Search

Stable carbon isotopes have been used in various applications for approximately 50 years, in many applications including the fields of medicine, criminology, and biology and recently has been used in the remediation field to track the degradation of various organic compounds. It is a commercially available investigation technology that is gaining in popularity and has unique applications related to monitored natural attenuation (MNA). To further discuss this technology and how it is used at MNA sites, we presented the following question to five guest panel members. © 2007 Wiley Periodicals, Inc.

The presence of three families of hopanoic acids, 17,21-secohopanoic acids, 25-norhopanoic acids, and 28-norhopanoic acids, is discussed. Oils from West Siberia and tar balls from the Seychelles Islands were found to contain relatively high proportions of 17,21-secohopanoic acids. These acids have not been previously reported in any oils or source rocks. A heavily biodegraded West Siberian oil, was found to contain an homologous series of 25-norhopanoic acids co-occurring with the 25-norhopanes as previously reported in only a small number of oils from Campos Basin, Brazil. 28-Norhopanoic acids have been reported in various sediments and extracts of the Monterey Shale, but in this study their occurrence has been extended to oils, degraded oils, and tar balls sourced from the Monterey Shale. The primary purpose herein is to report the occurrence of these acids and possible relationships between the acids and corresponding hydrocarbons.

Although tert-butyl alcohol (TBA) has not been used as a fuel oxygenate in Orange County, California, the concentrations of TBA in ground water at gasoline spill sites are high compared those of the conventional fuel oxygenate methyl tert-butyl ether (MTBE). In the year 2002, the geometric mean concentration of TBA was 839 lg/L compared to 627 lg/L for MTBE. There are two plausible sources of TBA, the TBA originally present in the gasoline and biodegradation of MTBE to TBA. Thirteen sites where the concentration of TBAwas >10 mg/L were selected for study. Biodegradation was evaluated by determining the stable carbon isotope ratio (d 13 C) of MTBE in the ground water. If MTBE was biodegraded, the residual MTBE should be enriched in the heavier carbon isotope 13 C. The historical highest concentration of MTBE in each monitoring well and the d 13 C of MTBE in the ground water were used to estimate the concentration of TBA produced from biodegradation of MTBE. Then, the estimated concentration of TBA was compared to the measured concentration. At each site, comparisons were made for the well in the source area, and the well in the plume outside the source area, that had the highest concentration of TBA. In the wells in the source areas, the estimate of TBA production accounted for the majority of TBA at 4 of the 13 sites. In the wells in the plume outside of the source area, the estimate accounted for the majority of TBA at six sites.

Problems related to the crystallization and deposition of heavy organic fractions during production, transportation and storage of crude oils can lead to considerable financial losses for the petroleum industry. The heavy organic fractions may include paraffins or waxes, resins, asphaltenes, and organometallic compounds that exist in crude oils in various quantities, states, and forms. The severity of the deposition problems varies widely and depends on factors such as the crude oil composition, operating conditions in the reservoir and production procedures. Problems associated with the solid deposits may be encountered anywhere in the production process from the reservoir to the refinery. In this paper, it is proposed to focus on production problems associated with certain fields in Tunisia. The problems manifested themselves through the accumulation of solid deposits in the storage tanks at a Tunisian terminal and originated from the mixtures of various crude oils transported to the terminal by pipeline. The principal analytical method for the characterization of the solids was high temperature gas chromatography following concentration of the wax fraction through a modification of the conventional acetone precipitation technique.

Extracts of 18 potential source rocks from the Qaidam, Liaohe, and Tarim Basins, China have been characterized by high temperature gas chromatography (HTGC) and found to contain high molecular weight hydrocarbons (HMWHCs) above C40. These rocks were originally formed in freshwater lacustrine, saline lacustrine, and terrigenous bog environments with mudstone, calcareous mudstone, coaly shale and coal lithologies. Their ages range from Triassic to Miocene and maturities from immature to mature covering a vitrinite reflectance range (Ro) for the Liaohe and Tarim samples of 0.54–0.84%. The combined distributions of the n-alkane and alkylcyclopentane homologues in the extracts can be used to characterize the nature of the original depositional environment. In certain samples the carbon number predominance of the n-alkanes changes from an odd/even predominance to even/odd predominance above C40 possibly suggesting different precursors for the n-alkanes above and below C40. Concentrations of the HMWHCs were also observed to increase with maturity of the source rocks. This is the first comprehensive report on the occurrence of HMWHCs in source rocks and their discovery introduces the possibility of using these compounds for oil/source rock correlation purposes in future studies along with the more conventional biomarkers.

Environmental forensics has emerged as an important area of environmental studies over the past two decades. One of the major areas of interest in environmental forensic investigations is to determine the origin or point of release of a spilled product. A wide variety of analytics are used to fingerprint the contaminant and potential sources in order to determine whether or not there is any relationship between them. If there are multiple possible sources in the area it may be difficult to narrow it down to a specific source. Furthermore, fingerprinting tools that may be useful with complex mixtures may not be directly applicable to single-component mixtures. In situations such as this, utilization of stable isotopes of the individual compounds becomes a particularly powerful tool for undertaking the correlations. The purpose of this chapter will be to provide a review along with some recent examples of the nature of the stable isotope information that is typically obtained in environmental forensic investigations and how this information may be interpreted. Examples will involve hydrocarbons, chlorinated solvents, and MTBE and BTEX compounds. Techniques will include gas chromatography (GC), gas chromatography–mass spectrometry (GCMS), stable isotopes—both bulk and gas—and chromatography–isotope ratio mass spectrometry (GCIRMS).

