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1.
The Esino Limestone of the western Southern Alps represents a differentiated Ladinian-Lower Carnian (?) carbonate platform comprised of margin, slope and peritidal inner platform facies up to 1000 m thick. A major regional subaerial exposure event lead to coverage by another peritidal Lower Carnian carbonate platform (Breno Formation). Multiphase dolomitization affected the carbonate sediments. Petrographic examinations identified at least three main generations of dolomites (D1, D2, and D3) that occur as both replacement and fracture-filling cements. These phases have crystal-size ranges of 3–35 μm (dolomicrite D1), 40–600 μm (eu-to subhedral crystals D2), and 200 μm to 5 mm (cavity- and fracture-filling anhedral to subhedral saddle dolomite D3), respectively.The fabric retentive near-micritic grain size coupled with low mean Sr concentration (76 ± 37 ppm) and estimated δ18O of the parent dolomitizing fluids of D1 suggest formation in shallow burial setting at temperature ∼ 45–50 °C with possible contributions from volcanic-related fluids (basinal fluids circulated in volcaniclastics or related to volcanic activity), which is consistent with its abnormally high Fe (4438 ± 4393 ppm) and Mn (1219 ± 1418 ppm) contents. The larger crystal sizes, homogenization temperatures (D2, 108 ± 9 °C; D3, 111 ± 14 °C) of primary two-phase fluid inclusions, and calculated salinity estimates (D2, 23 ± 2 eq wt% NaCl; D3, 20 ± 4 eq wt% NaCl) of D2 and D3 suggest that they formed at later stages under mid-to deeper burial settings at higher temperatures from dolomitizing fluids of higher salinity, which is supported by higher estimated δ18O values of their parent dolomitizing fluids. This is also consistent with their high Fe (4462 ± 4888 ppm; and 1091 ± 1183 ppm, respectively) and Mn (556 ± 289 ppm and 1091 ± 1183 ppm) contents, and low Sr concentrations (53 ± 31 ppm and 57 ± 24 ppm, respectively).The similarity in shale-normalized (SN) REE patterns and Ce (Ce/Ce*)SN and La (Pr/Pr*)SN anomalies of the investigated carbonates support the genetic relationship between the dolomite generations and their calcite precursor. Positive Eu anomalies, coupled with fluid-inclusion gas ratios (N2/Ar, CO2/CH4, Ar/He), high F− concentration, high F/Cl and high Cl/Br molar ratios suggest an origin from diagenetic fluids circulated through volcanic rocks, which is consistent with the co-occurrence of volcaniclastic lenses in the investigated sequence.  相似文献   

2.
The stable carbon isotopic ratios (δ13C) of methane (CH4) and carbon dioxide (CO2) of gas-rich fluid inclusions hosted in fracture-fill mineralization from the southern part of the Lower Saxony Basin, Germany have been measured online using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS). The data reveal that CH4 trapped in inclusions seems to be derived from different source rocks with different organic matter types. The δ13C values of CH4 in inclusions in quartz hosted by Carboniferous rocks range between −25 and −19‰, suggesting high-maturity coals as the source of methane. Methane in fluid inclusions in minerals hosted by Mesozoic strata has more negative carbon isotope ratios (−45 to −31‰) and appears to represent primary cracking products from type II kerogens, i.e., marine shales. There is a positive correlation between increasing homogenization temperatures of aqueous fluid inclusions and less negative δ13C(CH4) values of in co-genetic gas inclusions probably indicating different mtaturity of the potential source rocks at the time the fluids were released. The CO2 isotopic composition of CH4-CO2-bearing inclusions shows slight negative or even positive δ13C values indicating an inorganic source (e.g., water-rock interaction and dissolution of detrital, marine calcite) for CO2 in inclusions. We conclude that the δ13C isotopic ratios of CH4-CO2-bearing fluid inclusions can be used to trace migration pathways, sources of gases, and alteration processes. Furthermore, the δ13C values of methane can be used to estimate the maturity of the rocks from which it was sourced. Results presented here are further supported by organic geochemical analysis of surface bitumens which coexist with the gas inclusion-rich fracture-fill mineralization and confirm the isotopic interpretations with respect to fluid source, type and maturity.  相似文献   

