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1.
This study investigates the source rock characteristics of Permian shales from the Jharia sub-basin of Damodar Valley in Eastern India. Borehole shales from the Raniganj, Barren Measure and Barakar Formations were subjected to bulk and quantitative pyrolysis, carbon isotope measurements, mineral identification and organic petrography. The results obtained were used to predict the abundance, source and maturity of kerogen, along with kinetic parameters for its thermal breakdown into simpler hydrocarbons.The shales are characterized by a high TOC (>3.4%), mature to post-mature, heterogeneous Type II–III kerogen. Raniganj and Barren Measure shales are in mature, late oil generation stage (Rr%Raniganj = 0.99–1.22; Rr%Barren Measure = 1.1–1.41). Vitrinite is the dominant maceral in these shales. Barakar shows a post-mature kerogen in gas generation stage (Rr%Barakar = 1.11–2.0) and consist mainly of inertinite and vitrinite. The δ13Corg value of kerogen concentrate from Barren Measure shale indicates a lacustrine/marine origin (−24.6–−30.84‰ vs. VPDB) and that of Raniganj and Barakar (−22.72–−25.03‰ vs. VPDB) show the organic provenance to be continental. The δ13C ratio of thermo-labile hydrocarbons (C1–C3) in Barren Measure suggests a thermogenic source.Discrete bulk kinetic parameters indicate that Raniganj has lower activation energies (ΔE = 42–62 kcal/mol) compared to Barren Measure and Barakar (ΔE = 44–68 kcal/mol). Temperature for onset (10%), middle (50%) and end (90%) of kerogen transformation is least for Raniganj, followed by Barren Measure and Barakar. Mineral content is dominated by quartz (42–63%), siderite (9–15%) and clay (14–29%). Permian shales, in particular the Barren Measure, as inferred from the results of our study, demonstrate excellent properties of a potential shale gas system.  相似文献   

2.
Fullerene (nC60) and nanosilver (nAg) are nanomaterials with bactericide properties. The increments in their use raise questions about their potential environmental impacts, including estuarine ones. The polychaete Laeonereis acuta (Nereididae) secretes mucus that is colonized by bacteria communities. We analyzed the antioxidant and oxidative damage responses of anterior, middle and posterior region of L. acuta and bacteria communities after nC60 or nAg exposure during 24 h. Molecular analysis showed a prevalence of Vibrio genera in the communities. Bacteria biomass was lowered in worms exposed to 1.0 mg/L of nAg. nC60 reduced total antioxidant capacity of bacteria from worms exposed to 0.1 mg/L. Worms anterior region presented lower antioxidant capacity after exposure to 1.0 mg nC60/L, and the same was observed in the posterior region of worms exposed to 1.0 mg nAg/L. Lipid peroxidation was reduced in the anterior region of worms exposed to nC60 and the opposite was observed in the posterior region.  相似文献   

3.
The reproductive cycle of anchovy, Engraulis encrasicolus (L.), was studied from monthly random samples of purse seine catches. A total of 1477 anchovy specimens were collected from January to December 2003 in the Zrmanja River estuary (Novigrad Sea). The analysis was based on the temporal evolution of gonadosomatic index, mass and stage of gonads. The total length of anchovy ranged from 4.5 to 14.5 cm and mass from 0.56 to 19.80 g. Sex ratio was slightly different from 1:1; the females were insignificantly predominated (♂/♀ = 0.99). The period of reproductive activity was from April to September coinciding with the most developed stages of gonads as well as with the highest gonad weights, and gonadosomatic indices. To estimate the length at maturity, a sub sample of 454 anchovy was taken from May to July (peak of anchovy spawning period). The length at which 50% of anchovy were mature (L50) was calculated to be 8.2 cm. The length–weight relationship of anchovy was described by the expression: W = 3.51 × 10−3 LT3.211 (r2 = 0.998). The relationships between total length–standard length and total length–fork length are LT = 1.1405LS + 0.2420 and LT = 1.0425 LF + 0.3944, respectively.  相似文献   