Currently it is unclear if natural attenuation is an appropriate remedial approach for groundwater impacted by methyl tertiary butyl ether (MTBE). Site-characterization data at most gasoline release sites are adequate to evaluate attenuation in MTBE concentrations over time or distance. But, demonstrating natural biodegradation of MTBE requires laboratory microcosm studies, which could be expensive and time-consuming. Recently, compound-specific carbon isotope ratio analyses (13C/12C expressed in delta13C notation) have been used to demonstrate aerobic biodegradation of MTBE in laboratory incubations. This study explored the potential of this approach to distinguish MTBE biodegradation from other abiotic processes in an anaerobic groundwater plume that showed extensive decrease in MTBE concentrations. To our knowledge, this is the first study to use delta13C of MTBE data in groundwater and laboratory microcosms to demonstrate anaerobic biodegradation of MTBE. The delta13C of MTBE in monitoring wells increased by up to 31 per thousand (-25.5 per thousand to +5.5 per thousand) along with a 40-fold decrease in MTBE concentrations. Anaerobic incubations in laboratory microcosms indicated up to 20-fold reduction in MTBE concentrations with a corresponding increase in delta13C of MTBE of up to 33.4 per thousand (-28.7 per thousand to +4.7 per thousand) in live microcosms. Little enrichment was observed in autoclaved controls. These results demonstrate that anaerobic biodegradation was the dominant natural attenuation mechanism for MTBE at this site. The estimated isotopic enrichment factors (epsilon(field) = -8.10 per thousand and epsilon(lab) = -9.16 per thousand) were considerably larger than the range (-1.4 per thousand to -2.4 per thousand) previously reported for aerobic biodegradation of MTBE in laboratory incubations. These observations strongly suggest that delta13C of MTBE could be potentially useful as an "indicator" of in-situ MTBE biodegradation.

N-alkanes in extracts from possible carbonate source rocks of the Lower Ordovician Majiagou Formation in the central gas field of the Shanganning Basin and the Upper Sinian Dengying Formation in the Weiyuan gas field of the Sichuan Basin, are characterized by bimodal distributions with the dominant carbon numbers in the range C17-C21 and C25-C29. In most samples, the lower carbon number components are present in greater abundance than the higher carbon number ones. Most samples contain significant concentrations of waxy hydrocarbons (C22+) with C21-/C22+ ratios between 0.50 to 3. 16, and an average value of 1. 34. The n-alkanes in extracts of outcrops and shallow core samples of Upper Proterozoic and Lower Palaeozoic carbonate rocks in the western and southern parts of the North China Basin are of unimodal distributions dominated by n-alkanes maximizing in the C25-C29 range. These extracts have very high concentrations of waxy hydrocarbons with C21-/C22+ ratios all < 1. 0, ranging from 0. 14 to 0. 90 and averaging 0. 36. All of the extracts have a marked odd/even predominance in the high molecular weight n-alkane range regardless of whether they are from shallow or deep cores or out-crop samples. Simulation experiments were performed using typical sapropelic-type kerogens from the immature Sinian Lower Xiamalin Formation carbonate-rich shales collected at Jixian, Hebei Province, North China Basin, and the contemporary microplanktonic blue-green algaeSpirulina subsala. Results indicate that the unusual distribution of n-alkanes in the extracts of Upper Proterozoic and Lower Palaeozoic carbonate rocks possibly originated from algae in the source rocks at high levels of maturity and overmaturity.

Petroleum geochemistry is the outgrowth of the application of the principles and methods of organic chemistry to petroleum refining and petroleum geology. This paper reviews 120 years of petroleum geochemistry, from about 1860 to 1980, and includes a discussion of the formal recognition of petroleum geochemistry as an earth-science discipline starting in 1959 when a general petroleum geochemistry symposium was first organized at Fordham University, New York. A chronology of significant events, including concepts, techniques, and textbook publications, is presented. Because petroleum geochemistry has been a tool for petroleum exploration from the beginning, the early developments of surface prospecting, source-rock identification, and oil/oil and oil/source correlation are discussed, along with the application of geochemistry to petroleum migration, accumulation, and alteration. In addition the paper deals with the biomarker revolution, which began in earnest about 1964, and with early models of geothermal history. Concepts in petroleum geochemistry have continually evolved, enhanced by the development of new analytical techniques, leading to new discoveries concerning the origin and occurrence of petroleum.

A large number of underground gasoline storage facilities in the United States continuously leak gasoline into the subsurface, which makes gasoline a major groundwater contaminant. Gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS) are used currently to characterize contaminated groundwater and soils. Correlations of contaminants with suspected source(s) are extremely difficult by these techniques because many gasolines have similar hydrocarbon distributions. The present study applied the technique of isotope ratio monitoring gas chromatography–mass spectrometry (irmGC–MS) to 19 gasoline samples from different areas of the USA. This allows a much better correlation of gasoline contaminants to source. Data obtained indicate a wide range of δ 13 C values for 16 ubiquitous compounds in the gasolines The majority of samples could be distinguished from each other on the basis of δ 13 C hydrocarbon composition. The oxygenated additive methyl tertiary butyl ether (MTBE) was present in ten of the gasolines analyzed, and had a relatively narrow range of δ 13 C values (−30.4 to −28.3‰). Preliminary investigations were also made to determine the extent of carbon isotopic fractionation after simple water washing and evaporation experiments. Results indicate that the majority of compounds did not undergo significant carbon isotopic fractionation as a result of these processes.

Correlation of crude oils, or refined products, in the environment with suspected sources is typically undertaken through the use of GC and GCMS and in certain cases bulk carbon isotope compositions. However, with crude condensates, or refined products in particular, the absence, or low concentration, of biomarkers precludes their successful use for making unique correlations. An alternative and, sometimes, complimentary technique for correlation of such products is evolving through the use of combined gas chromatography-isotope ratio mass spectrometry (GCIRMS). This approach permits determination of the carbon and hydrogen isotopic composition of individual compounds in the crude oil or refined product to produce isotopic fingerprints for use in correlation studies. In this paper, it is proposed to review applications of GCIRMS to the correlation of various spilled products with their suspected sources in different environments. Whilst not proposing that this technique will replace GC or GCMS; it is prop...

