Lower Cretaceous lacustrine successions,North Yellow Sea Basin,eastern China: Rift basin sequence stratigraphy and stacking patterns in response to magmatic activity

A series of Mesozoic rift basins formed in eastern China were associated with magmatic activity and subduction along the Eurasia, Izanagi and Pacific plate margins. The impact of magmatic activity on lacustrine sequence development was documented with well-log and 3-D seismic data from the Jupiter Depression in the North Yellow Sea Basin. We identified key surfaces, retrogradational and progradational parasequence sets, and defined the characteristics of systems tracts and the internal sequence components for the Lower Cretaceous (K₁SQ1). A 2-D SEDPAK numerical stratigraphic forward modeling was used to further constrain sequence development in the Jupiter Depression by considering different modeling parameters and the spatial-temporal characteristics of magmatic activity. Modeling results were compared and matched with the sequence architecture observed from seismic and well interpretations. Magmatic activity impacts on the development of the K₁SQ1 sequence in the North Yellow Sea Basin include topographic variation, lake level fluctuation, and sediment supply ratios. Results suggest that magmatic upwelling uplifted the northwestern area of the Jupiter Depression and formed its slope break during the late Jurassic or early Cretaceous. Along with uplifting, relative lake level dropped sharply and lake accommodation was reduced, but with increased sediment supply. Therefore, sediment accumulated along the slope break as a lowstand systems tract. Later on, as lake level continuously rose, transgressive and highstand systems tracts were developed. The proposed stacking pattern provides an analog, and a useful model, for lacustrine sequence development in response to magmatic activities in eastern China and other rift basins of similar tectonic setting.     

Geochemical constraints on primary productivity in submarine hydrothermal vent plumes

The amount of metabolic energy available for primary production by chemolithoautotrophic microorganisms in a submarine hydrothermal plume is evaluated using geochemical models. Oxidation of elemental sulfur and metal sulfides precipitated in the hydrothermal plume represent the largest potential sources of metabolic energy in the plume (∼600 cal/kg vent fluid from each source). Among dissolved substrates, oxidation of H₂ potentially provides the greatest amount of energy (∼160 cal/kg). Smaller, but still significant, amounts of energy are also available from sulfate reduction (54 cal/kg), methanogenesis (17 cal/kg), and methanotrophy (13 cal/kg). Only negligible amounts of energy are available from oxidation of Fe(II) or Mn(II) compounds or Fe³⁺ reduction (<1 cal/kg vent fluid). The models suggest that most primary production in the plume should occur in the early stages of plume development from sulfur- and H₂-oxidizers entrained in the plume or colonizing the surfaces of minerals settling from the plume. The total primary productivity potential in the plume is estimated to be about 50 mg dry wt biomass/kg vent fluid. This translates to a global annual biomass production in hydrothermal plumes on the order of 10¹² g dry wt/yr, which represents only a small fraction of the total photosynthetic biomass production in the oceans (∼10¹⁷ g dry wt/yr). Nevertheless, biomass generated in hydrothermal plumes may represent a significant fraction of the organic matter in the deep ocean as well as that deposited in sediments in ocean basins.     

Major and trace element distributions in manganese nodules and micronodules as well as abyssal clay from the Clarion-Clipperton abyssal plain,Northeast Pacific

The contents of seven major components (TiO₂, Fe₂O₃, MgO, CaO, Na₂O, K₂O and P₂O₅) and 15 trace elements (Sc, V, Cr, Ni, Cu, Sr, Y, Zr, Ba, La, Ce, Nd, Eu, Yb and Th) were determined by ICP-AE spectrometry in 27 samples of manganese nodules, micronodules as well as abyssal clay collected by dredging from an area of nearly 1,9802 nautical miles in the central Clarion-Clipperton abyssal plain at a depth of about 4,500 m. Statistical analyses were used to compare among individual as well as pooled datasets, in addition to different indicators such as La/Th, Ni/Cu and LREE/HREE ratios for the Clarion-Clipperton samples, as well as between these and corresponding values for the upper continental crust (UCC), North America Shale Composite (NASC), and igneous Indian and Pacific Mid-Ocean Ridge Basalts (MORBs). The results show significant correlations between major components in the Clarion-Clipperton samples and Pacific Ocean MORB, whereas trace elements (excepting Ni and Cu) correlate better with the UCC and NASC. There is also depletion in LREEs, together with a Ce negative anomaly for all Clarion-Clipperton samples. The nodule, micronodule and abyssal clay datasets each reveal typical clusters of components such as P₂O₅ and Y, La, Nd, Eu, Tb, or Ni and Cu. Compared to abyssal clay, the nodule as well as micronodules show significant enrichment in Ni and Cu; nevertheless, an essentially constant Ni/Cu ratio indicates that all samples come from the sediment surface. The distributions of major components as well as trace elements for the Clarion-Clipperton samples present, to different degrees, characteristics common to both the upper continental crust and Mid-Ocean Ridge Basalt, strongly implying a hydrothermal origin, most probably from East Pacific Rise material transported by the Pacific North Equatorial Current.     

