土霉素在牙鲆体内的药代动力学研究

采用高效液相色谱法为定性、定量手段,研究土霉素在牙鲆(Paralichthys olivaceus)体内的药代动力学过程,采用DAS(Drug and Statistics)药代动力学程序对数据进行分析.结果表明,牙鲆单剂量口服土霉素后(200 mg/kg),血药经时过程符合二室模型,主要动力学参数如下:吸收半衰期(T(1/2)a)为10.043 h,单剂量给药后牙鲆体内出现最高质量分数的时间(Tmax)为4.000 h,单剂量给药后牙鲆体内最高血药质量分数(Cmax)为0.54 mg/L,药时曲线下总面积(CAU0-72)为17.15 (mg*h)/L,吸收速率常数(Ka)为0.223,消除速率常数(k)为0.476 h-1.牙鲆肌肉中土霉素的经时过程符合一级吸收一室模型,主要动力学参数:T(1/2)a为74.893 h,Tmax为4.000 h,Cmax为3.58 mg/L,CAU0-72为148.56 (mg*h)/L,Ka为0.731,k为2.991 h-1.牙鲆肝脏中土霉素的经时过程符合一级吸收一室模型,主要动力学参数:T(1/2)a为31.376 h,Tmax为4.000 h,Cmax为13.78 mg/L,CAU0-72为494.14 (mg*h)/L,Ka为0.876,k为4.940 h-1.     

Geochemical investigation of oils from Cretaceous to Eocene sedimentary sequences of the Abadan Plain,Southwest Iran

Oil samples from Lower Cretaceous to Eocene reservoirs in southwest Iran were analyzed using gas chromatography–mass spectrometry and gas chromatography–isotope ratio mass spectrometry for genetic classification of oil families and determining their maturity. The Studied oil samples are non-biodegraded and their gravity range from 18.3 to 37° API. The slight even/odd n-alkane predominance, coupled with low Pr/Ph values, suggests their likely source rocks with a predominance of algal organic matter, type IIS kerogen deposited under strongly reducing marine environments. The biomarker distribution of investigated oils is characterized by high concentration of both C₂₉ and C₃₀ hopanes and ratios of C₂₉/C₃₀H are generally greater than unity. There is a marked predominance of C₂₉ regular sterane over C₂₇ and C₂₈ homologs in our studied oils. High sterane/hopane values and cross plot of the δ¹³C sat versus δ¹³C aro show contribution of marine organic matter. Medium value of gammacerane index and other salinity indices show water density stratification and high salinity conditions of the environment of deposition. It can be concluded that the studied reservoirs, due to their variable maturity have different API gravity and contain two oil families (types A and B) with latter being deeper and comprising more mature oils.     

Biomarkers derived from heterolytic and homolytic cleavage of allylic hydroperoxides resulting from alkenone autoxidation

Laboratory incubation of alkenone mixtures with tert-butyl hydroperoxide and di-tert-butyl nitroxide (radical initiator) in hexane, as a means to simulate alkenone autoxidation processes, rapidly led to the formation of allylic hydroperoxides, whose presence was recently demonstrated in Emiliania huxleyi cells. After incubation in seawater and subsequent reduction with NaBH₄ (to reduce residual hydroperoxides before analysis), these reaction products quickly disappeared and were replaced by complex mixtures of n-alcohols, fatty acids, alkyldiols and hydroxyacids. Methyl alkenones produced saturated n-alkan-1-ols and fatty acids ranging from C₁₃ to C₁₆ and two series of C₁₃−C₁₆ (ω-1)-hydroxyacids and (1,ω-1)-diols. Ethyl alkenones also afforded C₁₃−C₁₆ saturated n-alkan-1-ols and fatty acids, accompanied by the production of C₁₄−C₁₇ (ω-2)-hydroxyacids and (1,ω-2)-diols. Deuterium labelling allowed us to show that most of the n-alkan-1-ols, hydroxyacids and alkyldiols resulted from the reduction during the NaBH₄ treatment of the corresponding aldehydes, ketoxyacids and ketoxyaldehydes formed from heterolytic or homolytic cleavages of allylic hydroperoxyl groups resulting from the oxidation of the double bonds of di- and triunsaturated alkenones. Amongst these products, the (ω-1)- and (ω-2)-hydroxyacids formed after NaBH₄ reduction of the (ω-1)- and (ω-2)-ketoxyacids were selected as potential biomarkers for alkenone autoxidation. Re-examination of lipid extracts of post-bloom seawater particulate matter samples from the DYFAMED station in the Ligurian Sea (where strong autoxidative alteration of the lipid distributions had previously been detected) showed the presence of significant amounts of 12-hydroxytetradecanoic, 13-hydroxytetradecanoic, 14-hydroxyhexadecanoic and 15-hydroxyhexadecanoic acids thus providing good evidence that these autoxidative processes occur in natural samples.     

