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1.
Analysis of the molecular composition of the organic matter (OM) from whole sediment samples can avoid analytical bias that might result from isolation of components from the sediment matrix, but has its own analytical challenges. We evaluated the use of GC × GC-ToFMS to analyze the pyrolysis products of six whole sediment samples obtained from above, within and below a 1 million year old OM-rich Mediterranean sapropel layer. We found differences in pyrolysis products <n-C22 between the OM-rich sapropel samples and the OM-poor background marls. The presence of alkyl pyrroles, probably derived from chlorophyll, in pyrolysates of the sapropels but not in those of the marls suggests that higher marine productivity and greater OM preservation accompanied deposition of the sapropels. Detection of tetramethyl benzenes considered to be pyrolysis products of isorenieratene in the sapropel samples is evidence that nitrogen-fixing green sulfur bacteria contributed to the high productivity. Greater abundances of shorter chain aliphatic hydrocarbons, pyrroles, furans and alkyl aromatics in the pyrolysates of sapropel samples relative to the marls confirm better preservation of marine OM in the sapropels. In addition, the presence of greater amounts of thiophenes in the sapropels than in the marls is consistent with the existence of euxinic conditions during sapropel deposition. The combination of whole sediment pyrolysis and GC × GC-ToFMS is promising, but the procedure requires careful selection of its multiple analytical variables, particularly the pyrolysis temperature and the operational features of the GC columns.  相似文献   

2.
Contamination of coastal marine sediments with polycyclic aromatic hydrocarbons is pervasive, with major sources including anthropogenic activity and natural seepage. Biodegradation serves as a major hydrocarbon sink with evaporation and dissolution responsible for the removal of low boiling range compounds and photo-oxidation acting on many multi-substituted aromatic compounds. In this work, first-order rate constants for aerobic biodegradation were quantified for naphthalene (N), benzothiophene (BT) and their alkylated congeners (1-4 carbon substituents (C1-C4)) in laboratory experiments with oil laden marine sediments from a natural seep. Rate constants were used as proxies for microbial preference, which follows the order: naphthalene > C1N > C2N > C1BT > C2BT > benzothiophene > C3BT > C3N > C4BT > C4N, with some overlap. The application of comprehensive two dimensional gas chromatography further enabled separation and quantification of multiple structural isomers for C2N-C4N and C2BT-C4BT, with 7-12 isomers resolved for each C2N-C4N and 4-7 isomers resolved for each C2BT-C4BT. A strong isomeric biodegradation preference was noted within each of these compound classes, with rate constants varying as much as a factor of 2 for structural isomers of the same compound class. Each isomer was consumed to a low, but non-zero concentration, suggesting that their residual load in sediment may be proportional to the number of structural isomers originally present, in addition to the pattern and the number of alkyl substitutions. The simultaneous first-order biodegradation rates observed for 52 aromatic hydrocarbons resolved in this study, along with reference compounds such as n-alkanes, lends support to the concept of broad scale metabolic specificity during aerobic biodegradation of petroleum.  相似文献   

3.
Bitumens of the Alberta tar sands share a similar primary source rock, but exhibit varying levels of degradation. In the Peace River tar sands area, the wide range of API gravity and sulphur content in Lower Cretaceous reservoirs is investigated in terms of biodegradation processes, using detailed geochemical analyses, burial history modelling and charge/degrade modelling. Decreasing tar sand degradation to the west can be attributed to increasing reservoir temperatures which retard biodegradation. Gething oils west of the Peace River tar sands are derived from the same source, but are minimally degraded due to reservoir pasteurization at 80 °C shortly after charging. Long charge times, reservoir filling and possibly compositional or very low temperature degradation retardation have limited biodegradation of the Alberta tar sands despite long oil residence times and low reservoir temperatures.  相似文献   

