Mark D. Hannington

Hydrous metasomatism of oceanic sub-arc mantle, Lihir, Papua New Guinea : petrology and geochemistry of fluid-metasomatised mantle wedge xenoliths

Abstract Ultramafic, mafic and sedimentary xenoliths have been recovered from a recently erupted, shoshonitic submarine cinder cone (Tubaf and Edison volcanoes) from the Tabar–Lihir–Tanga–Feni island arc, located in the New Ireland basin of Papua New Guinea. These samples represent a proxy drill hole that can be re-assembled into an ‘ophiolite-type’ model of oceanic lithosphere. Petrographic and geochemical examination of the gabbroic and depleted mantle xenoliths indicates that the New Ireland fore-arc lithosphere is a fragment of ancient Pacific Plate generated at a mid-ocean ridge spreading centre and transported to the Pacific–Australian Plate margin. Convergent margin processes subjected the harzburgitic mantle wedge to hydrofracturing and hydration metasomatism at T=790–1030°C as a consequence of dewatering of a subducted slab. Advection of a high-density, H2O-rich fluid containing a substantial dissolved component (alkali aluminosilicate melt and aqueous carbon and sulphur species) through these mantle fractures caused a net transfer of soluble elements from the lower to upper mantle wedge and created a network of oxidised (ΔFMQ≈1.8–2.0) metasomatised peridotite enriched in orthopyroxene, clinopyroxene, phlogopite, amphibole, magnetite, and Fe–Ni sulphides. The vein mineral assemblage magnetite+sulphide indicates precipitation from a hydrous fluid with high SO2/H2S, consistent with the hydrous fluid being derived from dehydration of subducted, altered oceanic crust. Preferential partial melting of these metasomatically enriched mantle wedge regions could account for the highly oxidised, sulphur- and alkali-rich nature of the high-K calc-alkaline volcanoes of the Tabar–Lihir–Tanga–Feni island chain.

Polymetallic massive sulfides at the modern seafloor a review

Polymetallic massive sulfides on the modern seafloor have been found in diverse volcanic and tectonic settings at water depths ranging from about 3700 to 1500 m. These deposits are located at fast-, intermediate-and slow-spreading mid-ocean ridges, on axial and off-axis volcanoes and seamounts, in sedimented rifts adjacent to continental margins and in subduction-related back-arc environments. High-temperature hydrothermal activity and large accumulations of polymetallic sulfides, however, are known at fewer than 25 different sites. Several individual deposits contain between 1 and 5 million tonnes of massive sulfide (e.g., Southern Explorer Ridge, East Pacific Rise 13°N, TAG Hydrothermal Field) and only two deposits (Middle Valley and Atlantis II Deep, Red Sea) are known to contain considerably higher amounts of sulfides ranging between 50 and 100 million tonnes. This range (1–100 million tonnes) is similar to the size of many volcanic-associated massive sulfide deposits found on land. However, the vast majority of known sulfide occurrences on the modern seafloor amount to less than a few thousand tonnes and consist largely of scattered hydrothermal vents, mounds and individual chimney structures. Recovered samples from about 25 deposits world-wide represent no more than a few hundred tonnes of material. The mineralogy of these samples includes both high (> 300°–350°C) and lower-temperature (< 300°C) assemblages consisting of varying proportions of pyrrhotite, pyrite/marcasite, sphalerite/wurtzite, chalcopyrite, bornite, isocubanite, barite, anhydrite and amorphous silica. Massive sulfide deposits in back-arc environments additionally may contain abundant galena, PbAsSb sulfosalts (including jordanite, tennatite and tetrahedrite), realgar, orpiment and locally native gold. Close to 1300 chemical analyses of these samples indicate that the seafloor deposits contain important concentrations of Cu and Zn comparable to those of massive sulfide deposits on land. The sediment-hosted deposits, while being somewhat larger than deposits on the sediment-starved mid-ocean ridges, appear to have lower concentrations and different proportions of the base metals due to fluid-sediment interaction. Initial sampling of sulfides in the back-arc spreading centers of the West and Southwest Pacific suggests that these deposits have higher average concentrations of Zn, Pb, As, Sb and Ba than deposits at the sediment-starved mid-ocean ridges. Gold and silver concentrations are locally high in samples from a number of mid-ocean ridge deposits (up to 6.7 ppm Au and 1000 ppm Ag) and may reach concentrations of more than 50 ppm Au and 1.1 wt% Ag in massive sulfides from immature back-arc rifts, that are dominated by felsic volcanic rocks. Precious metal contents of seafloor sulfides thus are well within the range of those found in land-based deposits. Although massive sulfide deposits have been found at water depths as shallow as 1500 m, boiling of the hydrothermal fluids may prevent the formation of typical polymetallic massive sulfides at shallower depths (i.e., less than a few hundred meters), where the hydrostatic pressure is too low to prevent phase separation. In this case, mineralization with distinct epithermal characteristics and significant amounts of precious metals can be expected.