3.
New petrographic and fluid inclusion data from core samples of Upper Permian dolomitic limestone (Hauptdolomit, Zechstein group, Stassfurt carbonate sequence) from a gas field located at the northern border of the Lower Saxony Basin (LSB) essentially improve the understanding of the basin development. The gas production at the locality is characterized by very high CO2 concentrations of 75–100% (with CH4 and N2).Samples consist of fine grained, mostly laminated and sometimes brecciated dolomitic limestone (mudstone/wackestone) from the transition zone between the shallow water zone (platform) and the upper slope. The study focuses on migration fluids, entrapped as fluid inclusions in diagenetic anhydrite, calcite, and fluorite, and in syn-diagenetic microfractures, as well as on the geochemistry of fluorite fracture mineralizations, obtained by LA-ICP-MS analysis. Fluid inclusion studies show that the diagenetic fluid was rich in H2ONaClCaCl2. Recrystallized anhydrite contains aqueous inclusions with homogenization temperatures (Th) of ca. 123 °C, but somewhat higher Th of ca. 142 °C was found for calcite cement followed by early Fluorite A with Th of 147 °C. A later Fluorite B preserves gas inclusions and brines with maximum Th of 156 °C. Fluorite B crystallized in fractures during the mobilization of CO2-bearing brines. Crossing isochores for co-genetic aqueous-carbonic and carbonic inclusions indicate fluid trapping conditions of 180–200 °C and 900–1000 bars. δ13C-isotopic ratios of gas trapped in fluid inclusions suggest an organic origin for CH4, while the CO2 is likely of inorganic origin.Basin modelling (1D) shows that the fault block structure of the respective reservoir has experienced an uplift of >1000 m since Late Cretaceous times.The fluid inclusion study allows us to, 1) model the evolution of the LSB and fluid evolution by distinguishing different fluid systems, 2) determine the appearance of CO2 in the geological record and, 3) more accurately estimate burial and uplift events in individual parts of the LSB.  相似文献   

4.
We discuss nitrous oxide (N2O) and methane (CH4) distributions in 49 vertical profiles covering the upper ∼300 m of the water column along two ∼13,500 km transects between ∼50°N and ∼52°S during the Atlantic Meridional Transect (AMT) programme (AMT cruises 12 and 13). Vertical N2O profiles were amenable to analysis on the basis of common features coincident with Longhurst provinces. In contrast, CH4 showed no such pattern. The most striking feature of the latitudinal depth distributions was a well-defined “plume” of exceptionally high N2O concentrations coincident with very low levels of CH4, located between ∼23.5°N and ∼23.5°S; this feature reflects the upwelling of deep waters containing N2O derived from nitrification, as identified by an analysis of N2O, apparent oxygen utilization (AOU) and NO3−, and presumably depleted in CH4 by bacterial oxidation. Sea-to-air emissions fluxes for a region equivalent to ∼42% of the Atlantic Ocean surface area were in the range 0.40–0.68 Tg N2O yr−1 and 0.81–1.43 Tg CH4 yr−1. Based on contemporary estimates of the global ocean source strengths of atmospheric N2O and CH4, the Atlantic Ocean could account for ∼6–15% and 4–13%, respectively, of these source totals. Given that the Atlantic Ocean accounts for around 20% of the global ocean surface, on unit area basis it appears that the Atlantic may be a slightly weaker source of atmospheric N2O than other ocean regions but it could make a somewhat larger contribution to marine-derived atmospheric CH4 than previously thought.  相似文献   