4.
The fast expansion of the global nanotechnology market entails a higher environmental and human exposure to nanomaterials. Silver nanoparticles (AgNP) are used for their antibacterial properties; however, their environmental fate is yet poorly understood. Iceland scallops (Chlamys islandica) were exposed for 12 h to three different silver forms, dissolved Ag(I) (Agdiss), small (S-NP, ∅ = 10–20 nm) and large AgNP (L-NP, ∅ = 70–80 nm), labeled with 110mAg, and bioaccumulation kinetics and tissue distribution using in vivo gamma counting and whole-body autoradiography were determined. All Ag forms were readily and rapidly accumulated. Elimination process was also fast and bi-exponential, with mean biological half-life ranging from 1.4 to 4.3 days and from 17 to 50 days for fast and slow compartments, respectively. Most of the radioactivity concentrated in the hepatopancreas. Agdiss and S-NP tissue distributions were similar indicating a rapid dissolution of the latter in the tissues, contrarily to L-NP which appeared to form long lasting aggregates in the digestive system. Estimated steady-state bioconcentration factors (BCF), ranging between 2700 and 3800 ml g−1 for dissolved and particulate silver forms, showed that C. islandica can accumulate significant quantities of Ag in a short time followed by an efficient depuration process.  相似文献   

5.
The effects of waterborne nitrite (3 mg/l NO2) on channel catfish were studied to evaluate changes in hematological parameters and phase I–II biotransformation in liver slices. Nitrite-exposed fish had significantly higher methemoglobin, blood and liver nitrite, and significantly lower pO2 than control fish. Total phase I-mediated metabolism of 7-ethoxycoumarin (EC) was not altered in nitrite-exposed fish compared with control fish (291±43 and 312±20 pmol/mg/h, respectively). However, phase II glucuronosyltransferase-mediated metabolism of 7-hydroxycoumarin (HC), both as a phase I metabolite of EC and as a parent substrate, was elevated in nitrite-exposed fish (204±17 and 1007±103 pmol/mg/h, respectively) as compared to control fish (149±14 and 735±87 pmol/mg/h) (P<0.05). Sulfotransferase-mediated metabolism of HC (as a metabolite of EC and as a parent substrate) was not notably altered in nitrite-exposed fish (95±16 and 617±33 pmol/mg protein/h, respectively) as compared with control fish (118±24 and 575±55 pmol/mg/h, respectively). These studies indicate that in vivo nitrite exposure and associated changes in hematological parameters do not appear to affect hepatic phase I EC biotransformation in channel catfish. However, subtle but significant changes in phase II glucuronidation, but not sulfation activity, were observed. The mechanism of these alterations is unclear. However, the data suggest that environmentally realistic concentrations of nitrite may affect the dynamics of conjugative metabolism in exposed fish.  相似文献   

6.
β-dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) concentrations were recorded from September 1999 to September 2000 in two geographically close ecosystems, differently affected by eutrophication: the Little Bay of Toulon and the Niel Bay (N.W. Mediterranean Sea, France). Little Bay had higher nutrient levels ([NO3−]max. = 30.3 μM; [PO43−]max. = 0.46 μM) and higher chlorophyll a concentrations ([chl a]mean = 2.4 μg/L) compared to Niel Bay ([NO3−]max. = 19.7 μM; [PO43−]max. = 0.17 μM; [chl a]mean = 0.4 μg/L). In the two sites, we measured dissolved (DMSPd < 0.2 μm) and particulate DMSP (DMSPp > 0.2 μm) concentrations. The DMSPp was particularly analysed in the 0.2–5, 5–90 and > 90 μm fractions. In the eutrophicated Little Bay, DMSPd concentrations showed a clear seasonality with high values from January to March (124–148 nM). The temporal profile of the DMSPp concentrations was similar, peaking in February–March (38–59 nM). In the less eutrophic Niel Bay, DMSPp concentrations were much lower (6–9 nM in March–April), whereas DMSPd concentrations were relatively high (110–92 nM in February–March). DMS concentrations were elevated from the end of the winter to the spring in Little Bay, ranging from 3 nM in October to 134 nM in March. In the less eutrophic Niel Bay, lower DMS levels were observed, generally not exceeding 20 nM. Each particulate fraction (0.2–5; 5–90; > 90 μm) contained less DMSP in Niel Bay than in Little Bay. At both sites, the 5–90 μm fraction made up most of the DMSPp. This 5–90 μm fraction consisted of microphytoplankton, principally Dinophyceae and Bacillariophyceae. The 5–90 μm biomass calculated from cell biovolumes, was more abundant in Little Bay where the bloom at the end of the winter (165 μg/L in March) occurred at the same time as the DMSP peaks. The estimated DMSPp to biomass ratio for the 5–90 μm fraction was always higher in Little Bay than in Niel Bay. This suggests that the high DMSP levels recorded in Little Bay were not only due to a large Dinophyceae presence in this ecosystem. Indeed, the peak of DMSPp to biomass ratio obtained from cell biovolumes (0.23 nmol/μg in March) was consistent with the proliferation of Alexandrium minutum. This Dinophyceae species may account for between 50% (2894 cells/L) and 63% (4914 cells/L) of the total phytoplankton abundance in the Little Bay of Toulon.  相似文献   

