Synthetic saline-aqueous and hydrocarbon fluid inclusions trapped in calcite at temperatures and pressures relevant to hydrocarbon basins: A reconnaissance study

We conducted reconnaissance experiments to synthesize aqueous and hydrocarbon inclusions trapped in calcite at conditions relevant to petroleum basins, and characterize the microthermometric properties of such inclusions. Fluid inclusions (FIs) were synthesized in a system of saline aqueous solution (5 or 20 wt% NaCl) coexisting with either heavy crude oil or gasoline under gas-undersaturated conditions, from 90 to 210 °C and 200–550 bar. The synthetic inclusions are not representative of gas-bearing systems, and methane (CH₄) was not detected in any aqueous inclusions. The FIs are mainly distributed along planar healed cracks, indicating that the inclusions formed by fracture healing in the calcite crystal. Microthermometric measurements were conducted on coeval aqueous and hydrocarbon inclusions, and Raman spectroscopic analyses were done on aqueous inclusions, to determine the properties of FIs trapped at these conditions.Homogenization temperatures of synthetic FIs are mostly lower than the experimental trapping temperature, although the FIs show high variability in measured homogenization temperature. Results allow comparison of T_h values for each sample with the expected T_h, isochores and pressure corrections calculated for the system H₂ONaCl. The latter parameters are broadly consistent with the known PVTX properties of H₂ONaCl fluids, suggesting little effect of hydrocarbons on the homogenization behavior, although the low precision of the T_h data limits this assessment. Nevertheless, this result is not unexpected considering that light hydrocarbons (gas) is not present in the experiments (as corroborated by Raman spectroscopy), a consequence of using “dead” oil in the experiments. Simulation of gas-bearing petroleum basins will require additional protocols for producing gas, either by in-situ cracking of the starting hydrocarbon material, or by other means. The reconnaissance experiments documented here provide a basis for such future experiments.     

Fluid inclusion and microfabric studies on Zechstein carbonates (Ca2) and related fracture mineralizations – New insights on gas migration in the Lower Saxony Basin (Germany)

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 (T_h) of ca. 123 °C, but somewhat higher T_h of ca. 142 °C was found for calcite cement followed by early Fluorite A with T_h of 147 °C. A later Fluorite B preserves gas inclusions and brines with maximum T_h 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.     

Geochemistry and charge history of oils from the Yuqi area of Tarim Basin,NW China

The geochemistry, origin and charge history of oils from the Yuqi area of Tarim Basin have been investigated, through GC, GC-MS and fluid inclusion microthermometry analysis. The Yuqi oils accumulated mainly in three intervals: (1) in the Lower-Middle Ordovician Yingshan Formation (O_1-2y) carbonate reservoirs; (2) in the overlying Upper Triassic Halahatang Formation (T₃h); and (3) in the Lower Cretaceous Yageliemu Formation (K₁y) sandstones. Oils from different reservoirs have distinct physical properties, varying from extra-heavy (O_1-2y), heavy (T₃h), to light oils (T₃h and K₁y). However, their geochemical compositions show a high degree of similarity, which indicates that they derive from the same source rock. Abundant tricyclic terpanes, gammacerane, dibenzothiophene and C₂₁C₂₂steranes, together with a low level of diasteranes, indicate an anoxic marine source rock for oils in the Yuqi area. Oil-oil correlation shows that Yuqi oils derive from the same source bed as Tahe oils. The co-occurrence of intact n-alkanes and 25-norhopanes in all the samples supports the proposition that there is a mixture of an early filled severely biodegraded oil and a late filled fresh oil.In this study, charge history is examined on the basis of integration of fluid inclusion homogenization temperature data with 1D burial-thermal history models. Two episodes of oil charging are identified in the O_1-2y reservoir (well YQX1-1) at around 436-420 Ma (Middle-Late Silurian) and 10-3 Ma (Miocene to Pliocene), respectively. For the samples from the T₃h and K₁y intervals, only one episode of oil charge is indicated by the homogenization temperatures of coexisting aqueous inclusions with an inferred timing around 10-3 Ma. The T₃h heavy oil reservoir is assumed to be a secondary hydrocarbon pool, which accumulated by re-migration and re-distribution of hydrocarbons from O_1-2y hydrocarbon pools. The few early biodegraded oils in the K₁y light oils were probably picked up along the migration pathway during the late fresh oil charging.     