The distinctive compositional evolution of glauconite in the Cretaceous Ukra Hill Member (Kutch basin,India) and its implications

An integrated study involving sedimentology, mineral chemistry and spectroscopy highlights a distinctive compositional evolution of Cretaceous glauconite within the Ukra Hill Member. Glauconite occurs at the top part of transgressive systems tract deposits built on a marine shelf. The concentration of glauconite steadily increases towards the maximum flooding surface, maximizing around 50%, and sharply falls at the onset of progradation. Unlike most Phanerozoic examples, Ukra glauconite forms by the variable degree of replacement of quartz, feldspar and mica grains. XRD, FEG-SEM and spectroscopy of glauconite pellets indicate an ‘evolved’ stage of maturation. Mossbauer spectroscopy reflects a minor substitution of Al^3+-Fe³⁺ (total) in tetrahedral sites and significant substitution of the same in octahedral sites. A consistently high value of K₂O as well as Fe₂O₃ contradicts the two popular theories, ‘layer lattice’ and ‘verdissement’, and support replacement origin of glauconite in a high a_Si+ and high a_K+ pore water environment. Incipiently formed glauconite records a marginal increase in K₂O content accompanied by release of Al₂O₃ and SiO₂ to form evolved glauconite pellets; those forming within quartz grains involve an addition of Fe₂O₃ (total) content during maturation. The minimal increase in K₂O content of incipiently formed glauconite, best exhibited by those formed within quartz grains is possibly related to stratigraphic condensation. Compositional evolution like this is exhibited by Precambrian glauconites involving abiotic substrates, but is unusual for the Phanerozoic. Original K₂O and Fe₂O₃ (total) content of glauconites is reduced around peripheries and fractures during diagenesis, adding to compositional variability.     

Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of pH and ionic strength

The sorption of yttrium and the rare earth elements (YREEs) by amorphous ferric hydroxide at low ionic strength (0.01 M ≤ I ≤ 0.09 M) was investigated over a wide range of pH (3.9 ≤ pH ≤ 7.1). YREE distribution coefficients, defined as _iK_Fe = [MS_i]_T / (M_T[Fe³⁺]_S), where [MS_i]_T is the concentration of YREE sorbed by the precipitate, M_T is the total YREE concentration in solution, and [Fe³⁺]_S is the concentration of precipitated iron, are weakly dependent on ionic strength but strongly dependent on pH. For each YREE, the pH dependence of log _iK_Fe is highly linear over the investigated pH range. The slopes of log _iK_Fe versus pH regressions range between 1.43 ± 0.04 for La and 1.55 ± 0.03 for Lu. Distribution coefficients are well described by an equation of the form _iK_Fe = (_Sβ₁[H⁺]^− 1 + _Sβ₂[H⁺]^− 2) / (_SK₁[H⁺] + 1), where _Sβ_n are stability constants for YREE sorption by surface hydroxyl groups and _SK₁ is a ferric hydroxide surface protonation constant. Best-fit estimates of _Sβ_n for each YREE were obtained with log _SK₁ = 4.76. Distribution coefficient predictions, using this two-site surface complexation model, accurately describe the log _iK_Fe patterns obtained in the present study, as well as distribution coefficient patterns obtained in previous studies at near-neutral pH. Modeled log _iK_Fe results were used to predict YREE sorption patterns appropriate to the open ocean by accounting for YREE solution complexation with the major inorganic YREE ligands in seawater. The predicted log _iK_Fe′ pattern for seawater, while distinctly different from log _iK_Fe observations in synthetic solutions at low ionic strength, is in good agreement with results for natural seawater obtained by others.     

CHEMINI: A new in situ CHEmical MINIaturized analyzer

“CHEMINI” is a new instrument developed for the measurement of seawater chemical parameters. It is a mono-parameter in situ chemical analyzer based on flow injection analysis and colorimetric detection. The deep-sea version of CHEMINI combines two modules to perform the analysis of dissolved iron [Fe (II) or Fe (II+III)] and total sulphide (H₂S+HS^?+S^2?) up to 6000 m depth. Detection limits are, respectively, 0.3 and 0.1 μM for iron and sulphide. The system proved highly reliable during the MoMARETO cruise on the Mid-Atlantic Ridge. The two CHEMINIs were used to describe the chemical environment in 12 mussel beds on the Tour Eiffel hydrothermal edifice.     

