Understanding geologic mechanisms that form karst is of global interest. An estimated 25% of the world's population obtains water from karst aquifers and numerous major petroleum reserves are found in paleokarst reservoirs, so characterization and classification of specific types of karst is essential for resource management. Sistema Zacatón, which includes the second deepest underwater cave in the world, is hypothesized to have formed from volcanogenic karstification, defined as a process that relies on four components to initiate and develop deep, subsurface voids: a carbonate matrix, preferential groundwater flowpaths (fractures), volcanic activity that increases groundwater acidity, and groundwater flux through the system. Phases of karstification creating this modern hydrogeological environment are defined using numerous methods: field mapping, 3-D imaging of surface and aqueous environments, geophysical investigations, physical and chemical hydrogeologic characterization, and microbial analysis. Interpretation of the results yields a multi-phased speleogenetic model of the karst, with most phases occurring in the late Pleistocene. The surface rocks are carbonate travertine with Pleistocene mammoth fossils found within the rock matrix, and are interpreted as a hydrothermal travertine terrace formed as nearby volcanic activity peaked, thus representing the end member of a carbonate mass transfer system originating deep in the subsurface. The modern karst system includes a dynamic set of deep, phreatic sinkholes, also called cenotes, which propagated up through the travertine, eventually exposing hydrothermal water supersaturated with carbon dioxide to the atmosphere. In some cases these cenotes have precipitated seals of a second stage of travertine as CO₂ degassed, capping the sinkhole with a hydrologic barrier of travertine. Evidence of these barriers is observed in aqueous physical and geochemical characteristics of the cenotes, as some have high hydrologic gradients and contrasting geochemistry to those of neighboring cenotes. Investigations of electrical resistivity geophysics and underwater sonar mapping support the hypothesis of the barriers and define the morphology in intermediate and final phases of sinkhole sealing. Volcanogenic karstification is not limited to Sistema Zacatón, although the localized nature coupled with rapid and extreme degrees of karstification makes it an ideal modern analogue for classifying other karst systems as volcanogenic. / text

The northern Lau Basin contains the northeastern-most part of the Tonga arc-basin system. Volcanic rocks associated with the recent-arc have been sampled from Tafahi and Niuatoputapu, and young basalts «1.5Ma) have been dredged from Northern Lau Spreading Centre (NLSC), the northeastern limb of the King's Triple Junction. The 1982 'Kallisto' cruise dredged two ophiolite sections, one containing boninitic, and the other tholeiitic, lavas, from the inner wall of the northern Tonga trench. The magma genesis of these lava suites is related to the structural and geochemical controls imposed during the tectonic evolution of the region. The geochemical controls result from processes related to the mantle dynamics in the northern Lau Basin, and to along-trench variations and the degree of influence of the subduction component. The lavas associated with the Central Lau Spreading Centre are derived from the Lau Basin mantle reservoir, which has Indian MORB mantle (!MM) isotopic characteristics. This reservoir has been present under the region since early-arc magmatism, as indicated by the trace elements and !MM isotopic signatures of the tholeiitic lavas from the eastern ophiolite section, and Eocene lavas from 'Eua. A reservoir with the geochemical characteristics of residual Samoan plume mantle underlies the northern Lau Basin. This mantle has been influxing through the rip in the Pacific plate, at the northern termination of the Tonga trench, since the Lau Basin began to open « 6Ma), as a result of processes relating to subduction roll-back. The north Tongan boninites, the lavas from Tafahi and Niuatoputapu have residual plume mantle sources. However, prior to the opening of the Lau Basin, the proto-Tonga trench formed a barrier to this influx, and therefore, the influence of the plume cannot be detected in lavas associated with the early-arc, such as the tholeiites from one of the ophiolite sections and the Eocene lavas from 'Bua. The variations in the trace element and Pb isotopic compositions of the lavas from the Northern Lau Spreading Centre indicate that mixing has occurred between Lau Basin and residual plume mantle end-members in the central northern Lau Basin. The residual plume mantle sources of the north Tongan boninites and the lavas from Tafahi, Niuatoputapu and the Tofua arc have been enriched by a subduction component, the characteristics of which are enrichment in Lll..E, Ph ± LREE. In the south, the subduction component is made up of fluids derived from subducted Pacific altered oceanic crust and pelagic sediments. However, in the north, it is comprised predominantly of fluids derived from Pacific volcanogenic sediments, with a contribution from altered oceanic crust and possibly subducted plume crust.

