[1] We present a comprehensive major and trace element dataset establishing ODP Site 801 as a geochemical reference for altered oceanic crust. The composition of old crustal sequences like those at Sites 801 and 1149 are critical to developing models of crustal aging and seawater chemistry evolution and to understanding the fate of crust consumed at subduction zones. Our estimate of the bulk composition of oceanic crust at Site 801 comprises ICP-AES and ICP-MS analyses of 117 discrete samples, 14 mixed composites and 5 glasses from the upper 500 m of Jurassic Pacific crust. Comparing the 801 “super-composite” with glass reveals enrichment of U (5x), Li (2x), K2O (4x), Rb (9x), and Cs (7x), similar to DSDP Sites 417/418, but little to no enrichment in Ba or Pb. The data also demonstrate good (∼10%) agreement between U measured on discrete samples and natural gamma logs, suggesting logging data is a reliable means of establishing bulk geochemical characteristics of oceanic crust. Data reported here serve to link other geochemical and mineralogical measurements on Site 801 and 1149 samples. We also document Boston University sample preparation procedures and instrument parameters for ICP-MS and ICP-AES analyses, and provide comparisons with other laboratories and techniques. We present new techniques for basaltic glass analyses using the Boston University 213 nm Nd-YAG LA-ICP-MS system, and show the data agree well with both solution-ICP-MS (5–10%) and ion probe measurements (∼10%).

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2002GC000435

Composition of altered oceanic crust at ODP Sites 801 and 1149

The discovery of metal-depositing hot springs on the sea floor, and especially their link to chemosynthetic life, was among the most compelling and significant scientific advances of the twentieth century. More than 300 sites of hydrothermal activity and sea-floor mineralization are known on the ocean floor. About 100 of these are sites of high-temperature venting and polymetallic sulfide deposits. They occur at mid-ocean ridges (65%), in back-arc basins (22%), and on submarine volcanic arcs (12%). Although high-temperature, 350°C, black smoker vents are the most recognizable features of sea-floor hydrothermal activity, a wide range of different styles of mineralization has been found. Different volcanic substrates, including mid-ocean ridge basalt, ultramafic intrusive rocks, and more evolved volcanic suites in both oceanic and continental crust, as well as temperature-dependent solubility controls, account for the main geochemical associations found in the deposits. Although end-member hydrothermal fluids mainly originate in the deep volcanic basement, the presence of sediments and other substrates can have a large effect on the compositions of the vent fluids. In arc and backarc settings, vent fluid compositions are broadly similar to those at mid-ocean ridges, but the arc magmas also supply a number of components to the hydrothermal fluids.
The majority of known black smoker vents occur on fast-spreading mid-ocean ridges, but the largest massive sulfide deposits are located at intermediate- and slow-spreading centers, at ridge-axis volcanoes, in deep backarc basins, and in sedimented rifts adjacent to continental margins. The range of deposit sizes in these settings is similar to that of ancient volcanic-associated massive sulfide (VMS) deposits. Detailed mapping, and in some cases drilling, indicates that a number of deposits contain 1 to 5 million tons (Mt) of massive sulfide (e.g., TAG hydrothermal field on the Mid-Atlantic Ridge, deposits of the Galapagos Rift, and at 13°N on the East Pacific Rise). Two sediment-hosted deposits, at Middle Valley on the Juan de Fuca Ridge and in the Atlantis II Deep of the Red Sea, are much larger (up to 15 and 90 Mt, respectively).
In the western Pacific, high-temperature hydrothermal systems occur mainly at intraoceanic back-arc spreading centers (e.g., Lau basin, North Fiji basin, Mariana trough) and in arc-related rifts at continental margins (e.g., Okinawa trough). In contrast to the mid-ocean ridges, convergent margin settings are characterized by a range of different crustal thicknesses and compositions, variable heat flow regimes, and diverse magma types. These variations result in major differences in the compositions and isotopic systematics of the hydrothermal fluids and the mineralogy and bulk compositions of the associated mineral deposits. Intraoceanic back-arc basin spreading centers host black smoker vents that, for the most part, are very similar to those on the mid-ocean ridges. However, isotopic data from both the volcanic rocks and the sulfide deposits highlight the importance of subduction recycling in the origin of the magmas and hydrothermal fluids. Back-arc rifts in continental margin settings are typically sediment-filled basins, which derive their sediment load from the adjacent continental shelf. This has an insulating effect that enhances the high heat flow associated with rifting of the continental crust and also helps to preserve the contained sulfide deposits. Large hydrothermal systems have developed where initial rifting of continental crust or locally thickened arc crust has formed large calderalike sea-floor depressions, similar to those that contained major VMS-forming systems in the geologic record. Hydrothermal vents also occur in the summit calderas of submarine volcanoes at the volcanic fronts of arcs. However, this contrasts with the interpreted settings of most ancient VMS deposits, which are considered to have formed mainly during arc rifting. Hydrothermal vents associated with arc volcanoes show clear evidence of the direct input of magmatic volatiles, similar to magmatic-hydrothermal systems in subaerial volcanic arcs. Several compelling examples of submarine epithermal-style mineralization, including gold-base metal veins, have been found on submarine arc volcanoes,and this type of mineralization may be more common than is presently recognized. 
Mapping and sampling of the sea floor has dramatically improved geodynamic models of different submarine volcanic and tectonic settings and has helped to establish a framework for the characterization of many similar ancient terranes. Deposits forming at convergent margins are considered to be the closest analogs of ancient VMS. However, black smokers on the mid-ocean ridges continue to provide critically important information about metal transport and deposition in sea-floor hydrothermal systems of all types. Ongoing sea-floor exploration in other settings is providing clues to the diversity of mineral deposit types that occur in different environments and the conditions that are favorable for their formation.