4.
Formation waters of the 14 km thick late Cretaceous–Cenozoic Beaufort–Mackenzie basin were examined as part of a larger project to better understand the petroleum potential of the region, where early exploration defined petroleum reserves of 744 × 109 bbls recoverable crude oil and 11.74 tcf gas. Historical water analyses (2583 samples from 250 wells drilled up to 5 km depth) were compiled and culled to remove incomplete and poor quality samples. The resultant database shows a broad range of salinity and water chemistry that has no systematic relationship with depth. Three main water types are defined, paleo seawater, and freshwaters related to a Miocene age gravity-driven flow system, and low TDS–high alkalinity waters. High alkalinity waters are isolated in overpressured fault blocks that were rapidly buried by post-Miocene Iperk shale deposition. The high alkalinities (up to 9000 mg/L) are interpreted to be related to in situ CO2 generation through anaerobic methanogenesis in response to freshwater invasion. The dominant control on biogenic gas generation appears to be maximum burial temperature rather than the modern temperature distribution. This is consistent with the paleopasteurization model that suggests once critical burial temperatures are reached, sterilized rocks are inhibited from further biodegradation, even when temperatures subsequently drop back into the habitable zone.  相似文献   

5.
Biodegradation of crude oil causes volumetrically important compositional changes, which lead to significant deterioration in quality, in particular during the early stages of alteration. To better understand these effects we focussed on a detailed assessment of light to moderate levels of alteration. We investigated a suite of 40 crude oil samples from five different petroleum systems to evaluate the extent of alteration occurring in reservoirs. Based on a comprehensive geochemical characterization, five individual crude oil sequences were defined, where compositional variability is mainly due to microbial activity in the reservoir. In particular, samples from the Gullfaks field (offshore Norway) and from a petroleum system offshore Angola illustrate that conventional molecular biodegradation parameters, such as the Pr/n-C17 and Ph/n-C18 alkane ratios are not suitable for defining the extent of biodegradation in petroleum reservoirs. Here, we suggest a new molecular biodegradation parameter, the degradative loss, that can be used to quantify depletion in individual crude oil constituents. The approach allows improved assessment of the extent of biodegradation in crude oil samples by means of the mean degradative loss. It is demonstrated that crude oil quality, as assessed from API gravity, can be predicted directly from the molecular composition of crude oils. Our data clearly indicate that the degradation patterns of light hydrocarbons and n-alkanes differ in different petroleum systems. This suggests that microbial communities are different and therefore generate different molecular degradation patterns which have to be evaluated individually for each system.  相似文献   

6.
The Western Slope of the Songliao Basin is rich in heavy oil resources (>70 × 108 bbl), around which there are shallow gas reservoirs (∼1.0 × 1012 m3). The gas is dominated by methane with a dryness over 0.99, and the non-hydrocarbon component being overwelmingly nitrogen. Carbon isotope composition of methane and its homologs is depleted in 13C, with δ13C1 values being in the range of −55‰ to −75‰, δ13C2 being in the range of −40‰ to −53‰ and δ13C3 being in the range of −30‰ to −42‰, respectively. These values differ significantly from those solution gases source in the Daqing oilfield. This study concludes that heavy oils along the Western Slope were derived from mature source rocks in the Qijia-Gulong Depression, that were biodegraded. The low reservoir temperature (30–50 °C) and low salinity of formation water with neutral to alkaline pH (NaHCO3) appeared ideal for microbial activity and thus biodegradation. Natural gas along the Western Slope appears mainly to have originated from biodegradation and the formation of heavy oil. This origin is suggested by the heavy δ13C of CO2 (−18.78‰ to 0.95‰) which suggests that the methane was produced via fermentation as the terminal decomposition stage of the oil.  相似文献   

7.
A series of higher thiadiamondoids and diamondoidthiols, including thiatetramantanes, tetramantanethiols, thiapentamantanes, pentamantanethiols, thiahexamantanes, hexamantanethiols and thiacylcohexamantane, was discovered in a gas condensate produced from a very deep (6274 m, 20,585 ft) petroleum reservoir in the Bon Secour Bay in the Mobile Bay gas field, located offshore Alabama in the northern Gulf of Mexico, USA. This appears to be the first reported natural occurrence of these compounds. Several isomers of higher thiadiamondoids and diamondoidthiols were identified using full scan gas chromatography-mass spectrometry (GC-MS) coupled with GC-sulfur chemiluminescence detection (GC-SCD) and GC × GC-time of flight mass spectrometry (GC × GC-TOFMS). These higher thiadiamondoids and diamondoidthiols are associated with abundant lower homologs including thiaadamantanes, thiadiamantanes, thiatriamantanes and their thiol groups. The origin of these compounds in petroleum has not been reported. It is speculated that similar to lower thiadiamondoids and diamondoidthiols, higher ones are possibly formed from the sulfurization of their precursor diamondoids during TSR, a conclusion supported by the occurrence of open-cage higher diamondoidthiols and sulfur isotopic data of higher thiadiamondoids and diamondoidthiols isolated from the Mobile Bay condensate. The presence of higher thiadiamondoids and diamondoidthiols is indicative of the occurrence of TSR and can be used to predict sour gas production.  相似文献   