Deducing patterns of fluid flow and mixing within the TAG active hydrothermal mound using mineralogical and geochemical data

The TAG active hydrothermal mound, located 2.4 km east of the neovolcanic zone at 26°N, Mid-Atlantic Ridge, is ∼200 m in diameter, exhibits 50 m of relief, and is covered entirely by hydrothermal precipitates. Eight different types of vent solids were recovered from the mound by the submersibles Alvin and Mir in 1986, 1990, and 1991. Detailed petrographic and geochemical studies of samples and their distribution are used to deduce patterns of fluid flow and seawater/hydrothermal fluid interaction. Geochemical modeling calculations using fluid composition data corroborate these interpretations. Current activity includes highly focused flow of 363°C fluid from a chimney cluster on the top of the mound and deposition of a high fS 2 -fO 2 mineral assemblage that reflects low concentrations of H 2 S in black smoker fluid. Slow percolation of black smoker fluid pooled beneath the black smoker cluster and entrainment of seawater result in formation of massive sulfide crusts and massive anhydrite. These three sample types are enriched in Co and Se. Blocks of sulfide and white smoker chimneys, enriched in Zn, Au, Ag, Sb, Cd, and Pb, are forming on the surface of the mound from black smoker fluid that has been modified by mixing with entrained seawater, precipitation of sulfides and anhydrite, and dissolution of sphalerite within the mound. This is the first time that on-going remobilization, zone refinement, and significant modification of high-temperature fluid in the near surface has been documented in a seafloor hydrothermal system. Deposits of ocherous material and massive sulfide with outer oxidized layers that formed during previous hydrothermal episodes are exposed on the steep outer walls of the mound. Studies of the full range of samples demonstrate that highly focused fluid flow, consequent seawater entrainment, and mixing within the mound can result in formation of a large seafloor hydrothermal deposit exhibiting sample types similar to those observed in Cyprus-type ore bodies.

The abundance of seafloor massive sulfide deposits

The possibility of mining seafl oor massive sulfide deposits has stirred debate about the sustainable use of this new resource and whether commercial development is worth the risk. Among the outstanding questions is how many deposits might be accessible to deep-sea mining. More than 300 sites of high-temperature hydrothermal venting have been identifi ed since the discovery of black smokers, but signifi cant massive sulfide accumulation has been found at only 165 of these sites. Estimates of the total number of vent fields and associated mineral deposits, based on plume studies and deposit occurrence models, range from 500 to 5000. We have used new deposit occurrence data from 10,000 km of ridge, arc, and backarc spreading centers to estimate the amount of massive sulfide in the easily accessible neovolcanic zones of the global oceans. The total accumulation in these areas is estimated to be on the order of 6 × 108 tonnes, containing ~3 × 107 tonnes of copper and zinc. This is similar to the total discovered copper and zinc in Cenozoic massive sulfi de deposits mined on land but is insuffi cient to satisfy a growing global demand for these metals.

Comparative mineralogy and geochemistry of gold-bearing sulfide deposits on the mid-ocean ridges