7.
《Marine Chemistry》2007,103(1-2):122-130
Phosphomolybdenum blue (PMB) paired with cetyltrimethylammonium bromide (CTAB) can be extracted using a solid phase extraction technique on C18 sorbent. Based on this, a novel on-line solid phase extraction method coupled with flow injection (FI) analysis and colorimetric detection has been established to determine nanomolar level orthophosphate in seawater. A stopped flow technique was employed to assure the complete formation of the PMB–CTAB compound, which was sequentially extracted on an in-line Sep-Pak C18 cartridge. The adsorbed PMB–CTAB can be rapidly eluted by 0.56 mol/L H2SO4 in ethanol, and determined with a spectrophotometer at 700 nm. Experimental parameters, including reaction temperature, sample loading flow rate, stopped time and eluting flow rate, were optimized throughout the experiments based on univariate experimental design. The results show that reaction temperature and stopped time were the major factors affecting the formation of PMB–CTAB. Silicate concentration up to 5000 times higher than that of orthophosphate would not interfere with the determination of orthophosphate. Using artificial seawater with salinity of 35 as a matrix under the optimized conditions, the standard curve shows a linear range between 3.2 and 48.5 nmol/L, and the recovery and the detection limit of the proposed method are 96.4% and 1.57 nmol/L, respectively. The relative standard deviation (RSD) (n = 8), which was determined daily for 8 days, was 4.52% for the artificial seawater at a concentration of 32.4 nmol/L orthophosphate. Two typical seawater samples were analyzed using both the proposed method and the MAGnesium hydroxide-Induced Coprecipitation (MAGIC) method. The results of the two methods show no significant difference using the t test. Compared to the MAGIC method, the proposed method has the advantage of being more sensitive, faster, sample saving and easy for on-line analysis.  相似文献   

8.
We investigated a year-long (September 1992 to August 1993) time series of total mass, calcium carbonate, organic carbon, opal, and alkenone fluxes in sinking particles collected with sediment traps moored at 1770 and 4220 m in the central equatorial Pacific. The total mass fluxes varied from 14.7 to 68.7 mg/m2/day at 1770 m, with greater fluxes in October–November and February–April, and from 14.6 to 50.4 mg/m2/day with peak fluxes during October–November at 4220 m. High flux in the spring season shown at 1770 m was not indicated at 4220 m; instead, a slight increase was shown during a broad period from March to June. The calcium carbonate fluxes varied from 10.8 to 49.1 mg/m2/day with higher fluxes in October–November and March–April at 1770 m, and from 8.9 to 37.0 mg/m2/day with a higher flux in October–November at 4220 m. The organic carbon fluxes varied from 0.36 to 5.91 mg/m2/day, with higher fluxes in October–November and March–April at 1770 m, and from 0.72 to 2.58 mg/m2/day at 4220 m. The annual mean organic carbon flux was 1.84 and 1.28 mg/m2/day at 1770 and at 4220 m, respectively. These values were less than half of those reported for the EqPac sediment trap experiment. The opal fluxes varied from 0.55 to 4.4 mg/m2/day at 1770 m and from 1.23 to 2.95 mg/m2/day at 4220 m. Alkenone fluxes varied significantly from 0.05 to 0.84 μg/m2/day, with high values in November, February–March, and June at 1770 m. For the 4220 m trap, these values ranged from 0.05 to 0.25 μg/m2/day, with slightly higher fluxes in April–May and June–July, which followed periods of high alkenone fluxes observed in February–April and June–July, respectively, at 1770 m depth. These values were remarkably low compared with those reported by the previous studies at other sites. U37K′ values were constantly high >0.95 throughout the collection period. However, relatively low U37K′ values (0.92 and 0.93) were occasionally observed during February to March. Estimated alkenone temperatures from those U37K′ values were about 27–29°C and consistent with the observed temperature of the upper layer at ca.100 m depth. The seasonal change of the U37K′ values could be affected by not only water temperature but also the relative amount of ‘warm’ and ‘cold’ types of alkenone producer in the central equatorial Pacific.  相似文献   