5.
The studied area is a 130 km long fast spreading graben in Central Greece. Its complex geodynamical setting includes both the presence of a subduction slab at depth responsible for the recent (Quaternary) volcanic activity in the area and the western termination of a tectonic lineament of regional importance (the North-Anatolian fault). A high geothermal gradient is made evident by the presence of many thermal springs with temperatures from 19 to 82 °C, that discharge along the normal faults bordering the graben.In the period 2004–2012, 58 gas and 69 water samples were collected and their chemical and isotopic analysis revealed a wide range of compositions.Two main groups of thermal waters can be distinguished on the basis of their chemical composition. The first, represented by dilute waters (E.C. <0.6 mS/cm) of the westernmost sites, is characterised by the presence of CH4-rich and mixed N2–CH4 gases. The second displays higher salinities (E.C. from 12 to 56 mS/cm) due to mixing with a modified marine component. Reservoir temperatures of 150–160 °C were estimated with cationic geothermometers at the easternmost sites.Along the graben, from west to east, the gas composition changes from CH4- to CO2-dominated through mixed N2–CH4 and N2–CO2 compositions, while at the same time the He isotopic composition goes from typical crustal values (<0.1 R/RA) up to 0.87 R/RA, showing in the easternmost sites a small (3–11%) but significant mantle input. The δ13C values of the CO2-rich samples suggest a mixed origin (mantle and marine carbonates).  相似文献   

6.
Elevated methane (CH4) concentrations (128–2692×103 nM) occur in the hypersaline anoxic brine pools of Bannock and Urania Basins, eastern Mediterranean Sea, compared to low concentrations (17–80×103 nM) in the sediments below the anoxic brines. The CH4 enrichment in the brines might be due to the long residence time of the brine in the Basin. An attempt is made to determine the sources for the enriched dissolved CH4 by considering the influence of hydrothermal activity, the occurrence of sapropel layers (biogenic) and dissolution of gas hydrates. Furthermore, it is suggested that the enriched CH4 in Bannock and Urania Basins is diffused and mixed with the overlying waters by local upward transport mechanisms that selectively move CH4 upward in these Basins.  相似文献   

7.
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 Q86.0F3.1R10.9 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 (Th) 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 (REESN) 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.  相似文献   

8.
Field observations indicate that tectonic compression, anticline formation and concomitant uplift events of marine Paleogene carbonates in eastern United Arab Emirates, which are related to the Zagros Orogeny, have induced brecciation, karstification, and carbonate cementation in vugs and along faults and fractures. Structural analysis, stable isotopes and fluid inclusion microthermometry are used to constrain the origin and geochemical evolution of the fluids. Fluid flow was related to two tectonic deformation phases. Initially, the flux of moderately 87Sr-rich basinal NaCl–MgCl2–H2O brines along reactivated deep-seated strike-slip faults have resulted in the precipitation of saddle dolomite in fractures and vugs and in dolomitization of host Eocene limestones (δ18OV-PDB −15.8‰ to −6.2‰; homogenization temperatures of 80–115 °C and salinity of 18–25 wt.% eq. NaCl). Subsequently, compression and uplift of the anticline was associated with incursion of meteoric waters and mixing with the basinal brines, which resulted in the precipitation of blocky calcite cement (δ18OV-PDB −22‰ to −12‰; homogenization temperatures of 60–90 °C and salinity of 4.5–9 wt.% eq. NaCl). Saddle dolomite and surrounding blocky calcite have precipitated along the pre- and syn-folding E–W fracture system and its conjugate fracture sets. The stable isotopes coupled with fluid-inclusion micro-thermometry (homogenization temperatures of ≤50 °C and salinity of <1.5 wt.% eq. NaCl) of later prismatic/dogtooth and fibrous calcites, which occurred primarily along the post-folding NNE–SSW fracture system and its conjugate fracture sets, suggest cementation by descending moderately 87Sr-rich, cool meteoric waters. This carbonate cementation history explains the presence of two correlation trends between the δ18OV-PDB and δ13CV-PDB values: (i) a negative temperature-dependent oxygen isotope fractionation trend related to burial diagenesis and to the flux of basinal brines, and (ii) positive brine-meteoric mixing trend. This integrated study approach allows better understanding of changes in fluid composition and circulation pattern during evolution of foreland basins.  相似文献   

