Application of Organic Geochemistry to Coastal Tar Residues from Central California

Tar residues are common on the coastline of the Monterey Bay National Marine Sanctuary. These coastal tar residues have been washed ashore and usually occur on headlands near the high-tide line. In this study, 18 coastal tar residues were collected and analyzed to determine their carbon isotopic compositions and the values of selected biomarker ratios. All of the residues have very heavy (¹³C-enriched) carbon isotopic compositions spanning a narrow range (δ¹³C = ?22.2 to ?23.4‰), and 28,30-bisnorhopane is present in all samples. These same geochemical characteristics are found in Monterey Formation oils from which the coastal tar residues were likely derived. These coastal residues could result from natural seeps or from accidental spills. Statistically the coastal tar residues can be organized into three groups, each of which may represent different spill or seep events. Seven samples of potential local representative sources for the tar residues were examined, but none could account for the coastal tars.     

Oil seepage and carbonate formation: A case study from the southern Gulf of Mexico

Oil seeps from the southern Gulf of Mexico can be regarded as natural laboratories where the effect of crude oil seepage on chemosynthesis‐based communities and carbonate precipitation can be studied. During R/V Meteor cruise 114 the seep sites UNAM (Universidad Nacional Autónoma de México) Ridge, Mictlan Knoll and Tsanyao Yang Knoll (Bay of Campeche, southern Gulf of Mexico) were investigated and sampled for authigenic carbonate deposits containing large amounts of liquid oil and solid asphalt. The δ¹³C values of individual carbonate phases including: (i) microcrystalline matrix aragonite and calcite; (ii) grey, cryptocrystalline to microcrystalline aragonite; and (iii) clear, fibrous aragonite cement, are between ?30‰ and ?20‰, agreeing with oil as the primary carbon source. Raman spectra reveal that residual heavy oils from all sites are immature and most likely originate from the same reservoir. Geochemical batch modelling using the software code PHREEQC demonstrates how sulphate‐driven oxidation of oil‐derived low‐molecular to high‐molecular weight hydrocarbons affects carbonate saturation state, and shows that the oxidation state of carbon in hydrocarbon compounds and oxidation rates of hydrocarbons control carbonate saturation and precipitation at oil seeps. Phase‐specific trace and rare earth element contents of microcrystalline aragonite and calcite, grey cryptocrystalline aragonite and clear aragonite were determined, revealing enrichment in light rare earth elements for grey aragonite. By comparing trace element patterns of carbonates with those of associated oils, it becomes apparent that liquid hydrocarbons constitute an additional source of trace metals to sedimentary pore waters. This work not only demonstrates that the microbial degradation of oil at seeps may result in the precipitation of carbonate minerals, it also elucidates that trace metal inventories of seep carbonates archive diagnostic elemental patterns, which can be assigned to the presence of heavy hydrocarbons in interstitial pore waters.     

柯坪隆起阿克苏油苗的地球化学特征及其成因研究

柯坪隆起区是塔里木盆地海相烃源岩露头发育较好的地区之一,但相关的油气研究报道不多。本文详细研究了塔里木盆地柯坪隆起区油苗的有机地球化学特征并进行了相关的成因分析。阿克苏油苗经历了严重的生物降解作用,饱和烃生物标志物所能提供的成因信息十分有限。原油沥青质组分及储层吸附/包裹烃受后生作用影响较小,综合分析油苗沥青质热解产物与吸附/包裹烃的生物标志物及其碳同位素组成可以获得更多有效的成因信息。研究结果表明,阿克苏油苗与其储层吸附/包裹烃具有不同来源。油苗、沥青质以及沥青质热解产物的碳同位素特征与已经报道的多数海相原油及其沥青质较为接近,与典型的寒武系烃源来源的原油差异显著。而储层吸附/包裹烃与已报道的典型寒武系烃源岩来源油的生物标志物及碳同位素特征比较类似,可能形成于较高的热演化阶段。     

