DEEP SEA MINERALS - Vol 1 - Sea-Floor Massive Sulphides

Rising global demand for metals and developments in technology have recently renewed industry interest in exploring, and exploiting, deposits of deep sea minerals (‘DSM’).

DEEP SEA MINERALS

1A

Sea-Floor Massive Sulphides A physical, biological, environmental, and technical review

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 1

Edited by Elaine Baker and Yannick Beaudoin

A Centre Collaborating with UNEP

Steering Committee Akuila Tawake (Chair) Secretariat of the Pacific Community/SOPACDivision Charles Roche Mineral Policy Institute Elaine Baker GRID-Arendal at the University of Sydney Yannick Beaudoin GRID-Arendal Malcolm R. Clark National Institute of Water & Atmospheric Research Ltd (NIWA) Daniel Dumas Commonwealth Secretariat Chuck Fisher Penn State University James R. Hein United States Geological Survey (USGS) Robert Heydon Offshore Council Harry Kore Government of Papua New Guinea Hannah Lily Secretariat of the Pacific Community/SOPAC Division

Reviewers Peter Crowhurst Nautilus Minerals Inc. John Feenan IHC Mining Hiroshi Kitazato Japan Agency for Marine-Earth Science and Technology (JAMSTEC) Gavin Mudd Monash University Christian Neumann GRID Arendal Andrew Thaler Duke University Cornel de Ronde Institute of Geological and Nuclear Sciences Phil Symonds Geoscience Australia David Cronan Royal School of Mines, Imperial College, London Steve Scott University of Toronto

Michael Lodge International Seabed Authority Linwood Pendleton Duke University, NOAA Sven Petersen IFM-GEOMAR

Cartography Kristina Thygesen GRID Arendal Riccardo Pravettoni GRID Arendal

Julian Roberts Commonwealth Secretariat Samantha Smith Nautilus Minerals Inc. Anne Solgaard GRID-Arendal Jan Steffen IUCN Arthur Webb Secretariat of the Pacific Community/SOPAC Division

Front Cover Alex Mathers

Technical Editors Claire Eamer Patrick Daley

Editors Elaine Baker and Yannick Beaudoin

Production GRID-Arendal

Authors Malcolm R. Clark National Institute of Water & Atmospheric Research Ltd (NIWA) Daniel Desbruyères IFREMER Chuck Fisher Penn State University Robert Heydon Offshore Council James R. Hein United States Geological Survey (USGS) Sven Petersen IFM-GEOMAR Ashley Rowden National Institute of Water & Atmospheric Research Ltd (NIWA) Samantha Smith Nautilus Minerals Inc. Elaine Baker GRID Arendal at the University of Sydney Yannick Beaudoin GRID Arendal

Acknowledgments Special thanks to Akuila Tawake and Hannah Lily from the Secretariat of the Pacific Community/SOPAC Division and Peter Harris from Geoscience Australia for final reviews of chapters. Citation Secretariat of the Pacific Community (2103) Deep Sea Minerals: Sea Floor Massive Sulphides, a physical, biological, environmental, and technical review . Vol. 1A, SPC

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 2

DEEP SEA MINERALS

1A

Sea-Floor Massive Sulphides A physical, biological, environmental, and technical review

CONTENTS

1.0 The Geology of Sea-Floor Massive Sulphides 1.1 The formation and occurrence of sea-floor massive sulphides 1.2 Metal concentrations and tonnages

7 8 12 19 20 23 24 27 29 30 33 35 36 39 40 43 45 48

2.0 Biology Associated with Sea-floor Massive Sulphide Deposits 2.1 Habitats and biodiversity associated with sea-floor massive sulphide deposits 2.2 Global distribution of vent organisms 2.3 Composition of vent communities in the western Pacific 3.0 Environmental Management Considerations 3.1 Environmental management objectives 3.2 General environmental management approaches and principles 3.3 Environmental studies 3.4 Defining characteristics of SMS systems 3.5 Environmental impacts 3.6 The potential extent of impacts 3.7 Mitigation and management measures 4.0 Processes related to the technical development of marine mining 4.1 Exploration 4.2 Mining

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 3

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 4

Introduction Hydrothermal vents were first discovered at the Galapagos Rift in 1977 (Corliss et al . 1979). Observa- tions made in 1979 from the manned submersible Alvin on the East Pacific Rise revealed vents where superheated water was emerging from the sea-floor at temperatures exceeding 350°C. These vents were actively formingmassive sulphide deposits rich inmetals. The resultant, chimney-shaped black smokers – so called because they emit smoke-like plumes of dark particles – hosted a vent-adapted biological ecosystem made up of a complex community of giant clams, tubeworms, and other previ- ously undiscovered creatures that rely on chemosynthetic bacteria for their survival. The history of early sea-floor hydrothermal-system research can be found in Lowell et al . (1995). On land, massive sulphide deposits created through volcanic action are major sources of copper, lead, and zinc. Many of the known deposits also contain significant amounts of gold and silver. The recognition that these deposits originally formed in the ocean helped promote exploration to discover marine sea-floor massive sulphide (SMS) deposits.

Flange crabs. Photo courtesy Chuck Fisher.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 5

Participating Paci c Island States

Marshall Islands

Federated States of Micronesia

Palau

Kiribati (Line Iss.)

Kiribati

Nauru

(Gilbert Iss.)

Kiribati

Papua New Guinea

(Phoenix Iss.)

Tuvalu

Solomon Islands

Cook Islands

Timor Leste

Samoa

Fiji

Vanuatu

Tonga Niue

Exclusive economic zone

Figure 1. The Pacific ACP States (i.e. Africa-Caribbean-Pacific Group of States) participating in the European Union funded SPC Deep Sea Minerals Project.