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Sea-Floor Tectonics and Submarine Hydrothermal Systems

Evaporites through time: Tectonic, climatic and eustatic controls in marine and nonmarine deposits

The Iberian Pyrite Belt, located in the SW Iberian Peninsula, contains many Paleozoic giant and supergiant massive sulphide deposits, including the largest individual massive sulphide bodies on Earth. Total ore reserves exceed 1500 Mt, distributed in eight supergiant deposits (>100 Mt) and a number of other smaller deposits, commonly with associated stockwork mineralizations and footwall alteration haloes. Massive sulphide bodies largely consist of pyrite, with subordi- nated sphalerite, galena and chalcopyrite and many other minor phases, although substantial diAerences occur between individual deposits, both in mineral abundance and spatial distribution. These deposits are considered to be volcanogenic, roughly similar to vol- canic-hosted massive sulphides (VHMS). However, our major conclusion is that the Iberian type of massive sulphides must be considered as a VHMS sub-type transitional to SHMS. This work is an assessment of the geological, geo- chemical and metallogenic data available up to date, including a number of new results. The following points are stressed; (a) ore deposits are located in three main geological sectors, with the southern one containing most of the giant and supergiant orebodies, whereas the northern one has mainly small to intermediate-sized de- posits; (b) ore deposits diAer one from another both in textures and mineral composition; (c) Co and Bi minerals are typical, especially in stockwork zones; (d) colloidal and other primary depositional textures are common in many localities; (e) a close relation has been found be- tween ore deposits and some characteristic sedimentary horizons, such as black shales. In contrast, relationships between massive sulphides and cherts or jaspers remains unclear; (f) footwall hydrothermal alterations show a rough zoning, the inner alteration haloes being charac- terized in places by a high Co/Ni ratio, as well as by mobility of Zr, Y and REE; (g) 18 O and D values indicate that fluids consist of modified seawater, whereas 34 S data strongly suggest the participation of bacterial-reduced sulphur, at least during some stages of the massive sul- phide genesis, and (h) lead isotopes suggest a single (or homogeneized) metal source, from both the volcanic piles and the underlying Devonian rocks (PQ Group). It is concluded that, although all these features can be compatible with classical VHMS interpretations, it is necessary to sketch a diAerent model to account for the IPB characteristics. A new proposal is presented, based on an alternative association between massive sulphide deposits and volcanism. We consider that most of the IPB massive orebodies, in particular the giant and su- pergiant ones, were formed during pauses in volcanic activity, when hydrothermal activity was triggered by the ascent and emplacement of late basic magmas. In these conditions, deposits formed which had magmatic activity as the heat source; however, the depositional environ- ment was not strictly volcanogenic, and many evolu- tionary stages could have occurred in conditions similar to those in sediment-hosted massive sulphides (SHMS). In addition, the greater thickness of the rock pile aAected by hydrothermal circulation would account for the enormous size of many of the deposits.