Re-Os elemental and isotopic systematics in crude oils

Analysis of 12 worldwide oil samples show that Re and Os abundances are positively correlated with the asphaltene content of oil. Light oils with <1% asphaltene content have basically no measurable Re or Os. Within oil, Re and Os are present dominantly in the asphaltene fraction (>83%), with <14% Re and Os found in the maltene fraction, this distribution is similar to other trace metals such as V and Mo. Rhenium and Os could be present in oil as metalloporphyrin complexes, but given their abundance in the asphaltene component they are also likely bound by heteroatomic ligands. The ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os values in asphaltene calculated at the estimated time of oil generation (Os_i) are similar to those of the whole oil, as expected from the elemental results. This suggests that the asphaltene fraction can be used to approximate the Re-Os isotopic compositions of the whole oil. Os isotopic compositions in oils show a considerable range, from ¹⁸⁷Os/¹⁸⁸Os of 1.9-6.0, and they correlate positively with the age of the proposed source rock. Re/Os ratios also show a large range and overlap the Re/Os ratios found in typical oil source rocks such as organic rich shale.     

Organic chemical characterization of sediment-trap particulates from San Nicolas,Santa Barbara,Santa Monica and San Pedro Basins,California

Particulate matter was collected during September–October, 1977, in particle traps suspended 30–60 m above the floor of San Nicolas, Santa Barbara, Santa Monica and San Pedro Basins, off the coast of southern California. The trap particulates were analyzed for C₁₅–C₃₅ hydrocarbons using gas chromatography (GC) and GC-mass spectrometry. Kerogens and humic acids were characterized by H/C, N/C, δ¹³C, δ¹⁵N and δ³⁴S ratios, and by electron-spin resonance. Hydrocarbons arising from fresh and weathered petroleum, marine autochthonous and terrestrial sources were identified. The rates of petroleum deposition during the collection period followed the order: San Nicolas Basin < Santa Barbara Basin ~ Santa Monica Basin < San Pedro Basin, with the largest amount of weathered petroleum being deposited in San Pedro Basin. The rates of petroleum deposition are correlated more strongly with human activities such as shipping, and the discharge of municipal and industrial wastes, than with natural submarine oil seepage. Analyses of kerogens and humic acids indicate that the majority of the organic matter in the trap particulates is of marine origin. The water column overlying Santa Barbara Basin appears to have the highest marine productivity of the four basins studied.     

Effects of an Acute Hypoxic Event on Microplankton Community Structure in a Coastal Harbor of Southern California

Fish mortality and hypoxic events occur in many coastal and inland systems and may result from natural or anthropogenically mediated processes. The effects of consequent changes in water biogeochemistry have been investigated for communities of benthic invertebrates and pelagic metazoans. The responses of micro-plankton assemblages, however, have remained largely unstudied. The northern basin of King Harbor, a small embayment within Santa Monica Bay, CA, USA, suffered a massive fish kill in March 2011 as a consequence of acute hypoxia. Dissolved oxygen concentrations < 0.1 ml?l^?1 were measured in the northern basin of the harbor for several days following the mortality event, and a strong spatial gradient of oxygen was observed from the northern basin to waters outside the harbor. The microplankton community within King Harbor differed significantly from a diatom-dominated community present in neighboring Santa Monica Bay. The latter region appeared unaffected by physicochemical changes, induced by the fish kill, that were observed within the harbor. A trophic shift was observed throughout King Harbor from a photoautotrophic-dominated assemblage to one of heterotrophic forms, with relative abundances of bacterivorous ciliates increasing by more than 80 % in the most impacted part of the harbor. Significant changes in community structure were observed together with dramatically reduced photosynthetic yield of the remaining phytoplankton, indicating severe physiological stress during the extreme hypoxia.     

The effects of source lithology, transport, deposition and sampling scale on the composition of southern California sand