9.
A total of 1125 specimens of sardine, Sardina pilchardus, ranging in total length from 4.9 to 12.5 cm (mean 8.31 ± 1.41 cm) and in weights between 1.02 g and 11.18 g (mean 4.40 ± 1.87 g) were randomly sampled using a beach seine from the Krka River estuary. Samples were collected monthly according to their occurrence in this area from October to February during 2002/03, 2003/04 and 2004/05, which is during the spawning period of this species. Monthly fluctuations in the length frequency distributions of sardine were observed during that time. The length–weight relationship of all sardine specimens was described by the equation: W=0.007L2.9587(r2 = 0.9626); and the isometric nature of relative growth was established (t = −5.1495; p < 0.05). According to the allometric condition factor Ka, sardine specimens were in better somatic condition at the beginning of their appearance (spawning period) in the Krka River estuary. The length at which 50% of sardines were mature (L50) was calculated to be 7.9 cm.  相似文献   

10.
《Marine Chemistry》2007,103(1-2):1-14
We succeeded in determining the Ce isotopic composition (138Ce/142Ce) in seawater with an error of 2σm = 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 εCe 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 εCe value was observed in Tokyo Bay, suggesting mantle-derived sources.  相似文献   

11.
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   

12.
UV-filters are increasingly used in cosmetics and in the protection of materials against UV-irradiation. The widespread occurrence of UV-filter residues in aquatic systems has been reported, but still little is known about their environmental effects. Some of these compounds negatively interact with the hormone system of fish, resulting in decreased fecundity and reproduction. Here we report on acute and chronic effects of UV-filters 3-(4-methylbenzylidene-camphor) (4MBC), 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC), benzophenone-3 (BP3) and benzophenone-4 (BP4) on Daphnia magna. The acute toxicity increased with log Pow of the compound. The LC50 values (48 h) of 4MBC, EHMC, BP3 and BP4 were 0.56, 0.29, 1.9 and 50 mg/L, respectively. A tentative preliminary environmental risk assessment (ERA) based on a limited set of data indicates that individual UV-filters should undergo further ecotoxicological analysis, as an environmental risk cannot be ruled out. Consequently new data on the environmental occurrence and the effects of UV-filters are needed for a more accurate ERA. When regarded as a mixture occurring in surface waters they may pose a risk for sensitive aquatic organisms.  相似文献   

13.
The Upper Cretaceous Mukalla coals and other organic-rich sediments which are widely exposed in the Jiza-Qamar Basin and believed to be a major source rocks, were analysed using organic geochemistry and petrology. The total organic carbon (TOC) contents of the Mukalla source rocks range from 0.72 to 79.90% with an average TOC value of 21.50%. The coals and coaly shale sediments are relatively higher in organic richness, consistent with source rocks generative potential. The samples analysed have vitrinite reflectance in the range of 0.84–1.10 %Ro and pyrolysis Tmax in the range of 432–454 °C indicate that the Mukalla source rocks contain mature to late mature organic matter. Good oil-generating potential is anticipated from the coals and coaly shale sediments with high hydrogen indices (250–449 mg HC/g TOC). This is supported by their significant amounts of oil-liptinite macerals are present in these coals and coaly shale sediments and Py-GC (S2) pyrograms with n-alkane/alkene doublets extending beyond nC30. The shales are dominated by Type III kerogen (HI < 200 mg HC/g TOC), and are thus considered to be gas-prone.One-dimensional basin modelling was performed to analysis the hydrocarbon generation and expulsion history of the Mukalla source rocks in the Jiza-Qamar Basin based on the reconstruction of the burial/thermal maturity histories in order to improve our understanding of the of hydrocarbon generation potential of the Mukalla source rocks. Calibration of the model with measured vitrinite reflectance (Ro) and borehole temperature data indicates that the present-day heat flow in the Jiza-Qamar Basin varies from 45.0 mW/m2 to 70.0 mW/m2 and the paleo-heat flow increased from 80 Ma to 25 Ma, reached a peak heat-flow values of approximately 70.0 mW/m2 at 25 Ma and then decreased exponentially from 25 Ma to present-day. The peak paleo-heat flow is explained by the Gulf of Aden and Red Sea Tertiary rifting during Oligocene-Middle Miocene, which has a considerable influence on the thermal maturity of the Mukalla source rocks. The source rocks of the Mukalla Formation are presently in a stage of oil and condensate generation with maturity from 0.50% to 1.10% Ro. Oil generation (0.5% Ro) in the Mukalla source rocks began from about 61 Ma to 54 Ma and the peak hydrocarbon generation (1.0% Ro) occurred approximately from 25 Ma to 20 Ma. The modelled hydrocarbon expulsion evolution suggested that the timing of hydrocarbon expulsion from the Mukalla source rocks began from 15 Ma to present-day.  相似文献   

