The sedimentation model of the Tuapse Trough (Black Sea)

Based on the new 2D and 3D seismic data from the Tuapse Trough (Black Sea), the principle peculiarities of sedimentation have been studied in detail. A sedimentation model of the focused Maikop and Karagan-Chokrak intervals of the geological section has been suggested. A system of fan complexes referred to Maikop age has been found.     

Spatial variation in fluid flow and geochemical fluxes across the sediment-seawater interface at the Carlos Ribeiro mud volcano (Gulf of Cadiz)

Submarine mud volcanism is an important pathway for transfer of deep-sourced fluids enriched in hydrocarbons and other elements into the ocean. Numerous mud volcanoes (MVs) have been discovered along oceanic plate margins, and integrated elemental fluxes are potentially significant for oceanic chemical budgets. Here, we present the first detailed study of the spatial variation in fluid and chemical fluxes at the Carlos Ribeiro MV in the Gulf of Cadiz. To this end, we combine analyses of the chemical composition of pore fluids with a 1-D transport-reaction model to quantify fluid fluxes, and fluxes of boron, lithium and methane, across the sediment-seawater interface. The pore fluids are significantly depleted in chloride, but enriched in lithium, boron and hydrocarbons, relative to seawater. Pore water profiles of sulphate, hydrogen sulphide and total alkalinity indicate that anaerobic oxidation of methane occurs at 34-180 cm depth below seafloor. Clay mineral dehydration, and in particular the transformation of smectite to illite, produces pore fluids that are depleted in chloride and potassium. Profiles of boron, lithium and potassium are closely related, which suggests that lithium and boron are released from the sediments during this transformation. Pore fluids are expelled into the water column by advection; fluid flow velocities are 4 cm yr⁻¹ at the apex of the MV but they rapidly decrease to 0.4 cm yr⁻¹ at the periphery. The associated fluxes of boron, lithium and methane vary between 7-301, 0.5-6 and 0-806 mmol m⁻² yr⁻¹, respectively. We demonstrate that fluxes of Li and B due to mud volcanism may be important on a global scale, however, release of methane into the overlying water column is suppressed by microbial methanotrophy.     

Actively forming Kuroko-type volcanic-hosted massive sulfide (VHMS) mineralization at Iheya North,Okinawa Trough,Japan

Modern seafloor hydrothermal systems provide important insights into the formation and discovery of ancient volcanic-hosted massive sulfide (VHMS) deposits. In 2010, Integrated Ocean Drilling Program (IODP) Expedition 331 drilled five sites in the Iheya North hydrothermal field in the middle Okinawa Trough back-arc basin, Japan. Hydrothermal alteration and sulfide mineralization is hosted in a geologically complex, mixed sequence of coarse pumiceous volcaniclastic and fine hemipelagic sediments, overlying a dacitic to rhyolitic volcanic substrate. At site C0016, located adjacent to the foot of the actively venting North Big Chimney massive sulfide mound, massive sphalerite-(pyrite-chalcopyrite ± galena)-rich sulfides were intersected (to 30.2% Zn, 12.3% Pb, 2.68% Cu, 33.1 ppm Ag and 0.07 ppm Au) that strongly resemble the black ore of the Miocene-age Kuroko deposits of Japan. Sulfide mineralization shows clear evidence of formation through a combination of surface detrital and subsurface chemical processes, with at least some sphalerite precipitating into void space in the rock. Volcanic rocks beneath massive sulfides exhibit quartz-muscovite/illite and quartz-Mg-chlorite alteration reminiscent of VHMS proximal footwall alteration associated with Kuroko-type deposits, characterized by increasing MgO, Fe/Zn and Cu/Zn with depth. Recovered felsic footwall rocks are of FII to FIII affinity with well-developed negative Eu anomalies, consistent with VHMS-hosting felsic rocks in Phanerozoic ensialic arc/back-arc settings worldwide.Site C0013, ∼100 m east of North Big Chimney, represents a likely location of recent high temperature discharge, preserved as surficial coarse-grained sulfidic sediments (43.2% Zn, 4.4% Pb, 5.4% Cu, 42 ppm Ag and 0.02 ppm Au) containing high concentrations of As, Cd, Mo, Sb, and W. Near surface hydrothermal alteration is dominated by kaolinite and muscovite with locally abundant native sulfur, indicative of acidic hydrothermal fluids. Alteration grades to Mg-chlorite dominated assemblages at depths of >5 mbsf (metres below sea floor). Late coarse-grained anhydrite veining overprints earlier alteration and is interpreted to have precipitated from down welling seawater as hydrothermal activity waned. At site C0014, ∼350 m farther east, hydrothermal assemblages are characterized by illite/montmorillonite, with Mg-chlorite present at depths below ∼30 mbsf. Recovered lithologies from distal, recharge site C0017 are unaltered, with low MgO, Fe₂O₃ and base metal concentrations.Mineralization and alteration assemblages are consistent with the Iheya North system representing a modern analogue for Kuroko-type VHMS mineralization. Fluid flow is focussed laterally along pumiceous volcaniclastic strata (compartmentalized between impermeable hemipelagic sediments), and vertically along faults. The abundance of Fe-poor sphalerite and Mg-rich chlorite (clinochlore/penninite) is consistent with the lower Fe budget, temperature and higher oxidation state of felsic volcanic-hosted hydrothermal systems worldwide compared to Mid Ocean Ridge black smoker systems.     

