Analysis of some aromatic hydrocarbons in a benzene-soluble bitumen from Green River shale

The hydrocarbon content of an aromatic fraction, isolated from the bitumen of Green River shale, was studied by mass spectrometry, infra-red spectrometry, gas chromatography and a dehydrogenation technique. The hydrocarbon types and their distribution in this aromatic fraction, as determined by mass spectrometry, include the following: C_nH_2n?6(10%), C_nH_{2n?8 (31 %)}, C_nH_2n?10(18%), C_nH_2n?12(12%), C_nH_2n?14(8%) and a series of alkenylbenzenes (20%). The carbon-number range, empirical formulae and quantity of each compound in the major types are reported. Mass spectra of several compounds and homologous mixtures of compounds isolated from the aromatic fraction are also given.     

Molecular characterization of Type I kerogen from the Green River Formation using advanced NMR techniques in combination with electrospray ionization/ultrahigh resolution mass spectrometry

This study describes a new approach for characterizing high molecular weight compounds in Type I kerogen, involving both nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron mass spectrometry (FTICR-MS). Kerogen isolated from the Mahogany zone of the Green River Formation was examined directly using high resolution magic angle spinning (HRMAS) NMR to obtain liquid-like multidimensional spectra. It was then successively extracted with n-pentane, dichloromethane and pyridine. Pyridine extraction was also performed for comparison with the successive extractions. Using solid-state NMR, we show that the sum of the successive extracts and the single pyridine extract are quantitatively representative of the unextracted kerogen. This suggests that a non-invasive characterization of Green River kerogen can be obtained by examining the soluble extracts, all of which were subjected to ESI-FTICR-MS to identify a wide series of compounds. Series of polar CHO, CHOS and CHON compounds between C₁₂ and C₅₀₊ were found. In all the extracts the two homologous series of acids (C_nH_2nO₂ and C_nH_2n−2O₄) dominated. Collision-induced dissociation was also employed to identify the different functional groups comprising the different series. The CHO series contained carboxylic acid and alkoxyl groups, whereas the CHOS and CHON series contained sulfoxide groups and nitrile-type compounds. The results also show that pyridine extraction can be used either for screening a large series of samples or for the specific study of CHO compounds. However for a detailed and complete study of the different homologous series we recommend using the successive extraction protocol.     

Tri- and tetraterpenoid hydrocarbons in the Messel oil shale

The high molecular weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high resolution gas chromatography and combined gas chromatography-mass spectrometry. The following compounds are present: perhydrolycopene (1; lycopane), together with one or more unsaturated analogues with the same skeleton; a series of 4-methylsteranes (2c) in higher abundance than their 4-desmethyl analogues; two series of pentacyclic triterpanes, one series (C₂₇-C₃₂) based on the hopane structure (3a-e), and the other (C₂₇-C₃₁) based on the 17α-H hopane structure (3a-d, 17αH); and an intact triterpene hop-17 (21)-ene [3c, Δ 17(21)]. Only two additional triterpanes were detected in minor concentrations, viz. 30-normoretane (3b, 21αH) and a C₃₁ triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment. Comparison of the tri- and tetraterpenoid hydrocarbons with those of the Green River Shale indicates differences in the organisms contributing to the two sediments.     

Possible carotenoid-derived structures in fossil kerogens

The unique KMnO₄ degradation products of β-carotene, previously identified as 2,2-dimethyl succinic acid (C₆) and 2,2-dimethyl glutaric acid (C₇) have been found in the oxidation products of Green River shale (Eocene, 52 × 10⁶yr) and Tasmanian Tasmanite (Permian, 220−274 × 10⁶yr) kerogens. These two compounds were also detected in KMnO₄ degradation products of young kerogens from lacustrine and marine sediments. The results indicate that kerogens incorporated carotenoids (possibly β-carotene) at the time of kerogen formation in surface sediments. Both acids are useful markers to obtain information on biological precursors contributing to the formation of fossil kerogens.     