The existence of known high-grade SMS deposits in the Pacific, and the progress towards ex- traction of metals from the Manus Basin site (Papua New Guinea), has increased interest around the region in the commercial development of SMS. To support Pacific Islands in governing and developing these natural resources, SOPAC Division of the Secretariat of the Pacific Community (SPC) is providing a range of information products, technical and policy support, and capacity building activities through the Deep Sea Minerals in the Pacific Islands Region: a Legal and Fiscal Framework for Sustainable Resource Management Project (Figure 1). This publication, created as part of that project, brings together expert knowledge on the geology and biology of SMS depos- its and information about best-practices related to environmental management and technical aspects of mineral exploration and extraction.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 6

1.0

The Geology of Sea-Floor Massive Sulphides James R. Hein 1 and Sven Petersen 2

1 U.S. Geological Survey, 400 Natural Bridges Dr., Santa Cruz, CA, 95060, USA 2 Helmholz Centre for Ocean Research Kiel (GEOMAR), 24148 Kiel, Germany

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 7

1.1

The formation and occurrence of sea-floor massive sulphides

Sea-floor massive sulphides (SMS) are deposits of met- al-bearing minerals that form on and below the seabed as a consequence of the interaction of seawater with a heat source (magma) in the sub-sea-floor region (Hannington et al . 2005). During this process, cold seawater penetrates through cracks in the sea-floor, reaching depths of several kilometres below the sea-floor surface, and is heated to temperatures above 400°C. The heated seawater leaches out metals from the sur- rounding rock. The chemical reactions that take place in this process result in a fluid that is hot, slightly acidic, reduced, and enriched in dissolved metals and sulphur. Due to the lower density of this evolved seawater, it rises rap- idly to the sea-floor, where most of it is expelled into the over- lying water column as focused flow at chimney vent sites. The dissolved metals precipitate when the fluid mixes with cold seawater. Much of the metal is transported in the hydrothermal plume and is deposited as fallout of particulate debris. The re- mainder of the metal precipitates as metal sulphides and sul- phates, producing black and white smoker chimneys (see box) and mounds (Figure 2). The minerals forming the chimneys and sulphide mounds in- clude iron sulphides, such as pyrite (often called fool’s gold), as well as the main minerals of economic interest. These include chalcopyrite (copper sulphide) and sphalerite (zinc sulphide). The precious metals gold and silver also occur, together with non-sulphide (gangue) minerals, which are predominantly sulphates and silicates. The metals originate from immiscible sulphides, ferromagnesian silicates, and feldspars that make up the volcanic rocks beneath the sea-floor (Hannington et al . 2005). It has been suggested that rising magmatic fluids may also be a source of ore metals, particularly at sites where hydro- thermal systems are producing SMS deposits in close associa- tion with subduction zones and island arcs. The enriched mag- matic fluid would then mix with the circulating seawater (Yang and Scott 1996; 2006). Since black smokers were first discovered, more than 280 sul- phide occurrences have been identified in all oceans (Han- nington et al . 2011), indicating that hydrothermal convection is widespread (Figure 3).

Most sulphide occurrences – 65 per cent – have been found along mid-ocean ridges (Hannington et al . 2011), with another 22 per cent occurring in back-arc basins and 12 per cent along submarine volcanic arcs. Very few sites – only 1 per cent – have been observed at intraplate volcanoes (Figure 4). Spreading centres (mid-ocean ridges and back-arc basins) have a com- bined length of 67 000 kilometres (Bird 2003), whereas subma- rine volcanic arcs have a total length of 22 000 kilometres, 93 per cent of which occurs in the Pacific (de Ronde et al . 2003). At mid-ocean ridges, high-temperature venting occurs mainly in the axial zones of the spreading centres and is associated with basaltic volcanism. At slow-spreading ridges, however, long-lived detachment faults may divert fluid flow away from the ridge axis. The associated sulphide deposits can, therefore, be found several kilometres away from the ridge axis. Volcanic arcs and back-arc basins develop as a result of subduction of oceanic crust at a convergent plate boundary. Hydrothermal systems in these environments are broadly similar to those at mid-ocean ridges. However, the geology and tectonic setting Hydrothermal chimneys discharge various colours of smoke, including black, grey, white, and yellow. The smoke is actually dense clouds of fine particles of sulphide, sul- phate, oxide minerals, and/or sulphur, all suspended in seawater. Black smokers have the highest fluid tempera- tures (greater than 330°C), and the particulates are pre- dominantly sulphide minerals. Particulates associated with white smokers are dominated by sulphate minerals that form at lower temperatures (300-150°C). Grey smokers expel both sulphide and sulphate minerals and form at in- termediate temperatures. Yellow smokers occur at several sites that are related to subduction zone processes (volca- nic arcs and back arcs). They form at the lowest tempera- tures and their particulates are mainly sulphur. This colour series also reflects the oxygen content of the fluid, with the amount of oxygen increasing as the mineral form moves from sulphide to sulphur to sulphate. The colours of smoke

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 8

Basics of a hydrothermal vent - a Black Smoker

O

CO 2

Mn 2+

3 He

Fe 2+

FeOOH

Particle fallout

CH 4

H 2

S

Dissolved metals

O

Hot focussed ow

Oxygen from seawater

S e a w a t e r

Metalliferous sediments

O

S e a w a t e r

Warm di use ow

Oxygen and potassium removed Calcium, sulfate, and magnesium removed

O

E v o l v e d s e a w a t e r

O

O

Sodium, calcium, and potassium added

HT reaction

Magmatic uids

Copper, zinc, iron, and sulfur added

Oceanic crust

Magma

O

Mantle

Figure 2. Basics of a hydrothermal vent. Seawater percolates through the sea floor and is modified by chemical exchange with the surrounding rocks and rising magmatic fluid. The altered seawater is released back into the ocean at the vent site and forms a hydro- thermal plume. The rising plume mixes rapidly with ambient seawater, lowering the temperature and diluting the particle concentra- tion. The plume will continue to rise through seawater as long as it is less dense than the surrounding seawater. Once the density of the hydrothermal plume matches the density of the seawater, it stops rising and begins to disperse laterally. In a scenario like this, 90 per cent of the metals are lost to the plume and do not take part in the metal deposit formation process.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 9

Global distribution of hydrothermal vent elds Active vent elds

Uncon rmed vent elds

Source: S. Beaulieu, K. Joyce, and S.A. Soule, 2010, Interridge andWoodshole

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 10

Distribution of known SMS occurrences

Intraplate volcanos

Submarine volcanic arcs

Back arc basins

Mid ocean ridges

Figure 4. Distribution of known sea-foor massive sulphide occurrences in different environments.