Geochemical characteristics of mud volcano fluids in the southern margin of the Junggar basin,NW China: implications for fluid origin and mud volcano formation mechanisms

Mud volcanoes can provide important information about the underlying strata, hydrocarbon accumulation, and recent neotectonic movements in an area. The fluids erupting from mud volcanoes provide important information about their formation and evolution. The ion concentration and the hydrogen and oxygen isotopes of the fluids that were erupted from the three mud volcano groups, Baiyanggou, Aiqigou, and Dushanzi, and nearby rivers in the southern margin of the Junggar basin, northwestern China, are studied. The concentrations of Na and Cl in mud volcano fluids are clearly elevated, displayed as the Na-Cl type. The δD and δ18O values of the fluids are similar between the Baiyanggou and Dushanzi mud volcanoes, which are mainly from ancient sedimentary pore water. However, the Aiqigou mud volcano is depleted in dissolved Cl and shows lower δ18O values with mixed sources, including deep pore and local meteoric water. Two types of mud volcanoes are proposed in this study. One type is low-energy mud volcanoes with a low volume of fluid of deep origin on the hillcrest, which display as mud pool/pie/hole. The other type is high-energy mud volcanoes having mixed fluid origin in the valley and formed in the shape of a mud cone (dome).     

Geochemical and geo-electrical study of mud pools at the Mutnovsky volcano (South Kamchatka,Russia): Behavior of elements,structures of feeding channels and a model of origin

This study presents data on the geochemical composition of boiling mud pools at the Mutnovsky volcano. The physicochemical characteristics of the pools and the concentrations of major, minor and trace elements in pool solutions vary widely. A comparison of the geochemical compositions of host rocks and solutions indicates that leaching from rocks is not the only source of chemicals in thermal solutions. Geophysical studies reveal the inner structure of thermal fields, which reflect the shapes of the underground reservoirs and feed channels. Using geophysical methods (electrical resistivity tomography and frequency domain investigations), it was shown that the vertical structure and complex geochemical zonation of the feed channels leads to a high contrast in the compositions of the mud solutions. These findings answer questions about the origin and composition of surface manifestations. To elucidate the mechanisms of solution formation, an attempt was made to describe the magmatic fluid evolution and the resulting mixing of waters by physical and mathematical models. The model illustrates fluid migration from a magma chamber to the surface. It is shown that the formation of brines corresponding to the mud pool composition is possible during secondary boiling.     

