Hydrothermal alterations of modern organic sediments at the Ashadze-1 hydrothermal field,Mid-Atlantic Ridge, 13° N

For the first time detailed investigations of hydrothermal alterations on microbiota of ore-bearing sediments of the Ashadze-1 field (13° N, Mid-Atlantic Ridge) were carried out and local mineral-geochemical zoning was established. For the first time for the region, enriching of Mg sediments related with hydrothermal activity was revealed. It was concluded that hydrotherms affecting sediments are characterized with a high Mg content.     

Coupled modeling of thermics and hydrogeology with the Cast3M code: application to the Rainbow hydrothermal field (Mid-Atlantic Ridge, 36°14′N)

We present a new numerical tool developed in the Cast3M software framework to model hydrothermal circulation. Thermodynamic properties of one-phase pure water are calculated from the International Association for the Properties of Water and Steam formulation. This new numerical tool is validated on several test cases of convection in closed-top and open-top boxes. Simulations of hydrothermal circulation in a homogeneous-permeability porous medium also give results in good agreement with already published simulations. This new numerical tool is used to construct a geometric and physical conceptual model of the Rainbow vent site at 36°14^′N on the Mid-Atlantic Ridge. Several configurations are discussed, showing that high temperatures and high mass fluxes measured at the Rainbow site cannot be modeled with hydrothermal circulation in a homogeneous-permeability porous medium. These high values require the presence of a fault or a preferential pathway right below the venting site. We propose and discuss a two-dimensional single-pass model that allows us to simulate both high temperatures and high mass fluxes. This modeling of the hydrothermal circulation at the Rainbow site constitutes the first but necessary step to understand the origin of high concentrations of hydrogen issued from this ultramafic-hosted vent field.     

Influence of igneous processes and serpentinization on geochemistry of the Logatchev Massif harzburgites (14°45′N,Mid-Atlantic Ridge), and comparison with global abyssal peridotites

We acquired bulk-rock analyses of Mid-Atlantic Ridge (MAR) harzburgites in order to understand the influence of submarine igneous and metamorphic processes on the distribution of incompatible elements (especially rare Earth elements or REEs) in abyssal peridotites. The geochemical characteristics of these Logatchev Massif serpentinized and talc-altered harzburgites, and spatially associated metagabbros were then compared with a compilation of global abyssal peridotites. The Logatchev harzburgites show light rare earth element (LREE) enrichments (average La _N /Yb _N = 2.81), positive correlations between LREEs (e.g. La, Ce, Pr, and Nd) and high field strength elements (HFSEs; e.g. Nb and Zr), and positive correlations between HFSEs and Th. Most global abyssal peridotites show similar trends. We suggest that the systematic enrichment of incompatible elements probably reflects a post-partial fusion magmatic refertilization. The compositional scatter exhibited by some serpentinized peridotites in Nb-LREE diagrams is probably due to the elimination of diopside during partial melting and significant impregnation by a melt produced in the Opx–Ol–Sp melting field rather than to later hydrothermal alteration. The correlation between Pb and Nd observed for most global abyssal peridotites, including the Logatchev harzburgites, indicates magmatic generation. The scatter of Pb in some rocks suggests that lead is likely mobile during serpentinization or weathering. Low to moderate water/rock (W/R) ratios in the harzburgites calculated from Sr isotopic compositions (5.98–26.20 for a close system and 1.66–2.72 for an open system), and the low abundance of REEs in Logatchev hydrothermal fluids indicate that the REE contents of abyssal peridotites probably were little influenced by hydrothermal alteration. Compared to this later alteration, the presence of small proportions of gabbroic melt (from 1:30 to 1:3 in our sample) that crystallized in the residual harzburgites modified their REE patterns significantly by elevating the LREEs.     

