He, Ne and Ar isotope compositions of fluid inclusions in hydrothermal sulfides from the TAG hydrothermal field, Mid-Atlantic Ridge

Helium, rieon and argon isotope compositions of fluid inclusions have been measured in hydrothermal sulfide samples from the TAG hydrothermal field at the Mid-Atlantic Ridge. Fluid-inclusion He-3/He-4 ratios are 2.2-13.3 times the air value (Ra), and with a mean of 7.2 Ra. Comparison with the local vent fluids (He-3/He-4=7.5-8.2 Ra) and mid-ocean ridge basalt values (He-3/He-4=6-11 Ra) shows that the variation range of He-3/He-4 ratios from sulfide-hosted fluid inclusions is significantly large. Values for Ne-20/Ne-22 are from 10.2 to 11.4, which are significantly higher than the atmospheric ratio (9.8). And fluid-inclusion Ar-40/Ar-36 ratios range from 287 to 359, which are close to the atmospheric values (295.5). These results indicate that the noble gases of fluid inclusions in hydrothermal sulfides are a mixture of mantle- and seawater-derived noble gases; the partial mantle-derived components of trapped hydrothermal fluids may be from the lower mantle; the helium of fluid inclusions is mainly from upper mantle; and the Ne and Ar components are mainly from seawater.

Coupled Ge/Si and Ge isotope ratios as geochemical tracers of seafloor hydrothermal systems: Case studies at Loihi Seamount and East Pacific Rise 9°50’N

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behaviour in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18°54’N, 155°15’W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9°50’N. Loihi offers the opportunity to understand contrasting Ge and Si behaviour in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and δ74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (Δ74/70Ge fluid-basalt up to 1.15 ‰ at EPR 9°50’N and 1.64 ‰ at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater-rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of -2.0 ± 0.6 ‰ (2sd), and a maximum value of -3.6 ± 0.6 ‰ (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9°50’N also demonstrates that Ge isotopes are fractionated by approximately -5.6 ± 0.6 ‰ (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the “missing Ge sink”, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and δ74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.

Element enrichment and U-series isotopic characteristics of the hydrothermal sulfides at Jade site in the Okinawa Trough

The geochemical and U-series isotopic characteristics of hydrothermal sulfide samples from the Jade site (127A degrees 04.5'E, 27A degrees 15'N, water depth 1300-1450 m) at Jade site in the Okinawa Trough were analyzed. In the hydrothermal sulfide samples bearing sulfate (samples HOK1 and HOK2), the LREEs are relatively enriched. All the hydrothermal sulfide samples except HOK1 belong to Zn-rich hydrothermal sulfide. In comparison with Zn-rich hydrothermal sulfides from other fields, the contents of Zn, Pb, Ag, Cd, Au and Hg are higher, the contents of Fe, Al, Cr, Co, Ni, Sr, Te, Cs, Ti and U lower, and the Pb-210 radioactivity ratios and Pb-210/Pb ratios very low. In the hydrothermal sulfide mainly composed of sphalerite, the correlations between rare elements Hf and U, and Hf and Mn as well as that between dispersive elements Ga and Zn, are strongly positive; also the contents of Au and Ag are related to Fe-sulfide, because the low temperature promotes enrichment of Au and Ag. Meanwhile, the positive correlations between Fe and Bi and between Zn and Cd are not affected by the change of mineral assemblage. Based on the Pb-210/Pb ratios of hydrothermal sulfide samples (3.99x10(-5)-5.42x10(-5)), their U isotopic composition (U-238 content 1.15-2.53 ppm, U-238 activity 1.07-1.87 dpm/g, U-234 activity 1.15-2.09 dpm/g and U-234/U-238 ratio 1.07-1.14) and their Th-232 and Th-230 contents are at base level, and the chronological age of hydrothermal sulfide at Jade site in the Okinawa Trough is between 200 and 2000 yr.