Gas reservoirs in the Dead Sea area: evidence from chemistry of combustion metamorphic rocks in Nabi Musa fossil mud volcano

Nabi Musa located at the northern tip of the Dead Sea at 31°48′ N, 35°25′ E is one of fifteen complexes of the Hatrurim Formation or the so-called “Mottled Zone” (MZ) which are fossil mud volcanoes. Self ignition of methane during their eruptions in the Middle–Late Pleistocene caused combustion metamorphism of sediments. Melting foci have been discovered in two craters of Nabi Musa volcano, with numerous veins of paralavas having particular calcic-silicic compositions (Ca₂SiO₄- and CaSiO₃-normative). Their major- and trace-element spectra bear signature of a mixed sedimentary protolith consisting of Cretaceous marine carbonates, marl, and quartz sand. The paralavas inherit high Sr, P, and U enrichments, positive La/La* and Y anomalies, and a negative Ce/Ce* anomaly from calcareous marine sediments, including bituminous and apatite-rich chalks. The presence of quartz arenite in the protolith is responsible for relatively high Ti, Nb, Zr, and Hf while the marl pelitic component accounts for MREE and LREE depletion. The suggested mixing models predict that the Nabi Musa paralavas result from combustion metamorphism of a sediment mixture with 53–60 wt.% chalk, 5–14 wt.% marl, and 27–44 wt.% quartz arenite. The history of mud volcanism at Nabi Musa began with small eruptions that mobilized gas and water from shallow (within 300 m) Turonian carbonate aquifers, and later explosive activity triggered violent gas blowouts from the older terrigenous reservoir of Aptian–Albian Nubian-type sandstone lying as deep as 1300–1500 m.     

Rapid, oxygen-dependent microbial Mn(II) oxidation kinetics at sub-micromolar oxygen concentrations in the Black Sea suboxic zone

Microbial Mn(II) oxidation kinetics in response to oxygen concentration were assessed in suboxic zone water at six sites throughout the Black Sea. Mn(II) oxidation rates increased asymptotically with increasing oxygen concentration, consistent with Michaelis-Menten enzyme kinetics. The environmental half-saturation constant, K_E, of Mn(II) removal (oxidation) varied from 0.30 to 10.5 μM dissolved oxygen while the maximal environmental rate, V_E−max, ranged from 4 to 50 nM h⁻¹. These parameters varied spatially and temporally, consistent with a diverse population of enzymes catalyzing Mn oxide production in the Black Sea. Coastally-influenced sites produced lower K_E and higher V_E−max constants relative to the Western and Eastern Gyre sites. In the Bosporus Region, the Mn(II) residence time calculated using our K_E and V_E−max values with 0.1 μM oxygen was 4 days, 25-fold less than previous estimates. Our results (i) indicate that rapid Mn(II) oxidation to solid phase Mn oxides in the Black Sea’s suboxic zone is stimulated by oxygen concentrations well below the 3-5 μM concentration reliably detected by current oceanographic methods, (ii) suggest the existence of multiple, diverse Mn(II)-oxidizing enzymes, (iii) are consistent with shorter residence times than previously calculated for Mn(II) in the suboxic zone and (iv) cast further doubt on the existence of proposed reactions coupling solid phase Mn oxide production to electron acceptors other than oxygen.     

Fluid migration and origin of a mud volcano in the Northern Apennines (Italy): the role of deeply rooted normal faults

ABSTRACT In the foothills of the Northern Apennines mud volcanoes are locally aligned along active normal faults, which allow surface leakage of fluids derived from deep sources (>3–6 km). The chemical and isotopic analysis of the fluids of a mud volcano, coupled with the reconstruction of its geological setting, allowed an investigation of the processes of migration and fluid flow. The fault system associated with the Regnano mud volcano drains a deep Miocene reservoir (foredeep marine deposits), which supplies formation water and thermogenic methane that has migrated from underlying Mesozoic carbonates. The muds from the volcano contain late Eocene microfossils and are extruded only during paroxysmal events. They have a shallower origin (about 1 km) from the base of Tertiary marine deposits deposited upon the upper tectonic nappe of the chain (Ligurian unit). This case study suggests that normal faults are very effective in controlling surface emissions.     