Gossans, the brightly coloured oxidation products of sulphide mineralised rocks, have acted as an exploration target for base and precious metals and sulphur for thousands of years. They are easily identified from remote sensing and field-based reconnaissance, and once found may be drilled to determine the character of mineralisation below. The number of targets drilled could potentially be reduced if gossans overlying significant mineralisation can be discriminated from their field relations, mineralogy and geochemistry. Previous such studies have focussed on porphyry-type systems, with less attention on the generally much lower tonnage volcanogenic massive sulphide (VMS) deposits. However, VMS continue to provide an economically important source of metals in Europe and elsewhere. The Troodos Massif in Cyprus was chosen for this study as it hosts a currently active Cu mine along with historically worked VMS, is little deformed and has a relatively well understood geological framework. Of particular interest are secondary Cu deposits (SCUD) which form due to weathering of primary massive sulphides (PMS). These can be worked at relatively lower financial and environmental cost, and at much lower grades (down to around 0.1 % Cu). The only currently mined SCUD in Cyprus is the Phoenix ore body at Skouriotissa, which lies immediately adjacent to, and structurally below the Phoukasa PMS. The questions addressed in this study are: 1) Do Cypriot PMS that were mined for Cu show original Cu enrichments, or is their elevated Cu content a result of supergene enrichment to form an SCUD? This was addressed by comparing the mineralogical, chemical and S isotopic compositions of PMS mined for Cu with those mined for pyrite only from across the Troodos; 2) Do gossans formed from Cu-rich sulphides show distinctive mineralogical and chemical signatures? The characteristics of gossans known to overlie prospective sulphide bodies were compared with those from barren PMS; 3) What circumstances promote the formation of SCUDs? In particular, did sulphide oxidation occur on the sea floor or in a terrestrial environment? It was considered likely that SCUD formation may require sea floor oxidation because this will result in limited Cu dispersion, due to both sharp pH and redox gradients and limited fluid flow when compared with terrestrial weathering, where the depth to the water table can be considerable. The question was addressed by comparing the field relations, chemistry and S and O isotope compositions of gossans thought to have formed on the sea floor (Skouriotissa - Phoenix) with those generated in a terrestrial setting (Kokkinopezoula, Mathiati and Sia). The remnants of primary VMS deposits mined for Cu in Cyprus (Phoukasa, Sia and Troulli) almost exclusively contain primary Cu sulphides such as chalcopyrite. Secondary Cu sulphides, mainly chalcocite and covellite, are only present in significant concentrations at Phoukasa and Troulli, with Cu oxides being found in Phoenix. At Phoukasa, secondary Cu sulphides have a mean δ34S = 3.69±0.08 ‰ similar to primary pyrite and chalcopyrite (mean δ34S = 3.78±0.08 ‰) suggesting formation from Cu-rich fluids that scavenged S from primary sulphides. Sulphide material collected from copper mines has Cu = 840 to > 10,000 ppm at Phoukasa; 167 to 3573 ppm at Sia; 288 to > 10,000 ppm at Troulli, while the Cu-barren deposits have generally lower Cu grades (Cu = 170 to 433 ppm at Kokkinopezoula; 327 to 1303 ppm at Mathiati north). There are no systematic differences in the S isotope compositions of pyrite between deposits mined for Cu and those not (average δ34S = 1.68, 3.74 and 7.1 ‰ for Cu-rich Sia, Lysos and Phoukasa, and 5.03 and 3.70 ‰ for Cu-poor Kokkinopezoula and Mathiati North sulphides, respectively). No consistent chemical differences (including chalcophile elements) could be