Diagenesis and origin of calcite cement in the Flemish Pass Basin sandstone reservoir (Upper Jurassic): Implications for porosity development

The Flemish Pass Basin is a deep-water basin located offshore on the continental passive margin of the Grand Banks, eastern Newfoundland, which is currently a hydrocarbon exploration target. The current study investigates the petrographic characteristics and origin of carbonate cements in the Ti-3 Member, a primary clastic reservoir interval of the Bodhrán Formation (Upper Jurassic) in the Flemish Pass Basin.The Ti-3 sandstones with average Q_86.0F_3.1R_10.9 contain various diagenetic minerals, including calcite, pyrite, quartz overgrowth, dolomite and siderite. Based on the volume of calcite cement, the investigated sandstones can be classified into (1) calcite-cemented intervals (>20% calcite), and (2) poorly calcite-cemented intervals (porous). Petrographic analysis shows that the dominant cement is intergranular poikilotopic (300–500 μm) calcite, which stared to form extensively at early diagenesis. The precipitation of calcite occured after feldspar leaching and was followed by corrosion of quartz grains. Intergranular calcite cement hosts all-liquid inclusions mainly in the crystal core, but rare primary two-phase (liquid and vapor) fluid inclusions in the rims ((with mean homogenization temperature (T_h) of 70.2 ± 4.9 °C and salinity estimates of 8.8 ± 1.2 eq. wt.% NaCl). The mean δ¹⁸O and δ¹³C isotopic compositions of the intergranular calcite are −8.3 ± 1.2‰, VPDB and −3.0 ± 1.3‰, VPDB, respectively; whereas, fracture-filling calcite has more depleted δ¹⁸O but similar δ¹³C values. The shale normalized rare earth element (REE_SN) patterns of calcite are generally parallel and exhibit slightly negative Ce anomalies and positive Eu anomalies. Fluid-inclusion gas ratios (CO₂/CH₄ and N₂/Ar) of calcite cement further confirms that diagenetic fluids originated from modified seawater. Combined evidence from petrographic, microthermometric and geochemical analyses suggest that (1) the intergranular calcite cement precipitated from diagenetic fluids of mixed marine and meteoric (riverine) waters in suboxic conditions; (2)the cement was sourced from the oxidation of organic matters and the dissolution of biogenic marine carbonates within sandstone beds or adjacent silty mudstones; and (3) the late phases of the intergranular and fracture-filling calcite cements were deposited from hot circulated basinal fluids.Calcite cementation acts as a main controlling factor on the reservoir quality in the Flemish Pass reservoir sandstones. Over 75% of initial porosity was lost due to the early calcite cementation. The development of secondary porosity (mostly enlarged, moldic pores) and throats by later calcite dissolution due to maturation of organic matters (e.g., hydrocarbon and coals), was the key process in improving the reservoir quality.     

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.     

Rare earth element characteristics of the carboniferous Huanglong Formation dolomites in eastern Sichuan Basin,southwest China: Implications for origins of dolomitizing and diagenetic fluids