9.
The exceptional development of coeval hydrocarbon and aqueous fluid inclusions (FI) in fluorite from the MVT-type ore deposit of Koh-i-Maran, Baluchistan (North Kirthar range, Pakistan), provides samples which are representative of the ore-forming fluid and which support the hypothesis of petroleum migration in the province. Primary brines at 125°C (10 wt% equ. NaCl) and secondary CH4-rich brines at 135°C (7 wt% equ. NaCl), are recognised to be associated with oil migration in the fluid inclusions. They support the model of a per ascensum MVT (Mississippi Valley Type) stratabound hydrothermal deposit. A pressure–temperature path of 120–125°C to 165–200 bars is calculated from microthermometric data and PVT modelling of hydrocarbon FI using the modified Peng–Robinson Equation of State (IFP software) from primary cogenetic inclusions (oil and brines).The composition of gas and oil fractions is obtained by a combination of Synchrotron FTIR microanalysis and gas chromatography performed on individual fluid inclusions. The oil entrapped as a coeval primary fluid phase is a light aliphatic normal oil in the range C8–C35 with a high CO2 content. The brown solid phase found systematically in the oil is probably asphaltene resulting from precipitation after trapping of the heavy fraction, which commonly occurs by decreasing pressure and temperature and\or by CO2 injection. Later CH4-rich brine influx probably modified part of the oil in the primary fluid inclusions because degraded oil is observed within such inclusions. Biomarkers obtained by GC-MS analysis indicate a terpane distribution quite similar to the nearest oil seepage in the Gokurt area. This result and the high CO2 content of organic fluid inclusions indicate a restricted/confined sedimentary environment for the source rock, which could correspond to the Eocene Carbonate formation with type-II organic matter. A possible additional input of gas from the Sambar formation is suggested as feasible. The link between the fluid inclusion data and the geodynamic evolution lead us to propose a circulation of basinal fluids driven mainly by the fault system during dewatering in the foredeep. In Pakistan, they are coeval to major compressional NW–SE Oligocene episode in the thrust belt. The origin of the fluorine may be found in the basin sediments as well as near the basement. The brines originated in salt structures recognized in eocambrian at the decollement level, the source rock was already mature.  相似文献   

10.
Understanding the role of the oceans in the Earth's changing climate requires comprehension of the relevant metabolic pathways which produce climatically important trace gases. The global ocean represents one of the largest natural sources of nitrous oxide (N2O) that is produced by selected archaea and/or bacteria during nitrogen (N) metabolism. In this study, the role of nitrite (NO2−) in the production of N2O in the upper water column of the oligotrophic North Pacific Subtropical Gyre was investigated, focusing primarily on the lower euphotic zone where NO2− concentrations at the primary NO2− maximum reached 195 nmol L−1. Free-drifting sediment trap arrays were deployed to measure N cycle processes in sinking particulate material and the addition of selected N substrates to unpreserved sediment traps provided an experimental framework to test hypotheses regarding N2O production pathways and controls. Sinking particles collected using NO2−-amended, unpreserved sediment traps exhibited significant production of N2O at depths between 100 and 200 m. Subsequent stable isotope tracer measurements conducted on sediment trap material amended with 15NO2− yielded elevated δ15N values of N2O, supporting N2O production via a NO2− metabolism pathway. Experiments on seawater collected from 150 m showed N2O production via NO2− metabolism also occurs in the water-column and indicated that the concentration of NO2− relative to NH4+ availability may be an important control. These findings provide evidence for the production of N2O via nitrifer-denitrification in the lower euphotic zone of the open ocean, whereby NO2− is reduced to N2O by ammonia-oxidizing microorganisms.  相似文献   