Covellite of the Semenov-2 hydrothermal field (13°31.13′ N,Mid-Atlantic Ridge): Enrichment in trace elements according to LA ICP MS analysis

As a result of LA ICP MS analysis of sulfides of the Semenov-2 hydrothermal field, it is established that covellite, which replaces Zn sulfides, is enriched in most trace elements. The Ga, Ni, and In contents in it do not vary, whereas Mn, Co, and Cd are lower than in sphalerite. The distribution of trace elements in covellite, which replaces Cu–Fe sulfides, is distinct: it is enriched in Cd, Sb, Pb, and Bi, whereas the contents of other elements are either lower or invariant. Covellite, which replaces Zn sulfides, is enriched in all trace elements relative to that replacing Cu–Fe sulfides. Enrichment of covellite in trace elements relative to primary sulfides was favored by oxidation of the hydrothermal fluid by seawater, which is similar to the processes of submarine oxidation of ancient massive sulfide deposits. Covellite is also a host to invisible gold and silver in ores of the Semenov-2 field along with toxic elements such as As, Se, Te, Tl, and Cd.     

Peridotite-gabbro-trondhjemite association of the Mid-Atlantic Ridge between 12°58′ and 14°45′N: Ashadze and Logachev hydrothermal vent fields

This study aimed at reconstructing the sequence of events in the magmatic and metamorphic evolution of peridotites, gabbroids, and trondhjemites of the oceanic core complexes of the Ashadze and Logachev hydrothermal vent fields. The study object was the collections of plutonic rocks made during cruises 22 and 26 of the R/V Professor Logachev, Cruise 41 of the R/V Akademik Mstislav Keldysh, and the Russian-French expedition Serpentine aboard the R/V Pourquoi pas? The data reported here suggest that the oceanic core complexes of the Ashadze and Logachev fields were formed via the same scenario in the two MAR regions. On the other hand, the analysis of petrological and geochemical characteristics of the rocks indicated that the oceanic core complexes of the MAR axial zone between 12°58′ and 14°45′N show a pronounced petrological and geochemical heterogeneity manifested in variations in the degree of depletion of mantle residues and the Nd isotopic compositions of the rocks of the gabbro-peridotite association. The trondhjemites of the Ashadze hydrothermal field can be considered as partial melting products of gabbroids under the influence of hydrothermal fluid. It was supposed that the presence of trondhjemites in the MAR oceanic core complexes can be used as a marker for the highest temperature deep-rooted hydrothermal systems. Perhaps, the region of the MAR axial zone in which petrologically and geochemically contrasting oceanic core complexes are spatially superimposed served as sites for the development of large hydrothermal clusters with a considerable ore-forming potential.     

Fluid elemental and stable isotope composition of the Nibelungen hydrothermal field (8°18′S,Mid-Atlantic Ridge): Constraints on fluid–rock interaction in heterogeneous lithosphere

Depending on the geological setting, the interaction of submarine hydrothermal fluids with the host rock leads to distinct energy and mass transfers between the lithosphere and the hydrosphere. The Nibelungen hydrothermal field is located at 8°18′S, about 9 km off-axis of the Mid-Atlantic Ridge (MAR). At 3000 m water depth, 372 °C hot, acidic fluids emanate directly from the bottom, without visible sulfide chimney formation. Hydrothermal fluids obtained in 2009 are characterized by low H₂S concentrations (1.1 mM), a depletion of B (192 μM) relative to seawater, lower Si (13.7 mM) and Li (391 μM) concentrations relative to basaltic-hosted hydrothermal systems and a large positive Eu anomaly, and display a distinct stable isotope signature of hydrogen (?²H_H2O = 7.6–8.7‰) and of oxygen (?¹⁸O_H2O = 2.2–2.4‰).The heavy hydrogen isotopic signature of the Nibelungen fluids is a specific feature of ultramafic-hosted hydrothermal systems and is mainly controlled by the formation of OH-bearing alteration minerals like serpentine, brucite, and tremolite during pervasive serpentinization. New isotopic data obtained for the ultramafic-hosted Logatchev I field at 14°45′N, MAR (?²H_H2O = 3.8–4.2‰) display a similar trend, being clearly distinguished from other, mafic-hosted hydrothermal systems at the MAR.The fluid geochemistry at Nibelungen kept stable since the first sampling campaign in 2006 and is evident for a hybrid alteration of mafic and ultramafic rocks in the subseafloor. Whereas the ultramafic-fingerprint parameters Si, Li, B, Eu anomaly and ?²H_H2O distinguish the Nibelungen field from other hydrothermal systems venting in basaltic settings at similar physico-chemical conditions and are related to the interaction with mantle rocks, the relatively high concentrations of trace alkali elements, Pb, and Tl can only be attributed to the alteration of melt-derived gabbroic rocks. The elemental and isotopic composition of the fluid suggest a multi-step alteration sequence: (1) low- to medium-temperature alteration of gabbroic rocks, (2) pervasive serpentinization at moderate to high temperatures, and (3) limited high-temperature interaction with basaltic rocks during final ascent of the fluid. The integrated water/rock ratio for the Nibelungen hydrothermal system is about 0.5.The fluid compositional fingerprint at Nibelungen is similar to the ultramafic-hosted Logatchev I fluids with respect to key parameters. Some compositional differences can be ascribed to different alteration temperatures and other fluid pathways involving a variety of source rocks, higher water/rock ratios, and sulfide precipitation in the sub-seafloor at Logatchev I.     