influence the composition of the hydrothermal fluids and also, ultimately, the mineralogy and chemical composition of the as- sociated sulphide deposits. The apparent differences are relat- ed to variations in host-rock composition, as well as to direct input of magmatic volatiles and metals into the hydrothermal circulation cell (Yang and Scott 1996; de Ronde et al . 2011). The occurrence and distribution of sulphide deposits seems to be related to overall magmatic activity along plate boundaries. The total number of vent sites that exist on themodern sea-floor is not known, although several hypotheses have been used to infer their abundance. Estimates based on Earth’s heat flow indicate that approximately one black smoker per kilometre of ridge axis is necessary to explain the heat flux through the oceanic crust (Mottl 2003). The distribution of hydrothermal plumes along the spreading axis and over volcanic arcs has also been used to infer similar values (Baker and German 2004; Baker 2007). It should be noted, however, that the latter approach only considers active hydrothermal fields. Evidence suggests that there are many more inactive sites than active sites (Hannington et al . 2011).

The largest black smoker discovered to date (since collapsed) measure­d almost 45 meters high and occurred on the Juan de Fuca Ridge. Following destruction, chimneys have been measured to grow as fast as 30 centimetres per day. The biggest chimneys are generally found on slow spreading ridges (like the Mid-Atlantic Ridge). On slowspreading ridges like the East Pacific Rise, chimneys are rarely more than 15 meters high. Photo courtesy of GEOMAR.

Figure 3. Global distribution of sea-floor hydrothermal sys- tems and related mineral deposits. Confirmed vents are those where hydrothermal activity has been observed at the sea floor. The unconfirmed sites are inferred to be active based on plume surveys. From version 2.0 of the InterRidge Global Database (Beaulieu 2010).

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 11

1.2

Metal concentrations and tonnages

While the number of discoveries of SMS occurrences is steadily rising, most deposits are small in size and tonnage of contained sulphide. Hydrothermal vent systems do not generally incorpo- rate metals into sulphide deposits efficiently. Much of the met- al is lost to the hydrothermal plume and dispersed away from the vent sites. Large deposits form only where sediments allow for efficient trapping of the metals due to metal-precipitation below the sea-floor (as in Middle Valley and Okinawa Trough; Zierenberg et al . 1998; Takai et al . 2012) or where hydrothermal

activity occurs for long periods of time, as with sulphide miner- alization related to large detachment faults. Based on informa- tion about the age of the sulphides and the underlying volcanic crust, it appears that tens of thousands of years are needed to form the largest known deposits, such as the Semyenov and Krasnov deposits of the Mid-Atlantic Ridge (Cherkashov et al . 2010). These deposits can be up to several hundreds of metres in diameter and are estimated to have total masses on the order of 5 to 17 million tonnes of contained sulphides.

Geochemistry of massive sulphides in various tectonic settings Geochemistry of massive sulphides in various tectonic settings

Concentration of mineral, percentage

Intracontinental rifted arc

20

Lead Zinc Copper

Intraoceanic back-arc basins

Ultrama c-hosted mid-ocean ridges

Volcanic arcs

15

10

Basalt-hosted mid-ocean ridges

Sedimented ridges

5

0

Continental lithosphere

Subducting slab

Mantle plume

Figure 5. Concentrations of copper, zinc and lead in sea-foor massive sulphides formed in different geological settings (Source: GEOMAR)

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 12

The composition of SMS deposits is highly variable, and not all elements contained in the sulphides are of commercial interest. For example, SMS deposits along the East Pacific Rise and, to some extent, those along theMid-Atlantic Ridge are primarily com- posed of iron sulphides that currently have no economic value. In contrast, sulphide occurrences in the southwest Pacific contain concentrations of copper and zinc, which make them more eco- nomically attractive (Figure 5). Valuable metals such as gold and silver are trace components of the sulphides, but can be highly en-

riched in some deposits, reaching concentrations of several tens of grammes/tonne for gold and several hundreds of grammes/tonne for silver (Figure 6). Other trace elements – bismuth, cadmium, gal- lium, germanium, antimony, tellurium, thallium, and indium – are normally contained in SMS in low quantities (at levelsmeasured in grammes/tonne), but can be significantly enriched in some depos- its, especially those that form at volcanic arcs. Weathering of old SMS on the seabed can upgrade the metal contents in the deposit due to the formation of secondary copper-rich sulphides.

Geochemistry of massive sulphides in various tectonic settings

Geochemistry of massive sulphides in various tectonic settings

Concentration of mineral, parts per million

Intracontinental rifted arc

1000

Silver Gold

800

600

Volcanic arcs

400

Intraoceanic back-arc basins

Ultrama c-hosted mid-ocean ridges

200

Basalt-hosted mid-ocean ridges

Sedimented ridges

0

Continental lithosphere

Subducting slab

Mantle plume

Figure 6. Concentrations of gold and silver in sea-foor massive sulphides formed in different geological settings (Source: GEOMAR)

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 13

The geochemical composition of SMS is not only variable on a re- gional scale, but also varies at the deposit or even hand-specimen scale, reflecting strong gradients in fluid temperatures (Figure 7). Copper-rich minerals typically line the high-temperature upflow zones and fluid conduits. The outer parts of the deposits consist of minerals that are rich in iron and zinc, such as pyrite, marcasite, and sphalerite. These are usually deposited at lower temperatures as the hydrothermal fluid mixes with seawater. As a result of this heterogeneity, the sampling of black smoker chimneys, which commonly show high concentrations of copper, might not be rep- resentative of the bulk composition of the deposits. Many pub- lished grades of sea-floor sulphide deposits are strongly biased due to sampling of high-temperature chimneys, which are easier to recover than sub-sea-floor mineralization. Unfortunately, with the exception of a few deposits that have been drilled through the Ocean Drilling Program or by commercial or scientific projects, lit- tle is known about the interiors of most SMS deposits.