The natural attenuation of polyaromatic hydrocarbons (PAHs) in the vadose zone of a naturally revegetated former industrial sludge basin (0.45 ha) was examined. This was accomplished by comparing the concentration of 16 PAH contaminants present in sludge collected below the root zone of plants with contaminants present at 3 shallower depths within the root zone. Chemical analysis of 240 samples from 60 cores showed the average concentration of total and individual PAHs in the 0-30 cm, 30-60 cm, and bottom of the root zone strata were approximately 10, 20, and 50%, respectively, of the 16, 800 ppm average total PAH concentration in deep non-rooted sludge. Statistically significant differences in average PAH concentrations were observed between each strata studied and the non-rooted sludge except for the concentrations of acenaphthene and chrysene present at the bottom of the root zone in comparison to sludge values. The rooting depth of the vegetation growing in the basin was dependent on both vegetation type and plant age. Average rooting depths for trees, forbs (herbaceous non-grasses), and grasses were 90, 60, and 50 cm, respectively. The deepest root systems observed (100-120 cm) were associated with the oldest (12-14 year-old) mulberry trees. Examination of root systems and PAH concentrations at numerous locations and depths within the basin indicated that plant roots and their microbially active rhizospheres fostered PAH disappearance; including water insoluble, low volatility compounds, i.e. benzo(a)pyrene and benzo(ghi)perylene. The reduced concentration of PAHs in the upper strata of this revegetated former sludge basin indicated that natural attenuation had occurred. This observation supports the concept that through appropriate planting and management practices (phytoremediation) it will be possible to accelerate, maximize, and sustain natural processes, whereby even the most recalcitrant PAH contaminants (i.e. benzo(a)pyrene) can be remediated over time.

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the δ 13 C values were observed although the samples had isotopically distinct δ-D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.

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.

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C120 in crude oils. As a result, hydrocarbons in waxes (> C20) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C40 were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C40) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes. # 2000 Elsevier Science Ltd. All rights reserved.

Diamantanes were identified in extracts from the Lower Ordovician Majiagou Formations (O1m5) of the central gas field, Shanganning Basin, China. At 3100‐3800 m, corresponding to Ro 1.9‐3.9%, the MDI [methyl diamantane index=4-MD/(1-MD+3-MD+4-MD)] ranges from 40 to 65% for the source rock extracts. Changes in the MDI index in the very mature sections (Ro>2.0%) are relatively small and no linear correlation between MDI and Ro ,o r MDI and depth, is noted, as previously reported, suggesting the possibility that the MDI may have limited applicability in maturity determinations. # 2000 Elsevier Science Ltd. All rights reserved.

The occurrence of high molecular weight hydrocarbons in a selected solid bitumen (ozocerite) and a waxy yellow crude oil from the Uinta Basin (Utah) have been studied by field ionization-mass spectrometry (FIMS). The FIMS spectra consisted predominantly of molecular ions ranging up to near mass 2000, and correspond to several series of hydrocarbons ranging up to C110. The use of FIMS permits the range of hydrocarbons identified in geological materials to be extended far beyond that identified by the usual chromatographic techniques. Moreover, from the FIMS spectra it was possible to extract the molecular ions corresponding to series of hydrocarbons with different degree of unsaturation or ring closures (different Z-numbers). The ozocerite solid bitumen consisted mainly of series of branched alkanes (CnH2n+2) and cyclic alkanes (CnH2n and CnH2n−2) up to C110 with a predominance of monocyclic alkanes in the high molecular weight region (above C40). The waxy yellow crude oil, on the other hand, contained only acyclic compounds, mainly n-alkanes, ranging up to C100.

Results of extraction experiments performed on immature Green River Formation source rock samples from the Black Shale Facies (Uinta Basin, Utah) demonstrate the potential of extracting high molecular weight hydrocarbons (HMWHC) with sequential dichloromethane:methanol/soxhlet and p -xylene/sonication techniques. The first soxhlet extraction step with DCM:MeOH removes lower molecular weight alkanes from the source rock while the HMWHC remain in the rock residue. Sonication of the rock residue with p -xylene recovers these HMWHC, showing distinct hydrocarbon distributions and preferences in high temperature gas chromatograms. Extracts obtained by using p -xylene/soxhlet with original source rocks and sequential soxhlet extraction instead of sonication have relatively lower concentrations of HMWHC. Sequential extraction of two other source rock types (Mahogany Shale and Black Shale Facies coal) did not result in detection of similar HMWHC in the extract. This indicates that the presence of these compounds in the Black Shale Facies of the Green River Formation is a primary source signal and a specific characteristic of this source rock.

Results are presented on changes in the content and composition of waxes and asphaltenes of oil produced during the transition from primary to secondary recovery following water flooding. Oil samples have been collected for a period of about three years from one well in Prairie Gem field in central Oklahoma. Wax and asphaltene fractions have been isolated from the produced oils and analyzed, qualitatively and quantitatively, by high temperature gas chromatography. The results demonstrate significant variations in the asphaltene and wax content of the oil produced during the transition period from primary to secondary water flood recovery, ranging from 0.7 to 5 wt%, and 11 to 33 wt%, respectively. Moreover, these variations are found to be accompanied by changes in wax composition and to precede specific production events. The oil produced a month before the response of the well to water flooding indicated an enhanced concentration of nC 22 –C 35 alkanes in the wax. The following episode of wax plugging in well equipment was preceded by increased amounts of asphaltenes and high molecular weight (nC 35 –C 50 ) alkanes in the wax of produced oils. Changes in the asphaltene and wax compositions are discussed in terms of processes displacing weakly adsorbed organic material from the pore spaces of the reservoir under increased reservoir pressure and flowing fluid volumes related to water flooding.