Gases in Taiwan mud volcanoes: Chemical composition,methane carbon isotopes,and gas fluxes

Mud volcanoes are important pathways for CH₄ emission from deep buried sediments; however, the importance of gas fluxes have hitherto been neglected in atmospheric source budget considerations. In this study, gas fluxes have been monitored to examine the stability of their chemical compositions and fluxes spatially, and stable C isotopic ratios of CH₄ were determined, for several mud volcanoes on land in Taiwan. The major gas components are CH₄ (>90%), “air” (i.e. N₂ + O₂ + Ar, 1–5%) and CO₂ (1–5%) and these associated gas fluxes varied slightly at different mud volcanoes in southwestern Taiwan. The Hsiao-kun-shui (HKS) mud volcano emits the highest CH₄ concentration (CH₄ > 97%). On the other hand, the Chung-lun mud volcano (CL) shows CO₂ up to 85%, and much lower CH₄ content (<37%). High CH₄ content (>90%) with low CO₂ (<0.2%) are detected in the mud volcano gases collected in eastern Taiwan. It is suggestive that these gases are mostly of thermogenic origin based on C₁ (methane)/C₂ (ethane) + C₃ (propane) and δ¹³C_CH4 results, with the exception of mud volcanoes situated along the Gu-ting-keng (GTK) anticline axis showing unique biogenic characteristics. Only small CH₄ concentration variations, <2%, were detected in four on-site short term field-monitoring experiments, at Yue-shi-jie A, B, Kun-shui-ping and Lo-shan A. Preliminary estimation of CH₄ emission fluxes for mud volcanoes on land in Taiwan fall in a range between 980 and 2010 tons annually. If soil diffusion were taken into account, the total amount of mud volcano CH₄ could contribute up to 10% of total natural CH₄ emissions in Taiwan.     

Paleocurrent and sedimentological studies in the Benue Trough,Nigeria

Paleocurrent analysis indicates an easterly and a westerly source, respectively, for the Cretaceous and Tertiary sediments in the middle and upper Benue Trough. Petrographic differentiation of the pre-Santonian and post-Santonian sediments is based on their feldspar contents. Petrographic evidence suggests that the Tertiary sediments are polycycled; this fact, coupled with the inferred westerly source, suggests that the present limits of the trough are not the paleolimits. Thus the rift boundary faults are probably further westward and eastward of the present trough margins.     

Radium-based pore water fluxes of silica, alkalinity, manganese, DOC, and uranium: A decade of studies in the German Wadden Sea

A decade of studies of metal and nutrient inputs to the back-barrier area of Spiekeroog Island, NW German Wadden Sea, have concluded that pore water discharge provides a significant source of the enrichments of many components measured in the tidal channels during low tide. In this paper we add studies of radium isotopes to help quantify fluxes into and out of this system. Activities of radium isotopes in surface water from tidal channels in the back-barrier area exhibit pronounced changes in concert with the tide, with highest activities occurring near low tide. Other dissolved components: silica, total alkalinity (TA), manganese, and dissolved organic carbon (DOC) exhibit similar changes, with patterns matching the Ra isotopes. Uranium follows a reverse pattern with highest concentrations at high tide. Here we use radium isotope measurements in water column and pore water samples to estimate the fluxes of pore waters that enter the tidal channels during low tide. Using a flushing time of 4 days and the average activities of ²²⁴Ra, ²²³Ra, and ²²⁸Ra measured in the back-barrier surface and pore waters, we construct a balance of these isotopes, which is sustained by a deep pore water flux of (2-4) × 10⁸ L per tidal cycle. This flux transports Ra and the other enriched components to the tidal channels and causes the observed low tide enrichments. An independent estimate of pore water recharge is based on the depletion of U in the tidal channels. The U-based recharge is about two times greater than the Ra-based discharge; however, other sinks of U could reduce the recharge estimate. The pore waters have wide ranges of enrichment in silica, alkalinity, manganese, DOC, and depletion of U with depth. We estimate concentrations of these components in pore water from the depth expected to contribute the majority of the pore water flux, 3.5 m, to determine fluxes of these components to the tidal channels. Samples from this depth have minimum concentrations of silica, alkalinity, manganese, and DOC. We also estimate the exports of these components (and import of U) due to mixing based on average measured concentrations in the tidal creeks and the 4-day flushing time. A comparison of these estimates reveals that the exports (negative in the case of U) equal or exceed the pore water fluxes. By using values slightly higher than the minimum concentrations at 3.5 m to calculate inputs, the two estimates could be forced to match. We conclude that pore water drainage is the major factor regulating fluxes of Ra isotopes, silica, alkalinity, manganese, DOC, and uranium in this system.     