Due to lack of information about the important subsurface component of deposits, it is difficult to estimate the re- source potential of most SMS. Initial estimates of the abun- dance and distribution of sulphide deposits in well-studied areas indicate that approximately 1 000 large sulphide de- posits may exist on the modern sea-floor (Hannington et al . 2011). However, some of the largest deposits, such as those along the central Mid-Atlantic Ridge, are dominated by iron sulphides of no commercial interest. Other factors that af- fect current commercial viability are water depth, distance to land, and sovereign jurisdiction. An analysis of known deposits indicates that only about ten individual deposits may have sufficient size and grade to be considered for fu- ture mining (Hannington et al . 2011). However, many small- er, metal-rich deposits could be incorporated into a single mining operation, making mining of these smaller SMS de- posits viable.

5 cm

Figure 7. Examples of sea-foor massive sulphides from various tectonic settings. Pyrite-rich chimney from the basalt-hosted Tur- tle Pits hydrothermal field, 5°S on the Mid-Atlantic Ridge (upper left). A massive chalcopyrite chimney from the ultramafic-hosted Logatchev hydrothermal field (lower left) and a gold-rich copper-zinc massive sulphide from the PACMANUS field, Papua New Guin- ea. Note the copper-rich core and the brownish zinc-rich exterior of the sample, exemplifying a typical temperature zonation in SMS. Barite constitutes a major part of this sample (right, scale on sample is 5 cm). Photo courtesy of GEOMAR.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 14

Bismarck Sea sea-floor massive sulphide CASE STUDY

The western Pacific is characterized by SMS systems related mainly to westward-dipping subduction zones, which produce hydrothermal activity along back-arc basins and island arcs (Martinez and Taylor 1996). The Bismarck Sea is a back-arc basin formed in the last three million years by the southward slab rollback of the Solomon Sea Plate under New Britain. Extensive exploration in the Bismarck Sea over the last few years has led to the discovery of numerous active and inactive hydrothermal systems within the national ju- risdiction of PNG (Both et al . 1986; Tufar 1990; Binns and Scott 1993; Auzende et al . 2000; Binns et al . 2002; Tivey et al . 2006; Jankowski 2010; Reeves et al . 2011). Currently, two SMS systems and two sulphate systems have been documented in the west-

ern part of the Bismarck Sea. The active Central Manus spreading centre hosts six SMS systems, while nine SMS systems have so far been located in the eastern Manus Basin, mainly associated with the young volcanic edifices at Pual Ridge and SuSu Knolls (Figure 8). At numerous other hydrothermally active sites in the Bismarck Sea, no sulphide deposits have been discovered. The complexity of the tectonic setting within the BismarckSea is re- flected in thewide range of compositions of volcanic rocks. Overall, the composition of magmas along the Manus Basin changes in a west-to-east direction, frommid-ocean-ridgebasalt tomore arc-like compositionsnearer theNewBritainArc (Sinton et al . 2003). Chem- ical changes also occur in the SMS systems themselves, linked to changes in the composition of substrate rocks, water depth, and

Pual Ridge

Desmos

Solwara 12

Pacmanus

Solwara 1

SuSu Knolls

Figure 8: Location of Pual Ridge and SuSu Knolls, as well as SMS deposits in the eastern Manus Basin. Underlying bathymetry is from the 2002 RV Sonne cruise SO166 (GEOMAR). Inset shows location of the easternManus Basin in relation tomajor plate tectonic structures.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 15

contribution of magmatic volatiles to the hydrothermal system. Most systems at the Willaumez and Central Manus spreading cen- tres are small and consist mainly of scattered zinc-rich chimneys with exit temperatures reaching 302°C (Gamo et al . 1996). Systems from the Pual Ridge and SuSu Knolls are distinguished by higher copper, gold, and silver contents (Table 1), making them especially interesting from an economic point of view. At the PACMANUS site near the crest of Pual Ridge, discontinuous vent fields occur over a strike length of two kilometres and show exit-fluid temperatures up to 358°C (Reeves et al . 2011). While some small mounds are pres- ent, scattered chimneys protruding from felsic volcanic rocks char- acterizemost sites. High-temperature venting, up to 332°C (Bach et al . 2012), and SMS systems have also been observed at the North Su and South Su sites. There, crosscutting volcanic ridges indicate structural control onmelt ascent and fluidmigration, a setting com- mon for many ancient land-based sulphide systems. This area also hosts the roughly 2.5-million-tonneSolwara 1 deposit (estimated at 2.6 per cent copper equivalent, or CuEq), over which the southwest

Pacific’s first mining lease for SMS mineral extraction has been granted. Additionally, several smaller active systems have been documented in the vicinity. Solwara 12 is associated with a caldera located between Pual Ridge and SuSu Knolls. A characteristic feature of many SMS systems in the eastern Ma- nus Basin is the contribution of magmatic volatiles and metals. This is evidenced by the intense alteration of the host lavas, low- pH fluids, occurrence of abundant elemental sulphur at sever- al sites (such as North Su and South Su), and the presence of metal-rich inclusions in host rocks (Yang and Scott 1996). The chemical data from Solwara 1 and Solwara 12 clearly show the difference in resource evaluation between surface sampling and drilling. The sub-sea-floor deposits have lower values of both base and precious metals, with a few exceptions. Present-day exploration techniques mainly search for water column anoma- lies produced by active vent systems, leaving considerable po- tential for the discovery of inactive systems in the area.

