hydrothermal activity may be related to the peculiar tectonic setting at Woodlark, where repeated ridge jumps and a re-location of the rotation pole both lead to axial magmatism being more widely distributed than at many other, more mature and stable mid-ocean ridges. These factors could inhibit the development of both a stable magmatic heat source and the deeply penetrating faults needed to create long-lived hydrothermal systems. We conclude that large seafloor massive sulfide deposits, potential targets for seafloor mineral exploration, will probably not be present along the spreading axis of the Woodlark Basin, especially in its younger, western portion.