Hydrate bearing clayey sediments: Formation and gas production concepts

Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO₂CH₄ replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.     

Geochemical characteristics and isotopic reversal of natural gases in eastern Kopeh-Dagh,NE Iran

Natural gas samples from two gas fields located in Eastern Kopeh-Dagh area were analyzed for molecular and stable isotope compositions. The gaseous hydrocarbons in both Lower Cretaceous clastic reservoir and Upper Jurassic carbonate reservoir are coal-type gases mainly derived from type III kerogen, however enriched δD values of methane implies presence of type II kerogen related material in the source rock. In comparison Upper Jurassic carbonate reservoir gases show higher dryness coefficient resulted through TSR, while presence of C₁C₅ gases in Lower Cretaceous clastic reservoir exhibit no TSR phenomenon. Carbon isotopic values indicate gas to gas cracking and TSR occurrence in the Upper Jurassic carbonate reservoir, as the result of elevated temperature experienced, prior to the following uplifts in last 33–37 million years. The δ¹³C of carbon dioxide and δ³⁴S of hydrogen sulfide in Upper Jurassic carbonate reservoir do not primarily reflect TSR, as uplift related carbonate rock dissolution by acidic gases and reaction/precipitation of light H₂S have changed these values severely. Gaseous hydrocarbons in both reservoirs exhibit enrichment in C₂ gas member, with the carbonate reservoir having higher values resulted through mixing with highly-mature-completely-reversed shale gases. It is likely that the uplifts have lifted off the pressure on shale gases, therefore facilitated the migration of the gases into overlying horizons. However it appears that the released gases during the first major uplift (33–37 million years ago) have migrated to both reservoirs, while the second migrated gases have only mixed with Upper Jurassic carbonate reservoir gases. The studied data suggesting that economic accumulations of natural gas/shale gases deeper than Upper Jurassic carbonate reservoir would be unlikely.     

Compaction model for quartzose sandstones application to the Garn Formation,Haltenbanken, Mid-Norwegian Continental Shelf

The compaction of quartzose sandstones is described by a macroscopical visco–elasto–plastic model, derived from microscopical considerations. This model considers that the reduction of total porosity (the relative pore volume) is related to the changes in the relative cemented volume and the relative intergrain volume. Furthermore, we consider that the variations of these two petrophysical parameters result from two physical mechanisms, mechanical compaction and closed system chemical compaction.The model has been calibrated for the Middle Jurassic Garn Formation from the Haltenbanken area of the Mid-Norwegian Continental Shelf. Around 300 data points from 17 wells have been used in this study. The viscous parameters have been optimised against the present day data. With total porosity data the best fit is obtained for an activation energy between 14 and 16 kJ/mole and a macroscopical viscosity at 15°C between 39 and 46 GpaMa (1.210²⁴–1.410²⁴ Pa.s). If quartz cement data are used, the best fit is obtained for an activation energy between 16 and 18 kJ/mole and a macroscopical viscosity at 15°C between 47 and 56 GpaMa (1.510²⁴–17.10²⁴ Pa.s).The visco–elasto–plastic compaction model has been tested in the Haltenbanken area of Mid Norway, with the result that observed porosity trends and pore pressures can be modelled. Using multiple 2-D basin modelling simulations the results of this model and its implications for fluid flow and petroleum systems analysis can be seen. The compaction method has significant impact on the simulated fluid flow and petroleum migration pattern.     

Three-dimensional forward stratigraphic modelling of the gravel-to mud-rich fan-delta in the slope system of Zhanhua Sag,Bohai Bay Basin,China

An important hydrocarbon reservoir is hosted by the third member of the Shahejie Formation (Es₃) in the Zhanhua Sag, Bohai Bay Basin. Seismic stratal slices reveal different characteristics of channels and fan-delta lobes between the south (slope break belt) and southwest (gentle slope) areas combined with lithology, wire-line logs and three-dimensional (3-D) seismic data in the southern slope of Zhanhua Sag. And an excellent analogue has been provided for understanding various key depositional evolution of fan-deltas in the slope system (from base to top: Es₃^L, Es₃^M and Es₃^U). The Sedsim, a three-dimensional stratigraphic forward modelling programme, is applied to simulate the evolution of fan-deltas in the southern slope break systems and southwestern gentle slope systems of the Zhanhua Sag by considering a number of key processes and parameters affecting the fan-deltaic deposition from 43 Ma to 38.2 Ma. Modelling results indicate that depositional types and scales evolved from the thickest medium-scale gravel- or sand-rich fan deltas (43 Ma ∼41.4 Ma, Es₃^L) to the thinnest small-scale mud-rich fan deltas and lacustrine mud (41.4 Ma ∼39.8 Ma, Es₃^M), and lastly to less thicker larger-scale mixed sand-mud fan deltas (39.8 Ma ∼38.2 Ma, Es₃^U). The types of slope system, sediment supply and lake-level change are three controlling factors for determining the source-to-sink architecture of the gravel-to mud-rich fan-deltas and sediment-dispersal characteristics. This study has demonstrated that the process-based modelling approach can be effectively used to simulate complex geological environments and quantify controlling factors.     