Marine dolostones of Carboniferous Huanglong Formation constitute major gas reservoir rocks in eastern Sichuan Basin. However, the investigation with respect to sources of dolomitizing and diagenetic fluids is relatively underexplored. The current study attempts to investigate the REE characteristics of dolomites using seawater normalization standard, and therefore discusses the origins of dolomitizing and diagenetic fluids, on the basis of continuous 47.33-m-long core samples from the second member of Huanglong Formation (C₂h₂) in eastern Sichuan Basin. Low Th, Sc, and Hf concentrations (0.791 × 10⁻⁶, 4.751 × 10⁻⁶, and 0.214 × 10⁻⁶, respectively), random correlation between total REE concentration (ΣREE) and Fe or Mn abundance, and seawater-like Y/Ho ratios (mean value of 45.612) indicate that the carbonate samples are valid for REE analysis. Based on petrographic characteristics, four dolomite types are identified, including micritic-sized dolomite (type Dol-1), fine-to medium-sized dolomite (type Dol-2), medium-to coarse-sized dolomite (type Dol-3), and coarse-to giant-sized saddle dolomite (type Dol-4). Dol-1 dolomites, characterized by positive Ce anomaly (mean value of 6.398), light REE (LREE) enrichment, and heavy REE (HREE) depletion with mean LREE/HREE ratio of 12.657, show micritic calcite-like REE patterns, indicating seawater origin of their dolomitizing fluids. Dol-1 dolomites were formed in sabkha environment whereas the dolomitizing fluids originated from evaporative brine water due to their micritic crystal sizes and tight lithology. Dol-2 dolomites, particularly subtype Dol-2a barely developing vuggy porosity, also show micritic calcite-like REE patterns, suggesting their dolomitizing fluids were seawater or seawater-derived fluids. This inference is confirmed by low Fe and Mn concentrations, which range from 651 μg/g to 1018 μg/g (mean value of 863 μg/g) and 65 μg/g to 167 μg/g (mean value of 105 μg/g), respectively, whereas homogenization temperatures (T_h, mean value of 103 °C) indicate that Dol-2 dolomites were formed under burial environment. Dol-3 dolomites, in form of cements of Dol-2 dolomites, show similar REE patterns to their host minerals (i.e., Dol-2 dolomites), indicating their parent source was possibly derived from Dol-2 dolomites. Dol-3 dolomites have high Fe and Mn concentrations with mean values of 3346 μg/g (ranging from 2897 μg/g to 3856 μg/g) and 236 μg/g (ranging from 178 μg/g to 287 μg/g), respectively, indicating the involvement of meteoric water. Meanwhile, it confirms that the dissolution in Dol-2 dolomites was caused by meteoric water leaching. Positive Eu anomalies (mean value of 1.406) in Dol-4 dolomites, coupled with high homogenization temperatures (mean value of 314 °C), suggest that Dol-4 dolomites precipitated from hydrothermal fluids. High Fe and Mn concentrations (mean values of 2521 μg/g and 193 μg/g, respectively) in Dol-4 dolomites likely results from interactions of hydrothermal fluids with deep burial clastic rocks.     

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.     

Rare earth elements in cold seep carbonates from the southwestern Dongsha area,northern South China Sea

The circulation of methane-rich fluids at cold seeps often leads to the precipitation of seep carbonates close to the seafloor along continental margins, which can be used as records of past fluid seepage. Rare earth element (REE) concentrations in seep carbonates have been used to trace fluid sources and provide information on associated biogeochemical processes at cold seeps. The REE concentrations of a series of carbonates collected from cold seeps in the southwestern Dongsha area of the northern South China Sea are analyzed in this study. The total REE contents (ΣREE) of the seep carbonates analyzed show a wide variation from 17 ppm to 523 ppm with an average ΣREE value of 54 ppm, which are higher than the typical marine carbonate values of ∼28 ppm commonly reported and also higher than those of the carbonates from other cold seep areas. A positive correlation between Fe–Mn content and ΣREE was observed. These results suggest that the seep carbonates of this study were primarily controlled by the methane-derived fluid from which they precipitated. The Fe-rich dolomite and siderite, which are the main components of the carbonates, are responsible for the enrichment of the REE. A slight positive Ce anomaly observed in the shale-normalized REE patterns of the studied seep carbonates suggests that they formed in anoxic conditions, and the correlations between Ce/Ce* and La_N/Sm_N, Ce/Ce* and Dy_N/Sm_N, Ce/Ce* and ΣREE further reveal that the REE characteristics of most seep carbonate samples preserve the original redox conditions in which they precipitated and late diagenesis has had little effect on the REE. However, the REE characteristics of sub-samples DS2-2B, DS1-6A and DS1-7A are very different from those of the other sub-samples, indicating a greater impact of late diagenesis and post-oxidation favored REE enrichment.     