Cyclical sedimentation patterns are common in unconventional resources shales, whether they be carbonate- or siliciclastic-dominated. In many resource shales the cyclical patterns have been related to eustatic sea level fluctuations, even though these fluctuations may sometimes be obscured by tectonic overprint. The cyclicity is reflected in repetitive sedimentation patterns which represent alternating relatively shallow/oxic- and deeper/anoxicwater deposition. Typical cyclicity might occur in the form of alternating clay/organic-rich and quartz/calcite-rich strata. In more carbonate-rich sequences, organic-rich marls might alternate with organic-poor limestones. This cyclicity can occur at a variety of stratigraphic scales and provides a sequence stratigraphic framework for mapping, correlation, and interpretations. Incised valley fill may provide a localized, thicker, more organic-rich stratigraphic section (‘sweet spot’), than adjacent areas. Within the context of geomechanics, these cyclical strata are termed ‘brittle-ductile couplets’. Using the Barnett and Woodford shales as examples, clay/organic-rich intervals tend to be relatively ductile (relatively low Young’s Modulus and high Poisson’s ratio) and cleaner quartz/calcite-rich intervals tend to be relatively brittle (relatively high Young’s Modulus and low Poisson’s ratio. In carbonate-rich deposits such as the Eagle Ford Formation, recrystallized, TOC-poor limestones tend to be stronger and more brittle than TOC-rich marls. Within the context of microseismic, microseisms may be vertically stratified or layered, with some horizons containing more events than other horizons. This stratification has been related to brittle-ductile couplets in at least one area, and placed within a sequence stratigraphic framework. Within the context of geochemistry, ductile strata tend to contain more TOC, and are thus better potential HC source rocks, than brittle strata, which contain less TOC. Biomarkers (geochemical fingerprints) are useful for interpreting sources and environments of deposition of organic matter, and ultimately used for environmental zonation of shales. Using these principles and observations, it is possible to build a sequence stratigraphic framework from multiple data sets to map and correlate brittle and ductile strata, organic-/hydrocarbon-rich zones, and more fracturable stratigraphic intervals. A suggested horizontal landing zone is the brittle strata within a brittle-ductile couplet. It is hypothesized that when hydraulically fractured, both brittle and ductile strata become fractured, and hydrocarbons move from the ductile to the brittle zone, whose fractures remain open after proppant emplacement. With time, ductile strata may close around the proppant and become sealed. Sequence stratigraphy Sequence stratigraphy provides a basis for subdivision of stratigraphic intervals into geologically realistic and cyclical patterns. These cyclical patterns are common in unconventional resource ‘shales’, whether they be carbonate- or siliciclastic-dominated. Shales with these patterns include Barnett Shale (Slatt et al, 2012), Woodford

Although polycyclic aromatic hydrocarbons (PAHs) have usually been found to persist under strict anaerobic conditions, in a previous study an unusual site was found in San Diego Bay in which two PAHs, naphthalene and phenanthrene, were oxidized to carbon dioxide under sulfate-reducing conditions. Further investigations with these sediments revealed that methylnaphthalene, fluorene, and fluoranthene were also anaerobically oxidized to carbon dioxide in these sediments, while pyrene and benzo[a]pyrene were not. Studies with naphthalene indicated that PAH oxidation was sulfate dependent. Incubating the sediments with additional naphthalene for 1 month resulted in a significant increase in the oxidation of [14C]naphthalene. In sediments from a less heavily contaminated site in San diego Bay where PAHs were not readily degraded, naphthalene degradation could be stimulated through inoculation with active PAH-degrading sediments from the most heavily contaminated site. Sediments from the less heavily contaminated site that had been adapted for rapid anaerobic degradation of high concentrations of benzene did not oxidize naphthalene, suggesting that the benzene- and naphthalene-degrading populations were different. When fuels containing complex mixtures of alkanes were added to sediments from the two sites, there was significant degradation in the alkanes. [14C]hexadecane was also anaerobically oxidized to 14CO2 in these sediments. Molybdate, a specific inhibitor of sulfate reduction, inhibited hexadecane oxidation. These results demonstrate that a wide variety of hydrocarbon contaminants can be degraded under sulfate-reducing conditions in hydrocarbon-contaminated sediments, and they suggest that it may be possible to use sulfate reduction rather than aerobic respiration as a treatment strategy for hydrocarbon-contaminated dredged sediments.

Summary Pores, spores, pollen and pellets are all important constituents of resource shales. Pores provide the storage place and, when connected, the transport route for hydrocarbon molecules. Conventional Scanning Electron Microscopy (SEM and FESEM) of pores from untreated surfaces from several resource shales reveal a common variety of pore types. An inexpensive method of analysis has been developed to measure porosity, and dimensions of pores. The shales exhibit a variety of porosities, but usually 1 µm in length) and nanopores (defined here as

the macromolecular structure of the pyrobitumen wurtzilite has been examined by a variety of chemical and analytical techniques, including desulfurization with lithium in ethylamine. The results of these analyses provide strong evidence for the presence of intermolecular sulfur linkages in the wurtzilite geopolymer matrix, which are thought to have formed via a process of low temperature “natural vulcanization”. The polymerized hydrocarbon components appear to be a complex mixture of n -alkanes, isoprenoids, and heterocompounds, offering further insight toward a bulk structural model for wurtzilite.