8.
Around half of world’s endowment of in-place oil and bitumen experienced biodegradation, which is now believed to be largely an anaerobic methanogenic process. However, the distribution and scale of methanogenic biodegradation in the world’s petroleum accumulations and the significance of its terminal product, secondary microbial methane, in the global gas endowment and carbon cycle are largely unknown. Here, I present geological and geochemical criteria to recognize secondary microbial methane in conventional petroleum reservoirs. These include the presence of biodegraded oil (as pools, legs or shows) in the reservoir or down-dip, the relatively dry (methane dominated) gas containing methane with δ13C values between −55‰ and −35‰ and, most importantly, CO2 with δ13C > +2‰. Based on these criteria, the presence of secondary microbial methane is apparent in 22 basins, probable in 12 basins and possible in six basins worldwide. Reservoirs apparently containing secondary microbial methane are mostly Cenozoic and clastic and occur at depths of 37-1834 m below surface/mudline and temperatures of 12-71 °C. Using the current global endowment of in-place oil and bitumen and reasonable assumptions about conversion of oil into methane during biodegradation, I estimated that ∼65,500 tcf of secondary microbial methane could have been generated in existing worldwide accumulations of oil and bitumen through their geological history. From 1461-2760 tcf in-place (845-1644 tcf recoverable) of secondary microbial methane may be accumulated as free and oil-dissolved gas in petroleum reservoirs. I also updated the inventory of primary microbial methane and estimated that the global primary microbial gas endowment (free and oil-dissolved) is from 676-797 tcf in-place (407-589 tcf recoverable). Secondary microbial methane may account for ∼5-11% of the global conventional recoverable gas endowment and appears more abundant than primary microbial gas (∼3-4% of the global gas endowment). Most of the generated secondary microbial methane probably is aerobically and anaerobically oxidized to CO2 in the overburden above petroleum reservoirs. However, some secondary microbial methane may escape from shallow reservoirs into the atmosphere and affect present and past global climate.  相似文献   

9.
Nineteen oil samples from Silesian Unit of the eastern Carpathian Overthrust have been characterised geochemically in order to determine the causes of compositional differences among them and elucidating the processes responsible for their differences. Some of analysed crude oils have undergone post-emplacement alteration in the reservoir such as biodegradation and evaporative fractionation. This explains much of the chemical and physical properties variability across individual fields from one tectonic unit. Geochemical correlation based on biomarker distributions showed a close relationship between all oils (included biodegraded oils). However, data based on the whole oil GC analysis of selected oils suggest that the process of evaporative fractionation may change the composition of lower molecular weight hydrocarbons of the oils in this region. This paper outlines the probable mechanisms for oil mixing in the region and describes how this can lead to observable lateral differences in the composition of oils.  相似文献   

10.
Fifty-three samples, including brines associated with oil and natural gas reservoirs and groundwater samples from deep boreholes, were collected from the Pacific and Japan Sea coastal regions in Japan. The 129I/127I and 36Cl/Cl ratios, and stable isotopes (δD and δ18O) are compared to investigate differences related to the geotectonic settings of the two regions. The δD and δ18O data indicate that brine and groundwater from the Pacific coastal region reflect mixing of meteoric water with connate seawater in the pores of sedimentary rocks. On the other hand, brine and groundwater from the Japan Sea coastal region have been hydrothermally altered. In particular, brines associated with petroleum accumulations at Niigata and Akita showed the same isotopic characteristics as fluids found in the Kuroko deposits of the Green Tuff region in northeastern Japan. There is little difference in the 36Cl/Cl ratios in brine and groundwater from the Pacific and Japan Sea coasts. Most brine and some deep groundwater, except those from the Pleistocene Kazusa Group, have already reached the average secular equilibrium ratio of 9.9 ± 2.7 × 10−15 for their mudstone and sandstone reservoirs. There was no correlation between the 36Cl/Cl ratios and differences in geotectonic setting between the Pacific and the Japan Sea coast. The molar I/Br ratio suggests that the I in all of water samples was of biogenic origin. The average 129I/127I ratio was 290 ± 130 × 10−15 to 294 ± 105 × 10−15 in both regions, showing no relationship to the different geotectonic settings. The uncontaminated brine and groundwater samples are likely to have retained the original 129I/127I ratios of marine I released from the old organic matter stored in sedimentary rock.  相似文献   

