Methyl ketones in high altitude Ecuadorian Andosols confirm excellent conservation of plant-specific n-alkane patterns

To reconstruct past shifts in the upper forest line (UFL) in the Northern Ecuadorian Andes we are studying the applicability of plant-specific patterns of lipids preserved in soils as proxies for past vegetation along an altitudinal transect. Longer chain length n-alkanes, (C₁₉–C₃₅) were previously found to occur in plant-specific patterns in the dominant vegetation in the area as well as in preliminary soil samples, and may serve as such a proxy. In the present study, we assessed the preservation of n-alkane patterns with depth in soils from five excavations along an altitudinal transect 3500–3860 m above sea level (m.a.s.l) in the area. We used the carbon preference index (CPI) as well as chain length distributions of n-alkanes and their most likely degradation products, n-methyl (Me) ketones, n-alcohols and n-fatty acids. Clear n-alkane patterns were found in all the soils and at all depths, while a clear relationship with the observed patterns of n-Me ketones identified them as the primary degradation product of the former. Very low average n-Me ketone/n-alkane ratio values were found, ranging from 0.03 to 0.15 at the top of the mineral soil, to 0.05–0.20 at the interface with an underlying palaeosol several thousand years old. The concurrent high CPI values indicate very limited degradation of n-alkanes with depth. Except for C₃₃, the shifts in n-Me ketone/n-alkane values were similar for all chain lengths investigated, signifying an absence of preferential degradation of individual n-alkanes. With one exception, all the soils showed a similar increase in n-Me ketone/n-alkane values with depth, indicating that the degradation rates were not influenced by altitude. This means that, even if the total concentration of n-alkanes decreases over time, the characteristic pattern remains intact, conserving their potential as a biomarker for past vegetation reconstruction in the area, as well as for investigation of degradation processes of soil organic carbon.     

Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbon and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin,Pakistan

The stable hydrogen isotopic compositions (δD) of selected aliphatic hydrocarbons (n-alkanes and isoprenoids) in eight crude oils of similar source and thermal maturity from the Upper Indus Basin (Pakistan) were measured. The oils are derived from a source rock deposited in a shallow marine environment. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker and aromatic hydrocarbon distributions. A plot of pristane/n-C₁₇ alkane (Pr/n-C₁₇) and/or phytane/n-C₁₈ alkane (Ph/n-C₁₈) ratios against American Petroleum Institute (API) gravity shows an inverse correlation. High Pr/n-C₁₇ and Ph/n-C₁₈ values and low API gravity values in some of the oils are consistent with relatively low levels of biodegradation. For the same oils, δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). The data are consistent with the removal of D-depleted low molecular weight (LMW) n-alkanes (C₁₄–C₂₂) from the oils. The δD values of isoprenoids do not change with progressive biodegradation and are similar for all the samples. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. For example, the moderately biodegraded oils show an unresolved complex mixture (UCM), loss of LMW n-alkanes (<C₁₅) and moderate changes in the alkyl naphthalene distributions. The relative susceptibility of alkyl naphthalenes at low levels of biodegradation is discussed. The alkyl naphthalene biodegradation ratios were determined to assess the effect of biodegradation. The dimethyl, trimethyl and tetramethyl naphthalene biodegradation ratios show significant differences with increasing extent of biodegradation.     

Impacts of nitrogen and phosphorus on atrazine-contaminated soil remediation and detoxification by Arthrobacter sp. strain HB-5