In order to investigate the formation of organosulphur compounds during the very early stage of diagenesis, experiments were designed to simulate sulphur incorporation from H2S, or elemental sulphur, into recently deposited natural sedimentary organic matter (cyanobacterial mats from salt ponds in Baja California) and performed under relatively mild reaction conditions (40°C, 2 to 30 days, hydrous and anhydrous). The sulphur-containing moieties in the reaction products were examined by pyrolysis-gas chromatography (GC) using a GC equipped with a flame photometric detector (FPD) and a flame ionization detector (FID), and pyrolysis-gas chromatography/mass spectrometry (GC/MS). Sulphur incorporation from H2S into recently deposited cyanobacterial mats occurred fairly readily, but elemental sulphur does not react as readily with the cyanobacterial mats. Sulphur incorporation into humic acids occurred more rapidly than into proto-kerogens. Sulphur incorporation into lipid fractions was not observed. Two major sulphur incorporation stages are proposed, with the formation of thiols by reaction between H2S and active carbonyl groups considered to be the most likely mechanism of sulphur incorporation in the first stage. The second stage of sulphur incorporation is proposed to be related to the reaction between H2S and proteinaceous organic matter.

Isotope ratios of volatile organic compounds (VOCs) in the environment are often of interest in contaminant fate studies. Adsorbent preconcentration-thermal desorption of VOCs can be used to collect environmental vapor samples for compound-specific isotope analysis (CSIA). While active adsorbent samplers offer logistic benefits in handling large volumes of air, their performance in preserving VOCs isotope ratios was not previously tested under sampling conditions corresponding to typical indoor air sampling conditions. In this study, the performance of selected adsorbents was tested for preconcentration of TCE (for determination of C and Cl isotope ratios), PCE (C and Cl) and benzene (C and H). The key objective of the study was to identify the adsorbent(s) permitting preconcentration of the target VOCs present in air at low μg/m3 concentrations, without significant alteration of their isotope ratios. Carboxen 1016 was found to perform well for the full range of tested parameters. Carboxen 1016 can be recommended for sampling of TCE, PCE and benzene, for CSIA, from air volumes up to 100 L. Variable extent of isotope ratio alteration was observed in the preconcentration of the target VOCs on Carbopack B and Carbopack X, resulting from partial analyte loss via adsorbent bed breakthrough and (possibly) via incomplete desorption. The results from testing the Carbopack B and Carbopack X highlight the need of adsorbent performance validation at conditions fully representative of actual sample collection conditions, and caution against extrapolation of performance data toward more challenging sampling conditions.

Based on recent studies of Barnett and Woodford gas shales in Texas and Oklahoma, a systematic characterization workflow has been developed that incorporates lithostratigraphy and sequence stratigraphy, geochemistry, petrophysics, geomechanics, well log, and three-dimensional (3-D) seismic analysis. The workflow encompasses a variety of analytical techniques at a variety of geologic scales. It is designed as an aid in identifying the potentially best reservoir, source, and seal facies for targeted horizontal drilling. Not all of the techniques discussed in this chapter have yet been perfected, and cautionary notes are provided where appropriate. Rock characterization includes (1) lithofacies identification from core based on fabric and mineralogic analyses (and chemical if possible); (2) scanning electron microscopy to identify nanofabric and microfabric, potential gas migration pathways, and porosity types/distribution; (3) determination of lithofacies stacking patterns; (4) geochemical analysis for source rock potential and for paleoenvironmental indicators; and (5) geomechanical properties for determining the fracture potential of lithofacies. Well-log characterization includes (1) core-to-log calibration that is particularly critical with these finely laminated rocks; (2) calibration of lithofacies and lithofacies stacking patterns to well-log motifs (referred to as gamma-ray patterns or GRPs in this chapter); (3) identification and regional to local mapping of lithofacies and GRPs from uncored vertical wells; (4) relating lithofacies to petrophysical, geochemical, and geomechanical properties and mapping these properties. Three-dimensional seismic characterization includes (1) structural and stratigraphic mapping using seismic attributes, (2) calibrating seismic characteristics to lithofacies and GRPs for seismic mapping purposes, and (3) determining and mapping petrophysical properties using seismic inversion modeling. Integrating these techniques into a 3-D geocellular model allows for documenting and understanding the fine-scale stratigraphy of shales and provides an aid to improved horizontal well placement. Although the workflow presented in this chapter was developed using only two productive gas shales, we consider it to be more generically applicable.

An outcrop-behind outcrop study was conducted in and adjacent to a 300 100 16 m (980 330 50 ft) quarry of the gas-producing Woodford Shale to structurally/stratigraphically characterize it from the pore to subregional scales using a variety of techniques. Strata around quarry walls were described and correlated to a 64 m (210 ft) long continuous core drilled 150 m (500 ft) back from the quarry wall and almost to the Woodford-Hunton unconformity. Borehole logs obtained include neutron and density porosity (NPHI and DPHI) logs, and logs from Elemental Capture Spectroscopy (ECS™), Combinable Magnetic Resonance (CMR-Plus™), Fullbore Formation MicroImager (FMI™), and sonic scanner (Modular Sonic Imaging Platform, or MSIP™)—all manufactured by Schlumberger. The strata around the quarry are horizontally bedded. Borehole logs were used to identify a basic threefold subdivision into an upper relatively porous quartzose interval; a middle, more clay-rich, and less porous interval; and a lower interval of intermediate quartz-clay content. These intervals correspond to the informally named upper, middle, and lower Woodford. Detailed core and quarry wall description revealed several types of finely laminated lithofacies, with varying amounts of total organic carbon (TOC). The FMI log revealed a much greater degree of variability in laminations than can be readily seen with the naked eye. Organic geochemistry and biomarkers are closely tied to these lithofacies and record cyclic variations in oxic-anoxic depositional environments, which correspond to relative sea level fall-rise cycles. At the scanning electron microscopy scale, microfractures and microchannels are common and provide tortuous pathways for gas (and oil) migration through the shales. Based on FMI and core analysis, fracture density is much greater in the upper quartzose lithofacies than in the lower, more clay-rich lithofacies. A laser imaging detection and ranging (LIDAR) survey around the quarry walls documented two near-vertical fracture trends in the quartzose lithofacies: one striking N85E with spacings of 1.2 m (4 ft) and the other striking N45E related to the present stress field. The FMI analysis only imaged the latter fracture set. Both log-derived and laboratory-tested geomechanical property measurements documented a significant relationship between shale fabric (laminations and preferred clay-particle orientation) and rock strength, and a secondary relationship to mineral composition. Porosity and microfractures or microchannels also appear to influence rock strength. This integrated study has provided insight into the causal relations among Woodford properties at a variety of scales. In particular, a stratigraphic (vertical) segregation of lithofacies can be related to cyclic variations in depositional environments. The resulting stratified zones exhibit variations in their hydrocarbon source and reservoir (fracturable) potential. Such information and predictive capability can be valuable for improved targeted horizontal drilling into enriched source rock and/or readily fracturable reservoir rock in the Woodford and perhaps other gas shales.