Location

size/tonnage N

Cu Zn

Au Ag

depth (m)

wt.%

ppm

Western Manus Basin Solwara 11

1.2 180 0.2 110

1390 - 1450 1310 2470 - 2500 2560 - 2590

- - - - - - -

26

1.6 16.9 0.3 19.6 1.2 21.0 1.1 21.3 7.7 15.2 1.4 19.2 2.1 18.6 8.1 0.9 7.1 1.6 7.4 9.2 6.0 8.3 6.3 10.6 7.4 22.5 7.0 22.6 7.3 3.6 9.1 30.7 9.7 5.4

Solwara 18

2

Central Manus Basin Vienna Woods, Solwara 2

10.0 355 15.2 642 2.5 165 3.3 97 2.8 105 15.0 174 5.0 23 6.4 34 4.8 39 6.8 191 14.6 282 19.9 296 13.7 267 13.7 425 3.6 56 4.7 546

215

Solwara 03 Solwara 10 Solwara 14 Solwara 16

31 12 14

2240 2240 2160

6

Eastern Manus Basin Suzette (Solwara 01) Suzette (Solwara 01)* Suzette (Solwara 01)*

90 000 m 2

250

1460 1460 1460 1183 1309 1635 - 1680 1680 1650 - 1815

1 030 000 t indicated 7.2 0.4

1 540 000 t

inferred

North Su South Su

- -

4 4

30 000 m 2 15 000 m 2 45 000 m 2 230 000 t 30 000 m 2 -

12 17

Solwara 05 (N of North Su) Solwara 09 (west of North Su) Solwara 12 (near Desmos) Solwara 12 (near Desmos)* Solwara 13 (Yuam Ridge) PACMANUS

336

10

1870 1870 2000

inferred

7

Table 1: Chemical composition of SMS from the Bismark Sea. For most sites, the average composition of surface samples is given, which might not be representative of the entire deposit. For Solwara 1 and 12, where a resource estimate has been published, the data on surface samples is also provided. (N= number of samples analysed; * = resource estimate; results for PACMANUS include data from Solwara 4, 6, 7, and 8, which are considered here to be part of the same hydrothermal system).

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 16

Photo courtesy of Chuck Fisher.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 17

References

Hannington, M.D., Jamieson, J., Monecke, T., Petersen, S. (2010). Modern sea-floor massive sulfides and base metal resources: toward an esti- mate of global sea-floor massive sulfide potential. Society of Economic Geologists Special Publication 15, 317-338. Hannington, M.D., Jamieson, J., Monecke, T., Peterson, S. and Beaulieu, S. (2011). The abundance of seafloor massive sulfide deposits. Geology 39, 1155-1158. Jankowski, P. (2010). Nautilus Minerals Inc. NI43-101 Technical Report 2009 PNG, Tonga, Fiji, Solomon Islands and New Zealand. Technical Report compiled under NI43-101. SRK Consulting Ltd, for Nautilus Min- erals Incorporated. Lipton, I. (2012) Mineral Resource Estimate: Solwara Project, Bismarck Sea, PNG. Technical Report compiled under NI43-101. Golder Associ- ates, for Nautilus Minerals Nuigini Inc. Lowell, R.P., Rona, P.A. and Von Herzen, R.P. (1995). Seafloor hydrothermal systems. Journal of Geophysical Research 100(B1), 327-352. Martinez, F. and Taylor, B. (1996). Backarc spreading, rifting, and micro- plate rotation, between transform faults in the Manus Basin. In: (Eds. Auzende, J.M., Collot, J.Y.) Seafloor Mapping in the West, Southwest and South Pacific; Results and Applications. Marine Geophysical Research- es. D. Reidel Publishing Company, Dordrecht, Netherlands, 203-224. Mottl, M. J., (2003). Partitioning of heat and mass fluxes between mi- docean ridge axes and flanks at high and low temperature. In: (Eds. Halbach, P., Tunnicliffe, V., and Hein, J. R.) Energy and mass transfer in hydrothermal systems. Dahlem University Press, Berlin 271–286. Reeves, E.P., Seewald, J.S., Saccocia, P., Bach, W., Craddock, P.R., Shanks III, W.C., P. Sylva, S.P., Walsh, E., Pichler, T. and Rosner, M. (2011). Geochemistry of hydrothermal fluids from the PACMANUS, Northeast Pual and Vienna Woods hydrothermal fields, Manus Basin, Papua New Guinea. Geochimica et Cosmochimica Acta 75, 1088-1123. Sinton, J.M., Ford, L.L., Chappell, B. and McCulloch, M.T., 2003. Magma genesis and mantle heterogeneity in the Manus Back-Arc basin, Papua New Guinea. Journal of Petrology 44, 159-195. Takai, K., Mottl, M. J., Nielsen, S. H. H., Birrien, J. L., Bowden, S., Brandt, L., Breuker, A., Corona, J. C., Eckert, S., Hartnett, H., Hollis, S. P., House, C. H., Ijiri, A., Ishibashi, J., Masaki, Y., McAllister, S., McManus, J., Moyer, C., Nishi- zawa, M., Noguchi, T., Nunoura, T., Southam, G., Yanagawa, K., Yang, S. and Yeats, C., (2012). IODP Expedition 331: Strong and expansive subseafloor hydrothermal activities in the Okinawa Trough. Scientific Drilling 13, 19-26. Tivey, M., Bach, W., Seewald, J., Tivey, M. and Vanko, D., (2006). Cruise re- port R/V Melville MGLN06: Hydrothermal systems in the eastern Manus basin: Fluid chemistry and magnetic structure as guides to subseafloor processes, Rabaul, Papua New Guinea July 21, 2006 – Suva, Fiji, Septem- ber 1, 2006. Woods Hole Oceanographic Institution. Tufar, W. (1990). Modern hydrothermal activity, formation of complex massive sulfide deposits and associated vent communities in the Ma- nus back-arc basin (Bismarck Sea, Papua New Guinea). Mitteilungen der Österreichischen Geologischen Gesellschaft 82, 183–210. Yang K. andScott S.D. (1996). Possible contribution of ametal-richmagmat- ic fluid to a sea-floor hydrothermal system. Nature 383(6659) 420-423. Yang K. and Scott S.D. (2006). Magmatic fluids as a source of metals in arc/ back-arc hydrothermal systems: evidence from melt inclusions and ves- icles. In: (Eds. D.M. Christie, C.R. Fisher and S-M Lee) Back Arc Spread- ing Systems: Geological, Biological, Chemical and Physical Interactions. American Geophysical Union, Geophysical Monograph 166, 163-184. Zierenberg, R.A., Fouquet, Y., Miller, D.J., Bahr, J.M., Baker, P.A., Bjerk- gard, T., Brunner, C.A., Duckworth, R.C., Gable, R., Gieskes, J., Good- fellow, W.D., Gröschel-Becker, H.M., Guerin, G., Ishibashi, J., Itturino, G., James, R.H., Lackschewitz, K.S., Marquez, L.L., Nehlig, P., Peter, J.P., Rigsby, C.A., Schultheiss, P., Shanks, W.C., Simoneit, B.R.T., Summit, M., Teagle, D.A.H., Urbat, M., and Zuffa, G.G. (1998). The deep structure of a sea-floor hydrothermal deposit. Nature 392, 485-488.