The relationship of atrazine-degrading bacteria Arthrobacter sp. HB-5 and nitrogen and phosphorus fertilizer to atrazine degradation and detoxification in soil was investigated in a microcosm pot experiment. Treatments of soil containing atrazine (AW) with atrazine plus strain HB-5 alone (A), together with atrazine and strain HB-5 plus nitrogen alone (AN), phosphate alone (AP), and nitrogen and phosphate together (ANP) were used to investigate atrazine degradation and ecotoxicity. Atrazine residues in the soils were determined by high performance liquid chromatography, while soil ecotoxicity was tested by micronucleus (MN) assay of Vicia faba root tip cells. The results showed that degradation of atrazine in soil could be facilitated by the treatment of strain HB-5 as well as strain HB-5 application with the addition of nitrogenous and/or phosphorus fertilizers. The degradation rates varied as the following: ANP > AP > AN > A > AW in different treatments. At 10 days post treatment, degradation efficiency of over 90 % was achieved in all strain HB-5 treatments except AW, but with no statistically significant differences found between treatments. Soil ecotoxicity was significantly reduced along with the degradation of atrazine by strain HB-5, and the ecotoxicity of soils with applied fertilizer was below that of treatments without fertilizer. On the seventh day and later, the MN frequencies of all treatments were decreased in the control levels except for AW. Thus, adjusting soil nutrient contents not only promoted strain HB-5 to remove atrazine in soil but also mitigated soil ecotoxicity effects caused by atrazine. These results are important keystones for future remediation of atrazine-contaminated soils.     

反硝化条件下苯生物降解的微环境研究

探讨了厌氧微环境中苯的生物降解.接种物来自北京郊区的稻田土.结果表明, 在富集培养和转移培养微环境中, 苯和甲苯的降解与硝酸盐还原作用同时发生.甲苯比苯更易降解, 甲苯的存在促进了苯的降解.这是一例反硝化条件下苯能被生物降解的研究      

Catagenesis and composition of petroleum: Origin of n-alkanes and isoalkanes in petroleum crudes

Distribution of n-alkanes and isoalkanes in ca. 50 petroleum crudes have been examined by the gas chromatography. Molar distributions of n-alkanes with respect to their c atom numbers in the majority of crudes follow the exponential law, which signifies a random, chemical nature of n-alkane-generating processes occurring in the catagenesis stage of petroleum maturation. Similar distributions of n-alkanes were found in the products of mild thermolysis of heavy n-alkanes.Isoalkanes represent a major, 10–25%, petroleum component. The principal types of isoalkanes in crudes are monomethyl-branched, with the branches randomly positioned in the chains, and dimethyl-branched with one of the methyl groups predominantly in the second position in the chains. Thermolysis studies of individual n-alkanes, alkanoic acids, and esters in the presence of various minerals provided an explanation of the n-alkane and isoalkane distributions. Selected heavy n-alkanes are initially formed in decarboxylation reactions of heavy n-alkanoic acids and esters. Extensive thermocracking produces mixtures of lighter n-alkane and α-olefins. The olefins, in the presence of acidic clays, are converted in cationic reactions into mixtures of predominantly mono- and dimethyl-branched isoalkanes.     

Intrinsic biodegradation of diesel fuel in an interval of separate phase hydrocarbons

Emerging acceptance of the limitations of separate phase product recovery has spawned interest in the intrinsic alteration of residual separate phase petroleum products. In this study the geochemical changes in a continuous core through soil containing a separate phase diesel fuel #2 (SPD) in contact with groundwater are investigated. Chemical heterogeneities are shown to exist which can be attributed to weathering, particularly intrinsic biodegradation. The results show that the aliphatic hydrocarbon content is reduced and the δ¹³C ratio of the aliphatic hydrocarbons increased from top to bottom in the core. Both changes are thought to be due to preferential biodegradation of (isotopically lighter) n-alkanes. A slight increase in the relative abundance of shorter chain n-alkanes (<n-C₁₇) was also observed. The distribution of the dominant aromatic hydrocarbons (C₀–C₃ alkyl-naphthalenes) is remarkably consistent throughout the core, although naphthalene is depleted below the oil–water interface. In spite of low oil saturation (S₀), little or no evidence of biodegradation is noted at the uppermost boundary of the SPD. However, intrinsic biodegradation is evident approximately 0.3 m above the oil–water interface in spite of higher S₀. The extent of the chemical changes attributable to biodegradation (described above) gradually increases below the oil–water interface, eventually reaching a maximum at the bottom of the SPD profile (∼1.2 m below the interface) where S₀ is again reduced. The relatively higher level of biodegradation observed at and below the oil–water interface may be attributed to the reduced S₀ in this zone. An estimate of the mass reduction in diesel fuel between the uppermost and bottommost parts of the core is calculated to be 23% (by weight), due predominantly to the biodegradation of n-alkanes.     