identified between gossans overlying Cu-rich as opposed to barren PMS. Gossans overlying the Lysos and Sia Cu-rich PMS, however, show an enrichment in Pb and Zn not observed in other gossans, and umbers, which are chemical sediments associated with VMS systems, often overlying gossans, show strong Cu enrichments in the vicinity of Cu-rich PMS. Umber samples from near the Cu-rich Phoukasa sulphide body contain > 10,000 to 35,400 ppm Cu, while those around Cu-poor Mathiati North contain 669 to 819 ppm Cu. There were no differences in the S isotope compositions of gypsum from sulphide bodies which were Cu-rich (δ34S = 5.9 to 6.9 ‰ for Sia, Phoukasa and Troulli) and Cu-poor (δ34S = 5.0 to 7.3 ‰ for Kokkinopezoula, Mathiati North). Regarding the environment of formation of SCUDs, an initial submarine oxidation of the Phoukasa VMS is considered likely as it is immediately overlain by marine pelagic sediments, while all other deposits studied are overlain by volcanics. In addition, volcanics in the vicinity of Phoukasa show large negative Ce anomalies (Ce/Ce* = 0.90 to 0.38, average = 0.71), consistent with sea floor alteration, compared with other localities such Kokkinopezoula (Ce/Ce* = 0.89 to 1.08, average = 0.97) and Sia (Ce/Ce* = 0.92 to 1.03, average = 0.99). Unfortunately, the S isotope composition of gypsum could not be used to determine the nature of the gossan-forming environment. Gypsums from all locations (average δ34S = 6.74±0.08 ‰) have δ34S values similar to, but slightly 34S enriched compared with their associated sulphides (average δ34S = 2.9±0.08 ‰) which indicates that their S isotope signature largely reflects that of S released during sulphide oxidation, as opposed to evaporation of sulphate-rich waters or direct precipitation from a similar solution (i.e., seawater). However, the oxygen isotope composition of gypsum (average δ18O = 6.2 ‰) from Sia (average δ18O = 2.4 ‰) reflects a mixture of atmospheric O (δ18O = 23.6 ‰) and Mediterranean meteoric water O (δ18O ≈-5.0 ‰), indicating a terrestrial environment of formation. Gypsum from Skouriotissa has an average δ18O = 6.6 ‰ which most likely indicates a combination of seawater and seawater-dissolved O (δ18O ≈23.5 ‰), despite some overlap with the composition of meteoric water and atmospheric O. In summary, it is proposed that the currently unique nature of Skouriotissa as hosting the only major SCUD in Cyprus is due largely to initial sea water alteration of the Phoukasa PMS resulting in limited Cu dispersion and localised Cu enrichment within the primary ore body. Subsequent uplift and alteration of the Phoukasa PMS led to the formation of a relatively high grade SCUD in the Phoenix deposit. The main outcomes of the study are a series of models for the development of gossans and associated lithologies in terrestrial and seafloor weathering environments in Cyprus. These incorporate a new term (retali) for acid leached volcanics in the footwall of PMS, and exploration-relevant field, mineralogical and chemical criteria for their discrimination from gossans, which overlie PMS. In agreement with an existing model, the formation of the Phoenix SCUD is interpreted as having been due to the downward migration of Cu-bearing acid fluids from the seafloor oxidation of the upper parts of the Phoukasa deposit. Secondary Cu mineralisation is thought to have taken place within the relatively reducing environment below the water table in lavas stratigraphically below the Phoukasa deposit. That the formation of SCUDs may require seafloor sulphide oxidation, and that this can be recognised in the mineralogy and chemical compositions of associated volcanics and gossans, provides new exploration criteria for SCUDs. However, it should be noted that the Phoenix deposit was the only SCUD examined in this study, and that this model should therefore be tested elsewhere.