Stable isotopes of carbon and nitrogen in suspended matter and sediments from the Godavari estuary

Spatial distribution of the carbon and nitrogen content and their isotopic enrichment in suspended matter and sediments were measured in the Godavari estuary to identify the sources and transformation mechanism of organic matter. Significant variability in isotopic distribution was found over the entire length of the Godavari estuary, suggesting multiple sources of organic matter. The mean isotopic ratios (δ¹³C_sed −25.1 ± 0.9, δ¹³C_sus −24.9 ± 1, δ¹⁵N_sed 8.0 ± 2 and δ¹⁵N_sus 6.5 ± 0.9‰) and elemental concentrations (C_sed 0.45 ± 0.2%, C_sus 0.9 ± 0.7%, N_sed 0.07 ± 0.05% and N_sus 0.16 ± 0.1%) support a predominantly terrigenous source. Significant enrichment in the isotopic ratios of δ¹³C from the upper to lower estuary in both suspended (−27.5 and −24.3‰, respectively) and sedimentary (−26.2 and −24.9‰, respectively) phases indicates a decrease in the influence of terrigeneous material toward the mouth of the estuary. A significant positive relationship exists between the δ¹³C of suspended and sediment, which indicates that these two organic carbon pools are likely coupled in the form of a significant exchange between the two phases. A positive relationship exists between chlorophyll a and suspended organic matter, which may mean that a significant source of organic carbon is the in situ produced phytoplankton. But, applying a simple mixing model to our isotopes, data yielded about 46% as the contribution of the terrestrial source to suspended matter, which may support the excessive heterotrophic activity in the Godavari estuary reported earlier.     

Denitrification prevails over anammox in tropical mangrove sediments (Goa,India)

Denitrification, anammox (Anx) and di-nitrogen fixation were examined in two mangrove ecosystems- the anthropogenically influenced Divar and the relatively pristine Tuvem. Stratified sampling at 2 cm increments from 0 to 10 cm depth revealed denitrification as the main process of N₂ production in mangrove sediments. At Divar, denitrification was ∼3 times higher than at Tuvem with maximum activity of 224.51 ± 6.63 nmol N₂ g⁻¹ h⁻¹ at 0–2 cm. Denitrifying genes (nosZ) numbered up to 2 × 10⁷ copies g⁻¹ sediment and belonged to uncultured microorganisms clustering within Proteobacteria. Anammox was more prominent at deeper depths (8–10 cm) mainly in Divar with highest activity of 101.15 ± 87.73 nmol N₂ g⁻¹ h⁻¹ which was 5 times higher than at Tuvem. Di-nitrogen fixation was detected only at Tuvem with a maximum of 12.47 ± 8.36 nmol N₂ g⁻¹ h⁻¹. Thus, in these estuarine habitats prone to high nutrient input, N₂-fixation is minimal and denitrification rather than Anx serves as an important mechanism for counteracting N loading.     

Metabolic activity of pelagic copepods from 5,000 to 7,000 m depth of the western subarctic Pacific,as inferred from electron transfer system (ETS) activity

This study demonstrates reduced electron transfer system (ETS) activity of mixed copepods collected from 5,000 to 7,000 m depths [3.21 ± 1.25 μl O₂ (mg protein)⁻¹ h⁻¹ at 10°C] as compared with mixed copepods from 0 to 200 m depths [5.93 ± 1.66 μl O₂ (mg protein)⁻¹ h⁻¹ at 10°C] of the western subarctic Pacific. At the in situ temperature of 1.5°C, the 5,000–7,000 m ETS data, in terms of wet mass (WM)-specific respiration rates (R), is equivalent to [0.052 ± 0.021 μl O₂ (mg WM)⁻¹ h⁻¹] which is similar to or greater than those reported for selected copepods or mixed mesozooplankton from <5,000 m depth by previous workers.     

Authigenic carbonates from methane seeps of the northern Congo fan: Microbial formation mechanism

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The δ¹³C values of the Hydrate Hole carbonates range from ?62.5‰ to ?46.3‰ PDB, while the δ¹³C values of the Diapir Field carbonate are somewhat higher, ranging from ?40.7‰ to ?30.7‰ PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of ¹⁸O (δ¹⁸O values as high as 5.2‰ PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO₃-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in δ¹³C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.     