The occurrence of ultra-deep heavy oils in the Tabei Uplift of the Tarim Basin,NW China

Deeply buried heavy oils from the Tabei Uplift of the Tarim Basin have been investigated for their source origin, charge and accumulation time, biodegradation, mixing and thermal cracking using biomarkers, carbon isotopic compositions of individual alkanes, fluid inclusion homogenization temperatures and authigenic illite K–Ar radiometric ages. Oil-source correlation suggests that these oils mainly originated from Middle–Upper Ordovician source rocks. Burial history, coupled with fluid inclusion temperatures and K–Ar radiometric ages, suggests that these oils were generated and accumulated in the Late Permian. Biodegradation is the main control on the formation of these heavy oils when they were elevated to shallow depths during the late Hercynian orogeny. A pronounced unresolved complex mixture (UCM) in the gas chromatograms together with the presence of both 25-norhopanes and demethylated tricyclic terpanes in the oils are obvious evidence of biodegradation. The mixing of biodegraded oil with non-biodegraded oil components was indicated by the coexistence of n-alkanes with demethylated terpanes. Such mixing is most likely from the same phase of generation, but with accumulation at slightly different burial depths, as evidenced by overall similar oil maturities regardless of biodegradation level and/or amount of n-alkanes. Although these Ordovician carbonate reservoirs are currently buried to over 6000 m with reservoir temperatures above 160 °C, no significant secondary hydrocarbon generation from source rocks or thermal cracking of reservoired heavy oil occur in the study area. This is because the deep burial occurred only within the last 5 Ma of the Neogene, and there has not been enough heating time for additional reactions within the Middle–Upper Ordovician source rocks and reservoired heavy oils.     

Hydrocarbon geochemistry of the Puget Sound region—I. Sedimentary acyclic hydrocarbons

Hydrocarbon compositions have been determined for ²¹⁰Pb-dated sediment cores collected at 23 sites within the inland marine waters of northwestern Washington State, U.S.A. Concentrations of total aliphatic hydrocarbons (TAH) and an unresolved complex mixture (UCM) are significantly higher in surface sediments near urban areas than at all other locations with a chronology that indicates a predominantly anthropogenic origin. Concentrations of chromatographically resolvable alkanes are comparatively uniform; the major constituents are plant wax n-alkanes and a naturally-occurring suite of fossil isoprenoid and n-alkanes. Pristane concentrations decrease sharply near the sea-sediment interface suggesting rapid degradation of a plankton-derived component. A saturated multibranched, but nonisoprenoid, C₂₀ hydrocarbon and two novel mono-olefinic analogs have been isolated along with a previously unreported suite for four acyclic multibranched C₂₅ polyenes. Structural and distributional similarities between the C₂₀ and C₂₅ multibranched hydrocarbons suggest that they may be structurally homologous and share a common source.     

The organic geochemistry of oil seeps from the Sierra de Perijá eastern foothills, Lake Maracaibo Basin, Venezuela

The organic geochemistry of samples from 11 oil seeps was studied. The samples were collected from the Cachirí area, Carboniferous Region of Tulé (Lake Maracaibo Basin, Venezuela), associated with the Tigre Fault. Biomarkers (hopanes, steranes, n-alkanes, acyclic isoprenoids, and aromatic steroids) were analyzed using gas chromatography-mass spectrometry (GC-MS). These hydrocarbon rich fluids have undergone biodegradation (2-6 on the Peters and Moldowan scale), showing both the partial loss of n-alkanes and the microbial degradation of isoprenoids and steranes. These oil seeps were generated from a mature calcareous source rock that was deposited in a marine paleoenvironment under reducing conditions. Moreover, these seeps are likely derived from the Cretaceous La Luna Formation that reached a level of maturity near the peak of oil generation in the study area. The nature of the studied oil seeps, together with the oil generation models reported for this rock unit in the study area, suggests that these oils are a mixture of an initially heavy, altered oil and a second migrated light crude oil resulting from two generation pulses from the La Luna Formation. Evidence for the presence of light oil trapped in the study area should prompt re-exploration in the northwestern coast of Lake Maracaibo in shallow reservoirs, previously discarded because they usually demonstrated a lack of light oils.     

