Biomarkers and compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern Llanos Basin,Colombia

Representative samples of crude oils from Cusiana, Cupiagua, Apiay, Castilla and Chichimene fields in the Eastern Llanos Basin of Colombia were analyzed to determine its compound-specific stable carbon isotope composition (CSIA) using gas chromatography–isotopic ratio–mass spectrometry (GC–IRMS). GC–IRMS analyses of n-alkanes allowed differentiating between Cretaceous and Cretaceous/Tertiary oil samples. Cretaceous sourced samples have δ¹³C-enriched values than Cretaceous/Tertiary sourced samples; the heavier isotope composition of these samples is due to their major terrigenous organic matter input. Their isotope distribution patterns suggest significant algal and/or bacterial contribution (marine origin). The analysis of the n-alkane fractions by GC–IRMS confirms that the organic matter has marine origin in those samples from Cusiana, Cupiagua and Apiay while Castilla and Chichimene have marine origin with terrestrial inputs. The results were confirmed by gas chromatography/FID and gas chromatography/mass spectrometry (GC/MS). Basic geochemical composition show that samples from Cupiagua/Cusiana fields and Apiay/Castilla/Chichimene fields in the Llanos basin, Colombia present different characteristics reflecting a specific for each depositional environment.     

Biogenic and abiogenic polynuclear aromatic hydrocarbons in sediments from two remote Adirondack lakes

Sediment cores from Sagamore Lake and Woods Lake in New York State's Adirondack Park, an area remote from industrial activities, were analyzed for polynuclear aromatic hydrocarbons (PAH) by high resolution gas chromatography/mass spectrometry (GC/MS). Their composition and distribution with depth in the sediment indicate that the parental PAH in the surface sediments are primarily produced by anthropogenic combustion of fossil fuels. Perylene in deep sediments is apparently transformed from natural precursors in the reducing environment, however, the exact precursors remain unknown. The rather even sediment distributions of the non-parental PAH differ from the parental, suggesting biogenic origins. Based on their chemical structures, retene and alkylated and partially hydrogenated phenanthrenes are believed to be biogenically converted from abietic acid; hydrochrysenes and hydropicenes, from pentacyclic triterpenes.     

气相色谱法测定地下水中有机氯农药和多氯联苯

建立了地下水中常见有机氯农药和多氯联苯的气相色谱分析方法。有机氯农药检出限均小于2.21ng/L,多氯联苯中PCB1检出限为5.20ng/L,其他目标组分检出限在1.30ng/L以下。两大类待测组分回收率均可以达到63.5%～110.2%,各组分精密度(RSD,n=5)在2.2%～17.3%。除异狄氏剂外,有机氯农药基体加标回收率为87.34%～133.76%。方法稳定性和重现性较好,样品前处理操作简便,适用于实验室分析或进一步改进。     

Identification and quantification of polyfunctionalized hopanoids by high temperature gas chromatography–mass spectrometry

Hopanoids are triterpenoids produced mainly by bacteria, are ubiquitous in the environment, and have many important applications as biological markers. A wide variety of related hopanoid structures exists, many of which are polyfunctionalized. These modifications render the hopanoids too involatile for conventional gas chromatography (GC) separation, so require either laborious oxidative cleavage of the functional groups or specialized high temperature (HT) columns. Here we describe the systematic evaluation and optimization of a HT–GC method for the analysis of polyfunctionalized hopanoids and their methylated homologs. Total lipid extracts are derivatized with acetic anhydride and no further treatment or workup is required. We show that acid or base hydrolysis to remove di- and triacylglycerides leads to degradation of several BHP structures. DB-XLB type columns can elute hopanoids up to bacteriohopanetetrol at 350 °C, with baseline separation of all 2-methyl/desmethyl homologs. DB-5HT type columns can additionally elute bacteriohopaneaminotriol and bacteriohopaneaminotetrol, but do not fully separate 2-methyl/desmethyl homologs. The method gave 2- to 7-fold higher recovery of hopanoids than oxidative cleavage and can provide accurate quantification of all analytes including 2-methyl hopanoids. By comparing data from mass spectra with those from a flame ionization detector, we show that the mass spectromet (MS) response factors for different hopanoids using either total ion counts or m/z 191 vary substantially. Similarly, 2-methyl ratios estimated from selected-ion data are lower than those from FID by 10–30% for most hopanoids, but higher by ca. 10% for bacteriohopanetetrol. Mass spectra for a broad suite of hopanoids, including 2-methyl homologs, from Rhodopseudomonas palustris are presented, together with the tentative assignment of several new hopanoid degradation products.     