Occurrence and influence of residual gas released by crush methods on pore structure in Longmaxi shale in Yangtze Plate,Southern China

The composition of gas released under vacuum by crushing from the gas shale of Longmaxi Formation in Upper Yangtze Plate, Southern China was systematically investigated in this study. The effect of residual gas release on pore structures was checked using low-pressure nitrogen adsorption techniques. The influence of particle size on the determination of pore structure characteristics was considered. Using the Frenkel-Halsey-Hill method from low-pressure nitrogen adsorption data, the fractal dimensions were identified at relative pressures of 0−0.5 and 0.5−1 as D₁ and D₂, respectively, and the evolution of fractal features related to gas release was also discussed. The results showed that a variety component of residual gas was released from all shale samples, containing hydrocarbon gas of CH₄ (29.58% −92.53%), C₂H₆ (0.97% −2.89%), C₃H₈ (0.01% −0.65%), and also some non-hydrocarbon gas such as CO₂ (3.54% − 67.09%) and N₂ (1.88%−8.07%). The total yield of residual gas was in a range from 6.1 μL/g to 17.0 μL/g related to rock weight. The geochemical and mineralogical analysis suggested that the residual gas yield was positively correlated with quartz (R²=0.5480) content. The residual gas released shale sample has a higher surface area of 17.20−25.03 m²/g and the nitrogen adsorption capacity in a range of 27.32−40.86 ml/g that is relatively higher than the original samples (with 9.22−16.30 m²/g and 10.84−17.55 ml/g). Clearer hysteresis loop was observed for the original shale sample in nitrogen adsorption-desorption isotherms than residual gas released sample. Pore structure analysis showed that the proportions of micro-, meso- and macropores were changed as micropores decreased while meso- and macropores increased. The fractal dimensions D₁ were in range from 2.5466 to 2.6117 and D₂ from 2.6998 to 2.7119 for the residual gas released shale, which is smaller than the original shale. This factor may indicate that the pore in residual gas released shale was more homogeneous than the original shale. The results indicated that both residual gas and their pore space have few contributions to shale gas production and effective reservoir evaluation. The larger fragments samples of granular rather than powdery smaller than 60 mesh fraction of shale seem to be better for performing effective pore structure analysis to the Longmaxi shale.     

Evolution of nC16H34-water–mineral systems in thermal capsules and geological implications for deeply-buried hydrocarbon reservoirs

Organic-inorganic interactions between hydrocarbons and most minerals in deeply buried reservoirs remain unclear. In this study, gold capsules and fused silica capillary capsules (FSCCs) with different combinations of nC₁₆H₃₄, water (distilled water, CaCl₂ water) and minerals (quartz, feldspar, calcite, kaolinite, smectite, and illite) were heated at 340 °C for 3–10 d, to investigate the evolution and reaction pathways of the organic–inorganic interactions in different hot systems.After heating, minerals exhibited little alteration in the anhydrous systems. Mineral alterations, however, occurred obviously in the hydrous systems. Different inorganic components affected nC₁₆H₃₄ degradation differently. Overall, water promoted the free-radical thermal-cracking reaction and step oxidation reaction but suppressed the free-radical cross-linking reaction. The impact of CaCl₂ water on the nC₁₆H₃₄ degradation was weaker than the distilled water as high Ca²⁺ concentration suppressed the formation of free radicals. The presence of different waters also affects the impact of different minerals on nC₁₆H₃₄ degradation, via its impact on mineral alterations. In the anhydrous nC₁₆H₃₄-mineral systems, calcite and clays catalyzed generation of low-molecular-weight (LMW) alkanes, particularly the clays. Quartz, feldspar, and calcite catalyzed generation of high-molecular-weight (HMW) alkanes and PAHs, whereas clays catalyzed the generation of LMW alkanes and mono-bicyclic aromatic hydrocarbons (M-BAHs). In the hydrous nC₁₆H₃₄-distilled water–mineral systems, all minerals but quartz promoted nC₁₆H₃₄ degradation to generate more LMW alkanes, less HMW alkanes and PAHs. In the nC₁₆H₃₄-CaCl₂ water–mineral systems, the promotion impact of minerals was weaker than that in the systems with distilled water.This study demonstrated the generation of different hydrocarbons with different fluorescence colors in the different nC₁₆H₃₄-water–mineral systems after heating for the same time, implying that fluorescence colors need to be interpreted carefully in investigation of hydrocarbon charging histories and oil origins in deeply buried reservoirs. Besides, the organic–inorganic interactions in different nC₁₆H₃₄-water–mineral systems proceeded in different pathways at different rates, which likely led to preservation of liquid hydrocarbons at different depth (temperature). Thus, quantitative investigations of the reaction kinetics in different hydrocarbon-water-rock systems are required to improve the prediction of hydrocarbon evolution in deeply buried hydrocarbon reservoirs.     