Biomarkers of Middle to Late Jurassic marine sediments from a canonical section: New records from the Yanshiping area,northern Tibet

The Yanshiping section, which includes the Quemo Co, Buqu, Xiali, Suowa and Xueshan Formations (Yanshiping Group) exposes organic-rich Middle to Late Jurassic deposits in the Qiangtang Basin of northern Tibet. The biostratigraphic data, from bivalves, brachiopods as well as dinoflagellate cysts, define a Bajocian to Tithonian age. This study focuses on the biomarkers present in these mudstones and limestones to determine the sources, thermal maturity and depositional environment of the organic matter. Most samples show a clear dominance of short-chain (C₁₅–C₂₀) n-alkanes with a maximum at C₁₉ or C₁₉ with a secondary maximum at C₂₃ except for the sample BP01(22)S1 where the predominant range is C₂₂ to C₂₆ with a maximum at C₂₄, significant CPI and odd-to-even predominance. The hopanoids and steroids suggest that the sources of organic matter were dominated by phytoplankton, especially algae, as the primary source. Furthermore, the Pr/Ph, Pr/nC₁₇ and Ph/nC₁₈, with relatively low values plus high abundance of 17α(H)-hopanes, support deposition in dysoxic to reducing, relatively shallow-water depositional settings, and the presence of gammacerane indicates normal marine salinity and/or water-column stratification. All samples are fairly mature with respect to petroleum generation, a conclusion supported by maturity parameters such as C₃₁ 22S/(22S + 22R) hopanes and C₂₉ ααα20S/(20S + 20R) steranes.     

Evidence for cyanobacterial inputs and heterotrophic alteration of lipids in sinking particles in the Alboran Sea (SW Mediterranean)

The different sources of lipid compounds present in sinking particles collected in a sediment trap mooring deployed in the Alboran Sea (SW Mediterranean) were elucidated using the molecular marker concept. A significant contribution of cyanobacterial lipids was identified based on the occurrence of a series of 3- and 5-methylalkanes and dimethylalkanes. Further evidence of cyanobacterial inputs was obtained by principal component analysis of all data showing diploptene and n-alkanes in the range C₁₄–C₂₂ clustered together with those branched alkanes. The use of methyl and dimethyl alkanes to trace cyanobacterial sources in the water column is proposed with advantage to sterols which are usually masked by phytoplanktonic sterols. The sterol distribution indicates phytoplankton as a major source with a contribution from heterotrophic zooplanktonic. Both fossil and biogenic sources can be contributors to the large unresolved complex mixture (UCM) found in these samples.     