Petroleum source rock characterisation and hydrocarbon generation modeling of the Cretaceous sediments in the Jiza sub-basin,eastern Yemen

Cretaceous sedimentary rocks of the Mukalla, Harshiyat and Qishn formations from three wells in the Jiza sub-basin were studied to describe source rock characteristics, providing information on organic matter type, paleoenvironment of deposition and hydrocarbon generation potential. This study is based on organic geochemical and petrographic analyses performed on cuttings samples. The results were then incorporated into basin models in order to understand the burial and thermal histories and timing of hydrocarbon generation and expulsion.The bulk geochemical results show that the Cretaceous rocks are highly variable with respect to their genetic petroleum generation potential. The total organic carbon (TOC) contents and petroleum potential yield (S₁ + S₂) of the Cretaceous source rocks range from 0.43 to 6.11% and 0.58–31.14 mg HC/g rock, respectively indicating non-source to very good source rock potential. Hydrogen index values for the Early to Late Cretaceous Harshiyat and Qishn formations vary between 77 and 695 mg HC/g TOC, consistent with Type I/II, II-III and III kerogens, indicating oil and gas generation potential. In contrast, the Late Cretaceous Mukalla Formation is dominated by Type III kerogen (HI < 200 mg HC/g TOC), and is thus considered to be gas-prone. The analysed Cretaceous source rock samples have vitrinite reflectance values in the range of 0.37–0.95 Ro% (immature to peak-maturity for oil generation).A variety of biomarkers including n-alkanes, regular isoprenoids, terpanes and steranes suggest that the Cretaceous source rocks were deposited in marine to deltaic environments. The biomarkers also indicate that the Cretaceous source rocks contain a mixture of aquatic organic matter (planktonic/bacterial) and terrigenous organic matter, with increasing terrigenous influence in the Late Cretaceous (Mukalla Formation).The burial and thermal history models indicate that the Mukalla and Harshiyat formations are immature to early mature. The models also indicate that the onset of oil-generation in the Qishn source rock began during the Late Cretaceous at 83 Ma and peak-oil generation was reached during the Late Cretaceous to Miocene (65–21 Ma). The modeled hydrocarbon expulsion evolution suggests that the timing of oil expulsion from the Qishn source rock began during the Miocene (>21 Ma) and persisted to present-day. Therefore, the Qishn Formation can act as an effective oil-source but only limited quantities of oil can be expected to have been generated and expelled in the Jiza sub-basin.     

Reactivity of dolomitizing fluids and Mg source evaluation of fault-controlled dolomitization at the Benicàssim outcrop analogue (Maestrat basin,E Spain)

The mechanisms responsible for the formation of huge volumes of dolomitized rocks associated with faults are not well understood. We present a case study for high-temperature dolomitization of an Early Cretaceous (Aptian–Albian) ramp in Benicàssim (Maestrat basin, E Spain). In this area, seismic-scale fault-controlled stratabound dolostone bodies extend over several kilometres away from large-scale faults. This work aims at evaluating different Mg sources for dolomitization, estimating the reactivity of dolomitizing fluids at variable temperature and quantifying the required versus available fluid volumes to account for the Benicàssim dolostones. Field relationships, stable ¹³C and ¹⁸O isotopes, as well as radiogenic ⁸⁷Sr/⁸⁶Sr isotopes, indicate that dolomitization at Benicàssim was produced by a high-temperature fluid (>80 °C). ¹³C and ¹⁸O isotopic compositions for dolomite vary from +0.5 to +2.9‰ V-PDB and from +21.1 to +24.3 V-SMOW, respectively. A Mg source analysis reveals that the most likely dolomitizing fluid was seawater-derived brine that interacted with underlying Triassic red beds and the Paleozoic basement. Geochemical models suggest that evolved seawater can be considerably more reactive than high-salinity brines, and the maximum reactivity occurs at about 100 °C. Mass-balance calculations indicate that interstitial fluids with high pressure and/or high temperature relative to the normal geothermal gradient cannot account for the volume of dolomite at Benicàssim. Instead a pervasive fluid circulation mechanism, like thermal convection, is required to provide a sufficient volume of dolomitizing fluid, which most likely occurred during the Late Cretaceous post-rift stage of the Maestrat basin. This study illustrates the importance of fluid budget quantification to critically evaluate genetic models for dolomitization and other diagenetic processes.     

Geochemical characteristics of the Paleogene shales in the Dongying depression,eastern China

Fluctuations in lacustrine sedimentary environments significantly affect distributions of organic matter (OM), uranium, and other elements in shales. In this study a high-resolution geochemical record of fluctuations in the paleo-depositional environment of a terrestrial lake basin is provided on the basis of extensive samples collected from the Member 3 of the Paleogene Shahejie Formation (Es₃) of the Niu-38 well in the Dongying Depression, Eastern China. These samples were tested for total organic carbon (TOC), element concentrations, and biomarkers to study the evolution and fluctuation in the depositional environments of an ancient lake basin and associated geochemical response. The evolution and fluctuation of the sedimentary environment from a deep lake to a semi-deep lake and then to a shallow lake delta were indicated by geochemical response. During this evolution, the values of TOC, S₁, S₂, Sr, and Ts/(Ts + Tm) remarkably decreased, whereas those of Co, Ni, Rb, Na, Fe/Mn, Fe/(Ca + Mg), and C₂₉ mortane/C₂₉ hopane significantly increased. The deep lake basin shows depositional fluctuations, as indicated by rock lithofacies and their geochemical parameters. A close interrelationship was observed among U concentration, TOC content, and inorganic element content. Uranium concentrations are positively correlated with TOC contents, Ca and Sr concentrations, and Sr/Ba and Ca/Mg ratios but negatively with K, Na, Ba, and Rb contents and Fe/(Ca + Mg) and Fe/Mn ratios. The observed increase in U concentration in the lower Es₃ section is closely related to surface adsorption by clay minerals and OM, together with some replacements of Ca and Sr by U in the shales.     