Precise determination of the cerium isotopic compositions of surface seawater in the Northwest Pacific Ocean and Tokyo Bay

We succeeded in determining the Ce isotopic composition (¹³⁸Ce/¹⁴²Ce) in seawater with an error of 2σ_m = 0.3–0.7 of ε unit. In this study, 1000–3000 L of seawater samples were passed through MnO₂ fibers to concentrate Ce and Nd for precise measurement of their isotope ratios. Four surface seawater samples of the northwestern Pacific and a coastal sample in Tokyo Bay were analyzed. Most Ce isotope ratios in the surface water showed positive ε_Ce values (+ 0.8 to + 1.4) in the northwestern Pacific Ocean. These values indicate that Ce in the surface water originates from the continental crust preferentially over mantle-derived materials. We examined binary mixing model between the continental crust and mid-ocean ridge basalt. However the model could not explain both isotopic compositions and concentrations, which implies that the atmospheric input was a possible pathway for Ce into the ocean. A negative ε_Ce value was observed in Tokyo Bay, suggesting mantle-derived sources.     

Isotopic constraints on the Si-biogeochemical cycle of the Antarctic Zone in the Kerguelen area (KEOPS)

Estimation of the silicon (Si) mass balance in the ocean from direct measurements (Si uptake-dissolution rates …) is plagued by the strong temporal and spatial variability of the surface ocean as well as methodological artifacts. Tracers with different sensitivities toward physical and biological processes would be of great complementary use. Silicon isotopic composition is a promising proxy to improve constraints on the Si-biogeochemical cycle, since it integrates over longer timescales in comparison with direct measurements and since the isotopic balance allows to resolve the processes involved, i.e. uptake, dissolution, mixing. Si-isotopic signatures of seawater Si(OH)₄ and biogenic silica (bSiO₂) were investigated in late summer 2005 during the KEOPS experiment, focusing on two contrasting biogeochemical areas in the Antarctic Zone: a natural iron-fertilized area above the Kerguelen Plateau (< 500 m water depth) and the High Nutrient Low Chlorophyll area (HNLC) east of the plateau (> 1000 m water depth). For the HNLC area the Si-isotopic constraint identified Upper Circumpolar Deep Water as being the ultimate Si-source. The latter supplies summer mixed layer with 4.0 ± 0.7 mol Si m^? 2 yr^? 1. This supply must be equivalent to the net annual bSiO₂ production and exceeds the seasonal depletion as estimated from a simple mixed layer mass balance (2.5 ± 0.2 mol Si m^? 2 yr^? 1). This discrepancy reveals that some 1.5 ± 0.7 mol Si m^? 2 yr^? 1 must be supplied to the mixed layer during the stratification period. For the fertilized plateau bloom area, a low apparent mixed layer isotopic fractionation value (?³⁰Si) probably reflects (1) a significant impact of bSiO₂ dissolution, enriching the bSiO₂ pool in heavy isotope; and/or (2) a high Si uptake over supply ratio in mixed layer at the beginning of the bloom, following an initial closed system operating mode, which, however, becomes supplied toward the end of the bloom (low Si uptake over supply ratio) with isotopically light Si(OH)₄ from below when the surface Si(OH)₄ pool is significantly depleted. We estimated a net integrated bSiO₂ production of 10.5 ± 1.4 mol Si m^? 2 yr^? 1 in the AASW above the plateau, which includes a significant contribution of bSiO₂ production below the euphotic layer. However, advection which could be significant for this area has not been taken into account in the latter estimation based on a 1D approach of the plateau system. Finally, combining the KEOPS Si-isotopic data with those from previous studies, we refined the average Si-isotopic fractionation factor to ? 1.2 ± 0.2‰ for the Antarctic Circumpolar Current.     

Community respiration/production and bacterial activity in the upper water column of the central Arctic Ocean