A comparative study of the mineralogy and geochemistry of sulfide deposits on mid-ocean ridges in the Northeast Pacific and the Mid-Atlantic reveals common characteristics associated with primary gold enrichment. Average gold contents of 0.8 to 5 ppm Au occur in sulfides from Southern Explorer Ridge and Axial Seamount (Northeast Pacific) and from the TAG hydrothermal field and Snakepit vent field (Mid-Atlantic Ridge). The enrichment of gold in these deposits is consistently related to a phase of late-stage, low-temperature ( 1 ppm Au occur exclusively in pyritic assemblages and commonly with abundant Fe-poor sphalerite and a suite of complex Pb—Sb—As sulfosalts. Amorphous silica and, locally, barite or carbonate are important constituents of the gold-rich precipitates but do not contain gold themselves. High-temperature (350°C) black smoker assemblages, consisting dominantly of pyrite, chalcopyrite, pyrrhotite, isocubanite and abundant anhydrite are uniformly gold-poor (≤0.2 ppm Au). To the extent that individual sulfides can be mechanically separated, chemical analyses by neutron activation indicate that gold is most abundant in sphalerite (up to 5.7 ppm Au) but also occurs in pyrite and marcasite. Samples of sphalerite with abundant inclusions of fine-grained sulfosalts locally contain up to 18 ppm Au, suggesting that sulfosalts may be repositories for gold. No free gold has been observed at 4000 × magnification of polished specimens, indicating that the gold is present only as submicroscopic inclusions or as a chemical constituent within the sulfides. Samples from gold-rich deposits in the Northeast Pacific and Mid-Atlantic are compared with similar but relatively gold-poor sulfides from the Galapagos Rift and 13°N on the East Pacific Rise (EPR), and with barren sulfides from 11°N EPR, 21°N EPR, the Endeavour Ridge, and the Southern Juan de Fuca Ridge. Trace element analyses of more than 170 samples show that gold enrichment in almost all of the deposits is associated with high concentrations of Ag, As, Sb, Pb and Zn, and locally with high Cd, Hg, Tl, and Ga. In contrast, gold is typically depleted in samples with high Co, Se, and Mo. The close association of Au with Ag, As, Sb, and Pb may reflect the common behavior of these metals as aqueous sulfur complexes (e.g., [Au(HS)−2]) at low temperatures. Similar mineralogical and geochemical associations are observed in sulfide deposits from modern back-arc settings and in the ancient geologic record.

Submarine volcanoes and high-temperature hydrothermal venting on the Tonga arc, southwest Pacific

Submarine hydrothermal vents and associated seafloor mineralization on the Tonga arc have been found for the first time, in the summit calderas of two shallow-water volcanoes, greatly extending the known areas and diversity of seafloor hydrothermal activity in the western Pacific region. The highest temperature vents (245–265 °C) occur at water depths of 385–540 m near the summit of one volcano at 24°S. The vents are spatially related to basaltic dike swarms exposed at a summit cone and in the caldera walls. Clusters of large (to 10 m high) barite, anhydrite, and sulfide chimneys on the summit cone are vigorously discharging clear hydrothermal fluids with temperatures on the seawater boiling curve. There is abundant evidence of phase separation, which can be seen as flame-like jets of steam (H2O vapor) at the chimney orifices. Pyrite, marcasite, sphalerite, and chalcopyrite line the interiors of the highest temperature vents, similar to black smoker chimneys on the mid-ocean ridges.

Elemental mercury at submarine hydrothermal vents in the Bay of Plenty, Taupo volcanic zone, New Zealand

Hot springs in active geothermal areas such as Yellowstone National Park, the Geysers geothermal field in California, and the Taupo volcanic zone in New Zealand are notably enriched in the trace metals Au, Ag, As, Sb, and Hg. Such near-surface hot springs have formed many of the worlds important deposits of gold and silver and some of the largest deposits of mercury. The majority of these are associated with continental geothermal systems in subaerial environments. Here we report the discovery of active mercury-depositing hot springs in a submarine setting, at nearly 200 m water depth, within the offshore extension of the Taupo volcanic zone of New Zealand. These vents contain the first documented occurrence of elemental mercury on the sea floor and provide an important link between offshore hydrothermal activity and mercury-depositing geothermal systems on land. The discovery has implications for mercury transport in sea-floor hydrothermal systems and underscores the importance of submarine volcanic and geothermal activity as a source of mercury in the oceans.