Bicyclic alkanes in source rocks of the Triassic Yanchang Formation in the Ordos Basin and their inconsistency in oil-source correlation

The Triassic Yanchang Formation is the main source rocks for Mesozoic oil in Ordos Basin. The formation includes 10 oil-bearing beds (Ch 1–Ch 10), that each can be further divided into two to three intervals. Abundant C₁₂–C₁₄ and C₁₅–C₁₆ bicyclic alkanes have been detected in the formation in the Xifeng oilfield, Ordos Basin. The C₁₂–C₁₄ group is dominated by C₁₂ and C₁₃, and the C₁₅–C₁₆ group contains abundant C₁₅. The groups show three distribution patterns: A) the C₁₂–C₁₄ group is the major component in the non-source rocks of the Ch 7-1 and Ch 8-1 intervals; B) both groups are abundant and are common in source rocks of the Ch 7-3 interval; and C) the C₁₅–C₁₆ group is the major component in source rocks of the Ch 7-3 interval and also in sediments that contain type Ⅰ or partial sapropel type Ⅱ₁ organic matter (OM) in the Ch 7-2 and Ch 8-1 intervals. Although thermal maturities of the source rocks in the Ch 7 section are similar, they show significant differences with respect to the drimane isomerisation index, which indicates that the drimane rearrangement is controlled by thermal evolution of the sediments, but may also be closely related to the depositional environment. This study determined that reducing environments are more conducive to preservation of drimane than oxic environments. The drimane isomerisation index and the value of the hopane parameter Tm/Ts are positively correlated. The parameter Tm/Ts varies over a wide range within the sequence, and the large variations may be a result of terrigenous OM input by turbidity currents and/or gravity flows, mixed with the autochthonous sediments. Abundant homodrimane in both source rocks may reflect reducing environments in deep lakes and major input of higher plant OM. Organic-rich shale and oil shale in the Ch 7-3 interval of the Yanchang Formation are the primary sources of oil in reservoirs in the Xifeng area. The crude oil is rich in bicyclic alkanes that are dominated by C₁₅–C₁₆ as source rocks with pattern C for bicyclic alkanes, which indicates an origin mainly from the Ch 7-3 interval. The main peaks in all of the crude oils are associated with 8β(H)-drimane and lower abundance of rearranged drimane. However, most of the source rocks have a main peak associated with 8β(H)-homodrimane or rearranged drimane. Weak microbial action, selective degradation and water washing may be the cause of the significant difference in bicyclic sesquiterpane composition between the crude oil and the source rocks. The result suggests that oil-source correlations based on the bicyclic sesquiterpanes are questionable.     

Organic geochemistry of sediments from chemosynthetic communities,Gulf of Mexico slope

We used a research submersible to obtain 33 sediment samples from chemosynthetic communities at 541–650 m water depths in the Green Canyon (GC) area of the Gulf of Mexico slope. Sediment samples from beneath an isolated mat of H₂S-oxidizing bacteria at GC 234 contain oil (mean = 5650 ppm) and C₁–C₅ hydrocarbons (mean = 12,979 ppm) that are altered by bacterial oxidation. Control cores away from the mat contain lower concentrations of oil (mean = 2966 ppm) and C₁–C₅ hydrocarbons (mean = 83.6 ppm). Bacterial oxidation of hydrocarbons depletes O₂ in sediments and triggers bacterial sulfate reduction to produce the H₂S required by the mats. Sediment samples from GC 185 (Bush Hill) contain high concentrations of oil (mean = 24,775 ppm) and C₁–C₅ hydrocarbons (mean = 11,037 ppm) that are altered by bacterial oxidation. Tube worm communities requiring H₂S occur at GC 185 where the sea floor has been greatly modified since the Pleistocene by accumulation of oil, thermogenic gas hydrates, and authigenic carbonate rock. Venting to the water column is suppressed by this sea-floor modification, enhancing bacterial activity in sediments. Sediments from an area with vesicomyid clams (GC 272) contain lower concentrations of oil altered by bacterial oxidation (mean = 1716 ppm) but C₁–C₅ concentrations are high (mean = 28,766 ppm). In contrast to other sampling areas, a sediment associated with the methanotrophic Seep Mytilid I (GC 233) is characterized by low concentration of oil (82 ppm) but biogenic methane (C₁) is present (8829 ppm).     