Ascending and descending particle flux from hydrothermal plumes at Endeavour Segment,Juan de Fuca Ridge

Bio-acoustic surveys and associated zooplankton net tows have documented anomalously high concentrations of zooplankton within a 100 m layer above the hydrothermal plumes at Endeavour Segment, Juan de Fuca Ridge. These and other data suggest that congregating epi-plume zooplankton are exploiting a food substrate associated with the hydrothermal plume. Ascending, organic-rich particles could provide a connection. Consequently, two paired sequentially sampling ascending and descending particle flux traps and a current meter were deployed on each of three moorings from July 1994 to May 1995. Mooring sites included an on-axis site (OAS; 47°57.0′N, 129°05.7′W) near the main Endeavour vent field, a “down-current” site 3 km west of the main vent field (WS), and a third background station 43 km northeast of the vent field (ES). Significant ascending and descending particle fluxes were measured at all sites and depths. Lipid analyses indicated that ascending POC was derived from mid-depth and deep zooplankton whereas descending POC also contained a component of photosynthetically derived products from the sea surface. Highest ascending POC fluxes were found at the hydrothermal plume-swept sites (OAS and WS). The limited data available, however, precludes an unequivocal conclusion that hydrothermal processes contribute to the ascending flux of organic carbon at each site. Highest ascending to descending POC flux ratios were also found at WS. Observed trends in POC, PMn/PTi, and PFe/PTi clearly support a hydrothermal component to the descending flux at the plume-swept WS site (no descending data was recovered at OAS) but not at the background ES site. Alternative explanations for ascending particle data are discussed. First-order calculations for the organic carbon input (5–22 mg C m⁻² d⁻¹) required to sustain observed epi-plume zooplankton anomalies at Endeavour are comparable both to measured total POC flux to epi-plume depths (2–5 mg C m⁻² d⁻¹: combined hydrothermal and surface derived organic carbon) and to estimates of the total potential in situ organic carbon production (2–9 mg C m⁻² d⁻¹) from microbial oxidation of hydrothermal plume H₂, CH₄ and NH₄⁺.     

Paleogene igneous intrusion and its effect on thermal maturity of organic-rich mudstones in the Beibuwan Basin,South China Sea

The seismic, drilling and logging data reveal that a large-scale igneous intrusion with a width of 14 Km and a maximum thickness of 170 m intruded within the Paleogene Liushagang Formation in the Fushan Depression, Beibuwan Basin, South China Sea (SCS). In this study, we report the geochemistry and Sr-Nd-Pb-Hf isotopic compositions of the igneous rocks, and evaluate the thermal effect induced by this large-scale igneous intrusion on the host rocks. The analyzed igneous samples exhibit strong enrichment in light rare earth elements (LREE) and large-ion lithophile elements (LILE), having characteristics similar to intra-plate oceanic island basalts (OIB). The Sr-Nd-Pb-Hf isotopic data display narrow ranges (e.g. ⁸⁷Sr/⁸⁶Sr_i = 0.7042–0.7044, ¹⁴³Nd/¹⁴⁴Nd_i = 0.5128–0.5129, ²⁰⁶Pb/²⁰⁴Pb_i = 18.90–18.94, εHf(t) = +7.56∼+9.60). Geochemical and isotopic compositions suggest a mixed mantle source between depleted mid-ocean-ridge-basalt (MORB) mantle (DMM)-like mantle and enriched mantle type II (EMII, possibly the Hainan mantle plume). Vitrinite reflectance values, major mineralogical changes together with a maturity-related biomarker [Ts/(Ts + Tm)] all reveal significant thermal effect induced by the igneous intrusion. Vitrinite reflectance values of the host rock are up to 2.5% in the intrusion region, whereas lower reflectance values (0.62–0.73%) occur in the unaffected area of the same strata. Moreover, our results suggest that the host rocks above the igneous intrusion are characterised by higher maturity than below, which should be attributed to the different behavior of hydrothermal fluids. These observations suggest that the thermal effect of large-scale thick igneous intrusions is much more intense than that of thin igneous intrusions, and the behavior of hydrothermal fluids induced by magmatic intrusive events should be a critical impact factor during heat transfer process.     