Degradation of carbon disulphide (CS2) in soils and groundwater from a CS2-contaminated site

This study is the first investigation of biodegradation of carbon disulphide (CS₂) in soil that provides estimates of degradation rates and identifies intermediate degradation products and carbon isotope signatures of degradation. Microcosm studies were undertaken under anaerobic conditions using soil and groundwater recovered from CS₂-contaminated sites. Proposed degradation mechanisms were validated using equilibrium speciation modelling of concentrations and carbon isotope ratios. A first-order degradation rate constant of 1.25 × 10^?2 h^?1 was obtained for biological degradation with soil. Carbonyl sulphide (COS) and hydrogen sulphide (H₂S) were found to be intermediates of degradation, but did not accumulate in vials. A ¹³C/¹²C enrichment factor of ?7.5 ± 0.8 ‰ was obtained for degradation within microcosms with both soil and groundwater whereas a ¹³C/¹²C enrichment factor of ?23.0 ± 2.1 ‰ was obtained for degradation with site groundwater alone. It can be concluded that biological degradation of both CS₂-contaminated soil and groundwater is likely to occur in the field suggesting that natural attenuation may be an appropriate remedial tool at some sites. The presence of biodegradation by-products including COS and H₂S indicates that biodegradation of CS₂ is occurring and stable carbon isotopes are a promising tool to quantify CS₂ degradation.     

Effect of leaf litter degradation and seasonality on D/H isotope ratios of n-alkane biomarkers

During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n-alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of early diagenesis on the δD values of n-alkanes. We therefore investigated the n-alkane patterns and δD values of long-chain n-alkanes from three different C3 higher plant species (Acer pseudoplatanus L., Fagus sylvatica L. and Sorbus aucuparia L.) that have been degraded in a field leaf litterbag experiment for 27 months.We found that after an initial increase of long-chain n-alkane masses (up to ∼50%), decomposition took place with mean turnover times of 11.7 months. Intermittently, the masses of mid-chain n-alkanes increased significantly during periods of highest total mass losses. Furthermore, initially high odd-over-even predominances (OEP) declined and long-chain n-alkane ratios like n-C₃₁/C₂₇ and n-C₃₁/C₂₉ started to converge to the value of 1. While bulk leaf litter became systematically D-enriched especially during summer seasons (by ∼8‰ on average over 27 months), the δD values of long-chain n-alkanes reveal no systematic overall shifts, but seasonal variations of up to 25‰ (Fagus, n-C₂₇, average ∼13‰).Although a partly contribution by leaf-wax n-alkanes by throughfall cannot be excluded, these findings suggest that a microbial n-alkane pool sensitive to seasonal variations of soil water δD rapidly builds up. We propose a conceptual model based on an isotope mass balance calculation that accounts for the decomposition of plant-derived n-alkanes and the build-up of microbial n-alkanes. Model results are in good agreement with measured n-alkane δD results. Since microbial ‘contamination’ is not necessarily discernible from n-alkane concentration patterns alone, care may have to be taken not to over-interpret δD values of sedimentary n-alkanes. Furthermore, since leaf-water is generally D-enriched compared to soil and lake waters, soil and water microbial n-alkane pools may help explain why soil and sediment n-alkanes are D-depleted compared to leaves.     