Sources and transport of lipids on Amazon continental shelf

Dissolved material and recent sediment from the Amazon continental shelf have been analyzed for hydrocarbons to study the sources and potential fate of the transported organic matter. Dissolvedn-alkanes are present at low concentrations (ppb level) and are dominated by lipids from marine phytoplankton with carbon number maxima (C_max) at C₁₈/C₂₂ and an even-to-odd carbon predominance < C₃₀ (CPI_17–27 from 0.18 to 0.54). In the sediments, bimodal distributions ofn-alkane chain length suggest a mixed input of terrestrial (C_max at C₂₇/C₂₉/C₃₁ and CPI_25–33 from 0.75 to 1.82) and phytoplanktonic/microbial (C_max at C₂₀ and CPI_15–25 from 0.38 to 0.62) organic matter. Sesquiterpenes were the most significant cyclic compounds in all the dissolved samples analyzed reflecting a contribution from resinous trees to the terrestrial organic pool. On the other hand, enhanced concentrations of these compounds in the dissolved phase on the northwest portion of the Amazon shelf, contrasting with decreased concentrations in the sediment samples, suggest that dissolved lipids are released from solid phase in the intensely stirred seabed. Structured organic matter in the sediment has been characterized as being composed of, on average: 19% plant cuticles, 25% woody tissue, 13% pollens and spores, 24% amorphous material, 7% bituminite and 12% altered organic material.     

Distributions of low molecular weight dicarboxylic acids in the North Pacific aerosol samples

Marine aerosol samples collected from the North Pacific atmosphere were studied for molecular distributions of dicarboxylic acids by using a capillary gas chromatography and mass spectrometery. A homologous series of dicarboxylic acids (C₂–C₁₀) was detected in the marine aerosol samples as dibutyl esters. All the samples showed that the smallest diacid (oxalic acid: C₂) was the most abundant and comprised 41–67% of the total diacids. The second most abundant species was malonic acid (C₃) or succinic acid (C₄). The diacids with more carbon numbers were generally less abundant. Total diacid concentration range was 17–1040 ng m^–3, which accounted for up to 1.6% of total aerosol mass. This indicates that low molecular weight dicarboxylic acids are important class of organic compounds in the marine atmosphere. The concentrations were generally higher in the western North Pacific and lower in the central North Pacific. The major portion of diacids is probably derived from the Asian Continent and East Asian countries by long-range atmospheric transport and partly fromin situ photochemical production in the marine atmosphere.     

Petroleum source rock potential of the Silurian Dadaş shales in the Hazro and Korudağ regions of Southeast Anatolia,Turkey

Shales of the Silurian Dadaş Formation exposed in the southeast Anatolia were investigated by organic geochemical methods. The TOC contents range from 0.24 to 1.48 wt% for the Hazro samples and 0.19 to 3.58 wt% for the Korudağ samples. Tmax values between 438 and 440 °C in the Hazro samples indicate thermal maturity; Tmax values ranging from 456 to 541 °C in the Korudağ samples indicate late to over-maturity. Based on the calculated vitrinite reflectance and measured vitrinite equivalent reflectance values, the Korudağ samples have a maximum of 1.91%R_(g-v), in the gas generation window, while a maximum value of 0.79%R_(amor-v) of one sample from the Hazro section is in the oil generation window. Illite crystallinity (IC) values of all samples are consistent with maturity results.Pr/Ph ratios ranging from 1.32 to 2.28 and C₂₉/C₃₀ hopane ratios > 1.0 indicate an anoxic to sub-oxic marine-carbonate depositional environment.The Hazro shales do not have any shale oil or shale gas potential because of their low oil saturation index values and early to moderate thermal maturation. At first glance, the Korudağ shales can be considered a shale gas formation because of their organic richness, thickness and thermal over-maturity. However, the low silica content and brittle index values of these shales are preventing their suitability as shale gas resource systems.     