加速溶剂萃取-气相色谱法测定土壤中有机氯农药和多氯联苯

试验了加速溶剂萃取土壤中有机氯农药和多氯联苯残留的最佳条件。结果表明,采用正己烷-丙酮混合溶剂(体积比1:1)为提取剂,萃取温度100℃,压力为10.3MPa;采用弗罗里硅土固相萃取柱对样品净化,毛细管柱分离,用配有电子捕获检测器的气相色谱进行检测,平均加标回收率为83.6%～109.0%,相对标准偏差(RSD,n=11)为1.11%～5.88%,检出限为0.69～1.85ng/g。方法简单、快捷、经济,适应于土壤中的有机氯农药和多氯联苯的测定。     

Laboratory methods for evaluating migrated high molecular weight hydrocarbons in marine sediments at naturally occurring oil seeps

A laboratory study has been conducted to determine the best methods for the detection of C₁₀–C₄₀ hydrocarbons at naturally occurring oil seeps in marine sediments. The results indicate that a commercially available method using n-C₆ to extract sediments and gas chromatography–flame ionization detection (GC–FID) to screen the resulting extract is effective at recognizing the presence of migrated hydrocarbons at concentrations from 50 to 5000 ppm. When non-biodegraded, the amount of oil charge is effectively tracked by the sum of n-alkanes in the gas chromatogram. However, once the charge oil becomes biodegraded, with the loss of n-alkanes and isoprenoids, the amount of oil is tracked by the quantification of the unresolved complex mixture (UCM). Gas chromatography–mass spectrometry (GC–MS) was also found to be very effective for the recognition of petroleum related hydrocarbons and results indicate that GC–MS would be a very effective tool for screening samples at concentrations below 50 ppm oil charge.     

超高效液相色谱串联质谱法快速测定地下水和含水层介质中16种全氟烷基酸

全氟烷基酸(PFAAs)是一种新型的持久有机污染物,在各种环境介质中被频繁检出。目前,PFAAs的检测方法主要包括液相色谱串联质谱法(HPLC-MS/MS)、超高效液相色谱串联质谱法(UPLC-MS/MS)、气相色谱法和光谱类方法。但是,上述方法多存在样品前处理过程复杂、周期长、成本高的问题,不适用于PFAAs的快速检测。为此,本文建立了一种快速测量地下水和含水层介质中16种PFAAs的UPLC-MS/MS方法。水样过0.22μm滤膜后直接测定浓度,土样经过超声离心后,取上清液过滤测量浓度。本方法分别为16种PFAAs建立了低浓度(5~50μg/L)和高浓度(100~500μg/L)两条校准曲线,相关系数R^2>0.99。地下水中16种PFAAs快速检测方法检出限为0.06~1.07μg/L,回收率为75%~120%,精密度(RSD)为2.61%~9.19%(除高浓度时全氟丁烷磺酸和全氟已烷磺酸分别为11.34%和14.70%外)。含水层介质中14种PFAAs(全氟十三酸和全氟十四酸除外)方法检出限为2.69~12.33ng/g,回收率为65%~103%,精密度(RSD)为1.96%~7.22%。     