Hydrothermal metasomatic alteration of carbonate bottom sediments in the Ashadze-1 field (13° N Mid-Atlantic Ridge)

We have performed the first detailed study of hydrothermal alteration of the Holocene-upper Pleistocene sediments in the recent Ashadze-1 hydrothermal field sampled during the 26th cruise of R/V Professor Logachev in 2005. It has been established that alterations in mineralogy and geochemistry are caused by the dissolution of calcite shells in bottom sediments and their metasomatic replacement with sulfides and other hydrothermal minerals. A zone of sediments enriched in magnesian hydrothermal minerals has been revealed in the sediments of the MAR for the first time. It is suggested that metasomatism is related to diffuse percolation of hydrothermal fluids through sediments.     

New hydrothermal sulfide fields of the Mid-Atlantic Ridge: Yubileinoe (20°09′ N) and Surprise (20°45.4′ N)

Two new sulfide fields (Yubileinoe, 20°09′ N, and Surprise, 20°45.4′ N) were discovered between 20°01′ and 20°54′ N within the Russian Application Area of the Mid-Atlantic Ridge (MAR). The Yubileinoe field is located at a depth of 2300–2550 m in the near-top area of the first rift ridge, which is a boundary of the western wall of the rift valley. This new field and the Zenith-Victory field, which was previously discovered in the eastern wall, occur symmetrically relative to the rift valley of this MAR segment. The Surprise field at a depth of 2800–2850 m is situated in the eastern wall of the rift valley, on the slope of the volcanic uplift. After the discovery of these inactive sulfide fields, the number of hydrothermal fields within the Russian Application Area reached ten.     

Chronology of Hydrothermal Activity Within the Yubileynoye Ore Field (Mid-Atlantic Ridge, 20°08′ N)

This paper reports on the integrated geochronological and geochemical methods used in studying the ore deposits and metalliferous sediments of the Yubileinoye field. This study gives the opportunity to carry out cross dating of hydrothermal deposits, including the ²³⁰Th/U dating of sulfides, the ²³⁰Th, ¹⁴C dating, and foraminiferal analysis of the sediments, and, on this basis, to reconstruct hydrothermal activity over time. It was established that the ores started forming about 100 000–123 000 years ago and were renewed 4–5 times with a frequency of 10–20 ka. As a result, the complex of pyrite-marcasite, chalcopyrite and sphalerite ores and the associated metal-bearing and ore-bearing sediments with consistent geochemical specialization were formed. The integrated geochronological and geochemical studies of the ores and sediments allow us to obtain detailed data on evolution of the hydrothermal ore-formation not only in the certain areas but also for the entire Mid-Atlantic Ridge.     