Late Cretaceous (Late Turonian,Coniacian and Santonian) petroleum source rocks as part of an OAE,Tarfaya Basin,Morocco

Late Turonian, Coniacian and Santonian source rock samples from a recently drilled well (Tafaya Sondage No. 2; 2010) in the Tarfaya Basin were analyzed for quantity, quality, maturity and depositional environment of the organic matter (OM). To our knowledge such a thick sequence of organic matter-rich Turonian to Santonian source rocks was investigated in that great detail for the first time. Organic geochemical and organic petrological investigations were carried out on a large sample set from the 200 m thick sequence. In total 195 core samples were analyzed for total organic carbon (C_org), total inorganic carbon contents and total sulfur (TS) contents. Rock-Eval pyrolysis and vitrinite reflectance measurements were performed on 28 samples chosen on the basis of their C_org content. Non-aromatic hydrocarbons were analyzed on selected samples by way of gas chromatography–flame ionization detection (GC–FID) and GC–mass spectrometry (GC–MS). The organic matter-rich carbonates revealed a high source rock potential, representing type I kerogen and a good preservation of the organic matter, which is mainly of marine (phytoplankton) origin. HI values are high (400–900 mg/g C_org) and in a similar range as those described for more recent upwelling sediments along the continental slope of North Africa. TS/C_org ratios as well as pristane over phytane ratios indicate variable oxygen content during sediment deposition. All samples are clearly immature with respect to petroleum generation which is supported by maturity parameters such as vitrinite reflectance (0.3–0.4%), T_max values (401–423 °C), production indices (S₁/(S₁ + S₂) > 0.1) as well as maturity parameters based on ratios of specific steranes and hopanes.     

Fluid circulation and formation of minerals and bitumens in the sedimentary rocks of the Outer Carpathians – Based on studies on the quartz–calcite–organic matter association

Different methods have been used to examine minerals and/or solid bitumens in three adjacent Carpathian regions of Poland, Ukraine and Slovakia. The minerals fill smaller and larger veins and cavities, where they occur either together or separately. They usually co-occur with the solid bitumens. All δ¹³C_PDB values measured for calcite lie in a relatively wide interval between −6.25‰ and +1.54‰, while most values fall into the narrower interval from below 0 to about −3‰. The general range of calcite δ¹⁸O results for the whole studied region is between +17.13‰ and +25.23‰ VSMOW or from about −11 to −5‰ VPDB, while the majority of these values are between +20.0 and 23.5‰ VSMOW (−10.53 and −8.00‰ PDB, respectively). δ¹⁸O_VSMOW results for quartz vary between +23.2 and 27.6. The carbonate percentage determined in some samples falls between from <2% CaCO₃ to >90% CaCO₃, while the TOC values changes from 0.09% to over 70%.The aliphatic fraction predominates in all studied samples, mainly in bitumens and oils. The composition of the aliphatic fraction is relatively homogeneous and points to a strong aliphatic, oil-like paraffin character of the bitumens. Such a composition is characteristic of the Carpathian oils and different from the rocks studied that contain the higher percentage of a polar fraction. The content of the aliphatic fraction in bitumens is only slightly higher than that in two oils used for comparison. The distribution of n-alkanes is variable in rocks, solid bitumens as well as inclusions in quartz and calcite. Two groups of bitumens may be distinguished. Those with a predominance of long-chain n-alkanes in the C₂₅–C₂₇ interval (in some cases from C₂₃–C₂₅ and without or with a very low concentration of short-chain n-alkanes in the interval of C₁₄–C₂₁) show also a high content of isoprenoids i.e. of pristane (Pr) and phytane (Ph). In all but one bitumen samples, Pr predominates over Ph. The second group comprises oils and rock samples with a characteristic predominance of short-chain n-alkanes in the interval from C₁₃–C₁₉ and a low percentage of the long-chain n-alkanes from the n-C₂₇–n-C₃₃ interval. Pristane and phytane exhibit a concentration comparable to that of C₁₇ and C₁₈ n-alkanes with a Pr predominance over Ph. Due to high maturity, only small amounts of the most stable compounds from the hopane group have been observed in the samples, also oleanane in one case. Among the aromatic hydrocarbons, phenanthrene and its methyl- and dimethyl-derivatives are dominant in bitumens, source rocks and inclusions in calcite and quartz. Occurrence of cyclohexylbenzene and its alkyl-derivatives as well as cyclohexylfluorenes in solid bitumens suggest that they formed from oil accumulations under the influence of relatively high temperatures in oxidizing conditions.Homogenization temperatures for aqueous/brine inclusions in quartz within the Dukla and Silesian units (Polish and Ukrainian segments) are between 125 and 183.9 °C, while salinities are low in the interval of 0.2–5.5 wt% NaCl eq. The inclusions in calcite homogenize at higher temperatures of almost 200 °C and the brine displays higher salinity than the fluid in the quartz. Two quartz generations may be distinguished by inclusion and isotope characteristics and the macroscopic diversity. Oil inclusions homogenize at 95 °C. One phase inclusions in quartz contain methane, CO₂ and nitrogen in variable proportions.     