The Glacier Creek volcanogenic massive sulfide (VMS) deposit is hosted within Late Triassic, oceanic back-arc or intra-arc, rift-related, bimodal volcanic rocks (Hyd or Tats Group) of the allochthonous Alexander terrane known as the Alexander Triassic Metallogenic Belt (ATMB). The deposit presently consists of four tabular massive sulfide lenses with a resource of 4.75 Mt. at 1.84% Cu, 4.57% Zn, 0.15% Pb, 0.28 g/t Au and 29.07 g/t Ag. A deposit-scale thrust fault offsets stratigraphy along the axial surface of a deposit-scale anticline. The massive sulfide lenses are barite-rich and are divided into 6 main ore-types based on mineral assemblages. There is a large range of sphalerite compositions, with low-Fe sphalerite dominant throughout the lenses and high-Fe sphalerite at the top and bottom of the lenses in pyrrhotite-rich zones. Lenses contain anomalous Sb, Hg and Tl. Gangue minerals include barite, quartz, barian-muscovite, calcite, albite, highly subordinate chlorite and locally hyalophane and celsian. Overlying massive sulfide is a tuffaceous hydrothermal sediment with anomalous REE patterns and local hyalophane. The general footwall to all four lenses is a thick unit of coherent to volcaniclastic feldspar-phyric basalt containing extensive lateral alteration. Four alteration facies are recognized based on mineral assemblages. Mass balance calculations for the footwall indicate general gains of S, Fe, Si and K with coincident loss of Ca, Na and Mg, along with trace element gains of Tl, Sb, Hg, Ba, Zn, Cu, As and loss of Sr with increased alteration intensity. Short wavelength infrared (SWIR) spectroscopy shows a general decrease in Na, K and Al content of muscovite and increase of Fe+Mg and Ba content towards ore. Integrated petrographic, mineral, chemical and sulfur-isotope data suggest a transition during deposit formation, from high-temperature, acidic, reduced hydrothermal fluids mixing with oxidized, SO4-rich seawater, to later cooler, low fO2-fS2 conditions of formation and a lack of SO4 in seawater.

The Glacier Creek volcanogenic massive sulfide (VMS) deposit is hosted within Late Triassic, oceanic back-arc or intra-arc, rift-related, bimodal volcanic rocks (Hyd or Tats Group) of the allochthonous Alexander terrane known as the Alexander Triassic Metallogenic Belt (ATMB). The deposit presently consists of four tabular massive sulfide lenses with a resource of 4.75 Mt. at 1.84% Cu, 4.57% Zn, 0.15% Pb, 0.28 g/t Au and 29.07 g/t Ag. A deposit-scale thrust fault offsets stratigraphy along the axial surface of a deposit-scale anticline. The massive sulfide lenses are barite-rich and are divided into 6 main ore-types based on mineral assemblages. There is a large range of sphalerite compositions, with low-Fe sphalerite dominant throughout the lenses and high-Fe sphalerite at the top and bottom of the lenses in pyrrhotite-rich zones. Lenses contain anomalous Sb, Hg and Tl. Gangue minerals include barite, quartz, barian-muscovite, calcite, albite, highly subordinate chlorite and locally hyalophane and celsian. Overlying massive sulfide is a tuffaceous hydrothermal sediment with anomalous REE patterns and local hyalophane. The general footwall to all four lenses is a thick unit of coherent to volcaniclastic feldspar-phyric basalt containing extensive lateral alteration. Four alteration facies are recognized based on mineral assemblages. Mass balance calculations for the footwall indicate general gains of S, Fe, Si and K with coincident loss of Ca, Na and Mg, along with trace element gains of Tl, Sb, Hg, Ba, Zn, Cu, As and loss of Sr with increased alteration intensity. Short wavelength infrared (SWIR) spectroscopy shows a general decrease in Na, K and Al content of muscovite and increase of Fe+Mg and Ba content towards ore. Integrated petrographic, mineral, chemical and sulfur-isotope data suggest a transition during deposit formation, from high-temperature, acidic, reduced hydrothermal fluids mixing with oxidized, SO4-rich seawater, to later cooler, low fO2-fS2 conditions of formation and a lack of SO4 in seawater.