For the past two or three decades geochemists have been concerned with the analyses and characterization of compounds, generally hydrocarbons, ranging from C1C40. Significant amounts of information have resulted from these studies which have been extremely useful in many geochemical and environmental studies. However, in the past two or three years the commercial development and availability of high temperature gas chromatography columns has lead to the investigation of the occurrence and distribution of high molecular weight hydrocarbons (HMWHC), and other compounds, in the carbon number range C40C100, present in oils, waxes, bitumens and rock extracts. The ability to study these compounds represents a major advance in organic geochemistry. In some samples these compounds may represent the bulk of the organic components but prior to development of the high temperature columns it was impossible to study their distributions. This paper will review advances that have occurred in terms of the application of high temperature gas chromatography (HTGC) to the analyses of fossil fuel samples and discuss the possible origin and significance of these compounds that have been identified. In addition, some of the potential problems involved in the analyses of these compounds will also be discussed.

We have analyzed the solvent extracts from three different types of native bitumens from the Uinta Basin in northeastern Utah by a variety of analytical techniques, including GC-IRMS, to evaluate variations in the paleodepositional environment during two periods of Lake Uinta deposition. The gilsonite and tabbyite bitumens are associated with Parachute Creek Member sediments deposited during a major expansion of ancient Lake Uinta. Compound specific isotopic analyses of s-carotane and phytane ( δ 13 C = −32.6 to −32.1% 0 ) from these bitumens reflect input from primary photosynthetic producers such as cyanobacteria. Sterane δ 13C values (−34.5 to −29.2%0) refflect contributions from lacustrine algae, while extremely depleted δ 13C values for methylhopanes (−58.1 to −61.5%0) suggest input from methanotrophic bacteria. Variations in the δ 13C values of the αβ-hopanes (−51.4 to 37.7%0) imply additional input from other bacterial sources. The wurtzilite bitumen was generated from the Saline Facies of the Green River Formation deposited during a later regression of Lake Uinta. Compound specific isotopic analyses of phytane ( δ 13 C = −30.1% 0 ) and steranes δ 13 C = −29.6 to −26.7% 0 ) from this bitumen indicate continued input from primary producers and eukaryotes. The higher relative concentrations of gammacerane ( δ 13 C = −26.9% 0 ) indicate increasing input from aerobic protozoa. We observed a slight enrichment in δ 13C in the wurtzilite extract (and several biomarkers) and suggest that this is a result of sulfate-reducing bacteria outcompeting methanogens, thereby, eliminating the influence of methanotrophs in this later saline stage of deposition.

Hydrocarbon exploration and environmental forensics may appear to be two unrelated topics but in many ways are closely related. Techniques that have been developed and utilized in the hydrocarbon exploration and exploitation industry for many decades have found their way to the forefront of environmental forensics area over the past decade. Whereas hydrocarbon exploration is geared towards finding new resources, environmental forensics is directed to looking at what happens to those resources as they, or products derived from them, are spilled into the environment. In the former one uses sophisticated techniques to correlate oils, or gases, with their suspected sources and in the later, one is trying to correlate the spilled product with its suspected source. The source may be a tanker, pipeline, underground storage tank or something similar. The most widely used techniques in both of these areas for many years have been gas chromatography (GC) and gas chromatography mass spectrometry (GCMS) but recent years have seen an exponential increase in the utilization of stable isotopes. There is nothing new about applying stable isotopes to exploration problems but the majority of the older applications utilized bulk isotope numbers for crude oil correlation studies. The availability of the combined gas chromatography-isotope ratio mass spectrometer systems (GCIRMS) over the past 10–20 years, has played an important role in the increased number of applications where stable isotopes have to be used to investigate problems in both of these areas.

At buildings with potential for vapor intrusion of volatile organic chemicals (VOCs) from the subsurface, the ability to accurately distinguish between vapor intrusion and indoor sources of VOCs is needed to support accurate and efficient vapor intrusion investigations. We have developed a method for application of compound-specific stable isotope analysis (CSIA) for this purpose that uses an adsorbent sampler to obtain sufficient sample mass from the air for analysis. Application of this method to five residences near Hill Air Force Base in Utah indicates that subsurface and indoor sources of tricholorethene and tetrachloroethene often exhibit distinct carbon and chlorine isotope ratios. The differences in isotope ratios between indoor and subsurface sources can be used to identify the source of these chemicals when they are present in indoor air.

Bitumens collected in the east zone of the Cigar Lake deposit have been analyzed by 13C nuclear magnetic resonance, pyrolysis – gas chromatography, Rock-Eval, and C. H, and O methods. Carbon and hydrogen isotopic compositions and uranium contents have been determined. Results indicate that the bitumens consist mainly of aromatic structures (Fa ≈ 60%) and have undergone a late oxidation process. Similarities in carbon isotopic composition (−27.5‰ > δ13C > −28.2‰) between barren bitumens (U 13C-enriched bitumens could have formed directly by hydrogenation of amorphous carbon, whereas mineralized, isotopically light bitumens from Cluff Lake (δ13C ≈ 48‰) may result from the polymerization of light hydrocarbons around uraninite grains.