Seawater normalized REE patterns of dolomites in Geshan and Panlongdong sections,China: Implications for tracing dolomitization and diagenetic fluids

In conventional studies of tracing dolomitization and diagenetic fluids, REEs of dolomites were widely used as been normalized by PAAS, NASC or chondrite. However, most dolomites are formed in seawater or seawater-derived fluids. Thus, we conduct a new attempt to normalize the REEs of dolomite using seawater standard, based on case studies on 36 Triassic limestone–dolomite samples from the Geshan section of southeast China and 26 Permian–Triassic dolomite samples from the Panlongdong section of northeastern Sichuan Basin, southwest China.The Geshan seawater-normalized (SN) REE patterns are characterized by notable positive Ce_SN (average Ce_SN/Ce* = 6.823, SD = 0.192) and negative Pr_SN anomalies (average Pr_SN/Pr* = 0.310, SD = 0.010), and slightly negative Gd_SN anomalis (average Gd_SN/Gd* = 0.864, SD = 0.053), with no obvious Eu_SN anomaly (average Eu_SN/Eu* = 1.036, SD = 0.094). The signatures of REE patterns barely changed during the dolomitization process. For the REE compositions of the Panlongdong dolomite, it can be found that (1) the recrystallization process can result in varied total REE concentrations (between 7.16 ppm and 37.87 ppm), but do not alter the REE patterns, including consistent positive Ce_SN anomalies (average = 4.074, SD = 0.27) and LREE enrichment (average Nd_SN/Yb_SN = 3.164, SD = 0.787); (2) meteoric incursion can reverse Ce anomaly, from the strong positive Ce anomalies (Ce_SN/Ce* = 5.059) to slightly positive (Ce_SN/Ce* = 2.459) or even negative Ce anomalies; and (3) hydrothermal fluid altered REE pattern is complicated by fluctuated distribution curve, negative Ce anomaly and positive Eu anomaly (Eu_SN/Eu* = 1.862). These results suggest that the seawater normalized REE patterns of dolomite can serve as an index to study the source of the dolomitization fluids and distinguish complex diagenetic processes, providing a complement to previous works.     

Geochemistry,reservoir characterization and hydrocarbon generation potential of lacustrine shales: A case of YQ-1 well in the Yuqia Coalfield,northern Qaidam Basin,NW China

Ever since a breakthrough of marine shales in China, lacustrine shales have been attracting by the policy makers and scientists. Organic-rich shales of the Middle Jurassic strata are widely distributed in the Yuqia Coalfield of northern Qaidam Basin. In this paper, a total of 42 shale samples with a burial depth ranging from 475.5 m to 658.5 m were collected from the Shimengou Formation in the YQ-1 shale gas borehole of the study area, including 16 samples from the Lower Member and 26 samples from the Upper Member. Geochemistry, reservoir characteristics and hydrocarbon generation potential of the lacustrine shales in YQ-1 well were preliminarily investigated using the experiments of vitrinite reflectance measurement, maceral identification, mineralogical composition, carbon stable isotope, low-temperature nitrogen adsorption, methane isothermal adsorption and rock eval pyrolysis. The results show that the Shimengou shales have rich organic carbon (averaged 3.83%), which belong to a low thermal maturity stage with a mean vitrinite reflectance (R_o) of 0.49% and an average pyrolytic temperature of the generated maximum remaining hydrocarbon (T_max) of 432.8 °C. Relative to marine shales, the lacustrine shales show low brittleness index (averaged 34.9) but high clay contents (averaged 55.1%), high total porosities (averaged 13.71%) and great Langmuir volumes (averaged 4.73 cm⁻³ g). Unlike the marine and marine-transitional shales, the quartz contents and brittleness index (BI) values of the lacustrine shales first decrease then increase with the rising TOC contents. The kerogens from the Upper Member shales are dominant by the oil-prone types, whereas the kerogens from the Lower Member shales by the gas-prone types. The sedimentary environment of the shales influences the TOC contents, thus has a close connection with the hydrocarbon potential, mineralogical composition, kerogen types and pore structure. Additionally, in terms of the hydrocarbon generation potential, the Upper Member shales are regarded as very good and excellent rocks whereas the Lower Member shales mainly as poor and fair rocks. In overall, the shales in the top of the Upper Member can be explored for shale oil due to the higher free hydrocarbon amount (S₁), whereas the shales in the Lower Member and the Upper Member, with the depths greater than 1000 m, can be suggested to explore shale gas.     