Mineralogical and chemical distribution of the Es3L oil shale in the Jiyang Depression,Bohai Bay Basin (E China): Implications for paleoenvironmental reconstruction and organic matter accumulation

The Es₃^L (lower sub-member of the third member of the Eocene Shahejie Formation) shale in the Jiyang Depression is a set of relatively thick and widely deposited lacustrine sediments with elevated organic carbon, and is considered to be one of the most important source rocks in East China. We can determine the mineralogy, organic and inorganic geochemistry of the Es₃^L shale and calculate paleoclimate indexes by using multiple geochemical proxies based on organic chemistry (total organic carbon [TOC] and Rock-Eval pyrolysis), major and trace elements, X-Ray diffraction, and carbon and oxygen isotope data from key wells alongside ECS (Elemental Capture Spectroscopy) well log data. These indicators can be used to analyze the evolution of the paleoenvironment and provide a mechanism of organic matter (OM) accumulation. The Es₃^L oil shale has high TOC abundance (most samples >3.0%) and is dominated by Type I kerogens. Additionally, the organic-rich shale is rich in CaO and enrichment in some trace metals is present, such as Sr, Ba and U. The positive δ¹³C and negative δ¹⁸O values, high Sr/Ba, B/Ga and Ca/Ca + Fe ratios and low C/S ratios indicate that the Es₃^L shales were mainly deposited in a semi-closed freshwater-brackish water lacustrine environment. The consistently low Ti/Al and Si/Al ratios reflect a restricted but rather homogeneous nature for the detrital supply. Many redox indicators, including the Th/U, V/(V + Ni), and δU ratios, pyrite morphology and TOC-TS-Fe diagrams suggest deposition under dysoxic to suboxic conditions. Subsequently, the brackish saline bottom water evolved into an anoxic water body under a relatively arid environment, during which organic-lean marls were deposited in the early stage. Later, an enhanced warm-humid climate provided an abundant mineral nutrient supply and promoted the accumulation of algal material. OM input from algal blooms reached a maximum during the deposition of the organic-rich calcareous shale with seasonal laminations. High P/Ti ratios and a strongly positive relationship between the P and TOC contents indicate that OM accumulation in the oil shale was mainly controlled by the high primary productivity of surface waters with help from a less stratified water column. Factors such as the physical protection of clay minerals and the dilution of detrital influx show less influence on OM enrichment.     

Organic geochemistry of the Japan Sea sediments-1: Bulk organic matter and hydrocarbon analyses of Core KH-79-3, C-3 from the Oki Ridge for paleoenvironment assessments

Organic geochemical study of bulk organic matter (OM), hopanoid hydrocarbon and normal hydrocarbon (C₂₃C₃₅) was conducted for a 936-cm-long sediment core sample from the Oki Ridge of the Japan Sea (Core KH-79-3, C-3; 37°03.5 N, 134°42.6E, water depth 935 m). Stable carbon isotopic ratios were also measured for both bulk OM and individual hydrocarbons. The following results were obtained: (1) The weight ratios of total organic carbon to total nitrogen range from 6.2 to 9.4 in the core. The ¹³C values of bulk OM range from –25.1–20.7%.. The ¹³C values of OM in the sections of 140190 cm are lower (–25–24) than those in the other sections (–23–21). This result indicates that OM in the core except for the 140190 cm sections is essentially of marine origin. (2) The ¹³C value of diploptene (a hopanoid hydrocarbon) in the last glacial maximum (LGM), is –66.3 (vs. PDB), which indicates it originating in methanotrophic bacteria. This result provides evidence to support for the previous ideas (Oba et al., 1980, 1984; Masuzawa and Kitano, 1984) that the bottom waters in the Japan Sea were anoxic in LGM. (3) Long chain (C₂₃C₃₅) n-alkanes of higher-plant wax origin were found throughout the core. Their concentration is high in 140190 cm in depth, suggesting that eolian dust load was high in LGM. (4) The n-alkane/TOC ratio increases with decreasing ¹³C values of bulk OM. This result indicates that the load of terrestrial (probably eolian dust-derived) OM to the Japan Sea became higher in colder climates. (5) The CPI values of long-chain n-alkanes are different in different ¹³O stages of paleoclimate, probably reflecting variations in species of terrestrial higher plants as a result of climatological adaptations.     