We evaluated the ability of the native microbiota in a low-temperature, sulfidic natural hydrocarbon seep (Zodletone) to metabolize short-chain hydrocarbons. n-Propane and n-pentane were metabolized under sulfate-reducing conditions in initial enrichments and in sediment-free subcultures. Carbon isotope analysis of residual propane in active enrichments showed that propane became enriched in (13)C by 6.7 (+/-2.0) per thousand, indicating a biological mechanism for propane loss. The detection of n-propylsuccinic and isopropylsuccinic acids in active propane-degrading enrichments provided evidence for anaerobic biodegradation via a fumarate addition pathway. A eubacterial 16S rRNA gene survey of sediment-free enrichments showed that the majority of the sequenced clones were phylogenetically affiliated within the Deltaproteobacteria. Such sequences were most closely affiliated with clones retrieved from hydrocarbon-impacted marine ecosystems, volatile fatty acid metabolizers, hydrogen users, and with a novel Deltaproteobacterial lineage. Other cloned sequences were affiliated with the Firmicutes and Chloroflexi phyla. The sequenced clones were only distantly (95%) related to other reported low-molecular-weight alkane-degrading sulfate-reducing populations. This work documents the potential for anaerobic short-chain n-alkane metabolism for the first time in a terrestrial environment, provides evidence for a fumarate addition mechanism for n-propane activation under these conditions, and reveals microbial community members present in such enrichments.

Isotope fractionation has been used with increasing frequency as a tool to quantify degradation of chlorinated aliphatic pollutants in the environment. The objective of this research was to determine if the electron donor present in enrichment cultures prepared from uncontaminated sediments influenced the extent of isotope fractionation of tetrachloroethylene (PCE), either directly, or through its influence on microbial community composition. Two PCE-degrading enrichment cultures were prepared from Duck Pond (DP) sediment and were incubated with formate (DPF) or H(2) (DPH) as electron donor. DPF and DPH were significantly different in both product distribution and extent of isotope fractionation. Chemical and isotope analyses indicated that electron donors did not directly affect the product distribution or the extent of isotope fractionation for PCE reductive dechlorination. Instead, restriction fragment length polymorphism (RFLP) and sequence analysis of the 16S rRNA clone libraries of DPF and DPH identified distinct microbial communities in each enrichment culture, suggesting that differences in microbial communities were responsible for distinct product distributions and isotope fractionation between the two cultures. A dominant species identified only in DPH was closely related to known dehalogenating species (Sulfurospirillum multivorans and Sulfurospirillum halorespirans) and may be responsible for PCE degradation in DPH. Our study suggests that different dechlorinators exist at the same site and can be preferentially stimulated by different electron donors, especially over the long-term (i.e., years), typical of in-situ ground water remediation.

The development of tandem mass spectrometry (MS-MS) and its combination with gas chromatography (GC-MS-MS) has greatly enhanced our ability to analyze exceedingly complex mixtures from a wide variety of sources, including fossil fuels. This paper describes a comparison of the conventional electron impact (El) mass spectral fragmentation patterns, obtained in the MS-MS precursor – product mode, of three oleanane isomers and one ursene, all of which are used as indicators of higher plant input to the sedimentary environment Results show that El and collision-activated dissociation (CAD) spectra are most similar at collision energies between −15 and −20 eV.The presence of methyl substituents in these pentacyclic terpenes plays an important role in the process of ring fragmentation: the daughter spectra of the M – 15 fragments can be used to obtain structural information, such as the positions of the double bonds.

Reductive dechlorination of tetrachloroethylene (PCE) and trichloroethylene (TCE) was studied in well-defined microcosms prepared with aquifer materials from three locations. Electron donors and terminal electron acceptors were added to both stimulate microbial activity and generate reactive minerals via microbial iron and sulfate reduction. The relative importance of abiotic and microbial PCE and TCE reductive dechlorination was then assessed by analysis of reaction products and kinetics and, in some cases, by stable carbon isotope fractionation. The predominant PCE and TCE transformation pathway in most microcosms was microbial reductive dechlorination. Rates of abiotic transformation were similar in magnitude to those for microbial reductive dechlorination in only a few cases where the activity of dechlorinating bacteria was low. Comparison of geochemical conditions with abiotic product recoveries showed thatthe greatest extent of abiotic reductive dechlorination occurred under iron- and sulfate-reducing conditions. Under these two geochemical conditions, high concentrations of Fe(II) and S(-II) solid species were present, suggesting the involvement of Fe(II) and S(-II) minerals in abiotic reductive dechlorination. Both abiotic and microbial dechlorination of PCE and TCE took place under almost all microcosm conditions; the relative rates of the two processes under field conditions will depend on factors such as the abundance of dechlorinating bacteria, soil properties, and the mass loading of reactive minerals.

Twelve oils from the Sirikit field of the Phisanulok Basin, Thailand, have been examined to determine the nature of their source materials, depositional environment, relative maturity and extent of biodegradation. The geochemical analyses performed in this study suggested that all of the oils were derived from similar types of organic source matter consisting of a mixture of bacterial, algal and higher plant material. The sterane contents of the oils were relatively low and conventional maturity parameters based on sterane ratios suggested the oils were relatively immature. Extensive strike/slip faults in the Phisanulok Basin may have led to rapid burial of the sediments during deposition preventing these ratios from having attained their equilibrium ratios.