11.
The availability of dissolved O2 can limit biodegradation of organic compounds in aquifers. Where O2 is depleted, biodegradation proceeds via anaerobic processes, including NO3-, Mn(IV)-, Fe(III)- and SO4-reduction and fermentation/methanogenesis. The environmental controls on these anaerobic processes must be understood to support implementation of management strategies such as monitored natural attenuation (MNA). In this study stable isotope analysis is used to show that the relative significance of two key anaerobic biodegradation processes (bacterial SO4 reduction (BSR) and methanogenesis) in a phenol-contaminated sandstone aquifer is sensitive to spatial and temporal changes in total dissolved phenols concentration (TPC) (= phenol + cresols + dimethylphenols) over a 5-a period. In general, 34SO4-enrichment (characteristic of bacterial SO4 reduction) is restricted spatially to locations where TPC < 2000 mg L−1. In contrast, 13C-depleted CH4 and 13C-enriched CO2 isotope compositions (characteristic of methanogenesis) were measured at TPC up to 8000 mg L−1. This is consistent with previous studies that demonstrate suppression of BSR at TPC of >500 mg L−1, and suggests that methanogenic microorganisms may have a higher tolerance for TPC in this contaminant plume. It is concluded that isotopic enrichment trends can be used to identify conditions under which in situ biodegradation may be limited by the properties of the biodegradation substrate (in this case TPC). Such data may be used to deduce the performance of MNA for contaminated groundwater in similar settings.  相似文献   

12.
Spillage and improper disposal of saline produced water from oil wells has caused environmental damage at thousands of sites in the United States. In order to improve understanding of the fate and transport of contaminants at these sites, the U.S. Geological Survey carried out multidisciplinary investigations at two oil production sites near Skiatook Lake, Oklahoma. As a part of this effort, the hydrology and subsurface transport of brine at OSPER site “A”, a tank battery and pit complex that was abandoned in 1973, was investigated. Based on data from 41 new boreholes that were cored and completed with monitoring wells, a large (∼200 m × 200 m × 20 m) plume of saline ground water was mapped. The main dissolved species are Na and Cl, with TDS in the plume ranging as high as 30,000 mg/L. Analysis of the high barometric efficiency of the wells indicated a confined aquifer response. Well-slug tests indicated the hydraulic conductivity is low (0.3–7.0 cm/day). Simplified flow and transport modeling supports the following conceptual model: (1) prior to the produced water releases, recharge was generally low (∼1 cm/a); (2) in ∼60 a of oil production enough saline produced water in pits leaked into the subsurface to create the plume; (3) following abandonment of the site in 1973 and filling of Skiatook Reservoir in the mid-1980s, recharge and lateral flow of water through the plume returned to low values; (4) as a result, spreading of the brine plume caused by mixing with fresh ground water recharge, as well as natural attenuation, are very slow.  相似文献   