Noble metals in sulfide assemblages from deep sectors of the active TAG mound (Mid-Atlantic Ridge, 26°08′ N)

Primary sulfides from cores of holes 957M, 957C, and 957H drilled during the ODP Leg 158 on the active hydrothermal TAG mound (Mid-Atlantic Ridge, 26°08′ N) were examined for the concentration of several elements. Based on 262 microprobe analyses, it has been established that the sulfides are characterized by an extremely heterogeneous distribution of noble metals (Au, Ag, Pt, and Pd) and several associated elements (Hg, Co, and Se). Noble metals are arranged in the following order in terms of decreasing abundance, i.e., concentration level above the detection limit (the number of analyses containing the specific element is given in parentheses): Au (65), Ag (46), Pt (21), and Pd (traces). The associated trace elements make up the following series: Co (202), Hg (132), and Se (49). Main carriers of the “invisible” portion of noble metals are represented by pyrite (Au, Hg), marcasite and pyrite (Ag, Co), sphalerite and chalcopyrite (Pt, Pd), and chalcopyrite (Se). The noble metal distribution in sulfides reveals a lateral zonality: the maximal concentration and abundance of Au in chalcopyrite (or Pt and Ag in chalcopyrite and pyrite) increase from the periphery (Hole 957H) to the center (holes 957C and 957M) of the hydrothermal mound, while the Au distribution in pyrite displays a reversed pattern. The Co distribution increases with depth. This work discusses the vertical zonality in the distribution of elements mentioned above and their response to the evolution of ore genesis.     

Variolitic lavas in the axial rift of the Mid-Atlantic Ridge and their origin (Sierra Leone area, 6°18′N)

Altered variolites described for the first time in the axial zone of the Mid-Atlantic Ridge are represented by rounded globules of andesite (icelandite) composition with light trachyandesite rim embedded in a picrobasaltic matrix. The globules were transferred with picrobasaltic melt and then floated to the surface of lava flow, while formation of leucocratic rims was presumably related to thermodiffusion (Soret effect) in a cooling heterogeneous melt. This heterogeneous melt was formed by penetration of ascending column of picrobasaltic magma in already existing small intracructsal magmatic chamber filled with residual icelanditetype andesite melt and involvement of the latter into a general upward movement. The rapid ascent of the melts in the oceanic spreading zones by means of turbulent flowing caused dispersion of the extragenous melt into small drops in a jet of picrobasaltic magma, without their interaction. Variolites were formed during cooling of such heterogeneous lava flow. No signs of liquid immiscibility were found in the studied variolites.     

Behavior of Trace Elements during Oxidation of Sphalerite of the Irinovskoe Hydrothermal Sulfide Field (13°20′ N,Mid-Atlantic Ridge)

Geology of Ore Deposits - The formation of present-day seafloor sulfide deposits is accompanied by their continuous oxidation and crystallization of insoluble Fe oxyhydroxides, which absorb metals...     

Calcium isotope constraints on the uptake and sources of Ca in a base-poor forest: A new concept of combining stable (δCa) and radiogenic (εCa) signals

Plant-available reserves of major base cations, Ca²⁺ and Mg²⁺, decreased markedly in soils over the past century, thus posing a potential threat to forest ecosystem health. Trees are thought to obtain dissolved Ca²⁺ ions mainly from an easily accessible soil-water reservoir also termed the ‘exchangeable cation pool’. The status of Ca reserves in this soil pool is sensitive to anthropogenic perturbations such as soil acidification induced by acid rain and/or excessive timber harvesting. Here we show that in a base-poor forest of the northeastern USA (i.e. Wachusett Mountain, Massachusetts) the ‘exchangeable Ca pool’ of deeper mineral soils has a unique isotope signature that is significantly enriched in the radiogenic ⁴⁰Ca, due to the dissolution of K-rich silicate minerals such as biotite. Using a simple isotope mass balance, and assuming that the input of Ca from biotite has a ε_Ca signature of ∼16, the results of our calculation indicate that the weathering of biotite may supply a sizeable fraction, up to 25%, of Ca²⁺ ions into the ‘exchangeable cation pool’ of deeper mineral soils. Importantly, samples of local vegetation (i.e. woody tissues of red oak) show no detectable excess of the radiogenic ⁴⁰Ca, and based on our model the upper limit of a possible biotite-derived Ca contribution in vegetation is estimated at ∼5%. We also found no evidence of the radiogenic ⁴⁰Ca signal in the samples of forest floor and the uppermost organic-rich soils (0-15 cm depth), which in turn suggest that over the long-term development of the forest and its organic matter accumulation, the vegetation growth must have also relied primarily on the non-radiogenic Ca sources. Based on our experimental data, such sources may include (i) wet atmospheric deposition, (ii) the organically-complexed Ca in topsoil horizons, and (iii) chemical weathering and/or fungal-mediated dissolution of apatite and Ca-rich plagioclase. Hence, our stable and radiogenic Ca isotope data indicate that the studied base-poor forest is able to bypass the ‘exchangeable cation pool’ of deeper (i.e. below 15 cm) mineral soils, and still manages to meet its nutritional requirements with respect to Ca. Another important implication of this study is that the organically-complexed Ca in the topsoil horizon (0-15 cm depth) has to be tightly bound to the ion exchange sites, otherwise the large radiogenic ⁴⁰Ca signatures present in the ‘exchangeable cation pool’ of deep mineral soils would be swamped by the downward gravitational flux of non-radiogenic Ca from the decaying organic matter and litterfall. Hence, the limited mobility of the organically-complexed Ca in soils and its tight biological cycling could explain the lack of a significant impact of vegetation on the Ca isotope systematics observed in large rivers.     