The Transverse Ranges of southern California represent an uplifted and variably dissected Mesozoic magmatic arc, and Mesozoic to Holocene sedimentary and volcanic strata deposited in convergent and transform tectonic settings. Modern sand within part of the Western Transverse Ranges represents: first-order sampling scale of the Santa Monica and the San Gabriel Mountains; second-order sampling scale of the Santa Clara River draining both mountain ranges; and third-order sampling scale of the beach system between the mouth of the Santa Clara River and the eastern Santa Monica Mountains, and turbidite sand of the Hueneme-Mugu submarine fan. Source lithology includes plutonic and metamorphic rocks of the San Gabriel Mountains, and sedimentary and volcanic rocks of the Santa Monica Mountains. First-order sands have large compositional variability. Sand from local coastal drainage of the Santa Monica Mountains ranges from basaltic feldspatholithic to quartzofeldspathic. Sand of the San Gabriel Mountains local drainages has three distinct petrofacies, ranging from metamorphiclastic feldspatholithic to mixed metamorphi/plutoniclastic and plutoniclastic quartzofeldspathic. Second-order sand is represented by the main channel of the Santa Clara River; the sand has an abrupt downstream compositional change, from feldspathic to quartzofeldspathic. Third-order sand (beaches and deep-sea turbidite samples) of the Santa Monica Basin is quartzofeldspathic. Beach sand is more quartz-rich than is Santa Clara river sand, whereas turbidite sand is more feldspar-rich than is beach sand. Deep-sea sand has intermediate composition with respect to second-order samples of the Santa Clara River and third-order samples of the beach system, suggesting that (1) the Santa Clara River is the main source of sediments to the marine environment; and (2) local entry points from canyons located near local drainages may generate turbidity currents during exceptional flood conditions. Petrologic data of modern sand of the study area are highly variable at first- and second-order scale, whereas third-order sand is homogenized. The homogenized composition of deep-marine sand is similar to the composition of most ancient sandstone derived primarily from the Mesozoic dissected magmatic arc of southern California. This study of the Western Transverse Ranges illustrates the effects of source lithology, transport, depositional environment, and sampling scale on sand composition of a complex system, which provides insights regarding actualistic petrofacies models.     

The beach: for enthusiasts of sun,surf and unusual geology,this is the place

The Carpinteria State Beach is a little known public park in Carpinteria, near Ventura, California, USA. Miocene‐age conglomerates and sandstone bluffs along the Pacific Ocean beachfront have featured continual natural oil seeps since the Pleistocene epoch. While not as famous as the La Brea Tar Pits of downtown Los Angeles, the park is the only public beach in North America where such a geological phenomenon is readily seen. Long used by the Chumash Indians for the asphaltum used to waterproof their seagoing canoes, asphaltum came into general use in the late nineteenth century. The beach is the former site of an industrial plant, devoted to removing and processing the asphaltum to yield many commercial products. Before it became a state park it served as a travel camp and a camp for World War II GIs suffering from battle fatigue.     

油气藏中沥青垫的研究进展

沥青垫是油气藏中沥青质相当富集的含油储层带，其沥青质的相对含量为２０％￣６０％，而对应的油层中其值不足２０％，沥青垫在凝析油气藏和轻质油藏中出现的频率高，常位于非渗透性隔层之上的高孔隙和较高水平渗透率的砂岩储层中，研究表明沥青垫的主要形成机理为：脱沥青作用，重力分离作用，生物降解作用和油－水相互作用，石油运移作用。     

Horseshoe crabs (Limulus polyphemus) in an urban estuary (Jamaica Bay, New York) and the potential for ecological restoration

We assessed the suitability of intertidal habitats for spawning by horseshoe crabs (Limulus polyphemus) at 12 proposed restoration sites identified by the United States Army Corps of Engineers along the shore of Jamaica Bay, a highly developed estuary in New York City. Based on beach geomorphology, we chose to quantify horseshoe crab activity at five of the sites during the May–July 2000 breeding season. Horseshoe crabs spawned intensively on small patches of suitable sand within larger areas of eroding shoreline with bulkheads and rubble fill. Small areas of sand behind grounded barges at Brant Point and Dubos Point had densities of over 100,000 eggs m⁻², which was equal to or greater than the egg densities on longer, more natural appearing beaches at Spring Creek and Dead Horse Bay, or at a sand spit at Bayswater State Park. There were no significant differences in the percentage of Jamaica Bay horseshoe crab eggs that completed development when cultured using water from Jamaica Bay or lower Delaware Bay, a less polluted location. Only 1% of the embryos from Jamaica Bay exhibited developmental anomalies, a frequency comparable to a previously studied population from Delaware Bay. We suggest that the distribution and abundance of horseshoe crabs at our study areas in Jamaica Bay is presently limited by the availability of suitable shoreline for breeding, rather than by water quality. Restoration efforts that increase the amount of sandy beach in this urban estuary have a good likelihood of benefiting horseshoe crabs and providing additional value to migrating shorebirds that use horseshoe crab eggs as food.     