Community metabolism (respiration and production) and bacterial activity were assessed in the upper water column of the central Arctic Ocean during the SHEBA/JOIS ice camp experiment, October 1997–September 1998. In the upper 50 m, decrease in integrated dissolved oxygen (DO) stocks over a period of 124 d in mid-winter suggested a respiration rate of ∼3.3 nM O₂ h⁻¹ and a carbon demand of ∼4.5 gC m⁻². Increase in 0–50 m integrated stocks of DO during summer implied a net community production of ∼20 gC m⁻². Community respiration rates were directly measured via rate of decrease in DO in whole seawater during 72-h dark incubation experiments. Incubation-based respiration rates were on average 3-fold lower during winter (11.0±10.6 nM O₂ h⁻¹) compared to summer (35.3±24.8 nM O₂ h⁻¹). Bacterial heterotrophic activity responded strongly, without noticeable lag, to phytoplankton growth. Rate of leucine incorporation by bacteria (a proxy for protein synthesis and cell growth) increased ∼10-fold, and the cell-specific rate of leucine incorporation ∼5-fold, from winter to summer. Rates of production of bacterial biomass in the upper 50 m were, however, low compared to other oceanic regions, averaging 0.52±0.47 ngC l⁻¹ h⁻¹ during winter and 5.1±3.1 ngC l⁻¹ h⁻¹ during summer. Total carbon demand based on respiration experiments averaged 2.4±2.3 mgC m⁻³ d⁻¹ in winter and 7.8±5.5 mgC m⁻³ d⁻¹ in summer. Estimated bacterial carbon demand based on bacterial productivity and an assumed 10% gross growth efficiency was much lower, averaging about 0.12±0.12 mgC m⁻³ d⁻¹ in winter and 1.3±0.7 mgC m⁻³ d⁻¹ in summer. Our estimates of bacterial activity during summer were an order of magnitude less than rates reported from a summer 1994 study in the central Arctic Ocean, implying significant inter-annual variability of microbial processes in this region.     

Fluid flow reconstruction in karstified Panormide platform limestones (north-central Sicily): Implications for hydrocarbon prospectivity in the Sicilian fold and thrust belt

Diagenetic analysis based on field and petrographic observations, isotope and microthermometric data was used to reconstruct the fluid flow history of the Cretaceous shallow water limestones from the Panormide platform exposed in north-central Sicily. Analysis focused on diagenetic products in cavities and dissolution enlarged fractures of the karstified limestones that occur just below a regional unconformity. The fluid flow history could be broken down into five stages that were linked to the kinematic and burial history of the region. (1) Petrography (zoned cathodoluminescence and speleothem textures) and stable isotopes (6.5 < δ¹⁸O_V-PDB < ?3.5‰ and 0 < δ¹³C_V-PDB < ?14‰) indicate that the earliest calcite phase was associated with karstification during emergence of the platform. Limestone dissolution at this stage is important with regard to possible reservoir creation in the Panormide palaeogeographic domain. (2) Fine-grained micrite sedimentation, dated as latest Cretaceous by nannopalaeontology and its ⁸⁷Sr/⁸⁶Sr isotope ratio (0.7078), marks replacement by marine fluids during subsequent submergence of the karstified platform. (3) The following calcite cement was still precipitated by marine-derived fluids (?7.0 < δ¹⁸O_V-PDB < ?5.0‰ and ?3.0 < δ¹³C_V-PDB < 0.5‰/T_m = ?2 to ?5 °C), but at increasingly higher temperatures (T_h = 60–120 °C). This has been interpreted as precipitation during Oligocene foredeep burial. (4) Hot (T_h = 130–180 °C), low saline (T_m < ?2.5 °C) fluids with increasingly higher calculated δ¹⁸O_SMOW signatures (+6 to +14‰) subsequently invaded the karst system. These fluids most likely migrated during fold and thrust belt development. The low salinity and relatively high δ¹⁸O_SMOW signatures of the fluids are interpreted to be the result of clay dewatering reactions. The presence of bitumen and associated fluorite with hydrocarbon inclusions at this stage in the paragenesis constrains the timing of oil migration in the region. (5) Finally, high saline fluids with elevated ⁸⁷Sr/⁸⁶Sr (0.7095–0.7105) signatures invaded the karst system. This last fluid flow event was possibly coeval with localized dolomitization and calcite cementation along high-angle faults of Pliocene age, as suggested by identical radiogenic signatures of these diagenetic products.     