Metalliferous Sediment and a Silica-Hematite Deposit within the Blanco Fracture Zone,Northeast Pacific

A Tiburon ROV dive within the East Blanco Depression (EBD) increased the mapped extent of a known hydrothermal field by an order of magnitude. In addition, a unique opal-CT (cristobalite-tridymite)-hematite mound was discovered, and mineralized sediments and rock were collected and analyzed. Silica-hematite mounds have not previously been found on the deep ocean floor. The light-weight rock of the porous mound consists predominantly of opal-CT and hematite filaments, rods, and strands, and averages 77.8% SiO₂ and 11.8% Fe₂O₃. The hematite and opal-CT precipitated from a low-temperature (≥ 115° C), strongly oxidized, silica- and iron-rich, sulfur-poor hydrothermal fluid; a bacterial mat provided the framework for precipitation.

Samples collected from a volcaniclastic rock outcrop consist primarily of quartz with lesser plagioclase, smectite, pyroxene, and sulfides; SiO₂ content averages 72.5%. Formation of these quartz-rich samples is best explained by cooling in an up-flow zone of silica-rich hydrothermal fluids within a low permeability system. Opal-A, opal-CT, and quartz mineralization found in different places within the EBD hydrothermal field likely reflects decreasing silica saturation and increasing temperature of the mineralizing fluid with increasing silica crystallinity.

Six push cores recovered gravel, coarse sand, and mud mineralized variously by Fe or Mn oxides, silica, and sulfides. Total rare-earth element concentrations are low for both the rock and push core samples. Ce and Eu anomalies reflect high and low temperature hydrothermal components and detrital phases.

A remarkable variety of types of mineralization occur within the EBD field, yet a consistent suite of elements is enriched (relative to basalt and unmineralized cores) in all samples analyzed: Ag, Au, S, Mo, Hg, As, Sb, Sr, and U; most samples are also enriched in Cu, Pb, Cd, and Zn. On the basis of these element enrichments, the EBD hydrothermal field might best be described as a base- and precious-metal-bearing, silica-Fe-oxide-barite deposit. Such deposits are commonly spatially and temporally associated with volcanogenic massive sulfide (VMS) ores. A plot of data for pathfinder elements shows a large hot spot at the northwestern margin of the field, which may mark a region where moderate to high temperature sulfide deposits are forming at depth; further exploration of the hydrothermal field to the northwest is warranted.     

Geochemistry and stable isotope constraints on high-temperature activity from sediment cores of the Saldanha hydrothermal field

The Saldanha hydrothermal field is hosted atop a mafic–ultramafic seamount, located at a non-transform offset on the Mid-Atlantic Ridge. Previous observations revealed a field where transparent low-temperature fluids discharge through centimeter-sized vents without the formation of chimney structures. We present geochemical and stable isotope (O and C) analyses from sediment samples collected at this field, both at and far from the vent area. Most sediments, including some directly adjacent to orifice vents, are pelagic oozes with only a weak hydrothermal overprinting. Hydrothermal precipitates are characterized by Fe–Mn oxyhydroxides and a minor amount of Cu–Zn sulphide minerals. However, one of the cores (SCD7) collected at the vent area shows a much stronger hydrothermal signature. This core is composed of a matrix of serpentine + talc ± chlorite with high porosity, where calcite + chalcopyrite + sphalerite/wurtzite ± pyrite–pyrrhotite were precipitated. In this core, metal enrichments, REE patterns, and the oxygen and carbon isotope composition of calcites indicate that mineralization must have occurred in the subsurface by high-temperature fluids, with minor mixing with seawater and with a significant magmatic contribution. Thus, while most samples confirm previous findings indicating that Saldanha hydrothermal fluid discharge is mainly diffuse and of low temperature, data from core SCD7 suggest that areas of high-temperature hydrothermal activity also occur, where temperatures of the fluids could reach > 260 °C and maximum temperatures of 330 °C. We suggest that fluids can flow through faults at the top of the mount and discharge in a more focused way through vent orifices, producing intense hydrothermal alteration of the sediments. At these locations complex hydrothermal processes occur, including reactions of the hydrothermal fluids with mafic and ultramafic rocks and magma degassing, as suggested by the carbon isotope composition of hydrothermal calcites. The high temperature of the fluid inferred from the geochemistry of the hydrothermal minerals requires a significant heat input to the system, suggesting an additional magmatic heat source to the already proposed exothermic serpentinization reactions.     

Volcanic rock alterations of the Kwanza Basin,offshore Angola - Insights from an integrated petrological,geochemical and numerical approach