The Iberian type of volcano-sedimentary massive sulphide deposits

Although the processes that govern iron isotope variations in nature are just beginning to be understood, multiple studies attest of the virtue of this system to solve important problems in geosciences and biology. In this article, we review recent advances in the geochemistry, cosmochemistry, and biochemistry of iron isotopes. In Section 2, we briefly address the question of the nucleosynthesis of Fe isotopes. In Section 3, we describe the different methods for purifying Fe and analyzing its isotopic composition. The methods of SIMS, RIMS, and TIMS are presented but more weight is given to measurements by MC-ICPMS. In Section 4, the isotope anomalies measured in extraterrestrial material are briefly discussed. In Section 5, we show how high temperature processes like evaporation, condensation, diffusion, reduction, and phase partitioning can affect Fe isotopic composition. In Section 6, the various low temperature processes causing Fe isotopic fractionation are presented. These involve aqueous and biologic systems.

/pdf/mass-spectrometry-and-natural-variations-of-iron-isotopes-3uzav4v78h.pdf

Mass spectrometry and natural variations of iron isotopes

THE hydrothermal circulation of sea water through permeable ocean crust results in rock–water interactions that lead to the formation of massive sulphide deposits. These are the modern analogues of many ancient ophiolite-hosted deposits1–4, such as those exposed in Cyprus. Here we report results obtained from drilling a series of holes into an actively forming sulphide deposit on the Mid-Atlantic Ridge. A complex assemblage of sulphide–anhydrite–silica breccias provides striking evidence that such hydrothermal mounds do not grow simply by the accumulation of sulphides on the sea floor. Indeed, the deposit grows largely as an in situ breccia pile, as successive episodes of hydrothermal activity each form new hydrothermal precipitates and cement earlier deposits. During inactive periods, the collapse of sulphide chimneys, dissolution of anhydrite, and disruption by faulting cause brecciation of the deposit. The abundance of anhydrite beneath the present region of focused hydrothermal venting reflects the high temperatures ( > 150 °C) currently maintained within the mound, and implies substantial entrainment of cold sea water into the interior of the deposit. These observations demonstrate the important role of anhydrite in the growth of massive sulphide deposits, despite its absence in those preserved on land.

/pdf/the-internal-structure-of-an-active-sea-floor-massive-1mmkb3qg5n.pdf

The internal structure of an active sea-floor massive sulphide deposit

Mineralogical, textural, chemical, and isotopic features of a vertical section through the active Trans-Atlantic Geotraverse (TAG) hydrothermal mound reveal the nature of subsurface mineralization. The multistage growth and evolution of the TAG mound occurs by the following processes: (1) near-surface ( 20 m depth) by sequential overgrowth, recrystallization and mineral dissolution; (3) hydrothermal mineralization within the mound, forming Fe-Cu sulfides, anhydrite and quartz; and (4) alteration and mineralization of basalt basement beneath the mound. During the long history of hydrothermal activity, these processes have driven the TAG mound toward a mineralogy dominated by pyrite and depleted in Cu, Zn, and trace elements. The basement beneath the mound is ultimately altered to pyrite-quartz. Sulfur-isotope composition of sulfides in the range +4.4‰ to +8.9‰ requires a deep hydrothermal source with elevated δ 34 S to generate an end-member fluid with estimated δ 34 S of +5.5‰. Vein-related sulfide mineralization is isotopically light, whereas sulfide disseminated in altered basalt is isotopically heavy. The systematic variations between sulfide generations and a general increase with depth are a result of sulfate reduction in a shallow seawater-hydrothermal circulation system developed around the hydrothermal feeder zone. This generates hydrothermal fluid and sulfide mineralization with a maximum δ 34 S of +8.9‰. Mixing between this shallow circulated fluid and the end-member hydrothermal component would explain the variations of up to 3‰ observed between different sulfide generations in the mound.

/pdf/petrology-of-hydrothermal-mineralization-a-vertical-section-1hjovgvzkj.pdf

J. Honnorez

Papers

The internal structure of an active sea-floor massive sulphide deposit

Petrology of hydrothermal mineralization: a vertical section through the TAG mound

Proceedings of the Ocean Drilling Program, 185 Initial Reports