Geochemistry,origin, and accumulation of petroleum in the Eocene Wenchang Formation reservoirs in Pearl River Mouth Basin,South China Sea: A case study of HZ25-7 oil field

The Pearl River Mouth Basin in the South China Sea has accumulated >2 km of Eocene sediments in its deep basin, and has become the exploration focus due to the recent discoveries of the HZ25-7 oil field in the Eocene Wenchang (E₂w) Formation. In this study, the geochemical characteristics of potential source rocks and petroleum in the HZ25-7 oil field are investigated and the possible origins and accumulation models developed. The analytical results reveal two sets of potential source rocks, E₂w and Enping (E₂e) formations developed in the study area. The semi-deep-to-deep lacustrine E₂w source rocks are characterized by relatively low C₂₉ steranes, low C₁₉/C₂₃ tricyclic terpane (<0.6), low C₂₄ tetracyclic terpane/C₃₀ hopane (<0.1), low trans-trans-trans-bicadinane (T)/C₃₀ hopane (most <2.0), and high C₃₀ 4-methyl sterane/ΣC₂₉ sterane (>0.2) ratios. In contrast, the shallow lacustrine and deltaic swamp-plain E₂e source rocks are characterized by relatively high C₂₉ steranes, high C₁₉/C₂₃ tricyclic terpane (>0.6), high C₂₄ tetracyclic terpane/C₃₀ hopane (>0.1), variable yet overall high T/C₃₀ hopane, and low C₃₀ 4-methyl sterane/ΣC₂₉ sterane (<0.2) ratios. The relatively low C₁₉/C₂₃ tricyclic terpane ratios (mean value: 0.39), low C₂₄ tetracyclic terpane/C₃₀ hopane ratios (mean value: 0.07), high C₃₀ 4-methyl sterane/ΣC₂₉ sterane ratios (mean value: 1.14), and relatively high C₂₇ regular sterane content of petroleum in the HZ25-7 oil field indicate that the petroleum most likely originated from the E₂w Formation mudstone in the Huizhou Depression. One stage of continuous charging is identified in the HZ25-7 oil field; oil injection is from 16 Ma to present and peak filling occurs after 12 Ma. Thin sandstone beds with relatively good connectivity and physical properties (porosity and permeability) in the E₂w Formation are favorable conduits for the lateral migration of petroleum. This petroleum accumulation pattern implies that the E₂w Formation on the western and southern margins of the Huizhou Depression are favorable for petroleum accumulation because they are located in a migration pathway. Thus exploration should focus in these areas in the future.     