The Lower Cretaceous presalt section of the Kwanza Basin (Angola) is in the spotlight following the discoveries of petroleum systems in this basin, and more generally in the South Atlantic. These systems are mostly composed of continental carbonates in close association with volcanic rocks. This work is focused on the study of an offshore Kwanza presalt volcanic sequence characterized as Valanginian trachytic subaerial lava flows. A detailed petrological analysis of the altered trachyte in association with fluid inclusion microthermometry was conducted in order to depict the initial mineralogy (albite, sanidine, titanomagnetite) and obtain a paragenetic sequence (quartz, siderite, kaolinite, calcite). Thermodynamic equilibrium modelling of the trachytes alteration by meteoric fluids, over a range of temperatures (25 °C–200 °C) and CO₂ partial pressure (pCO₂: 0.01 mbar to 100 bar), were performed with PHREEQC, and compared to the observed paragenetic sequence. Some numerical simulations reflect the observed paragenesis. As a result, the pCO₂ is constrained by the occurrence of siderite (from 0.1 bar at 50 °C to 30 bar at 125 °C) and kaolinite (from 0.2 bar at 50 °C to 1.2 bar at 125 °C). The simulations emphasize the need for a high pCO₂ in the hydrothermal system, to achieve the observed trachyte transformation. After reaching equilibrium with the trachytes, the simulated fluids highlight a mid-alkaline to near neutral pH with high Fe, HCO₃+CO₃, and alkali concentrations. The palaeofluids could have evolved from Ca- and Mg-rich to Ca- and Mg-poor with increasing temperature. Inversely, Si concentrations are positively correlated with increasing temperatures. This methodology, integrating a petrological approach and numerical simulations, proves to be a powerful tool leading to better understanding of the proxies (pCO₂, temperature, redox conditions) controlling paragenesis. To push further, these simulations are also a step toward improved understanding of palaeofluid evolutions in presalt systems and better prediction of reservoir quality.     

Enrichment and distribution of shale oil in the Cretaceous Qingshankou Formation,Songliao Basin,Northeast China

The Songliao Basin is a large-scale petroliferous basin in China. With a gradual decline in conventional oil production, the exploration and development of replacement resources in the basin is becoming increasingly important. Previous studies have shown that the Cretaceous Qingshankou Formation (K₂qn) has favorable geological conditions for the formation of shale oil. Thus, shale oil in the Qingshankou Formation represents a promising and practical replacement resource for conventional oil. In this study, geological field surveys, core observation, sample tests, and the analysis of well logs were applied to study the geochemical and reservoir characteristics of shales, identify shale oil beds, build shale oil enrichment models, and classify favorable exploration areas of shale oil from the Cretaceous Qingshankou Formation. The organic matter content is high in shales from the first member of the Cretaceous Qingshankou Formation (K₂qn¹), with average total organic carbon (TOC) content exceeding 2%. The organic matter is mainly derived from lower aquatic organisms in a reducing brackish to fresh water environment, resulting in mostly type I kerogen. The vitrinite reflectance (Ro) and the temperature at which the maximum is release of hydrocarbons from cracking of kerogen occurred during pyrolysis (T_max) respectively range from 0.5% to 1.1% and from 430 °C to 450 °C, indicating that the K₂qn¹ shales are in the low-mature to mature stage (Ro ranges from 0.5% to 1.2%) and currently generating a large amount of oil. The favorable depth for oil generation and expulsion is 1800–2200 m and 1900–2500 m, respectively as determined by basin modeling. The reserving space of the K₂qn¹ shale oil includes micropores and mircofractures. The micropore reservoirs are developed in shales interbedded with siltstones exhibiting high gamma ray (GR), high resistivity (Rt), low density (DEN), and slightly abnormal spontaneous potential (SP) in the well-logging curves. The microfracture reservoirs are mainly thick shales with high Rt, high AC (acoustic transit time), high GR, low DEN, and abnormal SP. Based on the shale distribution, geochemical characteristics, reservoir types, fracture development, and the process of shale oil generation and enrichment, the southern Taikang and northern Da'an are classified as two favorable shale oil exploration areas in the Songliao Basin.     

Effects of irradiance on benthic and water column processes in a Gulf of Mexico estuary: Pensacola Bay, Florida, USA

We examined the effect of light on water column and benthic fluxes in the Pensacola Bay estuary, a river-dominated system in the northeastern Gulf of Mexico. Measurements were made during the summers of 2003 and 2004 on 16 dates distributed along depth and salinity gradients. Dissolved oxygen fluxes were measured on replicate sediment and water column samples exposed to a gradient of photosynthetically active radiation. Sediment inorganic nutrient (NH₄⁺, NO₃⁻, PO₄³⁻) fluxes were measured. The response of dissolved oxygen fluxes to variation in light was fit to a photosynthesis–irradiance model and the parameter estimates were used to calculate daily integrated production in the water column and the benthos. The results suggest that shoal environments supported substantial benthic productivity, averaging 13.6 ± 4.7 mmol O₂ m⁻² d⁻¹, whereas channel environments supported low benthic productivity, averaging 0.5 ± 0.3 mmol O₂ m⁻² d⁻¹ (±SE). Estimates of baywide microphytobenthic productivity ranged from 8.1 to 16.5 mmol O₂ m⁻² d⁻¹, comprising about 16–32% of total system productivity. Benthic and water column dark respiration averaged 15.2 ± 3.2 and 33.6 ± 3.7 mmol O₂ m⁻² d⁻¹, respectively Inorganic nutrient fluxes were generally low compared to relevant estuarine literature values, and responded minimally to light exposure. Across all stations, nutrient fluxes from sediments to the water column averaged 1.11 ± 0.98 mmol m⁻² d⁻¹ for NH₄⁺, 0.58 ± 1.08 mmol m⁻² d⁻¹ for NO₃⁻, 0.01 ± 0.09 mmol m⁻² d⁻¹ for PO₄³⁻. The results of this study illustrate how light reaching the sediments is an important modulator of benthic nutrient and oxygen dynamics in shallow estuarine systems.     