13.
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.  相似文献   

14.
A comprehensive study was performed to characterize, for the first time, the mud, water, and gases released from onshore mud volcanoes located in the southern margin of the Junggar Basin, northwestern China. Chemical compositions of mud, along with the geology of the basin, suggest that a source of the mud is Mesozoic or Cenozoic shale. Oxygen and H isotope compositions of the released water suggest a local meteoric origin. Combined with the positive Eu anomalies of the water, a large 18O shift of the water suggests extensive interaction with rocks. Gases discharged from the mud volcanoes are predominantly thermogenic hydrocarbons, and the high δ13C values (>+20‰ VPDB) for CO2 gases and dissolved carbonate in muddy water suggest secondary methanogenesis with CO2 reduction after oil biodegradation.The enrichments of Eu and 18O in water and the low thermal gradient of the area suggest that the water-rock interactions possibly occur deeper than 3670 ± 200 m. On the other hand, considering the relationship to the petroleum reservoir around the mud volcanoes, the depth of the gases can be derived from about 3600 m, a depth that is greater than that generally estimated for reservoirs whose gas is characterized by 13C-enriched CO2. Oil biodegradation with CO2 reduction likely occurs at a shallower depth along the seepage system of the mud volcano. The results contribute to the worldwide data set of gas genesis in mud volcanoes. Moreover, they further support the concept that most terrestrial mud volcanoes release thermogenic gas produced in very deep sediments and may be early indicators of oil biodegradation, an important problem in the petroleum industry.  相似文献   

15.
This paper reports the analyses of unusual oils that accumulate in the Uzon Caldera, situated in the central volcanic region of Kamchatka, Russia. Gas chromatography–mass spectrometry (GC–MS) was used to determine the primary constituents, and the 13C and 14C compositions provided information about the potential source and age of the oils. The 14C ages determined are 1030 ± 40 a BP (measured) or 940 ± 40 a BP (conventional). The δ13C value is −30.6‰ versus the PDB standard, a value consistent with a biological origin. The nearly contemporary age of the C content indicates a geologically recent origin from biogenic detritus and not by synthesis from mantle C. The biogenic origin is supported by the presence of sterane and hopane biomarkers and the δ13C value of the bulk oil. The overall compositions of the oils indicate that they are derived from rapid hydrothermal alteration of algal/bacterial mat detritus buried by volcanic ashfall deposits of the Uzon Caldera. The oils represent the youngest hydrothermal petroleum reported to date.  相似文献   

16.
The occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) has been studied in oil columns from the Liaohe basin, NE China, characterized by varied degrees of biodegradation. The Es3 oil column has undergone light to moderate biodegradation – ranging from levels 2 to 5 on the [Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide: Interpreting Molecular Fossils in Petroleum and Ancient Sediments. Prentice Hall, Englewood Cliffs, NJ, p. 363] scale (abbreviated as ‘PM level’) – while the shallower Es1 column has undergone more severe biodegradation, ranging from PM level 5 to 8. Both columns show excellent vertical biodegradation gradients, with degree of biodegradation increasing with increasing depth toward the oil–water contact (OWC). The compositional gradients in the oil columns imply mass transport control on degradation rates, with degradation occurring primarily at the OWC. The diffusion of hydrocarbons to the OWC zone will be the ultimate control on the maximum degradation rate. The chemical composition and physical properties of the reservoired oils, and the ‘degradation sequence’ of chemical components are determined by mixing of fresh oil with biodegraded oil.The PAH concentrations and molecular distributions in the reservoired oils from these biodegraded columns show systematic changes with increasing degree of biodegradation. The C3+-alkylbenzenes are the first compounds to be depleted in the aromatic fraction. Concentrations of the C0–5-alkylnaphthalenes and the C0–3-alkylphenanthrenes decrease markedly during PM levels 3–5, while significant isomer variations occur at more advanced stages of biodegradation (>PM level 4).The degree of alkylation is a critical factor controlling the rate of biodegradation; in most cases the rate decreases with increasing number of alkyl substituents. However, we have observed that C3-naphthalenes concentrations decrease faster than those of C2-naphthalenes, and methylphenanthrenes concentrations decrease faster than that of phenanthrene. Demethylation of a substituted compound is inferred as a possible reaction in the biodegradation process.Differential degradation of specific alkylated isomers was observed in our sample set. The relative susceptibility of the individual dimethylnaphthalene, trimethylnaphthalene, tetramethylnaphthalene, pentamethylnaphthalene, methylphenanthrene, dimethylphenanthrene and trimethylphenanthrene isomers to biodegradation was determined. The C20 and C21 short side-chained triaromatic steroid hydrocarbons are degraded more readily than their C26–28 long side-chained counterparts. The C21–22-monoaromatic steroid hydrocarbons (MAS) appear to be more resistant to biodegradation than the C27–29-MAS.Interestingly, the most thermally stable PAH isomers are more susceptible to biodegradation than less thermally stable isomers, suggesting that selectivity during biodegradation is not solely controlled by thermodynamic stability and that susceptibility to biodegradation may be related to stereochemical structure. Many commonly used aromatic hydrocarbon maturity parameters are no longer valid after biodegradation to PM level 4 although some ratios change later than others. The distribution of PAHs coupled with knowledge of their biodegradation characteristics constitutes a useful probe for the study of biodegradation processes and can provide insight into the mechanisms of biodegradation of reservoired oil.  相似文献   