Long-chain carboxylic acids in pyrolysates of Green River kerogen

Long-chain fatty acids (C₁₀-C₃₂), as well as C₁₄-C21 isoprenoid acids (except for C₁₈), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C₁₆ followed by lesser amounts of C₁₈ and C₂₂ acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C₁₄, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C₁₈ and C₃₀. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.     

n-Alkan-2-one distributions in a northeastern China peat core spanning the last 16 kyr

Most research on long chain methyl ketones has focused on their origins and distributions. Their application in paleoclimate studies is less common than that of other n-alkyl lipids. The goal of this research was to explore this potential by studying n-alkan-2-ones from the Hani peat sequence in northeastern China. They were identified using gas chromatography-mass spectrometry (GC-MS) and showed a distribution ranging from C₁₉ to C₃₁ with a strong odd/even predominance. This type of distribution is considered to derive from Sphagum and microbial oxidation of n-alkanes. Comparison with climate sensitive indicators and macrofossil analysis shows that microbial oxidation of n-alkanes derived from higher plants was enhanced during the warm early Holocene period. This led us to develop three n-alkan-2-one proxies - C₂₇/ΣC_23-31 (C₂₇/HMW-KET), carbon preference index (CPI_H-KET) and average chain length (ACL_(27-31)-KET) - as possible indicators of paleoclimate in the peat-forming environment. These proxies, in combination with C₂₇n-alkane δD values and peat cellulose δ¹⁸O records, might allow examination of paleo-ecosystem behavior during climatic evolution in northeastern China over the past 16,000 yr.     

Effects of cations and anions on iron and manganese sorption and desorption capacity in calcareous soils from Iran

This study investigated the effect of cations and anions on the sorption and desorption of iron (Fe) and manganese (Mn) in six surface calcareous soil samples from Western Iran. Six 10 mM electrolyte background solutions were used in the study, i.e., KCl, KNO₃, KH₂PO₄, Ca(NO₃)₂, NaNO₃, and NH₄NO₃. NH₄NO₃ and NaNO₃ increased the soil retention of Fe and Mn, whereas Ca(NO₃)₂ decreased the soil retention of Fe and Mn. Iron and Mn sorption was decreased by NO₃ ^? compared with H₂PO₄ ^? or Cl^?. The Freundlich equation adequately described Fe and Mn adsorption, with all background electrolytes. The Freundlich distribution coefficient (K _F) decreased in the order H₂PO₄ ^? > Cl^? > NO₃ ^? for Mn and H₂PO₄ ^? > NO₃ ^? > Cl^? for Fe. The highest sorption reversibility was for Fe and Mn in competition with a Ca²⁺ background, indicating the high mobility of these two cations. A MINTEQ speciation solubility model showed that Fe and Mn speciation was considerably affected by the electrolyte background used. Saturation indices indicated that all ion background solutions were saturated with respect to siderite and vivianite at low and high Fe concentrations. All ion background solutions were saturated with respect to MnCO_3(am), MnHPO₄, and rhodochrosite at low and high Mn concentrations. The hysteresis indices (HI) obtained for the different ion backgrounds were regressed on soil properties indicating that silt, clay, sand, and electrical conductivity (EC) were the most important soil properties influencing Fe adsorption, while cation exchange capacity (CEC), organic matter (OM), and Mn-DTPA affected Mn adsorption in these soils.     