The giant Kidd Creek Mine is an Archean Cu-Zn-Ag deposit in the Abitibi Greenstone belt, located in the Superior Province of Canada and is one of the largest known base metal massive sulfide mines in the world with a tonnage of 170.7 Mt (Past production, Resource and Reserve). The massive sulfides in Mine D comprise a number of ore lenses that are interpreted to be the downplunge continuation of the Central orebody from the upper mine. These are referred to as the West, Main, and South lenses. The massive sulfides overlie a silicified rhyolitic unit at the top of a mixed assemblage of rhyolite flows, volcaniclastic sediments and ultramafic flows. The sheared nature of the fragmental units in the hanging wall of the deposit, at depth, illustrates the greater deformation that has occurred than in the upper mine. Metal zonation and the distribution of Cu stringer mineralization suggest that the West and Main lenses may be part of a single massive sulfide body (Main orebody) that has been structurally dismembered. The South Lens is a detached body, separated by late faults. The large Cu stringer zone beneath the West and Main lenses has a thickness of up to 150 metres, and is much broader and structurally remobilized in Mine D partially due to a newly identified series of vertically trending offset faults, that extends along the entire length of the massive sulfide bodies. A number of features of the North, Central and South orebodies in the upper part of the mine (e.g., Se-rich halo around Cu-rich zones) have been recognized in Mine D and provide an important framework for correlating the deep orebodies with the upper levels of the mine. Drilling below the current mine levels indicates that the massive sulfide and Cu stringer zones continue below 10,200 feet (3109 m) and highlight the remarkable continuity of the deposit downplunge with no end in sight. Two main ore suites have been recognized in the upper part of the mine and in Mine D: a low-temperature, polymetallic assemblage of Zn, Ag, Pb, Cd, Sn, Sb, As, Hg, ±Tl, ±W, and a higher-temperature suite of Cu, Co, As, Bi, Se, In, ±Ni. More than 25 different ore minerals and ore-related gangue minerals are present, including Co-As-sulfides, Cu-Sn-sulfides, Ag-minerals, and selenides. The massive ores consist mainly of pyrite, pyrrhotite, sphalerite, magnetite and chalcopyrite, together with minor galena, tetrahedrite, arsenopyrite, and native silver with a quartz and siderite gangue. Despite the high Ag content of the ores, the majority of the massive sulfides are remarkably Au poor except for a local gold zone that has been recognized in the deep mine in association with high-temperature mineralization. The trace elements in the ores exhibit strong zonation and diverse mineralogy. Spectacular albite porphyroblasts, up to 1 cm in size occur in the most Cu-rich ores of Mine D which are coincident with the peak of regional metamorphism and likely represent higher metamorphic or hydrothermal temperatures. Overall the orebodies have remained remarkably similar downplunge. However, unlike the upper part of the mine, pyrrhotite is dominantly hexagonal, only tetrahedrite was observed as the dominant sulfosalt, and magnetite occurs as both blebby porphyroblasts and as abundant intergrowths with sphalerite-chalcopyrite ores and siderite. These characteristics suggest that the deep mine has been subjected to higher metamorphic temperatures, possibly related to depth of burial, and that the original hydrothermal fluids may of had a lower H2S/CO2 and/or higher temperatures.

The Rävliden North deposit (Rävliden N) is a volcanogenic massive sulphide (VMS) deposit in the western part of the Skellefte district, northern Sweden. The district is one of Sweden’s major metallogenic provinces with a significant amount of VMS deposits. The Rävliden N deposit, discovered in 2011, contains copper, zinc, lead, silver and subordinate gold and occurs close to the largest VMS deposit in the district, the Kristineberg deposit, which has been mined for more than 70 years. The purpose of this master thesis is to study the composition, mineralogy and paragenetic relationships in different types of sulphide mineralization from the Rävliden N deposit. Emphasis is placed on characterizing the distribution and paragenetic relationships of silver-bearing minerals. The methods include core logging, sampling and mineralogical studies through light optical microscopy (LOM), scanning electron microscopy (SEM) and quantitative evaluation of mineralogy by scanning electron microscopy (QEMSCAN). Lastly, electron microprobe analysis (EMPA) was used to determine the chemical composition of silver-bearing minerals and sulphides. Mineralization types studied include 1: the main massive to semi-massive sulphide mineralization, 2: stratigraphically underlying stringer mineralization and 3: local, vein- and/or fault-hosted silver-rich mineralization in the stratigraphic hanging wall. The massive to semi-massive sulphide mineralization is dominated by sphalerite with lesser galena and pyrrhotite. In contrast, the stringer mineralization is dominated by chalcopyrite and pyrrhotite. The major minerals show evidence of a coeval formation and textural as well as structural evidence suggest that ductile deformation has affected the mineralization types. Notable evidence includes ball-ore textures, accumulation of minerals in pressure shadows and brittle fracturing of competent arsenopyrite and pyrite porphyroblasts and infilling by more incompetent sulphide minerals. The silver-bearing minerals identified are commonly spatially associated with galena and the major species is freibergite ((Ag,Cu,Fe)12(Sb,As)4S13), which also occur as inclusions in chalcopyrite mainly in the stringer mineralization. The stringer mineralization also contains notable amounts of hessite (Ag2Te). Notably, galena, pyrrhotite, freibergite and other sulphosalt minerals are commonly accumulated in pressure shadows near host rock fragments in the massive to semi-massive sulphide mineralization. The only gold-bearing mineral identified in this study is electrum (Au, Ag) in the stringer mineralization. The hanging wall mineralization locally comprises faulted and/or sheared massive sulphide mineralization which is compositionally similar to the main massive to semi-massive sulphide mineralization, besides a significantly higher content of freibergite. However, parts of the hanging wall mineralization are entirely dominated by sulphides and sulphosalts of silver, such as pyrargyrite (Ag3SbS3), pyrostilpnite (Ag3SbS3), argentopyrite (AgFe2S4), sternbergite (AgFe2S3) and stephanite (Ag5SbS4). These occur in structurally late settings, which along with consideration of their temperature stabilities suggest a late origin. Since the silver-bearing minerals in the massive to semi-massive sulphide mineralization and the two varieties of hanging wall mineralization contains the same metals, the mineralization in the hanging wall may have formed by late-stage remobilization of ore components from the underlying Rävliden N deposit. This negates the need for multiple mineralization events to explain the local silver-enriched zones in the hanging wall. The paragenetically late mineralization types contains high content of Ag-bearing minerals in relation to base metal sulphides. This suggests that remobilisation processes were important for locally upgrading the Ag-content.