Hydrocarbons in hydrothermal sulfides from the Rainbow Hydrothermal Field

The Rainbow Hydrothermal Field (36°N, Mid-Atlantic Ridge) is one of three presently known fields related to serpentinization of ultramafic rocks accompanied by formation of hydrogen- and methane rich solutions. Gas chromatographic and molecular gas chromatographic - mass spectrometric investigations of sulfide ores and sediments from this field confirmed predominantly biological nature of bitumoids related to high-temperature transformation of biomass of the hydrothermal biological community. At the same time ores of the Rainbow field contain significant amounts of compounds that are not directly related to biogenic synthesis. This fact suggests possibility of abiogenic synthesis of methane and even complex hydrocarbons during serpentinization of ultramafic rocks.

Seafloor hydrothermal activity in sediment core MV0502-15JC

A large diameter piston core containing 8.35 m of metalliferous sediment has been recovered from a small abyssal valley in the remote Southwest Pacific Basin (31°42.194'S, 143°30.331'W; 5082 m water depth), providing unique insight into hydrothermal activity and eolian sedimentation there since the early Oligocene. A combination of fish-teeth Sr-isotope stratigraphy and INAA geochemical data reveals an exponentially decreasing hydrothermal flux 31 Ma to the present. Although hydrothermal sedimentation related to seafloor spreading explains this trend, a complex history of late Eocene/early Oligocene ridge jumps, propagating rifts and plate tectonic reorganization of South Pacific seafloor could have also played a role. A possible hiatus in deposition, as recorded by changes in core composition just below 2 m depth, is beyond the resolution of the fish teeth Sr isotope dating method employed here; however, the timing of this interval may be coincident with extinction of the Pacific-Farallon Ridge at ~20 Ma. A low flux eolian component accumulating at this site shows an increase relative to the hydrothermal component above 2 m depth, consistent with dust-generating continental sources far to the west (Australia/New Zealand). This is the first long-term paleoceanographic record obtained from within the South Pacific "bare zone" (Rea et al., 2006), an anomalous region where Pacific seafloor has largely escaped sediment accumulation since the Late Cretaceous.

Geochemistry and mineralogy of a silica chimney from an inactive seafloor hydrothermal field (East Pacific Rise, 18°S)

An inactive vent field comprised of dead chimneys was discovered on the ultrafast East Pacific Rise (EPR) at 18°S during the research campaign NAUDUR with the R/V Le Nadir in December 1993. One of these chimneys was sampled, studied and found to be largely composed of silica-mineralized bacterial-like filaments. The filaments are inferred to be the result of microbial activity leading to silica (± Fe-oxyhydroxide) precipitation. The chimney grew from the most external layer (precipitated 226 ± 4 yr. B.P.) towards the central chimney conduit. Hydrothermal activity ceased 154 ± 13 yr. B.P. and the chimney conduit was completely sealed. Mixing between an end-member hydrothermal fluid and seawater explains the Sr–Nd isotopic composition of the chimney. Seawater was the major source of Sr to the chimney, whereas the dominant Nd source was the local mid-ocean ridge basalt (MORB) leached by the hydrothermal fluids. The mixing scenarios point to a dynamic hydrothermal system with fluctuating fluid compositions. The proportion of seawater within the venting fluid responsible for the precipitation of the silica chimney layers varied between 94 and 85%. Pb-isotope data indicates that all of the Pb in the chimney was derived from the underlying MORB. The precipitation temperatures of the chimney layers varied between 55 and 71 °C, and were a function of the seawater/end-member hydrothermal fluid mixing ratio. δ30Si correlates with the temperature of precipitation implying that temperature is one of the major controls of the Si-isotope composition of the chimney. Concentrations of elements across the chimney wall were a function of this mixing ratio and the composition of the end-member hydrothermal fluid. The inward growth of the chimney wall and accompanying decrease in wall permeability resulted in an inward decrease in the seawater/hydrothermal fluid mixing ratio, which in turn exerted a control on the concentrations of the elements supplied mainly by the hydrothermal fluids. The silica chimney is significantly enriched in U, likely a result of bacterial concentration of U from the seawater-dominated vent fluid. The chimney is poor in rare earth elements (REE). It inherited its REE distribution patterns from the parent end-member hydrothermal fluids. The dilution of the hydrothermal fluid with over 85% seawater could not obliterate the particular REE features (positive Eu anomaly) of the hydrothermal fluids.