Preservation of an ancient grassland biomarker signature in a forest soil from the French Massif Central

In response to the lack of studies focussing on the residence time of molecular biomarkers in soils, the lipid content of three soil profiles from the French Massif Central with different land use history were examined. The free neutral lipid content of two reference soil profiles developed under grassland and forest vegetation, and of a former grassland soil converted to forest about 60 years ago, was analysed using gas chromatography–mass spectrometry (GC–MS). Wax esters as well as the ratio of major homologues of n-alkanes and n-alkan-2-ones could be used to characterise the overlying vegetation in the reference forest and grassland soil profiles, but failed to distinguish the respective grassland and forest contributions to the profile of the soil that had changed use. For n-alkanes and n-alkan-2-ones, the failure might be attributed either to mixing of the molecular patterns inherited from the former and current plant cover, whereas for compounds such as wax esters simple degradation is likely to be involved. Conversely, iso- and anteiso-C_15:0 fatty acid methyl esters (FAMEs; of bacterial origin), steroids (tracing cattle faecal contamination), tricyclic diterpenoids and their oxygenated derivatives, as well as methoxyserratenes (inherited from Pinaceae) and triterpenyl acetates (specific to the Asteraceae), proved to be effective in distinguishing current land use for the reference soil profiles and for the converted soil. The persistence of these compounds in the changed use soil allowed us to estimate their residence time in soil.     

Evidence for in situ methanogenic oil degradation in the Dagang oil field

In situ biotransformation of oil to methane was investigated in a reservoir in Dagang, China using chemical fingerprinting, isotopic analyzes and molecular and biological methods. The reservoir is highly methanogenic despite chemical indications of advanced oil degradation, such as depletion of n-alkanes, alkylbenzenes and light polycyclic aromatic hydrocarbon (PAH) fractions or changes in the distribution of several alkylated polycyclic aromatic hydrocarbons. The degree of degradation strongly varied between different parts of the reservoir, ranging from severely degraded to nearly undegraded oil compositions. Geochemical data from oil, water and gas samples taken from the reservoir are consistent with in situ biogenic methane production linked to aliphatic and aromatic hydrocarbon degradation. Microcosms were inoculated with production and injection waters in order to characterize these processes in vitro. Subsequent degradation experiments revealed that autochthonous microbiota are capable of producing methane from ¹³C labelled n-hexadecane or 2-methylnaphthalene and suggest that further methanogenesis may occur from the aromatic and polyaromatic fractions of Dagang reservoir fluids. The microbial communities from produced oil–water samples were composed of high numbers of microorganisms (on the order to 10⁷), including methane producing Archaea within the same order of magnitude. In summary, the investigated sections of the Dagang reservoir may have significant potential for testing the viability of in situ conversion of oil to methane as an enhanced recovery method and biodegradation of the aromatic fractions of the oil may be an important methane source.     

The characteristics of the biomarkers and δ13C of n-alkanes released from thermally altered solid bitumens at various maturities by catalytic hydropyrolysis

Solid bitumen occurs extensively in the paleo-reservoirs of marine sequences in southern China. The fluids in these paleo-reservoirs have usually experienced severe secondary alteration such as biodegradation and/or thermal maturation. The concentrations of extractable organic matter (EOM) in the resulting solid bitumens are too low to satisfy the amount required for instrumental analysis such as GC–MS and GC–IRMS. It is also difficult to get enough biomarkers and n-alkanes by dry pyrolysis or hydrous pyrolysis directly because such solid bitumens are hydrogen poor due to high maturities. Catalytic hydropyrolysis (HyPy) can release much more EOM from solid bitumen at mature to highly over-mature stages than Soxhlet extraction, dry pyrolysis and hydrous pyrolysis. However, whether the biomarkers in hydropyrolysates can be used for bitumen-source or bitumen–bitumen correlations has been questionable. In this study, a soft biodegraded solid bitumen sample of low maturity was thermally altered to various maturities in a closed system. HyPy was then employed to release bound biomarkers and n-alkanes. Our results show that the geochemical parameters for source and maturity based on biomarkers released from these thermally altered bitumen residues by HyPy are insensitive to the degree of thermal alteration. Furthermore, the maturity parameters are indicative of lower maturity than bitumen maturation products at a corresponding temperature. This suggests that biomarker source and maturity parameters, based on the products of HyPy, remain valid for bitumens which have suffered both biodegradation and severe thermal maturation. The distributions of δ¹³C of n-alkanes in hydropyrolysates are also insensitive to the temperature used for bitumen artificial maturation. Hence, the δ¹³C values of n-alkanes in hydropyrolysates may also provide useful information in bitumen–bitumen correlation for paleo-reservoir solid bitumens.     