17.
The atmospheric 3He/4He ratio has been considered to be constant on a global scale, because the residence time of helium is significantly longer than the mixing time in the atmosphere. However, this ratio may be decreasing with time owing to the anthropogenic release of crustal helium from oil and natural gas wells, although this observation has been disputed. Here, we present the 3He/4He ratios of old air trapped in historical slags in Japan and of modern surface air samples collected at various sites around the world, measured with a newly developed analytical system. In air helium extracted from metallurgical slag found at refineries in operation between AD 1603 and 1907 in Japan, we determined a mean 3He/4He ratio of (5106 ± 108) × 10-5 RHESJ (where RHESJ is the 3He/4He ratio of the Helium Standard of Japan), which is consistent with the previously reported value of (5077 ± 59) × 10-5 RHESJ for historical slags in France and United Arab Emirates and about 4% higher than that of average modern air, (4901 ± 4) × 10-5 RHESJ. This result implies that the air 3He/4He ratio has decreased with time as expected by anthropogenic causes. Our modern surface air samples revealed that the 3He/4He ratio increases from north to south at a rate of (0.16 ± 0.08) × 10-5 RHESJ/degree of latitude, suggesting that the low 3He/4He ratio originates in high-latitude regions of the northern hemisphere, which is consistent with the fact that most fossil fuel is extracted and consumed in the northern hemisphere.  相似文献   

18.
Stepped heating and crushing experiments have been used to investigate the noble gas and halogen degassing behaviour of quartz in detail. Samples with diverse character were selected from the Eloise and Osborne, Iron Oxide Copper Gold (IOCG) ore deposits, and the Railway Fault, 13 km south of the Mt Isa Mine, in the Proterozoic Mt Isa Inlier of northeast Australia. Quartz has been shown to have a bimodal degassing profile. The first degassing mode at temperatures of <700 °C is caused by thermally induced mechanical decrepitation of fluid inclusions. Changes in the Br/Cl, I/Cl, Ar/Cl and 40Ar/36Ar composition of gas released at different temperatures up to 700 °C can be related to the decrepitation of different types of fluid inclusion observed by microthermometry. These variations with temperature permit deconvolution of the complex fluid inclusion assemblages associated with the IOCG samples; the ultra high salinity, multi solid (MS) and liquid-vapour-daughter (LVD) fluid inclusions, with a predominantly primary origin, decrepitate at higher temperatures than lower salinity liquid-vapour (LV) and monophase (M) fluid inclusions that have a predominantly secondary origin. Three of the IOCG samples have primary MS and LVD fluid inclusions characterized by molar Br/Cl values of between 0.25 × 10−3 and 0.66 × 10−3, I/Cl between 0.37 × 10−6 and 5.0 × 10−6, 40Ar/36Ar values of <1000 and low 36Ar concentrations of 0.7-1.0 × 10−6 cm3 cm−3H2O. These low values are most easily explained by the involvement of halite dissolution water in IOCG genesis. One of the IOCG samples has Br/Cl of 1.3-2.0 × 10−3 and I/Cl of 10 × 10−6, similar to juvenile magmatic fluids in Phanerozoic Porphyry Copper Deposits. This sample also has a higher 36Ar concentration of 3.5 × 10−6 cm3 cm−3H2O and a slightly elevated 40Ar/36Ar of 2236. Step heating reveals limited and non-systematic variation within the more homogenous population of LV fluid inclusions from the Railway Fault. The samples have mean values of 8.1 × 10−3 for Br/Cl; 9.4-12 × 10−6 for I/Cl; <2000 for 40Ar/36Ar; and 4.7-4.8 × 10−6 cm3 cm−3H2O for 36Ar concentration. The Br/Cl values are similar to those previously reported for basinal brines present in silicic alteration at the Mt Isa Mine and the additional data can be explained by interaction of such a bittern brine with fine grained sedimentary rocks in the sub-surface. The second mode of quartz degassing occurs between 1200 and 1450 °C and releases a greater volume of gas than the first degassing mode. Several lines of evidence, including microscope observations, indicate that the gas released at high temperature is also from the fluid inclusion reservoir. However, its release may be triggered by a metastable phase transition of quartz (∼1200 °C) and caution is required in interpretation of the fluid compositions obtained at these temperatures. The data provide an improved understanding of fluid inclusion decrepitation behaviour that is different to that obtained in lower temperatures experiments designed by other workers to investigate H-isotope fractionation.  相似文献   