Helium, neon and argon isotope compositions of fluid inclusions in massive sulfides from the Jade hydrothermal field, the Oldnawa Trough

Helium, neon and argon isotope compositions of fluid inclusions have been measured in massive sulfide samples from the Jade hydrothermal field in the central Okinawa Trough. Fluid-inclusion He-3/He-4 ratios are between 6.2 and 10.1 times the air value (Ra), and with a mean of 7.8Ra, which are consistent with the mid-ocean ridge basalt values [He-3/He-4 approximate to (6Rasimilar to 11Ra)]. Values for Ne-20/Ne-22 are from 10.7 to 11.3, which are significantly higher than the atmospheric ratio (9.8). And the fluid-inclusion Ar-40/Ar-36 ratios range from 287 to 334, which are close to the atmosperic values (295.5). These results indicate that the noble gases of trapped hydrothermal fluids in massive sulfides are a mixture of mantle- and seawater-derived components, and the helium of fluid inclusions is mainly from mantle, the nelium and argon isotope compositions are mainly from seawater.

A primer for the Environmental Impact Assessment of mining at seafloor massive sulfide deposits

Seafloor massive sulfides (SMS) contain commercially viable quantities of high grade ores, making them attractive prospect sites for marine mining. SMS deposits may also contain hydrothermal vent ecosystems populated by high conservation value vent-endemic species. Responsible environmental management of these resources is best achieved by the adoption of a precautionary approach. Part of this precautionary approach involves the Environmental Impact Assessment (EIA) of exploration and exploitative activities at SMS deposits. The VentBase 2012 workshop provided a forum for stakeholders and scientists to discuss issues surrounding SMS exploration and exploitation. This forum recognised the requirement for a primer which would relate concepts underpinning EIA at SMS deposits. The purpose of this primer is to inform policy makers about EIA at SMS deposits in order to aid management decisions. The primer offers a basic introduction to SMS deposits and their associated ecology, and the basic requirements for EIA at SMS deposits; including initial data and information scoping, environmental survey, and ecological risk assessment. © 2013 Elsevier Ltd.

Composition of hydrothermal massive sulfide deposits from ODP Site 158-957 and Leg 169 sites

Sulfide mineral major and trace element analyses were performed on more than 50 polished slabs representing mineralization from three seafloor hydrothermal massive sulfide deposits. Samples from the Bent Hill and ODP Mound massive sulfide deposits, both on the Juan de Fuca Ridge, can be contrasted with samples from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound on the Mid-Atlantic Ridge. The massive sulfide at Bent Hill is predominantly pyrite and pyrrhotite, with increasing amounts of copper-bearing sulfide minerals at the base of the massive sulfide body and through the stockwork to an interval 200 m below seafloor that hosts high copper mineralization (Deep Copper Zone). ODP Mound contains much more abundant sphalerite and copper-bearing sulfides as compared to either Bent Hill or TAG, which are predominantly pyrite with much less abundant chalcopyrite. Copper-bearing sulfides from the Deep Copper Zone beneath Bent Hill and the lowest sampled interval of ODP Mound are petrographically and chemically similar, but distinct from copper-bearing minerals higher in either sequence.

Origin of a native sulfur chimney in the Kueishantao hydrothermal field, offshore northeast Taiwan