The relative contributions of unicellular and filamentous diazotrophs to N2 fixation in the South China Sea and the upstream Kuroshio

We studied the seasonal, diel, and vertical distribution of phytoplankton N₂ fixation to understand the relative contributions of unicellular and filamentous nitrogen fixers (diazotrophs) to N₂ fixation and nitrogen recycling in the northern South China Sea (SCS) and the neighboring upstream Kuroshio. N₂-fixation rates were measured by the ¹⁵N₂ tracer technique (addition by bubble) on unicellular (<10 or 20 µm) and the filamentous diazotrophs (>10 or 20 µm, mostly Trichodesmium and Richelia) fractionated by 10- or 20-µm mesh sizes. The mean depth-integrated total (unicellular+filamentous) N₂-fixation rates in the SCS (51.7±6.2 µmol N m⁻² d⁻¹) averaged 1/3 of that in the Kuroshio (142.7±29.6 µmol N m⁻² d⁻¹), with higher rates in the winter than in other seasons in the SCS and the opposite seasonal pattern in the Kuroshio. Unicellular diazotrophs contributed 65% of the total N₂ fixation in the SCS, which were negatively correlated with surface temperature and, as for total N₂ fixation, were higher in the winter when Trichodesmium spp. were scarce. In comparison, the unicellular diazotrophs contributed 50% of total N₂ fixation in the Kuroshio, and their contributions were not significantly correlated with surface temperature. In both the SCS and the Kuroshio, the unicellular N₂ fixation was more important during the night than during the day, and in the deep euphotic layer than in the surface layer, even in the daytime. Our results show that the unicellular diazotrophs were important N₂ fixers and contributed significantly to N₂ fixation in the tropical marginal seas, more so in the SCS than the Kuroshio.     

The metabolic balance between autotrophy and heterotrophy in the western Arctic Ocean

The goal of this study was to explore how net community production (NCP) is influenced by the relationship between primary production and community respiration in the western Arctic Ocean. Plankton NCP and respiration were determined by measuring changes in oxygen in light and dark bottle incubations, respectively. Rates of NCP averaged over shelf, slope and basin waters were positive in summer 2002 (57±191 mmol O₂ m⁻² d⁻¹) and spring 2004 (85±86 mmol O₂ m⁻² d⁻¹) and negative in summer 2004 (−25±176 mmol O₂ m⁻² d⁻¹). Determinations of NCP obtained from bottle incubations were similar to rates inferred from in situ changes in dissolved inorganic carbon. An examination of the spatial variability of primary production and community respiration indicated that respiration is distributed more uniformly than primary production. A spatial offset between photosynthesis and respiration from the shelf to the Arctic basin was present in spring 2004, but was not seen at other times. NCP and the potential for export appear to be dependent on an uncoupling of primary production and community respiration. NCP continued into the summer after the stock of NO₃⁻ had been depleted. Our data suggest that the uniform distribution of respiration relative to primary production is an important factor influencing NCP and the potential for export in the western Arctic.     

Organic material accumulation of Carnian mudstones in the North Qiangtang Depression,eastern Tethys: Controlled by the paleoclimate,paleoenvironment, and provenance

The Late Triassic mudstones are considered to be the most significant hydrocarbon source rocks (TOC: 0.54%–3.29%) in the North Qiangtang Depression, eastern Tethys. Here, we present geochemical data from the Woruo Mountain Carnian mudstones, in order to investigate their paleoclimate, paleoenvironment, and provenance and to analyze the mechanism of organic material accumulation. The paleoclimate condition was warm and humid during the Carnian mudstones deposition, as indicated by moderate chemical index of alteration (CIA; 73–76), which may be connected with the Late Triassic Carnian stage global climate event in the Tethys. The low U/Th (0.17–0.25) and C_org/P_tot (7–33) ratio values and moderate manganese contents, reflect the oxidizing conditions during the Carnian mudstones deposition. The relatively high primary productivity in this study is supported by the relatively high P concentrations. The Al₂O₃–(CaO* + Na₂O)–K₂O ternary plot and Th/Sc–Zr/Sc crossplot reflect that the source areas have undergone a medium chemical weathering with weak sedimentary recycling. The TiO₂–Zr, Co/Th–La/Sc, La/Th–Hf, and La/Yb–∑REE bivariate diagrams indicate that the provenance of Carnian mudstones was primarily from felsic igneous rocks. The collision setting has been identified based on the multi-major elements discriminate plots in the present study. The Riwanchaka and Mayigangri masses to the southwest and south of the study area consisting mainly of Middle-Triassic granodiorite and Late-Triassic granite are likely responsible for supplying provenance to the Woruo Mountain Carnian mudstones, which have similar REE patterns. The relatively high TOC contents of Carnian mudstones are related to high paleoproductivity and fast sedimentation rates, which will lead to preservation of some organic matter even when bottom waters are completely oxidizing. The detrital input during the Carnian mudstones deposition would result in dilution of organic matter.     