Rates of nitrification along an estuarine gradient in Narragansett Bay

Rates of pelagic nitrification, measured using N-Serve-sensitive [¹⁴C]bicarbonate uptake, varied by as much as an order-of-magnitude among three sites along the salinity gradient of Narragansett Bay (Rhode Island, United States). Rates were always higher at the Providence River estuary site (0.04–11.2 μmol N I^?1 d^?1) than at either the lower Narragansett Bay site (0.02–0.98 μmol N I^?1d^?1) or the freshwater Blackstone River site (0.04–1.7 μmol N I^?1d^?1). Although temperature was the most important variable regulating the annual cycle of nitrification, ammonium concentrations were most likely responsible for the large differences in rates among the three sites in summer. At the levels found in this estuarine system, salinity and concentrations of oxygen or total suspended matter did not appear to have a direct measurable effect on nitrification and pH did only occasionally. Nitrification played an important role in the nitrogen cycle at all three sites. In Narragansett Bay, nitrification contributed 55% of the NO₂ ^? and NO₃ ^? entering annually, and was the major source during spring and summer. Water from offshore was the only other large source of NO₂ ^? and NO₃ ^?, contributing 34%. High summer rates of nitrification could support much of the phytoplankton uptake of NO₂ ^? and NO₃ ^?. In the Providence River estuary, the largest annual input of NO₂ ^? and NO₃ ^? was from rivers (54%), although nitrification (28%) and water from lower portions of the bay (11%) also made large contributions. Again, nitrification was most important in the summer. The high rates of nitrification in the Providence River estuary during summer were also likely to be important in terms of oxygen demand, and the production of nitric and nitrous oxides. In the Blackstone River, NO₂ ^? and NO₃ ^? concentrations increased as the river flowed through Rhode Island, and nitrification was a possible source.     

Stepwise pyrolysis-gas chromatography of kerogen in sedimentary rocks

Stepwise pyrolysis-gas chromatography is used to examine and characterize the carbonaceous matter in sedimentary rocks. Low-temperature steps remove material normally volatile or extracted by benzene-methanol. Successively-higher temperature steps degrade the insoluble carbonaceous matter (kerogen) into smaller molecular pieces. The sequential pyrolysis steps have the advantage of breaking the kerogen at several temperatures which may be related to bond type or strength. The pyrolysis product chromatograms from each step can be compared. The molecular sizes (chain length) of kerogens fragments can be determined. The results presented here show the molecules in the range C₁₁ to C₂₃ because: (1) they can be compared to normal petroleum source rock extractables; and (2) these large molecules give a feeling for the molecular construction of the kerogen.Green River and Antrim shales show low-temperature material which is indigenous and not modified compared to the pyrolyzed kerogen fragments in the range C₁₁C₂₃. Kupferletten shows low-temperature material of a narrow molecular weight range of C₁₅C₁₉ which is probably derived from the kerogen. Monterey shale low-temperature material appears to be unrelated to the kerogen as represented by its pyrolysis products. The Pierre shale kerogen shows molecules over the range C₁₁C₂₃. Kerogen from the Romney shale has no molecules large than C₈ in its pyrolysis products and no petroleum potential due to thermal and tectonic diagenesis.     

Biological markers from Green River kerogen decomposition

Isoprenoid and other carbon skeletons that are formed in living organisms and preserved essentially intact in ancient sediments are often called biological markers. The purpose of this paper is to develop improved methods of using isoprenoid hydrocarbons to relate petroleum or shale oil to its source rock. It is demonstrated that most, but not all, of the isoprenoid hydrocarbon structures are chemically bonded in kerogen (or to minerals) in Green River oil shale. The rate constant for thermally producing isoprenoid, cyclic, and aromatic hydrocarbons is substantially greater than for the bulk of shale oil. This may be related to the substantial quantity of CO₂ which is evolved coincident with the isoprenoid hydrocarbons but prior to substantial oil evolution. Although formation of isoprenoid alkenes is enhanced by rapid heating and high pyrolysis temperatures, the ratio of isoprenoid alkenes plus alkanes to normal alkenes plus alkanes is independent of heating rate. High-temperature laboratory pyrolysis experiments can thus be used to predict the distribution of aliphatic hydrocarbons in low temperature processes such as in situ shale oil production and perhaps petroleum formation. Finally, we demonstrate that significant variation in biological marker ratios occurs as a function of stratigraphy in the Green River formation. This information, combined with methods for measuring process yield from oil composition, enables one to relate time-dependent processing conditions to the corresponding time-dependent oil yield in a vertical modified-in situ retort even if there is a substantial and previously undetermined delay in drainage of shale oil from the retort.     

Control of nutrient concentrations in the Seekonk-Providence River region of Narragansett Bay,Rhode Island

Six synoptic samplings of nutrient concentrations of the water column and point-source inputs (rivers, sewage treatment plants) were conducted in the Seekonk-Providence River region of Narragansett Bay. Concentrations of nutrients (NH₄ ⁺, NO₂ ^?+NO₃ ^?, PO₄ ^?3, dissolved silicon, particulate N, particulate C) were predicted using a conservative, two-layer box model in order to assess the relative influence of external inputs and internal processes on observed concentrations. Although most nutrients were clearly affected by processes internal to the system, external input and mixing explained most of the variability in and absolute magnitude of observed concentrations, especially for dissolved constituents. In the bay as a whole, two functionally distinct regions can now be identified: the Seekonk-Providence River, where dissolved nutrient concentrations are externally controlled and lower Narragansett Bay where internal processes regulate the behavior of nutrients. A preliminary nitrogen budget suggests that the Seekonk-Providence River exports some 95% of the nitrogen entering the system via point sources and bottom water from upper Narragansett Bay.     