The determination of biomarker distributions by tandem mass spectrometry

The rapid development of biomarker geochemistry and its application to petroleum exploration problems has been due in no small part to gas chromatography-mass spectrometry (GC-MS). The recent availability of hybrid and triple stage quadrupole mass spectrometers have introduced a number of novel ways for the detection and identification of biomarkers present in extremely complex mixtures of organic compounds from various sources including crude oils and source rock extracts.A triple stage quadrupole mass spectrometer has been used in the MS/MS mode with both a gas chromatograph and direct insertion probe as inlet systems, to develop alternative methods for biomarker analyses. Selected ions formed in the ion source of the mass spectrometer are permitted to enter the collision cell where, following collision with an inert gas, the daughter ions are separated using the third quadrupole. In this manner specific parent/daughter ion relationships are utilized to monitor and resolve classes of biomarkers or individual components from within a complex mixture. Furthermore, deuterated analogues of naturally occurring biomarkers can be utilized for quantitation purposes since the parent/daughter relationship for the standard will differ, depending on the number of deuterium atoms present, even though the relative retention times are identical.The ability of MS/MS to resolve components spectrometrically as well as chromatographically greatly enhances the analytical short-column capabilities of this system. In this paper the utilization of GC-MS/MS and the direct insertion probe MS/MS to determine biomarker distributions in crude oils both qualitatively and quantitatively are discussed. The results from the study show that it is possible to use the probe data to rapidly correlate oils on the basis of their source materials and if necessary select samples for more detailed analysis by GC-MS/MS. A major advantage of the direct insertion probe method is speed of analysis although some component resolution is lost. In an effort to minimize this problem and still maintain the rapid analysis time, the use of short columns in the GC is also described. This approach provides the ability to undertake relatively rapid analyses with limited chromatographic resolution but at relatively high levels of sensitivity.     

Distribution and transport of hydrocarbons in surface sediments of the alaskan outer continental shelf

Surface sediments from the Outer Continental Shelf of Alaska were analyzed for hydrocarbons as part of an environmental survey sponsored by NOAA/BLM. Sediments were collected from the proposed oil lease areas of Beaufort Sea, southeastern Bering Sea, Norton Sound, Navarin Basin, Gulf of Alaska, Kodiak Shelf and lower Cook Inlet. Data on normal and branched alkanes and di- and triterpenoids from capillary gas chromatography (GC) and gas chromatography-mass spectrometry (GC/ MS) indicate that the area displays little evidence of petroleum hydrocarbons (i.e., seeps) except at a few isolated stations. Beaufort Sea sediments have the highest hydrocarbon budget, whereas Kodiak Shelf sediments have the lowest. The molecular markers of the hydrocarbons are of a mixed marine autochthonous and terrestrial allochthonous origin. Norton Sound and Cook Inlet sediments contain the highest levels of terrigenous lipids and Kodiak Shelf the lowest. The abundance of alkenes implies that relatively low oxidizing conditions exist in some of the depositional areas studied, suggesting that extraneous petroleum hydrocarbons introduced into these sediments would be expected to have a relatively long residence time. The distribution of polynuclear aromatic hydrocarbons (PAH) is complex and shows a pyrolytic origin. The data on perylene strongly favor the hypothesis that it is “performed” from terrigenous precursors and transported into the marine environment with no apparent in situ generation. Polynuclear aromatic hydrocarbons of diagenetic origin are probably dominant in Gulf of Alaska and Kodiak Shelf sediments.Two stations, north of Kalgin Island, in lower Cook Inlet and one in southeastern Bering Sea show typical weathered petroleum distribution of n-alkanes and triterpenoids. Probable pathways of transport and fate of petroleum hydrocarbons in case of an oil spill are also briefly discussed.     

Hydrothermal petroleum in the sediments of the Andaman Backarc Basin,Indian Ocean

Recent sediments of the Andaman Backarc Basin, Indian Ocean, between the Andaman Nicobar islands and the Malay Peninsula have been analyzed for biomarker lipids. Three cores were selected: one each from the fault zone in a deep basin (a graben between two fault systems), another from a location adjacent to the fault, and the third from the topographic high in the rift valley. The molecular composition of the lipid classes (n-alkanes, isoprenoids, alkylbenzenes, alkylcyclohexanes, hopanoids, polycyclic aromatic hydrocarbons, steranes, alcohols, sterols and fatty acids) was examined by gas chromatography (GC) and GC/mass spectrometry to understand the nature and source of the hydrocarbons present and the processes of maturation of organic matter. The data show that the hydrocarbons are of hydrothermal origin, derived from thermal alteration of sedimentary organic matter, consisting of a mixture predominantly of marine-derived components with some terrestrial inputs. Normal alcohols and fatty acids also corroborate the distribution of n-alkanes. The distribution profiles and various parameters computed from the concentration of the target compounds suggest that oxidative reactions and microbial degradation in this environment are insignificant. Triterpane and PAH compositions indicate that the thermal maturity of the bitumen in the samples is comparable to or lower than that found at other hydrothermal regions such as the Northern Juan de Fuca Ridge, Guaymas Basin and Escanaba Trough.     