Interhemispheric exchanges of mass and heat in the Atlantic Ocean in January–March 1993

Hydrographic, geochemical, and direct velocity measurements along two zonal (7.5°N and 4.5°S) and two meridional (35°W and 4°W) lines occupied in January–March, 1993 in the Atlantic are combined in an inverse model to estimate the circulation. At 4.5°S, the Warm Water (potential temperature θ>4.5°C) originating from the South Atlantic enters the equatorial Atlantic, principally at the western boundary, in the thermocline-intensified North Brazil Undercurrent (33±2.7×10⁶ m³ s⁻¹ northward) and in the surface-intensified South Equatorial Current (8×10⁶ m³ s⁻¹ northward) located to the east of the North Brazil Undercurrent. The Ekman transport at 4.5°S is southward (10.7±1.5×10⁶ m³ s⁻¹). At 7.5°N, the Western Boundary Current (WBC) (17.9±2×10⁶ m³ s⁻¹) is weaker than at 4.5°S, and the northward flow of Warm Water in the WBC is complemented by the basin-wide Ekman flow (12.3±1.0×10⁶ m³ s⁻¹), the net contribution of the geostrophic interior flow of Warm Water being southward. The equatorial Ekman divergence drives a conversion of Thermocline Water (24.58⩽σ₀<26.75) into Surface Water (σ₀<24.58) of 7.5±0.5×10⁶ m³ s⁻¹, mostly occurring west of 35°W. The Deep Water of northern origin flows southward at 7.5°N in an energetic (48±3×10⁶ m³ s⁻¹) Deep Western Boundary Current (DWBC), whose transport is in part compensated by a northward recirculation (21±4.5×10⁶ m³ s⁻¹) in the Guiana Basin. At 4.5°S, the DWBC is much less energetic (27±7×10⁶ m³ s⁻¹ southward) than at 7.5°N. It is in part balanced by a deep northward recirculation east of which alternate circulation patterns suggest the existence of an anticyclonic gyre in the central Brazil Basin and a cyclonic gyre further east. The deep equatorial Atlantic is characterized by a convergence of Lower Deep Water (45.90⩽σ₄<45.83), which creates an upward diapycnal transport of 11.0×10⁶ m³ s⁻¹ across σ₄=45.83. The amplitude of this diapycnal transport is quite sensitive to the a priori hypotheses made in the inverse model. The amplitude of the meridional overturning cell is estimated to be 22×10⁶ m³ s⁻¹ at 7.5°N and 24×10⁶ m³ s⁻¹ at 4.5°S. Northward heat transports are in the range 1.26–1.50 PW at 7.5°N and 0.97–1.29 PW at 4.5°S with best estimates of 1.35 and 1.09 PW.     