Organic geochemistry of the Vindhyan sediments: Implications for hydrocarbons

The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S₁ (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S₂ (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the T_max (temperature at highest yield of S₂) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH₄ (C₁), C₂H₆ (C₂), C₃H₈ (C₃) and nC₄H₁₀, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ¹³C₁) and ethane (δ¹³C₂) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C₁–C₄) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.     

Thio complexes of gold and the transport of gold in hydrothermal ore solutions

The solubility of gold in aqueous sulphide solutions has been determined from pH_20°C ≈ 4 to pH_20°C ≈ 9.5 in the presence of a pyrite-pyrrhotite redox buffer at temperatures from 160 to 300°C and 1000 bar pressure. Maximum solubilities were obtained in the neutral region of pH as, for example, with m_NaHS = 0.15 m, pH_20°C = 5.96, T = 309°C, P = 1000 bar where a gold solubility of 225 mg/kg was obtained. It was concluded that three thio gold complexes contributed to the solubility. The complex Au₂(HS)₂S^2? predominated in alkaline solution, the Au(HS)₂^? complex occurred in the neutral pH region, and in the acid pH region, it was concluded with less certainty that the Au(HS)° complex was present. Formation constants calculated forAu₂(HS)₂S^2? and Au (HS)₂^? emphasize their high stability. In the temperature range from 175 to 250°C, values of pβ for Au₂(HS)₂S^2? vary from ?53.0 to 47.9 (±1.6) and from ?23.1 to ?19.5 ( ± 1.5) for Au(HS)₂^?. Equilibrium constante for the dissolution reactions, $\text{Au° + H}{}_2\text{S + HS}{}^{\mathrm{?}}\text{? Au(HS)}{}_2{}^{\mathrm{?}}\text{+}\text{1}\text{2}\text{H}{}_2$ and 2Au° + H₂S + 2H8^? ? Au(HS)₂^? + H₂ vary from pK_m = +2.4 to +2.55 (±0.10) for Au₂(HS)₂S^2? and from pK_n = + 1.29 to + 1.19 (±0.10) for Au(HS)₂^? over the temperature range 175 to 250°C. Enthalpies of these dissolution reactions were calculated to be ΔH_m° = ?5.2 ±2.0 kcal/mol and ΔH_n° = +1.7 ±2.0 kcal/mol respectively. It was concluded that gold is probably transported in hydrothermal ore solutions as both thio and chloro complexes and may be deposited in response to changes in temperature, pressure, pH, oxidation potential of the system and total sulphur concentration.     

Sources and Processes Affecting Nitrate in a Dam-Controlled Subtropical River,Southwest China

Excess nutrient (N and P) loads are recognized as the major cause of serious water quality problems in China. River systems play a very important role in nitrate (NO₃ ^?) transportation and transformation in the aquatic environment. To understand and clarify the sources and processes affecting NO₃ ^? in river basins, we have examined spatial and temporal variations of concentration and dual-isotopic composition of NO₃ ^? in the dam-controlled Jialing River, a major tributary of the Yangtze River where land use is dominated by agriculture. Water samples were collected in July 2008 and February 2009 from the main channel of the Jialing River and its major tributaries. The δ¹⁵N and δ¹⁸O of NO₃ ^? range from 1.5 to 11.0 ‰ (average 6.2 ‰) and ?5.0 to 11.1 ‰ (average, 1.6 ‰), respectively. NO₃ ^? isotope data and δ¹⁸O of water interpreted in combination with hydrological and chemical data suggest that most of the NO₃ ^? input is from nitrification during the rainy season, and discharge of sewage and manure in the upper course and from cities accounts for much of the NO₃ ^? load during the dry season. The construction of cascade dams has led to retention of Si and a decrease in the Si/N ratio, implying that assimilation and/or denitrification may significantly affect NO₃ ^? in the dam area, as demonstrated by NO₃ ^? and dissolved Si concentrations, and \(\updelta^{ 1 5} {\text{N}}_{{{\text{NO}}_{3} }}\) and \(\updelta^{ 1 8} {\text{O}}_{{{\text{NO}}_{3} }}\) values. This study indicates that dual-isotopic data can be used to identify NO₃ ^? pollution sources and the processes NO₃ ^? has undergone during its retention and transport in the watershed of the dam-controlled Jialing River.     