Determination of organochlorine compounds in coastal marine sediments from the southern west of the Mediterranean Sea

Recent evidence suggests that polychlorinated biphenyls might also have adverse reproductive, developmental and endocrine effects. Although, the use of polychlorobiphenyls in Algeria has been banned for more than two decades, large quantities of these compounds containing products remain disseminated, mainly stored in obsolete or damaged equipments. This research describes a study to assess polychlorinated biphenyls distribution in marine sediments collected from the seaside of Tamentfoust touristic resort located in the eastern side of Algiers Bay. After microwave-assisted extraction and purification with both concentrated sulphuric acid and activated silica gel, the extracts were analyzed by gas chromatography with an electron capture detector. Relatively high contamination levels of polychlorinated biphenyls were found in samples collected from the port of Tamentfoust (15 to 70 ng/g d.w.), while the concentrations were lower in the stations located outside the port (0 to 26 ng/g d.w.). Compared with data previously reported by some other researchers, the polychlorobiphenyls concentrations found in this work showed an environmental persistence, but a decrease of approximately 5 times in 30 year i.e since the ban of the use of polychlorinated biphenyls. The predominant polychlorinated biphenyls congeners in all sediment samples were polychlorinated biphenyls138, 153, 180 and 187. This composition was similar to industrial mixture (Aroclor 1260). This probably indicated that the contamination originated from the port and has a continental source.     

Biomarkers in crude oil revealed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry: Depositional paleoenvironment proxies

Crude oil samples from two basins were analyzed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC–TOFMS) to better understand the compositional heterogeneity of branched-cyclic hydrocarbons. GC×GC–TOFMS and conventional GC–MS results were compared. GC×GC–TOFMS revealed a wide range of compounds, including tricyclic, tetracyclic and pentacyclic terpane series, rearranged hopanes, methyl hopanes, secohopanes, onoceranes and steranes. Assignment of methyl hopane and 8,14-secohopane series other than onocerane isomers was only possible due to the high peak capacity and sensitivity of GC×GC. The oils comprised a mixture of two end members: non-biodegraded oil with abundant tricyclic terpanes and hopanes, and severely biodegraded oil with abundant 8,14-secohopane and demethylated tricyclic terpanes. A predominance of two distinct series, 3β-methylhopane and onocerane, was detected only in the lacustrine samples (classification based on biomarker parameters). In contrast, the predominance of a 2α-methylhopane series and lack of onocerane were found only for the marine oil sample. The results suggest that the distribution of 3β- and 2α-methylhopane series and the presence or absence of onocerane isomers reflect genetic differences in the source organic matter and that these compounds are new classes of biomarkers that can used as depositional paleoenvironment proxies.     

Polycyclic aromatic hydrocarbons (PAHs) in lake sediments record historic fire events: Validation using HPLC-fluorescence detection

Understanding the natural mechanisms that control fire occurrence in terrigenous ecosystems requires long and continuous records of past fires. Proxies, such as sedimentary charcoal and tree-ring fire scars, have temporal or spatial limitations and do not directly detect fire intensity. We show in this study that polycyclic aromatic hydrocarbons (PAHs) produced during wildfires record local fire events and fire intensity. We demonstrate that high performance liquid chromatography with fluorescence detector (HPLC-FLD) is superior to gas chromatography–mass spectrometry (GC–MS) for detecting the low concentrations of sedimentary PAHs derived from natural fires. The HPLC-FLD is at least twice as sensitive as the GC–MS in selective ion monitoring (SIM) mode for parent PAHs and five times as sensitive for retene. The annual samples extracted from varved sediments from Swamp Lake in Yosemite National Park, California are compared with the observational fire history record and show that PAH fluxes record fires within 0.5 km of the lake. The low molecular weight (LMW) PAHs (e.g., fluoranthene, pyrene and benz[a]anthracene) are the best recorders of fire, whereas the high molecular weight (HMW) PAHs likely record fire intensity. PAHs appear to resolve some of the issues inherent to other fire proxies, such as secondary deposition of charcoal. This study advances our understanding of how PAHs can be used as markers for fire events and poses new questions regarding the distribution of these compounds in the environment.     