11.
Preservation of organic matter in estuarine and coastal areas is an important process in the global carbon cycle. This paper presents bulk δ13C and C/N of organic matter from source to sink in the Pearl River catchment, delta and estuary, and discusses the applicability of δ13C and C/N as indicators for sources of organic matter in deltaic and estuarine sediments. In addition to the 91 surface sediment samples, other materials collected in this study cover the main sources of organic material to estuarine sediment. These are: terrestrial organic matter (TOM), including plants and soil samples from the catchment; estuarine and marine suspended particulate organic carbon (POC) from both summer and winter. Results show that the average δ13C of estuarine surface sediment increases from −25.0 ± 1.3‰ in the freshwater environment to −21.0 ± 0.2‰ in the marine environment, with C/N decreasing from 15.2 ± 3.3 to 6.8 ± 0.2. In the source areas, C3 plants have lower δ13C than C4 plants (−29.0 ± 1.8‰ and −13.1 ± 0.5‰ respectively). δ13C increases from −28.3 ± 0.8‰ in the forest soil to around −24.1‰ in both riverbank soil and mangrove soil due to increasing proportion of C4 grasses. The δ13CPOC increases from −27.6 ± 0.8‰ in the freshwater areas to −22.4 ± 0.5‰ in the marine-brackish-water areas in winter, and ranges between −24.0‰ in freshwater areas and −25.4‰ in brackish-water areas in summer. Comparison of the δ13C and C/N between the sources and sink indicates a weakening TOM and freshwater POC input in the surface sedimentary organic matter seawards, and a strengthening contribution from the marine organic matter. Thus we suggest that bulk organic δ13C and C/N analysis can be used to indicate sources of sedimentary organic matter in estuarine environments. Organic carbon in surface sediments derived from anthropogenic sources such as human waste and organic pollutants from industrial and agricultural activities accounts for less than 10% of the total organic carbon (TOC). Although results also indicate elevated δ13C of sedimentary organic matter due to some agricultural products such as sugarcane, C3 plants are still the dominant vegetation type in this area, and the bulk organic δ13C and C/N is still an effective indicator for sources of organic matter in estuarine sediments.  相似文献   

12.
During the Subarctic Pacific Iron Experiment for Ecosystem Dynamics Study ΙΙ (SEEDS-II), we monitored variations in the concentrations of non-methane hydrocarbons (NMHCs), CH3Cl, N2O, and CH4 within a phytoplankton bloom. Stable isotopic compositions were also determined to evaluate the sources of the variations. Although there was little variation in either the concentrations or the stable isotopic compositions of alkenes, CH3Cl, N2O, and CH4 during the 23-day observation period, alkane concentrations increased substantially as the phytoplankton bloomed. The column-integrated quantities of alkanes increased to 3 times pre-bloom levels for C2H6, 5 times for C3H8, and 20 times for n-C4H10. The δ13C values of both C2H6 and C3H8 remained almost constant while concentrations increased, whereas that of n-C4H10 increased by about 12‰. To evaluate the sources of the alkanes produced during the bloom, we compared their δ13C values with those of alkanes produced in axenic phytoplankton cultures in our laboratory. We concluded that during the SEEDS-ΙΙ experiment the major portions of C2H6 and C3H8 were produced during the autolysis of diatoms cells, whereas n-C4H10 was produced during autolysis of other phytoplankton cells such as cryptophytes and dinoflagellates.  相似文献   

13.
Atmospheric dry deposition of nitrogen (N) and dinitrogen (N2) fixation rates were assessed in 2004 at the time-series DYFAMED station (northwestern Mediterranean, 43°25′N, 7°52′E). The atmospheric input was monitored over the whole year. Dinitrogen fixation was measured during different seasonal trophic states (from mesotrophy to oligotrophy) sampled during nine cruises. The bioavailability of atmospherically deposited nutrients was estimated by apparent solubility after 96 h. The solubility of dry atmospheric N deposition was highly variable (from ∼18% to more than 96% of total N). New N supplied to surface waters by the dry atmospheric deposition was mainly nitrate (NO3−) (∼57% of total N, compared to ∼6% released as ammonium (NH4+)). The mean bioavailable dry flux of total N was estimated to be ∼112 μmol m−2 d−1 over the whole year. The NO3− contribution (70 μmol NO3− m−2 d−1) was much higher than the NH4+ contribution (1.2 μmol NH4+ m−2 d−1). The N:P ratios in the bioavailable fraction of atmospheric inputs (122.5–1340) were always much higher than the Redfield N:P ratio (16). Insoluble N in atmospheric dry deposition (referred to as “organic” and believed to be strongly related to anthropogenic emissions) was ∼40 μmol m−2 d−1. N2 fixation rates ranged from 2 to 7.5 nmol L−1 d−1. The highest values were found in August, during the oligotrophic period (7.5 nmol L−1 at 10 m depth), and in April, during the productive period (4 nmol L−1 d−1 at 10 m depth). Daily integrated values of N2 fixation ranged from 22 to 100 μmol N m−2 d−1, with a maximum of 245 μmol N m−2 d−1 in August. No relationship was found between the availability of phosphorus or iron and the observed temporal variability of N2 fixation rates. The atmospheric dry deposition and N2 fixation represented 0.5–6% and 1–20% of the total biological nitrogen demand, respectively. Their contribution to new production was more significant: 1–28% and 2–55% for atmospheric dry deposition and N2 fixation, respectively. The dry atmospheric input was particularly significant in conditions of water column stratification (16–28% of new production), while N2 fixation reached its highest values in June (46% of new production) and in August (55%).  相似文献   