Size distributions of hydrocarbons in suspended particles from the Yellow River

Suspended particle samples from the Yellow River estuary were sorted into five grain size fractions to explore the effect of grain size distribution on organic matter content and composition. The n-alkanes and PAHs were determined for each size fraction. PAHs and n-alkanes were more abundant in the finer fractions and the loading decreases steadily with increasing of grain size. However, the total n-alkanes or PAHs normalized to organic C were lower in the smaller size fractions than those in the larger size fractions, suggesting n-alkanes or PAHs may be diluted by the addition of organic matter or gradually decreased by degradation in the smaller size fractions. The particulate n-alkanes in the Yellow River estuary consist of a mixture of compounds from terrigenous and riverine biogenic n-alkanes and more biogenic n-alkanes accumulate in finer particles. Particulate PAHs are related to combustion/pyrolysis processes of coal/wood, and the relative contribution of petrogenic PAHs increase with increasing grain size. The total particulate n-alkane and PAH discharges passing the Lijin Station are about 3.94 t d⁻¹ and 0.52 t d⁻¹, respectively. Fine particles (<32 μm) play a significant role in organic matter transfer.     

Deciphering biodegradation effects on light hydrocarbons in crude oils using their stable carbon isotopic composition: A case study from the Gullfaks oil field, offshore Norway

Compound-specific isotope analysis has become an important tool in environmental studies and is an especially powerful way to evaluate biodegradation of hydrocarbons. Here, carbon isotope ratios of light hydrocarbons were used to characterise in-reservoir biodegradation in the Gullfaks oil field, offshore Norway. Increasing biodegradation, as characterised, for example, by increasing concentration ratios of Pr/n-C₁₇ and Ph/n-C₁₈, and decreasing concentrations of individual light hydrocarbons were correlated to ¹³C-enrichment of the light hydrocarbons. The δ¹³C values of C₄ to C₉n-alkanes increase by 7-3‰ within the six oil samples from the Brent Group of the Gullfaks oil field, slight changes (1-3‰) being observed for several branched alkanes and benzene, whereas no change (<1‰) in δ¹³C occurs for cyclohexane, methylcyclohexane, and toluene. Application of the Rayleigh equation demonstrated high to fair correlation of concentration and isotope data of i- and n-pentane, n-hexane, and n-heptane, documenting that biodegradation in reservoirs can be described by the Rayleigh model. Using the appropriate isotope fractionation factor of n-hexane, derived from laboratory experiments, quantification of the loss of this petroleum constituent due to biodegradation is possible. Toluene, which is known to be highly susceptible to biodegradation, is not degraded within the Gullfaks oil field, implying that the local microbial community exhibits rather pronounced substrate specificities. The evaluation of combined molecular and isotopic data expands our understanding of the anaerobic degradation processes within this oil field and provides insight into the degradative capabilities of the microorganisms. Additionally, isotope analysis of unbiodegraded to slightly biodegraded crude oils from several oil fields surrounding Gullfaks illustrates the heterogeneity in isotopic composition of the light hydrocarbons due to source effects. This indicates that both source and also maturity effects have to be well constrained when using compound-specific isotope analysis for the assessment of biodegradation.     

A compound-specific n-alkane δC and δD approach for assessing source and delivery processes of terrestrial organic matter within a forested watershed in northern Japan

We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ¹³C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ¹³C values of odd carbon numbered C₂₃-C₃₃n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ¹³C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C₂₅-C₃₁n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.     