土壤中持久性有机污染物分析的前处理方法

对土壤样品的前处理技术进行了研究。采用加速溶剂萃取法(ASE)提取土壤中有机氯农药和多氯联苯类化合物,并且与索氏提取结果进行了对比,结果表明,ASE完全能取代传统的索氏提取方法。对固相萃取(SPE)柱净化的不同填料进行了实验筛选。比较了浓硫酸磺化法和SPE柱净化法对土壤中有机氯农药及多氯联苯的净化效果。优化了有机氯农药、多氯联苯凝胶渗透色谱(GPC)的净化条件。当样品基质比较复杂时,采用凝胶渗透色谱结合固相萃取柱的前处理方法,能得到很好的净化效果。土壤样品中持久性有机污染物采用加速溶剂提取结合固相萃取前处理过程的回收率为68%~106%,精密度小于7.7%。     

液-液萃取-气相色谱法测定水中9种有机氯农药

采用正己烷液-液萃取法提取,气相色谱法-电子捕获检测器测定水中9种有机氯农药。优化了实验条件:添加两种替代物作为分析过程的质量监控;使用浓硫酸磺化法净化去除杂质;采用Rtx-5MS和Rtx-1701柱双柱定性,保证数据准确可靠。9种有机氯农药的方法检出限为0.0017～0.0079μg/L,回收率为74.7%～105.1%,相对标准偏差(RSD,n=7)为4.2%～9.3%,9种农药在0.5～100μg/L内与峰面积呈良好的线性关系。方法检出限低,准确度和精密度高,简便,适用于批量样品的分析。     

Chemical characteristics and pollution sources of petroleum hydrocarbons and PAHs in sediments from the Beiluohe River,Northern China

To determine the degree of hydrocarbon contamination and the contribution of local petroleum industries to contaminant loadings in sediments from the Beiluohe River, China, 12 surface sediment samples were collected for geochemical analysis in 2005. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and the profiles of n-alkanes, biomarkers and polycyclic aromatic hydrocarbons (PAHs) in sediments were analyzed by gas chromatography with flame ionization detector and gas chromatography/mass spectroscopy. Concentrations of total hydrocarbons in the sediments varied from 12.1 to 3,761.5 μg g⁻¹ dry wt, indicating that most sediments in Beiluohe River was only slightly to moderately contaminated by hydrocarbons. Concentrations of PAHs for six samples (sum of 16 isomers) varied from 17.7 to 407.7 ng g⁻¹ dry wt and at present low levels of PAHs did not cause adverse biological effects in Beiluohe River sedimentary environment. PAH compositions, n-alkanes and biomarker profiles all suggested that there were different sources of contaminations in studied areas. n-Alkanes reflect two distinct sources: a fossil n-alkane series from crude oil at sites S40, S43, S87 and plantwax n-alkanes at sites S39 and S45. Judged by their PAH ratios, the sediments at site S15 were pyrolytic, sediments at S17 and S43 were petrogenic, and sediments at S39, S40 and S64 had a mixture source of pyrolytic and petrogenic.     