Auzende, J.M., Ishibashi, J., Beaudouin, Y., Charlou, J.L., Delteil, J., Don- val, J.P., Fouquet, Y., Gouillou, J.P., Ildefonse, B., Kimura, H., Nishio, Y., Radford-Knoery, J. and Ruellan, E. (2000). Rift propagation and ex- tensive off-axis volcanic and hydrothermal activity in the Manus Basin (Papua New Guinea): MANAUTE Cruise. InterRidge News 9(2), 21-25. Bach, W., Jöns, N., Thal, J., Reeves, E., Breuer, C., Shu, L., Dubilier, N., Borows- ki, C., Meyerdierks, A., Pjevac, P., Brunner, B., Müller, I., Petersen, I., Hour- dez, S., Schaen, A., Koloa, K., Jonda, L. and the MARUM Quest 4000m team (2012). Interactions between fluids, minerals, and organisms in sul- fur-dominated hydrothermal vents in the easternManus Basin, Papua New Guinea – a report from RV Sonne cruise 216. InterRidge News 21, 33-36. Baker, E. T. (2007). Hydrothermal cooling of midocean ridge axies: do measured and modeled heat fluxes agree? Earth and Planetary Science Letters 263, 140-150. Baker, E. T. and German, C. (2004). On the global distribution of hydrother- mal vent fields. In: Mid-Ocean Ridges: Hydrothermal Interactions between the Lithosphere and Oceans. (Eds: C. German, J. Lin and L. Parson) Ameri- can Geophysical Union Geophysical Monograph Series 148, 245-265. Binns, R.A. and Scott, S.D. (1993). Actively forming polymetallic sulfide deposits associated with felsic volcanic rocks in the eastern Manus back-arc basin, Papua New Guinea. Economic Geology 88, 2226-2236. Binns, R.A., Barriga, F.J.A.S., Miller, D.J. and Leg 193 Scientific Party (2002). Anatomy of an active hydrothermal system hosted by felsic volcanic rocks at a convergent plate margin: ODP Leg 193. JOIDES Journal 28, 2-7. Bird, P. (2003). An updated digital model of plate boundaries: Geochem- istry Geophysics Geosystems 4, 10. Both, R., Crook, K., Taylor, B., Brogan, S., Chappell, B., Frankel, E., Liu, L., Sinton, J. and Tiffin, D. (1986). Hydrothermal chimneys and associated fauna in the Manus back-arc basin, Papua New Guinea. EOS Transac- tion American Geophysical Union, v. 67, p. 489–490. Cherkashov, G., Poroshina, I., Stepanova, T., Ivanov, V., Beltenev, V., Laza- reva, L., Rozhdestvenskaya, I., Samovarov, M., Shilov, V., Glasby, G. P., Fouquet, Y., and Kuznetsov, V. (2010). Seafloor massive sulfides from the northern Equatorial Mid-Atlantic Ridge: new discoveries and per- spectives. Marine Georesources and Geotechnology 28, 222-239. Corliss, J.B., Dymond, J., Gordon, L.I., Edmond, J.M., Von Herzen, R.P., Bal- lard, R.D., Green, K., Williams, D., Bainbridge, A., Crane, K., Van Andel, T.H (1979). Submarine thermal springs on the Galapagos Rift. Science 203, 1073–1083. de Ronde, C. E. J., Massoth, G. J., Baker, E. T., and Lupton, J. E. (2003). Submarine hydrothermal venting related to volcanic arcs. In: (Eds. Simmons, S. F., and Graham, I.) Volcanic, Geothermal, and Ore-forming Fluids: Rulers and Witnesses of Processes within the Earth. Society of Economic Geologists Special Publication 10, p. 91-110. de Ronde, C. E. J., Massoth, G. J., Butterfield, D. A., Christenson, B. W., Ishibashi, J., Ditchburn, R. G., Hannington, M. D., Brathwaite, R. L., Lupton, J. E., Kamenetsky, V. S., Graham, I. J., Zellmer, G. F., Dziak, R. P., Embley, R. W., Dekov, V. M., Munnik, F., Lahr, J., Evans, L. J., and Takai, K., (2011). Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand. Mineralium Deposita 46, 541-584. Gamo, T., Okamura, K., Charlou, J-L., Urabe, T., Auzende, J-M., Shipboard scientific party of the ManusFlux Cruise, Ishibashi, J., Shitashima, K. and Kodama, Y. (1996). Chemical Exploration of hydrothermal activity in the Manus Basin, Papua New Guinea (ManusFlux cruise). Jamstec Deepsea Research 12: 335-345. Hannington, M. D., de Ronde, C., and Petersen, S. (2005). Sea-floor tec- tonics and submarine hydrothermal systems. In: (Eds. Hedenquist, J. W., Thompson, J. F. H., Goldfarb, R. J., and Richards, J. P.) Economic Ge- ology 100th Anniversary Volume, 111-141. Hannington, M. D., Jamieson, J., Monecke, T., Petersen, S., and Beaulieu, S. (2011). The abundance of seafloor massive sulfide deposits. Geology 39, 1155-1158.