14.
镉和汞两种重金属离子对四角蛤蜊的急性毒性   总被引：7，自引：1，他引：6       下载免费PDF全文
王晓宇  王清  杨红生 《海洋科学》2009,33(12):24-29
采用毒理学实验方法,比较研究了Cd~(2+)和Hg~(2+)对四角蛤蜊(Mactra veneriformis Reeve)急性毒性效应的差异,以期为进一步评价重金属离子对四角蛤蜊的毒性效应和作用机理等提供理论依据.死亡概率单位和实验液浓度对数的线性回归分析表明,Cd~(2+)对四角蛤蜊在24、48和96 h的半致死浓度(LC_(50))分别为15.961、5.149和2.383 mg/L,Hg~(2+)的LC_(50)分别为3.714、0.607和0.207 mg/L;Cd~(2+) 和Hg~(2+) 对四角蛤蜊的安全质量浓度分别为0.023 8 mg/L和0.002 1 mg/L,分别是我国渔业水质标准(GB11607-89)限定量的4.76倍和4.02倍.  相似文献   

15.
《Marine Chemistry》2007,103(1-2):30-45
The chemistry of dissolved Fe(III) was studied in the Scheldt estuary (The Netherlands). Two discrete size fractions of the dissolved bulk (< 0.2 μm and < 1 kDa) were considered at three salinities (S = 26, 10 and 0.3).Within the upper estuary, where fresh river water meets seawater, the dissolved Fe concentration decreases steeply with increasing salinity, for the fraction < 0.2 μm from 536 nM at S = 0.3 to 104 nM at S = 10 and for the fraction < 1 kDa from 102 nM to 36 nM Fe. Further downstream, in the middle and lower estuary, this decrease in the Fe concentration continues, but is far less pronounced. For all samples, the traditionally recognised dissolved strong organic Fe-binding ligand concentrations are lower than the dissolved Fe concentrations.Characteristics of dissolved Fe-binding ligands were determined by observing kinetic interactions with adsorptive cathodic stripping voltammetry. From these kinetic experiments we concluded that apart from the well-known strong Fe-binding organic ligands (L, logK′ = 19–22) also weak Fe-binding ligands (P) existed with an α value (binding potential = K′ · [P]) varying between 1011.1 and 1011.9. The presence of this relatively weak ligand explained the high concentrations of labile Fe present in both size fractions in the estuary. This weak ligand can retard or prevent a direct precipitation after an extra input of Fe.The dissociation rate constants of the weak ligand varied between 0.5 × 10− 4 and 4.3 × 10− 4 s− 1. The rate constants of the strong organic ligand varied between kd = 1.5 × 10− 3–17 × 10− 2 s− 1 and kf = 2.2 × 108–2.7 × 109 M− 1 s− 1. The dissociation rate constant of freshly amorphous Fe-hydroxide was found to be between 4.3 × 10− 4 and 3.7 × 10− 3 s− 1, more labile or equal to the values found by Rose and Waite [Rose, A.L., Waite, T.D., 2003a. Kinetics of hydrolysis and precipitation of ferric iron in seawater. Environ. Sci. Technol., 37, 3897–3903.] for freshly precipitated Fe in seawater.Kinetic rate constants of Fe with the ligand TAC (2-(2-Thiazolylazo)-p-cresol) were also determined. The formation rate constant of Fe(TAC)2 varied between 0.1 × 108 and 3.6 × 108 M− 1 s− 1, the dissociation rate constant between 0.2 × 10− 5 and 17 × 10− 5 s− 1 for both S = 26 and S = 10. The conditional stability constant of Fe(TAC)2 (βFe(TAC)2′) varied between 22 and 23.4 for S = 10 and S = 26 more or less equal to that known from the literature (logβFe(TAC)2′ = 22.4; [Croot, P.L., Johansson, M., 2000. Determination of iron speciation by cathodic stripping voltammetry in seawater using the competing ligand 2-(2-Thiazolylazo)-p-cresol (TAC). Electroanalysis, 12, 565–576.]). However, at S = 0.3 the logβFe(TAC)2′ was 25.3, three orders of magnitude higher. Apparently the application of TAC to samples of low salinity can only be done when the correct βFe(TAC)2′ is known.  相似文献   