14.
The concentration of Ca in the formation waters of petroleum reservoirs can play a major role in influencing the outcome of a number of processes that are of great significance to the oil industry. For example, formation water Ca concentration affects the risk of carbonate scale formation during production. In order to better understand the concentrations of Ca in formation waters, we have investigated the chemistries of formation waters from a range of onshore and offshore basins worldwide, using published sources, as well as unpublished data held by BP. Although calcium and sodium are the principal cations in almost all formation waters they vary enormously in their relative proportions. We have identified three distinct trends on a plot of XCa (Ca/(Na + Ca)) against Cl. Most data lie on a high-Ca trend, here termed Trend 1, and show an increase in XCa with salinity. We interpret this as tracking equilibration with Ca and Na-bearing minerals, with the ratio (mol Ca/mol Na2) remaining approximately constant irrespective of salinity for chloride-dominated fluids. At very high salinities, Br-enriched bittern brines that have taken part in dolomitisation lie at the Cl-rich end of this trend. Some brines remain Na-dominated up to very high salinities and define a distinct low-Ca trend, Trend 2. These are associated with dissolution of halite beds and are interpreted to arise when the amount of Na in the pore fluid greatly exceeds the amount of Ca available in minerals. We refer to such brines as mass-limited; the sparsity of Ca in the rock-fluid system constrains XCa to a low value. Remarkably few brines lie between these trends. Finally, dilute formation waters show very large variations in XCa and may have bicarbonate as the dominant anion. They define a distinct low-Cl trend, Trend 3. We conclude that the behaviour of Na and Ca in most formation waters reflects equilibration with minerals, and concentrations of Ca in solution are sensitive to pH and PCO2 as well as to chloride concentration. For some brines however, the amount of salts in solution is sufficient to overwhelm the buffering capacity of the wallrocks.  相似文献   

15.
Benthic fluxes of dissolved inorganic carbon, total alkalinity, oxygen, nutrients, nitrous oxide and methane were measured in situ at three sites of Río San Pedro salt marsh tidal creek (Bay of Cádiz, SW Spain) during three seasons. This system is affected by the discharges of organic carbon and nutrients from the surrounding aquaculture installations. Sediment oxygen uptake rates and inorganic carbon fluxes ranged respectively from 16 to 79 mmol O2 m? 2 d? 1 and from 48 to 146 mmol C m? 2 d? 1. Benthic alkalinity fluxes were corrected for the influence of NH4+ and NO3? + NO2? fluxes, and the upper and lower limits for carbon oxidation rates were inferred by considering two possible scenarios: maximum and minimum contribution of CaCO3 dissolution to corrected alkalinity fluxes. Average Cox rates were in all cases within ± 25% of the upper and lower limits and ranged from 40 to 122 mmol C m? 2 d? 1. Whereas carbon mineralization did not show significant differences among the sites, Cox rates varied seasonally and were correlated with temperature (r2 = 0.72). During winter and spring denitrification was estimated to account for an average loss of 46% and 75%, respectively, of the potentially recyclable N, whereas during the summer no net removal was observed. A possible shift from denitrification to dissimilatory nitrate reduction to ammonium (DNRA) during this period is argued. Dissolved CH4 and N2O fluxes ranged from 5.7 to 47 μmol CH4 m? 2 d? 1 and 4.3 to 49 μmol N–N2O m? 2 d? 1, respectively, and represented in all cases a small fraction of total inorganic C and N flux. Overall, about 60% of the total particulate organic matter that is discharged into the creek by the main fish farm facility is estimated to degrade in the sediments, resulting in a significant input of nutrients to the system.  相似文献   