The origin and charging directions of Neogene biodegraded oils: A geochemical study of large oil fields in the middle of the Shijiutuo Uplift,Bohai Sea,China

Two large oil fields (QHD32-6 and QHD33-1), located in the middle part of the Shijiutuo Uplift, have generally suffered mild biodegradation. Based on multivariate statistical analysis of the biomarker parameters, this study discussed the origin and charging directions for these two oil fields.In contrast to Ed₃-derived oil, all available oil samples from these two large oil fields displayed low C₁₉/C₂₃, C₂₄/C₂₆ and high G/H and 4-MSI, which are attributed to the mixtures of oils derived from the Shahejie (Es₁ and Es₃) source rocks. Oils in QHD32-6, which contain relatively more Es₃-derived oil, are called Group I oils, and most oils in QHD33-1, which share relatively more Es₁-derived oil, are called Group II oils. Our mixed oil experiments reveal the predominant Es₃- and Es₁-derived oil contribution for Group I and Group II oil groups, respectively; however, the selection of end member oils warrants further research.Based on comparisons of biomarker parameters, the QHD32-6 oil field was mainly charged in the north by oil generated from Shahejie formation source rocks in the Bozhong depression. However, oils from the north of QHD32-6 field display a remarkable difference to the oils in the south of this field, which may indicate that a charging pathway exists from the QHD33-1 field. Considering the variations in biomarker compositions in the west to -east and northwest to -southeast sections across the QHD33-1 and QHD32-6 oil fields, it can be deduced that Es₃-sourced oil migrated westward to the QHD32-6 traps, and then charging by Es₁ oil from the Bozhong Sag resulted in the QHD33-1 oil field being characterized by the mixture of Es₃- and Es₁-sourced oil. Moreover, migration of Es₁-derived oil from the Qinnan Sag was not identified, implying that the QHD33-1 oil field is mainly charged from the northeast of the Bozhong Sag.     

Charging of the Penglai 9-1 oil field,Bohai Bay basin,China: Functions of the delta on accumulating petroleum

The Penglai 9-1 (PL9-1) oil field, which contains China's third largest offshore oil accumulation (in-place reserves greater than 2.28 × 10⁸ ton or 1.49 × 10⁹ bbl), was found in shallow reservoirs (700–1700 m, 2297–5577 ft) within the most active fault zone in east China. The PL9-1 field contains two oil-bearing series, the granite intrusions in Mesozoic (Mz) and both the sandstone reservoirs in Neogene Guantao (Ng) and Neogene Minghuazhen (Nm) Formation. The origins of the PL9-1 field, both in terms of source rock intervals and generative kitchens, were determined by analyzing biomarker distributions for 61 source rock samples and 33 oil samples. The Mesozoic granite intrusions, which hold more than 80% of the oil reserves in the field, were charged in the west by oil generated from the third member (Es₃) of the Shahejie Formation in the Bodong depression. The Neogene reservoirs of the PL9-1 field were charged in the west by oil generated from the third member (Es₃) of the Shahejie Formation in the Bodong depression and in the south by oil generated from the first member (Es₁) of the Shahejie Formation in the Miaoxibei depression. Interactive contact between the large fan delta and the mature source rocks residing in the Es₃ Formation of the Bodong depression resulted in a high expulsion efficiency from the source rocks and rapid oil accumulation in the PL9-1 field, which probably explains how can this large oil field accumulate and preserve within the largest and most active fault zone in east China.     