Contrasting behavior of tungsten and molybdenum in the Okinawa Trough,the East China Sea and the Yellow Sea

By using catalytic current polarography and high-resolution inductively coupled plasma mass spectrometry, W and Mo in seawater were determined in the Okinawa Trough, a backarc rift, and in the East China Sea and the Yellow Sea. Mo was distributed conservatively throughout the study area, and its salinity-normalized concentration was 104 ± 6 nM (n = 105). W was also uniformly distributed south of the Kuroshio Current (56 ± 7 pM, n = 51). Anomalous high concentrations of W (maximum 254 pM) were found in the Iheya Graben in the middle Okinawa Trough (>1000 m depth), which were probably supplied by hydrothermal activity. The concentrations of Mo and W in the East China Sea and the Yellow Sea showed linear correlation with salinity (26 < S < 35). The Mo data can be explained by mixing of seawater and river water of the Changjiang (Mo = 10 nM; Qu et al., 1993). However, the values of W extrapolated to S = 0 were largely different between two cruises (1200 pM in May–June 1987 and 540 pM in June 1994) and much higher than the reported concentrations of 160 pM for world rivers by Turekian (1969) and 30 pM for unpolluted Japanese rivers by Sohrin et al. (1989). Moreover, significantly high W was observed in the bottom water at stations near the Changjiang River estuary and the western Yellow Sea. While these data may suggest that W is released from the anoxic sediments of the continental shelf, we need more data to elucidate the mechanism controlling the distribution of W.     

Quaternary iron-manganese deposits and associated pelagic sediments (radiolarian clay and chert, gypsiferous mud) from the Tyrrhenian Sea

Various types of pelagic sediments occur on a dolomitic basement located at some 1000 m depth on the eastern slope of the Tyrrhenian Sea, i.e. in the most internal, collapsed and presently submerged portion of southern Apennines. The deposits include laminated limonites, muds with manganosiderite nodules, radiolarian clays, opal chert, gypsiferous muds, lutites with calcareous plankton, and all are of Quaternary age. They are interpreted as products of the interactions between submarine hydrothermal activity and deep-sea sediments, and represent the first documented case of submarine hydrothermal sediments not directly connected to active ridges or volcanic buildings and deposits. The iron-rich sediments are very similar to many other reported examples of submarine thermal activity. The radiolarian clay displays very abundant and almost exclusively radiolarian tests, and no calcareous fossils, but shows numerous dissolution traces of carbonate skeletons. It has been interpreted as deriving from a primary bloom of siliceous plankton followed by an extensive leaching of the calcareous tests on the seafloor. The radiolarian chert shows a very early and yet unknown Opal-A cement. The immediate source of the cement is biogenous silica, whereas the ultimate source is the bloom of siliceous plankton triggered by the hydrothermal and volcanic activity. The gypsum muds are the result of a hydrothermal chemical remobilization of the Messinian sulphate beds which overlie the dolomitic basement.     

Black Sea chemocline oscillations during the Holocene: molecular and isotopic studies of marginal sediments

We measured δ¹³C values of free and sulfur-bound lipids and framboidal pyrite-size distributions in three sediment cores from the southern margins of the Black Sea. The margin cores show a marked difference in the occurrence of biomarkers from green sulfur bacteria compared with the deep-basin cores, as a result of deepening of the chemocline resulting from enhanced mixing and/or decreased light-penetration as a consequence of high turbidity and productivity in shelf waters. Quantitation of biomarkers suggests that photic-zone anoxia along the shelf margin was generally absent during the deposition of unit I, although occurred during the deposition of Unit IIb at two sites.     