16.
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 < δ18OV-PDB < ?3.5‰ and 0 < δ13CV-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 < δ18OV-PDB < ?5.0‰ and ?3.0 < δ13CV-PDB < 0.5‰/Tm = ?2 to ?5 °C), but at increasingly higher temperatures (Th = 60–120 °C). This has been interpreted as precipitation during Oligocene foredeep burial. (4) Hot (Th = 130–180 °C), low saline (Tm < ?2.5 °C) fluids with increasingly higher calculated δ18OSMOW 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 δ18OSMOW 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.  相似文献   

17.
The processes involved in the interaction between organic fluids and carbonates, and the resulting effect on reservoir quality during the evolution and maturation of organic matter remain unclear despite the fact that these processes influence the carbon and oxygen isotopic compositions of carbonates. Here, we provide new insights into these processes using data obtained from a detailed analysis of a mixed dolomitic–clastic and organic-rich sedimentary sequence within the middle Permian Lucaogou Formation in the Junggar Basin of NW China. The techniques used during this study include drillcore observations, thin section petrography, scanning electron microscopy (SEM) and electron probe microanalysis, and carbon and oxygen isotope analyses. Oil grades and total organic carbon (TOC) contents represent the amount of oil charging and the abundance of organic fluids within a reservoir, respectively, and both negatively correlate with the whole-rock δ13C and δ18O of the carbonates in the study area, indicating that organic fluids have affected the reservoir rocks. Secondary carbonates, including sparry calcite and dolomite overgrowths and cements, are common within the Lucaogou Formation. Well-developed sparry calcite is present within dark mudstone whereas the other two forms of secondary carbonates are present within the dolomite-rich reservoir rocks in this formation. Comparing thin section petrology with δ13C compositions suggests that the carbon isotopic composition of matrix carbonates varies little over small distances within a given horizon but varies significantly with stratigraphic height as a result of the development of secondary carbonates. The net change in whole-rock δ13C as a result of these secondary carbonates ranges from 1.8‰ to 4.6‰, with the secondary carbonates having calculated δ13C compositions from −18.6‰ to −8.5‰ that are indicative of an organic origin. The positive correlation between the concentration of Fe within matrix and secondary carbonates within one of the samples suggests that the diagenetic system within the Lucaogou Formation was relatively closed. The correlation between δ13C and δ18O in carbonates is commonly thought to be strengthened by the influence of meteoric water as well as organic fluids. However, good initial correlation between δ13C and δ18O of whole rock carbonates within the Lucaogou Formation (resulted from the evaporitic sedimentary environment) was reduced by organic fluids to some extent. Consequently, the δ13C–δ18O covariations within these sediments are not always reliable indicators of diagenetic alteration by organic fluids or meteoric water.The characteristics and δ13C compositions of the sparry calcite within the formation is indicative of a genetic relationship with organic acids as a result of the addition of organic CO2 to the reservoir. Further analysis suggests that both carbonate and feldspar were dissolved by interaction with organic CO2. However, dissolved carbonate reprecipitated as secondary carbonates, meaning that the interaction between organic fluids and dolomites did not directly improve reservoir quality, although this process did enhance the dissolution of feldspar and increase porosity. This indicates that the δ13C and δ18O of secondary carbonates and their influence on whole-rock carbonate isotopic values can be used to geochemically identify the effect of organic fluids on closed carbonate-rich reservoir systems.  相似文献   

18.
N2O Production, Nitrification and Denitrification in an Estuarine Sediment   总被引：1，自引：0，他引：1  
The mechanisms regulating N2O production in an estuarine sediment (Tama Estuary, Japan) were studied by comparing the change in N2O production with those in nitrification and denitrification using an experimental continuous-flow sediment–water system with15N tracer (15N-NO−3 addition). From Feburary to May, both nitrification and denitrification in the sediment increased (246 to 716 μmol N m−2 h−1and 214 to 1260 μmol N m−2 h−1, respectively), while benthic N2O evolution decreased slightly (1560 to 1250 nmol N m−2 h−1). Apparent diffusion coefficients of inorganic nitrogen compounds and O2at the sediment–water interface, calculated from the respective concentration gradients and benthic fluxes, were close to the molecular diffusion coefficients (0·68–2·0 times) in February. However, they increased to 8·8–52 times in May except for that of NO−2, suggesting that the enhanced NO−3 and O2supply from the overlying water by benthic irrigation likely stimulated nitrification and denitrification. Since the progress of anoxic condition by the rise of temperature from February to May (9 to 16 °C) presumably accelerated N2O production through nitrification, the observed decrease in sedimentary N2O production seems to be attributed to the decrease in N2O production/occurrence of its consumption by denitrification. In addition to the activities of both nitrification and denitrification, the change in N2O metabolism during denitrification by the balance between total demand of the electron acceptor and supply of NO−3+NO−2 can be an important factor regulating N2O production in nearshore sediments.  相似文献   