Sedimentary and residual gas geochemical characteristics of the Lower Cambrian organic-rich shales in Southeastern Chongqing,China

To study the sedimentary environment of the Lower Cambrian organic-rich shales and isotopic geochemical characteristics of the residual shale gas, 20 black shale samples from the Niutitang Formation were collected from the Youyang section, located in southeastern Chongqing, China. A combination of geochemical, mineralogical, and trace element studies has been performed on the shale samples from the Lower Cambrian Niutitang Formation, and the results were used to determine the paleoceanic sedimentary environment of this organic-rich shale. The relationships between total organic carbon (TOC) and total sulfur (TS) content, carbon isotope value (δ¹³C_org), trace element enrichment, and mineral composition suggest that the high-TOC Niutitang shale was deposited in an anoxic environment and that the organic matter was well preserved after burial. Stable carbon isotopes and biomarkers both indicate that the organic matter in the Niutitang black shales was mainly derived from both lower aquatic organisms and algaes and belong to type I kerogen. The oil-prone Niutitang black shales have limited residual hydrocarbons, with low values of S₂, I_H, and bitumen A. The carbon isotopic distribution of the residual gas indicate that the shale gas stored in the Niutitang black shale was mostly generated from the cracking of residual bitumen and wet gas during a stage of significantly high maturity. One of the more significant observations in this work involves the carbon isotope compositions of the residual gas (C₁, C₂, and C₃) released by rock crushing. A conventional δ¹³C₁–δ¹³C₂ trend was observed, and most δ¹³C₂ values of the residual gases are heavier than those of the organic matter (OM) in the corresponding samples, indicating the splitting of ethane bonds and the release of smaller molecules, leading to ¹³C enrichment in the residual ethane.     

Mechanisms of petroleum accumulation in the Bozhong sub-basin, Bohai Bay Basin, China. Part 1: Origin and occurrence of crude oils

The origin of the fourteen major oil fields in the Bozhong sub-basin, Bohai Bay basin was studied based on the results of Rock-Eval pyrolysis on more than 700 samples and biomarker analysis on 61 source rock samples and 87 oil samples. The three possible source rock intervals have different biomarker assemblages and were deposited in different environments. The third member of the Oligocene Dongying Formation (E₃d₃, 32.8–30.3 Ma in age) is characterized mainly by high C₁₉/C₂₃ tricyclic terpane (>0.75), high C₂₄ tetracyclic terpane/C₂₆ tricyclic terpane (>2.5), low gammacerane/αβ C₃₀ hopane (<0.15) and low 4-methyl steranes/ΣC₂₉ steranes (<0.15) ratios, and was deposited in sub-oxic to anoxic environments with significant terrigenous organic matter input. The first (E₂s₁, 35.8–32.8 Ma) and third (E₂s₃, 43.0–38.0 Ma) members of the Eocene Shahejie Formation have low C₁₉/C₂₃ tricyclic terpane and low C₂₄ tetracyclic terpane/C₂₆ tricyclic terpane ratios and were deposited in anoxic environments with minor terrestrial organic matter input, but have different abundances of 4-methyl steranes and gammacerane. The hydrocarbon-generating potential and biomarker associations of these three source rock intervals were controlled by tectonic evolution of the sub-basin and climate changes. Three oil families derived from E₂s₃, E₂s₁ and E₃d, respectively, and three types of mixed oils have been identified. All large oil fields in the Bozhong sub-basin display considerable heterogeneities in biomarker compositions and originated from more than one source rock interval, which suggests that mixing of oils derived from multiple source rock intervals or multiple generative kitchens, and/or focusing of oils originated from a large area of a generative kitchen, is essential for the formation of large oil fields in the Bozhong sub-basin. E₂s₃- and E₂s₁-derived oils experienced relatively long-distance lateral migration and accumulated in traps away from the generative kitchen. E₃d₃-derived oils had migrated short distances and accumulated in traps closer to the generative kitchen. Such a petroleum distribution pattern has important implications for future exploration. There is considerable exploration potential for Dongying-derived oils in the Bozhong sub-basin, and traps close to or within the generative kitchens have better chance to contain oils generated from the Dongying Formation.     