Fossil Coals (Gagates) from Pleistocene Sediments in Black Sea Terraces,Southeastern Crimea

Lithology and Mineral Resources - The marine Quaternary (Chaudian) terrace V in the outskirts of Sudak accommodates layers saturated with lenses and fragments of fossil coal scrutinized by the...     

Geology,U-Pb geochronology,and stable isotope geochemistry of the Tunca semi-massive sulfide mineralization,Black Sea region,NE Turkey: Implications for ore genesis

Upper Cretaceous volcano-sedimentary sequences of the Eastern Pontide orogenic belt, NE Turkey, are host to significant VMS mineralization, including near Tunca. The initial stages of felsic volcanism within the mineralized area are marked by the eruption of dacitic lavas and breccias of the Kızılkaya Formation. This was accompanied by the emplacement of domelike hematitic dacites. Autobrecciated and volcaniclastic rocks, both in situ and resedimented, were likely generated from extrusive portions of these dacite bodies. Basaltic volcanism is marked by the eruption of the lava flows and pillow lavas of the Çağlayan Formation. Hiatuses in basaltic activity are marked by thin horizons of volcaniclastics and mudstones. The uppermost felsic volcanic units were accompanied by resedimentation of autoclastic facies from previous volcanism and represent the latest phase of Upper Cretaceous volcanism in the area. The semi-massive sulfide mineralization is associated with a late stage of the initial felsic volcanism. U-Pb LA-ICP-MS zircon dating of a dacitic tuff breccia yielded an age of 88.1 ± 1.2 Ma (Coniacian-Upper Cretaceous), which is interpreted to be the age of the sulfide occurrences.A concentric zoned alteration pattern is observed in the footwall rocks. The alteration pattern is considered to have formed by lateral migration of hydrothermal fluids which had ascended along the discharge conduit. Fluid inclusion data indicate precipitation or mobilization processes within a relatively narrow temperature range of 152–255 °C (avg. 200 °C). The low-salinity fluids in the fluid inclusions, less than 5.9 wt% NaCl equivalent, are consistent with typical modified seawater-dominant hydrothermal vent fluids. Sulfur isotope analysis of the Tunca sulfides yields a narrow range of 1.5–4.1 per mil. These δ³⁴S values are also typical of many VMS deposits. Most of the recorded δ¹⁸O values (+7.1 to +14.0 per mil) are greater than 9 per mil. The most intensely hydrothermally altered rocks tend to have lower δ¹⁸O values relative to the less altered rocks. Collectively, the geologic relationships, mineralization style, and the lack of seafloor ore facies suggest that mineralization is principally of sub-seafloor origin. The most geologically reasonable interpretation of the genesis of the Tunca mineralization is the continuous interaction between the host rocks and seawater-derived fluids, without significant involvement of a magmatic fluid.     

Geochemistry of thirteen Voronin Trough cores,Kara Sea,European Arctic: Hg and As contaminants at a 1965 timeline

The potentially toxic elements Hg and As are found at high concentrations in surface/near-surface sediments from Arctic ocean cores collected from the Voronin Trough, Kara Sea, during 1965. The levels reach 2045 ppb for Hg and 270 ppm for As. Manganese high values (up to 1.27%) are also found in the cores’ surface/near-surface sections. Other heavy metals tracked by the Arctic Monitoring and Assessment Program (e.g., Cu, Ni, Pb, Sb, Ti, Zn) have baseline concentrations in the cores. The cores average >57% clay-size and >35% silt-size in their textural composition. The elevated contents may result from anthropogenic input for Hg and As with diagenesis adding to the As concentration. Possible sources for these elements are emissions and effluents from industry such as mining and smelting operations, and burning of fossil fuels in Siberia and the Urals. When discharged into the Kara Sea from Siberian catchments, the As and Hg likely attach to charged particulate surfaces of Fe oxy/hydroxides (for As) and particulate organic matter or clay minerals (for Hg). These are transported, entrained in ocean currents or adhered to pack ice, to the Voronin Trough where they deposit according to size and specific gravity.