The Glacier Creek volcanogenic massive sulfide (VMS) deposit is hosted within Late Triassic, oceanic back-arc or intra-arc, rift-related, bimodal volcanic rocks (Hyd or Tats Group) of the allochthonous Alexander terrane known as the Alexander Triassic Metallogenic Belt (ATMB). The deposit presently consists of four tabular massive sulfide lenses with a resource of 4.75 Mt. at 1.84% Cu, 4.57% Zn, 0.15% Pb, 0.28 g/t Au and 29.07 g/t Ag. A deposit-scale thrust fault offsets stratigraphy along the axial surface of a deposit-scale anticline. The massive sulfide lenses are barite-rich and are divided into 6 main ore-types based on mineral assemblages. There is a large range of sphalerite compositions, with low-Fe sphalerite dominant throughout the lenses and high-Fe sphalerite at the top and bottom of the lenses in pyrrhotite-rich zones. Lenses contain anomalous Sb, Hg and Tl. Gangue minerals include barite, quartz, barian-muscovite, calcite, albite, highly subordinate chlorite and locally hyalophane and celsian. Overlying massive sulfide is a tuffaceous hydrothermal sediment with anomalous REE patterns and local hyalophane. The general footwall to all four lenses is a thick unit of coherent to volcaniclastic feldspar-phyric basalt containing extensive lateral alteration. Four alteration facies are recognized based on mineral assemblages. Mass balance calculations for the footwall indicate general gains of S, Fe, Si and K with coincident loss of Ca, Na and Mg, along with trace element gains of Tl, Sb, Hg, Ba, Zn, Cu, As and loss of Sr with increased alteration intensity. Short wavelength infrared (SWIR) spectroscopy shows a general decrease in Na, K and Al content of muscovite and increase of Fe+Mg and Ba content towards ore. Integrated petrographic, mineral, chemical and sulfur-isotope data suggest a transition during deposit formation, from high-temperature, acidic, reduced hydrothermal fluids mixing with oxidized, SO4-rich seawater, to later cooler, low fO2-fS2 conditions of formation and a lack of SO4 in seawater.