Analyses of rare earth and trace element concentrations of native sulfur samples from the Kueishantao hydrothermal field were performed at the Seafloor Hydrothermal Activity Laboratory of the Key Laboratory of Marine Geology and Environment, Institute of Oceanology, Chinese Academy of Sciences. Using an Elan DRC II ICP-MS, and combining the sulfur isotopic compositions of native sulfur samples, we studied the sources and formation of a native sulfur chimney. The results show, when comparing them with native sulfur from crater lakes and other volcanic areas, that the native sulfur content of this chimney is very high (99.96%), the rare earth element (REE) and trace element constituents of the chimney are very low (Sigma REE < 21x10(-9)), and the chondrite-normalized REE patterns of the native sulfur samples are similar to those of the Kueishantao andesite, implying that the interaction of subseafloor fluid-andesite at the Kueishantao hydrothermal field was of short duration. The sulfur isotopic compositions of the native sulfur samples reveal that the sulfur of the chimney, from H2S and SO2, originated by magmatic degassing and that the REEs and trace elements are mostly from the Kueishantao andesite and partly from seawater. Combining these results with an analysis of the thermodynamics, it is clear that from the relatively low temperature (< 116 degrees C), the oxygenated and acidic environment is favorable for formation of this native sulfur chimney in the Kueishantao hydrothermal field.

VentBase:Developing a consensus among stakeholders in the deep-sea regarding environmental impact assessment for deep-sea mining-A workshop report

Mining seafloor massive sulfides for metals is an emergent industry faced with environmental management challenges. These revolve largely around limits to our current understanding of biological variability in marine systems, a challenge common to all marine environmental management. VentBase was established as a forum where academic, commercial, governmental, and non-governmental stakeholders can develop a consensus regarding the management of exploitative activities in the deep-sea. Participants advocate a precautionary approach with the incorporation of lessons learned from coastal studies. This workshop report from VentBase encourages the standardization of sampling methodologies for deep-sea environmental impact assessment. VentBase stresses the need for the collation of spatial data and importance of datasets amenable to robust statistical analyses. VentBase supports the identification of set-asides to prevent the local extirpation of vent-endemic communities and for the post-extraction recolonization of mine sites. © 2013.

The contribution of trace elements from seawater to chimneys: a case study of the native sulfur chimneys in the sea area off Kueishantao, northeast of Taiwan Island

Hydrothermal fluid containing abundant matter erupts from seafloor, meets ambient cold seawater and forms chimneys. So the main matter origins of chimneys are seawater and matter which are taken by hydrothermal fluid from deep reservoir. However, because of seawater's little contribution to the forming of chimneys, it is usually covered by the abundant matter which is taken by hydrothermal fluid. Therefore, chimneys formed in ordinary deep seawater hydrothermal activity, containing complex elements, cannot be used to study the seawater's contribution to their formation. While the native sulfur chimneys, formed by hydrothermal activity near the sea area off Kueishantao, are single sulfur composition (over 99%), and within chimneys distinct layers are seen. Different layers were sampled for trace element determination, with Inductively Coupled Plasma Mass Spectrometry (ICP-MS). By analyzing the data, we consider C-layer (secondary inner-layer) as the framework layer of the chimney which formed early (Fig. 4), and its trace elements derive from hydrothermal fluid. While the trace elements within A, B, D layers have undergone later alteration. A, B layers are affected by seawater and D layer by hydrothermal fluid. The increase of trace elements of A and B layers was calculated using C layer as background. Based on the known typical volume of chimneys of the near sea area off Kueishantao, we calculated the volume of seawater that contributed trace element to chimneys formation to be about 6.37 x 10(4) L. This simple quantified estimate may help us better understand the seafloor hydrothermal activity and chimneys.

Chemical composition and sulfur-isotope ratios in DSDP Legs 69-and 70

As part of the geochemical-petrological study of basalts recovered from DSDP Hole 504B (Leg 70) on the southern flank of the Costa Rica Rift, we investigated specially the relationships between the distribution and isotopic composition of sulfur of scattered and vein sulfides on the one hand, and the observed pattern and processes of secondary alterations on the other. The following groups of observations are essential: (1) variations in the contents and isotopic composition of sulfur of different forms of sulfides are clearly interrelated and are observed solely in porous horizons established on the basis of detailed geophysical experiments; (2) the enrichment of sulfides in the light sulfur isotope decreases from the upper to the lower horizons, and within horizons in the direction of the less-altered rock; (3) the increase of d34S values of scattered sulfides in individual permeable zones parallels a decrease in the degree of iron oxidation in the contents of crystallization water, and in the concentrations of Mg, K, and Li in the rock.