Rare-earth elements as geochemical criteria of endogenous sources of microelements contained in oil

This article presents data on the REE contained in 50 oil samples taken from six oil and gas regions that are based on oil fraction composition analysis using ICP MS. It is shown that regardless of the geological and tectonic structure of regions, oil composition, depth of deposit occurrence, and lithology of enclosing rocks, chondritenormalized curves of REE distribution in oil are different and have a europium maximum. The europium anomaly and the regularly increasing (Eu/Sm) _N and Eu/Eu* ratios under transition from asphaltene components to tars and then to oils are geochemically substantiated. Unlike oil, Devonian domanicites and Jurassic bazhenites, as well as their bituminous substance are characterized by a prominent negative europium anomaly (in the (Eu/Sm) _N ratio), which is typical of sedimentary rocks, modern seawater, and the upper crust of the earth as a whole. Based on the data obtained, the conclusion on the participation of deep fluid systems in the formation of the geochemical appearance of naphtydes is made.

     

Origin and alteration of oils and oil seeps from the Sinú-San Jacinto Basin, Colombia

Liquid hydrocarbons have been detected in the subsurface as well as in the surface in the Sinú-San Jacinto Basin (northwestern Colombia). The origin of the oils has not been conclusively established especially in the southern part of the basin. The most likely source rocks in the basin are the Ciénaga de Oro Fm. of the Oligocene-Early Miocene and the Cansona Fm. of the Upper Cretaceous. In this study, oil samples, seeps and source rock extracts were analyzed by GC and GC/MS, and δ¹³C was determined to identify the source facies. The sulphur content and gravity data were also considered.Two organic facies were identified: one constituted by terrestrial organic matter deposited in siliciclastic sediments in marginal marine to deltaic environments and the other made up of marine organic matter deposited in marine costal shelf to pelagic environments. The oils from the former organic facies have low sulphur contents, whereas the oils from the latter facies have high sulphur levels. Correlation of the oil seeps from the former facies with the Ciénaga de Oro Fm. has not been clearly established. The oil seeps from the latter facies correlate well with the extracts from the source rocks of the Cansona Fm., deposited along the fold belt of San Jacinto (east side). The oil seeps are affected by moderate to severe biodegradation, whereas the oil from the only oil producing well in the Sinú Basin (Floresanto-6 well) has not undergone biodegradation.     

An examination by GC×GC-TOFMS of organic molecules present inhighly degraded oils emerging from Caribbean terrestrial seeps of Cretaceous age

For our ancestors, oil seeps were both a fascination and a resource but as the planet's reserves of high quality low density oil becomes increasingly depleted, so there is now a renewed interest in heavier,biodegraded oils such as those encountered in terrestrial seeps. One such seep is Pitch Lake in the Caribbean island of Trinidad, which is the largest natural deposit of asphalt in the world. At the northern end of the Caribbean, oil emerges along a tectonic contact on the island on Cuba. The sources of the oils from these seeps are relatively recent and both are subject to intense weathering due to the tropical conditions. When analysed by gas chromatography(GC) both oils appear as unresolved complex mixtures(UCM) and show a very high degree of biodegradation thus presenting an analytical challenge. In this case study, these two Caribbean seep oils were analysed by comprehensive two dimensional GC with time of flight mass spectrometry(GC×GC-TOFMS) to expose many thousands of the individual compounds that comprise the UCM. The high chromatographic resolution of the GC×GC-TOFMS produced good quality mass spectra allowing many compounds including molecular fossil ‘biomarkers' to be identified. Compound classes included diamondoid hydrocarbons, demethylated hopanes and secohopanes, mono-and tri-aromatic steroids. D-ring aromatised structures of the 8,14-seco-hopanes,including demethylated forms were present in both oils but further demethylation, probably at position C-25 during biodegradation, was only observed in the Pitch Lake oil. Many polycyclic aromatic hydrocarbons(PAHs) were absent although the fungal-derived pentacyclic PAH perylene was present in both oils. The presence of the angiosperm biomarker lupane in the Pitch Lake oil constrained the age to the Late Cretaceous. The higher degree of biodegradation observed in the Cuban oil was likely due to relatively slow anaerobic processes whereas oil within Pitch Lake was probably subject to additional more rapid aerobic metabolism within the lake.     