19.
High resolution and multichannel seismic profiles coupled with multibeam echosounder (seafloor relief) data, acquired along the northern Sicily continental margin (southern Tyrrhenian Sea), document the occurrence of mound and pockmark features, revealing fluid escape processes. Along this margin, morphology of the high-gradient continental slope is irregular due to the presence of structural highs, slope failures and canyons, and is interrupted by flat areas at a mean depth of 1500 m.Seismostratigraphic analysis tools and methods were used to identify fluid escape structures and to work out a classification on the basis of their morpho-acoustic characteristics. The detailed 3D bathymetric chart was used to define the top view morphologic features and their areal distribution. With the aim to evaluate the geochemical content of fluids, we collected a 2.3 m long sediment core in correspondence of a pockmark at a depth of 414 m. Pore waters were sampled every 10 cm and analysed in relation to their conductivity (EC) and composition (δ18O, δD, Li, Na, K, Mg, F, Cl, Br, NO3, SO4).The new data show the occurrence of different types of structures with highly contrasting seismic and morphologic signatures, both dome-type and concave-upward structures. The latter have a characteristic circular shape and are known as pockmarks. Morphobathymetric, stratigraphic and structural data suggest that these structures occur along fault planes, mainly associated with diagenetic carbonates and fluid venting activity. Pockmarks could be the result of both fault and landslide structures, as they appear aligned along a straight direction and occur in proximity of the slope, and are associated with slope instabilities. The structural features are possibly associated with the recent tectonics mapped on-land as well as the widespread seismicity of the margin.Geochemical features reveal that pore water is slightly enriched in heavy isotopes with respect to Mediterranean seawater, while the distribution profiles of EC, ion concentration (Cl, SO4, Na, K, Mg, Ca), ion/Chloride ratios (Na/Cl, K/Cl, Ca/Cl, Mg/Cl and Alk/Cl) seem to indicate the existence of an external source of fluids and the occurrence of sediment-fluids interaction processes. A possible mechanism causing pore water freshening could be the destabilisation of gas hydrates.  相似文献   

20.
Fixed nitrogen is a key nutrient involved in regulating global marine productivity and hence the global oceanic carbon cycle. Oceanic nitrogen (N2) fixation is estimated to supply 8×1012 moles N y?1 to the ocean, approximately equal to current riverine and the atmospheric inputs of fixed N, and between 50 and 100% of current estimates of oceanic denitrification. However, the spatial and temporal variability of N2 fixation remains uncertain, mostly because of the normal low resolution sampling for diazotroph distribution and fixation rates. It is well established that N2 fixation, mediated by the enzyme nitrogenase, is a source of hydrogen (H2), but the extent to which it leads to supersaturation of H2 in oceanic waters is unresolved. Here, we present simultaneous measurements of upper ocean dissolved H2 concentration (nmol L?1), and rates of N2 fixation (μmol N m?3 d?1), determined using 15N2 tracer techniques (at 7 or 15 m), on a transect from Fiji to Hawaii. We find a significant correlation (r=0.98) between dissolved H2 and rates of N2 fixation, with the greatest supersaturation of H2 and highest rates of N2 fixation being observed in the subtropical gyres at the southern (～18°S) and northern (18°N) reaches of the transect. The lowest H2 saturation and N2 fixation were observed in the equatorial region between 8°S and 14°N. We propose that an empirical relationship between H2 supersaturations and N2 fixation measurements could be used to guide sampling for 15N fixation measurements or to aid the spatial interpolation of such measurements.  相似文献   

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