16.
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/86Sri = 0.7042–0.7044, 143Nd/144Ndi = 0.5128–0.5129, 206Pb/204Pbi = 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.  相似文献   

17.
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 CeSN (average CeSN/Ce* = 6.823, SD = 0.192) and negative PrSN anomalies (average PrSN/Pr* = 0.310, SD = 0.010), and slightly negative GdSN anomalis (average GdSN/Gd* = 0.864, SD = 0.053), with no obvious EuSN anomaly (average EuSN/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 CeSN anomalies (average = 4.074, SD = 0.27) and LREE enrichment (average NdSN/YbSN = 3.164, SD = 0.787); (2) meteoric incursion can reverse Ce anomaly, from the strong positive Ce anomalies (CeSN/Ce* = 5.059) to slightly positive (CeSN/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 (EuSN/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.  相似文献   

18.
Low and high resolution petrographic studies have been combined with mineralogical, TOC, RockEval and porosity data to investigate controls on the evolution of porosity in stratigraphically equivalent immature, oil-window and gas-window samples from the Lower Toarcian Posidonia Shale formation. A series of 26 samples from three boreholes (Wickensen, Harderode and Haddessen) in the Hils syncline was investigated. The main primary components of the shales are microfossiferous calcite (30–50%), clay minerals (20–30%) and Type II organic matter (TOC = 7–15%, HI = 630–720 mg/gC in immature samples). Characteristic sub-centimetric light and dark lamination reflects rapid changes in the relative supply of these components. Total porosities decrease from 10 to 14% at Ro = 0.5% to 3–5% at Ro = 0.9% and then increase to 9–12% at Ro = 1.45%. These maturity-related porosity changes can be explained by (a) the primary composition of the shales, (b) carbonate diagenesis, (c) compaction and (d) the maturation, micro-migration, local trapping and gasification of heterogeneous organic phases. Calcite undergoes dissolution and reprecipitation reactions throughout the maturation sequence. Pores quantifiable in SEM (>ca. 50 nm) account for 14–25% of total porosity. At Ro = 0.5%, SEM-visible macropores1 are associated mainly with biogenic calcite. At this maturity, clays and organic matter are not visibly porous but nevertheless hold most of the shale porosity. Porosity loss into the oil window reflects (a) compaction, (b) carbonate cementation and (c) perhaps the swelling of kerogen by retained oil. In addition, porosity is occluded by a range of bituminous phases, especially in microfossil macropores and microfractures. In the gas window, mineral-hosted porosity is still the primary form of macroporosity, most commonly observed at the organic-inorganic interface. Increasing porosity into the gas window also coincides with the formation of isolated, spongy and complex meso- and macropores within organic particles, related to thermal cracking and gas generation. This intraorganic porosity is highly heterogeneous: point-counted macroporosity of individual organic particles ranges from 0 to 40%, with 65% of organic particles containing no macropores. We suggest that this reflects the physicochemical heterogeneity of the organic phases plus the variable mechanical protection afforded by the mineral matrix to allow macroporosity to be retained. The development of organic macroporosity cannot alone account for the porosity increase observed from oil to gas window; major contributions also come from the increased volume of organic micro- and meso-porosity, and perhaps by kerogen shrinkage.  相似文献   