2D and 3D coexisting modes of thermal convection in fractured hydrothermal systems - Implications for transboundary flow in the Lower Yarmouk Gorge

Numerical investigations of 2D and 3D modes of large-scale convection in faulted aquifers are presented with the aim to infer possible transport mechanisms supporting the formation of thermal springs through fractured aquicludes. The transient finite elements models are based on idealized structural features that can characterize many hydrothermal systems. The sensitivity analysis of the fault permeability showed that faults cross-cutting the main regional flow direction allow groundwater to be driven laterally by convective forces within the fault planes. Therein thermal waters can either discharge along the fault traces or exit the fault through adjacent permeable aquifers. In the latter case, the resulting flow is helicoidally and transient. The location and the spacing between discharge areas can migrate with time, is not strictly constrained to the damage zones and reflects the wavelength of the multicellular regime in the fault zone.An illustrative example based on simplified structural data of the Lower Yarmouk Gorge (LYG) is presented. The numerical calculations indicate that crossing flow paths result from the coexistence of fault convection, developing for example along NE-SW oriented faults within the Gorge, and additional flow fields. The latter are induced either by topography NS gradients, e.g. perpendicular to the major axe of the Gorge, or by local thermal convection in permeable aquifers below the Eocene aquiclude. Sensitivity analysis of fault hydraulic conductivity (K) and the analytical solutions based on viscous-dependent Rayleigh theory show that K values between 2.3e⁻⁷ m/s and 9.3e^{– 7} m/s (i.e. 7 m/yr and 30 m/yr, respectively) favor coexisting transport processes. The uprising thermal plumes spread over several hundred meters forming clusters of springs, in agreement with observation, and which temperature fall within the measured ranges, i.e. 20 °C−60 °C. To some extent the models also reproduced the transient behavior of the spring temperature. Owing to the idealized nature of the presented models, the numerical results and the associated analytical solution can be applied to study the onset of thermal convection and resulting flow patterns of any fractured hydrothermal basin.     

Geophysical and geochemical observations on actively seeping hydrocarbon gases on the south-eastern Yellow Sea continental shelf

In the southeastern Yellow Sea, active seepage of hydrocarbon gases has been observed by high-resolution (3.5 kHz) seismic profiling both in 1987 and 2001, occurring through a large number of plumes from the topmost pre-Holocene sedimentary layer. It is strong enough to compensate for current speed, extending vertically up to the sea surface. The gas seepage often appears to be explosive to form craters and diapirs, although pockmarks are rare due to the redistribution of mobile palimpsest sands. In core-top seawater and sediments, the gases are characterized by high amounts of C₂, homogenous ¹³C₁ values and a large difference (19.7 on average) between ¹³C₁ (–55.2 to –53.6 PDB) and ¹³C₂ (–36.8 to –32.5 PDB) values. The gases are considered to be generated with a smaller amount of C₁ at the early thermal cracking stage of labile source materials, after which the C₂ gas is enriched in ¹³C by diffusion or biological alternation at the generation or accumulation site. The homogenous ¹³C₁ values may be one of the geochemical characteristics of gases acquired at depth which are less altered in the case of rapid diffusive gas migration to the seafloor.     

Oceanographic controls on the carbon isotopic compositions of sinking particles from the Cariaco Basin

This study examined the relationship between carbon isotopic composition of sinking organic matter (OM) and the biological, physical and chemical properties of the surface ocean in the Cariaco Basin. The ¹³C/¹²C ratio of OM (δ¹³C_org) in sinking particles was determined on sediment trap samples from four depths collected from 1996 to 1999 as part of the CArbon Retention In A Colored Ocean time series. Water column properties, including temperature, productivity, chlorophyll and concentration of dissolved CO₂, were concurrently measured on monthly cruises. The δ¹³C_org varied from a high of –17.7‰ to a low of –22.6‰ during the study period. The variation of the δ¹³C_org throughout seasonal cycles was directly proportional to the strength of upwelling and was negatively correlated with temperature (r²=0.64). During the 1996–1997 upwelling event, the strongest during the study period, the δ¹³C_org increased by 4.4‰ whereas during the 1998–1999 upwelling event, the weakest during the study period, the δ¹³C_org only increased by 3.3‰. Contrary to most previous studies, we observed a negative relationship (r²=0.53) between [CO_2 aq] and the estimated isotopic fractionation factor (ε_p). However, there was no correlation between ε_p and the calculated growth rates indicating that there was non-diffusive uptake of carbon into phytoplankton cells. It thus appears that [CO_2 aq] does not control the δ¹³C_org in the water column of the study site. The best explanation for the isotopic enrichment observed is a carbon concentrating mechanism (CCM) in phytoplankton. The existence of a CCM in phytoplankton has major implications for the interpretation of the δ¹³C_org in the Cariaco Basin.     