昭通示范区黄金坝气田五峰—龙马溪组页岩气储层地质特征

昭通国家级页岩气示范区黄金坝气田是继礁石坝和长宁—威远之后中国又一个在页岩气勘探、开发领域实现重大突破的地区,为了系统地展示黄金坝气田页岩气资源富集的储层条件,为未来的勘探工作提供参考,以五峰—龙马溪组页岩气储层为研究对象,从区域地质条件、储层岩石学、物性和地球化学4个方面对该页岩气储层进行了综合研究。结果表明稳定的区域构造和良好的顶底板条件是黄金坝地区页岩气资源富集的关键,良好的保存条件使储层维持了较高的压力(压力系数1);较高的孔隙度(平均4%)和TOC含量(目的层2%)提供了良好的储集空间,使储层具有较高的含气量(1.35~3.48 cm3/g,平均2.50 cm3/g);天然气地球化学数据表明,区内天然气主要成分为CH4(97%),其次还含有少量的C2H6、C3H8和CO2;天然气同位素数据表明烃类C同位素组成发生了倒转,表明储层具有良好的封闭性。但储层孔隙系统较为复杂,且非均质性极强,从而导致渗透率较低,在储层改造施工过程中应予以充分考虑。总体上,黄金坝气田具有较好的开发前景,生产测试表明,区内直井压裂产量为0.5×104~3.5×104m3/d/井,水平井压裂产量可达12×104~40×104m3/d/井。     

Seasonal and spatial water quality changes in the outflow plume of the Atchafalaya River,Louisiana, USA

The objective of this study was to examine the interaction between the Atchafalaya River and the Atchafalaya Delta estuarine complex. Measurements of suspended sediments, inorganic nutrients (NO₃ ^?, NH₄ ⁺, PO₄ ^3?), chlorophylla (chla), and-salinity were taken monthly from December 1996 to January 1998. These data were compiled by season, and the Atchafalaya River plume data were also analyzed using the Generalized Additive Model technique. There were significant decreases in NO₃ ^? concentrations during summer, fall, and winter as river water passed through the estuary, that were attributable to chemical and biological processes rather than dilution with ambient water. In some regions there were higher chla concentrations during summer and fall compared to winter and spring, when river discharge and the introduction of inorganic nutrients were highest, suggesting biological processes were active during this study. The presence of NH₄ ⁺, as a percentage of available dissolved inorganic nitrogen, increased with distance from the Atchafalaya River, indicative of remineralization processes and NO₃ ^? reduction. Mean PO₄ ^3? concentrations were often higher in the estuarine regions compared to the Atchafalaya River. During summer total suspended solid (TSS) concentrations increased with distance from the river mouth, suggesting a turbidity maximum. Highest chla concentrations were found in the bayous and shallow water bodies of the Terrebonne marshes, as were the lowest TSS concentrations. The low chla concentrations found in other areas of this study, despite high inorganic nutrient concentrations, suggest light limitation as the major control of phytoplankton growth. Salinity reached near seawater concentrations at the outer edge of the Atchafalaya River plume, but much lower salinities (<10 psu) were observed at all other regions. The Atchafalaya Delta estuarine complex buffers the impact of the Atchafalaya River on the Louisiana coastal shelf zone, with a 41% of 47% decrease in Atchafalaya River NO₃ ^? concentrations before reaching Gulf waters.     

A model of water allocation in alkali feldspar,derived from infrared-spectroscopic investigations

Polarizedinfrared (IR) spectra of sanidine crystals from Volkesfeld, Eifel show the existence of two broad pleochroic absorption bands at 3,400 and 3,050 cm^?1. Because overtones near 5,150 cm^?1 were observed, the former bands are assigned to OH stretching frequencies of H₂O molecules. On the basis of the pleochroic scheme of the bands it is proposed that H₂O molecules occur as structural constituents entering theM site of the sanidine structure; the plane of the H₂O molecules lies parallel to the symmetry plane.