The giant Kidd Creek Mine is an Archean Cu-Zn-Ag deposit in the Abitibi Greenstone belt, located in the Superior Province of Canada and is one of the largest known base metal massive sulfide mines in the world with a tonnage of 170.7 Mt (Past production, Resource and Reserve). The massive sulfides in Mine D comprise a number of ore lenses that are interpreted to be the downplunge continuation of the Central orebody from the upper mine. These are referred to as the West, Main, and South lenses. The massive sulfides overlie a silicified rhyolitic unit at the top of a mixed assemblage of rhyolite flows, volcaniclastic sediments and ultramafic flows. The sheared nature of the fragmental units in the hanging wall of the deposit, at depth, illustrates the greater deformation that has occurred than in the upper mine. Metal zonation and the distribution of Cu stringer mineralization suggest that the West and Main lenses may be part of a single massive sulfide body (Main orebody) that has been structurally dismembered. The South Lens is a detached body, separated by late faults. The large Cu stringer zone beneath the West and Main lenses has a thickness of up to 150 metres, and is much broader and structurally remobilized in Mine D partially due to a newly identified series of vertically trending offset faults, that extends along the entire length of the massive sulfide bodies. A number of features of the North, Central and South orebodies in the upper part of the mine (e.g., Se-rich halo around Cu-rich zones) have been recognized in Mine D and provide an important framework for correlating the deep orebodies with the upper levels of the mine. Drilling below the current mine levels indicates that the massive sulfide and Cu stringer zones continue below 10,200 feet (3109 m) and highlight the remarkable continuity of the deposit downplunge with no end in sight. Two main ore suites have been recognized in the upper part of the mine and in Mine D: a low-temperature, polymetallic assemblage of Zn, Ag, Pb, Cd, Sn, Sb, As, Hg, ±Tl, ±W, and a higher-temperature suite of Cu, Co, As, Bi, Se, In, ±Ni. More than 25 different ore minerals and ore-related gangue minerals are present, including Co-As-sulfides, Cu-Sn-sulfides, Ag-minerals, and selenides. The massive ores consist mainly of pyrite, pyrrhotite, sphalerite, magnetite and chalcopyrite, together with minor galena, tetrahedrite, arsenopyrite, and native silver with a quartz and siderite gangue. Despite the high Ag content of the ores, the majority of the massive sulfides are remarkably Au poor except for a local gold zone that has been recognized in the deep mine in association with high-temperature mineralization. The trace elements in the ores exhibit strong zonation and diverse mineralogy. Spectacular albite porphyroblasts, up to 1 cm in size occur in the most Cu-rich ores of Mine D which are coincident with the peak of regional metamorphism and likely represent higher metamorphic or hydrothermal temperatures. Overall the orebodies have remained remarkably similar downplunge. However, unlike the upper part of the mine, pyrrhotite is dominantly hexagonal, only tetrahedrite was observed as the dominant sulfosalt, and magnetite occurs as both blebby porphyroblasts and as abundant intergrowths with sphalerite-chalcopyrite ores and siderite. These characteristics suggest that the deep mine has been subjected to higher metamorphic temperatures, possibly related to depth of burial, and that the original hydrothermal fluids may of had a lower H2S/CO2 and/or higher temperatures.

Greenstone belts are dominated by volcanic rocks with lithogeochemical characteristics that reflect a range of possible geodynamic settings. Many analogies with modern tectonic settings have been suggested. Increasing exploration and comprehensive sampling of volcanic rocks in modern oceans provides the unique opportunity to characterize different melt sources from intraoceanic settings. This thesis examines geochemical data from more than 2850 submarine mafic and more than 2200 submarine felsic volcanic rocks, representing a wide range of settings. The results show significant geochemical variability spanning the full range of compositions of volcanic rocks found in ancient greenstone belts. This diversity reflects complex rift and spreading regimes, variations in crustal thickness, dry melting versus wet melting, mantle mixing and crustal contamination. Highly variable melting conditions are thought to be related to mantle heterogeneities, complex mantle flow regimes and short-lived tectonic domains, such as those caused by diffuse spreading, multiple overlapping spreading centers and microplate breakouts. Systematic differences in the volcanic rocks are revealed by a combination of principal components analysis and unsupervised hierarchical clustering. Rocks from most arc-backarc systems have strongly depleted mantle signatures and well-known subduction-related chemistry. This contrasts with rocks in Archean greenstone belts, which show no, or at least weaker, subduction-related chemistry and stronger mantle enrichment resulting from a less-depleted mantle, less wet-melting, and variable crustal contamination. The geochemistry of the modern volcanic rocks reflects lower mantle temperatures, thinner crust and subduction-related processes of present-day settings. However, rocks that are geochemically identical to those in Archean greenstone belts occur in many modern back-arc basins, such as the Lau Basin. Crustal growth and area-age relationships in the Lau Basin are similar to observed ages and compositions of volcanic assemblages in greenstone belts, such as the Blake River Group of the Abitibi Greenstone Belt. Such settings are recognized as favorable locations for volcanogenic massive sulfide (VMS) deposits, and therefore the particular geochemical signatures of the volcanic rocks are important for enhanced area selection in base and precious metal exploration.