南海北部莺歌海岭头岬近岸烃类渗漏喷口分布及气体地球化学

Natural hydrocarbon seeps in a marine environment are one of the important contributors to greenhouse gases in the atmosphere,including methane,which is significant to the global carbon cycling and climate change.Four hydrocarbon seep areas,the Lingtou Promontory,the Yinggehai Rivulet mouth,the Yazhou Bay and the Nanshan Promontory,occurring in the Yinggehai Basin delineate a near-shore gas bubble zone.The gas composition and geochemistry of venting bubbles and the spatial distribution of hydrocarbon seeps are surveyed on the near-shore Lingtou Promontory.The gas composition of the venting bubbles is mainly composed of CO_2,CH_4,N_2 and O_2,with minor amounts of non-methane hydrocarbons.The difference in the bubbles' composition is a possible consequence of gas exchange during bubble ascent.The seepage gases from the seafloor are characterized by a high CO_2 content(67.35%) and relatively positive δ~(13)C_(V_PDB) values(-0.49×10~(-3)-0.86×10~(-3)),indicating that the CO_2 is of inorganic origin.The relatively low CH_4 content(23%) and their negative δ~(13)C_(V-PDB) values(-34.43×10~(-3)--37.53×10~(-3)) and high ratios of C_1 content to C_(1-5) one(0.98-0.99)as well point to thermogenic gases.The hydrocarbon seeps on the 3.5 Hz sub-bottom profile display a linear arrangement and are sub-parallel to the No.1 fault,suggesting that the hydrocarbon seeps may be associated with fracture activity or weak zones and that the seepage gases migrate laterally from the central depression of the Yinggehai Basin.     

Estimating the parameters of pulsed sources from data on acoustic waves recorded in the atmosphere

The possibility of estimating the parameters of surface pulsed sources from data on acoustic waves recorded in the atmosphere is studied. Experimental values are given for peak pressure P ₊ of recorded acoustic signals, wave-profile area S ₊ in their positive phase, and length t ₊ of this phase, and the approximations of these parameters are obtained within wide ranges of source energy 10^–3 < E < 10¹⁰ kg TNT and scaled distances 1 < R/E ^1/3 < 4 × 10⁴ m/kg^1/3. Conventional methods of estimating the acoustic energy E according to data obtained from acoustic measurements in the atmosphere are analyzed, and ways to improve their accuracy are proposed. The influence of the type of explosions on the parameters P ₊, S ₊, and t ₊ of acoustic signals at long distances R/E ^1/3 > 500 m/kg^1/3 from explosions is shown.     

Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

The sources and distribution of organic matter (OM) in surface waters and sediments from Winyah Bay (South Carolina, USA) were investigated using a variety of analytical techniques, including elemental, stable isotope and organic biomarker analyses. Several locations along the estuary salinity gradient were sampled during four different periods of contrasting river discharge and tidal range. The dissolved organic carbon (DOC) concentrations of surface waters ranged from 7 mg l⁻¹ in the lower bay stations closest to the ocean to 20 mg l⁻¹ in the river and upper bay samples. There was a general linear relationship between DOC concentrations and salinity in three of the four sampling periods. In contrast, particulate organic carbon (POC) concentrations were significantly lower (0.1–3 mg l⁻¹) and showed no relationship with salinity. The high molecular weight dissolved OM (HMW DOM) isolated from selected water samples collected along the bay displayed atomic carbon:nitrogen ratios ([C/N]a) and stable carbon isotopic compositions of organic carbon (δ¹³C_OC) that ranged from 10 to 30 and from −28 to −25‰, respectively. Combined, such compositions indicate that in most HMW DOM samples, the majority of the OM originates from terrigenous sources, with smaller contributions from riverine and estuarine phytoplankton. In contrast, the [C/N]a ratios of particulate OM (POM) samples varied significantly among the collection periods, ranging from low values of 5 to high values of >20. Overall, the trends in [C/N]a ratios indicated that algal sources of POM were most important during the early and late summer, whereas terrigenous sources dominated in the winter and early spring.In Winyah Bay bottom sediments, the concentrations of the mineral-associated OM were positively correlated with sediment surface area. The [C/N]a ratios and δ¹³C_OC compositions of the bulk sedimentary OM ranged from 5 to 45 and from −28 to −23‰, respectively. These compositions were consistent with predominant contributions of terrigenous sources and lesser (but significant) inputs of freshwater, estuarine and marine phytoplankton. The highest terrigenous contents were found in sediments from the river and upper bay sites, with smaller contributions to the lower parts of the estuary. The yields of lignin-derived CuO oxidation products from Winyah Bay sediments indicated that the terrigenous OM in these samples was composed of variable mixtures of relatively fresh vascular plant detritus and moderately altered soil OM. Based on the lignin phenol compositions, most of this material appeared to be derived from angiosperm and gymnosperm vascular plant sources similar to those found in the upland coastal forests in this region. A few samples displayed lignin compositions that suggested a more significant contribution from marsh C₃ grasses. However, there was no evidence of inputs of Spartina alterniflora (a C₄ grass) remains from the salt marshes that surround the lower sections of Winyah Bay.     