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2.0

Biology Associated with Sea-floor Massive Sulphide Deposits Chuck Fisher 1 , Ashley Rowden 2 , Malcolm R. Clark 2 , and Daniel Desbruyères 3 1 Penn State University 2 National Institute of Water & Atmospheric Research, NIWA, Wellington 6021, New Zealand 3 IFREMER, Centre de Brest, F-29273 Brest Cedex, France

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 19

2.1

Habitats and biodiversity associated with sea-floor massive sulphide deposits

Hydrothermal vents occur in areas of undersea volcanic activi- ty, most commonly associated with plate boundaries. The same geochemical processes that contribute to the formation of SMS deposits also bring hot fluid, rich in reduced chemicals, to the sea-floor. These chemicals are toxic to most animals, but they can be used as an energy source for growth by chemoautotrophic bacteria, organisms that get energy through a chemical process rather than by photosynthesis. As a result, hydrothermal vents provide an abundant source of bacteria-based food in a chemical and thermal habitat that most animals cannot tolerate (Figure 9). However, a diverse array of animals has evolved the adapta- tions necessary to tolerate this extreme habitat and thrive. The list includes at least 600 species, called vent-endemic species, that are only known to exist at hydrothermal vents (Desbruyères et al . 2006a). Many vent-endemic species have evolved a sym-

biotic, or mutually beneficial, relationship with chemoautotro- phic bacteria, which allows them to benefit directly from the energy in hydrothermal vent fluids and reach densities of hun- dreds to thousands of individuals per square metre. Vent-en- demic species, along with a limited number of other species that can tolerate and indirectly benefit from the extreme envi- ronment, form distinct vent communities. In addition to the physiological challenges associated with ex- posure to extreme chemistry and widely varying temperatures, the vent-endemic species must also evolve adaptations to al- low them to exploit a habitat that is very patchy and ephemeral, likely to disappear suddenly. Hydrothermal venting is not con- tinuous along the plate margins. For example, vent site spacing along a spreading centre can range from a few kilometres to hundreds of kilometres. Within a site, sources of venting fluid

Energy

Energy

PHOTOSYNTHESIS PHOTOSYNTHE IS

CHEMOSYNTHESIS CHEMOSYNTHE IS

Food chain

F od chain

Sunlight

Sunlight

Algae

Algae

CO 2

CO 2

Coral

Coral

Sunlight

Sunlight

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CO 2

CO 2

+R Organic

molecules +R Organic

molecules

CO 2

CO 2

- 2 SO 4

- 2

HS - +2O 2

HS - +2O 2

SO 4

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F od chain

Animal tissue

Animal tissue

Energy

Energy

Organic molecules

Organic molecules

CO 2

CO 2

+R

+R

Animal tissue

Animal tissue

Mussels and snails

Mussels and snails

Bacteria

Bacteria

Hydrogen Sulphide Hydrogen Sulphide

Source:TBC

Source:TBC

Reduced chemicals Reduced chemicals

Figure 9. Chemoautotrophic symbiotic relationships. These relationships are similar to the symbiosis between shallow-water reef corals and their photosynthesizing algae. Like some species of corals, which must be exposed to sunlight to reap the benefits of their algal partners, vent animals must live exposed to hydrothermal vent fluids in order to benefit from their bacterial symbionts.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 20

Ancient lineages of stalked barnacles (Vulcanolepus sp) from the Lau Basin and Kermadec Volcanic Arc (left, photo courtesy of the NSF Ridge 2000 program) and Yeti crabs from Antarctic vents (right, photo courtesy of T. Shank) host symbiotic bacteria on their appendages. The bacteria are thought to provide food for the hosts.

might be anywhere from a metre to hundreds of metres apart (Ferrini et al . 2008; Baker 2009). Volcanic and tectonic activity are both common on active spreading centres, and both affect the point sources of hydrothermal fluid emission and the lon- gevity of individual sites. Tectonic activity can alter the hydro- thermal plumbing at a site, blocking or redirecting hydrother- mal venting. Volcanic activity can result in sites being partly or completely repaved with hot lava. Either type of activity can par- tially or completely wipe out the site’s endemic communities. Over about 25 years of intensive study of vent sites in the 9-10° latitude N area of the East Pacific Rise, scientists have observed two cycles of local extermination and recolonization of vent communities as a result of volcanic activity (Haymon et al . 1993; Tolstoy et al . 2006). The East Pacific Rise, howev- er, is a fast-spreading centre, where the plates move apart at a rate of more than 10 centimetres a year and large volumes of magma erupt, so these events may be more common here than at other vent sites. On the Mid-Atlantic Ridge, which is a slow-spreading centre where plates separate at approximately 2.5 centimetres a year, this kind of activity is much less fre- quent. One well-studied site on this ridge, the TAG site (Rona 1973) is thought to have been active for tens of thousands of years, although individual chimneys and sources of diffuse flow within the TAG mound are active for much shorter peri- ods (White et al . 1998). Because of the patchy and ephemeral

nature of hydrothermal venting, endemic faunal populations must have dispersal and recruitment capabilities that allow them to recolonize new sites regularly. However, the dispersal capabilities and resultant genetic connectivity among sites in an area varies by species and region (Vrijenhoek 2010). Vent community structure will reflect adaptations to the natural fre- quency and intensity of disturbance (Miller et al . 2011). At hydrothermal vents, both lava flows and sea-floor mineral deposition result in creation of hard substrate that rises above the surrounding sea-floor. These structures can provide habitat for other groups of animals that are not directly tied to active hy- drothermal flow and, in fact, are unlikely to tolerate exposure to hydrothermal fluid. Inactive (old) hydrothermal vent sites and inactive hydrothermal chimneys at active sites can both provide prime substrate for rich suspension-feeding assemblages dom- inated by corals and echinoids not normally found on the deep sea-floor. These animals are often slow-growing and long-lived (Probert et al . 1977). In addition to exposure to food broadly found in the benthic water, these communities may also benefit from primary production at nearby active vents (Erickson et al . 2009). The animals living on inactive-vent sulphide structures and the infauna of inactive sediments in the vicinity of venting are not well studied, although the indications are that these communities may also depend to some extent on production from vents (Levin et al . 2009).

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 21

b

a

c

d

e

f

g

h

Sea-floor images (a-d) showing inactive sulphide chimneys with rich assemblages of epifauna, including scleractinians (stony cor- als), echinoids (sea urchins), brisingids (sea stars) and crinoids (sea lilies); and (e-h) less dense assemblages of the same type of organisms on volcanic lavas away from SMS deposits. Rumble II West volcano, Kermadec Volcanic Arc. Photos courtesy of Neptune Resources (Kermadec) Ltd (a-d) and NIWA (e-h).