Stable isotope(δ~(13)C_(ker),δ~(13)C_(carb),δ~(18)O_(carb)) distribution along a Cambrian outcrop section in the eastern Tarim Basin,NW China and its geochemical significance

This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.     

Constraining the marine strontium budget with natural strontium isotope fractionations (Sr/Sr∗, δSr) of carbonates, hydrothermal solutions and river waters

We present strontium (Sr) isotope ratios that, unlike traditional ⁸⁷Sr/⁸⁶Sr data, are not normalized to a fixed ⁸⁸Sr/⁸⁶Sr ratio of 8.375209 (defined as δ^88/86Sr = 0 relative to NIST SRM 987). Instead, we correct for isotope fractionation during mass spectrometry with a ⁸⁷Sr-⁸⁴Sr double spike. This technique yields two independent ratios for ⁸⁷Sr/⁸⁶Sr and ⁸⁸Sr/⁸⁶Sr that are reported as (⁸⁷Sr/⁸⁶Sr∗) and (δ^88/86Sr), respectively. The difference between the traditional radiogenic (⁸⁷Sr/⁸⁶Sr normalized to ⁸⁸Sr/⁸⁶Sr = 8.375209) and the new ⁸⁷Sr/⁸⁶Sr∗ values reflect natural mass-dependent isotope fractionation. In order to constrain glacial/interglacial changes in the marine Sr budget we compare the isotope composition of modern seawater ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Seawater) and modern marine biogenic carbonates ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Carbonates) with the corresponding values of river waters ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_River) and hydrothermal solutions ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_HydEnd) in a triple isotope plot. The measured (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_River values of selected rivers that together account for ∼18% of the global Sr discharge yield a Sr flux-weighted mean of (0.7114(8), 0.315(8)‰). The average (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_HydEnd values for hydrothermal solutions from the Atlantic Ocean are (0.7045(5), 0.27(3)‰). In contrast, the (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Carbonates values representing the marine Sr output are (0.70926(2), 0.21(2)‰). We estimate the modern Sr isotope composition of the sources at (0.7106(8), 0.310(8)‰). The difference between the estimated (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_input and (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_output values reflects isotope disequilibrium with respect to Sr inputs and outputs. In contrast to the modern ocean, isotope equilibrium between inputs and outputs during the last glacial maximum (10-30 ka before present) can be explained by invoking three times higher Sr inputs from a uniquely “glacial” source: weathering of shelf carbonates exposed at low sea levels. Our data are also consistent with the “weathering peak” hypothesis that invokes enhanced Sr inputs resulting from weathering of post-glacial exposure of abundant fine-grained material.     

A superlarge deposit—Kalahari manganese ore field (Northern Cape,South Africa): Geochemistry of isotopes (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis

Study of carbonate inclusions in the Mamatwan-type oxide ores (braunite lutites) made it possible to reveal residual microbial structures in them. Their presence in manganese ores, the type of manganese oxide mineralization, isotope signatures of manganese carbonates, and available literature data on the geology of the Kalahari manganese field suggest that manganese ore formation was widespread at the postsedimentary stage of transformation of the primary microbial sediment. The deposit can be referred to the hydrothermal-metasomatic type.