19.
Water concentrates from Turia river (1.5 mg L−1 total organic C) obtained by nanofiltration (membrane mass cut-off 90 Da) were fractioned by non-ionic Amberlite resins (DAX8 and XAD4) to afford three samples termed as hydrophobic acid (50%), transphilic acid (24%) and hydrophobic neutral (12%). If a nanofiltration membrane 270 Da mass cut-off is used then about 50% of dissolved organic matter is not retained. These three fractions were characterized by analytical and spectroscopic techniques (1H NMR, MALDI–TOF-MS, ESI–API-MS, ESI–MS/MS). Overall, these data are compatible with the presence of oligosaccharides, oligopeptides and fatty acids as the main components of dissolved organic matter. Particularly revealing was the information from MALDI–TOF-MS and ESI–MS/MS where series of compounds differing in the number of hexose units were identified. The three fractions have many spectroscopic similarities and, particularly the hydrophobic and transphilic ones, are really almost identical. This similarity in the fraction composition shows that the conventional fractionation procedure is inefficient as a standard general method for separation of different compound types. The composition of dissolved organic matter was confirmed, and some individual organic compounds identified, by GC–MS analysis of the silylated derivatives obtained by reacting the fractions with a mixture of N,O-bis(trimethylsilyl)trifluoroacetamide with trimethylchlorosilane (10%). Thus, rather surprisingly, the dissolved organic matter of this natural raw water is predominantly composed of a relatively simple mixture of a few types of compounds with molecular weights well below 1100 Da (about six hexose units). These results, particularly the absence of detectable amounts of high molecular weight humic acids and low molecular weight phenolic compounds indicates that trihalomethanes formed in the water disinfection process by Cl2 really derive from oligosaccharides and oligopeptides. Also, the data suggests alternative strategies to effect a more efficient fractionation of the dissolved organic matter.  相似文献   

20.
生物降解原油中吡咯氮化合物组成的变化   总被引：1，自引：0，他引：1  
渤海海域地区近50个原油样品中性氮组分的GC／MS定量分析资料表明,油藏中的生物降解作用对原油的吡咯氮化合物含量和分布有明显影响。经与同源未降解原油比较,各种烷基咔唑和苯并咔唑在3。4级中轻度降解油中就出现明显降解迹象,随生物降解程度增高其含量逐渐减少,在6—8级严重降解油中它们的总含量降低到原有的五分之一左右。在3—4级中轻度降解油中,裸露型甲基咔唑异构体更容易被微生物侵袭而代谢,抗生物降解能力按1-甲基咔唑〉4-甲基咔唑〉2-、3-甲基咔唑顺序递减;当降解程度更高时,这些化合物降解速率相当,1-／4-MCA等比值相对稳定。低-中等降解阶段,不同类型二甲基咔唑异构体的抗生物降解能力也存在明显差异性,呈屏蔽型〉半屏蔽型〉裸露型降低;在生物降解水平进一步增高时,这些异构体之间的相对含量变化不大。生物降解作用对苯并咔唑系列化合物分布的影响具有不确定性,且随降解程度的增加变得更为显著,降解油中【a】／[c】苯并咔唑比值或增高或降低。生物降解原油中吡咯氮化合物的组成变化,使降解油的二次运移示踪面临新的问题。  相似文献   

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