Hydrous pyrolysis of Monterey asphaltenes

Hydrous pyrolysis of asphaltenes has been tested as a method to reconstruct the chemical composition of biodegraded oils and oil seeps. The asphaltenes of three oils (a nondegraded oil, a biodegraded oil, and a biodegraded oil seep) from the Monterey Formation were studied. Results show that the aliphatic fraction generated by hydrous pyrolysis is very similar in chemical composition to the non-degraded oil. This makes the method very useful in correlation studies of biodegraded and nondegraded oils. It also allows to roughly estimate the maturity of the source of the biodegraded oil or oil seep.     

Thermal treatment of the Athabasca oil sand bitumen and its component parts

The Athabasca oil sand bitumen, and its major component fractions, have been heated with and without added montmorillonite to simulate natural geological diagenesis. The products of the treatment of the whole bitumen were found to be essentially the sum of the products of the treatment of the component parts. The saturated hydrocarbon fraction underwent little change, with only minor cracking apparent. Some cracking and polymerization of the aromatic hydrocarbon fraction was noted. Geochemical analysis of these products indicated that the simulation had caused a continuation of the normal petroleum maturation sequence towards coke and gas. Treatment of the polar fraction and asphaltenes caused a continuation of the maturation sequence towards a ‘crude oil’, further treatment of which continued towards coke and gas. Geochemical examination of this ‘crude oil’ yielded information on the past history of the bitumen from the time of asphaltene formation. The geochemical evidence indicates that the Athabasca bitumen may have originated in an unusual marine environment, and that the maturation and exodus from its source rock differed from that of conventional crude oils. The overall results indicate that, except for the maturation of the polar and asphaltene fractions, the bio-degradation of a crude oil is not reversible by diagenetic means.     

Sea-level and tectonic control of middle to late Pleistocene turbidite systems in Santa Monica Basin, offshore California

Small turbidite systems offshore from southern California provide an opportunity to track sediment from river source through the turbidity‐current initiation process to ultimate deposition, and to evaluate the impact of changing sea level and tectonics. The Santa Monica Basin is almost a closed system for terrigenous sediment input, and is supplied principally from the Santa Clara River. The Hueneme fan is supplied directly by the river, whereas the smaller Mugu and Dume fans are nourished by southward longshore drift. This study of the Late Quaternary turbidite fill of the Santa Monica Basin uses a dense grid of high‐resolution seismic‐reflection profiles tied to new radiocarbon ages for Ocean Drilling Program (ODP) Site 1015 back to 32 ka. Over the last glacial cycle, sedimentation rates in the distal part of Santa Monica Basin averaged 2–3 mm yr^?1, with increases at times of extreme relative sea‐level lowstand. Coarser‐grained mid‐fan lobes prograded into the basin from the Hueneme, Mugu and Dume fans at times of rapid sea‐level fall. These pulses of coarse‐grained sediment resulted from river channel incision and delta cannibalization. During the extreme lowstand of the last glacial maximum, sediment delivery was concentrated on the Hueneme Fan, with mean depositional rates of up to 13 mm yr^?1 on the mid‐ and upper fan. During the marine isotope stage (MIS) 2 transgression, enhanced rates of sedimentation of > 4 mm yr^?1 occurred on the Mugu and Dume fans, as a result of distributary switching and southward littoral drift providing nourishment to these fan systems. Longer‐term sediment delivery to Santa Monica Basin was controlled by tectonics. Prior to MIS 10, the Anacapa ridge blocked the southward discharge of the Santa Clara River into the Santa Monica Basin. The pattern and distribution of turbidite sedimentation was strongly controlled by sea level through the rate of supply of coarse sediment and the style of initiation of turbidity currents. These two factors appear to have been more important than the absolute position of sea level.     