A model for growth of steep-sided vent structures on the Endeavour Segment of the Juan de Fuca Ridge: Results of a petrologic and geochemical study

Petrologic and geochemical studies of vent solids from the Main Endeavour Field (MEF) and the High Rise Field (HRF), Juan de Fuca Ridge, demonstrate that the steep-sided vent structures characteristic of these sites form dominantly by flange growth, combined with diffuse flow through sealed portions of structures, and incorporation of flanges into structures. Geochemical calculations suggest that the prevalence of amorphous silica and flanges in Endeavour deposits is the result of conductive cooling of vent fluids that have high concentrations of ammonia. At Endeavour, as the temperature of vent fluid decreases, ammonia-ammonium equilibrium buffers pH and allows more efficient deposition of sulfide minerals and silica from fluids that have a higher pH than conductively cooled ammonia-poor fluids present at most other unsedimented mid-ocean ridge vent sites. Deposition of silica stabilizes flanges and allows structures to attain large size. It also leads to diffuse flow and further conductive cooling by reducing the permeability and porosity of the structures and of feeder zones, thus decreasing entrainment of seawater. Most inactive vent samples recovered from areas peripheral to the HRF and MEF are similar to barite + silica rich samples from the Explorer Ridge and Axial Seamount and likely formed from precipitation of silica and barite on a biological substrate. Active white smoker chimneys from the Clam Bed Field, located south of the HRF, are pyrrhotite rich and likely formed from vent fluids that are depleted in Zn and Cd and enriched in Pb and Ba relative to fluids exiting trans-Atlantic geotraverse (TAG) and Cleft Segment white smoker chimneys.

First observations of high-temperature submarine hydrothermal vents and massive anhydrite deposits off the north coast of Iceland

High-temperature (250°C) hydrothermal vents and massive anhydrite deposits have been found in a shallow water, sediment-filled graben near 66°36′N in the Tjornes Fracture Zone north of Iceland. The site is located about 30 km offshore, near the small island of Grimsey. The main vent field occurs at a depth of 400 m and consists of about 20 large-diameter (up to 10 m) mounds and 1–3 m chimneys and spires of anhydrite and talc. A north–south alignment of the mounds over a 1-km strike length of the valley floor suggests that their distribution is controlled by a buried fault. Widespread shimmering water and extensive white patches of anhydrite in the sediment between the mounds indicates that the entire 1-km2 area occupied by the vents is thermally active. A 2-man research submersible JAGO was used to map the area and to sample vent waters, gases, and chimneys. Actively boiling hydrothermal vents occur on most of the mounds, and extensive two-phase venting indicates that the field is underlain by a large boiling zone (200×300 m). The presence of boiling fluids in shallow aquifers beneath the deposits was confirmed by sediment coring. The highest-temperature pore fluids were encountered in talc- and anhydrite-rich sedimentary layers that occur up to 7 m below the mounds. Baked muds underlie the talc and anhydrite layers, and pyrite is common in stockwork-like fractures and veins in the hydrothermally altered sediments. However, massive sulfides (pyrite–marcasite crusts) were found in only one relict mound. Subseafloor boiling has likely affected the metal-carrying capacity of the hydrothermal fluids, and deposition of sulfides may be occurring at greater depth. Although the mounds and chimneys at Grimsey resemble other deposits at sedimented ridges (e.g. Middle Valley, Escanaba Trough, Guaymas Basin), the shallow water setting and extensive boiling of the hydrothermal fluids represent a distinctive new type of seafloor hydrothermal system.

Discovery and Description of Giant Submarine Smectite Cones on the Seafloor in Eyjafjordur, Northern Iceland, and a Novel Thermal Microbial Habitat

ABSTRACT With the submersible JAGO and by scuba diving we discovered three remarkable geothermal cones, rising 33, 25, and 45 m from the seafloor at a depth of 65 m in Eyjafjordur, northern Iceland. The greatest geothermal activity was on the highest cone, which discharged up to 50 liters of freshwater per s at 72°C and pH 10.0. The cones were built up from precipitated smectite, formed by mixing of the hot SiO2-rich geothermal fluid with the cold Mg-rich seawater. By connecting a rubber hose to one outflow, about 240 liters of pure geothermal fluids was concentrated through a 0.2-μm-pore-size filter. Among 50 thermophilic isolates, we found members of Bacillus and Thermonema and a new unidentified low-G+C gram-positive member of theBacteria as well as one member of theArchaea, Desulfurococcus mobilis. Analysis of small-subunit rRNA genes PCR amplified and cloned directly from environmental DNA showed that 41 out of 45Bacteria sequences belonged to members of theAquificales, whereas all of the 10Archaea sequences belonged to theKorarchaeota. The physiological characteristics of isolates from different parts of the cones indicate a completely freshwater habitat, supporting the possibility of subterranean transmittance of terrestrial organisms.