Observed relationship between the drag coefficient,Cd, and stability parameter, (−z/L)

Momentum and heat flux were measured with a sonic anemometer at the Marine Observation Tower in the port of ItÔ. Under unstable conditions (T _w -T _a =3C4C), using the eddy correlation method, results show thatCd=(1.2±0.3)×10^–3 andCh=(1.5±0.3)×10^–3 at 5.5 m above mean sea level except for the case of weak winds.An unexpected relationship betweenCd and (–z/L) was observed, that is,Cd decreases as (–z/L) increases. If roughness variation over the sea is taken into account, we can explain the decrease in the range of (–z/L) less than 1, but not in the range greater than 1. This is due to a strong instability effect and the change of roughness class, from moderately rough to smooth.     

Dissociation constants of protonated cysteine species in seawater media

The dissociation constants (pK₁, pK₂ and pK₃) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK₃ in the Na–Mg–Cl solutions have been attributed to the formation of Mg²⁺ complexes with Cys²⁻ anions

Mg²⁺ + Cys²⁻ = MgCys

The stability constants have been fitted to

after corrections are made for the interaction of Mg²⁺ with H⁺.The pK₁ seawater measurements indicate that H₃Cys⁺ interacts with SO₄²⁻. The Pitzer parameters β⁰(H₃CysSO₄), β¹(H₃CysSO₄) and C(H₃CysSO₄) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK₂ and pK₃ in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK₁, pK₂ and pK₃ that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

Hydrocarbon migration and accumulation of the Suqiao buried-hill zone in Wen'an Slope,Jizhong Subbasin,Bohai Bay Basin,China

The hydrocarbon migration and accumulation of the Suqiao deep buried-hill zone, in the Jizhong Subbasin, the Bohai Bay Basin, eastern China, was investigated from the perspective of paleo-fluid evidence by using fluid inclusions, quantitative fluorescence techniques (QGF), total scanning fluorescence method (TSF) and organic geochemical analysis. Results show that the current condensate oil-gas reservoirs in the study area once were paleo-oil reservoirs. In addition, the reservoirs have experienced at least two stages of hydrocarbon charge from different sources and/or maturities. During the deposition of the Oligocene Dongying Formation (Ed), the deep Ordovician reservoirs were first charged by mature oils sourced from the lacustrine shale source rocks in the fourth member of Shahejie and Kongdian Formations (Es₄+Ek), and then adjusted at the end of Ed period subsequently by virtue of the tectonic movement. Since the deposition of the Neogene Minghuazhen Formation (Nm), the reservoirs were mainly charged by the gas that consisted of moderate to high-maturity condensate and wet gas sourced from the Es₄+Ek lacustrine shale source rocks and mature coal-derived gas sourced from the Carboniferous-Permian (C-P) coal-bearing source rocks. Meanwhile, the early charged oil was subjected to gas flushing and deasphalting by the late intrusion of gas. The widely distributed hydrocarbon inclusions, the higher QGF Index, and FOI (the frequency of oil inclusions) values in both gas-oil and water zone, are indicative of early oil charge. In addition, combined with the homogenization temperatures of the fluid inclusions (<160 °C) and the existence of solid-bitumen bearing inclusions, significant loss of the n-alkanes with low carbon numbers, enrichments of heavier components in crude oils, and the precipitation of asphaltene in the residual pores suggest that gas flushing may have played an important role in the reservoir formation.