Actinide speciation in aquatic systems

Nuclear test explosions and reactor wastes have deposited an estimated 16 × 10¹⁵ Bq of plutonium into the world's aquatic systems. However, plutonium concentration in open ocean waters is on the order 10^− 5 Bq/kg, indicating that most of the plutonium is quite insoluble in marine waters and has been incorporated into sediments. Actinide ions often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides were introduced into the aquatic system.Actinide solubility depends on such factors as the pH (hydrolysis), Eh (oxidation state), reaction with complexants (e.g., carbonate, phosphate, humic acid, etc.), sorption to surfaces of minerals and/or colloids etc., in the water. The most significant of these variables is the oxidation state of the metal ion. The simultaneous presence of more than one oxidation state for some actinides (e.g., plutonium) in a solution complicates actinide environmental behavior. Both Np(V)O₂⁺ and Pu(V)O₂⁺, the most significant states in natural, oxic waters are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation. The solubility of NpO₂⁺ can be as high as 10^− 4 M while that of PuO₂⁺ is limited by reduction to the insoluble tetravalent species, Pu(OH₄), (pK_sp = 56). The net solubility of hexavalent UO₂²⁺ in sea water is also limited by hydrolysis; however, it has a relatively high concentration due to formation carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(CO)₃(OH), is limiting species for the solubility of Am(III) in sea water. Thorium is found exclusively as the tetravalent species and its solubility is limited by the formation of quite insoluble Th(OH)₄.The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in natural waters which must be considered in assessing the environmental behavior of actinides. While much is understood about sorption of actinides on surfaces, the mode of migration of actinides in such waters and the potential effects of these radioactive species on marine bioto, much more is needed for a satisfactory understanding of the behavior of the actinides in the environment.     

Rates and regulation of nitrogen cycling in seasonally hypoxic sediments during winter (Boknis Eck,SW Baltic Sea): Sensitivity to environmental variables

This study investigates the biogeochemical processes that control the benthic fluxes of dissolved nitrogen (N) species in Boknis Eck – a 28 m deep site in the Eckernförde Bay (southwestern Baltic Sea). Bottom water oxygen concentrations (O_2−BW) fluctuate greatly over the year at Boknis Eck, being well-oxygenated in winter and experiencing severe bottom water hypoxia and even anoxia in late summer. The present communication addresses the winter situation (February 2010). Fluxes of ammonium (NH₄⁺), nitrate (NO₃⁻) and nitrite (NO₂⁻) were simulated using a benthic model that accounted for transport and biogeochemical reactions and constrained with ex situ flux measurements and sediment geochemical analysis. The sediments were a net sink for NO₃⁻ (−0.35 mmol m⁻² d⁻¹ of NO₃⁻), of which 75% was ascribed to dissimilatory reduction of nitrate to ammonium (DNRA) by sulfide oxidizing bacteria, and 25% to NO₃⁻ reduction to NO₂⁻ by denitrifying microorganisms. NH₄⁺ fluxes were high (1.74 mmol m⁻² d⁻¹ of NH₄⁺), mainly due to the degradation of organic nitrogen, and directed out of the sediment. NO₂⁻ fluxes were negligible. The sediments in Boknis Eck are, therefore, a net source of dissolved inorganic nitrogen (DIN = NO₃⁻ + NO₂⁻ + NH₄⁺) during winter. This is in large part due to bioirrigation, which accounts for 76% of the benthic efflux of NH₄⁺, thus reducing the capacity for nitrification of NH₄⁺. The combined rate of fixed N loss by denitrification and anammox was estimated at 0.08 mmol m⁻² d⁻¹ of N₂, which is at the lower end of previously reported values. A systematic sensitivity analysis revealed that denitrification and anammox respond strongly and positively to the concentration of NO₃⁻ in the bottom water (NO₃⁻_BW). Higher O_2−BW decreases DNRA and denitrification but stimulates both anammox and the contribution of anammox to total N₂ production (%R_amx). A complete mechanistic explanation of these findings is provided. Our analysis indicates that nitrification is the geochemical driving force behind the observed correlation between %R_amx and water depth in the seminal study of Dalsgaard et al. (2005). Despite remaining uncertainties, the results provide a general mechanistic framework for interpreting the existing knowledge of N-turnover processes and fluxes in continental margin sediments, as well as predicting the types of environment where these reactions are expected to occur prominently.