Origin of crude oils from oilfields in the Zagros Fold Belt,southern Iraq: Relation to organic matter input and paleoenvironmental conditions

Crude oil samples from Cretaceous and Tertiary reservoir sections in the Zagros Fold Belt oil fields, southern Iraq were investigated using non-biomarker and biomarker parameters. The results of this study have been used to assess source of organic matter, and the genetic link between oils and their potential source rocks in the basin. The oils are characterized by high sulphur and trace metal (Ni, V) contents and relatively low API gravity values (17.4–22.7° API). This indicates that these oils are heavy and generated from a marine source rock containing Type II-S kerogen. This is supported by their biomarker distributions of normal alkanes, regular isoprenoids, terpanes and steranes and the bulk carbon isotope compositions of their saturated and aromatic hydrocarbons. The oils are characterized by low Pr/Ph ratios (<1), high values of the C₃₅ homohopane index and C₃₁-22R/C₃₀ hopane ratios, relatively high C₂₇ sterane concentrations, and the predominance of C₂₉-norhopane. These biomarkers suggest that the oils were generated predominantly from a marine carbonate source rock, deposited under reducing conditions and containing plankton/algal and microorganisms source input. The presence of gammacerane also suggests water column stratification during source rock deposition.The biomarker characteristics of the oils are consistent with those of the Middle Jurassic Sargelu carbonate as the effective source rock in the basin. Biomarker maturity data indicate that the oils were generated from early maturity source rocks.     

Relationship between dissolved and particulate fatty acids and hydrocarbons, chlorophyll a and zooplankton biomass in Villefranche Bay, Mediterranean Sea

Dissolved, particulate, and plankton hydrocarbons and fatty acids have been analysed by gas chromatography and gas chromatography/mass spectrometry in samples taken during a 16-month period at two stations located in Villefranche Bay, Mediterranean Sea. The study has been conducted in connection with regular determinations of chlorophyll a, zooplankton biomass and species of net plankton samples. The n-alkanes show a regular distribution pattern of odd and even carbon numbered compounds between n-C₂₁ and n-C₃₆ with additional characteristics associated with biological phenomena: abundance of n-C₁₅ and n-C₁₇, predominance of pristane over n-C₁₇ in zooplankton-rich samples, predominance of even carbon numbered n-alkanes in the range C₁₈–C₂₀, generally associated with a mixture of higher molecular weight even carbon numbered n-alkanes, modifying the regular distribution of the n-alkanes. For the station located at the end of the bay, the correlation between particulate hydrocarbons, particulate n-alkanes and chlorophyll a contents ( 0.630) is significant — well below the 0.05 level. There is discussion of this correlation which indicates a possible direct contribution of phytoplankton to the hydrocarbons of seawater or other biochemical associations between plankton and dissolved organic matter. Polyunsaturated fatty acids such as C₂₀ and C₂₂ are more abundant in plankton and suspended matter than in seawater. Data relative to those components allow us to evaluate the percentage of living plankton in suspended matter. General trends indicate the existence of a relation between particulate fatty acid and zooplanktonic biomass concentrations in the bay water.     

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.     

Application of the fluorescence quenching titration method to the complexation of copper (II) in the Gironde Estuary (France)

Quenching of fluorescence emission by the Cu²⁺ ion is measured in five samples from the Gironde Estuary (France). Non-linear regression analysis allows us to calculate from experimental data the values of C_L (complexing capacities or total ligand concentrations), K (conditional stability constants) and I_ML (residual fluorescence at the end of the titration). The results obtained on the Gironde estuarine samples indicate that C_L values are very low (<0.1 micromolar) and K values decrease from upstream to downstream. The relatively high values of I_ML are an indication that much of the organic fluorescing matter does not bind to Cu²⁺.