Changes of lead and barium with time in California off-shore basin sediments

During ancient times the natural deposition fluxes of lead which can be leached with dilute acid from sediments in Santa Barbara, Santa Monica and San Pedro basins offshore from the Los Angeles Urban complex, were about 0.7, 0.1 and 0.2 μg Pb/cm² yr respectively. Since there was little difference in biological productivity in surface waters of these basins, it is proposed that clay is a major transport vehicle for sequestered soluble lead, which then explains why the lead deposition flux within the Santa Barbara basin was so much larger compared to the other basins. The fluxes of silicate mud in the basins in ancient times were about 92, 19 and 30 mg/cm² yr in Santa Barbara, Santa Monica and San Pedro basins respectively. Today deposition fluxes of acid soluble lead within these three basins are 3- to 9-fold greater, being about 2.1, 1.1 and 1.8 μg Pb/cm² yr respectively, partly in the form of directly deposited large sewage particles, which account for none, $\text{2}\text{3}$ and $\text{3}\text{4}$ of the total industrial lead deposition fluxes in the respective basins. Concentrations of leachable lead in varve dated sediment layers increase with time and isotopic compositions of these leads change in accordance with corresponding known changes of isotopic compositions of industrial lead in the Los Angeles atmosphere. Lead remaining in acid leached sediment residues originates from igneous and clay minerals, exhibiting no change in concentration or isotopic composition since pre-industrial times.Deposition fluxes of total barium in sediments among the three basins were proportional to mass deposition fluxes before 1950 in the same manner as for lead. Afterwards, there are barium concentration maxima with time in both Santa Monica and San Pedro Basin sediments which are attributable to industrial sewage rather than to episodic erosion from barium-rich sedimentary evaporite strata exposed locally along the shore. An increase of barium concentrations in present day Santa Barbara basin sediments may reflect dispersal of barium-rich drilling mud from local drilling operations.     

Origin of Crude Oil in the Lunnan Region,Tarim Basin

<正>The oil source of the Tarim Basin has been controversial over a long time.This study characterizes the crude oil and investigates the oil sources in the Lunnan region,Tarim Basin by adopting compound specific isotopes of n-alkanes and biomarkers approaches.Although the crude oil has a good correlation with the Middle-Upper Ordovician(O_(2+3)) source rocks and a poor correlation with the Cambrian-Lower Ordovician((?)-O_1) based on biomarkers,theδ~(13)C data of n-alkanes of the Lunnan oils show an intermediate value between(?)-O_1 and O_(2+3) genetic affinity oils,which suggests that the Lunnan oils are actually of an extensively mixed source.A quantification of oil mixing was performed and the results show that the contribution of the Cambrian-Lower Ordovician source rocks ranges from 11%to 70%(averaging 36%),slightly less than that of the Tazhong uplift.It is suggested that the inconsistency between the biomarkers andδ~(13)C in determining the oil sources in the Lunnan Region results from multiple petroleum charge episodes with different chemical components in one or more episode(s) and different sources.The widespread marine mixed-source oil in the basin indicates that significant petroleum potential in deep horizons is possible.To unravel hydrocarbons accumulation mechanisms for the Lunnan oils is crucial to further petroleum exploration and exploitation in the region.     

Origin and Source of Deep Natural Gas in Nanpu sag,Bohai Bay Basin,China

Natural gas exploration in Nanpu sag, Bohai Bay Basin, has achieved breakthroughs in recent years, and a number of natural gas and condensate wells with high yield have been found in several structures in the beach area. Daily gas production of single wells is up to 170,000 m3, and high-yield wells are mainly distributed in?the Nanpu No. 1 structural belt.?Studies have shown that these natural gases are mainly hydrocarbon gases, with methane content about 80% to 90% and ethane 6%-9%, so they are mainly wet gas; and non-hydrocarbons are at a low level.?Carbon isotopes of methane range from -42‰ to -36‰, and ethane from -28‰ to -26‰. Calculated maturity based on the relationship between δ13C and Ro of natural gas, the gases are equivalent to those generated from organic matter when Ro is 1.0%-1.7% (mainly 1.25%-1.32%). The natural gas is oil-type gas generated from the source rocks at mature to high mature stage, associated with condensate, so carbon isotopes of the gases are heavier. Natural gas in the Nanpu No.1 structural belt is mainly associated gas with condensate. The analysis of the origin and source of natural gas and condensate, combined with the monomer hydrocarbon carbon isotopes and biomarker, indicated that the main source rocks in the Nanpu No.1 structural belt were Es3 (the lower member of the Shahejie Formation), followed by Es1 (the upper member of the Shahejie Formation).?The high-mature hydrocarbons from source rocks in the deep sag mainly migrated through deep inherited faults into shallow traps and accumulated to form oil and gas pools. Therefore, there is a great potential for exploring gas in deep layers.