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 22

2.2

Global distribution of vent organisms

Hydrothermal vents with generally similar chemical/thermal habitats exist in all of the world’s oceans. However, there are significant differences among vent communities in different regions of the world. For example, the giant tubeworms that dominate many vent habitats in the eastern Pacific have nev- er been seen at Atlantic, Indian Ocean, or southwest Pacific vent sites. On the Mid-Atlantic Ridge, swarms of endemic vent shrimp with chemoautotrophic symbionts cover many hydro-

thermal chimneys. In the Indian Ocean, shrimp, anemones, and big, symbiont-containing snails constitute the largest portion of the biomass. Analysis of the composition of vent communities suggests at least five biogeographic provinces for vent fauna, although the number and boundaries of these provinces have yet to be resolved with any certainty (Van Do- ver et al 2002; Bachraty et al 2009; Moalic et al 2011; Rogers et al 2012).

The scaly foot snails found at vents on the Central Indian Ridge in the Indian Ocean have scales composed of iron sulphides and are the only animals known to produce metal armour. Photo courtesy of CL Van Dover.

Shrimp on theMid-Atlantic Ridge and on Indian Ocean vents (Rimi- caris sp) have lost their eyes but have evolved large light-sensing patches on their backs to “see” the chimneys they call home. They are not found in the southwest Pacific. Photo courtesy of IFREMER.

Because of the myriad of adaptations necessary to live at hydrothermal vents, most animals cannot survive there. However, the endemic vent fauna represent a source of evolutionary innovation not found elsewhere on earth. They often occur in extremely high densities at hydrothermal vents. Giant tubeworms (Riftia pachyptila) from the East Pacific Rise are among the fastest growing animals on earth. They have no mouth, gut, or anus and live their entire adult lives with one end of their bodies immersed in a hot tub and the other in ice-cold water. They are not found in the southwest Pacific. Photo courtesy of IFREMER.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 23

2.3

Composition of vent communities in the western Pacific

In the western Pacific, hydrothermal venting is widespread, not only along back-arc spreading centres, but also on undersea vol- canoes at a wide range of depths. Settings and styles of hydro- thermal venting are diverse in the western Pacific, and the chem- istry of hydrothermal fluid is also quite variable due to differences in geology and water-rock interactions at different depths. Fur- thermore, there are numerous and complex potential geographic and oceanographic barriers to dispersal between hydrothermal sites in the western Pacific, leading to isolation of populations and resultant speciation over evolutionary time (Desbruyères et al . 2006b). The cumulative result of all of these factors is the like- ly presence of multiple biogeographic provinces, associated with hydrothermal venting, between New Zealand and Japan. A recent analysis suggests there may be at least four biogeographic prov- inces within the western Pacific alone (Rogers et al 2012). Within most vent sites, one can further divide the animals and communities according to macrohabitat and microhabitat. The hottest habitat occupied by animals at vents is normally found near the top of active and growing chimneys and hydrothermal flanges. The latter are outgrowths from the main body of the sul- phide structure and are associated with pooling of high tempera-

ture fluid beneath the flange. Only a few specialized animals can tolerate this habitat, where body temperatures may approach 60°C (Cary et al . 1998; Girguis and Lee 2006). Other distinct hab- itats, with particular thermal and chemical characteristics, are inhabited by their own endemic vent animals (Henry et al . 2008; Podowski et al 2009, 2010). In the western Pacific, snails in the genus Alviniconcha normally occupy the warmest habitats and can tolerate temperatures up to about 45°C. Although sometimes found mixed in with Alviniconcha spp. snails, the snail Ifremeria nautilai is more often found in vent-fluid habitats with tempera- tures that range from a few degrees above ambient to about 20°C. The mussel Bathymodiolus brevior is often found in aggre- gations mixed with Ifremeria nautilai, but also seems to thrive when exposed to very dilute hydrothermal fluid at near-ambient temperatures. Each of these species of symbiont-containing fau- na is associated with a number of other species of vent animals that normally occur in the same habitats (Podowski et al . 2009, 2010). Current research suggests that the fauna associated with inactive hydrothermal structures or sediments are not endemic to vents, but are a subset of the filter-feeding communities found on other areas of hard substrate at similar depths in the region (Limen et al . 2006; Levin et al . 2009; Van Dover 2011).

A rather low-biomass animal community of shrimp, crabs, and specialized polychaete worms commonly covers the relatively new, often hot and bright-white surfaces near the tops of chimneys and on hydrothermal flanges. Austinogreid crabs, shrimp, and the scale worm Branchinotogluma segonzaci on a flange in the Tu’I Malila vent field on the Eastern Lau spreading centre. Photo courtesy of Chuck Fisher.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 24

In slightly cooler areas, both on chimneys and lavas, one can find high-biomass communities dominated by two genera of golf-ball- sized snails and/or specialized mussels. They live with a variety of endemic shrimp, worms, and crabs that tolerate constant exposure to warm, chemically rich, and normally toxic vent fluid.

A species of Alvinoconcha snail and the austinogreid crabs nestled in shimmering waters on the Eastern Lau spreading centre. Photo courtesy of NSF Ridge2000program.

Dense bed of the undescribed mussel Bathymodiolus sp. on Monowai volcano, Kermadec volcanic arc. Photo courtesy of NOAA/NIWA/GNS.

Aggregations of the snail Ifremeria nautilai on active hydrothermal chimneys on the Eastern Lau spreading centre. Photo cour- tesy of NSF Ridge 2000 program.

Even in peripheral areas with minimal exposure to very dilute vent fluid, one finds luxuriant communities of vent-endemic animals, including several species of anemones and barnacles.

Anemones and barnacles in the KiloMoana vent field on the ELSC. Photo courtesy of NSF Ridge 2000 program.

Anemones and barnacles in the Kilo Moana vent field on the ELSC. Photo courtesy NSF Ridge 2000 program.

THE GEOLOGY OF SEA-FLOOR MASSIVE SULPHIDES 25

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