Dolomitization of the Latemar platform: Fluid flow and dolomite evolution

The Anisian–Ladinian Latemar platform, northern Italy, presents a spectacularly exposed outcrop analogue for dolomitized carbonate reservoirs in relation to fracture-controlled igneous intrusions. Although the Latemar is one of the best studied carbonate platforms worldwide, timing and evolution of dolomitization and the link to fractures and dikes have not been explored in detail. Previous dolomite observations are based on a stratigraphically limited portion of the platform. This study extends observations to the complete exposed interval in which dolomite bodies occur, including those within the less accessible Valsorda valley.Numerous parallel mafic dikes crosscut the Latemar platform and border several of its large dolomite bodies (50 m wide, 100 m high). Within dikes and along dike-carbonate contacts, there are abundant dolomite veins that are geochemically related to surrounding dolomite bodies. Dolomitization is the result of limestone interaction with hydrothermal fluids delivered along these dikes. At dike boundaries, impermeable marble aureoles exist derived from contact metamorphism. The marble aureoles have locally shielded surrounding limestone from dolomitizing fluid. Dolomite occurs only where the ‘protective’ marble is missing or crosscut by fractures. Based on geometric relationships, we conclude that dikes and their damage zones formed the pathways for the dolomitizing fluids and functioned as boundaries for dolomite bodies.From field observations and petrography, we established a detailed paragenesis. Dolomitization started shortly after dike emplacement. There is an evolution in the Fe content of matrix dolomite and dolomite veins, from highly ferroan dolomite to non-ferroan (saddle) dolomite, alternating with episodes of silica cementation. Non-ferroan calcite precipitation followed dolomitization, possibly indicating concurrent depletion in Mg. This stage likely resulted in further limestone recrystallization rather than dolomitization. Stable and radiogenic isotopes suggest that the dolomitizing fluid comprised Carnian seawater with elevated Fe and Mg from interaction with other lithologies (possibly the nearby Predazzo intrusion).     

Diapycnal nutrient fluxes on the northern boundary of Cape Ghir upwelling region

In this study we estimate diffusive nutrient fluxes in the northern region of Cape Ghir upwelling system (Northwest Africa) during autumn 2010. The contribution of two co-existing vertical mixing processes (turbulence and salt fingers) is estimated through micro- and fine-structure scale observations. The boundary between coastal upwelling and open ocean waters becomes apparent when nitrate is used as a tracer. Below the mixed layer (56.15±15.56 m), the water column is favorable to the occurrence of a salt finger regime. Vertical eddy diffusivity for salt (K_s) at the reference layer (57.86±8.51 m, CI 95%) was 3×10⁻⁵ (±1.89×10⁻⁹, CI 95%) m² s⁻¹. Average diapycnal fluxes indicate that there was a deficit in phosphate supply to the surface layer (6.61×10⁻⁴ mmol m⁻² d⁻¹), while these fluxes were 0.09 and 0.03 mmol m⁻² d⁻¹ for nitrate and silicate, respectively. There is a need to conduct more studies to obtain accurate estimations of vertical eddy diffusivity and nutrient supply in complex transitional zones, like Cape Ghir. This will provide us with information about salt and nutrients exchange in onshore–offshore zones.     

A case study of near-inertial oscillation in the South China Sea using mooring observations and satellite altimeter data

A near-inertial oscillation (NIO) burst event in the west South China Sea (SCS) was observed by an upward-looking mooring Acoustic Doppler Current Profiler (ADCP) in summer 2004. The mooring station was located at 13.99°N, 110.52°E. The spectral analysis reveals that typhoon Chanchu is a major mechanism in triggering the NIO burst event. Before typhoon Chanchu passed over, the NIO signals were quite weak. The NIO band becomes the most energetic constituent of the circulation during the typhoon-wake period. The average peak power density (PD) reaches (5.3 ± 2.6) × 10² cm² s⁻² (cycles per hour, cph)⁻¹ with a maximum value of 9.0 × 10² cm² s⁻² cph⁻¹, i.e., 3.1 times higher than that of diurnal tide (DT), (1.7 ± 0.5) × 10² cm² s⁻² cph⁻¹. At the upper (80 m) and sub-upper (208 m) layers, the central frequency of the NIO band is 0.022 cph with a blueshift of about 9% above the inertial frequency f (0.02015 cph). At the lower layer (400 m), the central frequency of the NIO band is 0.021 cph with a blueshift of about 4% above the inertial frequency. The blueshifts are explained partially by the Doppler shift induced by the vorticity of mesoscale eddies. During the after-typhoon period, a resonance-like process between NIO and DT is observed in the upper layer. As the NIO frequency approaches the DT subharmonic frequency (0.5K₁), the PD of the NIO band rises sharply accompanied by a sharp drop of the PD of the DT band. The PD ratio of the two bands increases from 4.5 during the typhoon-wake period to 8 during the after-typhoon period, indicating the effect of the parametric subharmonic instability (PSI) mechanism.