Thirty oils from the Pauls Valley area of the Anadarko Basin, Oklahoma, have been analyzed for n-alkane, terpane and sterane distributions in an effort to classify genetically related oils. Ten rock samples from the area were also analyzed in an attempt to relate oil types to their possible source rocks. The Pauls Valley area, located near the southeast corner of the Anadarko Basin, has producing formations ranging in age from Middle Ordovician to Late Pennsylvanian. Trapping mechanisms responsible for the accumulation of hydrocarbons vary from purely structural traps, to fractured reservoirs, to up-dip truncations of reservoirs and up-dip pinchouts of sandstones. Results show that 85% of oils in the area probably have a common source, the Woodford Shale. A group of oils reservoired in the Viola Group exhibit distinct geochemical characteristics and are thought to have a different source. The differences between the oils from these two sources include: enhanced C24 tetracyclic terpane concentrations relative to C26 tricyclic terpanes; diminished C28–30 tricyclic terpanes relative to Ts and Tm; diminished C30-steranes relative to their C29 counterparts; predominance of C35 over C34 extended hopanes and an even/odd predominance of the normal alkane distribution. Extracts from the Viola Group generally exhibit the same qualities as the associated oils and the limestone is proposed as their probable source rock. The predominance of C29-steranes for oil samples which appear to have a marine source (inferred by their n-alkane distribution, the presence of C30-steranes and high levels of tricyclic terpanes) suggests that caution be used in the interpretation of terrigenous sources based on the high abundance of C29-steranes. The Deese Group, the Springer Formation, the Sylvan Shale, and the Arbuckle Group are not likely sources for the oils analyzed from the Pauls Valley area. Differences in API gravity and color, previously used to classify oils in this region, are not source-related but are related to maturation and migration effects.

The formation of melanoidins from d -lysine in the presence of H 2 S and N 2 was examined to clarify the effect of H 2 S on the condensation of sugars and amino acids. Significant amounts of dark brown-colored precipitates formed in a mixture of glucose and lysine heated at 80°C for 20 days under N 2 . However, the same solution heated at 80°C for 30 days under H 2 S showed no major change apart from a slight change in color to light brown. This observation indicates that the condensation of glucose and lysine proceeds very slowly in the presence of H 2 S compared to their condensation in the presence of N 2 . Instead, significant amounts of organosulphur compounds formed from the glucose-lysine solution and H 2 S as confirmed by py-GC (pyrolysis gas chromatography) using both FID (flame ionization detector) and FPD (flame photometric detector). The rapid reaction of H 2 S with reactive carbonyl groups of reducing sugars is proposed to hinder the progess of the condensation between reducing sugars and amino acids. The incorporation of sulphur from H 2 S into sedimentary organic matter in the very early stage of diagenesis could be one of important controlling factors governing the formation of melanoidin-like geopolymers in Recent sediments. The organic geochemical characteristics of kerogens in carbonate rocks (relatively low abundance and high organic sulphur contents) could be interpreted by the rapid reaction between H 2 S and reducing sugars in the very early stage of diagenesis.

Organonitrogen compounds are present in varying concentrations in aromatic fractions of various organic-rich geologic samples. Quinolines, benzoquinolines and carbazoles are the most important families of organonitrogen compounds in the aromatic fractions of crude oils and Phosphoria Formation pyrolysates. Aromatic fractions of oils generated from phosphatic shales contain higher concentrations of organonitrogen compounds than those from carbonate source rocks. Artificial maturation experiments on Phosphoria rocks at about 300°C yield high concentrations of quinolines relative to benzoquinolines and carbazoles, while higher temperature experiments yield high concentrations of benzoquinolines and carbazoles relative to quinolines. Organonitrogen compounds are potentially useful as indicators of the depositional environment of source rocks and maturity of crude oils.

The conventional approach to evaluate biodegradation of organic contaminants in groundwater is to demonstrate an increase in the concentration of transformation products. This approach is problematic for MTBE from gasoline spills because the primary transformation product (TBA) can also be a component of gasoline. Compound-specific stable isotope analysis may provide a useful alternative to conventional practice. Changes in the delta13C and deltaD of MTBE during biodegradation of MTBE in an anaerobic enrichment culture were compared to the delta13C and deltaD of MTBE in groundwater at nine gasoline spill-sites. The stable isotopes of hydrogen and carbon were extensively fractionated during anaerobic biodegradation of MTBE. The stable isotope enrichment factor for carbon (epsilonC) in the enrichment cultures was -13 (-14.1 to -11.9 at 95% confidence level), and the hydrogen enrichment factor (epsilonH) was -16 (-21 to -11 at 95% confidence level). The isotope enrichment factors for carbon and hydrogen during anaerobic biodegradation indicate that the first reaction is enzymatic hydrolysis of the O-Cmethyl bond. The ratio of epsilonH to epsilonC was consistent between the enrichment culture and the field site that provided the inoculum, and with the other eight sites, suggesting a common degradation pathway. Compound-specific isotope evidence is discussed in terms of its utility for monitoring in situ biodegradation, in particular, for measuring how much MTBE was degraded. For the studied field sites, significant biodegradation of the original mass of MTBE is suggested, in some cases exceeding 90%.

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW-SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH 4, thermogenic C2+ gases, and associated condensates were evaluated separately. Methane appears to have 3 origins: Group-1 CH4 is bacteriogenic (Calculated ?13CC1-C = -61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH4. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (?13CC1-C = -35.80‰; Hamitabat Field) and Group-3 (?13C 1-C = -49.10‰; Degirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C 2+ gases. The Group-2 C2+ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (?13C = -21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C2+ gases, produced from one field, were generated from isotopically light marine kerogen (?13C = -29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases. The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C2+ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases. Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (?13C = -21‰; -29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (Req = 0.55-0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin. © 2005 Elsevier Ltd. All rights reserved.