Dynamics of diesel fuel degradation in contaminated soil using organic wastes

Bioremediation is an effective measure in dealing with such contamination, particularly those from petroleum hydrocarbon sources. The effect of soil amendments on diesel fuel degradation in soil was studied. Diesel fuel was introduced into the soil at the concentration of 5 % (w/w) and mixed with three different organic wastes tea leaf, soy cake, and potato skin, for a period of 3 months. Within 84 days, 35 % oil loss was recorded in the unamended polluted soil while 88, 81 and 75 % oil loss were recorded in the soil amended with soy cake, potato skin and tea leaf, respectively. Diesel fuel utilizing bacteria counts were significantly high in all organic wastes amended treatments, ranging from 111 × 106 to 152 × 106 colony forming unit/gram of soil, as compared to the unamended control soil which gave 31 × 106 CFU/g. The diesel fuel utilizing bacteria isolated from the oil-contaminated soil belongs to Bacillus licheniformis, Ochrobactrum tritici and Staphylococcus sp. Oil-polluted soil amended with soy cake recorded the highest oil biodegradation with a net loss of 53 %, as compared to the other treatments. Dehydrogenase enzyme activity, which was assessed by 2,3,5-triphenyltetrazolium chloride technique, correlated significantly with the total petroleum hydrocarbons degradation and accumulation of CO₂. First-order kinetic model revealed that soy cake was the best of the three organic wastes used, with biodegradation rate constant of 0.148 day^?1 and half life of 4.68 days. The results showed there is potential for soy cake, potato skin and tea leaf to enhance biodegradation of diesel in oil-contaminated soil.     

N-Alkanes and polycyclic aromatic hydrocarbons (PAHs) profile of soil from some polluted sites in Niger Delta, Nigeria

Soil samples were collected at different locations from Etche and Obio Akpor local government area (LGA) of River State in Niger Delta. The n-alkane and polycyclic aromatic hydrocarbons were determined qualitatively and quantitatively using GC-FID. The concentration of PAHs in the soil samples ranged from 7.40 to 78.3 ng/g. The highest concentration of PAHs was recorded in Agbada 1 flow station, while the lowest concentration was recorded in Agbada 2 flow station. A significant level of pollution was also observed in the soil of Bomu pipeline at Obio Akpor LGA. Also, the distribution of n-alkanes in the samples was also used to assess the level of pollution in the studied area. Various n-alkanes and PAHs ratios were obtained to know the major source of pollution in the area under study. The main source of pollution was pyrolytic, which might be due to the gas flaring activities going on in the study area. Also, the results showed that n-alkanes could also be a complementary tool in assessing pollution and source apportionment.     

Diagenesis of organic matter and fine clay minerals: a comparative study

A geochemical study has been made of fine clay minerals and organic matter in subsurface shale samples from the Canadian Northwest Territories. The mixed layer clays comprise smectite-vermiculite-illite but are transformed during thermal diagenesis to a pseudo-quaternary system (smectitevermiculite-illite-chlorite) by incorporation of amorphous inorganic material. The first clay dehydration occurs prior to hydrocarbon generation and is accompanied by adsorption of K⁺ and substitution of Al³⁺ for Si⁴⁺ in the clay lattice. Vermiculite is an intermediary in the transformation of smectite to illite and in the presence of Ca²⁺ ions delays the second dehydration step to the zone where cracking of liquid hydrocarbons to gas occurs.Hydrocarbon generation commences at a vitrinite reflectance level of ? 0.5% R₀ maximum in both amorphous and woody-herbaceous organic matter but does not reach a significant level in the latter case until reflectance levels of 0.7% R₀ maximum. The pristane to phytane ratio and proportion of n-alkanes and acyclic isoprenoids increase during hydrocarbon generation from woody-herbaceous organic matter. Anomalous hydrocarbon yields from certain samples are attributed to high concentrations of plant resins. Destructions of liquid hydrocarbons by cracking commences at a reflectance level of 1.0% R₀ maximum and is essentially complete by a reflectance level of 1.4% R₀ maximum. The proportion of n-alkanes in the saturates decreases during cracking of the liquid hydrocarbons.