Thermal Degradation of PCDD/Fs Promoted by Alcohol Amines in Different Types of Incinerator Ashes

The low-temperature thermal treatment to degrade PCDD/Fs contained in fly ash was promoted by alcohol amines in a closed system. Three types of fly ash collected separately from municipal solid waste incinerator, medical waste incinerator and hazardous waste incinerator, were compared. Experimental design was used to investigate the homologue patterns of PCDD/Fs and distribution of the toxic congeners in fly ash from incinerator after thermal treatment promoted by alcohol amines. The effect of ethanolamine (MEA) on the hydrodechlorination reaction of polychlorinated aromatics pollutants on fly ash from solid waste incinerator was carried out, and the three ashes clearly showed different degradation potentials for PCDD/F during thermal treatment. Results from the present study indicate that (1) the concentration of alkaline species and metals strongly influenced the degradation of PCDD/F; (2) after addition of 8% MEA, the toxicity equivalent (TEQ) values of PCDD/Fs in fly ash were significantly lower than those obtained without MEA. 49%–71% of PCDD/Fs in TEQ was removed from different types of ash at 250℃ with 8% MEA; (3) the destruction and dechlorination are major mechanism for PCDD/Fs degradation.     

土壤中有机氯农药残留的分析技术研究进展

文章总结了近年来土壤中有机氯农药残留分析的样品前处理和测定方法的研究进展,重点阐述微波萃取法、加速溶剂萃取法、固相萃取法、固相微萃取法、基质固相分散萃取法、超临界流体萃取法等前处理技术及气相色谱技术、气相色谱-质谱联用技术等在土壤中有机氯农药残留分析中的应用,指出了未来的发展趋势。     

雅克拉凝析油气田油水界面甲烷天然释放及其源示踪

为评价油气田天然释放CH₄对大气CH₄源与汇的贡献, 采用静态箱法实地监测了新疆塔里木盆地雅克拉凝析油气田油水界面处甲烷的释放通量, 并采用在线大气甲烷碳同位素制样系统与稳定同位素质谱仪联机测试了通量箱甲烷碳同位素组成.结果表明, 由于油水界面边水活跃程度不同, 甲烷通量在空间变化很大, 最高的日释放通量达2.28 mg/m2·d, 最低-1.32 mg/m2·d, 日平均释放通量0.51 mg/m2·d, 标准偏差达1.23 mg/m2·d.油水界面处甲烷通量日变化规律基本相同, 凌晨至清晨时达到相对高点, 随后逐渐降低, 下午至傍晚时段为释放低值甚至负值, 夜晚时分又逐渐增加.通量箱中甲烷δ13C组成白天随甲烷浓度的线性降低而逐渐偏重, 夜晚δ13C随着甲烷浓度的线性增加而逐渐偏重.可见, 油水界面边水活跃, 其上方的土壤形成相对氧化的环境, 油气藏甲烷及烃类在向地表运移的过程中不断被土壤吸收氧化, 仅有少量运移至地表并逸散到大气中, 局部甚至均被吸收氧化, 而成为大气甲烷的汇.      

Characterization of permineralized kerogen from an Eocene fossil fern

The processes of organic maturation that occur during the permineralization of fossils and the detailed chemistry of the resulting products are incompletely understood. Primary among such processes is the geochemical alteration of biological matter to produce kerogen, such as that which comprises the cell walls of the fossils studied here: essentially unmetamorphosed, Eocene plant axes (specimens of the fossil fern Dennstaedtiopsis aerenchymata cellularly permineralized in cherts of the Clarno Formation of Oregon and the Allenby Formation of British Columbia). The composition and molecular structure of the kerogen that comprises the cell walls of such axes were analyzed using ultraviolet Raman spectroscopy (UV–Raman), solid state ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR) and pyrolysis–gas chromatography–mass spectrometry (py–GC–MS).Cellularly well-preserved fern axes from both geologic units exhibit similar overall molecular structure, being composed primarily of networks of aromatic rings and polyene chains that, unlike more mature kerogens, lack large polycyclic aromatic hydrocarbon (PAH) constituents. The cell walls of the Allenby Formation specimens are, however, less altered than those of the Clarno chert, exhibiting more prevalent oxygen-containing and alkyl functional groups and comprising a greater fraction of rock mass.The study represents the first demonstration of the effectiveness (and limitations) of the combined use of UV–Raman, ¹³C NMR and py–GC–MS for the analysis of the kerogenous cell walls of chert-permineralized vascular plants.