19.
Although extensive studies have been conducted on unconventional mudstone (shales) reservoirs in recent years, little work has been performed on unconventional tight organic matter-rich, fine-grained carbonate reservoirs. The Shulu Sag is located in the southwestern corner of the Jizhong Depression in the Bohai Bay Basin and filled with 400–1000 m of Eocene lacustrine organic matter-rich carbonates. The study of the organic matter-rich calcilutite in the Shulu Sag will provide a good opportunity to improve our knowledge of unconventional tight oil in North China. The dominant minerals of calcilutite rocks in the Shulu Sag are carbonates (including calcite and dolomite), with an average of 61.5 wt.%. The carbonate particles are predominantly in the clay to silt size range. Three lithofacies were identified: laminated calcilutite, massive calcilutite, and calcisiltite–calcilutite. The calcilutite rocks (including all the three lithofacies) in the third unit of the Shahejie Formation in the Eocene (Es3) have total organic carbon (TOC) values ranging from 0.12 to 7.97 wt.%, with an average of 1.66 wt.%. Most of the analyzed samples have good, very good or excellent hydrocarbon potential. The organic matter in the Shulu samples is predominantly of Type I to Type II kerogen, with minor amounts of Type III kerogen. The temperature of maximum yield of pyrolysate (Tmax) values range from 424 to 452 °C (with an average of 444 °C) indicating most of samples are thermally mature with respect to oil generation. The calcilutite samples have the free hydrocarbons (S1) values from 0.03 to 2.32 mg HC/g rock, with an average of 0.5 mg HC/g rock, the hydrocarbons cracked from kerogen (S2) yield values in the range of 0.08–57.08 mg HC/g rock, with an average of 9.06 mg HC/g rock, and hydrogen index (HI) values in the range of 55–749 mg HC/g TOC, with an average of 464 mg HC/g TOC. The organic-rich calcilutite of the Shulu Sag has very good source rock generative potential and have obtained thermal maturity levels equivalent to the oil window. The pores in the Shulu calcilutite are of various types and sizes and were divided into three types: (1) pores within organic matter, (2) interparticle pores between detrital or authigenic particles, and (3) intraparticle pores within detrital grains or crystals. Fractures in the Shulu calcilutite are parallel to bedding, high angle, and vertical, having a significant effect on hydrocarbon migration and production. The organic matter and dolomite contents are the main factors that control calcilutite reservoir quality in the Shulu Sag.  相似文献   

20.
Aerobic NH4+ oxidation rates were measured along the strong oxygen gradient associated with the oxygen minimum zone (OMZ) of the eastern tropical South Pacific off northern Chile (∼20°S) during 2000, 2003, and 2004. This process was examined by comparing NH4+ rates of change during dark incubations, with and without the addition of allylthiourea, a classical inhibitor of the ammonia monooxygenase enzyme of ammonium-oxidizing bacteria. The contribution of aerobic NH4+ oxidation in dark carbon fixation and NO2− rates of change were also explored. Thirteen samples were retrieved from the oxycline (252 to ⩽5 μM O2; 15 to ∼65 m depth) and three from the oxygen minimum core (⩽5 μM O2; 100–200 m depth). Aerobic NH4+ oxidation rates were mainly detected in the upper part (15–30 m depth) of the oxycline, with rates ranging from 0.16 to 0.79 μM d−1, but not towards the oxycline base (40–65 m depth). In the oxygen minimum core, aerobic NH4+ oxidation was in the upper range and higher than in the upper part of the oxycline (0.70 and 1.0 μM d−1). Carbon fixation rates through aerobic NH4+ oxidation ranged from 0.18 to 0.43 μg C L−1 d−1 and contributed between 33% and 57% of the total dark carbon fixation, mainly towards the oxycline base and, in a single experiment, in the upper part of the oxycline. NO2− consumption was high (up to 10 μM d−1) towards the oxycline base and OMZ core, but was significantly reduced in experiments amended with allylthiourea, indicating that aerobic NH4+ oxidation could contribute between 8% and 76% of NO2− production, which in turn could be available for denitrifiers. Overall, these results support the important role of aerobic NH4+ oxidizers in the nitrogen and carbon cycling in the OMZ and at its upper boundary.  相似文献   

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